E
Ease of Expansion in Gas Separation
Adele Brunetti
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, Rende,
Italy
Quite often during the operation of a system for
the treatment of gases, it is necessary to expand it
for treating greater streams. In some cases, future
expansion is contemplated even during the initial
phase of a project. In other cases, it could be a
necessity not foreseen during system design phase
(Miller and Stcker 1989; Brunetti et al. 2010).
Membrane system expansion is very easy,
since this only requires the addition of identical
modules. This is the advantage offered by the
modularity of membrane units and the reduced
equipment and control systems required for oper-
ating it. In comparison, considering the other ref-
erence technologies for gas separation, PSA and
absorption systems can also be expanded, but it
requires additional design considerations and
adds cost in the initial phase of the project.
The cryogenic units cannot be expanded if it is
not foreseen during the design phase. Generally
they can be over-dimensioned, and a capacity
increase is often obtained without modication
to the cold box itself through addition of a tail
gas compressor.
# Springer-Verlag Berlin Heidelberg 2016
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-662-44324-8
References
Brunetti A, Bernardo P, Drioli E, Barbieri G (2010) Mem-
brane engineering progresses and potentialities in gas
separations. In: Yampolskii Y, Freeman B (eds) Mem-
brane gas separation. Wiley, New York, pp 281312
Miller GQ, Stcker J (1989) Selection of a hydrogen sep-
aration process NPRA annual meeting, 1921 Mar,
San Francisco
Effective Diffusivity
Renzo Di Felice
University of Genova, Genova, Italy
Effective diffusivity is a convenient parameter
which is introduced when diffusion takes place
in non-homogenous media. Consider, for exam-
ple, the case where a species is diffusing through
porous particles, such as reactant diffusing inside
a catalytic solid. In this case, the molecules have
to travel for a longer distance given that the pores
of the catalytic particles are not straight, and
moreover diffusion takes place over a smaller
area due to the solid being wall impermeable.
These effects are taken into account by dening
an effective diffusivity as

e
Deff D
t
624 Effectiveness Factor

where e is the particle void fraction and thereby References

takes into account the reduced ow area available
and t is the tortuosity which considers the longer Di Felice R, Cazzola D, Cobror S, Oriani L (2008) Oxygen
permeation in PET bottles with passive and active
distance traveled by the molecules. It should be
walls. Packag Technol Sci 21:405415
stressed, however, that more often than not, the Maxwell JC (1873) A treatise on electricity and magne-
parameter inside the parenthesis is utilized as a tism, vol 1. Clarendon Press, Oxford
tting factor derived from experimental data Nielsen LE (1967) Models for the permeability of lled
polymer systems. J Macromol Sci A1(5):929942
rather than predicting factor from the solid phys-
ical characteristics. These result in the reported
tortuosity factor, for example, to assume rather
wild values, as high as ten, which are difcult to
justify with geometrical arguments alone.
Effectiveness Factor
The concept of effective diffusivity is also
Renzo Di Felice
applied for the case of species diffusing in hetero-
University of Genova, Genova, Italy
geneous media, such a polymer lled with a sec-
ond, less permeable, material. Maxwell (1873)
has obtained an exact expression, in the case of The concept of effectiveness factor is utilized
composite media lled with spheres, for the effec- when the effect of diffusion on the overall rate of
tive diffusivity given as a reacting process wants to be taken into account.
  Lets consider a catalytic solid particle where a
2 1 1 1
 2f  reaction takes place. For a species to react, it must,
D D D D
Deff D S  S  at the same time, diffuse inside the catalytic parti-
2 1 1 1 cle and react. It is intuitive that the diffusion step
f 
DS D DS D slows the overall process rate, and an effective-
ness factor is dened as
where D is the diffusion coefcient in the primary
media, Ds the diffusion coefcient through the actual rate of process
spheres, and f the sphere volume fraction. For

rate of process if diffusion were infinitively fast
the limiting case of the spheres being completely
impermeable, Maxwell expression simplify to This denition is equivalent to consider reactant
concentration on any point in the catalytic particle
1f
Deff D equal to that at the external surface.
f A rather straightforward mass balance allows
1
2 the determination of the effectiveness factor for a
Various empirical expressions have been reported single cylindrical pore where a rst-order reaction
in literature in order to take into account the devi- is taking place on the wall:
ation from sphericity of the foreign material. Par-
tanhf
ticularly simple and efcient is the expression

f
proposed by Nielsen (1967):
where f is the Thiele module dened as
1f
Deff D s
af
1 k
2 fL
Deff
where a is the dispersed material aspect ratio.
Nielsen relationship has been shown to do a sat- with L the pore length, k the chemical reaction
isfactory job against experimental evidence kinetic factor, and Deff the reacting species effec-
(Di Felice et al. 2008). tive diffusivity.
Electrical Double Layer
As expected the effectiveness factor approa-
ches 1 when Thieles module is very small, i.e.,
for very short pores or very slow reaction or very
high diffusion coefcients. On the other hand, for
very high value of Thiele modules, effectiveness
factor approaches the inverse of the Thiele
module.
The above result can be easily generalized for
the case of at plate by putting L equal to half the
plate width, for the case of long cylindrical pellets
by putting L equal to half the pellet radius, and to
the case of spherical pellets by putting L equal to
one third the sphere radius. Extension to kinetic
different from the rst order has been presented in
literature, and a summary can be found, for exam-
ple, in Sattereld (1991).
References
Sattereld CN (1991) Heterogeneous catalysis in industrial
practice. McGraw-Hill, New York
Electrical Double Layer
Karel Bouzek and Tomas Bystron
Faculty of Chemical Technology, University of
Chemistry and Technology Prague, Technick 5,
Prague 6, Czech Republic
An electrical double layer is usually considered to
form at the phase interface between two electri-
cally conducting media. In such a case, on one
side of the interface, an excess of positive charge
exists, which is counterbalanced by an identical
excess of negative charge localized on the oppo-
site side of the interface. The overall system
charge is thus equal to zero. In membrane science,
this denition has, to a certain degree, been mod-
ied, the reason being that membranes can be
produced from a broad spectrum of materials,
including (i) electronic conductors (e.g., metals),
(ii) ionic conductors (e.g., O2-conducting
ceramics), (iii) functionalized polymers providing
ionic conductivity through the liquid lling the
625
E
Electrical Double Layer, Fig. 1 Schematic sketch of
structure of the Electrical Double Layer for (a)
functionalized and (b) nonfunctionaalized membrane
materials
void volume of the material (ion-selective mem-
branes), and (iv) nonfunctionalized polymeric or
ceramic membranes.
Whereas, in the rst two cases, the traditional
denition is valid, in the last two, the situation is
different. This is due to the fact that the bulk
membrane material is neither an electronic nor
an ionic conductor. Hence the double layer only
forms on one side of the phase interface. The
Fig. 1 provides a schematic sketch of the two
mentioned cases. In the case of functionalized
materials, the charge-carrying groups covalently
bound to the polymeric backbone are oriented
towards the void volume of the membrane inte-
rior, thus forming an electrically charged lm
covering the phase interface on the side of the
solution. The charge of this lm is compensated
by that of the mobile ions present in the solution
and located close to the lm (see Fig. 1a).
In the case of the non-functionalized materials,
the surface charge xed to the surface of the solid
phase is formed by specic adsorption of ions of
one sign. Both the sign of the adsorbed ions and
the extent of the adsorption are determined by the
properties of the membrane material. In this case,
too, the xed charge is compensated by the charge
626
of ions moving in the system and located close to
the absorbed surface lm (see Fig. 1b).
An electrical double layer signicantly inu-
ences the properties of the membrane, mainly with
respect to its transport properties and behavior
under current load. In selected cases the surface
of the membrane materials is modied to achieve
the preferred adsorption and thus the required
transport and properties, including selectivity.
Electrical Interactions in Membranes
Karel Bouzek
Faculty of Chemical Technology, University of
Chemistry and Technology Prague, Technick 5,
Prague 6, Czech Republic
In general electrical (electrostatic) interactions
arise as a result of the interaction of electrically
charged particles (charge carriers) with sur-
rounding matter (electrically charged and neu-
tral) (Stuart 1989). In the case of membranes,
probably the most important interactions to con-
sider are those between electrically charged bod-
ies, such as ions dissolved in solution and
ion-conducting, functionalized, or even inert
membranes. In living systems the electrostatic
interactions between the charged/polar and neu-
tral/nonpolar side of a solute molecules with each
other and with a solvent are responsible for the
formation/assembly of monolayer and bilayer
biological membranes and their functioning.
On the uid side the charge carriers are typi-
cally mobile ions or colloidal particles of organic
and inorganic nature. These carriers interact with
the charge carriers xed in the material of the
membrane (see also the electrical double layer).
The charge xed in the membrane material is, in
principle, of dual origin: (i) it comes from the
component introduced and incorporated during
its synthesis, and (ii) it is the result of the specic
adsorption of ions on the surface of the solid
phase. Electrostatic interactions between xed
and freely moving charge carriers are responsible
not only for several phenomena characteristic of
Electrical Interactions in Membranes
membrane separation processes, such as the exis-
tence of Donnan potential, the selectivity of mass
transport, or mass transport enhancement under
current load by electroosmotic ux, but also for
the existence of life itself. These facts document
the importance of electrical interactions in mem-
brane materials with respect to their transport
properties.
References
Stuart McLaughlin (1989) The Electrostatic Properties of
Membranes. Annu. Rev. Biophys. Biophys. Chem.
18:113136
Electrical Potential
Karel Bouzek and Tomas Bystron
Faculty of Chemical Technology, University of
Chemistry and Technology, Prague, Technick 5,
Prague 6, Czech Republic
Electric potential is a scalar physical quantity
determined by the electric energy (or work in
general) necessary to transfer a unit positive elec-
tric charge from innity to the point of interest in a
studied system. The point in innity is formally
chosen as a reference state characterized by zero
electric potential. From this more or less abstract
and intuitive denition of the reference state, it is
apparent that the absolute value of electric poten-
tial is not available experimentally. However, it is
possible to measure electric potential difference,
known as voltage.
We can distinguish between outer (external)
and inner (internal) electric potential. In the case
of outer electric potential, the charge is transferred
to the closest proximity of the external surface of
the phase P. However, the distance from this sur-
face has to be large enough to avoid the appear-
ance of molecular and image forces. At the same
time it should not cause any weakening of the
electric interaction with the charge located on the
internal side of the phase interface. The inner
Electrically Enhanced Processes by Membrane Operations
electric potential is determined by the strength of
the electric eld in the interior of the phase P. It
thus represents the work necessary to transport the
charge from innity to the phase P. The difference
between the inner electric potential and the outer
electric potential corresponds to the surface poten-
tial of phase P (Arthur and Alice 1997).
References
Arthur W. Adamson, Alice P. Gast (1997) Elecrical
Aspects of Surface Chemistry, in Physical Chemistry
of Surfaces, 6th edn. John Wiley & Sons, Inc.
ISBN:0-471-14873-3)
Electrical Work in Membranes
Karel Bouzek
Faculty of Chemical Technology, University of
Chemistry and Technology Prague, Technick 5,
Prague 6, Czech Republic
An electrical work is dened as the work
connected with the charge carrier transport
between two points in an electric eld, i.e., from
point of potential 1 to point of potential 2. Thus,
electrical work in membranes is the product of the
transported electrical charge and the difference in
electric potentials between which it has passed
(Arthur and Alice 1997). Since the resistivity of
the membrane can be approximated by ohmic
resistivity, the electrical work dissipated in the
membrane is equal to the ohmic potential loss in
the membrane multiplied by the current load.
Expressed alternatively, it is equal to the square
of the current load multiplied by the ohmic
resistivity.
References
Arthur W. Adamson, Alice P. Gast (1997) Elecrical
Aspects of Surface Chemistry, in Physical Chemistry
of Surfaces, 6th edn. John Wiley & Sons, Inc. ISBN:
0-471-14873-3
627
Electrically Enhanced Processes by
Membrane Operations
Karel Bouzek
Faculty of Chemical Technology, University of
Chemistry and Technology Prague, Technick 5,
Prague 6, Czech Republic
E
Electrically membrane operations are typically
limited to systems involving electrically charged
particles. In such a case, the application of an
electric eld can often signicantly enhance the
ongoing process. In selected cases, it is the appli-
cation of an external electric eld that makes the
desired processes possible at all. By applying an
electric eld, electrically charged particles are
dragged in the direction determined by the polar-
ity of their charge and the vector of the electric
eld. This movement is responsible for electric
current ow through the system. Part of the
electric charge carried by one type of particles
corresponds to what is known as the transference
number of the given particle. It is proportional to
the particle mobility in the system and the electric
charge it carries (Colin 1976).
In the case of membrane operations enhanced
by an electric eld, generally functionalized
ion-selective membranes are considered. Electro-
dialysis and dialysis are typical representatives of
an electrically enhanced and a nonenhanced pro-
cess, respectively. Electrodialysis is used to desa-
linate a treated stream containing dissolved ions
by transporting them, due to the action of the
electric eld, against the concentration gradient
to the concentrate stream (Fernando et al. 2011).
In the case of dialysis the situation is the reverse,
since the dissolved species move in the direction
of the concentration gradient away from the
treated stream to the solution free of the removed
components owing along the opposite side of the
membrane. It is thus clear that electrodialysis is
typically a signicantly more intensive process in
terms of the desalination rate. At the same time, it
produces a signicantly lower volume of the
stream carrying the removed components. The
electric eld thus enhances the intensity of the
628
mass ux during membrane processes involving
charged species and makes it possible to transport
the charged species against the concentration gra-
dient. On the other hand, dialysis is not limited to
charged particles.
Electrically enhanced membrane operations
can also be carried out with nonfunctionalized
membrane materials or with membrane materials
carrying no xed electric charge, electroltration
being an example. Here, the applied electric eld
inuences the membrane operation indirectly by
preventing blockage of the membrane surface.
This is ensured by the electrophoretic transport
of the charged colloidal particles concentrated in
the solution away from the surface of the ltering
membrane, see also Electroltration.
It is, therefore, evident that the application of
an external electrical eld can signicantly
enhance or modify processes, including mem-
brane operations.
References
Colin A (1976) Vincent: The Motion of Ions in Solution
under the Inuence of an Electric Field. J. Chem. Educ,
vol. 53, pg. 490
Fernando Valero, Angel Barcel and Ramon Arbos
(2011). Electrodialysis Technology - Theory and
Applications, Desalination, Trends and Technologies,
Michael Schorr (Ed.), ISBN: 978-953-307-311-8,
InTech, DOI: 10.5772/14297. Available from: http://
www.intechopen.com/books/desalination-trends-and-
technologies/electrodialysis-technology-theory-and-
applications
Electrochemical Deposition
Track-Etch Membranes as Tools for Template
Synthesis of Nano-/Microstructures and Devices
Electrochemical Impedance
Spectroscopy
Impedance Spectroscopy, Membrane Charac-
terization by
Electrochemical Deposition
Electrochemical Impedance
Spectroscopy (EIS)
Impedance Spectroscopy
Electrochemical Membrane
Bioreactor
Bioelectrochemical MBR
Electrochemical Processing
Tanja Vidakovic-Koch
Max Planck Institute for Dynamics of Complex
Technical Systems, Magdeburg, Germany
In electrochemical processing, electrical energy is
supplied to or obtained from the electrochemical
system in order for chemical production or energy
conversion to take place (Bard and Stratmann
2007). The rst group of processes, also called
electrolytic, is not spontaneous. The second group
of processes, called galvanic, is spontaneous and it
delivers electrical energy. Electrolytic processes
can be further divided into two categories: inor-
ganic and organic. In inorganic electrochemical
processing, important commodity chemicals such
as sodium hydroxide, chlorine, and pure metals are
produced. The major inorganic electrochemical
processing technologies are chlor-alkali electroly-
sis and electrowinning of metals like aluminum or
copper. Nowadays, hydrogen production by water
electrolysis gets more on importance in context of
chemical storage of renewable electrical energy
(wind and photovoltaic) in hydrogen. The most
signicant commercial electroorganic synthesis is
Monsantos electrohydrodimerization (EHD) of
acrylonitrile to adiponitrile. Adiponitrile has an
importance in production of nylon 6-6. Examples
of galvanic systems are fuel cells and batteries. The
main product of galvanic systems is electrical
energy.
Electrochemical Regeneration
Electrochemical systems have some intrinsic
advantages over other types of chemical systems
like better control of a reaction rate, operation at
lower temperatures, and less environmental
impact. They take place in an electrochemical
reactor. The design of an electrochemical reactor
is inuenced by the state of aggregation of reac-
tants (gas, liquid, or solid), necessity of reactants
and/or products separation, required mass trans-
port conditions, and electrode materials. If prod-
uct or reactant separation is required, an
electrochemical reactor must contain a separator,
which is a membrane. Major requirements on a
membrane are good separation efciency, low
electrical resistance, no electron conductivity,
low cost, long operating life time, good dimen-
sional stability, and resistance to plugging and
fouling. In general permeable and semipermeable
membranes have been applied in electrochemical
processing. Permeable membranes are porous
materials lled with liquid electrolyte which per-
mit the bulk ow of liquid through their structure
and are thus nonselective regarding transport of
ions or neutral molecules. In electrochemical pro-
cesses, these are also referred to as diaphragms.
Permeable membranes can be made of inorganic
and organic materials and composites. Examples
of these materials are asbestos (chlor-alkali elec-
trolysis), polymers like polyethylene and polypro-
pylene (batteries), or composites like polymer
(polypropylene)-modied asbestos. Semiperme-
able membranes permit the selective passage
of certain species by virtue of molecular size
or charge. In electrochemical processes,
ion-conducting membranes (see solid electrolyte)
are broadly applied. In general, ion-conducting
membranes have higher separation efciency
and lower electrical resistance than diaphragms,
but they are also more costly and impose higher
requirements on system purity.
References
Bard AJ, Stratmann M (eds) (2007) Encyclopedia of elec-
trochemistry. Macdonald DD, Schmuki P (eds) Elec-
trochemical engineering, vol 5. Wiley-VCH Verlag
GmbH & Co. KGaA, Weinheim
629
Electrochemical Regeneration
Tanja Vidakovic-Koch
Max Planck Institute for Dynamics of Complex
Technical Systems, Magdeburg, Germany
In electrochemical regeneration electrical energy
is applied to restore some important property, like
E
adsorption capacity or catalyst activity of a tech-
nical system. Electrochemical regeneration relies
on principles of electrochemistry and relates to
electrochemical processing. Electrochemical
regeneration is conveniently conducted in situ
with an electron as only reagent requiring simple
handling and equipment. A technical setup for
electrochemical regeneration requires in general
two electrodes, an electrolyte and a power supply.
In addition a membrane can be added to the setup
in order to separate anode and cathode depart-
ment. Some examples of electrochemical regen-
eration are electrochemical regeneration of
activated carbon-based adsorbents in wastewater
treatment and regeneration of enzymatic cofactors
in electroenzymatic processes.
Organic pollutants in wastewaters can be
removed by adsorption using, e.g., activated car-
bon as an adsorbent. This process is normally
operated using a batch of adsorbent with sufcient
capacity to operate for many months before
reaching saturation. Once loaded, adsorbent
must be disposed or regenerated. One option for
adsorbent regeneration is electrochemical regen-
eration (Brown et al. 2004). The loaded adsorbent
is located in a form of a packed or uidized bed in
the anode (anodic regeneration) or cathode
(cathodic regeneration) compartment of the reac-
tor. The efciency of the regeneration depends on
the processing time, voltage gradient, an electro-
lyte, and a compartment. According to literature
the efciency of cathodic regeneration is higher
than of anodic regeneration. The mechanism of
electrochemical regeneration is ascribed at the
rst place to local pH changes close to anode or
cathode. At the anode side due to oxygen evolu-
tion reaction a pH decrease can be expected, while
at the cathode side due to hydrogen evolution pH
630
value will increase. This pH changes induce
organic pollutants desorption. In the next step,
dissolved pollutants can be oxidized at the anode.
In the case of the cathodic regeneration they have
rst to mitigate from the cathode to the anode. This
might be mass transfer controlled leaving some
residues in the cathode, unless very large currents
or long regeneration times are employed.
Further example of electrochemical regenera-
tion is regeneration of enzymatic cofactors in
electroenzymatic processes (Wichmann and
Vasic-Racki 2005). Redox enzymes are very
selective and specic catalysts, which can enable
a number of partial oxidation or reduction reac-
tions for industrial applications at mild conditions.
Broader industrial application of redox enzymes
has been so far hindered by their dependence on
expensive cofactors (e.g., nicotinamide adenine
dinucleotide (NAD)), which are consumed in the
reaction (e.g., Eq. 1) and have to be regenerated
for a process to be economical:
CO2 NADH H HCOOH NAD (1) et al. 2007). Applications of electrochemistry are
Electrochemical regeneration offers a possibility
of cofactor regeneration. In this respect especially
regeneration of NAD has been studied since
NAD-dependent oxidoreductases are of great
industrial interest. The electrochemical regenera-
tion can be represented by this reaction:
NAD H 2e NADH (2) are owing through the electrolyte which is exclu-
This reaction is however not selective enough and
the kinetics is very sluggish on most known elec-
trode materials. Some improvements have been
achieved by using surface-modied electrodes.
Another strategy is to add an additional mediator
according to
NAD Medred NADH Medox (3) and kinetics (Butler-Volmer or Tafel equations)
Medox H 2e Medred (4) force for the electrochemical reaction to take
Electrochemical cofactor regeneration is still not a
mature technology, and further improvements in
electrode materials are needed to make this option
feasible.
Electrochemistry
References
Brown NW, Roberts EPL, Garforth AA, Dryfe RAW
(2004) Electrochemical regeneration of a carbon-
based adsorbent loaded with crystal violet dye.
Electrochim Acta 49:32693281
Wichmann R, Vasic-Racki D (2005) Cofactor regeneration
at the lab scale. Adv Biochem Eng Biotechnol
92:225260
Electrochemistry
Tanja Vidakovic-Koch
Max Planck Institute for Dynamics of Complex
Technical Systems, Magdeburg, Germany
Electrochemistry is a branch of chemistry which
studies charge transfer processes across an elec-
tried interface also called an electrochemical
double layer (Bockris and Reddy 1988, Hamann
broad including electrochemical processing, elec-
troanalysis electrochemical sensors, electrochem-
ical regeneration, and corrosion. In addition,
many important processes in biological systems
like photosynthesis and cell respiration are inher-
ently electrochemical processes.
The main feature of an electrochemical system
is a separation of ionic- and electronic ows. Ions
sively an ionic conductor, while electrons ow
through an outer electrical circuit which is exclu-
sively an electron conductor. These two ows are
interconverted at the electrode/electrolyte inter-
face across the electrochemical double layer by
means of an electrochemical reaction The poten-
tial difference in the electrochemical double layer
is related to thermodynamics (Nernst equation)
of an electrochemical reaction and it is a driving
place. This unique feature of electrochemistry
makes easy to control the reaction rate by elec-
trons at different energies.
Electrochemical processes can be spontaneous
(Gibbs free energy, DG <0), called galvanic, and
Electrodeionization
nonspontaneous DG>0, called electro-
lytic. Instead in terms of Gibbs free energy, spon-
taneity of an electrochemical process can be
expressed in terms of cell voltage, where a posi-
tive value stands for a galvanic system and a
negative for an electrolytic. The relationship
between the cell voltage and Gibbs energy is
given by equation DG = nFUr, where n stands
for number of exchanged electrons, F for a Fara-
day constant, and Ur for an equilibrium cell
voltage.
Many electrochemical systems require pres-
ence of separators. This is usually a membrane
which can be a permeable, termed diaphragm, or
semipermeable, termed membrane. The latter type
usually in addition to separation serves as an
electrolyte, so-called solid electrolyte in electro-
chemical systems. An example is ceramic yttria-
stabilized zirconia (YSZ) membrane which has
found an application in solid oxide fuel cells.
The ionic conductivity of this material is provided
by O2 ions.
References
Bockris JOM, Reddy AKN (1988) Modern electrochem-
istry. Plenum Press, New York
Hamann CH, Hamnett A, Vielstich W (2007) Electrochem-
istry, 2nd edn. Wiley-VCH Verlag GmBH, Weinheim
Electrodeionization
Karel Bouzek
Faculty of Chemical Technology, University of
Chemistry and Technology Prague, Technick 5,
Prague 6, Czech Republic
Electrodeionization represents a variant of elec-
trodialysis, modied in order to allow treatment of
low-salinity and low-conductivity media. This
technique is typically applied to produce high-
purity water suitable for use, for example, in ener-
getics. It combines the advantages of ion
exchange with those of electrodialysis.
631
This technology is based on an electrodialysis
unit with a diluate and also, in selected cases, a
concentrate chamber lled with ion-exchanger
particles. They can be arranged as monopolar
beds (formed by particles of one polarity ion
exchanger), as layered beds (cation- and anion-
exchanger particles lled separately in several
alternating layers), or as a mixed bed (uniform
mixture of both types of ion-changer particles).
The ion-exchange phase takes on the role of
E
electroconductive media, thus reducing ohmic
drop in the dilute chamber. At the same time it
provides a three-dimensional interface for the
removal of traces of ions present in the solution.
Two regions are typically distinguished in the
electrodeionization operation: (i) ions removal
and (ii) solvent splitting. Within the rst region
the electrodeionization unit works bellow mass
transfer limitation. It means, ux of ions to the
solution ion exchanger interface driven by the
current load used has a value well below mass
transfer limitation in a dilute chamber. The func-
tion of the ion-exchange bed consists in providing
a pathway for ions trapped in the dilute channel to
the ion-selective membranes separating dilute/
concentrate chambers. In a second domain, how-
ever, the current load exceeds limiting current
density, i.e. limiting ux of ions present from
solution to the solution ion exchanger interface.
In such a case sufcient number of ions to trans-
port corresponding electrical charge is provided
by decomposition (dissociation) of the solvent
(typically water). In contrast to electrodialysis,
this splitting does not take place only at the
solution-membrane interface but also at the con-
tact of the cation- and anion-selective phase
(Alvarado and Chen 2014).
In the case of a concentrate chamber, the role of
the ion-exchange phase again consists in reducing
ohmic drop in the channel while maintaining the
concentration of the ions in the liquid phase at a
minimum to reduce back diffusion from the con-
centrate to the dilute chamber.
The quality of the stream produced is compa-
rable to that of the ion-exchange process. The
advantage of electrodeionization is that it is a
continuous process that does not require a regular
regeneration phase of operation. This feature of
632 Electrodialysis

electrodeionization has a further important
advantage. It saves a signicant amount of
corresponding chemicals and reduces the salinity
of the waste streams produced. Such technology is
thus a suitable component for closed loop tech-
nologies which, on ending, discharge removed
salts in the solid form and avoids production of
contaminated liquid streams.
References
Alvarado L, Chen A, (2014) Electrodeionization: Princi-
ples, Strategies and Applications, Electrochim. Acta
132:583
Electrodialysis
Heiner Strathmann
Universitt Stuttgart, Institute of Chemical
Process Engineering Stuttgart, Baden-
Wurttemberg, Germany
The principle of electrodialysis is illustrated in
Fig. 1 which shows a series of alternating anion-
and cation-exchange membranes arranged
between two electrodes. The membranes are sep-
arated by a spacer gasket and form individual
cells, through which an electrolyte solution is
pumped. When an electrical potential difference
between the electrodes is established, the cations
migrate toward the cathode. They pass through
the cation-exchange membrane, but they are
retained by the anion-exchange membrane. Like-
wise the anions migrate toward the anode and pass
through the anion-exchange membrane but are
retained by the cation-exchange membrane. The
overall result is that an electrolyte is concentrated
in alternate compartments, while its ion content is
depleted in the other compartments. In an indus-
trial size electrodialysis stack, 100400 cell pairs
are arranged between the electrodes. Various
spacer and stack constructions such as the
so-called sheet ow are used in practical applica-
tions (Schaffer and Mintz 1966).
The concept of a sheet ow stack is illustrated
in Fig. 2 which shows the arrangement of the
spacers and membranes in a stack. The spacers
not only separate the membranes and provide the
proper mixing of the solutions in the cells, but in
their frames, they also contain the manifolds for
the two different ow streams in the stack.
Practical problems which affect the efciency
of electrodialysis are concentration polarization
and membrane fouling. Concentration polariza-
tion which determines the so-called limiting cur-
rent density is controlled by hydrodynamic
parameters of the feed ow in the stack. Mem-
brane fouling is controlled by a technique which is
referred to as clean in place or electrodialysis
reversal (Katz 1979).
The total costs in electrodialysis are the sum of
the plant capital and the plant operating costs. The

Electrodialysis, Concentrate
Fig. 1 Schematic diagram
illustrating the principle of Diluate
electrodialysis A C A C C
+ + + +
+ +
+
+ +
Anode + + Cathode
+ + + +
+ +
+ + +
+ +
+ + + + + + +
+ +
Electrode + + Electrode
rinse + + rinse
Feed

Repeating unit
Electrodialysis Reversal 633

Ion-exchange
Electrode membrane
cell

Concentrate
Diluate

Electrode
rinse solution

E
Feed solution

Feed solution

Electrode Diluate cell

Spacer Concentrate cell

Electrodialysis, Fig. 2 Schematic drawing illustrating the construction of a sheet ow stack design

capital related costs are proportional to the
required membrane area for a given capacity
plant and a for a given feed and product
concentration. The operating costs are propor-
tional to the required desalination energy which
is the function of the transferred ions, i.e., the
concentration difference between the feed and
product ion concentration. The energy EV
required to desalinate 1 m3 of water by electrodi-
alysis is given by
Fr A
CP i
 f 
EV C  Cp
x References
A major disadvantage especially for the produc-
tion of potable water is the fact that only ions are
removed, while uncharged components such as
microorganisms or organic contaminants will not
be eliminated. Another disadvantage of electrodi-
alysis is the relatively high energy consumption
when solutions with high salt concentrations have
to be processed. Thus, electrodialysis can only be
cost-effectively applied in water desalination in a
certain range of feed water salt concentration and
required product water (Strathmann 2010).

Here rACP is the area resistance of the cell pair,
which can be estimated from measurements of
membrane resistance and conductivities of solu-
tions, F is the Faraday constant, i is the current
density, Cf and Cp are the feed and product water
concentrations, and x is an efcient term which is
generally close to 1.
Electrodialysis has advantages and limitations
compared to other deionization processes such as
reverse osmosis. A main advantage of electrodi-
alysis compared to reverse osmosis is that very
little feed pretreatment is required and higher
brine concentrations can be achieved.
Katz WE (1979) The electrodialysis reversal process.
Desalination 28:3140
Schaffer LH, Mintz MS (1966) Electrodialysis. In:
Spiegler KS (ed) Principles of desalination. Academic,
New York, pp 320
Strathmann H (2010) Electrodialysis, a mature technology
with a multitude of new applications. Desalination
264:268288
Electrodialysis Reversal
Reverse Electrodialysis (RED)
634 Electrodialysis Reversal in High Supersaturation Mode

stack as illustrated in Fig. 1 which shows a typical

Electrodialysis Reversal in High
Supersaturation Mode
Reverse Electrodialysis in High Supersatura-
tion Mode
Electrodialysis with Bipolar
Membranes
Heiner Strathmann
Universitt Stuttgart, Institute of Chemical
Process Engineering Stuttgart, Baden-
Wurttemberg, Germany
The conventional electrodialysis can be combined
with bipolar membranes and utilized to produce
acids and bases from the corresponding salts.
A bipolar membrane is a laminate of an anion on
a cation-exchange layer. In this process
monopolar cation- and anion-exchange mem-
branes are installed together with bipolar mem-
branes in alternating series in an electrodialysis
repeating unit of an electrodialysis stack with
bipolar membranes is composed of three cells,
two monopolar membranes and a bipolar mem-
brane. The outer cells of the repeating unit are fed
with a salt solution, the inner cells with water, or a
diluted acid and base. When an electrical potential
gradient is applied across a repeating unit, protons
and hydroxide ions which are generated in the
bipolar membrane generate with the cations and
anions removed from the salt solution, an acid and
a base on either side of the bipolar membrane. The
process design is closely related to that of the
conventional electrodialysis using the sheet ow
stack concept (Liu et al. 1977; Simons 1993).
The utilization of electrodialysis with bipolar
membranes to produce acids and bases from the
corresponding salts is economically very attractive
and has a multitude of interesting potential appli-
cations in the chemical industry as well as in bio-
technology and water treatment processes. Its key
component is the bipolar membrane. The bipolar
membrane schematically illustrated in Fig. 2 con-
sists of a laminate of an anion- and a cation-
exchange membrane with a 45 nm thick catalytic
transition layer in between. In Fig. 2 this transition

Base Acid Base Acid

Repeating
cell unit
cm bpm am cm bpm am
+ + + +
+ + + +
+ + + +
M + + + + +


+
+ H + + + M + M+ + H+ +
+
+ +
+ + +
+ +
+ OH + +
+

+ X + X +
OH + + + +
+ + + +
+ + + +
+ + + X +
+ + + +
+ + + +
+ + + +

Salt solution Salt solution Salt solution

Electrodialysis with Bipolar Membranes, cell unit consisting of a cation-exchange membrane (cm), a
Fig. 1 Schematic drawing illustrating the principle of bipolar membrane (bpm), and an anion-exchange mem-
the electrodialytic production of an acid and a base from brane (am)
the corresponding salt with bipolar membranes. Repeating
Electrodialysis with Bipolar Membranes
Cation-exchange Anion-exchange
layer layer
H2O + H2O
Cathode +
Anode
+
+ brane is rather expensive, and its useful life time
H+ +
OH
+ as well as that of the anion-exchange membrane is
+
+ rather limited in strong bases. The operating costs
Bipolar membrane
Electrodialysis with Bipolar Membranes,
Fig. 2 Schematic drawing illustrating the electrodialytic
water dissociation in a bipolar membrane with water dif-
fusing into the reaction region between the cation- and
anion-exchange layers of the membrane and protons and
hydroxide migrate to the corresponding electrode
layer has been articially magnied. Water is dif-
fusing through both membrane layers into the tran-
sition layer where it gets electro-catalytically
dissociated into H+- and OH-ions, which
migrate toward cathode and anode into the outer
solutions.
The energy required for the water dissociation
can be calculated from the Nernst equation for a
concentration chain between solutions of different
pH-values. It is given by:
DG FD 2:3RTDpH
Here DG is the Gibbs free energy and DpH and
D are the pH-value and the potential difference
between the two solutions separated by the bipolar
membrane. For 1 mol/L acid and base in the two
phases separated by the bipolar membrane, DG is
0,022 kWh/mol and D is ca. 0,83 V at 25  C.
Compared to the ohmic potential drop over the
membranes, the required potential drop for water
splitting in the transition layer is much more pro-
nounced. The determination of the costs for the
production of acids and bases from the
corresponding salts follows the same general pro-
cedure as applied for the cost calculation in elec-
trodialysis desalination. The overall costs are the
investment-related costs and the operating costs.
The investment-related costs are dominated by the
membrane costs and are proportional to the
635
required membrane area for a given capacity
plant. They are a function of the current density
applied in a given stack operation. A unit cell
contains a bipolar membrane, a cation- and an
anion-exchange membrane. The bipolar mem-
in electrodialysis with bipolar membranes are
strongly determined by the energy requirements
E
which are composed of the energy required for the
water dissociation in the bipolar membrane and
the energy necessary to transfer the salt ions from
the feed solution and protons and hydroxide ions
from the transition region of the bipolar mem-
brane into the acid and base solutions. The energy
consumption due to the pumping of the solutions
through the stack can generally be neglected.
Since bipolar membranes became available as
commercial products, a large number of applica-
tions have been identied and studied on a labo-
ratory or pilot plant scale. However, in spite of the
obvious technical and economical advantages of
the technology, large-scale industrial plants are
still quite rare (Gineste et al. 1996). The main
reasons for the reluctant use of bipolar membrane
electrodialysis are poor membrane stability at
very high or low pH-values and insufcient
permselectivity at high ion concentrations, which
results in a substantial product salt contamination,
low current efciency, and short membrane life.
Nevertheless, there are a number of smaller-scale
applications in the chemical process industry, in
biotechnology, in food processing, and in waste-
water treatment.
References
Gineste JL, Pourecelly G, Lorrain Y, Presin F, Gavach C
(1996) Analysis of factors limiting the use of BPM: a
simplied model to determine trends. J Membr Sci
112:199208
Liu KJ, Chlanda FP, Nagasubramanian KJ (1977) Use of
bipolar membranes for generation of acid and base: an
engineering and economic analysis. J Membr Sci
2:109124
Simons R (1993) Preparation of high performance bipolar
membranes. J Membr Sci 78:1323
636
Electrodriven Membrane Processes
Seung-Hyeon Moon
School of Environmental Science and
Engineering, Gwangju Institute of Science and
Technology (GIST), Gwangju, South Korea
Introduction
Electrolyte membranes or ion exchange mem-
branes (IEMs) are ion-selective membranes for
separation or charge transfer through the mem-
branes. Electrodriven membrane processes
employ IEMs under an electric eld to perform
(i) mass separation for concentration or dilution of
ions in aqueous phase; (ii) chemical synthesis
with an electrochemical reaction, such as
chlorine-alkaline electrolysis and production of
hydrogen via water electrolysis; and (iii) energy
conversion and storage involving the conversion
of chemicals into electrical energy and vice versa.
Non-charged porous membranes are also used in
some energy conversion processes to separate
anolyte and catholyte solutions.
Separation Processes
Applications of the rst type are mainly found in
separation of ionic species under an electric eld.
Cations move toward a cathode and permeate
through a cation exchange membrane while
anions move toward an anode and permeate an
anion exchange membrane. Due to rejection of
non-permeable ion by the membranes, electro-
lytes are concentrated or diluted in a compart-
ment. Typical processes in this category are
electrodialysis, bipolar membrane electrodiaysis,
electrodeionization, and membrane capacitive
deionization. Without an electric eld, diffusion
dialysis enables to purify acid or base solutions
containing metallic contaminants.
Electrodialysis (ED) is an electrochemical
separation process using an electrical potential as
a driving force. Electrodialysis systems typically
consist of a cell arrangement with a series of
Electrodriven Membrane Processes
alternating anion and cation exchange membranes
between an anode and a cathode. Within ion
exchange membranes, charged groups are
attached to the polymer backbone of the mem-
brane material. These xed charged groups par-
tially or completely exclude ions of the same
charge (co-ions) from the membrane, so that an
anion exchange membrane (AEM) with xed pos-
itively charged groups excludes positive ions but
is freely permeable to negatively charged ions,
referred to as counterions. Similarly, a cation
exchange membrane (CEM) with xed negatively
charged groups is freely permeable to positively
charged ions. When an aqueous salt solution is
circulated in the cell under an electrical potential,
the positively charged cations migrate toward the
cathode and the negatively charged anions toward
the anode. The overall result is a potential drop
across the cell pairs as well as a change in the ion
concentration in alternate compartments. The
depleted solution is generally referred to as the
diluate and the concentrated solution as the con-
centrate. Electrodialysis is used for desalination of
various salt solutions including seawater as well
as production of table salt (Fig. 1).
A bipolar membrane (BPM) in which the
anion- and cation-exchangeable layers
(AEL/CEL) are adjoined together easily splits
water molecules into protons and hydroxyl ions
under a reverse bias condition. Accordingly intro-
duction of inorganic substances into the bipolar
membrane is known to be an effective technique
for generation of acid and base. Two or three
compartment stack congurations may be chosen
depending on the product specication, i.e.,
CEM-BPM, AEM-BPM, or CEM-BPM-AEM. It
is expected that water-splitting electrodialysis
using bipolar membrane can make zero-emission
possible and be applied as a clean technology by
recycling salt by-products after splitting to acid
and base. Developments of high-performance
bipolar membranes further expand use of bipolar
membrane electrodialysis in chemical, biochemi-
cal, and environmental industries (Fig. 2).
Electrodeionization (EDI) or continuous
electrodeionization (CEDI) is a hybrid separation
process that removes ionized species from liquids
using electrically active media and an electrical
Electrodriven Membrane Processes
Electrodriven Membrane
Processes, Fig. 1 An
Electrodialysis Cell
Electrodriven Membrane
Processes, Fig. 2 A
Bipolar Membrane
Electrodialysis Cell
potential activating ion transport. The electrically
active media, such as an ion exchange resin in
CEDI devices, may function to alternately collect
and discharge ionized species or to facilitate the
transport of ions continuously by ionic or elec-
tronic substitution mechanisms. Unlike an ion
exchange process, CEDI does not require
chemicals to regenerate the ion exchange resin
or concentrate the wastewater. In a CEDI system,
the ion exchange resin bed plays a major role in
the reduction of the high electrical resistance in
the diluate compartment, while the ion exchange
membranes lead to depletion and concentration of
the solutions in the diluate and concentrate com-
partments, respectively. The CEDI process is
capable of achieving high levels of purication
637
and the concentration of dissolved ionic solutes at
a relatively low salt concentration (Fig. 3).
Membrane capacitive deionization (MCDI)
is an advanced capacitive deionization (CDI) with
the help of ion exchange membranes. A CDI sys-
tem is operated by adsorption and desorption of
ions on carbon electrodes. When an electric poten-
tial is applied to CDI cells, charged ions in con-
taminant water are adsorbed onto the surface of
charged electrodes and forms an electric double
layer due to the charged electrode and adsorbed
ions, producing puried water. Often CDI leads to
a higher energy consumption and a lower opera-
tion efciency due to mobility of unwanted ions.
To avoid this phenomenon, ion exchange mem-
branes are introduced to CDI for ion selectivity,
638
Electrodriven Membrane
Processes, Fig. 3 An
Electrodeionization Cell
which is called membrane CDI (MCDI). A MCDI
employs two types of ion exchange membranes,
i.e., cation exchange and anion exchange mem-
branes. The AEM and CEM are positioned in
front of the positively and negatively charged
electrodes, respectively. While counterions are
attracted onto the electrode surface, simulta-
neously co-ions expelled from the counter elec-
trode. The selectivity of ion exchange membranes
prevents reverse adsorption and prohibits the
mobility of unwanted ions.
Diffusion dialysis is a membrane separation
process in which transport of selective ions is
driven by a concentration difference over an ion
exchange membrane. The diffusion dialyzer for
acid recovery consists of a multitude of compart-
ments made of gaskets arranged alternately with
anion exchange membranes, which allow acids to
permeate but retain metal salts. The gasket sur-
rounds a meshlike spacer by which mixing in a
Electrodriven Membrane Processes
compartment is enhanced. The acid feed enters the
bottom of every alternate compartment, as water
is fed from the upper part of the stack to contact
the acid feed counter currently. Permeate acids are
collected from the bottom of the permeate com-
partment as puried acid product. The depleted
feed ows out of the upper part as an efuent
containing high concentrations of metal salts and
a low concentration of remaining acid. Similarly a
cation exchange membrane is used to recover base
from metal salts.
Chemical Synthesis Processes
Applications of the second types are electrolysis
processes to generate chemicals by electrode reac-
tions and ion substitution through membranes.
A chlor-alkali process involves electrode
reactions for the electrolysis of NaCl solution.
Electrodriven Membrane Processes
Electrodriven Membrane Processes, Fig. 4 A Membrane Capacitive Deionization Cell
The process produces caustic soda (NaOH) and
chlorine (Cl2) that are used in a wide range of
industries. The most common chlor-alkali process
is the electrolysis of aqueous sodium chloride in a
membrane cell. The membrane is a cation perme-
able one which allows positive ions to pass
through it. That is, the only the sodium ions
from the NaCl solution may pass through the
membrane and not the chloride ions. The advan-
tage of the membrane process is that the sodium
hydroxide solution is formed in a cathode com-
partment which is not contaminated with NaCl
solution. Also puried NaCl should be supplied
to obtain pure NaOH solution. Chlorine is gener-
ated at anode by oxidation of chloride ion. As a
clean energy, hydrogen had been drawing more
attention. One of hydrogen sources is electrolysis
of water, splitting water to hydrogen and oxygen.
Various catalysts and energy sources are investi-
gated to improve the efciency as a reverse pro-
cess of a fuel cell.
Electro-ion substitution reaction can be car-
ried out in an ED stack in which membranes are all
of the same kind, either anion or cation exchange
membranes. In a unit cell consisting of two com-
partments with CEMs, acid and feed streams ow.
When an electric current is supplied to the stack,
protons in the acid stream (HX) are transported to
the feed stream (NaA) and convert the negatively
charged organics (A) to free acid (HA). As a result
the inorganic cations in the feed stream, in this case
sodium ions, are transported to the acid compart-
ment to meet the electroneutrality (NaX) in the feed
stream, completing an ion exchange reaction,
639
NaA + HX ! HA + NaX. A four-compartment
double decomposition cell consists of a series of
anion and cation exchange membranes arranged in
an alternating pattern between anode and cathode.
When the cell is operated with four different
streams, ion substitution or salt metathesis reaction
occurs, AX + BY ! AY + BX (Fig. 4).
Energy Conversion Processes
Applications of the third types are found in vari-
ous energy conversion and storage systems where
charge carriers are selectively permeate through a
membrane. Charge carriers are generated from
electrode reactions or initially supplied as
supporting electrolytes. When charge carriers
move between anolyte and catholyte without
mixing of active materials, a separator type mem-
brane may be used. This type of applications
includes fuel cell, lithium ion battery, redox ow
battery, reverse electrodialysis, etc.
Polymer electrolyte fuel cells (PEFCs) are
commonly considered to be one of the most likely
potential alternative power sources due to their
convenient operating temperature, high-energy
conversion efciency, and ease of integration
into hybrid systems. Electricity is generated by
potential difference between anode where hydro-
gen or fuel is oxidized to proton with the help of
catalyst and cathode where oxygen is reduced and
reacts with proton. A polymer electrolyte mem-
brane is placed between the anode and cathode
catalysts to insulate between electrodes. Polymer
640
Electrodriven Membrane
Processes, Fig. 5 A
Diffusion Dialysis Cell
electrolyte membrane (PEM) sandwiched with
two catalyst layers is called a membrane-electrode
assembly (MEA). Peruorinated sulfonic acid
membranes such as Naon , Flemion ,
Aciplex , and Dow series have been widely
used due to their high proton conductivity and
good thermal and chemical stability.
Hydrocarbon-based membranes, however, are
generally less stable and subject to fast degrada-
tion, yet to be improved for practical applications.
Recent efforts have focused on the commerciali-
zation of PEFCs in a range of applications, includ-
ing use in portable devices, residences, stationary
applications, and vehicles (Fig. 5).
A lithium ion battery is a rechargeable battery
in which lithium ions move between anode and
cathode with redox reactions during charge and
discharge cycles. A separator is required to pre-
vent mixing of anolyte and catholyte while lith-
ium ions permeate freely in electrolyte solution.
Often the separator is prepared as a multilayer
porous membrane due to requirement of shut-
down and meltdown. The lithium ion battery is
rapidly growing due to the widespread use of
wireless electronics such as cell phones and laptop
computers. Moreover, concerns about global
warming and oil shortages have led to the devel-
opment of high energy density Li ion batteries
Electrodriven Membrane Processes
used for energy storages and electric vehicles. In
these applications, safety is a key parameter. The
safety of battery is closely linked to the battery
separator absorbing a highly ammable liquid
electrolyte. Although typical separators based on
semicrystalline polyolen materials such as poly-
ethylene (PE) and polypropylene (PP) are
mechanically strong and relatively inexpensive,
their low melting temperature possibly causes
physical contact between two electrodes over
180  C. The physical contact triggers thermal
runaway, which results in explosive burning of
the highly ammable liquid electrolyte (Fig. 6).
A redox ow battery is an energy storage
device in which potential difference of a redox
couple generates (discharge) or stores (charge)
electric energy. Positive and negative electrolytes
are stored separately and the electrolyte solutions
are fed into a cell for energy conversion. A variety
of membranes are used for RFB systems
depending on the charge carrier, electrolyte sol-
vent, and redox couple. Membranes must possess
two main properties: preventing the undesirable
cross-mixing of the negative and positive electro-
lytes to minimize self-discharge, while selectively
conducting the charge carrier ions through the
membrane to complete the redox circuit during
the passage of current. Typically monovalent
Electrodriven Membrane Processes
Electrodriven Membrane
Processes, Fig. 6 Electro-
Ion Substitution Cell
Electrodriven Membrane
Processes, Fig. 7 A Salt
Methathesis Cell
selective cation exchange membrane or a thin
anion exchange membrane is used to prevent
crossover of the cationic redox couples when pro-
ton is a charge carrier. A RFB is a promising
technology due to several advantages such as its
large capacity, convenient operating temperature,
long cycle life, and so on. On the other hand, the
use of an aqueous electrolyte severely restricts the
energy density as is determined by the cell
potential that is constrained by the electrochemi-
cal stability window of water. Along with com-
mercialization of aqueous RFBs, nonaqueous
RFBs which can offer a higher density have
drawn considerable interest from energy storage
641
researchers. Furthermore, nonaqueous organic
electrolytes provide a wider potential window of
operation due to the high solubility of various
metalligand complexes in an organic solvent.
Nonaqueous RFB systems require ion exchange
membranes or non-charged porous membranes
depending on the electrochemical properties
and molecular size of charge carriers employed
(Fig. 7).
Reverse electrodialysis (RED) is an ion
exchange membrane process for renewable
energy generation. Electric potential occurs as a
result of Donnan equilibrium where two solutions
containing permeable ions are separated by a
642
Electrodriven Membrane
Processes, Fig. 8 A
Polymer Electrolyte
Membrane Fuel Cell
corresponding ion exchange membrane. Using a
similar cell structure to electrodialysis, electricity
can be generated by diffusion of ions using con-
centrated salt solution and diluted solution, called
reverse electrodialysis (RED). Typically seawater
and river water may be used as feed solution in a
modied electrodialysis cell. Other salinity
gradient power generation is pressure-retarded
osmosis using pressure difference due to the
concentration difference across an osmotic mem-
brane including a polymer electrolyte active layer
(Fig. 8).
Perspectives
Electrodialysis has been studied and industrial-
ized for nearly a century as a leading electrodriven
membrane process. Along with the appearance of
advanced ion exchange membranes, various sep-
aration and reaction processes are following elec-
trodialysis in many industries as demands for
compact and environmentally friendly processes
are growing continuously. Last several decades
energy-related electrodriven membrane processes
are growing rapidly with the help of membranes
as a key component. Many membranes originally
developed for separation processes have
expanded their applications for energy conversion
and storage. Accordingly the membranes should
be characterized in terms of electrochemical prop-
erties to improve the performance appropriately,
Electroendosmosis
i.e., ionic conductivity, transport number, oxida-
tive stability, and power density.
Electroendosmosis
Electroosmosis, Overview of
Electro-Fenton Process
Marc Cretin1,2 and Mehmet A. Oturan3
1
Institut Europen des Membranes,
ENSCM-UM-CNRS (UMR 5635), Universit de
Montpellier, Montpellier Cedex 5, France
2
National School of Chemistry of Montpellier,
University of Montpellier, Montpellier, France
3
Laboratory of Earth Materials and Environment,
University Paris-Est, Marne La valle,
Champs-sur-Marne, France
The electro-Fenton process is one of the most
popular electrochemical advanced oxidation pro-
cesses. As all the advanced oxidation process
(AOPs), electro-Fenton (EF) process is based on
the in situ production and reactions of the hydroxyl
radicals (OH), the second powerful oxidant (after
uorine) with E0 (OH/OH) = 2.80 V/SHE and a
very reactive species (Brillas et al. 2009; Oturan
Electrofiltration
and Aaron 2014). OH is able to mineralize any
organic pollutants and therefore used in AOPs in
order for destruction of persistent organic
pollutants.
Contrary to anodic oxidation process (Panizza
and Cerisola 2009) in which OHs are produced at
anode surface from water oxidation (Panizza and
Cerisola 2009), in the EF process, OHs are gen-
erated in the bulk of solution from electrochemi-
cally assisted Fentons reactions:
H2 O ! OH H e
H2 O2 Fe2 H ! Fe3 OH H2 O surface area carbon-felt cathode is a very promis-
In the classical Fenton process, the Fentons
reagent (H2O2 + Fe2+) is added externally to the
reaction medium. This leads to the formation of
Fe(OH)3 sludge and promotes wasting reactions
that decrease process efciency. EF process has a
great advantage to generate in situ H2O2 (from
two-electron reduction of O2) and regenerate
ferrous iron ions (from initially added catalyst)
as schematized on the following electrochemical
reactions:
O2 2H 2 e ! H2 O2 Oturan MA, Aaron JJ (2014) Advanced oxidation pro-
Fe3 e Fe2
There is no accumulation of Fe3+ and other
reagents (H2O2 and Fe2+), so sludge formation
occurs and parasitic reactions are minimized to
enhance mineralization (transformation of
organics to CO2 and water) efciency.
In the case of using a high O2 evolution anode
such as boron-doped diamond (BDD) lm
anode, OH are formed simultaneously at the
anode as well as in the bulk solution from the
electrogenerated Fentons reagent. The oxidation
power and mineralization efciency are extremely
high (Dirany et al. 2010).
The OH thus formed by the process in a con-
tinuous and catalytic way will react with the
organic pollutants present in the medium until
643
their mineralization, i.e., transformation to CO2,
H2O, and inorganic ions.
This EF process has been shown to be more
efcient and cost-effective than some widely
AOPs such as Fenton oxidation and ozonation
for the treatment of organic pollutants species
(Brillas et al. 2009; Oturan and Aaron 2014). It
was successfully applied to the removal of toxic
and persistent organic pollutants from water such
as synthetic dyes, chlorinated aromatics, chloro-/
E
nitrophenol herbicides, insecticides, fungicides
and other pesticides, and pharmaceutical and per-
sonal care products. The results of these studies
have shown that the EF process using a large
ing technology due to its simplicity, low cost, and
outstanding performance, which is mainly due to
the quick and efcient cathodic regeneration of
the Fe2+ catalyst.
References
Brillas E, Sirs I, Oturan MA (2009) Electro-Fenton process
and related electrochemical technologies based on
Fentons reaction chemistry. Chem Rev 109:65706631
Dirany A, Sirs I, Oturan N, Oturan MA (2010) Electro-
chemical abatement of the antibiotic sulfamethoxazole
from water. Chemosphere 81:594602
cesses in water/wastewater treatment: principles and
applications. A review. Crit Rev Environ Sci Tech.
doi:10.1080/10643389.2013.829765
Panizza M, Cerisola G (2009) Direct and mediated anodic
oxidation of organic pollutants. Chem Rev 109:65416569
Electrofiltration
Karel Bouzek
Faculty of Chemical Technology, University of
Chemistry and Technology Prague, Technick 5,
Prague 6, Czech Republic
Electroltration represents a modication of
dead-end membrane micro- or ultraltration. It
targets a signicant reduction of the ltration
644 Electrolyzers

Electrofiltration,
Fig. 1 Schematic sketch of
electroltration principle,
Fw stands for driving force
due to the friction between
the particle and owing
solvent molecules and Fe
stands for driving force
resulting from action of the
applied electric eld E on
the particle carrying
electrical charge

time and focuses especially on the ltration and/or
concentration of colloidal substances that other-
wise rapidly build up a deposit of colloidal parti-
cles on the surface of the membrane, which
strongly hinders permeation of the uid phase.
The basic principle is that colloidal particles
usually carry an electric charge. Hence, by apply-
ing an appropriate electric eld, colloidal particles
can be moved in the direction opposite to the uid
ow, thus keeping the surface of the ltrating
membrane free of the deposit (Henry et al.
1977). A schematic sketch of this arrangement is
shown in the Fig. 1.
As the ltrating membrane remains unimpeded
by a deposit of colloidal particles, the pressure
drop across it remains relatively low. In contrast,
the separator covered by the layer of colloidal
particles attracted by the electric eld does not
permit a signicant uid ow. This results in a
reduction of the shear stress forces in the depos-
ited lm of separated colloid. These facts make
electroltration especially promising for the sep-
aration of biotechnology-derived products, the
reason being that such products are typically sen-
sitive to high shear stress forces while at the same
time they are electrically charged. The mild con-
ditions of electroltration thus enable their prop-
erties to be preserved during the process of their
separation (Gzke and Posten 2010).
References
Henry jr. JD, Lawler LF, Kuo CHA (1977) A solid/liquid
separation process based on cross ow and
electroltration. AIChE Journal 23:851
Gzke G, Posten C (2010) Electroltration of Biopoly-
mers. Food Eng. Rev. 2:131
Electrolyzers
Antonino Salvatore Arico
CNR-ITAE Institute, Messina, Italy
One of the main processes occurring in an
electrolyzer device is the water electrolysis. Elec-
trolysis of water is the dissociation of water mol-
ecules into hydrogen and oxygen gases. For this
Electrolyzers 645

process, in the presence of liquid water at 298 K Anode Cathode

and 1 bar, DG is 237 kJ mol1 (corresponding to H2O 2H+ + 2e- + 0.5O2 2H+ + 2e- H2
~1.23 V), DS is 163 J mol1 K1 Erev = 1.23 V vs. RHE Erev = 0.00 V vs. RHE
(TDS ~0.25 V), whereas DH is 286 kJ mol1. Metal
Pt/C
The thermoneutral potential at which this reaction Oxides
occurs in the absence of external heat supply is O2 H2
Eth,DH = 1.48 V (upper heating value
3.54 kWhNm3 H2) (Millet et al. 2011). If
Solid Polymer
Electrolyte C
steam is fed to the device, the reaction enthalpy A A
H+
is reduced by ~40 kJ mol1 corresponding to the N T
O H+
H E
vaporization enthalpy. Water electrolysis is tradi- D H+
O
tionally carried out in alkaline media with several E D
commercial electrolyzers available on the market. E
Water electrolyzers using a solid polymer electro-
Electron Flow
lyte are less common and generally use expensive H2O H2O
materials such as noble metal electrocatalysts and
H2O H2 + 0.5O2 E rev = 1.23 V
Naon membranes (Barbir 2005; Siracusano
et al. 2010). Polymer electrolyte membrane Electrolyzers, Fig. 1 Principle of operation of a PEM
(PEM) electrolyzers represent a viable alternative water electrolysis cell
to alkaline electrolyzer using KOH or NaOH as
electrolytes for hydrogen generation. The advan-
tages of SPE water electrolyzers especially con-
cern with increased safety, high energy density,
pressure operation that may reach 50100 bars.
and low maintenance. In the PEM water
Thus, a proper thickness is necessary for the poly-
electrolyzer, water is usually supplied to the
mer electrolyte separator (around 100 mm). For
anodic compartment where oxygen evolution
high-pressure operation in PEM electrolyzers,
occurs, whereas hydrogen is produced at the cath-
reinforced PFSA membranes provide a proper
ode by protons transported through the protonic
combination of good conductivity and high
membrane (Fig. 1). The electrodes are usually
mechanical strength.
composed of a platinum electrocatalyst for hydro-
gen evolution, whereas metal oxides (e.g., IrO2,
RuO2, etc.) are used for the anode due to their
enhanced activity and stability than Pt for this
References
reaction (Marshall et al. 2007; Siracusano
Barbir F (2005) PEM electrolysis for production of
et al. 2010). The performance of an SPE hydrogen from renewable energy sources. Sol Energy
electrolyzer is strongly related to the characteris- 78:661
tics of the membrane and electrode assembly Marshall A, Brresen B, Hagen G, Tsypkin M, Tunold R
(2007) Hydrogen production by advanced proton
(MEA) where the electrochemical reactions take
exchange mebrane (PEM) water electrolysers
place at triple-phase boundary. Therefore, the Reduced energy consumption by improved
interface between solid polymer electrolyte and electrocatalysis. Energy 32:431
electrocatalyst layers should be characterized by a Millet P, Mbemba N, Grigoriev SA, Fateev VN,
Aukauloo A, Etivant C (2011) Electrochemical per-
suitable extension; furthermore, the contact resis- formances of PEM water electrolysis cells and perspec-
tance between the catalytic layer and the mem- tives. Int J Hydrog Energy 36:4134
brane should be as low as possible. Generally, Siracusano S, Baglio V, Di Blasi A, Briguglio N, Stassi A,
Naon membrane is used as conducting polymer Ornelas R, Trifoni E, Antonucci V, Arico AS
(2010) Electrochemical characterization of single cell
electrolyte in PEM electrolyzer systems. How-
and short stack PEM electrolyzers based on a nanosized
ever, low levels of H2 and O2 crossover are nec- IrO2 anode electrocatalyst. Int J Hydrog Energy
essary for PEMWE application due to the high- 35:5558
646
Electromembrane
Grarld Pourcelly
Institut Europeen des Membranes, CC 047,
Universite Montpellier II, Place Eugene Bataillon,
Montpellier, France
Electromembrane or charged membrane stands
for ion-exchange membrane [IEM]. They are used
in a number of processes which are rather different
in their basic concept, their practical applications,
and their technical relevance (Strathmann 2004).
All IEM separation processes are based on the
same fundamental principle which is the coupling
of the transport of electrical charges, i.e., an elec-
trical current with a transport of mass, i.e., cations
or anions, through a permselective membrane due
to an externally applied or internally generated
potential gradient. There are two types of IEM:
(i) monopolar and (ii) bipolar membranes.
Monopolar membranes are either cation-
exchange membranes which contain negatively
charged groups xed to the polymer matrix or
anion-exchange membranes which contain posi-
tively charged groups xed to the polymer matrix.
Electromembrane, a
Fig. 1 (a) Cation-
exchange membrane with a Counter-ion pathway
homogeneous structure; (b)
ion-exchange membrane
with a heterogeneous
structure prepared from an
ion-exchange resin powder
in a binder polymer (From
Strathmann 2010)
b
Counter-ion pathway
Electromembrane
In a cation-exchange membrane, the xed nega-
tive charges are in electrical equilibrium with
mobile cations (counterions) in the interstices of
the polymer as shown in Fig. 1 (Strathmann
2010). In this case, the mobile anions are referred
to as coions. They are more or less excluded from
the polymer matrix because of their electrical
charge which is identical to that of the xed ions
(Donnan exclusion (Donnan 1911)). Thus, the
selectivity of an IEM results from the exclusion
of coions from the membrane phase. The proper-
ties of IEM are determined by different parame-
ters such as the density of the polymer network,
the hydrophobic/hydrophilic character of the
polymer matrix, the nature and the ratio of xed
ion-exchange groups, the cross-linking ratio, etc.
The most desired properties of IEM are (i) high
chemical and thermal stabilities, (ii) high mechan-
ical and dimension stabilities, (iii) high
permselectivity, (iv) low electrical resistance,
(v) and a low cost.
Bipolar membranes (BPMs) are composed of
two layers of ion exchangers joined by a hydro-
philic junction (Pourcelly et al. 2009). The diffu-
sion of water from both sides of the BPM allows
its dissociation under the electrical eld to gener-
ate protons and hydroxyl ions, which further
Counter-ion Co-ion Fixed ion
Polymer matrix
Solution filled gaps
Ion-exchange resin Binder polymer
Electromembrane Processes
Electromembrane, Fig. 2 Principle of a bipolar membrane. Left hand: water dissociation under electrical eld. Right
hand: the two ion-exchange layers bearing xed anion- or cation- exchange groups
migrate from the junction layer through the
cation- and anion-exchange layers of the BPM as
depicted in Fig. 2. The requirements for suitability
of BPM include that for monopolar membranes
but also an experimental potential to achieve the
water-splitting capability as close as possible as
the theoretical value equal to 0.83 V at 25  C.
Nowadays, superior styrene-divinylbenzene
copolymer membranes can be easily purchased,
peruorinated membranes with great chemical
stability are on the market, and BPM with an
industrial-scale lifetime (>20,000 h) is available.
References
Donnan FG (1911) Theory of membrane equilibrium and
membrane potential in the presence of non-dialysing
electrolyte. Z Electrokem Angew Phys Chem
17:572581
Pourcelly G, Bazinet L (2009) Developments of
BPM technology in food and bio-industries. In:
Pabby AK, Rizvi SSH, Sastre AM (eds) Handbook of
membrane separations, CRC Press, Boca Raton,
pp 581634
Strathmann H (ed) (2004) In: Ion exchange membrane
separation processes. Membrane technologies series,
Elsevier, Amsterdam
Strathmann H (2010) Electrodialysis: a mature technology
with a multitude of new applications. Desalination
264:268288
647
Electromembrane Processes
Gerald Pourcelly
Institut Europeen des Membranes, CC 047,
Universite Montpellier II, Place Eugene Bataillon,
Montpellier, France
Electromembrane processes involve ion-exchange
membranes. They can be divided into three
types: (i) Separation of components such as
salts or acids and bases from electrolyte solu-
tions. In this case, the driving force for the ion
transport across the membrane is an electrical
potential as in electrodialysis or a concentration
gradient as in both diffusion dialysis and Donnan
dialysis. (ii) The second type of processes
involves an electrochemical reaction producing
chemicals such as chlorine, acids and bases, or
organic and inorganic compounds. The most
known process of this type is the chlorine-alkali
production where the ion-exchange membrane is
the key component. (iii) The third type of
ion-exchange membrane processes involves the
conversion of chemical into electrical energy and
vice versa. The solid polymer electrolyte fuel cell
is the most signicant application (Strathmann
2004).
648
CONCENTRATE (OUTLET)
DILUATE (OUTLET)
ELECTROLYTE
Na+ Na
+
Na
+
+ +
Na Na Na
ANODE
Cr Cr Cr
Cr Cr Cr
D C D C D C
Electromembrane Processes, Fig. 1 Scheme of a conventional two-compartment electrodialysis stack (C): concen-
trate, (D): diluate compartments
(i): In dialysis, the driving force for the com-
ponent transport is a difference of concentration
between the two solutions separated by a mem-
brane. In diffusion dialysis and Donnan dialysis
the driving force is also a concentration gradient
but the membrane is carrying anions or cations
according to its permselectivity. Diffusion dialysis
with anion exchange membranes is used on a large
scale to recover acids from pickling solutions
(Kobuchi et al. 1987). Donnan dialysis is used
for water softening or for recovering organic
acids from their salts (Kliber and Wisnieskwi
2011).
Electrodialysis (ED) is used to transport salt
ions from one solution through ion-exchange
membranes to another solution under the inu-
ence of an applied electric potential difference.
The elementary cell consists of a feed (diluate)
compartment and a concentrate (brine) compart-
ment formed by an anion exchange membrane
and a cation exchange membrane placed between
two electrodes. In almost all practical ED pro-
cesses, multiple ED cells (few hundreds) are
arranged into a conguration called an ED stack
Fig. 1.
Conventional ED is used mainly for desalina-
tion of saline solutions (chemicals) or milk whey
(food industry). It can be combined with bipolar
membranes (bipolar membrane electrodialysis)
Electromembrane Processes
Na
+ +
Na Na
+
+ + +
Na Na
CATHODE
Cr Cr
Cr Cr Cr
D C D C D
DILUATE (INLET)
CONCENTRATE (INLET)
and used to produce acids and bases from their
corresponding salts, Fig. 2. This process is eco-
nomically very attractive and has several interest-
ing potential applications mainly in food industry,
ne chemicals, or biotechnologies (Pourcelly
et al. 2009).
(ii): The most known membrane electrolysis
processes are for the production of chlorine and
caustic soda (Pletcher and Walsh 1990) or special
organic compounds (Sata 1991). In the chlorine-
alkali process, the cells are arranged in a
similar way as in an electrodialysis stack but in
two different congurations using monopolar or
bipolar electrodes. Due to the severe operating
conditions (80  C, 35 wt% NaOH, wet chlorine),
the membrane is a composite structure of
sulfonated and carboxylated peruorinated
reinforced polymers.
(iii): Ion-exchange membranes are used today
also as key components in energy storage and
conversion systems such as batteries and fuel
cells. A fuel cell is an electrochemical reactor in
which energy is converted into electrical energy.
Generally fuel cells are fed with hydrogen which
is transformed into protons at a catalytic anode
with electrons. Protons then migrate across a pro-
ton conducting membrane and combine with oxy-
gen to produce water at the catalytic cathode
(Lucia 2014).
Electroosmosis
Electromembrane Processes, Fig. 2 Electrodialysis with bipolar membrane. Scheme of a three-compartmentcell
References
Kliber S, Wisnieskwi JA (2011) Removal of bromate and
associated anions from water by Donnan dialysis with
anion exchange membranes. Desalin Water Treat
35:158163
Kobuchi Y, Motomura H, Noma Y, Hanada F (1987)
Application of ion exchange membranes to recover
acids by diffusion dialysis. J Membr Sci 27:173179
Lucia U (2014) Overview on fuel cells. Renew Sustain
Energy Rev 30:164169
Pletcher D, Walsh FC (1990) Industrial electrochemistry.
Chapman & Hall, London
Pourcelly G, Bazinet L (2009) Developments of BPM
technology in food and bio-industries. In: Pabby AK,
Rizvi SSH, Sastre AM (eds) Handbook of membrane
separations. CRC Press, Boca Raton, pp 581634
Sata T (1991) Ion exchange membranes and separation
processes with chemical reactions. J Appl Electrochem
21:283294
Strathmann H (2004) In: Ion exchange membrane separa-
tion processes. Membrane technologies series.
Elsevier, Amsterdam
Electronic and Ionic Conductivity
Mixed Conducting Membranes
649
Electroosmosis
Karel Bouzek
Faculty of Chemical Technology, University of
Chemistry and Technology Prague, Technick 5,
Prague 6, Czech Republic
Electroosmosis is the term used for the convective
ow of a solution containing charge carriers, e.g.,
in the form of dissociated salts, through the
pores or structure of a material with an
electrically charged internal surface. In the eld
of membrane processes, this phenomenon is typ-
ically discussed in connection with the utilization
of ion-selective membranes under current load.
However, it can potentially occur in any mem-
brane material. The schematic sketch of the prin-
ciple of electroosmotic ux initiation in an
ion-selective membrane pore (void space) is
shown in Fig. 1.
The driving force of electroosmotic ux is the
electric eld. Flux velocity is directly proportional
to the hydraulic permeability of a membrane and
650
Electroosmosis, Fig. 1 The schematic sketch of a prin-
ciple of electroosmotic ux initiation in the membrane with
an electric charge carriers xed on the pore (void fraction)
wall
indirectly proportional to the viscosity of the pore
uid. The latter parameter represents an excess of
free charge carriers of one sign in the bulk of the
pore uid. An excess of one-sign charge carriers is
possible on account of an intrinsic property of an
ion-selective membrane, i.e., the presence of
charge-carrying functional groups in the mem-
brane structure. These ion groups are bonded by
a covalent bond to the backbone of the membrane
material. They are thus xed and immobilized in
the structure. In the case of conventional mem-
brane materials, the role of xed charge can be
carried out by ions specically adsorbed on the
pore walls or along the backbone of membrane
materials. The charge carried by functional groups
and/or adsorbed in the internal structure of the
membrane has to be compensated by an excess
charge of opposite sign present in the pore uid.
The electroosmotic convective ow of the pore
uid is induced by friction force between the
solvated mobile charge carriers (ions) moving
under the action of the electric eld and the sur-
rounding liquid phase molecules (Squires and
Bazant 2004).
Electroosmotic ux represents one of the
mechanisms of mass transfer through an
ion-selective membrane. Its signicance increases
with increasing current load and, thus, the inten-
sity of the electric eld applied across the mem-
brane (Fila and Bouzek 2008).
Electroosmosis, Overview of
Cross-References
Electroosmosis, Overview of
References
Fila V, Bouzek K (2008) The effect of convection in the
external diffusion layer on the results of a mathematical
model of multiple ion transport across an ion-selective
membrane. J Appl Electrochem. 38:1241
Squires TM, Bazant MZ (2004) Induced-charge electro-
osmosis. J Fluid Mech 509:217
Electroosmosis, Overview of
Dianne Wiley1 and Gustavo Fimbres Weihs2
1
School of Chemical and Biomolecular
Engineering, The University of Sydney, Sydney,
NSW, Australia
2
Ctedras CONACYT, Instituto Tecnolgico de
Sonora, Cd. Obregn, Sonora, Mexico
Synonyms
Electroosmosis; Electroendosmosis; Electro-
osmosis; Electroosmotic ow; EOF
Electro-osmosis is the movement of liquid in
response to an applied electric eld across a con-
duit such as a membrane, capillary tube,
microchannel, or porous material.
The application of an external electric eld
near a solid/liquid interface may result in the
motion of liquid with respect to an adjacent
charged surface. These associated effects are
known as electrokinetic phenomena (Hunter
1981), rst observed by Reuss in 1808 (Reuss
1809). Electrokinetic phenomena include
electro-osmosis, electroacoustics, electrophoresis,
diffusiophoresis, streaming potential, zeta poten-
tial, and sedimentation potential. The earliest
experiments on electrokinetic phenomena focused
on electro-osmosis because these are the easiest to
conduct (Wall 2010). Early investigators included
Wollaston, Porrett, Napier, Faraday, and Daniell.
Electroosmosis, Overview of 651

Electroosmosis,
Overview of, Membrane
Fig. 1 Schematic
representation of electro- - - - - - - - - -
osmosis in a membrane EDL + + + + + + + +
pore, showing the effect of
the electric eld on the
electric double layer (EDL) + Fluid
and the resulting drag on the
bulk uid Electric Field
EDL + + + + + + + +
- - - - - - - - - E
Membrane

In electro-osmosis, the bulk uid moves relative
to a charged surface due to an external electric
eld.
The chemical equilibrium between a solid sur-
face (such as a membrane) and a uid containing
charged species typically leads to the interface
acquiring a net xed electrical charge (most
often negative for membranes), characterized by
the zeta potential (z). The presence of co-ions
(similarly charged ions) and counterions
(oppositely charged ions) results in attraction
and repulsion of ions in the vicinity of a charged
surface. This phenomenon, coupled with the ran-
dom thermal motion of the ions, creates an electric
double layer (EDL) or Debye layer in the region
near the interface. Electroneutrality is not
maintained within the EDL, because there is an
excess of counterions compared to co-ions in
order to neutralize the surface charge (Probstein
2005). When an electric eld is applied to the
uid, the net charge in the electrical double layer
is induced to move by the resulting Coulomb
force. The movement of ions drags bound solvent,
causing bulk uid motion due to momentum
transfer, as depicted in Fig. 1. The resulting ow
is termed electro-osmotic ow. Electro-osmosis
can only occur if there are charged species in the
uid that can respond to the electric eld
(Jagannadh and Muralidhara 1996).
Electro-osmosis can be described mathemati-
cally using the momentum transport equation, as
the resulting body force due to an electric eld on
a charged uid (Hu and Li 2007). The net charge
density of the uid (re) can be related to the
electric potential (f) and the permittivity of the
uid (e) by Poissons equation:
e2 f re (1)
Under negligible convective or electrophoretic-
induced ow, the charge density follows a
Boltzmann distribution (Hunter 1981), and the
charge density can be obtained by solving the
nonlinear PoissonBoltzmann equation:
2 f  k2 sinhf 0 (2)
where the constant k depends on the ionic com-
position (Russel et al. 1989). Although solutions
to Eq. 2 can only be obtained numerically for
complex geometries, it can be linearized using
the DebyeHuckel approximation, which leads
to the following electric potential distribution:
 
y
f zexp (3)
lD
where y is the distance from the surface, and
lD = 1/k is the Debye length.
In membrane systems, electro-osmosis can be
approximated through the HelmholtzSmo-
luchowski (HS) velocity equation:
ezEx
us  (4)
m
The HS approximation described by Eq. 4 is an
articial slip velocity implemented on a charged
652
surface. It can be used to simulate the effect of
electro-osmosis on the velocity in a conduit at the
outer edge of the EDL (Probstein 2005). This
equation implies that the electro-osmotic ow
velocity is proportional to the applied electric
eld. Other equations that are relevant to electro-
osmosis under different conditions include the
HuckelOnsager equation and the Henry
equation.
Most common applications of electro-osmosis
are in capillary electrophoresis, capillary
electrochromatography, and microuidic devices
in elds as diverse as biophysics, dewatering,
geomechanics, medicine, microchips, oil and gas
production, and separations including in mem-
brane separation. There are a number of important
applications in membrane technology. At the fun-
damental level, electro-osmosis can be used to
determine the zeta potential of membranes
(Bowen and Clark 1984). It can also be benecial
for the operation of membrane separation sys-
tems, and has found numerous applications in
microltration and ultraltration processes
(Bowen 1993), in particular to do with the miti-
gation of membrane fouling. This is because sur-
face activity and membrane charge, two
phenomena closely related to membrane fouling,
cannot be inuenced through hydrodynamic
forces such as increased shear. Electro-osmosis
can be used for membrane cleaning and restora-
tion (Bowen et al. 1989), for backwashing
(Bowen and Sabuni 1994), for releasing lter
cakes in dead-end membrane processes (Bowen
and Ahmad 1997), and for enhancing ux (Sarkar
and De 2010).
Although the use of DC electric elds in mem-
brane separation processes has been in practice for
several decades, anode corrosion is a signicant
problem that has discouraged its wider application
(Jagannadh and Muralidhara 1996). Nevertheless,
the development and availability of corrosion-
resistant materials has enabled recent develop-
ments and commercialization of these techniques.
Electro-osmosis has also found applications in
RO processes, leading to improved recovery
through membrane backwashing (Spiegler and
Macleish 1981) or by increasing the level of
mixing in the boundary layer (Liang et al. 2014).
Electroosmosis, Overview of
Cross-References
Backwashing
Electrical Double Layer
Electroosmotic Drag in Membranes
Membrane Fouling
Surface Charge Density
Zeta Potential
References
Bowen WR (1993) Electrochemical aspects of
microltration and ultraltration. In: Howell JA,
Sanchez V, Field RW (eds) Membranes in
bioprocessing: theory and applications. Springer, Dor-
drecht, pp 265291
Bowen WR, Ahmad AL (1997) Pulsed electrophoretic
lter-cake release in dead-end membrane processes.
AIChE J 43(4):959970
Bowen WR, Clark RA (1984) Electro-osmosis at micropo-
rous membranes and the determination of zeta-
potential. J Colloid Interface Sci 97(2):401409
Bowen WR, Sabuni HAM (1994) Electroosmotic membrane
backwashing. Ind Eng Chem Res 33(5):12451249
Bowen WR, Kingdon RS, Sabuni HAM (1989) Electrically
enhanced separation processes: the basis of in situ
intermittent electrolytic membrane cleaning (iiemc)
and in situ electrolytic membrane restoration (iemr).
J Membr Sci 40(2):219229
Hu G, Li D (2007) Multiscale phenomena in microuidics
and nanouidics. Chem Eng Sci 62(13):34433454
Hunter RJ (1981) Zeta potential in colloid science: princi-
ples and applications. Academic, London
Jagannadh SN, Muralidhara HS (1996) Electrokinetics
methods to control membrane fouling. Ind Eng Chem
Res 35(4):11331140
Liang YY, Fimbres Weihs GA, Wiley DE (2014) Approx-
imation for modelling electro-osmotic mixing in the
boundary layer of membrane systems. J Membr Sci
450:1827
Probstein RF (2005) Physicochemical hydrodynamics: an
introduction, 2nd edn. Wiley, New York
Reuss FF (1809) Sur un novel effet de llectricit
galvanique. Mmoires de la Socit Impriale des
Naturalistes de Moskou 2:327337
Russel WB, Saville DA, Schowalter WR (1989) Colloidal
dispersions. Cambridge University Press, Cambridge,
UK
Sarkar B, De S (2010) Electric eld enhanced gel con-
trolled cross-ow ultraltration under turbulent ow
conditions. Sep Purif Technol 74(1):7382
Spiegler KS, Macleish JH (1981) Molecular (osmotic and
electro-osmotic) backwash of cellulose acetate
hyperltration membranes. J Membr Sci 8(2):173192
Wall S (2010) The history of electrokinetic phenomena.
Curr Opin Colloid Interface Sci 15:119124
Electroosmotic Drag in Membranes
Electroosmotic Drag Flux
Electroosmotic Drag in Membranes
Electroosmotic Drag in Membranes
Dianne Wiley1 and Gustavo Fimbres Weihs2
1
School of Chemical and Biomolecular
Engineering, The University of Sydney, Sydney,
NSW, Australia
2
Ctedras CONACYT, Instituto Tecnolgico de
Sonora, Cd. Obregn, Sonora, Mexico
Synonyms
Electroosmotic drag ux; Electroosmotic water
transport; EOD
Electroosmotic drag in membranes refers to the
movement of water or other electroneutral sol-
vents through a membrane, associated with the
movement of ions under the inuence of an elec-
tric eld.
The zeta potential at the interface between a
membrane and an electrolyte generally leads to
the creation of an electric double layer (EDL).
When an electric eld is applied to uid within
an EDL, the net charge is induced to move by the
resulting Coulomb force. The movement of ions
drags bound solvent, causing bulk uid motion
Electroosmotic Drag
in Membranes,
Fig. 1 Schematic
representation of
electroosmotic drag in a
membrane pore. The
Drag
electric eld causes the
dissolved ions to experience +
a net force, and these ions
transfer momentum to the
solvent molecules through
viscous drag
653
due to momentum transfer (viscous drag). This
bulk uid motion due to an external electric eld
is termed electroosmosis (De Groot 1966) and can
occur in any uid with a net charge, including in
membrane channels or within membrane pores
(Fig. 1).
Electroosmotic drag (EOD) is the underlying
mechanism responsible for solvent transport in a
number of membrane techniques including:
E
EOD in electrodialysis (ED), often called
water transport, is one of the reasons for
losing current density (Indusekhar and
Krishnaswamy 1965). ED has many industrial
applications including the production of chlo-
rine, NaOH, and other inorganic acids and
bases (de Groot et al. 2011).
EOD of water in proton exchange membranes
(PEMs, also referred to as polymer electrolyte
membranes), which leads to water manage-
ment issues (Zawodzinski et al. 1995).
EOD of methanol in direct methanol fuel cells
(DMFCs), leading to methanol crossover
(Heinzel and Barragn 1999).
In vanadium redox batteries (VRBs), EOD can
cause vanadium crossover and capacity loss
(Agar et al. 2013).
EOD in electroosmotic pumps (EOPs) is used
to generate ow or pressure (Wang et al. 2006).
EOPs can be used to aid with the hydration of
PEMs for fuel cells.
EOD is a mechanism for producing
anomalous ux through charged membranes
(e.g., NF membranes) due to the selective
Membrane
+ Electric Field
Drag
Membrane
654
passage of one type of charged ion over the
other, leading to the axial rearrangement of the
EDLs (Sasidhar and Ruckenstein 1982).
EOD is of particular importance in PEMs such
as Naon and sulfonated polyetherketones, used
in fuel cells and VRBs. Water management criti-
cally impacts the performance of PEMs for fuel
cells, as their proton conductivity increases with
hydration. Too little water can dry the membrane,
leading to a reduction in conductivity and conse-
quently lower cell performance. Too much water
can ood the membrane and lead to cathode
ooding problems. In addition to the generation
of water at the cathode catalyst layer due to the
electrochemical reaction, water is also transported
through the membrane (Lee et al. 2008). The
permeate ux of water in a PEM is governed by
two main mechanisms: (a) the osmotic ux due to
a chemical potential gradient across the mem-
brane, which is inuenced by both the activity of
the solution (osmotic pressure) and the hydro-
static pressure, and (b) the electroosmotic ux
due to the drag induced by the proton ux (Ren
and Gottesfeld 2001).
In order to optimize water concentration in a
fuel cell membrane, it is important to quantify
electroosmotic drag. The electroosmotic water
ux can be related to the proton ux through
the membrane by means of the electroosmotic
drag coefcient (psdrag), which is dened as
the number of water molecules transported
through the membrane per proton as the chemical
potential gradient of water tends to zero (Ise
et al. 1999).
Cross-References
Direct Methanol Fuel Cell (DMFC)
Electrical Double Layer
Electrodialysis
Polymer Electrolyte Membrane Fuel Cell
(PEMFC)
Proton-Exchange Membranes for Fuel Cells
Zeta Potential
Electroosmotic Flow
References
Agar E, Knehr KW, Chen D, Hickner MA, Kumbur EC
(2013) Species transport mechanisms governing capac-
ity loss in vanadium ow batteries: comparing Naon
and sulfonated Radel membranes. Electrochim Acta
98:6674
De Groot SR (1966) Thermodynamics of irreversible pro-
cesses, 4th edn. North-Holland, Amsterdam
de Groot MT, de Rooij RM, Bos AACM, Bargeman G
(2011) Bipolar membrane electrodialysis for the alka-
linization of ethanolamine salts. J Membr Sci
378(12):415424
Heinzel A, Barragn VM (1999) A review of the state-of-
the-art of the methanol crossover in direct methanol
fuel cells. J Power Sources 84(1):7074
Indusekhar VK, Krishnaswamy N (1965) Diffusion effect
during electrodialysis with ion-exchange membranes.
J Appl Polym Sci 9(7):26312632
Ise M, Kreuer KD, Maier J (1999) Electroosmotic drag in
polymer electrolyte membranes: an electrophoretic
NMR study. Solid State Ion 125(14):213223
Lee PH, Han SS, Hwang SS (2008) Three-dimensional
transport modeling for Proton Exchange Membrane
(PEM) fuel cell with micro parallel ow eld. Sensors
(Basel) 8(3):14751487
Ren X, Gottesfeld S (2001) Electro-osmotic drag of water
in poly(peruorosulfonic acid) membranes.
J Electrochem Soc 148(1):A87A93
Sasidhar V, Ruckenstein E (1982) Anomalous
effects during electrolyte osmosis across charged
porous membranes. J Colloid Interface Sci
85(2):332362
Wang P, Chen Z, Chang H-C (2006) A new electro-osmotic
pump based on silica monoliths. Sens Actuators
B 113(1):500509
Zawodzinski TA, Davey J, Valerio J, Gottesfeld S (1995)
The water content dependence of electro-osmotic
drag in proton-conducting polymer electrolytes.
Electrochim Acta 40(3):297302
Electroosmotic Flow
Electroosmosis, Overview of
Electroosmotic Water Transport
Electroosmotic Drag in Membranes
Electrophoresis
Electrooxidation
Marc Cretin
Institut Europen des Membranes, ENSCM-UM-
CNRS (UMR 5635), Universit de Montpellier,
Montpellier Cedex 5, France
National School of Chemistry of Montpellier,
University of Montpellier, Montpellier, France
Electrooxidation is a direct anodic oxidation tech-
nique to remove biorefractory pollutants by direct
electrolysis in which pollutants exchange elec-
trons with the anode surface without intermediate
substances. It differs from indirect anodic oxida-
tion. Indeed by indirect anodic oxidation, pollut-
ants are oxidized by OHs radicals generated by
water oxidation on a high O2 evolution anode
such as boron-doped diamond (BDD).
Direct anodic oxidation is possible using noble
metals (Pt and Pd), metal oxide (IrO2, PbO2), or
carbon-based (boron-doped diamond) anodes,
before oxygen evolution. The rst stage is the
pollutant adsorption on the anode surface. The
second stage is the oxygen (as a source of elec-
trons) transfer from water to the organic pollutant
using electric energy (i.e., anodic polarization)
through the so-called electrochemical oxygen
transfer reaction (EOTR). A typical example of
EOTR often cited in the literature (Panizza and
Cerisola 2009) to illustrate direct electrooxidation
is anodic incineration of phenol as follows:
C6 H5 OH 11H2 O ! 6CO2 28H 28e
The complete phenol oxidation to CO2 (i.e., min-
eralization) is obtained at the anode, and protons
liberated in this reaction are reduced at the cathode
to hydrogen. The pollutant mineralization rate
depends mainly on the nature of the anodic
material, the choice of the anodic potential
(xed before oxygen evolution), and chemical
and physical parameters such as electrolyte and
pollutant composition and concentration and
temperature.
655
The main limitation of electrooxidation is the
decrease of the electrocatalytic activity of the
electrode because of the fast formation of a poly-
mer layer from oxidation intermediates on the
anode surface. Film formation depends on the
adsorption properties of the electrode surface,
the concentration and the nature of organic com-
pounds, their degradation intermediates, the pres-
ence of oxygen, etc. Then electrodes presenting a
surface with weak adsorption properties are pro-
E
moted to gain in stability (Panizza and Cerisola
2003). Nevertheless, in anaerobic conditions, the
formation of the polymer fouling layer remains
the limiting factor of the mineralization.
To overcome this poisoning effect, anode must
be polarized over oxygen evolution to promote
water discharge, leading to hydroxyl radical
(OH) formation on specic electrode like boron-
doped diamond. The electrochemical formation of
this powerful oxidant avoids then polymer fouling
layer formation and then the decrease of the
electrocatalytic activity of the electrode. More
details can be found concerning this electrochem-
ical advanced oxidation process (EAOP) in the
entry indirect anodic oxidation.
References
Panizza M, Cerisola G (2003) Inuence of anode material
on the electrochemical oxidation of 2-naphthol part 1.
Cyclic voltammetry and potential step experiments.
Electrochim Acta 48:34913497
Panizza M, Cerisola G (2009) Direct and mediated anodic
oxidation of organic pollutants. Chem Rev
109:65416569
Electrophoresis
Catherine Charcosset
Universit Lyon 1, Lyon, Villeurbanne, France
The term electrophoresis refers to the motion of
suspended particles in an applied electric eld.
Among separation techniques, electrophoresis is
656
widely used in research and development and
quality control in disciplines such as biochemis-
try, immunology, genetics, and molecular biology
(Westermeier 2001). Electrophoresis is based on
the differential migration of charged species in a
semiconductive medium under the inuence of an
electric eld. Separation of many different kinds
of species including proteins, DNA, nucleotides,
drugs, and many other biochemicals is obtained
upon differences in size, charge, and hydropho-
bicity. The technique was rst reported in 1937 by
Arne Tiselius who won the Nobel Prize in Chem-
istry in 1948 for the separation of different serum
proteins by a method called moving-boundary
electrophoresis. Since then, a number of
improved techniques have been introduced such
as gel electrophoresis, capillary electrophoresis,
and two-dimensional electrophoresis.
Gel electrophoresis uses an electric current
passed through an agarose or polyacrylamide gel
(SDS-PAGE) to separate the molecules in a sample
on the basis of their differences in molecular size
and charge. As the sample migrates in the gel in
response to the electric current, the smaller species
move more quickly than the larger species, which
results in a distinct banded pattern in the gel. This
banded pattern may be visualized via the applica-
tion of staining agents, such as ethidium bromide,
which reveals the gel bands under UV light, or
silver stain, which is typically used to detect pro-
teins. The silver stain is compatible with mass
spectrometry techniques for further analysis of the
protein composition. Capillary electrophoresis
(CE) involves a combination of both polyacryl-
amide gel electrophoresis (SDS-PAGE) and high-
performance liquid chromatography (HPLC)
(Ahuja and Jimidar 2008). High voltages of
500 V/cm or greater are generated within narrow
capillaries (20200 mm). The high voltages cause
electroosmotic and electrophoretic movement of
buffer solutions and ions, respectively, within the
capillary. Two-dimensional gel electrophoresis
(2-D electrophoresis) separates species in two
steps, according to two independent properties. In
a common technique, the rst dimension is isoelec-
tric focusing, which separates proteins according to
their isoelectric points; the second dimension is
SDS polyacrylamide gel electrophoresis
Electrophoresis
(SDS-PAGE), which separates proteins according
to their molecular size. The method involves plac-
ing the sample in gel with a pH gradient and
applying a potential difference across it.
Cellulose acetate membranes are other current
supporting media for electrophoresis separation
(Westermeier 2001). They are used for routine clin-
ical analysis and related applications, as well as for
the analysis of molecules in physiological uids.
These membranes have large pores and therefore
have a low sieving effect on molecules. The elec-
trophoretic separation is thus entirely based on
charge density. The matrix exerts little effect on
diffusion so that the separated zones are relatively
wide and the resolution and limit of detection area
is low. For these reasons, cellulose acetate mem-
branes are often replaced by gel electrophoresis.
Other supporting membranes for electrophore-
sis include Naon membranes, a type of peruor-
osulfonic acid membrane, and cation-exchange
membranes, which are chemically resistant and
consist of a pore-structure cluster network (Fang
et al. 2004). These membranes are widely used in
the eld of chloralkali industry and in fuel cells.
A Naon membrane contains hydrophilic pores
(1020 and 5060 in size) acting as very
narrow electrophoresis channels. The xed-
charge sites (SO3) on the hydrophilic pore
surface provide a strong charged background.
Naon membrane electrophoresis is a potentially
attractive technique for the separation of small
organic molecules like amino acids or ions.
Cross-References
Ion-Exchange Membranes
References
Ahuja S, Jimidar M (2008) Capillary electrophoresis
methods for pharmaceutical analysis. Academic,
Amsterdam
Fang C, Wu B, Zhou X (2004) Naon membrane electro-
phoresis with direct and simplied end-column pulse
electrochemical detection of amino acids. Electropho-
resis 25:375380
Westermeier R (2001) Electrophoresis in practice, 3rd edn.
Wiley-VCH, Weinheim
Electrophoretic Deposition
Electrophoretic Deposition
Catherine Charcosset
Universit Lyon 1, Lyon, Villeurbanne, France
Electrophoretic deposition (EPD), also called
electrocoating, e-coating, cathodic electrodeposi-
tion, or electrophoretic coating, is a simple and
effective technique for coating of charged parti-
cles on substrates (Besra and Liu 2007). It has
several advantages including continuous
processing, uniform deposition and control of
the thickness, and morphology of a deposited
lm by adjustment of the deposition time and
applied potential. In EPD, charged powder parti-
cles, dispersed or suspended in a liquid medium,
are attracted and deposited onto a conductive sub-
strate of opposite charge on application of a DC
electric eld. There are two types of electropho-
retic deposition (Fig. 1). When the particles are
positively charged, the deposition happens on the
negative electrode (cathode) and the process is
termed cathodic electrophoretic deposition. The
deposition of negatively charged particles on pos-
itive electrode (anode) is called anodic electro-
phoretic deposition. By suitable modication of
the surface charge on the particles, any of the two
modes of deposition is possible. This technique is
convenient for stable suspensions containing
charged particles free to move when an electric
eld is applied. Therefore, EPD can be applied to
any material that is available as a ne powder
(e.g., <30 mm particle size) or as a colloidal
Electrophoretic a b
Deposition,
Fig. 1 Schematic of
electrophoretic deposition
process. (a) Cathodic EPD
and (b) anodic EPD
657
suspension, including metals, polymers, ceramics,
and glasses.
The fundamental mechanisms of EPD are
described in the literature mainly in the framework
of the DerjaguinLandauVerweyOverbeek
(DLVO) theory and in relation to the distortion of
the particle double layer under the application of a
DC electric eld (Corni et al. 2008). However,
numerous other theories (occulation by particle
accumulation, particle charge neutralization, elec-
E
trochemical particle coagulation, electrical double
layer distortion, and thinning mechanism) have
been proposed to explain the particle interactions
and the kinetics of deposition.
Several examples of membrane preparation
using an EPD technique are reported. For exam-
ple, EPD is used as a seeding method for making
zeolite membranes (Abdollahi et al. 2007). Zeo-
lites are crystalline structures which possess uni-
form and molecular-sized pores. Zeolite
membranes have a great potential in separation
and catalysis processes owing to their unique
pore structures and adsorption properties and
their high thermal, mechanical, and chemical sta-
bility compared with polymeric membranes.
Since zeolites are negatively charged particles,
they can be effectively attracted to the substrates
of positive charge. By the aid of EPD, an oriented
continuous layer of nano-sized zeolite seeds is
formed on the support and acts as nuclei for the
next step which is crystal growth under hydrother-
mal situation.
The EPD technique is also used for the prepa-
ration of membrane electrode assembly for fuel
cell (Morikawa et al. 2004). A membrane
+
+
+
+ +
+
+ +
+ +
658
electrode assembly can be prepared by EPD pro-
cess onto a Naon membrane. A suspension
consisting of ethanol, carbon powders with Pt
catalyst, and Naon polymer is used to obtain a
stable dispersed solution. The thickness of the
prepared catalyst layer is controlled by EPD dura-
tion or concentration of suspension. The cell
obtained may present a higher electrochemical
performance compared with ordinary cells.
Cross-References
Electrophoretic Painting
Fuel Cell Membrane
Zeolite Membrane
References
Abdollahi M, Ashrazadeh SN, Malekpour A (2007) Prep-
aration of zeolite ZSM-5 membrane by electrophoretic
deposition method. Microporous Mesoporous Mater
106:192200
Besra L, Liu M (2007) A review on fundamentals and
applications of electrophoretic deposition (EPD). Prog
Mater Sci 52:161
Corni I, Ryan MP, Boccaccini AR (2008) Electrophoretic
deposition: from traditional ceramics to nanotechnol-
ogy. J Eur Ceram Soc 28:13531367
Morikawa H, Tsuihiji N, Mitsui T, Kanamura K (2004)
Preparation of membrane electrode assembly for fuel
cell by using electrophoretic deposition process.
J Electrochem Soc 151:A1733A1737
Electrophoretic Mobility
Catherine Charcosset
Universit Lyon 1, Lyon, Villeurbanne, France
When an electric eld is applied across a given
medium, charged solutes or particles suspended in
the electrolyte are attracted toward the electrode
of opposite charge. Viscous forces acting on the
component tend to oppose this movement. When
equilibrium is reached between these two oppos-
ing forces, the solutes or particles move with
constant velocity. The velocity is dependent on
Electrophoretic Mobility
factors such as the strength of electric eld or
voltage gradient, the dielectric constant of the
medium, the viscosity of the medium, and the
zeta potential of the particles.
The electrophoretic mobility, m (m2/Vs), is the
observed electrophoretic velocity, v (m/s), divided
by electric eld strength, E (V/m):
v
m
E
The electrophoretic velocity is the distance of
migration divided by time, also called velocity
of migration. Mobilities are sometimes expressed
with a negative sign, because migration of the
solutes or particles generally occurs in the direc-
tion opposite to the electrophoretic eld (which is
taken as reference).
The electrophoretic mobility of charged sol-
utes, including proteins, is predicted using the
Debye-Huckel-Henry theory (OConnor
et al. 1996). This theory is valid only for spherical
nonconducting particles at low zeta potentials,
with ions present in the electrical double layer
behaving as point charges. The Debye-Huckel-
Henry theory gives the mobility as
ze f kr
m
6p
r 1 kr
where z is the net charge (dimensionless), e the
elementary charge (C), r the particle radius (m),

the viscosity (kg m1 s1), and f(kr) is the
Henry correction factor, which has values
between 1 and 1.5. The Debye-Huckel parameter,
k, is dened by
2e2 N A I
k2
ekT
where NA is the Avogadros constant (kmol1), I is
the ionic strength (kmol m3), e is the permittivity
(J1 C2 m1), k is the Boltzmanns constant
(J K1), and is T the temperature. OBrien and
White (1978) obtained a more rigorous solution to
the equations describing the electrophoretic
mobility of a rigid spherical particle with a uni-
form charge density. The predictions of this model
Electrophoretic Painting
coincide with those of the Debye-Huckel-Henry
theory for systems with zeta potentials less than
25 mV.
The electrophoretic mobility of proteins has
been determined through several microltration
membranes under conditions of zero concentra-
tion driving force and with negligible adsorption
on to the membranes occurring during the exper-
iment (OConnor et al. 1996). The initial mobility
of both proteins is close to free-solution values at
the same pH, after correction for the ionic strength
of the buffer. This effect is explained by the effect
of reduced free area in the membrane which is
compensated by a corresponding increase in the
potential gradient. Data were also obtained for
mixtures of two proteins. Interactions occur
when the two proteins are oppositely charged,
changing the apparent mobilities from the free
solution values.
Cross-References
Electrical Potential
Electrophoresis
References
OBrien RW, White LR (1978) Electrophoretic mobility of
a spherical colloidal particle. J Chem Soc Faraday
Trans 1:16071626
OConnor AJ, Pratt HRC, Stevens GW (1996) Electropho-
retic mobilities of proteins and protein mixtures in
porous membranes. Chem Eng Sci 51:34593477
Electrophoretic Painting
Catherine Charcosset
Universit Lyon 1, Lyon, Villeurbanne, France
Electrophoretic painting, also called electropho-
retic deposition of paint, electrodeposition paint-
ing, or E-coating, is an economical and corrosion-
resistant technique for applying coatings to elec-
trically conducting materials. It is widely used to
659
coat many industrial products such as automobile
bodies and parts, tractors and heavy equipment,
metal furniture, and beverage containers. The pro-
cess is carried out with the use of anodes and
cathodes in the painting tank. There are two
types of electrophoretic painting: anaphoretic
and cataphoretic painting. In anaphoretic painting
the proles will be the anode, and in cataphoretic
painting the proles will be the cathode. In the
electrophoretic painting process, evolution of
E
oxygen gas will take place at the anode, and
hydrogen gas will be evolved at the cathode.
The electrophoretic paint is continuously cir-
culated to avoid settling of the paint solids and
heat resulting from the pumping process as well as
from the passage of electric current. Dry coating
thicknesses of the order of 20 mm are normally
applied, using a voltage of 150200 V for a time
of 12 min. After painting, the proles are rinsed
before stowing at temperatures of 180200  C for
2030 min. The electrophoretic paint may contain
a water-soluble acrylic-based paint, the resin
being rendered soluble by the addition of suitable
amines such as melamine. When current is passed
through the paint, the resin and pigments will
migrate to the anode while the amine will be
discharged at the cathode. During paint deposition
the level of amine will increase, and this causes a
decrease in paint deposition rate if allowed to
continue. The most usual processes used for
removal of excess amine are ultraltration often
in combination with reverse osmosis.
After electrophoretic painting, ultraltration
continuously treats the paint bath to produce per-
meate needed for rinsing metal parts (Agana
et al. 2011). While permeate is used for rinsing,
the mixture of paint and rinse water is returned to
the paint bath from the downstream rinse system.
The volume in the paint bath remains constant,
and the process leads to a closed loop cycle
including a multistage rinse system. No wastewa-
ter is produced and almost no deionized water is
required for the purpose of rinsing. Different types
of membranes are available for various types of
paint. The type and size of the membrane modules
are related to the needs of bath volume and char-
acteristic parameters of the paint bath, such as
total solids, pH, and temperature.
660
Cross-References
Electrophoretic Deposition
Permeate
References
Agana BA, Reeve D, Orbell JD (2011) Optimization of the
operational parameters for a 50 nm ZrO2 ceramic mem-
brane as applied to the ultraltration of post-
electrodeposition rinse wastewater. Desalination
278:325332
Electrospun Nanofiber Membrane
for Biosensors
Michele Modesti, Carlo Boaretti and
Martina Roso
Department of Industrial Engineering, University
of Padova, Padova, Italy
A biosensor is an analytical device comprising
three main elements: a biological recognition ele-
ment able to interact specically with a target, a
transducer able to convert a change in property of
the solution or surface into a recordable signal,
and a processing system which is able to amplify
and quantify the signal. The involved biomolecu-
lar interactions in the bio-receptor/analyte
complex can be based on antibody-antigen inter-
actions, enzymatic interactions, nucleic acid inter-
actions, and cellular or analyte/synthetic receptor
interactions.
Biosensors are generally classied according
to transduction modes and recognition elements
(DOrazio 2003; Rodriguez-Mozaz et al. 2004) in
ve principal transducer classes that are electro-
chemical, optical, thermometric, piezoelectric,
and magnetic. Moreover, electrochemical sensors
may be subdivided into potentiometric, ampero-
metric, or conductometric types (Thevenot
et al. 2001). Biosensors represent nowadays the
answer to a pressing need of advanced solutions
for sensitive detection of the physiological
chemicals involved in clinical diagnosis.
Electrospun Nanofiber Membrane for Biosensors
Within this scenario, electrospinning is an eco-
nomic and versatile technology for producing
one-dimensional nanomaterials that possess high
specic surface area and high porosity. In this
technology, an electried jet of polymer solution
is obtained by applying a relatively high electric
tension. If the viscoelastic forces on the polymer
solution are sufcient to contrast jet breaking, a
nonwoven web of bers ranging from few nano-
meters to several microns is collected on a proper
support. Several reviews and books about
electrospinning (Bhardwaj and Kundu 2010;
Ramakrishna et al. 2005; Wendorff et al. 2012)
are available for having a better understanding of
this technique. The majority of electrospun bers
are polymer-based or polymer-inorganic compos-
ites. It has been shown they have a good biocom-
patibility and consequently they represent a good
candidate for biosensor fabrication especially as a
matrix for protein or enzyme immobilization
(Li et al. 2014).
Among biosensors, monitoring changes in
extracellular glucose concentration is one of the
most important ones because it is related to both
brain disease and neurological disorders, and it is
also the key analyte for medical diagnostics and
management of diabetes. A complete and exhaus-
tive review on glucose biosensor and all the basic
principles of them can be found in the scientic
literature (Yoo and Lee 2010). The most common
glucose biosensors achieve specic recognition of
glucose by immobilization of the enzyme glucose
oxidase (GOD) on the surface of electrodes Wu
and Fan (2013). The basic concept of the glucose
biosensor is based on the fact that the immobilized
GOD catalyzes the oxidation of b-D-glucose by
molecular oxygen, producing gluconic acid and
hydrogen peroxide. Three general strategies are
used for the electrochemical sensing of glucose:
by measuring oxygen consumption, by measuring
the amount of hydrogen peroxide produced by the
enzyme reaction, or by using a diffusible or
immobilized mediator to transfer the electrons
from the GOD to the electrode (Yoo and Lee
2010). At this regard, polyvinyl alcohol (PVA)
nanobers have been shown to be useful in pro-
ducing an amperometric glucose biosensor (Ren
et al. 2006) which exhibited a rapid response time
Electrospun Nanofiber Membrane for Biosensors
(1 s) and a higher output current (mA level) to
glucose in the normal and diabetic level. The
linear concentration response range from 1 to
10 mM and the lower detection limit (0.05 mM)
of the sensor can meet the demand in the detection
of the glucose in medical diagnosis.
In enzyme-based biosensors, the sensitivity
and longevity of the biorecognition element are
functions of the physical design and the enzyme
stability over time (Wilson and Gifford 2005).
Moreover, temperature, pH, and other chemicals
can easily affect the activity and stability of the
immobilized enzyme as well as the immobiliza-
tion chemistry and the microenvironment of the
enzyme on the electrode (Marx et al. 2011).
In order to get an efcient enzyme encapsula-
tion and the absence of interference from other
coexisting electroactive species, the biocomposite
based on Prussian blue, chitosan, and polyvinyl
alcohol has been fabricated by electrodeposition
and subsequent electrospinning in enzyme-
friendly conditions. Prussian blue (PB), known
as articial peroxidase, has been employed in exploited to construct a variety of enzyme-free
fabricating amperometric glucose biosensors
because of its well-known capabilities for enhanc-
ing electron transport and excellent catalytic
activity toward H2O2 reduction at a low
overpotential. The modied electrode has been
shown to exhibit such a rapid direct electron trans-
fer rate that the glucose sensor exhibited excellent
performance, which includes wider linearity,
lower detection limit, and good stability in opti-
mized conditions (Wu and Yin 2013).
Another way for improving sensitivity and
lifetime of the immobilized enzyme is the appli-
cation of conducting polymers to bioelectronic
surfaces; the advantage of using such electrospun
polymers is related to their ability to increase the
signal-to-noise ratio (S/N), and, at the same time,
they are a suitable matrix for the immobilization
and entrapment of enzymes (Yang et al. 2014).
For instance, Yang et al. compared the
performance of enzyme-entrapped conducting
polymer nanobers (NFs) with reference to its
conducting polymer lm (F) counterpart. Among
different conducting polymers, poly
(3,4-ethylenedioxythiophene) (PEDOT) has been
chosen as support for GOD enzyme because of its
661
chemical stability and good electrical
conductivity. Poly(L-lactide) (PLLA) has been
electrospun on Pt microelectrodes followed by
the electrochemical deposition of PEDOT-GOD
on the Pt microelectrodes and around PLLA
nanobers. Comparing the performance of the
two different nanostructured sensors (PEDOT-F
vs. PEDOT-NFs), it has been shown that the
increase of surface area related to the nanobers
affects both the impedance of the biosensor
E
(which is sensitively lower) (Abidian et al. 2010)
and it allows more GOD to be entrapped on the
biosensor. Both of these results contribute to the
increased sensitivity of the PEDOT-NFs-GOD
biosensors.
Nevertheless, the scientic research on biosen-
sors is moving also toward the design and devel-
opment of nonenzymatic glucose sensors based
on direct oxidation of glucose at modied elec-
trode surface (Kong et al. 2012). According to
Ding et al. (2010), metals (Au, Pt, Ni, Cu) and
metal oxides (ZnO, CuO, etc.) have been
glucose sensors. Among the aforementioned
metal oxides, cobalt oxide nanobers (Ding
et al. 2010) have been obtained by electrospinning
and subsequent calcination, and they have been
used for glucose detection in an alkaline medium.
The developed sensor has been shown to have a
fast response time (less than 7 s), a high sensitivity
of 36.25 mA mM1cm2, good reproducibility
and selectivity, and a detection limit of 0.97 mM
(S/N = 3). The high sensitivity and low detection
limit has been hypothesized to be related to the
excellent catalytic property of the as-prepared
Co3O4 nanobers and to their highly porous 3D
network. The latter provides high specic surface
area and numerous active sites, and it allows the
access of analytes to the active catalytic sites with
minimal diffusion resistance. Another attempt to
get nonenzymatic glucose sensor has been
reported in the research of Cao et al. (2011),
wherein nickel oxide microbers (NiO-MFs)
have been directly immobilized onto the surface
of uorine tin oxide (FTO) electrode by
electrospinning followed by calcination
without using any immobilization matrix. The
amperometric performance of glucose at
662
NiO-MFs-modied electrode have shown an
ultrasensitive current (1785.41 mA mM1 cm2)
response and low detection limit of 3.3  108M
(S/N = 3).
Despite the presence of enzyme-based and
nonenzyme-based biosensors, there are also other
support-enzyme hybrid substrate materials for bio-
sensors. An example that has been investigated by
researchers was based on water-stable PVA and
PVA/poly(ethyleneimine) (PEI) nanobers deco-
rated with silver nanoparticles (AgNPs) (Zhu
et al. 2013). By combining an in situ reduction
approach and electrospinning technique, a H2O2,
glutathione (GSH), and glucose detection
biosensor has been obtained, showing a high sen-
sitive detection of H2O2 with a detection limit of
5 mM and a fast response, broad linear range, low
detection limit, and excellent stability and
reusability.
Looking at the aforementioned literature, it
appears evident that the ongoing trend in biosen-
sor fabrication is the use of specic nanomaterials
to get better sensitivity, lower detection limit,
and linear response range. Further evidence of
this is the H2O2-modied electrode based on
hemoglobin (Hb) collagen and carbon nanotubes
(CNTs) proposed by Li et al. (2014). Hb has been
used because of its similar structure to peroxidase,
CNTs for the electrical properties, and collagen
for its excellent biocompatibility. Therefore,
the resulting hemoglobin-collagen-carbon nano-
tube (Hb-collagen-CNT) composite nanober-
modied electrode has excellent performance,
thanks to the great surface area and the
high porosity of the three-dimensional reticular
structure which ensures more channels for both
electron transfer and diffusion of H2O2.
Among enzymes currently used in biosensor
fabrication, urease (Sawicka et al. 2005), fructose
dehydrogenase (Marx et al. 2011),
a-chymotrypsin (a proteolytic enzyme acting in
the digestive systems of many organisms) (Jia
et al. 2002), and lipase (Li et al. 2007; Ye
et al. 2006) represent just a few examples of the
ongoing research. The large surface area of
electrospun nanobers has been found to be
important for increasing both the amount of
immobilized enzymes and their own catalyzing
Electrospun Nanofiber Membrane for Biosensors
activity, thanks to an effective reduction of the
diffusion resistance of the substrates/products.
Further challenge in detecting DNA repair rep-
resents a key factor in cancer diagnostic. Due to
the subtlety of DNA damage, it is difcult to sense
the presence of damaged repair with high selec-
tivity and sensitivity. In this regard immobilizing
DNA on gold/polymeric electrospun nanobers
and their use in electrochemical sensing of DNA
repair processes have been shown to be very prom-
ising, showing the potential of these low-cost
devices for sensing applications (McWilliams
et al. 2014). Polyacrylonitrile electrospun bers
coated with gold nanoparticles have been tested
and thiolated DNA has been assembled on these
bers. It has been demonstrated that the bers
themselves become the working electrode of the
sensors, modied with either the lesion-bearing or
defect-free DNA monolayers. From the reported
assays, the device sensitivity has been found to be
on the order of femtomoles per electrode, and it
means that sensing can be accomplished with even
1 ng of enzyme.
References
Abidian MR, Corey JM, Kipke DR, Martin DC
(2010) Conducting-polymer nanotubes improve electri-
cal properties, mechanical adhesion, neural attachment,
and neurite outgrowth of neural electrodes. Small 6:421
Bhardwaj N, Kundu SC (2010) Electrospinning: a fasci-
nating ber fabrication technique. Biotechnol Adv
28:325347
Cao F, Guo S, Ma H, Shan D, Yang S, Gong J (2011) Nickel
oxide microbers immobilized onto electrode by
electrospinning and calcination for nonenzymatic glu-
cose sensor and effect of calcination temperature on the
performance. Biosens Bioelectron 26:27562760
DOrazio P (2003) Biosensors in clinical chemistry. Clin
Chim Acta 334:4169
Ding Y, Wang Y, Su L, Bellagamba M, Zhang H, Lei Y
(2010) Electrospun Co3O4 nanobers for sensitive and
selective glucose detection. Biosens Bioelectron
26:542548
Jia HF, Zhu GY, Vugrinovich B, Kataphinan W, Reneker
DH, Wang P (2002) Enzyme-carrying polymeric
nanobers prepared via electrospinning for use as
unique biocatalysts. Biotechnol Prog 18:10271032
Kong FY, Li XR, Zhao WW, Xu JJ, Chen HY
(2012) Graphene oxidethionineAu nanostructure com-
posites: preparation and applications in non-enzymatic
glucose sensing. Electrochem Commun 14:5962
Electrospun Nanofibers for Water and Wastewater Treatment Applications
Li SF, Chen JP, Wu WT (2007) Electrospun polyacryloni-
trile nanobrous membranes for lipase immobilization.
J Mol Catal B: Enzym 47:117124
Li J, Mei H, Zheng W, Pan P, Sun XJ, Li F, Guo F, Zhou
HM, Ma JY, Xu XX, Zheng YF (2014) A novel hydro-
gen peroxide biosensor based on hemoglobin-collagen-
CNTs composite nanobers. Coll Surf 284B. 118:7782
Marx S, Jose MV, Andersen JD, Russel AJ
(2011) Electrospun gold nanober electrodes for bio-
sensors. Biosens Bioelectron 26:29812986
McWilliams MA, Anka FH, Balkus JK, Slinker JD
(2014) Sensitive and selective real-time electrochemi-
cal monitoring of DNA repair. Biosens Bioelectron
54:541546
Ramakrishna S, Fujihara K, Teo WE, Lim TC, Ma Z
(2005) An introduction to electrospinning and
nanobers. World Scientic, Singapore
Ren G, Xu X, Liu Q, Cheng J, Yuan X, Wu L, Wan Y
(2006) Electrospun poly(vinyl alcohol)/glucose oxi-
dase biocomposite membranes for biosensor applica-
tions. React Funct Polym 66:15591564
Rodriguez-Mozaz S, Marco MP, Lopez de Alda MJ,
Barcel D (2004) Biosensors for environmental moni-
toring of endocrine disruptors: a review article. Anal
Bioanal Chem 378:588598
Sawicka K, Gouma P, Simon S (2005) Electrospun
biocomposite nanobers for urea biosensing. Sensor
Actuat B-Chem 108:585588
Thevenot DR, Toth K, Durst RA, Wilson GS (2001) Elec-
trochemical biosensors: recommended denitions and
classication. Biosens Bioelectron 16:121131
Wendorff JH, Agarwal S, Greiner A (2012)
Electrospinning. Materials, processing and applica-
tions. Wiley-VCH, Weihneim
Wilson GS, Gifford R (2005) Biosensors for real-time in
vivo measurements. Biosens Bioelectron 20:2388
Wu J, Fan Y (2013) Sensitive enzymatic glucose biosensor
fabricated by electrospinning composite nanobers and
electrodepositing Prussian blue lm. J Electroanal
Chem 694:15
Wu J, Yin F (2013) Sensitive enzymatic glucose biosensor
fabricated by electrospinning composite nanobers and
electrodepositing Prussian blue lm. J Electroanal
Chem 694:15
Yang G, Kampstra KL, Abidian MR (2014) High-
performance conducting polymer nanober biosensors
for detection of biomolecules. Adv Mater. doi:10.1002/
adma.201400753
Ye P, Xu ZK, Wu J, Innocent C, Seta P (2006) Nanobrous
membranes containing reactive groups: electrospinning
from poly(acrylonitrile-co-maleic acid) for lipase
immobilization. Macromolecules 39:10411045
Yoo EH, Lee SY (2010) Glucose biosensors: an overview
of use in clinical practice. Sensors 10:45584576
Zhu H, Du ML, Zhang Z, Wang P, Bao SY, Wang LN, Fu
YQ, Yao JM (2013) Facile fabrication of AgNPs/
(PVA/PEI) nanobers: high electrochemical efciency
and durability for biosensors. Biosens Bioelectron
49:210215
663
Electrospun Nanofibers for Water
and Wastewater Treatment
Applications
Michele Modesti, Carlo Boaretti and
Martina Roso
Department of Industrial Engineering, University
of Padova, Padova, Italy
E
Water pollution is the contamination of water
bodies (e.g., lakes, rivers, oceans, aquifers, and
groundwater), and it occurs when pollutants are
discharged directly or indirectly into water bodies
without adequate treatment to remove harmful
compounds. Direct sources include efuent out-
falls from factories, reneries, waste treatment
plants, etc., that emit uids of varying quality
directly into urban water supplies. Indirect
sources include contaminants that enter the water
supply from soils/groundwater systems and from
the atmosphere via rainwater. Soils and ground-
waters contain the residue of human agricultural
practices (fertilizers, pesticides, etc.) and improp-
erly disposed of industrial wastes. Atmospheric
contaminants are also derived from human prac-
tices (such as gaseous emissions from automo-
biles, factories, and even bakeries).
Contaminants can be broadly classied into
organic, inorganic, radioactive, and acid/base.
Moreover, bacteria and virus represent a danger-
ous class of contaminating agents, which are
responsible of diseases in developing countries.
Microbial Control of Water
Currently the basic water treatments for microbial
control require chemical disinfectants and
membrane-based ltration systems. If the forma-
tion of harmful disinfection by-products from
chemical disinfectants is the potential drawback
that makes their use not completely reliable
(Li et al. 2008), water ltration membrane is
affected by biofouling and virus penetration. Bio-
fouling can be considered as a biotic form of
664 Electrospun Nanofibers for Water and Wastewater Treatment Applications
organic fouling, and it represents a major problem
in nanoltration (NF) and reverse osmosis
(RO) membrane ltration.
At this regard, electrospun nanobers have
been found to be a good candidate for improving
the performance of ltering media. Antifouling
properties can be achieved by plasma treatment
or surface graft polymerization of nanobers, as
suggested by the literature (Musale and Kumar
2000). Another advantage related to the use of
electrospun nanobers for microbial control is
the capability to get a wide range of assemblies,
for instance, antimicrobial nanobers themselves
and nanobiocides, which include metal, metal-
oxide nanoparticles, engineered nanomaterials
(fullerenes and carbon nanotubes), and natural
substances (Botes and Cloete 2010). For instance,
nanoparticles of Ag, TiO2, and ZnO represent
low-cost materials with a well-known antimicro-
bial activity that can be properly attached to
nanobers reducing potential toxicity and
leaching effects.
Polyurethane, poly(vinylidene) uoride-co-
hexauoro-propylene (PVDF-HFP), and polycar-
bonate with quaternary ammonium salt are just
few examples of antimicrobial nanolters which
have been shown to have a very good ltration
efciency of 0.3 mm size particles (99.93 %) and a
very strong antimicrobial activities against both
S. aureus and E. coli (Yao et al. 2008, 2009; Kim
et al. 2007).
Desalination
Another challenging task related to the water issue
regards the need of alternative sources in order to
tackle the higher demand for fresh water and
energy resources. Desalination technology that
converts seawater into clean water has been
found to be a suitable approach for it. Among
the different membrane separation processes,
membrane distillation (MD), electrodialysis
(ED), reverse osmosis (RO), freeze desalination
(FD), ion exchange (IX), and nanoltration
(NF) have been developed as desalination tech-
nologies (Sundarrajan and Ramakrishna 2013).
Nanoltration is a type of pressure-driven mem-
brane process with properties in between reverse
osmosis (RO) and ultraltration (UF), which has
been found to be adequate for desalination with
low salt content. According to the established
technology, in order to reduce the resistance and
enhance the ux, thin lm composite membranes
(TFC) are commonly used. They are based on
three layer, that is, a nonwoven fabric as support,
a middle porous support, and a top layer which is
responsible for the selective salt removal. Within
this scenario, electrospun nanobers can be used
as a mid-layer membrane in order to achieve
higher ux and low fouling behavior than the
commercial NF membranes (Yung et al. 2010).
Nevertheless, the applicability of electrospun
membranes as self-supporting NF membranes
has been proved (Kaur et al. 2012) even though
a careful optimization of the whole system needs
further studies in terms of process optimization
and cost analysis.
As regards desalination by membrane distilla-
tion (MD), nanobrous membranes based on
electrospun polymers (polyvinylideneuoride,
PVDF) and copolymers (PVDF-co-F6PP, PVDF-
co-hexauoropropene) have been proven to
reduce the energy requirements of direct contact
membrane distillation process, thanks to the
higher permeate ows (Khayat et al. 2011; Shih
2011) than PTFE commercial membranes. Very
good performance in a direct contact membrane
distillation setup could be achieved also by self-
supporting carbon nanotube (CNT) membranes
(Dume et al. 2011), which have to be properly
modied for enhancing their hydrophobicity and
that allow to get a 99 % salt rejection and a ux
rate of 12 kg/m2.
Heavy Metal Ions Removal
Water pollution by heavy metal ions is another
important related issue because long-term expo-
sure to metal ions such as lead (Pb) can result in
acute or chronic damage to the brain and the
central nervous system on humans. Furthermore,
heavy metals are dangerous because they tend to
Electrospun Nanofibers for Water and Wastewater Treatment Applications
bioaccumulate, i.e., the concentration of a chem-
ical increases in a biological organism over time,
compared to the chemicals concentration in the
environment (Lee et al. 2013). Among the tech-
nologies employed for the treatment of contami-
nated water (chemical oxidation, precipitation, IE,
RO), adsorption and membrane separation could
be enhanced by electrospun nanobers. In the
literature several examples are reported, the cen-
tral ideas of which are:
i. The functionalization of the bers with such
molecules able to bind metal ions
ii. The surface modication of polymer in order
to vary certain properties, such as hydrophi-
licity or hydrophobicity, water absorbency,
adsorption capacity, and resistance to micro-
bial attack
iii. The production of mixed nanocomposite
bers
As regards the functionalization of bers (point
i), rhodanine is a heterocyclic molecule that
belongs to the sulfur-containing N and O organic
compounds which possesses uptake performance
toward Ag (I), Pb (II), and Hg (II) ions (Lee
et al. 2013). On the other hand cellulose and
chitosan-/polyacrylamide-modied nanobers
have been proven to be suitable for the adsorption
of trace of metals (Cd, Pb, Cu, Cr, and Ni) from
the river water and treated water (Musyoka
et al. 2013). Their adsorption capacity has been
enhanced (point ii) by surface modication
using furan-2,5-dione. The electrospun iron
oxidealumina ber systems represent an exam-
ple of nanocomposite bers (point iii) that have
been used as adsorbent for the removal of heavy
metal ions, i.e., Cu2+, Ni2+, Pb2+, and Hg2+ from
aqueous system (Mahapatra et al. 2013).
References
Botes M, Cloete TE (2010) The potential of nanobers and
nanobiocides in water purication. Crit Rev Microbiol
36:6881
Dume L, Germain V, Sears K, Sch utz J, Finn N, Duke M,
Cerneaux S, Cornu D, Gray S (2011) Enhanced
665
durability and hydrophobicity of carbon nanotube
bucky paper membranes in membrane distillation.
J Membr Sci 376:241246
Kaur S, Sundarrajan S, Gopal R, Ramakrishna S
(2012) Formation and characterization of
polyamide composite electrospun nanobrous mem-
branes for salt separation. J Appl Polym Sci 124:
E205E215
Khayet M, Payo G, Carmen AS, Carmen M (2011) Nano-
structured at membranes for direct contact membrane
distillation. WO/2011/117443
Kim SJ, Nam YS, Rhee DM, Park HS, Park WH
(2007) Preparation and characterization of antimicro- E
bial polycarbonate nanobrous membrane. Eur Polym
J 43:31463152
Lee CH, Chiang CL, Liu SJ (2013) Sep Purif Technol
118:737743
Li Q, Mahendra S, Lyon DY, Brunet L, Liga MV, Li D,
Alvarez PJJ (2008) Antimicrobial nanomaterials
for water disinfection and microbial control:
potential applications and implications. Water Res
42:45914602
Mahapatra A, Mishra BG, Hota G (2013) Electrospun
Fe2O3Al2O3 nanocomposite bers as efcient
adsorbent for removal of heavy metal ions
from aqueous solution. J Hazard Mater 258259:
116123
Musale DA, Kumar A (2000) Solvent and pH resistance of
surface crosslinked chitosan/poly(acrylonitrile) com-
posite nanoltration membranes. J Appl Polym Sci
77:17821793
Musyoka SM, Ngil JC, Mamba BB (2013) Remediation
studies of trace metals in natural and treated water using
surface modied biopolymer nanobers. Phys Chem
Earth 66:4550
Shih JH (2011) A study of composite nanober membrane
applied in seawater desalination by membrane distilla-
tion. Masters Thesis, National Taiwan University of
Science and Technology
Sundarrajan S, Ramakrishna S (2013) New directions in
nanoltration applications are nanobers the right
materials as membranes in desalination? Desalination
308:198208
Yao C, Li X, Neoh KG, Shi Z, Kang ET
(2008) Surface modication and antibacterial activity
of electrospun polyurethane brous membranes with
quaternary ammonium moieties. J Membr Sci
320:259267
Yao C, Li X, Neoh KG, Shi Z, Kang ET (2009)
Antibacterial activities of surface modied electrospun
poly(vinylidene uoride-co-hexauoropropylene)
(PVDF-HFP) brous membranes. Appl Surf Sci
255:38543858
Yung L, Ma H, Wang X, Yoon K, Wang R, Hsiao BS,
Chu B (2010) Fabrication of thin-lm nanobrous
composite membranes by interfacial polymerization
using ionic liquids as additives. J Membr Sci
365:5258, new container
666
Electrospun Nanofibrous
Membranes
Martina Roso, Carlo Boaretti, Alessandra
Lorenzetti and Michele Modesti
Department of Industrial Engineering, University
of Padova, Padova, Italy
Introduction
Nanobers are an interesting and versatile class of
one-dimensional (1-D) nanomaterials, with diam-
eters ranging from tenths to hundreds of nanome-
ters, which have been recognized as promising
due to their outstanding properties in terms of
high porosity, excellent pore interconnectivity,
small diameters, and high surface-to-volume
ratio. Among the different nanober manufactur-
ing technologies, electrostatic spinning or
electrospinning represents the easiest, most prom-
ising, and versatile method for the generation of
aligned or randomly distributed nanobers of a
rich variety of different materials like synthetic
and natural polymers (Huang et al. 2003), com-
posites (Sahay et al. 2012), ceramics (Dai
et al. 2011), and metals (Wu et al. 2007).
With this technique that is essentially a varia-
tion of the electrostatic spray (or electrospraying),
a ber is produced thanks to the solidication of
an electried jet of a solution that is stretched by
the repulsive action of surface charges and evap-
oration of solvent. The main difference with
respect to electrospraying is the presence of high
elongational viscous forces generated by the chain
entanglements of the polymer present in the solu-
tion that, thanks to the application of a strong
electric eld, prevent the formation of liquid drop-
lets in favor of a rapid whipping jet. The
electrospun solution is essentially polymer
based, with the possibility to add metal or ceramic
precursors that after electrospinning treatments
can generate the corresponding nanobers.
An extensive research activity has been carried
in the last years toward the evaluation of
electrospun nanobrous membranes (ENMs) in
the context of membrane technology, fueled by
Electrospun Nanofibrous Membranes
the advantages offered in terms of cost and pro-
ductivity over more complicated bottom-up
approaches, exibility of the membranes, and
the potential upscaling for industrial production
(Persano et al. 2013).
Fundamentals
The generation of nanobers by electrospinning
starts from a solution of a proper solvent in which
the desired material is dissolved at a suitable con-
centration. This solution is usually poured in a
syringe or a pipette from which it is let own
through a nozzle using a micropump, and by
means of a high-voltage direct current power sup-
ply (550 kV), an electrostatic eld is applied
between the nozzle and a metal collector with
opposite polarity. By increasing the intensity of
the electric eld, a charge is induced on the sur-
face of the solution at the tip of the capillary. The
mutual repulsion of the charges elongates the
hemispherical drop to form a conical shape
(Taylor cone). Once that the electric eld has
reached a threshold value, the electrostatic
force overcomes the surface tension and a
charged jet of solution is ejected from the tip of
the Taylor cone, producing a jet that travels
toward the metal collector. During this last phase
the jet undergoes a whipping process in which it is
stretched and the solvent of the solution evapo-
rates leaving a ber that is collected on a grounded
collector.
The morphology and diameter of electrospun
nanobers depend on a wide range of parameters,
which can be classied according to three main
different categories:
Solution parameters: type of solvent, viscosity,
molecular weight and molecular weight distri-
bution, vapor pressure, surface tension, and
solution conductivity
Process parameters: solution feeding rate,
electric eld strength, distance between the
tip and the collector, needle diameter, compo-
sition, geometry, and motion of the collector
Ambient parameters: temperature, humidity,
and air velocity.
Electrospun Nanofibrous Membranes
Between them viscosity has a prominent role in
relation to the morphology of the nanobers. For
polymer solutions of low viscosity, surface ten-
sion is the dominant aspect and just beads or
beaded nanobers are obtained. As the viscosity
of the solution is increased, the beads become
bigger, the average distance between them longer,
and the shape of the beads changes from spherical
to spindle-like with a decrease of the ber diam-
eter. At a suitable concentration, smooth
nanobers without defects can be obtained, but
with a progressive increment of its value, the
bers increase their diameter until they change
their shape into micro-ribbons. Usually the proper
viscosity is dened in relation to the specic
polymer-solvent system, and for a given
polymer-solvent system, it can change according
to the molecular weight of the polymer. Complex
architectures like core-shell, porous, and hollow
structures can be formed by electrospinning
through the incorporation of nanoparticles into
bers, co-electrospinning of different polymers,
or employing solutions with different boiling
point solvents, while modication of the
electrode-collector system allows to orientate the
bers and to obtain 3-D structures (Teo
et al. 2011).
Electrospun nanobers can also be obtained
from polymer melts at high temperature, from a
combination of a magnetic and electric eld, aer-
ated polymer solution, and from multi-jet devices
in order to improve production rate.
Applications
The interesting properties related to the possibility
of obtaining nanometric bers from
electrospinning allow their use for several poten-
tial applications, with a multidisciplinary perspec-
tive. Broadly speaking it is possible to identify
four main areas of interest (Ramakrishna
et al. 2005): bioengineering, environmental engi-
neering and biotechnologies, energy and electron-
ics, and, nally, defense and security. In this
framework the specic elds of applications in
which electrospun nanobers are directly in con-
tact with membrane technology are several,
667
including the most traditional and advanced tech-
nologies: air and water ltration, fuel cell mem-
branes and battery membrane separators,
biomedical applications, and many others. Most
of these applications havent already reached their
industrial level, but the promising results from the
research eld and their different potential applica-
tions are believed to encounter the interest of
industry and governments. Actually the most
industrially developed products based on ENMs
E
are lters for air purication. Potential products
ready to market are related to liquid ltration and
energy storage, in the short-medium period, and to
the biomedical eld, in the medium-long period
(Persano et al. 2013).
Air and Water Filtration
ENMs high specic surface, porosity and perme-
ability, tailorable thickness, and ber diameters
are desirable features for ltration applications.
These materials have been employed for several
years for air ltration and recently, at a research
level, even for microltration, ultraltration, and
nanoltration in the eld of water treatment. The
advantages of electrospun nanobers compared to
conventional air lter media are related to a higher
ltration efciency, lower pressure drops, and
energy savings. Indeed, nanobers with diameters
lower than 0.5 mm have much higher capability to
collect ne particles because of the slip ow that
increases diffusion, interception, and inertial
impaction efciencies, determining a lower drag
force around the bers and, thus, lower pressure
drops. In addition these media are easy to clean,
enabling them to signicantly extend the life of
lters and reducing the maintenance costs. Their
potentials have shown possible applications in air
ltering media (Barhate and Ramakrishna 2007),
especially for high-efciency particulate and
low-penetration air lters, lters for transportation
applications, adsorptive catalytic gas lter for res-
pirators, lter media for pulse clean cartridges in
dust collection, and cigarette lters for smoke
ltration.
ENMs can be employed also for water treat-
ment (Cloete et al. 2013) and generally show high
ux rate and low transmembrane pressure with
performance comparable to those commercially
668
available. The main interesting application in this
area is related to desalination, VOC gas stripping,
oil/water emulsion separation, microbial, organic
compounds, and heavy metal removal. However,
for solid-liquid ltration, very high surface-to-
volume ratios promote membrane fouling. For
this reason and for improving membrane perfor-
mances, ENMs can be surface modied (Nasreen
et al. 2013), in order to add functional groups or
functionality, with processes like in situ graft and
interfacial polymerization, plasma treatment, wet
treatment, coating, and blending with surface-
modifying agents. A main drawback for the
employment of electrospun nanobers for such
applications is their mechanical strength which is
not sufcient to withstand macroscopic impact
during ltration application such as normal liquid
or air ows passing through them. Hence, they
need to be used as active coating layer on existing
melt-blown supportive brous media (composite
membrane) or the bers need to be bonded to
enhance mechanical properties.
Fuel Cell and Battery Separator Membranes
Another area in which ENMs can have promising
applications is that of energy-related applications
and devices (Cavaliere et al. 2011), especially for
polymer fuel cell and lithium-ion battery electro-
lyte membranes.
Research efforts on polymeric proton
exchange membranes for fuel cells have led the
interest of researchers toward the employment of
ENMs as porous reinforcing mats to minimize
in-plane swelling and shrinking. Nanobers are
also able to increase proton conductivity with
respect to bulk lm, thanks to their highly oriented
ionic domains (Dong et al. 2010) and provide
good mechanical strength, while the remarkable
exibility of their production process allows to
adequately tailor their nal morphology for com-
posite membranes. Fuel cell membranes are semi-
permeable membranes that have the function to be
proton conductive, electron insulating, and dense
in order to avoid fuel crossover. For this reason
two types of approaches can be used when
employing electrospinning for such application.
The rst is related to the electrospinning of
Electrospun Nanofibrous Membranes
nonconductive or less conductive polymer into a
porous matrix, which acts as mechanical rein-
forcement when the pores are lled with a highly
proton-conductive component. Alternatively, a
highly proton-conducting matrix is electrospun
into a porous ber mat and subsequently
reinforced with a secondary polymer to provide
mechanical stability. The proton-conductive poly-
mers are usually chosen between peruoro-
sulfonic acid and sulfonated polymers that can
be coupled with organic or inorganic particles as
conductor enhancers or to improve strength and
hydrophilicity.
Electrospun mats are also attractive alterna-
tives to polymer gel electrolytes for lithium-ion
batteries, since they can be employed as matrix in
which the electrolyte can be encapsulated improv-
ing ionic conduction across the membrane and
mechanical strength while providing good water
uptake. In these elds the most widely studied
polymer has been poly(vinylidene uoride)
(PVDF) thanks to its good electrochemical and
thermal stability. However, PVDF-based gel poly-
mer electrolyte with its high crystallinity limits the
ion migration, lowering the battery performance.
ENMs with their porous membrane are capable to
overcome this problem, and PVDF and other
alternative polymers and blend have been
explored by electrospinning with encouraging
results.
Biomedical Applications
Nanober research applications in the biomedical
eld have a multifaceted perspective spreading
between tissue engineering, drug delivery, and
wound dressing (Agarwal et al. 2008). Tissue
engineering is an emerging multidisciplinary
area in which nanobers represent an important
advancing front for the production of suitable
scaffolds of different materials that can mimic
natural extracellular matrix. To this purpose
ENMs have been tested as natural, synthetic, and
composite scaffolds for different types of targeted
tissue including blood vessel, cartilage, bone,
nerve, and many others. The small diameter of
the bers and their high surface area are benecial
for cell attachment and bioactive factor loading,
enhancing cell growth.
Electrospun Nanofibrous Membranes
Drug delivery membranes incorporate a drug
component that can be patched on wound of sur-
gery or encapsulated into pharmaceutical capsules
to deliver the drug through the digestive system of
the patient. Polymeric electrospun drug delivery
systems are advantageous for such task because
they can deliver drugs efciently to a localized
area, with the possibility to vary the release rate by
simply varying the ber diameter or the loading
dosage. The possibility of choosing different
materials, processes, and processing conditions
allows to reach the desired encapsulation ef-
ciency, preserving bioactivity (Zamani
et al. 2013). Several drugs have been incorporated
successfully into electrospun media obtaining bet-
ter performance over normal cast lm and with the
possibility to load insoluble drug for enhancing
their dissolution.
ENMs have also exhibited potential in wound
dressing thanks to the possibility to generate
homogeneous scaffolds, provide uniform
adherence, and wet wound surface without uid
accumulation. They can provide high gas perme-
ation and protection from infection and dehydra-
tion, extending their applications on different
types of wounds as compared to traditional
wound dressing materials and opening new
doors for the next generation of wound dressing
materials.
Other Applications
Electrospun materials from stable polymers or
ceramic bers are also ideal candidates as sup-
ports for homogeneous and heterogeneous catal-
ysis in gas phase, since they can provide high
surface area and high porosity. The catalyst,
which is usually a semiconductor, can be the
nanobrous mat itself, or it can be subsequently
added by surface modications or deposition.
Examples are organic or inorganic nanobers on
which metals or semiconductor nanoparticles are
deposited or embedded for catalytic (Basheer
2013) and photocatalytic oxidation (Modesti
et al. 2014) and synthesis (Formo et al. 2009) of
organic compounds in gas phase. The advantages
of the high surface areas of the catalytic lters
obtainable with this technique are related to
higher activity with respect to common porous
669
catalysts for the abatement of selected
compounds.
The characteristics of ENMs match well the
requirements for different types of sensing
devices (Ding et al. 2009) including acoustic
wave, resistive, gravimetric, photoelectric, opti-
cal, and amperometric sensors. Indeed, ENMs
high surface area has the potential to provide
unusually high sensitivity, fast response time,
and lower detecting limits. In this case different
E
approaches can be employed to provide a sensing
capability to nanobers, such as electrospinning
of a polymeric sensing material, incorporation of
sensing molecules into nanobers, or application
of sensing material on nanober surface via coat-
ing/grafting technique, employing organic and
inorganic polymer.
Other potential applications of ENMs include
afnity membranes for protein purication
(Ma et al. 2005) and protective clothing against
nanoparticles (Faccini et al. 2012) on textile
support.
Cross-References
Nanober
Oil-Water Emulsion
Proton-Exchange Membranes for Fuel Cells
Ultraltration (UF)
References
Agarwal S, Wendorff JH, Greiner A (2008) Use of
electrospinning for biomedical applications. Polymer
49:56035621
Barhate RS, Ramakrishna S (2007) Nanobrous ltering
media: ltration problems and solutions from tiny
materials. J Membr Sci 296:18
Basheer C (2013) Nanober-membrane-supported TiO2 as
a catalyst for oxidation of benzene to phenol. J Chem
2013:17
Cavaliere S, Subianto S, Savych I, Jones DJ, Roziere J
(2011) Electrospinning: designed architectures for
energy conversion and storage devices. Energy Envi-
ron Sci 4:47614785
Cloete TE, de Kwaadsteniet M, Gule NP, Klumperman B
(2013) Electrospun nanobrous membranes for water
treatment applications. In: Lens PNL, Virkutyte J,
Jegatheesan V, Kim SH, Al-Abed S (eds)
670
Nanotechnology for water and wastewater treatment.
IWA Publishing, London, pp 283294
Dai Y, Liu W, Formo E, Sun Y, Xia Y (2011) Ceramic
nanobers fabricated by electrospinning and their
applications in catalysis, environmental science,
and energy technology. Polym Adv Technol
22:326338
Ding B, Wang M, Yu J, Sun G (2009) Gas sensors based on
electrospun nanobers. Sensors 9:16091624
Dong B, Gwee L, Salas-de la Cruz D, Winey KI, Elabd YA
(2010) Super proton conductive high-purity Naon
nanobers. Nano Lett 10:37853790
Faccini M, Vaquero C, Amantia D (2012) Development of
protective clothing against nanoparticle based on
electrospun nanobers. J Nano Mater 2012(892894) 9
pages. doi:10.1155/2012/892894
Formo E, Yavuz MS, Lee EP, Lane L, Xia Y (2009)
Functionalization of electrospun ceramic nanobre
membranes with noble-metal nanostructures for cata-
lytic applications. J Mater Chem 19:38783882
Huang ZM, Zhang YZ, Kotaki M, Ramakrishna S (2003)
A review on polymer nanobers by electrospinning and
their applications in nanocomposites. Compos Sci
Technol 63:22232253
Ma Z, Kotaki M, Ramakrishna S (2005) Electrospun
nanober as afnity membrane. J Membr Sci
265:115123
Modesti M, Roso M, Boaretti C, Besco S, Hrelja D,
Sgarbossa P, Lorenzetti A (2014) Preparation of smart
nano-engineered electrospun membranes for methanol
gas-phase photoxidation. Appl Catal B 144:216222
Nasreen SAAN, Sundarrajan S, Nizar SAS,
Balamurugan R, Ramakrishna S (2013) Advancement
in electrospun nanobrous membranes modication
and their application in water treatment. Membranes
3:266284
Persano L, Camposeo A, Tekmen C, Pisignano D (2013)
Industrial upscaling of electrospinning and applications
of polymer nanobers: a review. Macromol Mater Eng
298:504520
Ramakrishna S, Fujihara K, Teo WE, Lim TC, Ma
Z (2005) An introduction to electrospinning and
nanobers. World Scientic, Singapore
Sahay R, Kumar PS, Sridhar R, Sundaramurthy J,
Venugopal J, Mhaisalkar SG, Ramakrishna S
(2012) Electrospun composite nanobers and their
multifaceted applications. J Mater Chem
22:1295312971
Teo WE, Inai R, Ramakrishna S (2011) Technological
advances in electrospinning of nanobers. Sci Technol
Adv Mater 12:013002 (19pp)
Wu H, Zhang R, Liu X, Lin D, Pan W (2007)
Electrospinning of Fe, Co, and Ni nanobers: synthe-
sis, assembly and magnetic properties. Chem Mater
19:35063511
Zamani M, Prabhakaran M, Ramakrishna S (2013)
Advances in drug delivery via electrospun and
electrosprayed nanomaterials. Int J Nanomedicine
8:29973017
Electrospun Polyethersulfone Nanofiber Membranes
Further Readings
Andrady AL (2008) Science and technology of polymer
nanobers. Wiley, Hoboken
Ding B, Yu J (2014) Electrospun nanobers for energy and
environmental applications, Nanostructure science and
technology series. Springer, Berlin
Jayakumar R, Shantikumar N (2012) Biomedical applica-
tions of polymer nanobers, advances in polymer sci-
ence. Springer, Berlin
Modesti M, Lorenzetti A, Roso M (2011) Nanobers via
electrospinning. Encyclopedia of nanoscience and
nanotechnology, vol 17. America Scientic, Valencia,
California, pp 231312
Wendorff JH, Agarwal S, Greiner A (2012)
Electrospinning: materials, processing and applica-
tions. Wiley-VCH, Singapore
Electrospun Polyethersulfone
Nanofiber Membranes
Michele Modesti, Carlo Boaretti and
Martina Roso
Department of Industrial Engineering, University
of Padova, Padova, Italy
Electrospun polyethersulfone (PES) nanober
membranes are semipermeable membranes
obtained by electrospinning that have been
explored for possible applications concerning
water ltration (microltration, nanoltration,
and engineered osmosis), composite polymer
electrolyte membranes, and tissue engineering.
Polyethersulfone (PES) is a high-performance
aromatic polymer which belongs to the family of
polysulfones. The basic repeating unit of the polymer
backbone consists of para-linked aromatic groups
connected by ether and sulfone groups (see Fig. 1).
PES is synthesized by polycondensation of
4,4-sulfonylbisphenol (bisphenol S) with
O
O S
O n
Polyethersulfone (PES)
Electrospun Polyethersulfone Nanofiber Mem-
branes, Fig. 1 Repetitive unit of polyethersulfone
Electrospun Polyethersulfone Nanofiber Membranes
4,4-dichlorophenyl sulfone via nucleophilic sub-
stitution at high-reaction temperature (up to
285  C) in the presence of a suitable solvent like
diphenyl sulfone, sulfolane, or N-methyl-2-
pyrrolidone (Parker et al. 2012).
PES is a widely employed polymer for mem-
brane fabrication due to its interesting properties in
terms of high glass transition temperatures, good
mechanical strength and stiffness, and outstanding
thermal and oxidative resistance. This polymer can
be electrospunned from solutions of suitable con-
centration with polar aprotic solvents (e.g.,
dimethylacetamide) in order to produce nanobers
with average diameters of 0.752 mm and average
specic surface area of 1530 m2/g, by changing
the process parameters (Kwak et al. 2013).
Electrospun nanobrous membranes (ENMs)
are a new class of energy-saving membranes that
are under extensive study because of their high
interconnected porosity and tunable pore size that
can give high permeability and selectivity. One of
the most important elds of interest for ENMs is
water ltration for which these membranes could
overcome some intrinsic limitations of conven-
tional porous polymeric membranes. However
ENMs suffer of poor mechanical strength, while
PES, even if extensively used for commercial
membranes, is a highly hydrophobic polymer so
the synthesis of composite membranes is the usual
approach to solve these issues. PES ENMs can be
employed for dye and heavy metal removal by
blending with polymers that incorporate func-
tional groups that have binding/chelating capabil-
ity (Min et al. 2012; Wu et al. 2014). The
mechanical properties of these membranes can
be improved by interber adhesion/junction
(Yoon et al. 2009; Homaeigohar et al. 2012),
while the hydrophilicity can be increased by oxi-
dation treatment (Yoon et al. 2009).
A combination of both improvements can be
achieved by incorporation of hydrophilic inor-
ganic particles which can also allow a higher
thermal stability (Homaeigohar et al. 2011). PES
ENMs can be employed even as a middle layer in
thin lm composite polymeric membranes for
engineered osmosis with the advantage to provide
higher osmotic uxes than their commercial coun-
terparts (Bui et al. 2011).
671
Other potential applications concern polymeric
scaffolds as substrate for stem cell culture made of
pristine (Christopherson et al. 2009;
Ardeshirylajimi et al. 2013) and modied (Chua
et al. 2006; Shabani 2009) PES, for which both the
ber diameter and the type of functionalization
can have a prominent role in the inltration, dif-
ferentiation, and proliferation of the cells.
The high stability of the polymer and its chain
exibility due its structure make PES a suitable
E
candidate as non-uorinated replacement for pro-
ton exchange membranes, especially for direct
methanol fuel cells. By sulfonation it is possible
to introduce proton conducting functional groups
along the polymer chain, while by electrospinning
a suitable nanobrous web can be produced. This
nonwoven structure can be lled with Naon to
obtain a compact membrane with higher electro-
chemical performances with respect to Naon
112 and Naon 117 dense membranes (Shabani
et al. 2010; Hasani-Sadrabadi et al. 2011).
Cross-References
Electrospun Nanobrous Membranes
Proton-Exchange Membranes for Fuel Cells
Ultraltration (UF)
References
Ardeshirylajimi A, Hosseinkhani S, Parivar K,
Yaghmaie P, Soleimani M (2013) Nanober-based
polyethersulfone scaffold and efcient differentiation
of human induced pluripotent stem cells into osteoblas-
tic lineage. Mol Biol Rep 40:42874294
Bui NN, Lind ML, Hoek EMV, McCutcheon JR
(2011) Electrospun nanober supported thin lm com-
posite membranes for engineered osmosis. J Membr
Sci 385386:1019
Christopherson GT, Song H, Mao HQ (2009) The inu-
ence of ber diameter of electrospun substrates on
neural stem cell differentiation and proliferation. Bio-
materials 30:556564
Chua KN, Chai C, Lee PC, Tang YN, Ramakrishna S,
Leong KW, Mao HQ (2006) Surface-animated
electrospun nanobers enhance adhesion and expan-
sion of human umbilical cord blood hematopoietic
stem/progenitor cells. Biomaterials 27:60436051
Hasani-Sadrabadi MM, Shabani I, Soleimani M,
Moaddel H (2011) Novel nanober-based triple-layer
672
proton exchange membranes for fuel cell applications.
J Power Sources 196:45994603
Homaeigohar SS, Mahdavi H, Elbahri M (2011) Extraor-
dinarily water permeable sol-gel formed
nanocomposite nanobrous membranes. J Colloid
Interface Sci 366:5156
Homaeigohar S, Koll J, Lilleodden ET, Elbahri M (2012)
The solvent induced interber adhesion and its inuence
on the mechanical and ltration properties of
polyethersulfone electrospun nanobrous microltration
membranes. Sep Purif Technol 98:456463
Kwak NS, Jung WH, Park HM, Hwang TS
(2013) Electrospun polyethersulfone brous mats: sul-
fonation, its characterization and solution-phase ammo-
nium sorption behavior. Chem Eng J 215216:375382
Min M, Shen L, Hong G, Zhu M, Zhang Y, Wang X,
Chen Y, Hsiao BS (2012) Micro-nano structure poly
(ether sulfones)/poly(ethyleneimine) nanobrous afn-
ity membranes for adsorption of anionic dyes and heavy
metal ions in aqueous solution. Chem Eng J 197:88100
Parker D, Bussink J, Hendrik T, van De Grampel J,
Wheately GW, Dorf EH, Ostlinning E, Reinking K,
Schubert F, Junger O, Wagener R (2012) Polymer,
high-temperature. In: Ullmanns encyclopedia of
industrial chemistry, 7th edn. Wiley-VCH Verlag
GmbH & Co. KGaA, Weinheim
Shabani I, Haddadi-Asl V, Seyedjafari E, Babaeijandaghi,
Soleimani M (2009) Improved inltration of stem cells
on electrospun nanobers. Biochem Biophys Res
Commun 382:129133
Shabani I, Hasani-Sadrabadi MM, Haddadi-Asl V,
Soleimani M (2010) Nanober-based polyelectrolytes
as novel membranes for fuel cell applications. J Membr
Sci 368:233240
Wu JJ, Lee HW, You JH, Kau YC, Liu SJ (2014) Adsorp-
tion of silver ions on polypyrrole embedded
electrospun nanobrous polyethersulfone membranes.
J Colloid Interface Sci 420:145151
Yoon K, Hsiao BS, Chu B (2009) Formation of functional
polyethersulfone electrospun membrane for water puri-
cation by mixed solvent and oxidation processes.
Polymer 50:28932899
Embryonic Stem (ES) Cell
Loredana De Bartolo
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, Rende,
Italy
Embryonic stem (ES) cell is a totipotent stem cell
derived from an early stage embryo, which is called
blastocyst. This stage is reached 45 days after
Embryonic Stem (ES) Cell
fertilization and contains from 64 to several hun-
dred cells organized in an outer shell, the
trophectoderm, and the inner cell mass (ICM).
The ICM is the locus of pluripotent cells destined
to yield all the tissues of the developed organism.
In the process of obtaining embryonic stem cells,
the trophectoderm is removed by immunosurgery,
and the ICM is disaggregated and plated on feeder
cells. Ethical issues surround the derivation of
human ES cells from in vitro fertilized blastocysts.
Embryonic stem cells have pluripotency and
indenite replication characteristics. These cells
have the capacity to give rise to differentiated prog-
eny representative of all three embryonic germ
layers (ectoderm, endoderm, and mesoderm). ES
cells are able to differentiate in all cell types differ-
ently from adult stem cells that can produce only a
limited number of cell types. It is possible to modu-
late the differentiation of stem cells in a given phe-
notype by using specic growth factors and
molecules, which trigger the differentiation process.
ES cells for their ability of propagating them-
selves indenitely represent a valuable tool for
both research and regenerative medicine. They
can serve as an unlimited source of any cell type
in the body; human ES cells could yield highly
effective in vitro models for use in drug discovery
programs and provide a renewable source of cells
for use in transplantation therapy. Cell therapies
based on the use of ES cells have been proposed
for tissue replacement after injury or disease.
Adult stem cells, isolatable from bone marrow,
adipose tissue, tooth pulp, and many other loca-
tions of the body, are capable of self-renewal and
can be readily expanded ex vivo for several pas-
sages without losing their self-renewal capacity.
Mesenchymal stem cells can differentiate into
multiple tissue-forming cell lineages such as oste-
oblasts, chondrocytes, adipocytes, tenocytes, and
myocytes. Recent work on the differentiation of
bone marrow-derived mesenchymal stem cells
into neuron-like cells is another demonstration of
considerable plasticity of adult mesenchymal
stem cells. Stem cells are often a preferred cell
source for regeneration of multiple cell lineage
tissues. The ability to expand stem cells is desired
to generate cells for tissue engineering in clinical
and pharmaceutical applications (Rahaman and
Emulsification
Mao 2005). Conventional methods for expanding
stem cells or progenitor cells comprised polysty-
rene culture dishes and component of extracellular
matrix such as collagen. Alternatively biocompat-
ible and biodegradable materials have been pro-
posed to support cells and promote their
differentiation and proliferation toward the forma-
tion of a tissue (Piscioneri et al. 2011).
Advances in cell-based therapies would not
have been possible without the innovative design
and fabrication of several generations of biomate-
rials. Novel biomaterials with distinct properties
are necessary to accommodate the growth and
interactions of multiple cell lineages in composite
tissue constructs (Grifth 2000). Membrane sys-
tems provide the temporary structural framework
for tissue-forming cells to synthesize extracellular
matrices and other functional components in the
intended shape and dimensions (De Bartolo and
Bader 2013). They can respond on the key
demands for utilizing cell-based therapies to engi-
neer composite tissue constructs with a purposeful
orientation toward anatomic structures that the
tissue-engineered constructs are intended to regen-
erate. Development of new intelligent biomaterials
in synergy with cell biology will advance stem cell-
based clinical therapeutics. Engineered membranes
have the potential to mimic and control the physi-
cal, chemical, and biological factors necessary for
guiding stem cell differentiation (Pavlica
et al. 2009). They are currently being investigated
to act as scaffolds to guide and improve 3D tissue
formation, substrates to enhance cell culturing
techniques, vehicles for cell delivery, and sources
of immobilized and/or time-released factors. They
can be applied to the regeneration of numerous
tissue types, including the liver, pancreas, bone,
cartilage, skin, and nerves, and are being used for
the in vitro realization of physiological models.
References
De Bartolo L, Bader A (2013) Biomaterials for stem cell
therapy: state of art and vision for the future. CRC
Press, Boca Raton
Grifth LG (2000) Polymeric biomaterials. Acta Mater
48:263277
Pavlica S, Piscioneri A, Peinemann F, Keller M,
Milosevic J, Staeudte A, Heilmann A, Schulz-
673
Siegmund M, Laera S, Favia P, De Bartolo L,
Bader A (2009) Rat embryonic liver cell expansion
and differentiation on NH3 plasma-grafted PEEK-
WC-PU membranes. Biomaterials 30:65146521
Piscioneri A, Campana C, Salerno S, Morelli S, Bader A,
Giordano F, Drioli E, De Bartolo L (2011) Biodegrad-
able and synthetic membranes for the expansion and
functional differentiation of rat embryonic liver cells.
Acta Biomater 7:171179
Rahaman MN, Mao JJ (2005) Stem cell-based composite
tissue constructs for regenerative medicine. Biotechnol
Bioeng 91(3):261284
E
Emulsification
Emma Piacentini
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, Rende,
Italy
Emulsication is a process by which one phase is
broken up, dispersed, and distributed in a second
immiscible or partially miscible phase (Leal-
Calderon et al. 2007). Many different emulsica-
tion methods can be identied, and they can be
distinguished in nonmechanical and mechanical
methods. The nonmechanical methods include the
dispersed phase precipitation and the phase inver-
sion. Changes in the phase behavior of the sub-
stances to be emulsied, promoted by variation of
temperature or composition or by mechanical
stress, are used to achieve the desirable state of
the system. The mechanical methods of producing
emulsions include the use of high-speed mixers,
colloid mills, high-pressure valve homogenizers,
ultrasonic homogenizers, microuidization, and
membrane emulsication. Depending on the nature
of the starting materials, emulsication can be dis-
tinguished into two categories. The creation of an
emulsion directly from two separate liquids is
dened as primary emulsication, whereas the
reduction in size of the droplets in preformed emul-
sion is dened as secondary emulsication (Fig. 1).
The physical processes that occur during emul-
sication can be highlighted by considering the
behavior of two immiscible liquids in a container
such as oil and water. Their thermodynamically
674
PRIMARY
EMULSIFICATION
Oil
Water
Emulsification, Fig. 1 Emulsication
most stable state consists of a layer of oil on top of
a layer of water that allows to minimize the con-
tact area between the two phases. To create and
emulsion, it is necessary to supply energy in order
to disrupt and mix the oil and water which is
usually achieved by mechanical agitation. The
droplets formed are constantly moving around
and frequently collide and coalesce with neigh-
boring droplets. The presence of an emulsier
prevents the merging together of the droplets
after they are formed. The emulsier adsorbs to
the surface of the droplets during emulsication
and forms a protective membrane that prevents
the droplets from coming close enough together
to coalesce. The rates of droplet disruption, drop-
let coalescence, and emulsier adsorption within a
particular homogenizer depend on the ow prole
that the uids experience: (i) laminar ow which
is a regular, smooth, and well-dened ow with
relatively low ow rate; (ii) turbulent ow which
is an irregular, chaotic, and ill-dened ow with
relatively high ow rate characterized by the for-
mation of eddies within the uid; and (iii)
cavitational ow which is an extremely complex
ow because of the formation of small cavities
that implode and generate shock waves. The ten-
dency for one ow regime is a consequence of the
balance of viscous and inertial forces acting on the
uid expressed by the Reynolds number:
inertial forces L vrc
Re
viscous forces
c
where L is some characteristic length of the sys-
tem, v is the average uid ow velocity, rc is the
density of the uid, and
c is the viscosity of the
Emulsification
SECONDARY
EMULSIFICATION
uid. When the viscous forces generated within a
uid dominate the inertial forces (low Re), the
ow prole is laminar; when the inertial forces
dominate (high Re) in the ow prole, it is turbu-
lent. The size of the droplets produced by a
homogenizer depends on a balance between the
two opposing physical processes: droplet disrup-
tion and droplet coalescence. The interfacial
forces that tend to hold the droplets together and
the disruptive forces generated within the homog-
enizer that tend to pull the droplets apart are
involved in droplet disruption process. To deform
and disrupt a droplet during homogenization, it is
necessary to apply an external force that is signif-
icantly larger than the interfacial force. The inter-
facial force is described by the Laplace equation:
4g
DP
d
where g is the interfacial tension between the two
liquids, d is the droplet diameter, and DP is the
Laplace pressure which acts across the interface
toward the center of the droplet. The equation
indicates that the pressure required to disrupt a
droplet increases as the interfacial tension
increases or as the droplet size decreases. For a
droplet to be broken up during homogenization,
the disruptive forces must exceed the interfacial
forces and their duration must be longer than the
time required for droplet deformation. The rela-
tive magnitude of disruptive and interfacial forces
is characterized by the Weber number (We):
disruptive forces
We
interfacial forces
Emulsification by Membrane Operations 675

Emulsification, Table 1 The type of homogenizers used for emulsification

Homogenizer Droplet size and size Energy density
type Droplet formation mechanism Productivity distribution (J m3)
High-speed mixer Droplets break up in TI, TV, and Batch or >2 mm, polydisperse Low-high
LV ow regime continuous
Colloid mill Droplets break up in LV and TV Continuous >1 mm, polydisperse Low-high
ow regime 103108
High-pressure Droplets break up in TI, TV, LV, Batch or >0.1 mm, Medium-high
homogenizer and CI ow regime continuous polydisperse 106108
Ultrasonic Droplets break up in CI ow Continuous >0.1 mm, Medium-high
regime polydisperse 106108
E
Microuidization Droplets break up in TI and TV Batch or <0.1 mm, Medium-high
ow regime continuous polydisperse 106 to 2  108
Membrane Droplet detachment by wall shear Continuous >0.3 mm, narrow Low-medium
stress <103108
TI turbulent inertial, TV turbulent viscous, LV laminar viscous, CI cavitational

During homogenization droplet-droplet collisions

are particularly rapid because of the intense Emulsification by Membrane
mechanical agitation of the emulsion. Droplet Operations
coalescence will depend on the time taken for
the emulsier to be adsorbed to the surface of Emma Piacentini and Lidietta Giorno
the droplets relative to the time between droplet- Institute on Membrane Technology, National
droplet collisions. The ow prole and the nature Research Council of Italy, ITM-CNR, Rende,
of the emulsier used inuenced these times. Italy
The characteristics of the different type of
homogenizers are reported in Table 1.
High-speed mixer and colloid mills are suitable
Emulsions can be generated using membrane
for preparing emulsions with relatively large drop-
operations by: (i) direct membrane emulsication,
let sizes (>1 mm), while the other types of homog-
where a microporous membrane is used to dis-
enizers can be used to prepare submicron droplets.
perse one of two immiscible liquids as a form of
High-speed mixers, ultrasonic homogenizers,
droplets into another liquid or by (ii) premix mem-
microuidizer, and membrane homogenizers can
brane emulsication, where a course emulsion is
be used for primary emulsication, whereas high-
extruded through the membrane pores in order to
pressure valve homogenizers and colloid mills are
generate ne droplet emulsion. A pressure is
most suitable for secondary emulsication. Most of
required to cause the dispersed phase to permeate
these homogenizers have high productivity and
through the membrane. If any shear is applied on
they are able to work in a batch or continuous
the membrane surface, droplets can be spontane-
operation mode. In particular, membrane homoge-
ously detached from the pore outlets on the action
nizers have appreciably lower productivity than the
of the interfacial tension when they reach a certain
other major types of homogenizers. The use of
size. The method is referred as static membrane
membrane homogenizers may be particularly use-
emulsication (Kukizaki 2009). The shear on the
ful where narrow droplet size distributions are
membrane surface can be generated by moving
important such as for drug delivery.
the continuous phase or using moving mem-
branes. The method is referred as dynamic mem-
References brane emulsication. The shear stress is generated
by the continuous phase owing tangentially to
Leal-Calderon F, Schmitt V, Bibette J (2007) Emulsion the membrane surface (cross-ow membrane
science basic principles. Springer, New York emulsication) (Williams et al. 1998) or stirred
676 Emulsification by Membrane Operations

Emulsification by Membrane Operations, Table 1 Different membrane operations used for the production emulsion
droplets
Advantages Disadvantages
Dynamic membrane emulsication
Stirred ME Suitable for low volumes of continuous Emulsion production at batch scale
phase
Useful to study the effect of different The shear stress at the membrane surface is
experimental conditions on the emulsion nonuniform and depends on the cell geometry
preparation

Cross-ow ME Constant shear stress at the membrane Emulsion droplet breakup as a consequence of
surface the recirculation
Suitable for large-scale production and High dispersed phase concentration is obtained
continuous or semicontinuous operation after a long time of operation

Cross-ow ME Constant shear stress at the membrane High dispersed phase concentration is obtained
with static surface after a long time of operation
promoter Suitable for large-scale production and
continuous or semicontinuous operation
Suitable to prevent droplet breakup

Pulsed-ow ME Suitable for large-scale production and

continuous or semicontinuous operation
Able to prevent droplet breakup
High dispersed phase concentrations
obtained in a single pass

Rotating ME Suitable for large-scale production and Complicated and more expensive design
continuous or semicontinuous operation Higher power consumption
Able to prevent droplet breakup
High dispersed phase concentrations
obtained in a single pass

(continued)
Emulsification by Membrane Operations
Emulsification by Membrane Operations, Table 1 (continued)
Advantages
Vibrating ME Suitable for large-scale production and
continuous or semicontinuous operation
Able to prevent droplet breakup
Static membrane emulsication
Simple experimental setup
Low energy input
Able to prevent droplet breakup
(stirred membrane emulsication) (Stillwell
et al. 2007). The use of static turbulence pro-
moters in cross-ow membrane emulsication
allows increasing the shear stress at the membrane
surface while maintaining a low value along the
circuit out of the membrane (Koris et al. 2011).
Alternatively, a periodic ow pulsation is gener-
ated in the continuous phase without recirculation
(pulsed-ow membrane emulsication) (Holdich
et al. 2013). Moving membranes can be used
instead of the commonly used stationary mem-
branes. The droplet detachment from the mem-
brane surface is controlled by rotating
(Vladisavljevi and Williams 2006) or vibrating
(Holdich et al. 2010) the membrane within an
otherwise static continuous phase. Membrane
operations used for the production emulsion drop-
lets are described in Table 1.
Emulsication by membrane operation is con-
trolled by:
Membrane parameters, including porosity,
mean pore size, pore geometry, pore distance,
and membrane surface wettability
Phase parameters, including interfacial ten-
sion, emulsier type and concentration, viscos-
ity and density of dispersed and continuous
677
Disadvantages
Complicated and more expensive design
Higher power consumption
Nonuniform temporal distribution of shear stress
on the membrane surface
E
Emulsion production at batch scale
The production of uniform droplets is possible
only at low dispersed phase ux with low
productivity
phases, phase composition, pH, and ionic
strength
Process parameters, including wall shear
stress, transmembrane pressure, membrane
module conguration, and temperature
Comparing to the conventional emulsication
processes, emulsication by membrane operation
permits to obtain a better control of droplet size
and droplet size distribution, low energy and
material consumption, and modular and easy
scale-up. Nevertheless, productivity (m3/day) is
much lower, and therefore the challenge in the
future is the development of new membranes
and innovative membrane operations to keep the
known advantages and maximize the
productivity.
References
Holdich RG, Dragosavac MM, Vladisavljevic GT,
Kosvintsev SR (2010) Membrane emulsication with
oscillating and stationary membranes. Ind Eng Chem
Res 49:38103817
Holdich RG, Dragosavac MM, Vladisavljevic GT,
Piacentini E (2013) Continuous membrane emulsica-
tion with pulsed (oscillatory) ow. Ind Eng Chem Res
52:507515
678
Koris A, Piacentini E, Vatai G, Bekassy-Molnar E,
Drioli E, Giorno L (2011) Investigation on the effects
of a mechanical shear-stress modication method dur-
ing cross-ow membrane emulsication. J Membr Sci
371:2836
Kukizaki M (2009) Shirasu porous glass (SPG) membrane
emulsication in the absence of shear ow at the mem-
brane surface: inuence of surfactant type and concen-
tration, viscosities of dispersed and continuous phases,
and transmembrane pressure. J Membr Sci 327:234243
Stillwell MT, Holdich RG, Kosvintsev SR, Gasparini G,
Cumming IW (2007) Stirred cell membrane emulsi-
cation and factors inuencing dispersion drop size and
uniformity. Ind Eng Chem Res 6:965972
Vladisavljevi GT, Williams RA (2006) Manufacture of
large uniform droplets using rotating membrane emul-
sication. J Colloid Interface Sci 299:396402
Williams RA, Peng SJ, Wheeler DA, Morley NC,
Taylor D, Whalley M, Houldsworth DW (1998) Con-
trolled production of emulsions using a crossow mem-
brane, part II: industrial scale manufacture. Chem Eng
Res Des 76:902910
Emulsifier
Emma Piacentini
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, Rende,
Italy
Emulsiers are a class of molecules with surface
active properties (Dickinson 2009). This behavior
is due to their amphiphilic structure which
Emulsifier,
Fig. 1 Emulsier structure
and emulsier distribution
at water-in-oil and oil-in- Hydrophilic Head
water emulsion interface
Water-in-oil emulsion
Emulsifier
contains both a polar or hydrophilic head and a
nonpolar or hydrophobic tail (Fig. 1). A measure
of the degree to which an emulsier is hydrophilic
or lipophilic is given by the hydrophilic-lipophilic
balance (HLB) determined by calculating values
for the different regions of the molecule. Emulsi-
ers adsorb at interfaces between two immiscible
liquid anchoring its hydrophilic part into water
and its lipophilic part into oil decreasing the inter-
facial tension between them (Fig. 1). This facili-
tates droplets disruption during homogenization
and, in the case of membranes, lowering the min-
imum emulsication pressure. Emulsiers have
an important role in emulsion stabilization against
droplets coalescence and/or aggregation provid-
ing electrostatic repulsion, steric repulsion, and/or
strength to the interfacial layer of the droplets.
Emulsiers are normally classied according
to the head group type as ionic (anionic and cat-
ionic), nonionic, and amphoterics (zwitterionics).
Anionic emulsiers contain anionic functional
groups at their head, such as sulfate (sodium
dodecyl sulfate, SDS), sulfonate, phosphate, and
carboxylates. Cationic emulsiers contain cat-
ionic functional groups at their head, such as
pH-dependent primary, secondary, or tertiary
amines and permanently charged quaternary
ammonium cation (cetyl trimethylammonium
bromide, CTAB). Nonionic emulsiers have
polar headgroups and they include glycol and
glycerol esters, polyoxyethylene esters,
EMULSIFIER
Hydrophobic Tail
Oil-in-water emulsion
Emulsion
polyoxyethylene ethers, polyoxyethylenepo-
lyoxypropylene copolymers, sorbitan derivatives,
and sucrose esters. Zwitterionic (amphoteric)
emulsiers have both cationic and anionic centers
attached to the same molecule. The cationic part is
based on primary, secondary, or tertiary amines or
quaternary ammonium cations. The anionic part
can be more variable and include sulfonates,
sultaines, betaines, and phosphates (lecithin).
A variety of emulsiers are natural products
derived from plant or animal tissue such as hydro-
colloids (high molecular weight polysaccharides)
and proteins.
References
Dickinson E (2009) Hydrocolloids as emulsiers and
emulsion stabilizers. Food Hydrocolloids 23:
14731482
Emulsifiers
Amphiphilic Molecules
Emulsion
Emma Piacentini
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, Rende,
Italy
An emulsion consists of two immiscible liquids
(usually oil and water) with one of the liquids
(dispersed phase or internal) dispersed as a form
of spherical droplets in the other (continuous phase
or external) (Israelachvili 1994). Depending upon
the nature of the dispersed phase, the emulsions are
classied as (i) oil-in-water emulsions (O/W)
consisting of oil droplets dispersed in an aqueous
phase and (ii) water-in-oil emulsions (W/O)
consisting of aqueous droplets dispersed in an oil
phase. It is also possible to prepare various types of
679
multiple emulsions, for example, water-in-oil-in-
water emulsions (W/O/W), in which water droplets
are dispersed within larger oil droplets which are
themselves dispersed in an aqueous phase and
oil-in-water-in-oil emulsions (O/W/O) consisting
of oil droplets dispersed in larger water droplets
which are themselves dispersed in an oil phase.
The preparation of an emulsion is termed emul-
sication and the agents used for this purpose are
termed emulsiers. Other agents, such as emul-
E
sion promoters or stabilizers, are often added to an
emulsion to promote the emulsifying process, for
example, by increasing the viscosity or providing
a protective colloid action. The preparation of
emulsions involves breaking up the internal
phase by supplying mechanical or chemical
energy. When an emulsion is formed, the interface
between the phases is considerably increased as a
result of the droplet formation. The liquid always
tends to reduce its surface or interface to a mini-
mum; therefore, an increase in interface is possi-
ble only if energy is supplied. The work that must
be expended on drop division is:
dA g dI
where dA is the work to be expended and dI is the
increase in interface. The proportionality factor is
the interfacial tension g between the phases to be
emulsied. Thus, if the interfacial tension
between the two phases is high, considerable
mechanical energy is required for emulsication
unless an emulsier is added; if the interfacial
tension is low, little mechanical energy is
consumed.
According to the droplet size, emulsions are
classied as follows:
Macroemulsions: these usually have a size
range of 0.15 mm.
Nanoemulsions: these usually have a size
range of 20100 nm.
Micellar emulsions or microemulsions: these
usually have a size range of 550 nm.
If the droplet size exhibits a wide statistical
distribution, the emulsion is described as polydis-
perse, in contrast to monodisperse systems with a
680
Emulsion, Fig. 1 The
various breakdown
processes in emulsions
No change in droplet size and size distribution
FLOCCULATION
CREAMING
SEDIMENTATION
uniform droplet size. The ideal particle size
depends on the available methods of preparation
and industrial application in each case. Another
important emulsion property is the ratio of the
volume of the dispersed phase (Vi) to the volume
of the continuous phase or (Ve) is called the phase
volume ratio (F). If F < 0.43 (Vi = 30 % of total
volume), the ow properties of the emulsion are
determined primarily by the continuous phase. If
F > 0.43, the viscosity of the emulsion generally
increases. As F increases, either phase reversal or
cream formation occurs.
Emulsion stability should match its applica-
tion. Thus, for a number of applications, the emul-
sion should be stable under very specic
conditions, but it should break after its purpose
has been achieved according to a specic condi-
tion (such as temperature, pH, or salts, or the like).
An emulsion is stable if fusion of the droplets is
prevented by a sufciently high energy barrier
(Tadros 2013). In general, the energy barrier is
built up by the lm of emulsier that forms at
the surface of the droplets. Several breakdown
processes may occur on storage depending on
Emulsion
Change in droplet size and size distribution
OSTWALD
RIPENING
EMULSION COALESCENCE
PHASE
INVERSION
particle size distribution and density difference
between the droplets and the medium (Fig. 1).
In sedimentation, the uniform dispersion of the
droplets is disturbed by aggregation, which leads
to settling or creaming of the internal phase. This
process results from external forces usually grav-
itational or centrifugal. When such forces exceed
the thermal motion of the droplets (Brownian
motion), a concentration gradient builds up in
the system with the larger droplets moving faster
to the top (if their density is lower than that of the
medium) or to the bottom (if their density is larger
than that of the medium) of the container. To keep
an emulsion stable, such aggregation must be
prevented since droplet aggregates sediment
faster than individual small droplets. Sedimenta-
tion is not always necessarily accompanied by
coalescence. Although the distribution has been
altered, the original dispersion can be restored by
shaking or stirring. Flocculation refers to aggre-
gation of the droplets (without any change in
primary droplet size) into larger units. It is the
result of the van der Waals attraction that is uni-
versal with all disperse systems. Flocculation
Emulsion
occurs when there is no sufcient repulsion to
keep the droplets apart to distances where the
van der Waals attraction is weak. Flocculation
may be strong or weak, depending on the force for coalescence is the surface or lm uctu-
magnitude of the attractive energy involved. One
way to overcome the van der Waals attraction is
by electrostatic stabilization using ionic surfac-
tants, which results in the formation of electrical
double layers that introduce a repulsive energy
that overcomes the attractive energy. The second
and most effective method of overcoming occu-
lation is by steric stabilization using nonionic
surfactants or polymers. Ostwald ripening
(disproportionation) results from the nite solu-
bility of the liquid phases. Liquids that are referred
to as being immiscible often have mutual solubil-
ities that are not negligible. With emulsions,
which are usually polydisperse, the smaller drop-
lets will have larger solubility when compared
with the larger ones (due to curvature effects).
With time, the smaller droplets disappear and
their molecules diffuse to the bulk and become
deposited on the larger droplets. With time, the
droplet size distribution shifts to larger values.
Several methods may be applied to reduce Ost-
wald ripening: (i) Addition of a second dispersed
phase component that is insoluble in the continu-
ous medium. In this case, partitioning between
different droplet sizes occurs, with the component
having low solubility expected to be concentrated
in the smaller droplets. During Ostwald ripening
in a two-component system, equilibrium is
established when the difference in chemical
potential between different size droplets (which
results from curvature effects) is balanced by the
difference in chemical potential resulting from
partitioning of the two components. This effect
reduces further growth of droplets.
(ii) Modication of the interfacial lm at emulsion
interface. By using surfactants that are strongly
adsorbed at the emulsion interface (i.e., polymeric
surfactants) and that do not desorb during ripening
(by choosing a molecule that is insoluble in the
continuous phase), the rate could be signicantly
reduced. In coalescence, the individual droplets
fuse together. First, the smaller droplets are
681
absorbed by the larger droplets, and then increas-
ingly larger drops merge together until two con-
tinuous phases are nally formed. The driving
ations which results in close approach of the drop-
lets whereby the van der Waals forces is strong
thus preventing their separation. Two droplets can
only coalesce if the intervening layer of liquid is
pierced when they approach each other. There-
fore, coalescence is opposed in two ways by the
E
emulsier lm surrounding the droplets. First, as
in the case of aggregation, the like charges of the
electrical double layer prevent them from
approaching each other. Second, the buildup of
an elastic surface lm causes the emulsion drop-
lets to bounce off each other when they collide.
Coalescence is always followed by accelerated
settling or creaming, which destroys the emulsion
completely. The emulsion is then broken and can-
not be reconstituted by shaking or stirring. The
driving force for prevention of coalescence is to
produce a stable lm that can be achieved by two
mechanisms and their combination: (i) increased
repulsion both electrostatic and steric and
(ii) dampening of the uctuation. In general,
smaller droplets are less susceptible to surface
uctuations and hence coalescence is reduced.
This explains the high stability of nanoemulsions.
The phase inversion refers to the process whereby
there will be an exchange between the disperse
phase and the medium. For example, an O/W
emulsion may with time or change of conditions
invert to a W/O emulsion. In many cases, phase
inversion passes through a transition state
whereby multiple emulsions are produced. Phase
inversion of emulsions can be one of two types:
transitional inversion induced by changing the
facers that affect the HLB of the system, for
example, temperature and/or electrolyte concen-
tration, and catastrophic inversion, which is
induced by increasing the volume fraction of the
disperse phase.
Emulsions have application in several indus-
trial systems such as food emulsion, for example,
mayonnaise, salad creams, deserts, and bever-
ages; personal care and cosmetics, for example,
682
hand creams, lotions, hair sprays, and sunscreens;
and pharmaceuticals, paints, and bitumen
emulsions.
References
Israelachvili J (1994) The science and applications of
emulsions - an overview, Colloids and Surfaces A:
Physicochemical and Engineering Aspects 91: 18.
Tadros TF (2013) Emulsion Formation, Stability, and
Rheology, in Emulsion Formation and Stability
(ed T. F. Tadros), Wiley-VCH Verlag GmbH & Co.
KGaA, Weinheim, Germany.
Emulsion Characterization
Volker Gaukel, Heike Schuchmann and
Richard Bernewitz
Food Process Engineering, Karlsruhe Institute of
Technology (KIT), Karlsruhe, Germany
The production of emulsions via membrane pro-
cesses is investigated since 30 years and started
with investigations from Nakashima et al. with
porous glass membranes (Nakashima
et al. 1991). There are several principles of mem-
brane emulsication as, e.g., direct emulsication
and premix emulsication. But nevertheless
which process is used, the characterization of the
emulsion is an important issue.
Besides the emulsions ingredients, which are
dened by the manufacturer, there are many struc-
ture parameters which inuence the physical sta-
bility, the color, the rheological behavior, or the
controlled release properties of the emulsion.
If the kind of emulsion is not known, the rst
characterization method must identify if it is an oil
in water (o/w) or water in oil (w/o) emulsion. In
many cases this can be easily done by a dilution
test. This means that an o/w emulsion can be
diluted with a hydrophilic phase and w/o emulsions
can be diluted with a hydrophobic phase. Measure-
ment of conductivity of the emulsion is another
possibility as o/w emulsions have in general a
much higher conductivity than w/o emulsion.
Emulsion Characterization
These tests cannot identify if a double emulsion
(e.g., oil in water in oil phase) is present. This must
be investigated with microscopic methods.
The two main characteristics of an emulsion,
which inuence the physical stability, the color,
and the rheological behavior, are the drop size
distribution (DSD) and the disperse phase content
(DPC) (Schuchmann 2007).
The DPC is set by the manufacturer and is
constant when using premix membrane emulsi-
cation. Using other membrane emulsication pro-
cesses like cross ow devices, the DPC of
emulsions is adjusted by the rate of ow of the
oil and water phase or by recirculation time of the
continuous phase/emulsion and changes continu-
ously. Regarding multiple emulsions, additional
instability mechanisms may lead to changes of
DPC while emulsifying and storing. The DPC
can be measured with differential scanning calo-
rimetry (DSC) (Schuch et al. 2013; Dalmazzone
et al. 2009), NMR (Bernewitz et al. 2011; van
Duynhoven et al. 2007), or rheological character-
istics of single and double emulsions.
The DSD depends on several factors as the kind
and pore size of the membrane, the transmembrane
ux, the shear forces at the membrane surface, as
well as the composition of the emulsion (kind of
emulsier, viscosity of the phases, etc.). The DSD
can be measured with various methods which are
referred here. The DSD can also change during
storage and distribution of an emulsion leading to
a product deterioration and phase separation.
A rough indication for the physical stability of an
emulsion can be the zeta potential (z), whereas z
>30 mV indicates a stable emulsion. Another
method is a Dynamic Mechanical Analysis
(DMA) of the emulsion (Brummer 2006).
As the changes of DSD are often very slow and
cannot be monitored over the whole shelf life of a
product, there are several test procedures to accel-
erate this process. A procedure is to rise the stor-
age temperature from room temperature to
4050  C which accelerates the deterioration pro-
cesses by the factor 2. Other means are the expo-
sure of the emulsion to many short temperature
abuses or to a centrifugal eld which can shorten
the monitoring time by the factor 102,000. It
should be kept in mind that all the acceleration
Emulsion Liquid Membrane (ELM)
techniques may change the structure of the emul-
sion and may lead to differing results compared to
real storage conditions.
References
Bernewitz R, Guthausen G, Schuchmann HP (2011) NMR
on emulsions: characterisation of liquid dispersed sys-
tems. Magn Reson Chem 49:93104
Brummer R (2006) Most important test methods. In: Rhe-
ology essentials of cosmetic and food emulsions.
Springer, Berlin, pp 7580
Dalmazzone C, Noik C, Clausse D (2009) Application of
DSC for emulsied system characterization. Oil & gas
science and technology rev. IFP 64(5):543555
Nakashima T, Shimizu M, Kukizaki M (1991) Membrane
emulsication by microporous glass. Eng Mater
61&62:513516
Schuch A, Khler K, Schuchmann HP (2013) Differential
scanning calorimetry (DSC) in multiple W/O/W emul-
sions: a method to characterize the stability of inner
droplets. J Therm Anal Calorim 111(3):18811890
Schuchmann HP (2007) In: Brckel U, Meier W,
Wagner G (eds) Product design and engineering: best
practices, vol 1. Wiley-VCH, Weinheim, p 63
van Duynhoven PM, Maillet B, Schell J, Tronquet M,
Goudappel GJW, Trezza E, Bulbarello A, van
Dusschoten D (2007) A rapid benchtop NMR method
for determination of a droplet size distributions in food
emulsions. Eur J Lipid Sci Technol 109(11):10951103
Further Reading
Mcclements DJ (2007) Critical review of techniques and
methodologies for characterization of emulsion stabil-
ity. Crit Rev Food Sci Nutr 47(7):611649
Schramm LL (1992) Emulsions fundamentals and appli-
cations in the petroleum industry, vol 237. American
Chemical Society, Washington, DC
Emulsion Liquid Membrane (ELM)
Vladimir S. Kislik
Campus Givat Ram, Casali Institute of Applied
Chemistry, The Hebrew University of Jerusalem,
Jerusalem, Israel
Emulsion liquid membrane, ELM, is a system in
the form of double emulsions (for details, see
Chakraborty et al. 2010). It may be of two types:
water-in-oil emulsion dispersed in an external
683
aqueous phase and oil-in-water emulsion dis-
persed in an outer organic phase. The membrane
phase in the water-in-oil-in-water (W/O/W) type
is the immiscible oil phase separating the aqueous
phases, while in the O/W/O type, the immiscible
water phase separating the two organic phases
acts as the LM. Hence, the liquid membrane
serves here a dual purpose: (a) permitting selec-
tive transfer of one or more components through it
from external phase to internal droplets and vice
E
versa a`nd (b) preventing mixing of external and
internal phases. The emulsion is dispersed in the
feed solution, and mass transfer from the feed to the
internal receiving phase takes place. ELMs were
rst used for separation of hydrocarbons from
wastewater with high separation efciency. Com-
pared to conventional processes, emulsion liquid
membrane (ELM) process has some attractive fea-
tures, for example, simple operation, high ef-
ciency, extraction and stripping in one stage, larger
interfacial area, and scope of continuous operation.
Since an ELM is a thin lm of liquid (oil or
aqueous) composed of surfactants and their sol-
vents between a feed and a receiving phase, any
immiscible liquid can serve as a membrane
between two liquid or gas phases containing a
solute at different concentrations. If the solute is
soluble in the membrane phase and has a reason-
able diffusivity through the membrane, then its
selective transport through the membrane from
higher to lower concentration can be achieved.
This type of permeation has simple mechanism
and not of much technical importance.
At facilitated transport mechanism, liquid
membrane incorporates a reactive component or
carrier, reacting reversibly and selectively with
species of interest to carry the formed complexes
across the LM to the internal phase, and dissoci-
ates, discharging the solute to the internal phase.
The unchanged carrier then diffuses back to the
membrane-external phase interface (see Fig. 1).
A small amount of carrier is required in the mem-
brane phase even for achieving a high degree of
separation. At different proton concentrations in the
aqueous phase or using another ions, ion exchange
processes between two LM surfaces occur. This
phenomenon is called coupled mass transport. If
the transports of these two different species occur
684
Organic
M2+
MR2 M2+
Strip
H+
RH
H+
Feed
Feed Phase Membrane
I Phase II
Cm
Cmc
Ci
Cmc
H+
Ci
Emulsion Liquid Membrane (ELM), Fig. 1 Schematic
representation of the liquid membrane globule and concen-
tration prole of solute through ELM
in the same direction, it is called cotransport, while
transport in opposite direction is called
countertransport. Evidently the process leads to
the transport of targeted ionic species across the
membrane against their concentration gradient.
This so-called uphill transport will continue
until one driving factor (difference of chemical
potentials) is balanced by the difference between
chemical potentials of another transported ion.
The ELM technique has great potential for
recovery and removal of different metal ions.
Separation of metals like copper, zinc, cadmium,
cobalt, nickel, mercury, uranium, chromium, rhe-
nium, and several others, including noble metals
like gold and silver, lanthanides, and rare earths,
was studied. To date, there are two industrial
plants installed for zinc recovery from wastewater
in Austria, having a capacity of 75 m3/h and
700 m3/h, removing zinc selectively from 500 to
3 ppm. Bis(2-ethylhexyl) dithiophosphoric acid
Emulsion Liquid Membrane for Wastewater Treatment
has been used as carrier. One more plant with the
200 m3/h capacity in Germany and the 200 m3/h
capacity plant in the Netherlands.
Weak acids like phenol and cresol and weak
bases like ammonium and amines have been suc-
cessfully removed from wastewater. Among them,
the separation-concentration of phenol has been
intensively investigated. Phenol removal from
wastewater was commercialized in China. Phenol
is removed from about 1,000 ppm to 0.5 ppm with
an extraction efciency of greater than 99.95 %.
ELM technology has been applied to a great
extent for separation of mixtures of saturated and
Strip Phase
III aromatic hydrocarbons, of amino acids, and of
H+
strong acids like nitric acid and thiocyanate. Cya-
nide removal from wastewater in gold processing
is commercialized in China. Cyanide is reduced
from about 130 ppm to 0.5 ppm with an extraction
efciency of 99.6 %.
ELM has promise in the elds of biotechnol-
ogy and biomedicine and has found application in
the separation of organic acids, fatty acids, puri-
cation of antibiotics, enzyme-catalyzed reactions,
and detoxication of blood.
References
Chakraborty M, Bhattacharya C, Datta S (2010) Emulsion
hybrid liquid membranes: denitions and classication,
theories, module design, applications, new directions and
perspectives. In: Kislik V (ed) Liquid membranes princi-
ples and applications in chemical separations & waste-
water treatment, 1st edn. Elsevier, Boston, pp 141200
Emulsion Liquid Membrane
for Wastewater Treatment
N. Othman
Faculty of Chemical and Energy Engineering,
Universiti Teknologi Malaysia, Skudai, Johor,
Malaysia
Emulsion liquid membranes are known as double
emulsion system. The advantage of this process is
extraction and stripping process occurred
Emulsion Liquid Membrane for Wastewater Treatment
simultaneously in one single-step operation, and
equilibrium limitation can be removed. It also can
reduce the amount of expensive extractant; high
uxes and high selectivity are possible. It is also
possible to treat any source of wastewater
containing organics and metals even at low con-
centration. The primary emulsions of water in oil
emulsion were prepared by emulsifying two
immiscible phases of the stripping solution and
organic liquid membrane phase with a surfactant
to produce an emulsion. This primary emulsion is
then dispersed in the solution or phase to be
treated. Mass transfer takes place between the
feed phase and the internal phase through the
liquid membrane phase. The illustration and sche-
matic diagram of the process is shown in Fig. 1.
The organic liquid membrane may contain a car-
rier to facilitate the extraction process. The carrier
will act as a shuttle to carry the solute from exter-
nal interface to the internal interface or receiving
Phase I Phase II Phase III
Emulsion Liquid Membrane for Wastewater Treat-
ment, Fig. 1 A schematic diagram of emulsion liquid
membranes
Emulsion Liquid
Membrane Phase III
for Wastewater
Treatment, Fig. 2 The
A A
mechanism of couple
transport in emulsion liquid
membrane
685
phase. At the external interface, the carrier will
form carrier-solute complexes and diffuse to the
internal interface and release the solute into the
receiving phase by the reaction with the stripping
agent. For example, in metal separation from
wastewater, even in very low concentration, the
carrier will selectively combine with the solutes to
form a metal-carrier complex, and the complex
will permeate through the membranes from the
outer to the inner interface. At the inner interface,
E
the complex decomposes by the reversal of the
equilibrium reaction, and the metal ion is liberated
into the internal phase and the regenerated carrier
goes back into the membrane phase. The mecha-
nism of removal and recovery of the solute/metal
assisted by the carrier is illustrated in Fig. 2.
The major problem associated with ELMs in
the wastewater treatment is emulsion stability. If
the emulsion globules break and the inner droplet
phase spills into the continuous phase, the sepa-
ration is lost. Interfacial shear between the contin-
uous phase and membrane phase causes the liquid
membrane to thin and, in some cases, rupture.
Another problem is osmotic swelling although
it is rarely mentioned in the literature. This phe-
nomenon occurs when water in external phases
diffuses through the organic membrane phase and
swells the inner aqueous droplet phase. The
increased volume of the internal phase leads to
increased breakage and dilution of the concen-
trated solute in the droplet phase.
For the last three decades, this method has
attracted many studies in the area of hydrometal-
lurgy such as separation of metal ions either from
wastewater or from ores (Othman et al. 2006; Reis
and Carvalho 1993; Reed et al. 1987; Marr 1984;
Membrane phase
Phase II
A A
Carrier A solute
molecule
686
Draxler and Marr 1986; Babcock et al. 1986). It
has been reported that emulsion liquid membrane
system has been successfully used to recover cop-
per selectively from waste stream of mine solu-
tions (Wright et al. 1995).
From the viewpoint of practical application in
wastewater treating processes, recovery processes
for copper (Volkel et al. 1980; Goto et al. 1989a),
uranium (Hayworth et al. 1983), and zinc (Marr
1984) were examined in test plant. The rst appli-
cation of emulsion liquid membrane (ELM) on an
industrial scale was the process to remove zinc
from wastewater at a textile plant in Austria
(Draxler and Marr 1986).
In order to get a better understanding of emul-
sion liquid membrane process and the system
potentials, the extraction performance must be
studied based on the kinetics and thermodynamic
aspects. The parameters that affect the solute
extractability and selectivity should be identied.
The parameters such as stripping agent types and
acidity that control the mass transfer of solute,
volume ratio of emulsion to external phase that
affects the mass transfer area of extraction pro-
cess, and carrier concentration, type of diluents,
swelling, residence time, and agitation rate that
control the extraction performance and the
breakup rate of emulsion should be studied.
References
Babcock WC, Friesen DT, Lachapelle ED (1986) Liquid
membranes for separating uranium from vanadium and
uranium from molybdenum. J Membr Sci
26(3):303312
Draxler J, Marr R (1986) Emulsion liquid membranes. Part
I: phenomenon and industrial application. Chem Eng
Process 20:319329
Goto M, Kondo K, Nakashio F (1989) Acceleration effect
of anionic surfactants on extraction rate of copper with
liquid surfactant membrane containing LIX65N and
nonionic surfactant. J Chem Eng Jpn 22:7998
Hayworth HC, Ho WS, Burns WA Jr, Li NN (1983) Extrac-
tion of uranium from wet process phosphoric acid by
liquid membranes. Sep Sci Technol 18(6):493521
Marr R (1984) Pilot plant studies of liquid membrane
separation. Proceeding of Eng. Found. Conf. On New
Directions in Separation technology, Davos
Othman N, Mat H, Goto M (2006) Separation of silver
from photographic wastes by emulsion liquid mem-
brane system. J Membr Sci 282(12):171177
Emulsion Pertraction Technology for Zinc Recovery
Reed DL, Bunge AL, Noble RD (1987) Inuence of reac-
tion reversibility on continuous-ow extraction by
emulsion liquid membrane. In: Noble RD, Way JD
(eds) Liquid membranes: theory and applications.
American Chemical Society, Washington, DC
Reis MTA, Carvalho JMR (1993) Recovery of zinc from
industrial efuent by emulsion liquid membranes.
J Membr Sci 84:201211
Volkel W, Halwachs W, Schugerl K (1980) Copper extrac-
tion by means of a liquid surfactant membrane process.
J Membr Sci 6:1931
Wright JB, Nilsen DN, Hundley G, Galvan GJ (1995) Field
test of liquid emulsion membrane technique for copper
recovery from mine solutions. Miner Eng 8:549556
Emulsion Pertraction Technology
for Zinc Recovery
Immaculada Ortiz and Eugenio Bringas
Department of Chemical and Biomolecular
Engineering, University of Cantabria, Santander,
Cantabria, Spain
The emulsion pertraction technology (EPT) is a
separation process that combines the ability of
liquid membranes to promote the uphill transport
of target species by the coupling between mass
transfer and chemical reaction and the benets of
using membrane contactors, namely, large inter-
facial area, nondispersive contact, and indepen-
dent ow of the uid phases. Figure 1 shows the
ow diagram of the EPT process that comprises
two essential process units: a microporous hollow
ber membrane contactor (see Fig. 2) and the
emulsion vessel that contains a pseudo-emulsion
consisting of the organic phase formulated with a
selective organic carrier and the dispersed strip-
ping solution. The target solute is chemically
transferred from the aqueous feed to the organic
phase that is embedded in the pores of the hollow
bers due to their hydrophobic character. Next,
the solute-carrier complex diffuses to the interface
between the organic and the droplet of stripping
phase where the back-extraction reaction occurs.
The solute is recovered from the internal aqueous
phase after emulsion settling (San Romn
et al. 2010; Urtiaga et al. 2010; Carrera
Emulsion Pertraction Technology for Zinc Recovery 687

Hollow Fiber Contactor

Feed Solution Rafinate AC A + C
Mass
AC
transfer
A C

Back-extraction

Extraction

A + C AC
Emulsion
Concentrate AC E
Pore
C
Emulsion Tank
Feed A
Solution Hollowfiber

Stripping Emulsion
droplet

Emulsion Pertraction Technology for Zinc Recovery, Fig. 1 Performance of the EPT process

et al. 2009; Bringas et al. 2006; Urtiaga
et al. 2005; Klaassen and Jansen 2001). In the
forthcoming section, the potential of the EPT
technology to develop separation processes with
zinc recovery is evaluated.
Recovery of Zinc from Liquid Wastes
by EPT
Zincs electropositive nature makes it well-suited
for use as a coating for protecting iron and steel
products from corrosion. For this reason, the sur-
face treatment industry accounts for almost half
zinc modern-day demand. The processes involved
in the surface treatment of components are pre-
dominantly water-based, and thus the generation
and management of complex liquid wastes is an
issue of concern (Bringas et al. 2012). EPT has
been proven to be an efcient technology to per-
form both the selective removal and recovery of
zinc from different wastes produced in the context
of surface treatment industry: (i) spent pickling
acids (SPA) generated in the hot-dip galvanizing
process (see composition in Table 1) and (ii) spent
chromium-based passivation baths (SPB)
employed in zinc electroplating operations (see
composition in Table 1).
Figures 3 and 4 depict the separation and
recovery objectives to be achieved by the appli-
cation of EPT to the treatment of SPA and SPB.
Under the usual composition of SPA, zinc
forms anionic chlorocomplexes (ZnCl42 and
ZnCl3) while iron is present in the form of neu-
tral or cationic compounds (Regel et al. 2001).
Tributyl phosphate (TBP) and water are reported
as the most suitable extraction and back extraction
reagents enabling the selective separation and
concentration of zinc with minimum iron extrac-
tion (Cierpezewski et al. 2002). On the other hand,
the information provided by the equilibrium iso-
therms depicted in Fig. 5 conrms the commercial
selective carrier bis(2,4,4- trimethylpenthyl)
phosphinic acid (Cyanex272) as a suitable reagent
to formulate the liquid membrane due to its capac-
ity to selectively separate Fe3+ and Zn2+ (tramp
ions) from chromium under the typical pH condi-
tions (1.82.5) of the passivation baths. Sulphuric
acid is selected as stripping agent (Urtiaga
et al. 2010).
Figure 6 shows the kinetic results obtained
with the SPA-TBP-water and the EPT process.
688 Emulsion Pertraction Technology for Zinc Recovery

Emulsion Pertraction
Technology for Zinc
Recovery,
Fig. 2 Characteristics of
hollow ber contactors for a
bench scale EPT process

Parameter/Characteristic Value/Description

Fiber material Polypropylene

Shell material Polypropylene

Type of fiber X-50

Internal diameter of the

fiber 240 m

Thickness 30 m

Average pore diameter 0.04 m

Porosity 40%

Effective lenght 0.15

Interfacial area 1.4 m2

Number of fibers 10200

Emulsion Pertraction Technology for Zinc Recovery, It is concluded that the extraction (EX) and back-
Table 1 Physical-chemical properties of spent pickling extraction (BEX) percentages of zinc and iron,
acids (SPA) and spent chromium-based passivation baths
(SPB) when steady state conditions (regarding zinc
kinetics) are reached, are respectively, 79 %
SPA SPB
(EX Zn), 98 % (BEX Zn), 23 % (EX Fe), and
Parameter Value Parameter Value
38 % (BEX Fe). Under these operation condi-
pH 0 pH 1.82.5
tions, the maximum value of selectivity of zinc
Zn2+ (mg/L) 122,000 Zn2+ 250011,780
(mg/L) over iron in the stripping solution is 15 kg of
Fe2+ (mg/L) 100,000 Fe3+ 2090 Zn/kg of iron (Ortiz et al. 2004; Samaniego
(mg/L) et al. 2006; Samaniego et al. 2007; Carrera
Cl (mg/l) 300,000 Cr3+ 45009350 et al. 2009; Bringas et al. 2012). On the other
(mg/L) hand, the efciency of the EPT process to carry
Free acidity, 1 NO 67,520
3
out the regeneration of real passivation baths is
H+ (mol/L) (mg/L)
demonstrated in Fig. 7 which shows reductions
Emulsion Pertraction Technology for Zinc Recovery 689

FEED SOLUTION SEPARATION PROCESS SEPARATION AND RECOVERY OBJECTIVES

TBP Raffinate Coagulant (FeCl3)
(FeCl2, HCl)

Spent Pickling Acids Emulsion Pertraction

(Zn2+, HCL, Fe2+) Technology

Electrolytic
recovery of zinc
Stripping solution
Service (ZnCl2, HCl) Galvanizing
E
water
process

Emulsion Pertraction Technology for Zinc Recovery, Fig. 3 Treatment of spent pickling acids by EPTwith zinc recovery

FEED SOLUTION SEPARATION PROCESS/OBJECTIVES RECOVERY OBJECTIVES

Metallic pleces from zinc Regenerated passivation bath

electroplating: Incoming of (Cr3+)
Zn2+ and Fe3+

Spent Passivation Emulsion Pertraction

Bath Technology

Electrolytic
recovery of zinc
Stripping solution
(ZnSO4)
H2SO4 Cyanex272 Electroplating
process

Emulsion Pertraction Technology for Zinc Recovery, Fig. 4 Regeneration of chromium-based passivation baths by
EPT with zinc recovery

Emulsion Pertraction
Technology for Zinc Selective separation
Recovery,
Fig. 5 Extraction 100
iron
isotherms of iron, zinc, and
chromium with Cyanex272
75
% Extraction

50

25
chromium

zinc
0
0 1 2 3 4 5 6 7
Equilibrium pH
690 Emulsion Pertraction Technology for Zinc Recovery

Emulsion Pertraction Zn in SPA

Technology for Zinc 120
Recovery, Zn in stripping
Fig. 6 Evolution with time 100 Fe in SPA
of iron (discontinuous line) Fe in stripping
and zinc (continuous line)

CZn - CFe (g L-1)

concentration in the SPA and 80
stripping solution (0.5 L of
SPA with the composition 60
indicated in Table 1; 1 L of
organic solution containing
50 % v/v TBP in Shellsol 40
D70; 1 L of water)
20

0
0 30 60 90 120 150 180
t (min)

Emulsion Pertraction 100

Technology for Zinc
% Extraction
Recovery,
80
Concentration (kg m3)

Fig. 7 Extraction Stripping composition

percentages and
% Extraction

concentrations in the
stripping solution after 3 h 60
of EPT regeneration of SPB
using Cyanex272 as 40
selective extractant
0.43 kg m3
20 0.003 kg m3

0
[Zn] [Fe] [Cr]

in the zinc and iron contents higher than 80 % Future Directions

after 3 h of experimental running with an
almost negligible variation of the chromium
concentration. Furthermore, zinc is selectively
recovered in the stripping solution (con-
centration >35 kg/m3) being the concentrations
of iron (<0.45 kg/m3) and chromium
(<0.003 kg/m3) almost negligible (Urtiaga
et al. 2010; Bringas et al. 2011; Diban
et al. 2011; Bringas et al. 2012).
Therefore, these results conrm the EPT pro-
cess as a suitable alternative to perform the treat-
ment of spent pickling acids and spent passivation
baths allowing at the same time the zinc recovery
for further reuse as was illustrated by Figs. 3
and 4.
Future development will require research and
development activities in the following areas:
1. Determination of the optimal operational con-
ditions to: (i) maximize the extraction and
back-extraction kinetics and (ii) achieve max-
imum values of selectivity which permit the
exploitation of the different process streams
generated after the application of the EPT
process.
2. Analysis of the long-term performance of the
separation process to evaluate the stability of
the selective carrier which guarantees the pro-
cess economic viability.
Emulsion Rupture by Membranes
References
Bringas E, San Romn MF, Ortiz I (2006) Separation and
recovery of anionic pollutants by the emulsion
pertraction technology. Remediation of polluted
groundwaters with Cr(VI). Ind Eng Chem Res
45:42954303
Bringas E, Mediavilla R, Urtiaga A, Ortiz I (2011) Devel-
opment and validation of a dynamic model for regen-
eration of passivating baths using membrane
contactors. Comp Chem Eng 35:918927
Bringas E, San Romn MF, Urtiaga AM, Ortiz I (2012)
Integrated use of liquid membranes and membrane
contactors: enhancing the efciency of L-L reactive
separations. Chem Eng Process. doi:10.1016/j.
cep.2012.11.005
Carrera JA, Bringas E, San Romn MF, Ortiz I (2009)
Selective membrane alternative to the recovery of zinc
from hot-dip galvanizing efuents. J Membr Sci
326:672680
Cierpezewski R, Miesiac I, Regel-Rosocka M,
Sastre AM, Szymanowski J (2002) Removal of zinc
(II) from spent hydrochloric acid solutions from
zinc hot galvanizing plants. Ind Eng Chem Res
41:598603
Diban N, Mediavilla R, Urtiaga A, Ortiz I (2011)
Zinc recovery and waste sludge minimization from
chromium passivation baths. J Hazard Mater
192:801807
Klaassen R, Jansen AE (2001) The membrane contactor:
environmental applications and possibilities. Environ
Prog 20:3743
Ortiz I, Bringas E, San Romn MF, Urtiaga AM
(2004) Selective separation of zinc and iron from
spent pickling solutions by membrane-based solvent
extraction. Sep Sci Technol 39:24412455
Regel M, Sastre AM, Szymanowski J (2001) Recovery
of zinc(II) from HCl spent pickling solutions
by solvent extraction. Environ Sci Technol 35:
630635
Samaniego H, San Romn MF, Ortiz I (2006) Modelling of
the extraction and back-extraction equilibria of zinc
from spent pickling solutions. Sep Sci Technol
41:757769
Samaniego H, San Romn MF, Ortiz I (2007) Kinetics of
zinc recovery from spent pickling efuents. Ind Eng
Chem Res 46:907912
San Romn MF, Bringas E, Ibez R, Ortiz I (2010) and the oil. However, membranes can be used
Liquid membrane technology: fundamentals and
review of its applications. J Chem Technol Biotechnol
85:210
Urtiaga A, Abelln MJ, Irabien JA, Ortiz I (2005) Mem-
brane contactors for the recovery of metallic com-
pounds. Modelling of copper recovery from WPO
processes. J Membr Sci 257:161170
Urtiaga A, Bringas E, Mediavilla R, Ortiz I (2010)
The role of liquid membranes in the selective
separation and recovery of zinc for the regeneration
of Cr(III) passivation baths. J Membr Sci 356:8895
691
Emulsion Rupture by Membranes
Jose Coca
Department of Chemical and Environmental
Engineering, University of Oviedo, Oviedo,
Spain
Emulsions are homogeneous mixtures that consist E
of a dispersed phase (oil droplets in O/W emul-
sions) distributed uniformly in a continuous phase
(water). Ultraltration (UF) and microltration
(MF) membranes have been used for the treatment
of O/W emulsions produced in industries such as
steel works, metal nishing, pharmaceuticals,
cosmetics, food, etc. Oil droplets are recovered
as retentate and the aqueous phase permeates the
membrane. The production of 1 t of steel may
demand up to 200 t of water, the largest water
usage corresponding to the rolling mills. Mem-
brane performance diminishes when oil droplets
fall below the micron range and problems become
more pronounced when ionic surfactants are pre-
sent, as they increase repulsive forces between
droplets.
Demulsication is commonly achieved by
chemical or electrostatic methods. Chemical
demulsication destabilizes the disperse phase
by two mechanisms: coagulation (inorganic
salts) and occulation (organic polymers).
The disadvantage of chemical demulsication
is that the bulk phase has to be further treated
before discharge. Electrostatic demulsication
is ineffective for emulsions with high water
content and sparking during treatment may
generate new compounds from the surfactant
as coalescers by forcing the emulsion through
the pores of the membrane (Kajitvichyanukul
et al. 2011).
Hydrophilic membranes induce coalescence
of O/W emulsions while hydrophobic membranes
can be used for the demulsication of W/O emul-
sions (Fig. 1). The main factors affecting mem-
brane demulsication are (Daiminger et al. 1995;
Hong et al. 2003; Kocherginsky et al. 2003):
692
qO/W > 90
Oil
Hydrophilic membrane
qO/W < 90
Oil
Hydrophobic membrane
Emulsion Rupture by Membranes, Fig. 1 Inuence of
membrane characteristics in oil droplet rejection
Membrane pore size, transmembrane pressure
(DP), and imposed in-pore shear rates affect
coalescence. The smaller the membrane pore
size and the lower DP, the better
demulsication efciency. However, small
pores coupled with a low DP would lead to
low permeation ux.
If the DP is below a critical value (DPc), the
emulsion rejection can be maximized. Above a
DPc the membrane acts as a coalescer and the
droplets wet the membrane enabling the oil
droplets to coalesce.
Membrane demulsication seems to be inde-
pendent of the initial disperse phase concentra-
tion and membrane thickness.
The demulsication process is determined by
interactions between droplets and membrane
surface.
So far, membranes as coalescers do not show
great advantages with respect to conventional
coalescing techniques, e.g., ber-bed coalescence
and electrostatic coalescers. New chemically
treated ceramic membranes and silicon carbide
supports have a great potential for oil-water appli-
cations since they are abrasion and solvent
Emulsion Separation by Membranes
resistant, easy to clean by backushing, and
have a low cost and longer life than the previous
generation membranes.
References
Daiminger U, Nitsch W, Plucinski P, Hoffmann S (1995)
Novel techniques for oil/water separation. J Membr Sci
99:197203
Hong A, Fane AG, Burford R (2003) Factors affecting
membrane coalescence of stable oil-in-water emul-
sions. J Membr Sci 222:1939
Kajitvichyanukul P, Hung Y-T, Wang LK (2011) Mem-
brane technologies for oilwater separation. In: Wang
LK, Chen JP, Hung Y-T, Shammas NK (eds) Handbook
of environmental engineering, vol 13, Membrane
and desalination technologies. Springer, Dordrecht,
pp 639668
Kocherginsky NM, Tan CL, Lu WF (2003) Demulsication
of water-in-oil emulsions via ltration through a
hydrophilic polymer membrane. J Membr Sci 220:
117128
Emulsion Separation by Membranes
Jose Coca
Department of Chemical and Environmental
Engineering, University of Oviedo, Oviedo,
Spain
Separation of oily emulsions from wastewaters is
generally carried out by a combination of chemi-
cal and mechanical methods. Chemicals
(coagulants and occulants) are used to destabi-
lize the oil-water interface allowing the oil drop-
lets to coalesce. Mechanical methods include
gravity-based settlers, skimmers, dissolved air o-
tation (DAF), centrifuges, electro-coalescers, etc.
Pressure-driven membrane processes
(microltration MF, ultraltration UF, and reverse
osmosis RO) may be used to separate oil and
water phases. The water molecules move through
the membrane (permeate) and a concentrated
emulsion (retentate or concentrate) is obtained.
Some components of the emulsion may also
move through the membrane, depending on their
characteristics and size and the nature of the
Emulsion Treatment with Membranes
Oily wastewater Free oil removal
Centrifugal
separator
Equalization
tank
Filter
Settleable solids
Emulsion Separation by Membranes, Fig. 1 Hybrid UF system for oily wastewater treatment
membrane, leading to contamination of the per-
meate. Fouling and scaling of the membrane lead
to a poor performance and membrane cleaning
procedures must be taken into account.
When MF is used for oil-water separation,
particulates, emulsied oil, and microbial contam-
inants can be removed. Cross-ow velocities may
range between 3 and 6 m/s and transmembrane
pressures (TMPs) between 100 and 770 kPa. The
main limitation of membrane processes is the
decline of the permeate ux over time because
of concentration polarization, membrane fouling
(due to surfactant or oil adsorption on the pore
walls), gel layer formation, pore blocking by oil
droplets, pH, and temperature.
Often it is not possible to use a simple mem-
brane system to perform an oil-water separation:
some efuents may cause severe membrane foul-
ing and pretreatment is necessary to maintain a
high and steady ux. In these situations, inte-
grated-membrane or membrane-based hybrid
processes may be suitable alternatives to obtain
good process performance and to extend mem-
brane life (Coca et al. 2013). A typical membrane
hybrid process for oily wastewaters is shown in
Fig. 1.
Usually the process starts with the removal of
settleable solids and free-oating oil prior to
membrane treatment, mainly UF. This can be
accomplished in a tank with free-oil removal
equipment, such as a skimmer, or by a rotating
brush strainer, a pressure or vacuum lter to
remove solids, and a centrifugal separator or a
hydrocyclone to remove oil and solids. The
remaining oily wastewater (mainly stable O/W
693
Concentrate
UF
Process
tank
Final concentrate Oil-free permeate
disposal discharge
E
emulsion) is then transferred to a process tank
and pumped through the UF unit to remove the
emulsied oil. The retentate containing the oil is
recycled to the process tank, and the permeate is
continuously withdrawn. This process is com-
monly used in the automobile industry (Cheryan
and Rajagopalan 1998).
References
Cheryan M, Rajagopalan N (1998) Membrane processing
of oily streams. Wastewater treatment and waste reduc-
tion. J Membr Sci 151:1328
Coca J, Gutirrez G, Benito JM (2013) Treatment of oily
wastewater by membrane hybrid processes. In: Coca-
Prados J, Gutirrez-Cervell G (eds) Economic sustain-
ability and environmental protection in mediterranean
countries through clean manufacturing methods.
Springer, Dordrecht, pp 3561
Emulsion Treatment
with Membranes
Jose Coca
Department of Chemical and Environmental
Engineering, University of Oviedo, Oviedo,
Spain
An emulsion is a homogeneous mixture of two
immiscible liquids, with one of them (typically oil)
dispersed as droplets into the other. Emulsion drop-
lets usually range between 0.1 and 20 mm in diam-
eter. The two main categories of emulsions are
694
Chemical addition
(coagulants/flocculants)
Oily Free oil
wastewater
Centrifugation
Feed
tank
Settleable solids
Emulsion Treatment with Membranes, Fig. 1 UF process for oily wastewater treatment
oil-in-water (O/W, >30 % water) and water-in-oil
(W/O, <25 % water): water and highly polar liquids
are hydrophilic, while nonpolar liquids are consid-
ered oils. Emulsions consist of two phases: an
internal or discontinuous phase (nally divided
droplets) and an external or continuous phase
(which keeps the droplets in suspension), which
are bound together at the interphase. A surfactant
reduces the interfacial tension between the two
phases binding them together. Industrial oily waste-
waters can be classied as: free oil (Dp 150 mm),
dispersed oil (Dp = 20150 mm), stable emulsied
oil (Dp  20 mm), and dissolved oil (Dp 5 mm).
Free oils and dispersed O/W emulsions can be
removed by mechanical methods such as gravity
settling, skimming, coalescence, centrifugation,
etc. (Alther 1998; Stewart and Arnold 2008). Stable
emulsied oils and dissolved oils cannot be
removed efciently by conventional methods
because of the small droplet size and low oil
concentration.
Membrane processes are increasingly being
applied for treating O/W emulsions due to their
advantages: high-quality permeate and removal
efciency, lower capital costs than with thermal
processes, and compact design. Some of the most
promising membrane O/W treatments are dehy-
dration of emulsions by pervaporation, reverse
Emulsion Treatment with Membranes
UF
Process
tank
Concentrate Oil-free permeate
disposal (to sewer)
osmosis (RO), occulation followed by
microltration (MF), MF, membrane distillation,
nanoltration (NF), and ultraltration
(UF) (Cheryan 1998; Chakrabarty et al. 2010).
A typical UF-based system for oily wastewa-
ters, operated in a semi-batch recycle mode, is
shown in Fig. 1. The nal concentrate volume
may be only 35 % of the initial oily wastewater
volume. The system must be cleaned after a cer-
tain time to restore the permeate ux. O/W emul-
sions may be reduced by 8590 % by volume and
with an oil concentration in the retentate of
7075 %.
MF or UF processes cannot remove dissolved
oil components in water. For that purpose, other
methods, such as RO or NF, are required. The
choice of membrane material is important: inor-
ganic membranes are chemically robust and
expensive; polymeric membranes have lower
resistance to aggressive feeds and are more sus-
ceptible to fouling, but are considerably cheaper.
In spite of the fact that efuent oil concentrations
of 5 ppm or less can be achieved with membranes,
they have not found wide practical applications so
far. Membrane systems suffer from concentration
polarization and fouling problems that lead to a
substantial ux decline with time. Membranes
must be replaced every 35 years.
Emulsions Drop Size Distribution, Measurement of
O/W emulsions can sometimes be treated by a
combination of two membrane processes (e.g.,
UF/NF, UF/RO or NF/RO) to obtain a high-
quality water efuent.
References
Alther G (1998) Put the breaks on wastewater emulsions.
Chem Eng 105:8288
Chakrabarty B, Ghoshal AK, Purkait MK (2010) Cross-
ow ultraltration of stable oil-in-water emulsion using
polysulfone membranes. Chem Eng J 185:447456
Cheryan M (1998) Ultraltration and microltration hand-
book, 2nd edn. Technomic, Lancaster
Stewart M, Arnold A (2008) Emulsions and oil treating
equipment: selection, sizing and troubleshooting. Gulf
Professional Publishing, Burlington
Emulsions Drop Size Distribution,
Measurement of
Volker Gaukel, Richard Bernewitz and
Heike Schuchmann
Food Process Engineering, Karlsruhe Institute of
Technology (KIT), Karlsruhe, Germany
The drop size distribution (DSD) of an emulsion
has inuence on the physical stability, the color,
and the rheological behavior of the emulsion and is
therefore an important means of characterization.
The DSD can be measured with various
methods. In principle one can distinguish between
methods which measure physical characteristics
of single drops or physical characteristics of the
bulk emulsion. The latter are often used for the
characterization of an emulsion in terms of quality
control where it is only necessary to notice differ-
ences between a reference and a product or where
it is sufcient to attain the DSD results only after a
calibration against a system with known DSD.
Examples are rheological behavior, dielectric
spectrometry, dynamic scanning calorimetry,
focused beam reectance, or dynamic reection
measurements. An advantage of these methods is
695
often that they are fast and may be used online or
at least without diluting the sample.
For the measurement of DSD, a physical char-
acteristic which is connected to the drop size of a
single drop-like sedimentation velocity, diffrac-
tion of light at the drop surface, projected area in
a microscopic image, etc., is necessary. This
makes clear that the basis of the calculation of
DSD varies between different methods, and one
should not expect the same DSD results from
E
different measuring methods. In addition during
the calculation procedure, it is partly necessary to
make assumptions and simplications, and there-
fore DSD results are very sensitive to the calcula-
tion parameters which are set by the manufacturer
or which can be set by the user of the equipment.
The most common techniques for DSD mea-
surement are presented in Table 1 which shows the
measuring principle as well as the analyzable drop
size range and some restrictions of the method.
Progress in the eld of emulsions has evolved
complex structures, like multiple emulsions
(Muschiolik 2007; Jimnez-Colmenero 2013).
As in a multiple emulsion, there are more than
one DSD to determine the complex structure that
challenges the common measuring techniques.
However, progress in the eld of DSD determina-
tion of double emulsions has been made. Espe-
cially PFG-NMR and IA of confocal laser
scanning microscopy images offer possibilities
for the characterization of double emulsions
(Schuster et al. 2012).
Another important issue in the context of DSD
measurements is the illustration and interpreta-
tion. DSDs are statistical distributions and can be
shown as cumulative or density distributions.
Especially showing the latter, it is very important
to consider all the rules of their calculation. To the
authors knowledge, there are many measurement
devices with very weak software concerning this
point. For simplication and interpretation of
results, it is very common to show only mean
values of the DSD as, e.g., the Sauter Mean Diam-
eter or statistical values like the median or modal
value. Some insights on this topic are given in
(Hess 2004; Sommer 2001).
696 Enantiocatalytic Membrane

Emulsions Drop Size Distribution, Measurement of, Table 1 Overview on the most important measurement
techniques for drop size analytics in emulsions
Physical
characteristic for
Method size measurement Size range Additional information
Sedimentation Sedimentation (50 nm) Range for the use of centrifuges in brackets. For
velocity of a 1 mm1 mm small drops, very high dilution necessary
single drop
(Statistical) image Projected area (0,1 nm) Size range depending on the image source.
analytics (IA) 1 mm20 mm Electron microscopy in brackets. Information on
structure and double emulsion detection possible.
High number of drops necessary for reliable
statistical analysis
Laser diffraction (LD) Diffraction of (50 nm) In brackets: with additional light sources and
light at the drop 1 mm2 mm scattering information, necessity of complex
surface refraction index. High dilution necessary
Dynamic laser light Diffusion rate 1 nm1 mm Dispersed phase content up to 10 % possible.
scattering (DLS) Drop sedimentation leads to measurement error
Pulsed eld gradient Coefcient of 0,2100 mm Measurement without dilution possible.
nuclear magnetic diffusion Characterization of some parameters of double
resonance (PFG-NMR) emulsions

References process of a particular enantiomer from a racemic

Hess WF (2004) Representation of particle size distribu-
tions in practice. Chem Eng Technol 27(6):624629
Jimnez-Colmenero F (2013) Potential applications of
multiple emulsions in the development of healthy and
functional foods. Food Res Int 52(1):6474
Muschiolik G (2007) Multiple emulsions for food use.
Curr Opin Colloid Interface Sci 12(45):213220
Schuster S, Bernewitz R, Guthausen G, Zapp J, Greiner
AM, Khler K, Schuchmann HP (2012) Analysis of
W1/O/W2 double emulsions with CLSM: statistical
image processing for droplet size distribution. Chem
Eng Sci 81:8490
Sommer K (2001) 40 years of presentation particle size
distributions yet still incorrect? Part Part Syst Charact
18(1):2225
mixture. The most popular reaction using the
technique is esterication, where Candida rugosa
lipase or Candida antarctica lipase is the biocat-
alyst for the reaction (Giorno et al. 2007; Lau
et al. 2010). The application of membranes, espe-
cially in the production of drugs and other ne
chemicals, has become a trend in recent years and
it will be one of the best techniques for the bulk
synthesis of such compounds (Lau et al. 2010; Li
et al. 2003). Hollow ber membrane with a par-
ticular molecular weight cutoff is the best choice
to use as the immobilization matrix.
References

Giorno L, DAmore E, Drioli E, Cassano R, Picci N (2007)

Enantiocatalytic Membrane
Mohamad Hekarl Uzir
School of Chemical Engineering, Universiti Sains
Malaysia, Penang, Malaysia
Enantiocatalytic membrane is a type of mem-
brane immobilized with a particular catalyst
(mainly enzyme) onto the shell side for the pur-
pose of carrying out an in situ reaction-separation
Inuence of -OR ester group length on the catalytic
activity and enantioselectivity of the free lipase and
immobilized in membrane used for the kinetic resolu-
tion of naproxen esters. J Catal 247:194200
Lau SY, Uzir MH, Kamaruddin AH, Bhatia S (2010)
Lipase-catalysed dynamic resolution of racemic ibu-
profen ester via hollow bre membrane reactor: model-
ling and simulation. J Membr Sci 357(1-2):109121
Li N, Giorno L, Drioli E (2003) Effect of immobilization
site and membrane materials on multiphasic
enantiocatalytic enzyme membrane reactors. In: Li N,
Drioli E, Ho W, Lipscomb G (eds) Advanced mem-
brane technology. New York Academy of Sciences,
New York, pp 436452
Enantiomers
Enantiomer Discrimination
(Enantioselectivity)
Mohamad Hekarl Uzir
School of Chemical Engineering, Universiti Sains
Malaysia, Penang, Malaysia
Enantiomer discrimination (or chiral discrimina-
tion) is a method used to distinguish between two
enantiomers for the purpose of separating the
compounds. The terms is also related to enantios-
electivity where it refers to the discrimination of a
given reactant A when it reacts with two alterna-
tive reactants B and C or in two different ways
(probably at two different sites) with a reactant
B (McNaught and Wilkinson 1997). A number of
methods have been established to undergo enan-
tiomer discrimination; these include mass spec-
troscopy (Czerwenka and Lindner 2004;
Czerwenka et al. 2004), nuclear magnetic reso-
nance (NMR) (Gafni et al. 1998; Molabaasi and
Talebpour 2011), and crystal recognition
(Ballesteros et al. 1995; Huai et al. 2006; Klaholz
et al. 2000). These methods have been specically
developed based on a particular compound with
its own characteristics of crystal structure.
References
Ballesteros E, Gallego M, Valcarcel M, Grases F (1995)
Enantiomer discrimination by continuous precipitation.
Anal Chem 67(18):33193323
Czerwenka C, Lindner W (2004) Enantiomer discrimina-
tion of peptides by tandem mass spectrometry: inu-
ence of the peptide sequence on chiral recognition.
Rapid Commun Mass Spectrom 18:27132718
Czerwenka C, Maier NM, Lindner W (2004) Enantiomer
discrimination by mass spectrometry: noncovalent
interaction of an N-derivatized dipeptide with various
cinchona alkoloid derivatives and comparison with
enantioselective liquid-phase separations. Anal
Bioanal Chem 379:10391044
Gafni A, Cohen Y, Kataky R, Palmer S, Parker D (1998)
Enantiomer discrimination using lipophilic cyclodex-
trins studied by electrode response, Pulsed-
GradientSpin-Echo, (PDSE) NMR and relaxation rate
measurements. J Chem Soc Perkin Trans 2(1):1924
Huai Q, Sun Y, Wang H, MacDonald D, Aspiotis R,
Robinson H, Huang Z, Ke H (2006) Enantiomer
697
discrimination illustrated by high resolution crystal
structure of type 4 phosphodiesterase. J Med Chem
49(6):18671873
Klaholz B, Mitschler A, Belema M, Zusi C, Moras D (2000)
Enantiomer discrimination illustrated by high-resolution
crystal structures of the human nuclear receptor hRARg.
Proc Natl Acad Sci USA 97(12):63226327
McNaught AD, Wilkinson A (Eds.), (1997) IUPAC - Com-
pendium of Chemical Terminology, Blackwell Science,
Oxford, England, UK
Molabaasi F, Talebpour Z (2011) Enantiomeric discrimi-
nation and quantication of the chiral organophospho-
rus pesticide fenamiphos in aqueous samples by a novel E
and selective 13P nuclear magnetic resonance spectro-
scopic method using cyclodextrin as chiral selector.
J Agric Food Chem 59(3):803808
Enantiomers
Mohamad Hekarl Uzir
School of Chemical Engineering, Universiti Sains
Malaysia, Penang, Malaysia
Enantiomers are types of stereoisomer whose
structures are mirror image of each other, and
they are not superimposable. The property is spe-
cial to most chiral compounds and exists both
naturally or from a particular chemical synthesis
(Solomons and Fryhle 2004). It represents the
intrinsic property of the building block of life,
which consists of amino acids, sugars, peptides,
proteins, and polysaccharides (Maier et al. 2001).
The simplest compound that exhibits enantio-
meric property is 2-butanol with the structural
formulae given in Fig. 1.
The existence of enantiomers of a particular
compound can be determined when there is a
molecule containing one tetrahedral atom with
four different groups attached to it, as shown in
the two structures of 2-butanol above (McMurry
CH3 CH3
HO H
H OH
C C
C2H5 C2H5
Enantiomers, Fig. 1 Structural formula of 2-butanol
showing two different enantiomers
698
2004). Specialized drugs are mainly made of com-
pounds that exhibit enantiomeric properties; these
include (S)-ibuprofen, (S)-naproxen, (S)-
citalopram, and (+)-norcisapride. As can be appar-
ently seen, only one type of enantiomer acts as an
active compound compared to their
corresponding structures. This shows that the syn-
theses of such drugs are somewhat important, in
particular, for use in pharmaceutical and medical
sectors. Some of the processes carried out to
obtain the compounds are tedious and require a
number of reagents as well as different catalysts.
This will then lead to high cost of production
(Maier et al. 2001; Tramper 1996).
References
Maier NM, Franco P, Lindner W (2001) Separation of
enantiomers: needs, challenges, perspectives.
J Chromatogr A 906(1):333
McMurry J (2004) Organic chemistry. Thomson Books/
Cole, Belmont
Solomons TWG, Fryhle CB (2004) Organic chemistry.
Wiley, New Jersey
Tramper J (1996) Chemical versus biochemical conver-
sion: when and how to use biocatalysts. Biotechnol
Bioeng 52(1):290295
Enantiomers Production by
Membrane Operations
Mohamad Hekarl Uzir
School of Chemical Engineering, Universiti Sains
Malaysia, Penang, Malaysia
Enantiomer production is a process of forming
enantiomer of interest through membrane separa-
tion. The current method of kinetic resolution and
in situ membrane separation is a highly effective
process which requires less energy and short reac-
tion time (Lau et al. 2011). Most of the works
related to product separations involved lipase
enzyme immobilized onto the membrane matri-
ces. These include the production of naproxen
ester (Giorno et al. 2003, 2007) and ibuprofen
ester (Lau et al. 2010).
Enantiomers Production by Membrane Operations
References
Giorno L, Li N, Drioli E (2003) Use of stable emulsion to
improve stability, activity and enantioselectivity of
lipase immobilized in a membrane reactor. Biotech
Bioeng 84(6):677685
Giorno L, DAmore E, Drioli E, Cassano R, Picci N (2007)
Inuence of -OR ester group length on the catalytic
activity and enantioselectivity of the free lipase and
immobilized in membrane used for the kinetic resolu-
tion of naproxen esters. J Catal 247:194200
Lau SY, Uzir MH, Kamaruddin AH, Bhatia S (2010)
Lipase-catalysed dynamic resolution of racemic ibu-
profen ester via hollow bre membrane reactor: model-
ling and simulation. J Membr Sci 357(12):109121
Lau SY, Fadzil NG, Kamaruddin AH, Bhatia S, Uzir MH
(2011) Conceptual design and simulation of a plant for
the production of high purity (S)-ibuprofen acid using
innovative enzymatic membrane technology. Chem
Eng J 166(2):726737
Enantiomers Separation by
Membrane Operations
Mohamad Hekarl Uzir
School of Chemical Engineering, Universiti Sains
Malaysia, Penang, Malaysia
Enantiomers separation is a process of separat-
ing isomers in a racemic mixture into their
individual enantiomer. The use of membranes in
chiral separation can be divided into two
main categories, namely, adsorption-type
enantioselective membranes and membrane-
assisted resolution with non-enantioselective
solid membranes (Pirkle and Bowen 1994; Xie
et al. 2008). The former is entirely based on the
transport mechanism with an aid of chiral carriers.
The work of Gumi and co-workers reported a
detail account of the transfer of the (S)-
propranolol attached to the N-hexadecyl-L-
hydroxyproline through the formation of ionic
pair, which is then being transported through the
polysulfone-based membrane (Gumi et al. 2005).
The latter is a technique mostly coupled with
enzymes as biocatalysts. The enzyme is initially
immobilized onto the shell side of the membrane
matrix before carrying out the required resolution,
Enantioselective Separations, Membrane Operations
either kinetic resolution or dynamic kinetic resolu-
tion. For example, the work of Long and
co-workers successfully utilized Candida rugosa
lipase as the source of biocatalyst for the kinetic
resolution of (S)-ibuprofen ester (Long et al. 2005).
References
Gumi T, Ferreira Q, Viegas R, Crespo J, Coelhoso I,
Palet C (2005) Enantioselective separation of propran-
olol by chiral activated membranes. Sep Sci Technol
40(4):773789
Long W, Kow P, Kamaruddin A, Bhatia S (2005) Compar-
ison of kinetic resolution between two racemic ibupro-
fen enters in an enzymatic membrane reactor. Process
Biochem 40(7):24172425
Pirkle W, Bowen W (1994) Preparative separation of enan-
tiomers using hollow-bre membrane technology. Tet-
rahedron Asymmetry 5(5):773776
Xie R, Chu L-Y, Deng J-G (2008) Membranes and mem-
brane processes for chiral resolution. Chem Soc Rev
37:12431263
Enantioselective Membrane
Mohamad Hekarl Uzir
School of Chemical Engineering, Universiti Sains
Malaysia, Penang, Malaysia
Enantioselective membrane is a type of membrane
used to separate chiral compounds into their indi-
vidual enantiomer. The usual type of membrane
used for separation purposes is of polymeric type
(Ceynowa 1998; Higuchi et al. 2010; Xie
et al. 2008). The mechanism of chiral separation
can be categorized into two different types of
membranes, namely, diffusion-selective mem-
branes and sorption-selective membranes.
Diffusion-selective type of membranes are basi-
cally made of polymer without any specic chiral
selectors (i.e., the polymer itself has chiral prop-
erties); however, sorption-selective membranes
can be designed in such a way that a particular
chiral selector can be immobilized can be
immobilized onto the surfaces of the polymer
membranes, which later gives less selective
699
diffusion, but provides highly selective sorption
(Hadik et al. 2002; Higuchi et al. 2010).
References
Ceynowa J (1998) Separation of racemic mixtures by
membrane methods. Chem Anal 43(6):917933
Hadik P, Szabo L, Nagy E (2002) D, L-lactic acid and D,
L-alanine enantio separation by membrane process.
Desalination 148(13):193198
Higuchi A, Tamai M, Ko Y-A, Tagawa Y-I, Wu Y-H,
E
Freeman B, Bing J-T, Chang Y, Ling Q-D (2010) Poly-
meric membranes for chiral separation of pharmaceuti-
cals and chemicals. Polym Rev 50(2):113143
Xie R, Chu L-Y, Deng J-G (2008) Membranes and mem-
brane processes for chiral resolution. Chem Soc Rev
37:12431263
Enantioselective Separations,
Membrane Operations
Mohamad Hekarl Uzir
School of Chemical Engineering, Universiti Sains
Malaysia, Penang, Malaysia
Enantioselective separations refer to separation
methods used to separate racemic mixture into
individual enantiomer with the aid of membrane
matrix/module. In order to measure the level of
selectivity, the percent enantiomeric excess (% ee)
of a mixture needs to be determined (see enantios-
electivity). Membranes have been successfully
used in chiral separation with various types as
well as with different abilities: direct separation
type of membrane made from polymer/liquid and
separation with nonselective membrane assisted
by chiral carriers/support (Maier et al. 2001;
Pirkle and Bowen 1994).
References
Maier NM, Franco P, Lindner W (2001) Separation of
enantiomers: needs, challenges, perspectives.
J Chromatogr A 906(1):333
Pirkle W, Bowen W (1994) Preparative separation of enan-
tiomers using hollow-bre membrane technology. Tet-
rahedron Asymmetry 5(5):773776
700
Enantioselective Synthesis
Mohamad Hekarl Uzir
School of Chemical Engineering, Universiti Sains
Malaysia, Nibong Tebal, Penang, Malaysia
Enantioselective synthesis is a chemical/bio-
chemical reaction where only one enantiomer of
a chiral product is preferentially formed. The syn-
thesis can be divided into two different types,
namely, catalytic synthesis and biocatalytic trans-
formation. Nowadays, chemical catalysis has
been continuously improved, especially in terms
of yields and percentage enantiomeric excesses
(%e.e), for instance, the synthesis of spirocyclic
oxindolo-b-lactam, a combination of indole and
b-lactam, which acts as antibacterial, antiviral,
and antifungal agents (Zhang et al. 2014). The
structure of spirocyclic oxindolo-b-lactam or
commercially known as chartelines is given in
Fig. 1.
Zhang and coworkers reported that the con-
struction of chartelines started from the bifunc-
tional N-heterocyclic carbine undergoing
Staudinger reaction of ketenes with isatin-derived
ketimines. For such a highly complex compound,
the %e.e reached up to 95 % with the yield of
89 %. Similar goes to the synthesis of g-, d-, and
e-chiral-1-alcoloids, reported by Xu and
coworkers (2014).The reaction was based on
Cl
R1
R2
N
N
Br
N School of Chemical Engineering, Universiti Sains
N H
Br
Compound A: R1=R2=Br
Compound B: R1=Br, R2=H
Compound C: R1=R2=H
Enantioselective Synthesis, Fig. 1 Chemical structure
of spirocyclic oxindolo-b-lactam
Enantioselective Synthesis
both chemical and biological catalyses utilizing
Zr for the carboalumination reaction and later
applying lipase originated from Pseudomonas
cepacia for the acetylation reaction. However,
by comparing both types of reactions, biocatalysis
has been known to provide better yield as well
as %e.e (Tsai and Dordick 1996). One of the
recent works in the development of pharmaceuti-
cally active compounds has been reported by Wen
and colleagues where the group managed to syn-
thesize (S)-propranolol through a coupled reac-
tion with kinetic resolution as a recycling route
utilizing Candida antarctica lipase B. The result
showed an improve %e.e up to 100 % (Wen
et al. 2014).
References
Tsai S-W, Dordick JS (1996) Extraordinary enantiospe-
cicity of lipase catalysis in organic media induced by
purication and catalyst engineering. Biotechnol
Bioeng 52(2):296300
Wen Y, Hertzberg R, Gonzalez I, Moberg C (2014) Minor
enantiomer recycling: application to enantioselective
synthesis of beta-blockers. Chem-A Eur J 20(13):
38063812
Xu S, Oda A, Kamada H, Negishi E (2014) Highly
enantioselective synthesis of g-, d-, and e-chiral 1-
alkanols via Zr-catalyzed asymmetric carboalu-
mination of alkenes (ZACA)-Cu- or Pd-catalyzed
cross-coupling. Proc Natl Acad Sci U S A 111(23):
83688373
Zhang H, Gao Z, Ye S (2014) Bifunctional N-heterocyclic
carbene-catalyzed highly enantioselective synthesis of
spirocyclic oxindolo-beta-lactam. Org Lett 16(11):
30793081
Enantioselective Synthesis by
Membrane Operations
Mohamad Hekarl Uzir
Malaysia, Penang, Malaysia
Enantioselective synthesis by membrane opera-
tions refers to chemical reactions to produce one
enantiomer from a racemic mixture utilizing
Enantioselective Transport of Amino Acids by Membrane Operations
membrane as a medium of separation. The process
occurs in situ, where the product formed from the
reaction will be directly separated into the
required enantiomeric compound (Giorno
et al. 1995; Long et al. 2005). Another enantio-
meric synthesis, which applied the hollow-ber
membrane module, is from the work of Hadik and
co-workers. The polymeric membrane made
from polypropylene was used together with a
chiral selector, N-3,5-dinitrobenzoyl-L-alanine
octylester, initially dissolved in toluene (Hadik
et al. 2002). Hollow-ber membrane has also
been applied with different types of chiral selec-
tors for large-scale separation processes. The
reported results suggested that N(1-naphthyl)-
leucine provided a wide range of enantiomeric
separation of amino acid derivatives with %ee of
up to 95 % (Pirkle and Bowen 1994).
References
Giorno L, Molinari R, Drioli E, Bianchi D, Cestic P (1995)
Performance of a biphasic organic/aqueous hollow
bre reactor using immobilized lipase. J Chem Technol
Biotechnol 64(4):345352
Hadik P, Szabo L, Nagy E (2002) D, L-lactic acid and D,
L-alanine enantio separation by membrane process.
Desalination 148(13):193198
Long W, Kow P, Kamaruddin A, Bhatia S (2005) Compar-
ison of kinetic resolution between two racemic ibupro-
fen enters in an enzymatic membrane reactor. Process
Biochem 40(7):24172425
Pirkle W, Bowen W (1994) Preparative separation of enan-
tiomers using hollow-bre membrane technology. Tet-
rahedron Asymmetry 5(5):773776
Enantioselective Transport of Amino
Acids by Membrane Operations
Keiji Sakaki
National Institute of Advanced Industrial Science
and Technology (AIST), Research Institute for
Sustainable Chemistry, Tsukuba, Ibaraki, Japan
Amino acids are molecules that contain an
amino group (NH2), a carboxylic acid group
(COOH), and a side chain in each structure and
701
are the structural units of proteins. The most of
amino acids found in nature are categorized as
a-amino acid in which the amino group is attached
to the carbon atom adjacent to the carboxylic acid
group. An a-amino acid can exist in either of two
optical isomers except glycine, and the isomer is
normally described as L- or D-amino acid. The major-
ity of amino acids in living organisms are L-isomers.
Optical isomers, including amino acids, frequently
show different bioactivity from each other. So, opti-
E
cal resolution of amino acids has been an important
subject in various industries dealing with pharma-
ceuticals, foods, agrochemicals, and so on.
Optical resolution with membrane processes has
potential merits over other separation methods like
crystallization or chromatography. Membrane oper-
ation can be carried out continuously and it enables
the large-scale separation. Optical resolution of
amino acids can be achieved by the function of chiral
recognition sites of solid membranes and liquid
membranes. The method using liquid membranes
is described in another site, so solid membranes for
enantioselective separation are explained here.
A main research topic on enantioselective mem-
branes is the design of the membranes that have the
chiral recognition sites. Some enantioselective solid
membranes have been reported as follows.
Membranes Prepared from Chiral
Polymers
Polypeptide and polysaccharide, like cellulose,
alginate, and chitosan, and their derivatives are
chiral polymers, and membranes from these
chiral polymers have been applied to the
enantioselective separation of racemic amino
acids. The separation factor of these membranes
toward racemic tryptophan is usually in the range
of 1.15.0 (Higuchi et al. 2010). Membranes pre-
pared from polymers with chiral branch have been
also reported.
Membranes Added with Chiral Selectors
Enantioselective membranes can be prepared by
the addition of chiral selectors that show
702 Enantioselectivity

enantioselective afnity toward amino acids. Yoshikawa M, Izumi J, Kitano T (1995) Molecularly
Cyclodextrins, bovine serum albumin (BSA), imprinted polymeric membranes for optical resolution.
J Membr Sci 108:171175
and DNA have been used as chiral selectors. The
membranes added with these chiral selectors
showed the separation factor of 1.12.7 toward
amino acids (Higuchi et al. 2010).
Enantioselectivity

Mohamad Hekarl Uzir

Molecular Imprinting Membranes
School of Chemical Engineering, Universiti Sains
(MIMs)
Malaysia, Penang, Malaysia
Molecular imprinting membranes are fabricated
by incorporating the template molecules into the
Enantioselectivity is the preferential formation of
membranes and then removing the template mol-
a chemical reaction (mainly with metal complexes
ecules. The formed cavities in the membranes
catalysts) of one enantiomer compound over the
show the specic afnity with the template mole-
other (McNaught and Wilkinson 1997). The
cules and their analogue (Yoshikawa et al. 1995).
extent of enantiomeric reactions is determined
Although MIMs currently show low enantios-
by the percentage enantiomeric excess (% e.e)
electivity, this method has the potential of higher
given by;
enantioselectivity (Xie et al. 2008).
Solid enantioselective membranes can be
SR
divided into two classes: diffusion-selective mem- % e:e  100
SR
branes and sorption-selective membranes (van der
Ent et al. 2001; Xie et al. 2008). A diffusion- References
selective membrane is dened as a membrane
with no specic chiral selectors for the chiral McNaught AD, Wilkinson A (Eds.), (1997) IUPAC - Com-
interaction but consists of a chiral polymer. Dif- pendium of Chemical Terminology, Blackwell Science
fusion selectivity is caused by the chiral discrim- Ltd., Oxford, England, UK
ination during diffusion. On the other hand, in a
sorption-selective membrane, chiral selectors are
embedded in a polymer matrix. To reach perme-
ation selectivity in sorption-selective membranes, Enantiospecificity
the selectively adsorbed population has to be
mobile. An electrical potential is sometimes used Mohamad Hekarl Uzir
for the purpose. School of Chemical Engineering, Universiti Sains
Malaysia, Penang, Malaysia

References
Enantiospecicity is the ability of an enzyme
Higuchi A, Tamai M, Ko Y, Tagawa Y, Wu Y, Freeman B, to convert a racemic mixture into a particular
Bing J, Chang Y, Ling Q (2010) Polymeric membranes enantiomer. The degree of specicity is interre-
for chiral separation of pharmaceuticals and chemicals. lated with that of selectivity, which equation
Polym Rev 50:113143
suggested by Lopez and coworkers (Lopez
van der Ent EM, vant Riet K, Keurentjes JTF, van der Padt
A (2001) Design criteria for dense permeation-selective et al. 1990):
membranes for enantiomer separations. J Membr Sci
185:207221 "  1  0:5 #2
Xie R, Chu L, Deng J (2008) Membranes and membrane tanh F=E0:5  E =F
Eo E 2
processes for chiral resolution. Chem Soc Rev tanhF1  F1
37:12431263
Encapsulation 703

where Complex coacervation: Coacervation caused

by the interaction of two oppositely charged
 

ln 1  c 1 eep macromolecules.
E  

Internal phase separation: Phase separation

ln 1  c 1  eep
and
 
vobs R 2
F molecules dispersed in an aqueous solution.
Deff So 3
and c is the conversion of the particular
reaction (Tsai and Dordick 1996). If the calculated
intrinsic enantioselectivity is extremely high,
therefore, the reaction can be considered as
enantiospecic.
References
Lopez JL, Wald SA, Matson SL, Quinn JA
(1990) Multiphase membrane reactors for separating
stereoisomers. Ann N Y Acad Sci 613(Enzyme Engi-
neering 10):155166
Tsai S-W, Dordick JS (1996) Extraordinary enantiospe-
cicity of lipase catalysis in organic media induced by
purication and catalyst engineering. Biotechnol
Bioeng 52(2):296300
Encapsulation
Goran T. Vladisavljevi and Richard G. Holdich
Department of Chemical Engineering,
Loughborough University, Loughborough,
Leicestershire, UK
Synonyms
Encapsulation: entrapping, enclosing, enveloping;
Amphiphilic substances: Amphiphiles
Definitions
Encapsulation: Coating or entrapping of active
ingredient inside a solid shell or within a liquid
or solid matrix of another material.
within emulsion droplets consisted of a mixture
of polymer, good solvent and poor solvent, usu-
ally triggered by removal of good solvent.
Micelles: Spherical aggregates of surfactant
Liposomes: Spherical vesicles whose shells
E
consist of single or multiple concentric bilayers
resulting from the self-assembly of phospholipids
in an aqueous solution.
Colloidosomes: Shperical vesicles whose shells
consist of coagulated or fused colloid particles.
Polymersomes: Shperical vesicles whose
shells consist of amphiphilic block copolymers.
Amphiphilic molecules: Surface active mole-
cules made up of two parts, a polar or electrically
charged hydrophilic part and a hydrophobic part,
most often an alkyl chain.
Polycondensation: A polymerization in which
the growth of polymer chains proceeds by con-
densation reactions between molecules of all
degrees of polymerization.
Layer-by-layer polyelectrolyte deposition: A
thin lm fabrication technique based on deposit-
ing alternating layers of oppositely charged poly-
electrolytes with wash steps in between.
Encapsulation is a process of enclosing or
entrapping a core material (liquid, gas, solid par-
ticles, cells, dissolved active ingredients, etc.)
inside a solid shell or within a solid or liquid
matrix for the purpose of controlled or triggered
release, immobilization, isolation, or protection of
the encapsulated material. The material being
encapsulated is called the core material, and the
carrier material used for envelopment or entrap-
ment is called the shell material. Typical examples
of core materials are ink or dye for carbonless
copy papers, liquid crystals for microparticle-
based displays, phase-change material for smart
textiles, high-molecular-weight gases for ultra-
sound contrast imaging, genetic material for
in vitro compartmentalization, active food ingre-
dients for functional food products, enzymes for
biocatalytic reactors, drugs, pesticides, fra-
grances, antimicrobial agents, etc.
704
a Core/shell b Matrix type
c Multiple cores d Multiple shells
Encapsulation, Fig. 1 Schematic diagrams of capsules
with different morphologies
Encapsulation efciency (EE) is dened as the
percentage of core material incorporated into the
microcapsules relative to the total amount of the
core material added during encapsulation process:
EE = (mE/mT) 100 %, where mE is the mass of the
core material incorporated and mT is the total mass
of the core material added. Loading capacity
refers to the percentage of core material incorpo-
rated within the microcapsules relative to the total
mass of the microcapsules (i.e., core + shell
material).
Two main types of capsules can be distin-
guished, core/shell (reservoir) type and matrix
type. In the core/shell capsule (Fig. 1a), the shell
material completely surrounds and contains an
internal core material (the internal phase). The
strategies used for formation of shell are spray
coating, complex coacervation, polymer precipi-
tation by internal phase separation, interfacial
reaction that may include polycondensation or
cross-linking, and layer-by-layer polyelectrolyte
deposition (Yow and Routh 2006). The core mate-
rial can be released from core/shell capsules by
simple molecular diffusion through the shell or by
Encapsulation
deliberately compromising the integrity of the
shell, e.g., by exposing the microcapsule to envi-
ronmental stresses such as mechanical forces,
change of pH, temperature, or ionic strength, or
by chemical or biochemical degradation of the
shell. A special class of core/shell capsules are
micelles and vesicles (liposomes, polymersomes,
and colloidosomes), formed by self-assembly of
amphiphilic molecules (phospholipids and
diblock copolymers) or particles (Dinsmore
et al. 2002). Micelles are formed spontaneously
when amphiphiles are dispersed in a polar solvent
at concentrations that exceed a critical level,
known as the critical micelle concentration
(CMC). Micelles containing solubilized materials
are referred to as microemulsions. A difference
between micelles and vesicles is that vesicles are
not a thermodynamically stable state of amphi-
philes and do not form spontaneously, e.g., with-
out input of external energy (Tadros 1993).
In the matrix-type capsule (Fig. 1b) the core
material is distributed uniformly throughout a
matrix of shell material. The most common
release pattern from matrix-type capsules is rst
order in which the release rate decreases exponen-
tially with time until the active ingredient is
exhausted. Typical matrix-type capsules are mul-
tiple emulsions, hydrogel particles, solid lipid
particles, polymeric particles, etc. Hybrid struc-
tures consisting of a number of hierarchically
assembled homogenous phases may be
engineered that allow for even ner control over
the functionality of microcapsules (Fig. 1c, d).
References
Dinsmore AD, Hsu MF, Nikolaides MG, Marquez M,
Bausch AR, Weitz DA (2002) Colloidosomes: selec-
tively permeable capsules composed of colloidal parti-
cles. Science 298:10061009
Tadros TF (1993) Industrial applications of dispersions.
Adv Colloid Interface Sci 46:147
Yow HN, Routh AF (2006) Formation of liquid
corepolymer shell microcapsules. Soft Matter
2:940949
Encapsulation Application
Encapsulation Application
Goran T. Vladisavljevic
Department of Chemical Engineering,
Loughborough University, Loughborough,
Leicestershire, UK
Synonyms
Bichromal particles synonym: Two-colored
particles; Microencapsulation synonym:
Microentrapment
Definitions
Carbonless Copy Paper - Paper coated on the back
side with colorless dye or ink capsules, that burst
under the pressure of writing or typing and react
with colorless clay particles coated on the upper
surface of the second sheet.; Phase Change Mate-
rial - A substance with a high heat of fusion that
absorb or release a high amount of energy during
melting of freezing, thus acting as a thermal
energy storage; Electrophoretic display - a display
that forms images by rearranging charged pigment
particles with an applied electric eld.
Microencapsulation can be done:
1. To protect the encapsulated material against
oxidation or deactivation due to reactions
with reactive species from the environment.
2. To mask the organoleptic properties like color,
taste, and odor of the actives.
3. To achieve controlled/triggered/targeted
release.
4. For safe handling of toxic materials.
5. To achieve in vitro compartmentalization or
immobilization of biological materials and
catalysts.
Microencapsulated materials are utilized in
agriculture, pharmaceuticals, foods, cosmetics
705
and fragrances, textiles, paper, paints, coatings
and adhesives, toner applications, and many
other industries.
Carbonless copy paper developed by Green
and Schleicher in the 1950s was the rst commer-
cial product to employ microcapsules. A coating
of microencapsulated colorless ink is applied to
the top sheet of the paper, and a developer is
applied to the subsequent sheet. When pressure
is applied by writing, the capsules break and the
E
ink reacts with the developer to produce the dark
color of the copy. Paper-like displays with low
power consumption such as rotating bichromal
microspheres system and microencapsulated elec-
trophoretic system are other examples of commer-
cial applications of microencapsulated ink
(Yoshizawa 2004). In the rotating bichromal sys-
tem (Gyricon), bichromal capsules with oppo-
sitely charged hemispheres are free to rotate
within oil-lled cavities. In the microencapsulated
electrophoretic display system (E ink), oppositely
charged black and white particles move under an
applied electric eld in a clear liquid encapsulated
within a transparent capsule.
Todays textile industry makes use of
microencapsulated materials to enhance the
properties of nished goods. One application
increasingly utilized is the incorporation of
microencapsulated phase change materials
(PCMs), such as parafn wax. Phase change
materials absorb and release heat in response to
changes in environmental temperatures. When
temperatures rise, the phase change material
melts, absorbing excess heat, and feels cool. Con-
versely, as temperatures fall, the PCM releases
heat as it solidies, and feels warm. Microencap-
sulation is also used in thermochromic and pho-
tochromic fabrics, which change color with
changes in temperature or light, insect-repellent
fabrics, which ward off mosquitoes, and scented
fabrics, which release fragrance (Nelson 2002).
Pesticides are encapsulated to be released over
time, allowing farmers to apply the pesticides less
often rather than requiring very highly concen-
trated and perhaps toxic initial applications
706
followed by repeated applications to combat the
loss of efcacy due to leaching, evaporation, and
degradation.
Ingredients in foods are encapsulated for sev-
eral reasons (Gouin 2004). Most avorings are
volatile; therefore, encapsulation of these compo-
nents extends the shelf life of products by
retaining the food avors within that would oth-
erwise evaporate out and be lost. Some ingredi-
ents are encapsulated to mask taste, such as
nutrients added to fortify a product without
compromising the products intended taste. Alter-
natively, avors are sometimes encapsulated to
last longer, as in chewing gum. Some food ingre-
dients must be encapsulated to be protected from
oxidation or other degradation reactions caused
by exposure to light, moisture, or oxygen. Micro-
encapsulation preserves lactic acid bacteria, both
starters and probiotics, in food and during the
passage through the gastrointestinal tract, and
may contribute to the development of new func-
tional foods.
Many drug formulations for oral, intravenous,
ocular, and subcutaneous administration are
microencapsulated to achieve controlled,
targeted, or triggered release of active ingredients.
Aspirin, for example, can cause peptic ulcers and
bleeding if doses are introduced all at once.
Microencapsulation of cells and enzymes is
used to improve efciency of bioreactors since
very high volumetric productivity can be
achieved; encapsulated biocatalysts typically
have greater thermal and operational stability
and downstream processing is simplied, since
the encapsulated biocatalyst can easily be recov-
ered and reused. In molecular biology, single-cell
encapsulation is used to achieve high-throughput
screening in directed evolution experiments.
References
Gouin S (2004) Microencapsulation: industrial appraisal of
existing technologies and trends. Trends Food Sci
Technol 15:330347
Nelson G (2002) Application of microencapsulation in
textiles. Int J Pharm 242:5562
Yoshizawa H (2004) Trends in microencapsulation
research. KONA 22:2331
Encapsulation Efficiency
Encapsulation Efficiency
Emma Piacentini
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, Rende,
Italy
The encapsulation efciency (EE%) is dened by
the concentration of the incorporated material
(such as active ingredients, drugs, fragrances, pro-
teins, pesticides, antimicrobial agents, etc.)
detected in the formulation over the initial con-
centration used to make the formulation.
Encapsulation efciency (EE %) was calcu-
lated using below formula:
EE % Wt =Wi  100%
where Wt is the total amount of the incorporated
material and Wi is the total quantity of incorpo-
rated material added initially during the prepara-
tion. Wt and Wi can be determined using
spectroscopic or chromatographic method. If the
capsule shell material is a polymer, it can be
dissolved in the solvent, and the incorporated
molecule will get soluble and it can be quantied.
If the incorporated molecule is not soluble in that
solvent, it can be extracted by adding the capsules
in a liquid in which the target molecule is soluble
(also by multiple extraction). If the core material is
a liquid (such as emulsions), the amount of the
encapsulated material can be evaluated after
induced separation of the liquid dispersed phase
and liquid continuous phase (i.e., simple emul-
sions) or in the outer liquid phase (i.e., W2 in
water-in-oil-in-water (W1/O/W2) emulsions).
The amount of water retained within the oil drop-
lets during emulsication is also signicant for
double emulsion. The methods used in this partic-
ular case enclose the measure of the outer water
phase conductivity by differential scanning calo-
rimetry (DSC) (Schuch et al. 2013).
The encapsulation efciency can be inuenced
by (i) the partition coefcient of the target mole-
cule in the solvents used in the preparation of the
formulation, (ii) the method used to carry out the
Encapsulation Techniques 707

encapsulation process (temperature, pH, mechan- Encapsulation Techniques, Table 1 Classification of

ical stress), and (iii) the size distribution of the dispersion techniques used in encapsulation processes
capsules (Jyothi et al. 2010). Liquid/air dispersion Liquid/liquid dispersion
Atomization Emulsication
Pressure nozzle High pressure
References homogenizers
Two-uid nozzle Ultrasound homogenizers
Jyothi NVN, Prasanna PM, Sakarkar SN, Prabha KS, Spinning disc Static mixers
Ramaiah PS, Srawan GY (2010) Microencapsulation Dripping/jet breakup Rotor/stator devices
techniques, factors inuencing encapsulation ef- Simple dripping Microuidic devices
ciency. J Microencapsul 27:187197 Electrostatic Membrane emulsication E
Schuch A, Khler K, Schuchmann HP (2013) Differential extrusion
scanning calorimetry (DSC) in multiple W/O/W emul-
Coaxial air/liquid Microchannel
sions, a method to characterize the stability of inner
ow emulsication
droplets. J Therm Anal Calorim 111:18811890
Jet cutting Inkjet printing
Centrifugal nozzle Micellization
Vibrating nozzle

Encapsulation Techniques
Encapsulation Techniques, Table 2 Common methods
Goran T. Vladisavljevic of solid shell/matrix formation in encapsulation processes
Department of Chemical Engineering, Mechanical/
Loughborough University, Loughborough, thermal Physicochemical Chemical
Leicestershire, UK Cooling Solvent removal Suspension
polymerization
Freezing Evaporation or One stage
drying (direct)
The encapsulation technique of choice depends on
Two stage
the type and physical properties of the core and (droplet swelling)
shell material. The chosen encapsulation tech- Pan coating Liquid Interfacial
nique should give a high encapsulation efciency extraction polycondensation
and loading capacity of actives, capsules should Fluidized Layer-by-layer Sol-gel chemistry
not exhibit aggregation or adherence, capsules bed coating deposition
Top spray Self-assembly
should have a narrow particle size distribution
Bottom Simple/complex
without tails, threads, or dents on the surface, spray coacervation
and the process should be suitable for industrial Tangential Ionotropic
scale production. spray gelation
Depending on the initial physical state of the Wurster Internal phase
core phase, two different fabrication routes can be process separation
distinguished: (i) coating solid particles by shell-
forming material in a uidized bed or pan coater
and (ii) dispersing a capsule-forming material in evaporation, cooling, or cross-linking in a hard-
the form of droplets in another immiscible liquid ening bath. Emulsication routes involve emulsi-
or air, followed by droplet solidication. There is cation of a solution or suspension of actives,
a variety of atomization and dripping processes by followed by shell/matrix formation by internal
which a liquid phase can be dispersed in another gelation, polymerization, layer-by-layer electro-
immiscible uid (Table 1). static deposition, internal phase separation, coac-
Depending on the chemical composition of the ervation, etc. (Table 2).
shell-forming material, solidication of air Hydrogel capsules contain a hydrophilic active
suspended droplets can be achieved by solvent entrapped within a hydrophilic polymer network
708
that can absorb and hold large amount of water.
A gel network can be formed by chemical gelation
(polymerization by free radical processes or via
condensation) or by physical gelation, which can
involve heating (heat-setting gels), cooling (cold-
setting gels), or the addition of multivalent coun-
terions (ionotropic gelation). In the internal
ionotropic gelation, the droplets of W/O emulsion
contain a gel-forming polymer (e.g., alginate) and
a cross-linking agent in a nondissociated form
(e.g., calcium carbonate), whereas the continuous
oil phase contains a species (e.g., hydrogen ions)
that diffuses into the droplets and triggers the
release of cross-linking agent in its active form
and subsequent gelation. In the external
ionotropic gelation, the droplets initially contain
only a gel-forming polymer, and cross-linking
occurs in a hardening bath (Zhang et al. 2007).
Coacervation involves the phase separation of
one or more polymers from the initial solution and
the subsequent deposition of the newly formed
coacervate phase around the active ingredient
suspended or emulsied in the same reaction
media. In simple coacervation, phase separation
is achieved by addition of desolvating agent
(alcohol or salt) or by change in temperature or
pH, whereas complex coacervation involves reac-
tion between two oppositely charged polymers.
The three basic steps in coacervation are
(i) phase separation in a suspension or emulsion
of active ingredient which leads to a three-phase
system consisting of a polymer-rich liquid
phase (coacervate phase), a polymer-lean liquid,
and a solid or liquid phase containing active
ingredient; (ii) deposition of the coacervate
phase onto the dispersed particles or droplets;
and (iii) hardening of the coating (Zuidam and
Shimoni 2010).
Solid lipid microparticles contain the active
ingredient entrapped within a high melting point
lipid, such as fatty alcohols, fatty acids, fatty acid
esters of glycerol, hydrogenated fatty acid esters,
waxes, etc. Solid lipid microparticles can be fab-
ricated by a temperature-controlled emulsication
of high melting point lipids followed by cooling
or by emulsication/solvent evaporation method.
In the latter case, a high melting point lipid is
dissolved in an organic solvent, and the mixture
Encapsulation: Entrapping, Enclosing, Enveloping
is emulsied with an aqueous phase at room tem-
perature. The solid particles are then formed by
evaporation of the organic solvent. Hydrophilic
actives can be encapsulated by forming a W/O/W
emulsion prior to solvent evaporation or cooling
(Jaspart et al. 2005).
Liposomes are usually prepared using two
approaches: (i) hydration of dry lipid lms with
an aqueous solution of actives resulting in forma-
tion of large multilamellar vesicles (MLV), which
is then followed by size reduction of MLVs by
sonication, microuidization, repetitive freezing
and thawing, or extrusion through track-etch
polycarbonate membranes, and (ii) mixing a
nonaqueous lipid solution with an aqueous solu-
tion (Walde and Ichikawa 2001).
References
Jaspart S, Piel G, Delattre L, Evrard B (2005) Solid lipid
microparticles: formulation, preparation, characterisa-
tion, drug release and applications. Expert Opin Drug
Deliv 2:113
Walde P, Ichikawa S (2001) Enzymes inside lipid vesicles:
preparation, reactivity and applications. Biomol Eng
18:143177
Zhang H, Tumarkin E, Sullan RMA, Walker GC,
Kumacheva E (2007) Exploring microuidic routes to
microgels of biological polymers. Macromol Rapid
Commun 28:527538
Zuidam NJ, Shimoni E (2010) Overview of microencap-
sulates for use in food products or processes and
methods to make them. In: Zuidam NJ, Nedovi VA
(eds) Encapsulation technologies for active food ingre-
dients and food processing. Springer, New York,
pp 329
Encapsulation: Entrapping,
Enclosing, Enveloping
Encapsulation
Engineered Organs
Bioarticial Organs, Membrane Operations of
Enhanced Oil Recovery (EOR) 709

hydrocarbon gaseous phase in order to have it

Engineered Organs and Tissue
Bioarticial Organs and Tissue
Enhanced Oil Recovery (EOR)
Arnaud Baudot
Physics and Analysis Division, IFP Energies
Nouvelles, Solaize, France
Enhanced oil recovery (EOR) aims at increasing
the oil elds recovery yield, thanks to high-
pressure injection of water or carbon dioxide.
Injection of pressurized carbon dioxide leads to
the maintenance of high pressures in the reservoir
and to an improvement of oil displacement,
thanks to several physical effects: decrease of oil
viscosity due to carbon dioxide solubilization,
stripping effects, and modication of multiphase
equilibria due to CO2 solubilization in the reser-
voir aqueous phase. When the oil reaches the
surface, carbon dioxide is purged with the associ-
ated gas. Since the volumes of concerned carbon
dioxide are very large from 140 to 280 Nm3 par
extracted barrel (Mazur and Chan 1982) it is
necessary to separate carbon dioxide from the
recycled to the reservoir (after pressurization).
Since the quantity of CO2 dissolved in oil varies
over a large range of values during the whole
production of the reservoir (levels from 40 % up
to 90 % can be observed after a few years of
production (Cooley and Dethloff 1985)), it is rather
difcult to design a cost-effective CO2 removal
unit that could operate during the entire life of the
reservoir. Therefore, modular CO2 removal units
E
such as membrane operations offer much exibility
for such an operation (Table 1).
The rst large-scale EOR project operating
membranes has been carried out in the Sacroc oil
eld located in Western Texas. Carbon dioxide
injection was launched in 1972 (at a ow
range up to 240,000 Nm3/h). Three CO2 recovery
units were initially installed: two hot potassium
carbonate-based absorption units (operated by
Sun Explo with a 190,000 Nm3/h capacity leading
to a reduction of carbon dioxide from 24 % to
0.5 % and Chevron, with a 54,000 Nm3/h lower-
ing CO2 content down to 1 %) and an amine
(MEA)-based absorption unit (operated by
Monsanto, with a 20,000 Nm3/h capacity). At
the end of the 1970s, realizing that the level of
CO2 was raising at a higher rate than expected,
Chevron contacted Cynara in order to install and
operate two gas permeation units upstream of the
hot potassium carbonate absorption columns. The

Enhanced Oil Recovery (EOR), Table 1 Comparison of relative investment costs (CAPEX) and operating costs
(OPEX) of membrane-based, solvent-based, and hybrid processes for carbon dioxide capture (EOR applications)
CAPEX
rf. Cryo.a Mem.
Operating Study realized OPEX KCO3
conditions by Year rf. + Mem. Mem. +DEA DEA Cryo.a TEA chaud
175.000 m3/h Amoco 1982 47 M$ 1 2.2 1.56 1.48
90 % CO2, (Goddin 20.4 M$/a 1 1.76 1.39 1.12
18 bar 1982)
118.000 m3/h Permea 1983 16.1 M$ 1.50 1 1.31
80 % CO2 (Boustany 6.5 M$/a 1.31 1 1.82
et al. 1983)
190.000 m3/h Fluor 1984 1 0.63 0.63b
40 % CO2 Engineering 1 0.56 0.68b
Schendel and
Seymour
1985)
a
Cryo.: cryogenic distillation (Ryan-Holmes process (Kohl and Nielsen 1997))
b
Hot potassium carbonate + membrane
710 Enhanced Oil Recovery (EOR)

Enhanced oil recovery 1 2 3 4 5 6

(Kvaerner Membrane Systems)
3
Flow rate (103 Nm3/h) 26.5 7.4 18.9 11.2 15.3 3.8
Pressure (bar) 16 25 20 26 5 1
5 6 2
CO2 70 10 93.4 35.4 95.2 86.2
CH4 9.6 26.9 2.9 20 2.0 6.7
C2 6.3 10.0 1.0 14.0 0.7 2.4 1
Composition (% mol.) C3 5.6 18.4 0.6 12.9 0.4 1.5
i-C4 2.5 8.6 - 6.0 - 0.2
n-C4 1.3 4.3 - 3.0 - 0.1
H2S 0.6 0.01 0.8 0.1 0.9 0.4 4
N2 4.1 11.8 1.1 8.6 0.7 2.5

CH4 (C2+) recovery yield = 77,8 % (73 %)

Enhanced Oil Recovery (EOR), Fig. 1 EOR example of permeation application (Spillman 1989)

treatment capacities of the membrane units were, Medal:

respectively, 60,000 Nm3/h at 35 bar feed pressure
prior to the Sun unit and 25,000 Nm3/h at 33 bar
feed pressure prior to the Chevron unit. Cynara
chose to operate a single-stage conguration, the
membrane module being installed in parallel. The
membrane operation proved to be highly exible
and reliable, as the membrane modules remained
in operation twice longer than the expected life-
time (more than 5 years instead of 23 years)
without any selectivity decrease. A slight decrease
in membrane permeability has nevertheless been
observed throughout the operation, and it was
necessary to add more modules in order to main-
tain the production level of the membrane opera-
tion (Marquez and Hamaker 1986).
Since then, other membrane companies have
seen their products involved in other EOR
projects:
Kvaerner membrane systems (Chapel
et al. 1999):
Dallas Production Inc. (Texas) treated
200,000 Nm3 of gases containing up to
25 % of carbon dioxide in 1994 during a
feasibility study that lasted for 18 months.
After this test, the membrane unit was in
operation treating 1200 Nm3/h.
Hydrocarbon Operating, Inc. (Texas)
processed 590 Nm3/h at 51 bar feed pres-
sure in 1994 on a pilot skid composed of
two tubular membrane modules.
A Medal membrane unit was operated at the
need of the 1990s to process 14,200 Nm3/h
at 56 bar, 48 % CO2, reducing the retentate
CO2 concentration down to 6 %.
Cynara (Kohl and Nielsen 1995):
Amoco, Texas (1994): Cynara membranes
were used to process 35,000 up to
120,000 Nm3/h of gas containing 80 % CO2.
Mobil, Salt Creek (1992): Cynara membranes
were used to process 76,000 up to
120,000 Nm3/h of containing 70 % CO2.
Shell, Texas: Cynara membranes were used to
process 13,000 Nm3/h of gas containing
70 % CO2 (Fig. 1).
References
Boustany K, Narayan RS, Stookey DJ (1983) Economics
of removal of carbon dioxide from hydrocarbon gas
mixtures. In: Abstracts 62nd Annual Gas Processors
Association, San Francisco, CA, pp 146149
Chapel DG, Mariz CL, Ernest J (1999) Recovery of CO2
from ue gases: commercial trends. In: Oral Presenta-
tion Canadian Society of Chemical Engineers Annual
Meeting, Saskatoon, Sakatchewan, Canada.
Cooley TE, Dethloff WL (1985) Field-tests show mem-
brane processing attractive. Chem Eng Prog 81:4550
Goddin CS (1982) Comparison of processes for treating
gases with high CO2 content. In: Abstracts 61st Annual
Gas Processors Association Convention, Dallas, TX,
pp 6068
Kohl A, Nielsen R (1997) Gas purication, 5th edn. Gulf
Publishing Co, Houston, pp 12381295
Environmentally Friendly Solvents and Diluents
Marquez JJ, Hamaker RJ (1986) Development of mem-
brane performances during SACROC operations. In:
Oral presentation at AIChE Spring National Meeting
and Petro. Expo86. New Orleans, LA
Mazur WH, Chan MC (1982) Membranes for natural-gas
sweetening and CO2 enrichment. Chem Eng Prog
78:3843
Schendel RL, Seymour JD (1985) Take care in picking
membranes to combine with other processes for CO2
removal. Oil Gas J 83:8486
Spillman RW (1989) Economics of gas separation mem-
branes. Chem Eng Prog 85:4162
Environmentally Friendly Solvents
and Diluents
Zhaoliang Cui
State Key Laboratory of Materials-Oriented
Chemical Engineering, College of Chemistry and
Chemical Engineering, Nanjing Tech University,
Nanjing, China
Non-solvent-induced phase separation (NIPS)
and thermally induced phase separation (TIPS)
are two major methods for polymeric porous
membrane preparation. Solvents and diluents
play important roles in NIPS and TIPS processes,
respectively, inuencing the nal membrane
properties during polymeric membrane formation.
Applicable solvents for the NIPS process are N,
N-dimethyl acetamide (DMAc), N,N-dimethyl
formamide (DMF), hexamethyl phosphoramide
(HMPA), N-methyl pyrrolidone (NMP),
tetramethylurea (TMU), triethyl phosphate
(TEP), trimethyl phosphate (TMP), acetone
(Ac), and tetrahydrofuran (THF), while applicable
diluents for the TIPS process are dimethyl phthal-
ate (DMP), diethyl phthalate (DEP), dibutyl
phthalate (DBP), dihexyl phthalate (DHP), ethyl
acetoacetate (EAA), propylene glycol carbonate
(PGC), diphenyl ketone (DPK), diphenyl carbon-
ate (DPC), cyclohexanone, camphor, and
butyrolactone. Most of the above solvents/dilu-
ents are toxic, making the work atmosphere
detrimental for workers and environment. Since
711
many membrane processes are employed with
the objective of environmentally improving the
process industry, toxic solvents/diluents reduce
their contributions to environmental protection.
Thus, nding more environmentally friendly
solvents/diluents is becoming an important
topic in the membrane preparation eld (Cui
et al. 2013a).
Recently, efforts have been done to develop
environmentally friendly solvents for NIPS pro-
E
cess and diluents for TIPS process. These sol-
vents/diluents should yield the membranes
promising properties and performances without
discharging toxicity to environment. It is much
better if the solvents/diluents can be recovered
easily. Dimethyl sulfoxide (DMSO) and glycerin
triacetate (GTA), which can be employed for
NIPS and TIPS process, are relatively less
toxic. They have been used for polymeric mem-
brane preparation. Acetyl tributyl citrate (ATBC)
(Cui et al. 2013b), which is more environmentally
friendly, was introduced to prepare poly(vinyli-
dene uoride) (PVDF) membranes via TIPS pro-
cess. Dimethyl sulfone (DMSO2) (Liang
et al. 2013) was used as a universal crystallizable
diluent to fabricate polar polymer membranes
(PVDF, polyacrylonitrile (PAN) and cellulose
acetate (CA)) via TIPS method. This diluent is
easy to recover because of its crystallizable prop-
erty. The membranes fabricated by above diluents
presented promising mechanical properties and
water permeability. Ionic liquid is a type of
green solvents, which probably can be used for
polymeric membrane preparations. CA mem-
branes (Xing et al. 2010) have been formed via
phase inversion employing 1-butyl-3-
methylimidazolium thiocyanate ([BMIM]SCN)
as the solvent and were recycled. The morphol-
ogy, porosity, and pure water permeability of the
CA membranes fabricated by reused solvents
were quite comparable to the CA membranes
produced by new solvents.
Researchers started to pay attention to
develop environmentally friendly solvents/dil-
uents, and preliminary progress has been
made. However, this is far from the require-
ments, and more efforts are needed to contrib-
ute to this eld.
712
References
Cui Z, Drioli E, Lee YM (2013a) Recent progress in
uoropolymers for membranes. Prog Polym Sci
39(1):164198. doi:10.1016/j.progpolymsci.2013.
07.008
Cui Z, Hassankiadeh NT, Lee SY, Lee JM, Woo KT,
Sanguineti A, Arcella V, Lee YM, Drioli E (2013b)
Poly (vinylidene uoride) membrane preparation with
an environmental diluent via thermally induced phase
separation. J Membr Sci 444:223236
Liang HQ, Wu QY, Wan LS, Huang XJ, Xu ZK
(2013) Polar polymer membranes via thermally
induced phase separation using a universal crystalliz-
able diluent. J Membr Sci 446:482491. doi:10.1016/j.
memsci.2013.07.008
Xing DY, Peng N, Chung TS (2010) Formation of cellulose
acetate membranes via phase inversion using ionic
liquid, [BMIM]SCN, as the solvent. Ind Eng Chem
Res 49:87618769
Environmentally Responsive
Membranes
Magnetically Responsive Membranes
Enzymatic (Peroxidase) Membrane
Bioreactor
Mara. T. Moreira1, Gemma Eibes2,
Thelmo Lu-Chau2, Roberto Taboada-Puig2,
Adriana Arca-Ramos2, Gumersindo Feijoo2,
Juan M. Lema2 and Lucia Lloret3
1
Department of Chemical Engineering, School of
Engineering, University of Santiago de
Compostela, Santiago de Compostela, Spain
2
Department of Chemical Engineering, Institute
of Technology, University of Santiago de
Compostela, Santiago de Compostela, Spain
3
Chemical and Environmental Engineering
Department, Federico Santa Maria Technical
University, Santiago, Chile
Enzymatic (peroxidase) membrane bioreactor is
an enzymatic reactor coupled to a membrane in a
number of congurations that allows the
Environmentally Responsive Membranes
separation of the enzyme and its reuse in the
enzymatic process.
This technology is especially suitable in con-
tinuous operation by ensuring the recovery and
reusability of the enzymes, allowing the
minimization of large consumptions of biocata-
lyst. Various enzymatic membrane bioreactor
congurations are possible, i.e., enzyme
suspended in solution in a reactor connected
with a membrane unit, immobilized enzyme
within the membrane matrix itself, or entrapped
enzyme in gel or microcapsules.
Among these setups, the retention of the
enzyme by an ultraltration membrane is a very
interesting alternative to overcome the washing
out of the catalyst with the treated efuent but
also to avoid the enzyme immobilization which
is usually related with high costs, complex pro-
cedures, and loss of enzyme catalytic activity. In
this system the enzyme is added into a reactor tank
which is coupled with an ultraltration membrane
to enable the retention of the free enzyme and its
recycling back to the reaction vessel. Thereby, by
using an enzymatic membrane reactor, it is possi-
ble to separate the biocatalyst from products
and/or other substrates by a semipermeable mem-
brane that creates a selective physical/chemical
barrier (Fig. 1).
This type of bioreactor offers important bene-
ts: high enzyme loads, prolonged enzyme activ-
ity, high ow rates, reduced energy requirements,
straightforward operation, and scale-up, and also,
fresh enzyme can be easily added to maintain
constant enzymatic levels. Indeed, this system
has been successfully operated for the continuous
application of peroxidases (Lpez et al. 2004) and
laccases (Lloret et al. 2013). Specically,
peroxidase-based membrane bioreactors were
applied for the transformation of various com-
pounds with bioremediation purposes, for exam-
ple, for the removal of dyes (Orange II) and
estrogenic compounds (estrone, estradiol,
ethinylestradiol, etc.). Orange II was successfully
transformed by manganese peroxidase (MnP) in
an enzymatic membrane bioreactor which
consisted of a 250-mL stirred tank reactor
(Lpez et al. 2004 in Fig. 1) connected to a
polyethersulfone synthetic membrane (Prep/
Enzymatic Membrane Reactor (EMR) 713

MnP
[Fe3+]
H2O2
Mn3+

H2O Mn2+

MnP [2]
H2O2 Products
MnP-I MnP-II
[Fe4+=0 P] [Fe4+=0]
H2O2 Mn2+ Mn3+
Organic acid
Mn2+ E
H2O
Target compounds
MnP-III
[1]

Enzymatic (Peroxidase) Membrane Bioreactor, Fig. 1 Scheme of an enzymatic (peroxidase) membrane reactor

Scale-TFF Millipore) with a molecular weight References

cutoff of 10 kDa (Lloret et al. 2013 in Fig. 1).
Three stock solutions: H2O2 (94312 mM); Mn2+
(33 mM), Orange II (0.1 g/L), and organic acid
(1 mM); and MnP (7,000 U/L, 125225 U/L in the
tank), were fed into the bioreactor by independent
variable speed peristaltic pumps, thus initiating
the catalytic cycle of the enzyme. Under the best
conditions evaluated, high decolorization yield
can be achieved and minimal enzymatic deactiva-
tion, rendering an efciency of 42.5 mg Orange II
oxidized per unit consumed of MnP.
The ndings obtained with the proposed reac-
tor conguration allow its application as a novel
treatment method for contaminated wastewaters.
The simplicity of the operation, which mainly
relies on the control of H2O2 dosage, promotes
the peroxidase membrane bioreactor for further
scale-up applications. The oxidative potential of
the MnP-H2O2-Mn2+ system appears to be gen-
eral enough to be applied for the transformation of
a wide range of compounds. The main require-
ment is that the oxidation potential of a particular
substrate has to be lower than that provided by the
enzymatic cycle, being the main factors affecting
the stoichiometry and kinetics of the process the
MnP activity, dosage rate of H2O2, and concen-
tration of the target compound.
Lloret L, Eibes G, Moreira MT, Feijoo G, Lema JM
(2013) Removal of estrogenic compounds from ltered
secondary wastewater efuent in a continuous enzy-
matic membrane reactor. Identication of transforma-
tion products. Environ Sci Technol 47:45364543
Lpez C, Moreira MT, Feijoo G, Lema JM (2004) Dye
decolourization by manganese peroxidase in an enzy-
matic membrane reactor. Biotechnol Prog 20:7481
Enzymatic Membrane Reactor (EMR)
Lidietta Giorno
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, Rende,
Italy
Synonyms
Enzyme membrane reactor
A general denition of an enzyme membrane
reactor (EMR) is a reactor system where a mem-
brane separation is used to keep larger compo-
nents in the reactor vessel (i.e., enzymes and/or
714
macromolecular substrates), while low-
molecular-weight molecules (i.e., products
and/or inhibitors) are allowed to pass freely
through the membrane, thus leaving the reactor
as permeate (Drioli and Giorno 1999). In this
setup, several advantages of immobilized prepa-
rations, together with easy recovery of deactivated
enzymes and replacement with fresh catalysts are
achieved; inhibitors are continuously removed
from the reaction vessel. The direct and deep
contact between substrates and biocatalysts limits
diffusional resistances, while no activity losses
due to xation to the support occur, thus maxi-
mizing the activity of the biocatalyst. On the other
hand, enzyme stability is not improved.
Both dead-end and continuous stirred tank
reactor (CSTR) ultraltration cells with at mem-
branes can be used as enzymatic reactors.
Performance of dead-end units is largely
affected by the ow dynamics of the system; in
fact, mixing of substrates and catalysts is not fully
accomplished, and concentration polarization
phenomena strongly limit reactor performance.
Continuous stirred tank reactors have been
more widely adopted, both due to the possibility
of concentration polarization control and easy
modeling of enzyme kinetic behavior.
Assuming complete mixing within the reactor
so that enzyme and substrate concentration in the
reactor vessel are uniform, and the latter is equal
to its value in the permeate, substrate mass bal-
ance in molar form can be written as:
Sf  S=t R S, P (1) membrane molecular weight cutoff. It is conven-
where
Sf = feed substrate concentration, ML3
S = substrate concentration, ML3
t = reactor time constant, T
R = reaction rate, MT1 L3
Product steady state mass balance similarly
will be:
P  Pf =t R S, P (2) AE0 = initial enzyme activity, or product mass per
where
Enzymatic Membrane Reactor (EMR)
P = product concentration, ML3
Pf = feed product concentration, ML3
Assuming that substrate conversion obeys the
simple Michaelis-Menten model, substrate steady
state mass balance reduces to:
XSf X=1  X K0M K E V=Q (3)
 
R being expressed as K E S= K0M S .
X Sf  S=Sf = conversion degree
KM0
= enzyme Michaelis-Menten constant, ML3
K = enzyme kinetic constant, T1
E = enzyme concentration, ML3
V = reaction volume, L3
Q = ow rate, L3 T1
The equation in this form is a useful tool to
estimate parameters of reaction kinetics. Instead
of performing nonlinear parameters estimation
procedures, the functional dependence of XSf on
X=1  X can be plotted. The plotshould look
like a stright line whose slope is K0M and
whose intersection with the XSf axis is given by
the point of coordinate (Vmaxt).
Enzyme activity is usually not constant with
time. Physicochemical changes in enzyme struc-
ture, thermal denaturation, and microbial contami-
nation cause enzyme activity to continuously
decrease with time. When enzymes or cells are
compartmentalized in UF cells, biocatalyst
losses can even occur due to the wrong choice of
tional to measure the enzyme stability in terms
of its half-life time (t1/2), that is, the time at
which enzyme activity is reduced to half its initial
value. It can be calculated from the following
equations:
2:303 AE 0:693
Kd log 0 t1=2 (4)
# AE # Kd
Kd = enzyme deactivation constant, T1
# = operation time, T
unit time and reaction volume, M T1
AE# = enzyme activity at time #, M T1
Enzymatic Membrane Reactor (EMR)
Since biotransformations by means of enzymes
are continuous processes, as long as the reactor
working life is longer than the native enzyme half-
life, enzyme activity decay with time must be
taken into account in order to correctly assess
reactor performance. A transient substrate mass
balance on the CST reactor leads to the equation
V dS t=dt Q Sf  S t  Vmax V (5) to accumulate in a thin layer immediately
where
V = reaction volume, L3
S = substrate concentration, ML3
Sf = feed substrate concentration, ML3
Vmax = enzyme reaction rate at saturating sub-
strate concentration, ML3 T1
Q = ow rate, L3 T1
Let us assume that substrate inlet concentration
is much higher than the enzymes apparent
0
Michaelis constant, KM so that enzyme kinetics
is expressed according to zero order kinetics, that
is, R KE Vmax . Enzyme activity decay can
be expressed in terms of the Arrhenius equation:
E Eo exp Kd t (6)
where
E = enzyme concentration, ML3
E0 = initial enzyme concentration, ML3
Kd = enzyme deactivation constant, T1
Equation 5 then takes the form
Sf  S t =t  dS t=dt E = enzyme concentration, ML3
Vmaxo exp Kd t (7)
Integration of the differential Equation 7 leads
to estimate the outlet substrate concentration:
S t Vmaxo exp  t=t  exp Kd t = enzyme macromolecules, integration of Equa-
1=t  Kd Sf
(8)
Estimation of the deactivation constant can be
graphically carried out from Equation 7 plotting
715
lnfSf  S t =t  dS t=dtg vs t. A straight line
is thus obtained whose slope is given by Kd
and the line intersects the vertical axis at the point
of coordinate (ln Vmax).
When the reacting solution is fed to the system,
low-molecular-weight products leave the reactor
permeating the membrane, whereas enzymes are
partially or totally rejected. Then, enzymes tend
upstream from the membrane causing polarization
E
phenomena to occur. The extent to which concen-
tration polarization affects reactor performance
depends on the balance of rejected solutes, e.g.,
enzymes or cells, accumulation due to membrane
rejection and back diffusion to the bulk phase, and
eventually on the ow dynamics of the reacting
vessel.
For macromolecules (like most biocatalysts), if
membrane properties are carefully chosen, mem-
brane rejection is usually very good, while biocat-
alyst back diffusion towards the bulk phase is
extremely slow. The effect of concentration polar-
ization on such reactor performances can then be
signicant.
Applying the thin lm theory to a region
immediately upstream from the membrane results
in the following steady state mass balance
equation:
J E De dE=dx (9)
under the boundary condition (BC)
x ! 1 E Es
where
J = volumetric ux, L3L2T1
ES = enzyme concentration in the bulk liquid
phase, ML3
De = enzyme diffusion coefcient, L2T1
Under the assumption of totally rejected
tion 9 allows one to express the ratio of enzyme
concentration in the bulk solution in the presence
of concentration polarization to its value in
the absence of concentration polarization phe-
nomena as:
716
ES =Eo 1=f1  a a=b exp b  1 g products and/or inhibitors are continuously
(10)
Enzyme concentration at the membranesolution
interface can thus be related to enzyme concentra-
tion in the bulk phase by the following equation:
Ew ES exp b (11)
where the dimensionless parameter b is a measure
of convective mass transfer, J, relative to the over-
all mass transfer, D/d, more generally KS.
The change of enzyme bulk concentration can
be dramatic, with changes in permeate ow rate,
and applied pressure. Changes in enzyme bulk
concentration may induce a large reduction in
reaction rate within the membrane reactor. Under
given stirring conditions, therefore, a critical
value of ow rate and hence of applied pressure
does exist. At ow rates lower than the critical
value, the reactor always attains steady operation
conditions, and correspondingly outlet product
concentration is constant. Beyond the critical
value, concentration polarization phenomena pro-
mote the localization of a large fraction of
enzymes near the membrane surface, seldom lead-
ing to an enzymatic gel formation. Correspond-
ingly, an accelerated deactivation of enzyme
activity is superimposed on reactor performance
thus hindering the attainment of steady state con-
ditions. Experimental evidence suggests that the
contribution of polarized enzymes to overall con-
version can be negligible, due to the consistency
of product concentration in the bulk phase of the
reactor and in the permeate.
When macromolecular substrates are involved
in the transformation under study, concentration
polarization phenomena affect the EMR perfor-
mance more severely. Diffusion limitations of
macromolecular substrates hamper the use
of immobilized enzymes in the hydrolysis of
high-molecular-weight substrates. By selecting
membranes with an appropriate molecular weight
cutoff, both enzyme and substrate are retained in
an EMR in touch with each other, and hydrolysis
Enzymatic Membrane Reactor (EMR)
removed from the system. Soluble enzymes can
then act directly on substrate macromolecules
without diffusion limitations and steric hindrance
imposed by enzyme xation to a solid support.
The stirring features of CST EMRs moreover
assures that substrates and/or inhibitors within
the reactor vessel are maintained at the lowest
possible concentration level. Such reactor cong-
uration is then extremely useful when substrate
inhibited reaction patterns are involved or when
inhibiting species are assumed to exist in the feed
stream.
Dialtration, semicontinuous, and continuous
operational modes can be used.
Operating the reactor in a semicontinuous con-
dition and adding substrate so as to keep its bulk
concentration constant leads to meaningful
changes in reactor performance as compared to
the dialtration mode. Under both operational
mode, permeate ow rate continuously decreases
with time.
When EMRs are operated continuously, feed-
ing a slurry of substrate macromolecules to the
reactor, concentration polarization phenomena
play a dominant role. The presence within the
reaction vessel of contaminants or intermediate
products, which are not fully hydrolyzed by the
enzymatic system under study can lead to mem-
brane fouling or to the formation of a gel layer at
the membrane surface. Under such conditions, the
ltration rate continuously decreases with time,
and it may happen that substrate conversion does
not attain steady state conditions. The addition of
enzymes capable of hydrolyzing such foulants to
low-molecular-weight compounds usually
improves reactor performance, eventually
approaching steady state conditions in terms of
both permeate ow rate and substrate conversion.
In addition, antifouling procedures including suit-
able feed pretreatment or procedures to reduce
concentration polarization can be used.
Equation 11 demonstrates the dependence of
enzyme concentration at the upstream membrane
surface on the ow dynamics of the reaction ves-
sel. Due to the monotonicity of the exponential
Enzymatic Membrane Reactor in Supercritical CO2
function, at given applied pressure operational
conditions improving mass transfer in the bulk
phase (i.e., increasing axial ow rate improves
KS or D/d) diminish concentration polarization.
High stirring speeds usually improve ltering per-
formance of a CST at membrane reactor, albeit at
the expense of partial enzyme deactivation.
Reactor congurations other than dead end or
CSTR/UF cell can offer improvements.
The use of hollow ber ultraltration modules
in cross-ow ltration mode strongly improves
both reactor performance and economics. Capil-
lary membranes are characterized by a favorable
surface to volume ratio; advantages from this fea-
ture are not only related to lower overall plant size
but also to the increase of the surface to price ratio.
Flushing enzyme/substrate solution through UF
module tangentially to the membrane surface at
a high linear velocity reduces the extent of con-
centration polarization avoiding the formation of a
secondary enzymatic gel membrane. Provided
that the volume of the UF module is small relative
to the total volume, and that recirculation ow rate
is much larger than permeate ux, system kinetic
behavior can be modeled in terms of a CST
reactor.
References
Drioli E, Giorno L (1999) Biocatalytic membrane reactors:
application in biotechnology and the pharmaceutical
industry. Taylor & Francis, London
Enzymatic Membrane Reactor
in Supercritical CO2
Gilbert M. Rios
Place Eugene Bataillon, IEM European
Membrane Institute, Montpellier, France
Enzymes are catalysts obtained from nature
(proteins), which work in mild conditions and
717
present very specic activities. They are one of
the main tools of life as it developed since the
origin. Enzymes are divided into six classes,
based on the type of reaction that is catalyzed.
Lipases are important enzymes that belong to the
class of hydrolases; they catalyze hydrolytic reac-
tions. Candida antarctica lipase B (CalB) is one
of the most widely used lipases, because this
enzyme accepts a broad spectrum of different sub-
strates. Most of the time enzymes are immobilized
E
for industrial applications. The main reason to
immobilize enzymes lies in the reduction of
costs by enabling efcient separation, recycling,
and reuse of the expensive enzymes. The choice
for the best immobilization method depends on
the enzyme, the type of reaction, and the reaction
environment.
The use of porous membrane reactor for enzy-
matic catalysis represents from this viewpoint a
breakthrough technology which offers many
advantages as compared to other more classical
systems (immobilization on divided solid parti-
cles in xed, uidized, or moving beds): continu-
ous mode, reduction of product/substrate
inhibition, free enzyme end-products, and the pos-
sibility to set up monophasic or biphasic
systems even if there can be some drawback
related to membrane fouling. The full activity may
be maintained inside the reactor by the rejection of
enzyme molecules (Fig. 1) either freely circulat-
ing (a) or immobilized on/in the membrane (b). In
that case, the membrane is the catalyst media
(functionalization) and the reaction occurs during
membrane crossing. The convective control due
to the application of a low transmembrane pres-
sure (very small thickness of the porous layer: a
few microns) is responsible for the mass transfer
increase. The membrane is a macrosystem
resulting from the assembly of swarms of
microsystems: each pore represents a particular
microreactor.
The main practical use of enzymatic catalysis
in supercritical carbon dioxide (scCO2) has to be
found in producing high-added-value products
since the process remains expensive. Lipases
have proven to be rather stable and active during
718 Enzymatic Membrane Reactor in Supercritical CO2

a S P b S
a b

S E

E S P
E
P P

P
membrane membrane Diffusion convection

Enzymatic Membrane Reactor in Supercritical CO2, Fig. 1 Basic mechanisms

Pressure SCFE + NF process

20 MPa
Retentate
(recycled)
Pure SCF Extraction Membrane
chamber separation

Permeate :
1.0 XCO2 SCF + Dispersed molecules
SCF

Fluidification process Molecules

Retentate Pressure
Viscous
SCF (recycled)
liquid Membrane 20 MPa
injection
separation
chamber

Permeate :
Viscous liquid + Dissolved SCF
SCF
0.2 XCO2

Viscous liquid

Enzymatic Membrane Reactor in Supercritical CO2, Fig. 2 Plant schemas

long-term reactions in scCO2. However, it cannot the possibility of easier separation steps with com-
be stated that performing reactions in scCO2 will plete removal of the solvent (Fig. 2).
always result in a higher activity. This is highly The future perspectives for enzymatic mem-
dependent on the type of reaction, the enzyme, brane reactors in scCO2 can be found in the
and the applied conditions. The main advantage of combination of improving the stability and
CO2, a very stable and nontoxic uid, is therefore activity of the potentially interesting
Enzymatic Ultrafiltration Membranes (Immobilization of Urease and Trypsin)
enzymes other types of enzymes are attractive
for use in scCO2 as well, such as oxygenases,
epoxide hydrolases, aldolases, or decarbo-
xylases and an improved integration of the
reaction and separation sections. Very interest-
ing studies conducted lately on transesteri-
cation reactions with the xed enzyme
conguration (Fig. 1b), either using pure SC
uid solvent containing dissolved substrates or
for transforming oils after the injection of a
small quantity of pressurized CO2 in order to
decrease viscosity, are worth mentioning.
References
Dijkstra ZJ (2006) The potential of enzymatic catalysis in
supercritical uids. PhD thesis, Eindhoven University
of Technology (NL). ISBN-10: 90-386-2698-3/ISBN-
13: 978-90-386-2698-7
Pommier E, Delebecque N, Paolucci-Jeanjean D, Pina M,
Sarrade S, Rios GM (2007) Effect of working condi-
tions on vegetable oil transformation in an enzymatic
reactor combining membrane and supercritical CO2.
J Supercritl Fluids 41(3):380385
Rios GM (2009) Enzymatic membrane reactor. Plenary lec-
ture. PERMEA, Prague. 911 June 2009. http://www.
imc.cas.cz/sympo/permea09/programme_plenary.html
Enzymatic Ultrafiltration Membranes (Immobilization of Urease and Trypsin), Fig. 1 Scheme of layer-by-layer
adsorption of polyelectrolytes on membrane
719
Enzymatic Ultrafiltration Membranes
(Immobilization of Urease
and Trypsin)
Christophe Innocent
Institut Europen des Membranes, ENSCM,
CNRS, Universit de Montpellier, Montpellier,
France
E
The sodium alginate was used as an anionic poly-
electrolyte. The polyethyleneimine was used as a
cationic polyelectrolyte. Trypsin (enzyme which
catalyzed the hydrolysis of peptide bonds in
which the carboxyl groups are contributed by the
lysine and arginine residues) was applied as a
positively charged polyelectrolyte and the urease
(enzyme which catalyzes the hydrolysis of urea to
ammonium and carbon dioxide) as a negatively
charged polyelectrolyte. For adsorption of the
polyelectrolyte layers, the supporting membrane
(polyacrylonitrile-modied membrane negatively
charged) was immersed in the solution of the
cationic polyelectrolyte, rinsed with the buffer
solution to remove excess of polycations on
720
membrane surface, immersed in the solution of
the anionic polyelectrolyte, and rinsed with the
buffer solution again. These steps were repeated
to form multiple polyelectrolyte bilayers based on
the electrostatic layer-by-layer self-assembly
(Fig. 1).
References
Decher G (1997) Fuzzy nanoassemblies: toward layered
polymeric multicomposites. Science 277:12321237
Enzyme Compartmentalization
Rosalinda Mazzei
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, Rende,
Italy
Synonyms
Immobilization of enzymes
In biology enzyme compartmentalization is ef-
ciently carried out by biomembrane or biological
membrane that permits to conne specic func-
tions given by enzymes in a precise space. The
enzymes can be localized inside the delimited
compartments or on the membrane surface.
In eukaryotic cells the corresponding delimited
spaces or compartments are called organelles,
from which the main are the endoplasmic reticu-
lum, Golgi apparatus, nucleus, mitochondria,
lysosomes, endosomes, and peroxisomes. Each
membrane-enclosed organelle contains a specic
set of proteins free or on the membrane surface
that regulates many vital biochemical processes.
For instance, lipid metabolism is catalyzed mostly
by membrane-bound enzymes.
Starting from nature simulation, in biotechnol-
ogy process, enzyme compartmentalization can
be obtained by immobilizing proteins on supports
or delimiting them by support compartments.
Membranes can be optimal supports for enzyme
compartmentalization; in fact they are widely
Enzyme Compartmentalization
used for the production of membrane bioreactors
or biocatalytic membrane reactors (Mazzei
et al. 2010). In particular, asymmetric hollow
ber membrane can be used as efcient support
to compartmentalize enzymes by entrapment into
the sponge membrane layer. The general mem-
brane requirement is that the pores in the dense
layer are small enough to retain enzyme mole-
cules and at the same time large enough to freely
pass substrates and products (Mazzei et al. 2013).
References
Mazzei R, Drioli E, Giorno L (2010) Biocatalytic mem-
branes and membrane bioreactors. In: Drioli E and
Giorno L (eds) Comprehensive membrane science and
engineering, vol 3. Elsevier B.V., Oxford, pp 195212
Mazzei R, Piacentini E, Drioli E, Giorno L (2013) Mem-
brane bioreactors for green processing. In: Boodhoo K,
Harvey A (eds) Process intensication for green chem-
istry: engineering solutions for sustainable chemical
processing. John Wiley & Sons, Ltd., Chichester,
pp 227250
Enzyme Membrane Reactor
Enzymatic Membrane Reactor (EMR)
Enzyme Membrane Reactors
Membrane Bioreactors
Enzymes Immobilized on Lumen
Rosalinda Mazzei
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, Rende,
Italy
Synonyms
Immobilization of enzymes
Ethanol Production by Continuous Fermentation-Pervaporation
Enzymes Immobilized on Lumen, Fig. 1 Scheme of
tubular biocatalytic membrane with biocatalyst
immobilized on lumen surface
This particular kind of immobilization is generally
referred to enzymes immobilized into the mem-
brane lumen surface of tubular membranes for the
production of biocatalytic membrane and biocat-
alytic membrane reactors. A scheme of a cross
section of a biocatalytic asymmetric hollow ber
membrane is reported in Fig. 1, in which the place
that the biocatalyst was immobilized on the mem-
brane lumen surface is highlighted.
The biocatalyst can be also compartmental-
ized/segregated in the lumen of tubular membrane
so conned in a dened region of the membrane
module space. In these reactors, the enzymes or
cells are not linked to the membrane. The mem-
brane in this particular case can retain the enzyme
or the cell which is not lost in the efuent stream,
while low-molecular-weight products and inhibi-
tors can be removed through the membrane
(Strathmann et al. 2006).
References
Strathmann H, Giorno L, Drioli E (2006) An introduction
to membrane science and technology. Consiglio
Nazionale delle Ricerche, Roma
EOD
Electroosmotic Drag in Membranes
721
EOF
Electroosmosis, Overview of
Ethanol Production by Continuous
Fermentation-Pervaporation
E
Wanqin Jin
State Key Laboratory of Materials-Oriented
Chemical Engineering, Nanjing University of
Technology, Nanjing, China
Ethanol production by continuous fermentation-
pervaporation is a process that couples ethanol
fermentation with in situ pervaporation
(PV) recovery of ethanol from fermentation broth.
With the fast increasing of fossil fuel consump-
tion and the deterioration of environment, it is
commonly accepted that the fossil fuel for
human energy use has to be replaced generally
by renewable resources. Compared with tradi-
tional resources, bioethanol produced by fermen-
tation process can be sustainably developed
without extra yield of greenhouse gas (Peng
et al. 2011). Bioethanol is produced from renew-
able resources (biomass) by ethanol fermentation
process. However, usually, the maximum concen-
tration of solvents (ethanol) does not exceed
8 wt% owing to the end-product inhibition on
microorganism, resulting in high energy cost to
separate ethanol from the dilute fermentation
broth by distillation. Therefore, several in situ
product-removal technologies, such as adsorp-
tion, gas stripping, liquid-liquid extraction,
perstraction, pervaporation, and reverse osmosis,
have been developed. These technologies could
be coupled with ethanol fermentation process to
decrease the effect of product inhibition and
improve the sugar utilization and solvent produc-
tivity (Vane 2005).
Pervaporation coupled with fermentation,
which is also called fermentation-pervaporation
coupled process, has been regarded as the most
promising separation method because this process
722 Ethanol Production by Continuous Fermentation-Pervaporation
Ethanol Production by Continuous Fermentation-Pervaporation, Fig. 1 Ethanol fermentation-pervaporation
coupled process
can in situ extract organic components which is
harmless for microorganisms in mild condition.
Figure 1 shows its typical ow chart (Vane 2005).
A pervaporation membrane module is connected
to the fermentor to form a circulation of fermen-
tation broth. Preheated fermentation solution is
continuously circulated from fermentor through
the membrane upstream side with another side
being vacuumed using vacuum pump. Therefore,
ethanol solvent can be selectively and continu-
ously removed from the fermentation broth and
then concentrated in the membrane downstream
side. As a result, ethanol concentration in the
broth is kept at low level to facilitate the continu-
ous fermentation process as well as enhance the
solvent productivity. In addition, a microltration/
ultraltration unit can be alternatively installed
before the pervaporation module, in order to lter
microbes and avoid the biofouling of
pervaporation membranes.
PV membranes can be made from either poly-
meric or inorganic materials, even both of them
(Peng et al. 2011). The polymeric pervaporation
membranes for extracting ethanol from fermenta-
tion broth include polydimethylsiloxane (PDMS)
membranes, poly[1-(trimethylsilyl)-1-propyne]
(PTMSP) membranes, poly(ether block amide)
(PEBA) membranes, liquid membranes, other
modied polymer membranes, as well as porous
polypropylene (PP) membranes and polytetra-
uoroethylene (PTFE) membranes. Among
them, the commonly used PDMS membranes
with good selectivity and stability are regarded
as the most potential PV membranes for ethanol
recovery application (Xiangli et al. 2008). The
typical inorganic membrane for PV is hydropho-
bic zeolite membrane, such as ZSM-5 and
Silicalite-1 membrane.
References
Peng P, Shi B, Lan Y (2011) A review of membrane
materials for ethanol recovery by pervaporation. Sep
Sci Technol 46:234246
Vane LM (2005) A review of pervaporation for product
recovery from biomass fermentation processes. J Chem
Technol Biotechnol 80:603629
Xiangli FJ, Wei W, Chen YW, Jin WQ, Xu NP (2008) Opti-
mization of preparation conditions for polydimethyl-
siloxane (PDMS)/ceramic composite pervaporation
membranes using response surface methodology.
J Membr Sci 311:2333
EthanolWater Mixtures: Separation by Pervaporation
EthanolWater Mixtures: Separation
by Pervaporation
Kew-Ho Lee
Center for Membranes, Korea Research Institute
of Chemical Technology (KRICT), Yuseong-gu,
Daejeon, South Korea
Pervaporation is an important membrane process
in chemical industries in which valuables are iso-
lated from the liquid mixture. Liquid and vapor
separation by thermal processes has always been
highly energy intensive, and new separation pro-
cesses taking advantage of mass transfer through
dense membranes have already shown they enable
very signicant energy savings as compared to
more classic technologies (Anne et al. 2002).
Membranes can be used for the selective removal
of water from aqueous organic mixtures.
Pervaporation (PV) is a separation process that
involves separation of liquid mixtures, in contact
with a membrane. With feed solution on one side,
permeate is removed as a vapor from the other
side (Brian et al. 2011); pervaporation (PV) is a
very well-known membrane process for the sepa-
ration of liquid and vapor mixtures due to its
energetic aspects (EP 909209A1 1999; EP
944575A1 1999; EP 880400A1 1998).
EthanolWater Mixtures:
Separation by
Pervaporation,
Fig. 1 Solution-diffusion
mechanism (Graham 1866)
723
Pervaporation mostly allows a variety of possible
application areas: dewatering of organic uids
like alcohols, ketones, ethers, etc. (EP 765682A1
1997); separation of mixtures from narrow boiling
temperatures to constant (azeotrope) boiling tem-
peratures (EP 811420A1 1997); removal of
organic pollutants from water and air streams
(EP 749351A1 1996); separation of fermentation
products; and separation of organic-organic liquid
mixtures (Kujawski 2000). Pervaporation is also
E
considered as so-called clean technologies, espe-
cially well suited for the treatment and recycling
of volatile organic compounds and pollution pre-
vention (Anne et al. 2002).
Transport mechanism of PV through poly-
meric membranes was studied by many research
groups, and it was explained by the solution-
diffusion model (Binning et al. 1961; Paul and
Paciotti 1975; Lee 1975; Mulder and Smolders
1984; Kataoka et al. 1991a, b). According to the
solution-diffusion model, each component of the
permeation molecules dissolves into the mem-
brane and diffuses through the membrane due to
the concentration gradient (Mikihiro et al. 1998)
(Fig. 1).
Transport through the membrane is driven by
the vapor pressure difference between the feed
solution and the permeate vapor. The vapor pres-
sure difference can be maintained by applying a
vacuum on the permeate side or by cooling the
1. Sorption
Micrivoids
Polymer
2. Diffusion
Microchannels
3. Desorption
724 EthanolWater Mixtures: Separation by Pervaporation

EthanolWater Mixtures: Separation by Pervaporation, Table 1 PV dehydration of ethanol through various

polymeric membranes (Brian et al. 2011)
Polymer Feed (wt% water) Temp. ( C) Separation factor Flux (g/m2h)
Regenerated cellulose 50 45 5.0 2060
Cellulose acetate 4 60 5.9 200
Teon-g-polyvinylpyrrolidone 4 25 2.9 2200
Peruorinated polymer on PAN support 1.3 50 387 1650
Naon-H+ 4 70 2.5 5000
Polyacrylonitrile-polyvinylpyrrolidone 4 20 3.2 2200
Poly(maleimide-co-acrylonitrile) 15 15 33 8
Poly(acrylic acid-co-acrylonitrile) 18 15 877 13
Polystyrene 4 40 101 5
Poly(vinyl chloride) 4 40 63 3
Alginic acid 4 40 8.8 48
5 60 13 2800
Chitosan 4 40 2208 4
Chitosan acetate salt 4 40 2556 2
Chitosan/glutaraldehyde 4 40 202 7
PVA/25 % TEOS, annealed at 160  C 15 40 329 5
PVA/25 % TEOS, annealed at 130  C 15 40 893 4

permeate vapor so that it condenses, thus creating
a partial vacuum. Commercial systems for the
dehydration of concentrated alcohol and other
solutions have been developed since the 1980s,
much of the push coming from interest in the
production of pure ethanol as an alternative liquid
fuel, where PV can be used to dehydrate (Brian
et al. 2011).
Pervaporation Membranes
Polymeric Membranes
For dehydration, where the small molar volume
favors the preferential sorption of water, materials
have to be selected with a higher afnity for water
than for the other component. The polymeric
materials can be broadly classied into three cat-
egories: glassy polymers, rubbery or elastomeric
polymers, and ionic polymers. In general, the
glassy and ionic polymers are more suited for
making water-selective membranes for
dehydration.
For water-selective membranes, the most
important factor responsible for the separation is
the specic interaction between water and the
polymer. To obtain high selectivities, it is
necessary to use polymers, which contain specic
groups/active centers, capable of strong interac-
tions with water.
The highest uxes are those for the hydrophilic
membranes based on cellulose and Naon and
grafts of hydrophilic poly(vinylpyrrolidone) on
Teon and polyacrylonitrile. The PVA/TEOS
membranes are exceptions in that they are hydro-
philic but exhibit low uxes (Brian et al. 2011)
(Table 1).
The emphasis is on selectivity, postulated to be
determined by selective sorption and selective
diffusion. Selective sorption is governed by the
presence in the membrane of active centers such
as charged sites which are capable of specic
interaction with water, while selective diffusion
is governed by the rigidity and regularity of the
polymer structure and the nature of the polymer
interspace, exemplied by the degree of swelling
and the frequency of the cross-links. The results
for a series of membranes made by grafting neu-
tral or charged polymers onto supporting mem-
branes are reported in (Table 2).
Polysalts, formed from anionic and cationic
polyelectrolytes, would be appropriate for
obtaining both highly permeable and highly selec-
tive membranes (Semenova et al. 1997) (Table 3).
EthanolWater Mixtures: Separation by Pervaporation 725

EthanolWater Mixtures: Separation by Pervaporation, Table 2 PV dehydration of 20 % aqueous ethanol at 70  C

using graft polymer membrane having different charges (Brian et al. 2011)
Host polymer Grafted polymer Graft site charge Separation factor
Polyvinylidene uoride 4-Vinylpyridine Neutral 9
Polyvinylidene uoride N-Vinyl-imidazole Neutral 10
Polyvinyl uoride N-Vinylmethyl-acetamide Neutral 4
Polyvinyl uoride N-Vinyl-pyrrolidone Neutral 7
Polyacrylonitrile Acrylic acid Neutral 10
Polyacrylonitrile K+ acrylate Anionic 500
Polyvinyl uoride K+ acrylate Anionic 156
Polyvinylidene uoride Quaternized 4-vinylpyridine Cationic 175 E
Polyvinylidene uoride Quaternized N-vinylimidazole Cationic 61
Polyvinylidene uoride 4-Vinylpyridine/BrCH2COOH Zwitterionic 76
Polyvinyl uoride Vinylimidazole/BrCH2COOH Zwitterionic 63

EthanolWater Mixtures: Separation by Pervaporation, Table 3 PV dehydration of aqueous ethanol with mem-
brane based on various polysalts (Brian et al. 2011)
Feed (wt% Temp. Separation Flux
Polyanion Polycation water) ( C) factor (g/m2h)
Poly(acrylonitrile-co- Poly(acrylonitrile-co-vinyl pyridine) 10 5000 400
acrylic acid)
Cellulose-SO3-Na+ Polyethyleneimine 16 50 295 1900
Cellulose-SO3-Na+ PolyDADMAC, linear 16 50 140 3200
Cellulose-SO3-Na+ Same, but branched 16 50 123 4900
Cellulose-SO3-Na+ Poly-N, N-dimethyl-3, 5- 16 50 123 2700
dimethylenepiperidine chloride
Aromatic polyamide Polyethyleneimine 20 60 15 300
sulphonate
Poly(acrylic acid) Chitosan
On polysulphone supporting membrane 5 30 1008 132
No supporting membrane 5 30 2216 33
Na+ polystyrene Polyallylamine HC1 6.2 70 70 230
sulphonate
Na+ CMC Chitosan 10 70 1062 1140
Na+ CMC N-Ethyl-4-vinyl-pyridinium bromide 10 70 782 1320
Anionic PVA Cationic PVA
DS 2.3 % DS 2.9 % 4.6 75 2250 378
DS 5.0 % DS 5.2 % 4.6 75 1910 284

The best performers in terms of ux, which at a Hybrid Membranes

maximum of 5 kg/m2h never achieve high values,
are charged polymers of one type or another,
including polysalts. Anionic and polysalt mem-
branes are superior. For anionic polymers, the
proton form has a signicantly higher ux than
the metal or quaternary ammonium salt versions,
owing to the greater free space within the polymer
network (Table 4).
Many a times, the polymeric membranes may fail
to meet the desired separation requirements. In
such cases, it becomes necessary to add ller
materials such as ceramics and zeolites to improve
the separation properties of the membrane. There
are several reports showing good separation per-
formance for ethanol/water mixture using zeolite
membranes (Kita et al. 1995; Sano et al. 1994).
726 EthanolWater Mixtures: Separation by Pervaporation

EthanolWater Mixtures: Separation by Pervaporation, Table 4 Highest fluxes for PV dehydration of aqueous
ethanol (Brian et al. 2011)
Separation
Membrane polymer Mem. type Feed (wt% water) Temp. ( C) Flux (g/m2h) factor
Naon-H+ Anionic 4 70 5000 2.5
Cellulose-SO3-Na+ and Polysalt 16 50 4900 125
polyDADMAC, branched
K+ acrylate graft on poly(vinyl Anionic 20 70 4700 156
uoride)
PEI/PAA on RO membrane Polysalt 10+ 70 4050 1075
Cellulose-SO3-Na+ and Polysalt 16 50 3200 140
polyDADMAC, linear
K+ acrylate graft on PAN Anionic 20 70 3000 500

EthanolWater Mixtures: Separation by Pervaporation, Table 5 PV dehydration of ethanol using PVA/inorganic

hybrid membranes (Brian et al. 2011)
Crosslinker Feed (wt% water) Temp. ( C) Separation factor Flux (g/m2h)
TEOS (160  C) 15 40 329 50
TEOS (130  C) 15 40 893 40
PEG blend and TEOS 15 50 300 46
No PEG 15 50 160 500
Poly(acrylic acid) copolymer and TEOS 15 40 250 18
g-Aminopropyl-triethoxysilane 5 50 537 36
Sulphated zirconia 5 50 263 10
10 50 142 105
20 50 86 183
30 50 61 1036

Kita et al. made NaA-type zeolite membrane by
hydrothermal synthesis. NaA zeolite membrane is
a water-selective membrane, and the PV separa-
tion factor of water/ethanol system was over
10,000 at 348 K. For ethanol permselective mem-
branes, Sano et al. (1994) prepared polycrystalline
silicalite membrane by the hydrothermal
synthesis.
The silicalite membrane showed high ethanol
permselectivity, and a separation factor of 58 was
realized at 333 K by PV. Silicalite membranes
seem to have great potential for the ethanol recov-
ery by PV (Table 5).
References
Anne J, Robert C, Pierre LND, Bruno C (2002) Industrial
state-of-the-art of pervaporation and vapour perme-
ation in the western countries. J Membr Sci 206:87117
Binning RC, Lee RJ, Jennings JF, Martin EC (1961) Sepa-
ration of liquid mixtures by permeation. Ind Eng Chem
53:45
Brian B, Manh H, Zongli X (2011) A review of membrane
selection for the dehydration of aqueous ethanol by
pervaporation. Chem Eng Process 50:227235
EP 749351A1 (1996) Device for separating mixtures or for
purifying substances by pervaporation
EP 765682A1 (1997) Apparatus for separating liquid
media with two membranes having their primary sides
connected by an intermediate space
EP 811420A1 (1997) Composite membrane for selective
separating organic substances by pervaporation
EP 880400A1 (1998) Composite membrane with a support
membrane made in particular of a microporous material
EP 909209A1 (1999) Pervaporisation and module for car-
rying out said process
EP 944575A1 (1999) Esterication of fermentation-
derived acids via pervaporation
Graham T (1866) On the absorption and dialytic separation
of gases by colloid septa. Philos Mag J Sci 32:401420
Kataoka T, Tsuru T, Nakao S, Kimura S (1991a) Perme-
ation equations developed for prediction of membrane
performance in pervaporation, vapor permeation and
Ethyl Cellulose (EC) Membrane
reverse osmosis based on the solution
diffusion can be substituted with epoxy groups up to about
model. J Chem Eng Jpn 24:326
Kataoka T, Tsuru T, Nakao S, Kimura S (1991b) Mem-
brane transport properties of pervaporation in
ethanol
water system using polyacrylonitrile and cel- ties and durability, outstanding gas separation
lulose acetate membranes. J Chem Eng Jpn 24:334
Kita H, Horii K, Ohtoshi Y, Tanaka K, Okamoto K (1995)
Synthesis of a zeolite NaA membranefor pervaporation
of water/organic liquid mixtures. J Mater Sci Lett 14:206
Kujawski W (2000) Application of pervaporation and
vapor permeation in environmental protection. Pol
J Environ Stud 91:1326
Lee CH (1975) Theory of reverse osmosis and some other
membrane permeation operations. J Appl Polym Sci 1983
Mikihiro N, Takeo Y, Sin-ichi N (1998) Ethanol/water
transport through silicalite membranes. J Membr Sci
144:161171
Mulder MHV, Smolders CA (1984) On the mechanism of
separation of ethanol/water mixtures by pervaporation
I. Calculations of concentration proles. J Membr Sci
17:289
Paul DR, Paciotti JD (1975) Driving force for hydraulic
and pervaporative transport in homogeneous mem-
branes. J Polym Sci 13:1201
Sano T, Yanagishita H, Kiyozumi Y, Mizukami F, Haraya K
(1994) Separation of ethanol/water mixture by silicalite
membrane on pervaporation. J Membr Sci 95:221
Semenova SI, Ohya H, Soontarapa K (1997) Hydrophilic
membranes for pervaporation: an analytical review.
Desalination 110:251286
Ethyl Cellulose (EC) Membrane
Hongyang Ma, Benjamin S. Hsiao and
Benjamin Chu
Department of Chemistry, Stony Brook
University, Stony Brook, NY, USA
Ethyl cellulose (EC) membrane has mainly been
used for separation of light gases, such as He, O2,
N2, CH4, CO2, propane, and propylene. The
hydroxyl groups on the glucose unit of cellulose
OH
HO OH Etherification
O O
O O
HO OH O
OH n
Ethyl Cellulose (EC) Membrane, Fig. 1 Etherication of cellulose with maximum content of epoxy of about 55 %
727
55 %, where ethyl cellulose exhibits good thin
lm-forming ability, excellent mechanical proper-
performance, and cost-effectiveness. Ethyl cellu-
lose can be dissolved in organic solvents (e.g.,
chloroform) and ethyl cellulose thin lm can be
formed via solvent evaporation. The nonporous
ethyl cellulose membrane has been used to sepa-
rate light gases, where the solubility coefcient
E
and the diffusion coefcient are two major param-
eters to determine the membrane performance for
gas separation. This performance is also
inuenced by the content of epoxy groups,
which vary with different manufacturers (Houde
et al. 1997; Li et al. 2001; Ito et al. 1989) (Fig. 1).
Another important application of ethyl cellu-
lose is in lm coating of drug tablets. Although the
tablet coating does not have a therapeutic value, it
does offer the psychological importance in aiding
patients to take the medication. The incorporation
of color, avor, and other additives in the ethyl
cellulose-coated tablets can improve esthetic and
organoleptic values and improve stability and
handling capability and drug release properties.
For example, ethyl cellulose is a water-insoluble
polymer, which can be used to protect the hydro-
lysis of the drug by surface coating. The drug
release rate can be adjusted by varying the thick-
ness of the lm and/or the composition of hydro-
phobic and hydrophilic components in the coating
(Sakellariou et al. 1995). Similarly, ethyl cellulose
can be used to formulate microcapsules where the
target drug(s) can be tailored with controlled
release rate, as well as improved efcacy, safety,
processibility, and stability (Rogers et al. 2012). It
is interesting to note that hydrophobic ethyl cel-
lulose and hydroxypropyl cellulose, which is
OR
RO OR
O
O
RO OR O
OR n
R = H or CH2CH3
728
more hydrophilic, are often combined together
synergistically for varying biomedical applica-
tions (Donbrow et al. 1980).
References
Donbrow M, Sanuelov D (1980) Zero order drug delivery
from double-layered porous lms: release rate proles
from ethyl cellulose, hydroxypropyl cellulose and
polyethylene glycol mixtures. J Pharm Pharmacol
32:463470
Houde AY, Stern SA (1997) Solubility and diffusivity of
light gases in ethyl cellulose at elevated pressures:
effects of epoxy content. J Membr Sci 127:173183
Li XG, Kresse I, Xu ZK, Springer J (2001) Effect of
temperature and pressure on gas transport in ethyl cel-
lulose membrane. Polymer 42:68016810
Ito A, Hwang ST (1989) Permeation of propane and pro-
pylene through cellulosic polymer membranes. J Appl
Polym Sci 38:483490
Sakellariou P, Rowe RC (1995) Interactions in cellulose
derivative lms for oral drug delivery. Prog Polym Sci
20:889942
Rogers TL, Wallick D (2012) Reviewing the use of
ethylcellulose, methylcellulose and hypromellose in
microencapsulation. Part 3: applications for microcap-
sules. Drug Dev Ind Pharm 38:521539
Ethylene Off-Gas
Paola Bernardo
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, Rende,
Italy
Ethylene off-gas is a light gas mixture containing
various concentrations of ethylene, propylene,
hydrogen, methane, ethane, propane, and minor
amounts of higher hydrocarbons, nitrogen, and
other trace components.
The main ethylene-bearing off-gas streams are
produced during the petroleum rening from uid
catalytic cracking (FCC) units and delayed
cokers. FCC units alone produce signicant
amounts of ethylene and hydrogen, owing to the
high feed ow rates processed. Other sources for
ethylene off-gas streams are the deep catalytic
cracking processes.
Ethylene Off-Gas
Renery and petrochemical ethylene-
containing off-gas streams usually contain vary-
ing amounts of heavy C4C10 hydrocarbons,
including alkanes, olens, and aromatics, together
with small quantities of water, nitrogen oxides,
carbon monoxide, carbon dioxide, acetylene,
methylacetylene, propadiene, butenes, and higher
hydrocarbons. FCC off-gases are available at
1017 bar and typically contain 818 vol.% of
ethylene, 39 vol.% of propylene, and 1220
vol.% of hydrogen, depending on the FCC feed
composition and cracking severity (Netzer 2003).
In general, ethylene-bearing off-gas streams con-
tain relatively dilute concentrations of olens,
such as ethylene, with methane, ethane, and
hydrogen which are potentially recoverable.
Hydrogen and light hydrocarbons (ethylene,
propylene, and LPG) have an increasing world-
wide demand. Being more valuable as chemical
and plastic feedstocks than they are as fuels, the
recovery from off-gas streams of these valuable
compounds represents an interesting possibility to
increase revenue in reneries (Hoffmann and
Kaufmann 2012). Indeed, renery and petro-
chemical ethylene off-gas streams are typically
burnt in are stacks or as fuel, since the recovery
of the olens by conventional means, such as
fractionation, is considered as not economically
viable. Considering the high cost of producing
ethylene by thermal cracking of hydrocarbon
feedstocks, which is the primary production pro-
cess for ethylene, the recovery of olens repre-
sents a substantial conservation of resources
(Eldridge 1993). The available separation
methods are absorption, adsorption, distillation,
and membrane separation. Membrane technology
represents a cost-effective, exible, and safe pro-
cess for recovering ethylene and associated
hydrogen from renery and petrochemical
off-gas streams (Ohlrogge et al. 2010).
The use of a membrane system for vaporgas
separation allows valuable feedstocks to be recov-
ered and recycled to the polymerization section in
polyethylene and polypropylene production
(Baker et al. 1998). Polyolen plants involve pre-
sent losses of monomers and other hydrocarbon
feedstocks (typically $1$3 million per year in
one plant). Vent streams, containing monomer
Ethylene Production by Membrane Operations
contaminated with light gases (e.g., N2 and H2),
are usually ared. Monomer recovery with
hydrocarbon-selective rubbery membranes is the
largest application of vapor separation mem-
branes. The vent stream is compressed and cooled
to condense hydrocarbons. The gas not con-
densed, still containing a signicant amount of
hydrocarbons, is sent to the membrane system
and separated into a hydrocarbon-enriched stream
as permeate and a nitrogen stream. The permeate
is recycled to the compressor and then to the
condenser where the hydrocarbon is recovered;
the nitrogen stream is recycled to the degassing
bin (Baker et al. 1998).
Analogous membrane processes are applied to
recover ethylene in ethylene oxide and in vinyl
acetate production. The purge gas for a typical
ethylene oxide plant contains approximately
2030 % ethylene, 1012 vol.% argon, 110
vol.% carbon dioxide, 13 vol.% ethane,
50 vol.% methane, and 45 vol.% oxygen.
A similar vent gas mixture is produced in the
vinyl acetate process. A membrane recovery unit
fed with these purge streams will produce an
ethylene-enriched permeate stream and an
argon-enriched residue stream (Jacobs and Billig
2005). These systems achieve an ethylene
recovery greater than 70 %, partly recover meth-
ane (the diluent gas), and reduce hydrocarbon
burning.
References
Baker RW, Wijmans JG, Kaschemekat JH (1998) The
design of membrane vapour-gas separation systems.
J Membr Sci 151:5562
Eldridge RB (1993) Olen/parafn separation technology:
a review. Ind Eng Chem Res 32:22082212
Hoffmann K, Kaufmann D (2012) Recovery of valuable
olen products from renery off-gas streams. Chem
News 1419
Jacobs ML, Billig BJ (2005) Achieving ethylene ef-
ciency. Hydrocarb Eng
Netzer D (2003) A combination process for manufacturing
ethylene, ethylbenzene and styrene. EP Patent
1,017,651 B1
Ohlrogge K, Wind J, Brinkmann T (2010) Membranes for
recovery of volatile organic compounds. In: Drioli E,
Giorno L (eds) Comprehensive membrane science and
engineering, vol 2. Elsevier, Oxford, pp 213242
729
Ethylene Production by Membrane
Operations
Paola Bernardo
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, Rende,
Italy
E
Ethylene (C2H4), also called ethene, is a colorless
and ammable gas derived from natural gas and
petroleum. Being particularly reactive, ethylene rep-
resents one of the largest volume compounds and a
key building block in the petrochemical industry,
with a worldwide demand that has grown steadily.
The conventional ethylene production process
is steam cracking. A hydrocarbon feedstock (such
as naphtha, liqueed petroleum gas, ethane, pro-
pane, or butane) is thermally cracked in the pres-
ence of steam, producing a mixture of hydrogen,
methane, ethylene, ethane, and heavier compo-
nents. Most of the dilution steam and heavier
products are condensed by a rapid quenching,
while the cooled gases are compressed, sent to a
scrubbing for the acid gas removal, and subcooled
for the successive separations. A distillation train
performs the separation and purication of the
gaseous products, representing an energy con-
suming step, highly heat integrated and requiring
refrigeration (Ren et al. 2006). This provides a
strong drive for evaluating alternative methods
for separation and recovery purposes. Coke for-
mation requires discontinuous operation for reac-
tor cleanup. Different wastes are generated
including caustic scrubber efuent, dilution
steam condensate, coke and tar at the condensate
separators, and vent gases generated during start-
ups and shutdowns. Overall, this process is very
capital intensive and energy consuming (Ren
et al. 2006). This type of hydrocarbon feedstock
affects the process capital cost as well as the
amounts and types of waste streams. Cleaner and
simplied processes are related to the use of eth-
ane. Multiple companies are considering this
option, driven by the large volumes of shale gas
being recently recovered which provides sizable
volumes of very low-cost ethane (Armor 2013).
730
The integration of membrane separation systems
and of membrane contactors (such as membrane
distillation, membrane strippers and scrubbers,
etc.) and membrane reactors might benecially con-
tribute to redesign industrial operations. Indeed,
membrane technology has many advantages over
other conventional technologies, including lower
capital and operating costs, low maintenance, low
space requirements, exibility, and ease of installa-
tion and operation (Strathmann 2011).
An ethylene production cycle by steam crack-
ing was redesigned by integrating different mem-
brane systems ( gas separation modules,
microltration, and membrane contactors) into
a reference plant producing 800,000 t/year of eth-
ylene and consuming ca. 30 GJ/t ethylene
(Bernardo et al. 2004). Membrane gas separation
to remove hydrogen from compressed gas allows
a debottlenecking, reducing signicantly the
energy required in the cryogenic distillation for
hydrogen/methane separation, permitting less
severe operating conditions with respect to the
conventional cycle (Engler and Dupuis 2000).
Gas separation was also proposed to produce
oxygen-enriched air to be used instead of air for
combustion and/or decoking. Hydrocarbon
removal from water streams using membrane
contactors, capable to operate more efciently
with respect to conventional scrubbing units
(Gaeta 2009), could achieve a removal greater
than 90 %. Membrane contactors could be also
applied for acid gas removal from the furnace
efuent. Water used for scrubbing of the nest
fraction of coke particles during decoking can be
processed in a microltration membrane unit,
recovering up to 90 % of the water and allowing
its reuse in the plant. The replacement of tradi-
tional operations with membrane units, such as
membrane contactors for washing water purica-
tion in the hot section and the membrane gas
separation for the hydrogen recovery, determine a
smaller exergetic loss with respect to the conven-
tional industrial cycle (Bernardo et al. 2004).
Membrane reactors with inorganic membranes
able to operate at high temperature were investi-
gated for alternative ethylene productions,
benetting from the product continuous removal
to shift a chemical equilibrium or from a reactant
Ethylene/Ethane Separation by Membranes
continuous feeding to control the reaction selec-
tivity. Some examples, related to the conversion
of ethane, include the dehydrogenation by means
of hydrogen permeable metallic membranes
(Galuszka et al. 2008) and the exothermic oxida-
tive dehydrogenation using perovskite mem-
branes, which operate under a mixed
ion-electron conduction (Lobera et al. 2011).
References
Armor JN (2013) Emerging importance of shale gas to both
the energy & chemicals landscape. J Energy Chem
22:2126
Bernardo P, Criscuoli A, Clarizia G, Barbieri G, Drioli E,
Fleres G, Picciotti M (2004) Applications of membrane
unit operations in ethylene process. Clean Technol
Environ Policy 6(2):7895
Engler Y, Dupuis G (2000) Process for recovering olens.
U.S. Patent 6,141,988
Gaeta S (2009) Membrane contactors in industrial applica-
tions. In: Drioli E, Giorno L (eds) Membrane opera-
tions: innovative separations and transformations.
Wiley-VCH, Weinheim, pp 499512
Galuszka J, Giddings T, Clelland I (2008) Catalytic dehydro-
genation of ethane in hydrogen membrane reactor. In:
Bose AC (ed) Inorganic membranes for energy and envi-
ronmental applications. Springer, New York, pp 299311
Lobera MP, Escolstico S, Serra JM (2011) High ethylene
production through oxidative dehydrogenation of eth-
ane membrane reactors based on fast oxygen-ion con-
ductors. Chem Cat Chem 3:15031508
Ren T, Patel MK, Blok K (2006) Olens form conventional
and heavy feedstocks: energy use in steam cracking and
alternative processes. Energy 31(4):425451
Strathmann H (2011) Introduction to membrane science
and technology. Wiley-VCH, Weinheim
Ethylene/Ethane Separation
by Membranes
Paola Bernardo
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, Rende,
Italy
The separation of ethylene from ethane and pro-
pylene from propane is a challenging operation. It
is involved in the production of light olens, such
Ethylene/Ethane Separation by Membranes
as ethylene and propylene, which represent the
most important building blocks in the petrochem-
ical industry. Cryogenic distillation, convention-
ally applied to this separation, is highly energy
intensive, requiring expensive tall columns, oper-
ated under low temperature and high pressure,
with very high reux ratios and requiring ethyl-
ene/propylene refrigeration systems for
low-temperature cooling (Eldridge 1993).
Due to the complexity and difculty of the
separation process, mixtures including olens
produced in the petroleum and rening process
are often used as fuel. Membrane separation, rec-
ognized as a low-energy method, appears the most
promising among alternative separation tech-
niques, such as extractive distillation, adsorption,
and absorption, to recover these valuable com-
pounds (Rungta et al. 2013). Polymeric mem-
branes, cheap and with an easy processability,
have low olen/parafn separation factor, espe-
cially those based on rubbery polymers (Rungta
et al. 2013). The experimentally observed ethyl-
ene/ethane and propylene/propane upper bound,
based on the most reliable data of various poly-
meric membranes, were presented in two critical
reviews (Rungta et al. 2013; Burns and Koros
2003, respectively). Glassy polymers have been
studied intensively for this separation. However,
when applied to mixtures and/or at high gas activ-
ities, these materials are prone to plasticization
which causes swelling of the polymer matrix and
results in a higher permeability coupled with a
loss of selectivity. Strategies to overcome plasti-
cization include thermal curing and chemical
cross-linking, which reduce the polymer free vol-
ume, and the addition of nanollers (Goh
et al. 2011; Ploegmakers et al. 2013).
Facilitated transport membranes based on the
p-complexation mechanism are broadly investi-
gated for olen/parafn separation (Faiz and Li
2012). The specic interaction between the hybrid
molecular orbitals of the olens and the atomic
orbitals of the transition metals results in revers-
ible chemical bonds stronger than those formed by
van der Waals forces, but can be broken by simply
increasing the temperature or decreasing the pres-
sure. These systems allow high selectivity for
the bound component. Silver-based facilitated
731
transport membranes were studied more exten-
sively due to low-cost and relatively weak inter-
actions with olens (possible decomplexation).
However, carrier poisoning and short life span of
the polymeric membranes are typically reported
(Rungta et al. 2013). Chitosan-based membranes,
impregnated with silver nitrate as a facilitation
agent, showed performance stability over thou-
sands of hours of operation in eld tests (Kamza
et al. 2013). Ionic liquids, selected as additives for
E
facilitated transport membranes, have a negligible
vapor pressure that avoids solvent losses by evap-
oration and offer more afnity for the olens
compared to the parafns, providing stability to
the metallic cation dissolved inside and acting as a
medium for facilitated transport with mobile car-
rier (Fallanza et al. 2013).
Carbon molecular sieve membranes showed
the potential to surpass the polymeric ethylene/
ethane upper bound performance (Rungta
et al. 2013). These membranes are usually pre-
pared by the pyrolysis of polymeric precursors
such as polyimide materials. However, major
issues are represented by their brittleness and
poor mechanical strength.
In the eld of inorganic membranes, metal
organic frameworks were recently considered for
preparing membranes to be applied to the olen/
parafn separation (Bux et al. 2011).
The concept of hybrid processes, combining a
membrane system with a conventional one, has
drawn signicant attention for the olen/parafn
separation. Savings in total costs and energy
(up to 30 %) could be obtained with a mem-
brane/distillation hybrid system (Caballero
et al. 2009).
References
Burns RL, Koros WJ (2003) Dening the challenges for
C3H6/C3H8 separation using polymeric membranes.
J Membr Sci 211:299309
Bux H, Chmelik C, Krishna R, Caro J (2011) Ethene/
ethane separation by the MOF membrane ZIF-8:
molecular correlation of permeation, adsorption, diffu-
sion. J Membr Sci 369:284289
Caballero JA, Grossmann IE, Keyvani M, Lenz ES
(2009) Design of hybrid distillation vapor membrane
732
separation systems. Ind Eng Chem Res
48(20):91519162
Eldridge RB (1993) Olen/parafn separation technology:
a review. Ind Eng Chem Res 32:2208
Faiz R, Li K (2012) Polymeric membranes for light olen/
parafn separation. Desalination 287:8297
Fallanza M, Ortiz A, Gorri D, Ortiz I (2013) Polymerionic
liquid composite membranes for propane/propylene
separation by facilitated transport. J Membr Sci
444:164172
Goh PS, Ismail AF, Sanip SM, Ng BC, Aziz M (2011)
Recent advances of inorganic llers in mixed matrix
membrane for gas separation. Sep Purif Tech
81:243264
Kamza A, Keyvani M, Towe G (2013) Stable facilitated
transport membrane for olen/parafn separation. In:
Fuels and petrochemicals division, AIChE Spring
Meeting and Global Congress on Process Safety, San
Antonio. 28 Apr 2 May 2013
Ploegmakers J, Japip S, Nijmeijer K (2013) Mixed matrix
membranes containing MOFs for ethylene/ethane sep-
aration. Part A: membrane preparation and characteri-
zation. J Membr Sci 428:445453
Rungta M, Zhang C, Koros WJ, Xu L (2013) Membrane-
based ethylene/ethane separation: the upper bound and
beyond. AIChE J 59(9):34753489
Evapomeation (EV)
Tadashi Uragami
Organization for Research and Development of
Innovative Science and Technology (ORDIST),
Kansai University, Suita, Osaka, Japan
Presently, pervaporation (PV) is applied as the
chosen membrane separation technique for the
separation of water/organic, organic/water, and
organic/organic mixtures. However, it seems
that conventional PV is not the most efcient
membrane separation process for the treatment
of some liquid mixtures as follows. Because the
polymer membranes used in PV are directly in
contact with the liquid feed solutions as shown in
Fig. 1, however, specically designed chemical
and physical properties of the membrane are often
impaired by swelling or shrinking of the mem-
brane due to sorption of the feed components.
Swelling or shrinking of the polymer membranes
is disadvantageous for the membrane perfor-
mance with respect to the separation of mixtures.
Evapomeation (EV)
Evapomeation (EV),
Fig. 1 Principle of Feed liquid
pervaporation (PV)
Membrane
vacuum
Evapomeation (EV), vacuum
Fig. 2 Principle of
evapomeation (EV)
Membrane
Feed liquid
A novel membrane separation technique known
as evapomeation (EV) (Uragami et al. 1988;
Uragami and Saito 1989; Uragami 1991, 1992,
1993a, b; Uragam 1994; Uragami 1998, 2005,
2006a, b, 2008) makes use of the advantages of
PV but reduces the negative effects of swelling on
membrane performance. In this technique, the
feed solution is fed to the membrane without
directly contacting the polymer membrane. This
is accomplished by vaporizing the liquid feed so
that only vapor is supplied to the polymer mem-
brane as shown in Fig. 2. Therefore, swelling or
shrinking of the polymer membranes due to con-
tact with the feed solutions is minimized.
The advantages of EV compared to PV are as
follows:
1. In the EV process, membranes are not in direct
contact with liquid feed mixtures as only
vapors are supplied to the membranes. Accord-
ingly, any swelling or shrinking of the mem-
brane due to the feed mixtures is minimized,
and consequently an improvement in mem-
brane performance may be expected.
Evaporation Casting
2. Because the organic liquid mixtures are vapor-
ized, interactions between component mole-
cules are signicantly weakened, and
consequently the separation performance is
remarkably improved.
3. In EV, contaminants in a liquid feed mixture,
such as macromolecular solutes, can lead to
fouling of the membrane; this problem is
avoided in EV.
4. During EV, both temperature of the feed solu-
tion and the membrane surroundings can be
controlled; hence, an improvement in the per-
meation and separation characteristics of the
membrane can be achieved.
References
Uragam T (1994) Separation method of mixed solutions.
Japanese Patent 1,883,353
Uragami T (1991) Method of separating a particular com-
ponent from its liquid solution. US Patent 4,983,303,
European Patent 0,273,267
Uragami T (1992) Separation of organic liquid mixtures
through chitosan and chitosan derivative membranes
by pervaporation and evapomeation methods. In: Brine
CJ, Sandford PA, Zikakis JP (eds) Advance in chitin
and chitosan. Elsevier Applied Science, Oxford,
pp 594603
Uragami T (1993a) Method of separating a particular com-
ponent from its liquid solution. European Patent
0,273,267
Uragami T (1993b) Method of separating a particular com-
ponent from its liquid solution. Brazilian Patent
P-8707041-3
Uragami T (1998) Structures and properties of membranes
from polysaccharide derivatives. In: Dumitriu S
(ed) Polysaccharide structural diversity and func-
tional versatility. Marcer Dekker, New York/Basel/
Hong Kong, pp 887924
Uragami T (2005) Structures and functionalites of mem-
branes from polysaccharides derivatives. In: Dumitriu
S (ed) Polysaccharides structural diversity and func-
tional versatility, 2nd edn. Marcer Dekker, New York/
Basel/Hong Kong, pp 10871122
Uragami T (2006a) Polymer membranes for separation of
organic liquid mixtures. In: Yampolskii Y, Pinnau I,
Freeman BD (eds) Materials science of membranes
for gas and vapor separation. John Wiley & Sons,
Chichester, pp 355372
Uragami T (2006b) Separation materials derived from
chitin and chitosan. In: Uragami T, Tokura S (eds) Mate-
rial science of chitin and chitosan, KODANSHA.
Springer, Tokyo/Berlin/Heidelberg/New York,
pp 113163
733
Uragami T (2008) Structural design of polymer membranes
for concentration of bio-ethanol. Polym J 40:485
Uragami T, Saito M (1989) Analysis of permeation and
separation characteristics: a new technique for separa-
tion of aqueous alcoholic solution through alginic acid
membranes. Sep Sci Technol 24:54
Uragami T, Saito M, Takigawa K (1988) Comparison of
permeation and separation characteristics for aqueous
alcoholic solutions by pervaporation and new
evapomeation methods through chitosan membranes.
Makromol Chem Rapid Commun 9:361
E
Evaporation Casting
Francesco Galiano
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, Rende,
Italy
Evaporation casting or dry-casting involves the
evaporation of a solvent (or a mix of solvents)
from a starting solution and the subsequent for-
mation of a polymeric membrane by precipitation.
In this process a polymer is dissolved in a suitable
solvent and the solution obtained is spread out
across an appropriate support. Then, the solvent
is left to evaporate, in inert atmosphere or con-
trolled environment, inducing the polymer precip-
itation and generating a membrane generally with
a dense structure (Fig. 1). In evaporation casting,
in fact, the precipitation process is much slower
than the precipitation obtained by immersion cast-
ing. As a consequence, the membranes present,
usually, an isotropic and less porous structure.
Some other components, called commonly
nonsolvents, can be also added to the initial poly-
meric solution. In this case, the solvent, the more
Evaporation Casting, Fig. 1 Evaporation casting
process
734
volatile element of the system, will evaporate
faster leading to a higher polymer/nonsolvent
concentration responsible for the polymer precip-
itation. The evaporation process can proceed until
the membrane has completely formed or it can be
stopped by immersing the cast lm in a coagula-
tion bath containing a nonsolvent (Baker 2004).
By prolonging or reducing the evaporation time
before immersion in the coagulation bath, it is
possible to tune the pore size of the membrane.
When the starting polymeric solution is cast on
different support, as porous thin lms or other
kinds of membranes, an asymmetric membrane
with a dense skin layer deposited on a porous
support can be obtained.
References
Baker W (2004) Membrane technology and applications,
2nd ed. Wiley, West Sussex, England, Chapter 3,
pp 112113
Ex Situ Zeolite Synthesis
Seeded Hydrothermal Synthesis for Zeolite
Preparation
External Coagulant in Fiber
Preparation
Khayet Mohamed
Department of Applied Physics, Universidad
Complutense de Madrid, Madrid, Spain
External coagulant is a non-solvent liquid or a
mixture of solvent/non-solvent in a collecting
bath (coagulation bath) used for fabrication of
bers by the dry-/wet-spinning technique or the
wet-spinning technique. Coagulation of the exter-
nal surface of the nascent ber can start immedi-
ately after its extrusion from the spinneret (wet
spinning) or after the as-spun ber crosses an air
Ex Situ Zeolite Synthesis
gap (i.e., distance between the spinneret and the
coagulation bath) through which the external sur-
face experiences coalescence and orientation of
polymer aggregates (wet/dry spinning). In gen-
eral, the nascent ber is partially coagulated by
the internal coagulant (bore liquid) and/or through
the air gap by solvent evaporation, and nally the
coagulation is completed in the coagulation bath
by an external coagulant.
The type of the external coagulant affects con-
siderably the structural morphology of the
resulted ber. Usually, water is the preferred
external coagulant because of its low cost and
environmental friendliness. The proper choice of
the coagulant is very important because the rate of
demixing (i.e., phase separation) and the resultant
inner and outer surface structures of the hollow
ber strongly depend on the chemistry and the
composition of the coagulant. The molecular
sizes and solubility parameters of the used solvent
and the internal and the external coagulant play
important roles on hollow ber morphology. Sol-
vent of a large size may have difculties to leach
out during the coagulation step. The difference in
solubility parameters between the spinning dope
solution and the bore liquid (internal coagulant) or
the external coagulant affects the coagulation rate
and subsequently the porosity of the spun hollow
ber membrane.
The interactions between solvent and external
coagulant and between solvent and polymer play
important roles affecting the rate of polymer pre-
cipitation. The temperature of the external coagu-
lant affects also the polymer precipitation rate.
The maximum amount of solvent that can be
added to the non-solvent in the coagulation bath
can be roughly determined by the position of the
binodal (liquid-liquid boundary separating
the miscible region from the immiscible one) in
the ternary phase diagram presenting the compo-
sition of the polymer, solvent, and non-solvent.
When the binodal shifts toward the polymer/sol-
vent axis, more solvent can be added in the exter-
nal coagulant. It is also possible to change from
porous to nonporous external ber surface by
adding solvent to the coagulation bath (Mulder
1992). For example, when a strong coagulant
such as water for poly(vinylidene uoride),
External Coagulant in Fiber Preparation
External Coagulant in Fiber Preparation,
Fig. 1 Cross-sectional scanning electron microscopy
(SEM) structure of PVDF hollow ber membranes pre-
pared with different coagulants: (a) water coagulant;
PVDF, polymer is used for hollow ber fabrica-
tion, a dense and smooth surface with no obvious
pores is formed. However, when a weaker coagu-
lant is employed such as methanol, which may be
mixed with water, the roughness of the formed
hollow ber surface may increase considerably
due partially to the formation of pores. These are
the reasons for using the coagulants: 80 wt.%
N-methylpyrrolidone (NMP) aqueous solution
by Wang et al. (2008) for preparation of PVDF
hollow ber membranes and 80 wt.% methanol
aqueous solution by Bonyadi and Chung (2007)
for fabrication of dual hydrophilic/hydrophobic
hollow ber membranes for direct contact mem-
brane distillation (DCMD) process. Figure 1
shows the effects of the external coagulant on
the cross-sectional structure of porous hydropho-
bic hollow ber membranes (Khayet et al. 2002).
Water and 50 % (by volume) ethanol in water
were used as internal and external coagulants. In
Fig. 1a prepared with water as internal and exter-
nal coagulants, long nger-like voids are formed
near the inner surface, while smaller cavities are
formed near the outer surface. Between the inner
and outer layers, sponge-like structure appears. In
Fig. 1b the outer layer is eliminated when ethanol
is added to the external coagulant. The addition of
ethanol delays the external coagulation process
and the nger-like structure changes to a sponge-
like structure. The slow coagulation of the hollow
735
(b) internal coagulant water and external coagulant 50 %
ethanol in water (Reprinted from (Khayet et al. 2002).
Copyright 2002, with kind permission from Elsevier)
ber membranes can be explained on the basis of
the mutual diffusivity of solvent/non-solvent
exchange and solubility parameters of the mate-
rials involved in hollow ber spinning. The addi-
tion of ethanol in water reduces the diffusion of
non-solvent into the nascent hollow ber mem-
brane and consequently decreases the rate of pre-
cipitation. Khayet et al. (2002) observed an
increase of the external surface roughness of
PVDF hollow bers when ethanol was added to
the external coagulant and attributed the result to
the increase of the pore size at the outer surface as
ethanol was added in the coagulation bath.
References
Bonyadi S, Chung TS (2007) Flux enhancement in mem-
brane distillation by fabrication of dual layer
hydrophilic-hydrophobic hollow ber membranes.
J Membr Sci 306:134146
Khayet M, Feng CY, Khulbe KC, Matsuura T (2002) Prep-
aration and characterization of polyvinylidene uoride
hollow ber membranes for ultraltration. Polymer
43:38793890
Mulder M (1992) Basic principles of membrane technol-
ogy. Kluwer Academic Publishers, Dordrecht
Wang KY, Chung TS, Gryta M (2008) Hydrophobic PVDF
hollow ber membranes with narrow pore size distri-
bution and ultra-skin for the fresh water production
through membrane distillation. Chem Eng Sci
63:25872594
736
Extracellular Polymeric Substance
(EPS)
Loreen O. Villacorte
FMC Technologies, Separation Innovation and
Research Center, Arnhem, The Netherlands
Extracellular polymeric substances or EPSs are
biosynthetic polymers from prokaryotic
(bacteria, archaea) and eukaryotic (algae, fungi)
microorganisms, which either form (loose or
tight) slimes around the microbial cells or are
excreted as discrete gels to the surrounding envi-
ronment. Typically, EPSs are heterogeneous mix-
tures of polysaccharides, proteins, nucleic acids,
lipids, and other polymeric compounds. The
highly diverse chemical composition of EPS is a
result of the different processes related to their
production and their immediate environment:
active microbial secretion, shedding of cell sur-
face materials, cell lysis, and adsorption from the
environment (Wingender et al. 1999).
EPSs are often associated with the formation of
biolms and microbial aggregates. In biolm sys-
tems, they are mainly responsible for binding cells
and other particulate materials together and to the
solid-liquid interface (Characklis and Wilderer
1989). In surface water sources, suspended EPSs
are responsible for the formation of large aggre-
gates of organic and inorganic suspended mate-
rials including living and dead microorganisms in
the water (e.g., marine snow or mucilage). These
aggregates are held together by a type of EPS
mainly comprising of surface-active, algae-
derived anionic polysaccharides collectively
known as transparent exopolymer particles
(Alldredge 2002). The latter has been recently
identied as one of the major initiators of aquatic
biolms as it can form conditioning lms on the
solid-liquid interface conducive for bacterial
attachment (Bar-Zeev et al. 2012).
Over the years, the important role of EPS in the
microbial activities in natural aquatic systems is
widely recognized. Moreover, it has also been
identied to cause serious problems in technical
systems ranging from the shipping industry,
Extracellular Polymeric Substance (EPS)
power industry, microelectronics, and food indus-
tries to water purication (Flemming et al. 2009).
In water supply systems, such problems are due to
either organic or biological fouling of reservoirs,
pipelines, media lters, and separation membranes.
EPS accumulation in membrane ltration sys-
tems can cause increase of operating pressure and
cleaning frequency due to blockage of membrane
pores as well congestion along the feed channel
(Flemming et al. 1997). In NF/RO systems, it can
directly cause decline in permeate water quality
(e.g., salt rejection) due to hindered back diffusion
of rejected salts and can indirectly cause mem-
brane damage due to long exposure of cleaning
chemicals and very high feed channel pressure
drop (Vrouwenvelder et al. 2011). It has been
proposed that the removal of planktonic EPS
from the feedwater by pretreatment with dissolved
air otation (DAF) and/or UF/MF membranes can
effectively minimize biofouling in NF/RO sys-
tems. However, this is still subject to extensive
debate and investigations.
During algal blooms, very sticky EPS materials
(including TEPs) produced by phytoplankton and
bacterioplankton can cause physically irreversible
(or non-backwashable) fouling in dead-end MF/UF
systems (Villacorte et al. 2010). In this case, chem-
ically enhanced backwashing (CEB) can be effec-
tive in restoring membrane permeability. However,
applying an optimal dose of coagulant
(conventional or in-line) prior to membrane ltra-
tion has been found to effectively minimize the need
for chemical cleaning (e.g., Schurer et al. 2012).
Cross-References
Transparent Exopolymer Particle
References
Alldredge AL (2002) Marine snow. In: Nybakken JW,
Broenkow WW, Vallier TL (eds) Interdisciplinary
encyclopedia of marine sciences. Grolier Academic
Reference, Danbury
Bar-Zeev E, Berman-Frank I, Girshevitz O, Berman
T (2012) Revised paradigm of aquatic biolm forma-
tion facilitated by microgel transparent exopolymer
particles. Proc Natl Acad Sci USA 109(23):91199124
Extracorporeal Blood Oxygenation Devices, Membranes for
Characklis WG, Wilderer PA (1989) Glossary. In:
Characklis WG, Wilderer PA (eds) Structure and func-
tion of biolms. Wiley, Chichester, pp 369371
Flemming H-C, Schaule G, Griebe T, Schmitt J,
Tamachkiarowa A (1997) Biofouling the Achilles
heel of membrane processes. Desalination 113:215225
Flemming H-C, Murthy PS, Venkatesan R, Cooksey KE
(eds) (2009) Marine and industrial biofouling,
vol 4, Springer Series on Biolms. Springer, Berlin
Lens P, OFlaherty, Moran AP, Stoodley P, Mahony T (eds)
(2003) Biolms in medicine, industry and environmen-
tal biotechnology: characteristics, analysis and control.
IWA Publishing, London
Schurer R, Janssen A, Villacorte L, Kennedy MD
(2012) Performance of ultraltration & coagulation in
an UF-RO seawater desalination demonstration plant.
Desalination Water Treat 42:5764
Villacorte LO, Schurer R, Kennedy MD, Amy G,
Schippers JC (2010) The fate of transparent
exopolymer particles in integrated membrane systems:
a pilot plant study in Zeeland, The Netherlands. Desa-
lination Water Treat 13:109119
Vrouwenvelder JS, Kruithof J, Van Loosdrecht M (2011)
Biofouling of spiral wound membrane systems. IWA
Publishing, London
Wingender J, Neu TR, Flemming H-C (eds) (1999) Micro-
bial extracellular polymeric substances: characteriza-
tion, structure, and function. Springer, Berlin
Extracorporeal BALs
Bioarticial Liver Support System (BLSS)
Extracorporeal Blood Oxygenation
Devices, Membranes for
Mnica Faria1 and Maria Norberta De Pinho2
1
Chemical Engineering, Columbia University,
New York, NY, USA
2
Chemical Engineering, Instituto Superior
Tcnico, Universidade de Lisboa, Lisbon,
Portugal
Introduction to Extracorporeal Blood
Oxygenation
In physiology, respiration is dened as the trans-
port of oxygen from the outside air to the cells
737
within tissues and the transport of carbon dioxide
in the opposite direction. The heart and lungs
work together to ensure the circulation and the
exchange of the respiratory gases. During circu-
lation, the heart pumps oxygen-depleted blood to
the lungs and then receives oxygen-enriched
blood from the lungs for distribution to the rest
of the body. In the lungs, the gas exchange pro-
cess takes place in grapelike clusters of air sacs
known as the alveoli. There are about 300 million
E
alveoli in the lungs with a combined surface area
of approximately 70 m2. This is the area through
which the bloodgas exchange takes place
(Weibel 2009). Fresh air entering the lung carries
oxygen with a partial pressure of oxygen (PO2) of
160 mmHg; the presence of moisture in the lung
alveoli results in reduction of the PO2 to
104 mmHg. The same air that enters the lung
carries carbon dioxide with a partial pressure of
carbon dioxide (PCO2) of 0.3 mmHg. The carbon
dioxide delivered to the lung from the blood in
the venous ends of the pulmonary capillaries
raises the PCO2 in the alveoli to 40 mmHg
(McArdle et al. 2005). At the arterial ends of
the pulmonary capillaries, oxygen diffuses from
the air in the alveoli into the blood, and carbon
dioxide diffuses from the blood into the alveoli
because of differences in partial pressures. The
heart then receives the oxygenated blood from
the lungs and distributes it to tissues in the rest of
the body. In most tissues, the PO2 is less than
40 mmHg and the PCO2 is greater than
45 mmHg so, because of the differences in partial
pressures, oxygen diffuses out of the arterial ends
of tissue capillaries into the cells, and carbon
dioxide diffuses out of the cells into the blood.
The heart pumps the oxygen-depleted blood back
to the venous ends of the pulmonary capillaries
entering the alveoli with a PO2 of 40 mmHg and
PCO2 of 45 mmHg (Fox 2007).
In June of 2011, the World Health Organiza-
tion classied heart diseases as the worldwide
number one cause of death (WHO 2011). The
treatment of many cardiac-related diseases such
as coronary artery bypass grafting, valve repair,
and aortic aneurysm repairs involves complex
open-heart procedures where surgeons need to
operate on a motionless heart in an almost
738
Extracorporeal Blood Oxygenation Devices, Membranes for, Fig. 1 Main components and the function of the
extracorporeal membrane blood oxygenation system
bloodless surgical environment. Cardiopulmo-
nary bypass (CPB) is a technique in which a
heartlung machine temporarily takes over the
function of the heart and lungs during surgery,
maintaining the circulation of blood as well as
the oxygen and carbon dioxide contents of the
body. Figure 1 shows the main components and
the function of the heartlung machine. In the
operating theater, the heartlung machine pro-
vides mechanical circulatory replacement of the
heart by means of a pump and of the lungs through
a blood oxygenator (BO). During CPB, the sur-
geon inserts large catheters or cannulas into the
vena cava and the aorta and then administers a
chemical solution to cause the heart to stop beat-
ing (cardioplegia). Oxygen-depleted blood is
diverted from the upper chambers of the heart to
a reservoir in the heartlung machine. From there,
the blood is then transferred to the BO which
infuses the blood with oxygen and allows carbon
dioxide to diffuse in the opposite direction. Other
Extracorporeal Blood Oxygenation Devices, Membranes for
components of the bypass machine include spe-
cial lters that capture air bubbles and a heat
exchanger that cools the blood during surgery
and warms it at the conclusion of surgery to pre-
pare for returning the body to its own cardiovas-
cular circulation. The blood is cooled to maintain
the bodys metabolism at a lower rate, reducing
the oxygen consumption. At the conclusion of the
operation, the surgeon withdraws the cannulas
and restores the ow of blood in the body and
the heartbeat.
The heartlung machine is also used in inten-
sive care units and cardiac catheterization labora-
tories, as an extracorporeal life support (ECLS)
system for maintaining blood ow and respira-
tion. The diseased heart or lung(s) is replaced by
this technology, providing time for the organ to
heal. The heartlung machine can also be used
with venoarterial extracorporeal membrane oxy-
genation (ECMO), which is used primarily in the
treatment of lung disease and is considered a
Extracorporeal Blood Oxygenation Devices, Membranes for
standard therapy for the treatment of respiratory
failure in neonatal patients (Grenvik et al. 1999;
Roy et al. 2000).
In adult and pediatric patients, clinical ECMO
is a treatment of last resort for individuals who
would otherwise die despite maximal therapy
(Bartlett et al. 2000). Since the 1990s, this treat-
ment has grown continuously in the treatment of
adult patients with respiratory dysfunction, for
oxygenation and carbon dioxide removal, and as
a lung-protective ventilatory strategy in order to
rest the lungs and provide optimal conditions
for the recovery of lung function (Ghosh
et al. 2009). Despite the current limited applica-
tion of ECMO in adults, a randomized controlled
trial (RCT) is recruiting patients in the United
Kingdom to evaluate the cost-effectiveness and
clinical benet of modern ECMO technique
(Peek et al. 2006). This RCT will be one of the
rst RCTs performed in adults since the bench-
mark NIH trial during the 1970s (Zapol
et al. 1979) and could reveal an increase in the
rate of survival of patients with severe, but poten-
tially reversible, respiratory failure without severe
outcomes of disability, if technical and clinical
advancements improve outcomes.
Clinical Practice, Risks, and History
of Extracorporeal Blood Oxygenation
Blood is a complex tissue designed to sustain the
body by continuous circulation within a vast net-
work of blood vessels coated with endothelial
cells. These unique cells simultaneously maintain
the uidity of blood and ensure integrity of the
vascular system. Contact with the surgical wound
and diversion of blood into the heartlung
machine trigger a massive defense reaction that
stimulates all types of blood cells and ve plasma
protein systems to produce a myriad of vasoactive
cytotoxic and cell-signaling substances into the
circulation. Platelets, neutrophils, monocytes,
and endothelial cells are the major cellular actors,
and complement, contact, intrinsic coagulation,
extrinsic coagulation, and brinolytic protein sys-
tems are the primary plasma participants. When
activated, these cells and proteins initiate complex
and overlapping reactions and interactions with a
multitude of target molecules to create a whole
739
body inammatory response (Kirklin et al. 1983;
Edmunds and Colman 2006). Although the safety
of CPB has been established with low mortality
rates, it is still associated to risks such as blood
clots and air bubbles that can cause embolism
(occlusion of a blood vessel), hemolysis or dam-
age to red blood cells, and immune system acti-
vation or systemic inammatory response.
Studies show that presently patients undergoing
cardiac surgery with CPB can still experience
E
systemic inammatory response syndrome
(SIRS) (Segal et al. 1998; Onorati et al. 2010).
This results in severe and irreversible effects such
as cerebral injury and cognitive impairment (Lund
et al. 2005), endothelial injury (Verrier and Boyle
1996), organ dysfunction and impaired hemosta-
sis (Hsu 1997) also known as the process of blood
clotting, blood coagulation or thrombus forma-
tion, graft occlusion, perioperative strokes and
pulmonary thromboembolism (Valley
et al. 2010), and even postoperative morbidity
and mortality (Hammon 2008; Vallely
et al. 2010).
In order to prevent in-circuit thrombosis,
or clotting, patients undergoing CPB or
ECMO require the administration of systemic
anticoagulation agents. Unfractionated heparin,
which suppresses the action of thrombin, the key
enzyme in the thrombotic portion of the defense
reaction, has been the elected anticoagulant for
over half a century. Although the results are gen-
erally satisfactory, there are sometimes controver-
sial effects due to (i) thrombin being, in certain
patients, only partially suppressed by heparin
(Janvier et al. 1996; Edmunds and Colman
2006) or (ii) major hemorrhaging even after the
patients are subjected to correction of the
coagulopathy with antibrinolytic drugs
(Chalwin et al. 2008). About 3070 % of patients
undergoing coronary artery bypass grafting under
CPB require homologous blood transfusions
(Scott et al. 1992). The major risks such as
SIRS, activation of the blood coagulation cascade,
blood cell trauma, thrombosis, clotting,
hemorrhaging, etc., which patients submitted to
CPB and EMCO encounter, are all due to the
contact of the blood with foreign surfaces of mate-
rials with inadequate blood compatibility also
740
known as hemocompatibility. Among these sur-
faces contacting blood in the extracorporeal blood
oxygenation system, the membranes for the gas
exchange are of primordial importance due to
their extensive surface area.
The start of the historical development of
extracorporeal circulation is strongly related to
Csar Julian Jean Le Gallois (17701814). In the
monograph published in 1812, Experiences sur le
principe de la vie, he suggested that a part of the
body might be preserved by a mechanical heart
replacement and some kind of external perfusion
device (Le Gallois 1812). After the rst idea of
external perfusion devices by Le Gallois, the rst
attempts of oxygenating blood outside the body
were made by the physiologist Alexander
Schmidt, in 1876, when he perfused an isolated
dog kidney with oxygenated blood (Kramme
2011). The original BO, invented by von Frey
and Gruber (Kay 1992), in 1885 was the lm
BO; it used rotating cylinders to spread blood in
a continuously renewed thin lm while oxygen
owed over it. Though there was direct contact
between the blood and gas phases, the gas
exchange efciency was low, leading to devices
that had very large priming volumes. Using the
same principle, John Gibbon, best known for
inventing the heartlung machine, developed his
rst lm BO in 1937 (Gibbon 1937) and, after
years of tests and improvements, performed the
rst successful open-heart surgery with extracor-
poreal blood oxygenation in 1953 (Gibbon 1954;
Edmunds 2004). After this, several forms of sup-
plying oxygen to the blood were attempted, with
more or less success, enabling the development of
many models of oxygenators of which only a few
were clinically employed such as the bubble BOs.
In these devices, the gas exchange efciency was
increased by dispersing bubbles of oxygen
directly into the blood, which resulted in signi-
cantly reduced priming volumes compared to the
lm BOs (Cahn and Li 1974). On the other hand,
bubbling gas through blood led to foam forma-
tion, and therefore defoaming agents such as
silicone compounds had to be added to the
blood (Kremesec 1981). In 1955, DeWall
et al. performed the rst successful CPB proce-
dure using a bubble BO (DeWall et al. 1966). The
Extracorporeal Blood Oxygenation Devices, Membranes for
DeWallLillehei bubble oxygenator (Lillehei
et al. 1955; DeWall et al. 1966) was a major
breakthrough and well accepted by surgeons. It
was a simple disposable device where oxygen
bubbles were dispersed into an oxygenation
chamber containing venous blood that was
pumped from the patients body and then was
defoamed in a defoaming compartment before
returning to the patient. Although the benets of
bubble versus lm BOs have been often debated,
both have their own limitations. For lm BOs,
though the blood surface area was large, the gas
transfer efciency was often compromised by
channeling of the blood ow (Niiya and Noble
1985; Ho and Sirkar 1992) and a very large prim-
ing volume was usually required to obtain suf-
cient gas exchange. On the other hand, bubble
BOs caused signicant damage to the blood due
to the foam formation with devastating conse-
quences such as denaturation of plasma proteins,
gas emboli, fat emboli, brin emboli, and
neurocognitive decits (Lee et al. 1961, 1969;
Hill et al. 1969). Despite the nonphysiological
conditions of the bloodgas interface present in
bubble oxygenators, these were used until
15 years ago in around 23 % of open-heart sur-
gery worldwide (Wiese 2010).
Membrane Blood Oxygenators
and Principle of Membrane Blood
Oxygenation
Membrane blood oxygenators (MBOs) were rst
developed when the scientists introduced a
nonporous symmetric membrane between the
blood and gas phases to avoid direct contact
between the two phases in an attempt to improve
the hemocompatibility of BOs (Kolff and Balzer
1955; Clowes et al. 1956; Marx et al. 1962;
Dorson et al. 1968; Guidoin et al. 1978). This
represented a signicant breakthrough in the
development of blood oxygenation as the mem-
brane provides a barrier in the bloodgas interface
and that minimizes the risk of air embolism
(Iwahashi et al. 2004). Microporous MBOs are,
in fact, the state-of-the-art technology for extra-
corporeal blood oxygenation. Another advantage
Extracorporeal Blood Oxygenation Devices, Membranes for
Extracorporeal Blood Oxygenated blood
Oxygenation Devices, 100 mmHg O2
Membranes for, 40 mmHg CO2
Fig. 2 The principle of
membrane blood
oxygenation
200 cm3 (STP) / min CO2
Oxygen depleted blood
40 mmHg O2
46 mmHg CO2
of MBOs is in the device design and fabrication
which, because of the dened blood channels,
allows for precisely controlled blood ow charac-
teristics and, therefore, possibilities for optimal
efciency in gas exchange.
As in the natural lungs, transport of gas into
blood is driven by the partial pressure difference
of the respiratory gases between the blood and
the gas separated by the membrane. According
to the pressure differences, gas diffuses through
the membrane from the side of high partial pressure
to the side of low partial pressure. Figure 2 sche-
matically shows the principle of membrane blood
oxygenation. In order to be clinically functional for
an average healthy adult weighing around 70 kg, at
rest, the MBO must deliver, at standard tempera-
ture and pressure conditions, approximately
250 mL of oxygen per minute and remove the
corresponding carbon dioxide production of about
200 mL per minute. The controlling factor in the
design of these bloodgas exchange devices is the
permeability of the membranes toward oxygen and
carbon dioxide. The equivalent oxygen partial
pressure in venous blood is about 40 mmHg and
about 104 mmHg for arterial blood. Use of air as
the supply gas and at ambient pressure gives a
driving force for oxygenation of about 88 mmHg.
In contrast, in venous blood, the CO2 partial pres-
sure is about 45 mmHg which, assuming that the
exchanging air has negligible CO2 content, consti-
tutes the maximum driving force for CO2 removal
from the blood. The initial challenge in membrane
technology was to produce reliable membranes
with high permeabilities for oxygen, and much
741
Membrane
O2
250 cm3 (STP) / min CO2
E
CO2 / O2
emphasis was placed on oxygen transfer as the
controlling factor in the design of the bloodgas
exchanger system. However, in some cases,
removal of CO2 from the blood may be a limiting
factor in the design (Bungay et al. 1986; Stamatialis
et al. 2008).
Development of Membrane Blood
Oxygenators
The very rst discovery of oxygen transfer across
an articial membrane was made by Kolff and
Berk in 1944 when they found that venous blood
was being oxygenated while owing through a
cellophane dialyzer that was in contact with oxy-
gen containing dialysate (Kolff et al. 1944). This
discovery stimulated the development of the use
of gas permeable membranes in order to separate
the blood phase from the gas phase in the BOs.
The rst plate-type membrane oxygenator was
built by Clowes Jr. in 1956 (Clowes et al. 1956).
Clowes membrane oxygenator was based on the
SkeggsLeonards (Skeggs et al. 1949; Skeggs
2000) plate dialyzer with its dialysis membrane
replaced with a supported ethylcellulose at sheet
membrane. In order to have the sufcient oxygen-
ating capacity for perfusion in an adult, it had to
have a multilayered system with a very large
membrane surface area of approximately 25 m2.
In 1956, Kolff developed the rst coil-type
membrane oxygenator (Kolff et al. 1956b) by
substituting the cellophane membrane in his own
developed articial kidney, the Kolff rotating
742
drum (Kolff 1954; Kolff et al. 1956a; Kolff and
Watschinger 1956), with a nonporous symmetric
dense polyethylene (PE) membrane. The blood
owed in a spiral mode, whereas the oxygen
owed parallel to the axis of the cylinder. To use
this membrane oxygenator for an adult patient, it
was necessary to assemble eight coil units with an
enormous membrane surface area for effective gas
exchange (Kolff et al. 1956a).
The second generation of nonporous symmet-
ric membranes appeared in the 1960s with the
development of silicone rubber which displayed
increased oxygen and carbon dioxide permeabil-
ities. The carbon dioxide permeability of silicone
is about ve times greater than the oxygen perme-
ability, and this partially compensates for the
smaller available driving force for carbon dioxide
transfer (Haworth 2003). Since the diffusion coef-
cient of oxygen and carbon dioxide in air is
about four orders of magnitude higher than in
blood, the gas-side mass transfer resistance was
negligible. The major resistance to respiratory gas
transfer was due to the membrane and the blood-
side concentration boundary layer (Weissman and
Mockros 1969). This brought about a major
advance in establishing the technical feasibility
of membrane oxygenators in the 1960s and
1970s as the required membrane area could be
optimized to less than 6 m2. Kolobow took advan-
tage of the development of silicone rubber and in
1963 developed an oxygenator utilizing the same
conguration of Kolffs coil lung but with a dif-
ferent assembly. A silicone rubber envelope
reinforced with nylon knit was wrapped around
a central core, and pure humidied oxygen was
passed through it under a negative pressure. The
blood owed across the at tubing parallel to the
axis of the cylinder. The average priming volume
of these units was of 0.1 L/m2, and they could
oxygenate venous blood at rate of approximately
1 L/m2/min (Kolobow and Bowman 1963). In
1965, Bramson et al. commercialized the rst
disposable nonporous symmetric silicone MBO
with an integrated heat exchanger (Bramson
et al. 1965). In 1971, Kolobow (Kolobow
et al. 1971) improved his rst disposable coil
membrane oxygenator by using membranes fab-
ricated from silicone rubber deposited on a fabric
Extracorporeal Blood Oxygenation Devices, Membranes for
with an irregular structure. This membrane was
originally manufactured by Fuji Systems in
Tokyo, and its unique structure permitted
enhanced secondary ow effects that improved
the gas exchange capability. The improved
Kolobow oxygenator was successfully used in
the clinical eld, rst as an oxygenator for CPB
during cardiac surgery, and later in respiratory
assist devices was the only oxygenator available
for long-term application of ECMO for acute
respiratory failure patients (Kolobow
et al. 1971). In 1972, J. P. Hill reported the rst
successful treatment of adult respiratory distress
with ECMO (Hill 1977), and after 3 years of this
success, the rst neonatal ECMO survival case
was described by R. H. Bartlett (Bartlett
et al. 1976). This was the beginning of successful
ECMO application, and it has been shown to be
most effective in the treatment of newborn and
pediatric patients (Bartlett et al. 1982).
The real breakthrough in MBOs came in the
1980s with the development of hydrophobic
microporous membranes. These membranes
were made from polytetrauoroethylene (PTFE)
and the membrane pore diameters ranged from
0.02 to 0.1 mm. The respiratory gases pass through
the membrane pores rather than diffuse through
the membrane material and, consequently, offer
a much lower resistance to gas transfer than
the nonporous membranes. Polypropylene
(PP) microporous membranes were introduced
soon after and displaced the PTFE membranes
because they have lower cost and better mechan-
ical properties, which offered better control of the
blood channel geometry (Haworth 2003).
In 1981, Y. Nose (Nos and Malchesky 2000)
started to work on the rst microporous hollow
ber membrane oxygenator the Monsanto oxy-
genator. Although the gas exchange characteris-
tics were reasonable, the device leaked a large
amount of plasma through the membrane walls.
The rst commercially available hollow ber oxy-
genators, the Capiox MBO, composed of PP
microporous membranes was developed in 1981
by Terumo Corporation (Terumo Corporation,
Tokyo, Japan) and Suma (Suma et al. 1981). In
order to avoid plasma leakage, the inner surface of
the microporous PP hollow bers was coated with
Extracorporeal Blood Oxygenation Devices, Membranes for
a silicone layer with a thickness of approximately
0.2 mm. In these two MBOs, the blood was
pumped inside the bundle of hollow bers
(luminal ow), while the gases circulated on the
outer side. As the venous blood entered each ber,
it was surrounded by an oxygen-rich ventilating
gas mixture which passed through the ber walls
into the bloodstream (Weissman and Mockros
1968; Dutton et al. 1971; Suma et al. 1981;
Tanishita et al. 1994). It was soon found that, for
routine short-term perfusion, these types of MBOs
presented no real advantage over bubble models
mainly due to thrombus formation within the
bers (Calaore et al. 1987; Bergdahl and
Bergdahl 1989). In the 1980s, microporous
MBOs with intraluminal ow accounted for only
20 % of all blood oxygenators sold in the United
States (Voorhees and Brian 1996). At that time,
the gas transfer performance of MBOs was not yet
comparable with that of bubble blood oxygena-
tors, and, furthermore, the MBOs were complex
to operate.
The disadvantages presented by the MBOs trig-
gered a series of studies on mass transfer efcien-
cies, pressure drops, and shear stresses through
blood ow paths in different module congura-
tions. Designers of at sheet MBO modules
focused on incorporating passive mixing of the
blood to reduce the blood-side resistance to gas
transfer, and in 1984, an oxygenator was intro-
duced in the market by Cobe Cardiovascular
(Cobe Cardiovascular, Arvada, Colorado), with a
high gas transfer efciency and a membrane sur-
face area of only 2.5 m2. This was achieved
through the introduction of spacers over the at
sheet microporous membranes to induce mixing
on the blood side (Elgas and Gordon 1984). Exten-
sive studies of MBO modules with hollow ber
intraluminal blood ow (Alpha et al. 1986;
Gassman et al. 1987) led to the design of hollow
ber modules with blood owing on the outside of
the hollow bers (extraluminal ow), while oxy-
gen was administered through the inside of the
membranes. In 1985, the Johnson and Johnson
Extracorporeal Maxima Oxygenator (Johnson and
Johnson Cardiovascular, Anaheim, California) was
presented as a highly efcient and compact
MBO. It contained microporous cross-wound
743
hollow bers where the blood owed over and
under the outside of the bers (extraluminal ow)
while oxygen crossed from within the hollow bers
into the blood (Iatridis et al. 1985). In the 1980s, the
Kuraray Corporation (Osaka, Japan) began on the
development of a new device the MENOX
oxygenator that contained a silicone-coated
microporous polyolen membrane. The reason
behind the silicone coating is to reduce the plasma
leakage through the membrane pores and to correct
E
any defects at the surface of the membrane. The
developers claim that the membranes are
non-plasma-leaking and that the MENOX oxygen-
ator could be used in ex vivo experiments for up to
5 months (Nos 2001). Another coating developed
by Medtronic Inc. (Minnesota, USA) comprised of
an alkoxysilane/alkylsilane copolymer, preferably
aminoalkylsiloxane, was used to coat microporous
hollow ber membrane blood oxygenators,
increasing the resistance of the bers to passage
of blood plasma through the micropores (Plunkett
2002).
Nevertheless, in both cases, the coating pro-
vides an additional layer or second skin and
introduces an additional barrier to the gas transfer,
altering therefore a severe limiting factor of the
oxygen mass transfer to the blood.
The technological advances of MBOs devel-
oped during the 1980s permitted the increase of
the gas transfer efciency and reduction of
membrane surface area and priming volume. As
a consequence of these improvements and
with the general migration from blood owing in
the luminal to the extraluminal space of hollow
bers, by 1992, MBOs accounted for more than
98 % of all blood oxygenators sold in the United
States.
State of the Art of Commercial Membrane
Blood Oxygenators
The technical and medical progress of MBOs has
been intrinsically associated to the development
of membranes that can assure physiological trans-
port rates of oxygen and carbon dioxide and of
module congurations that are compact with min-
imal membrane surface area per unit volume and
with low resistance to oxygen transfer, particu-
larly on the blood side.
744
A membrane, in a very general sense, is a
semipermeable barrier that can be made of inor-
ganic or organic materials. In MBOs, organic
polymers are the membrane materials of selection
due to their physicochemical and structural versa-
tility. According to their structure, membranes can
be divided in four main categories: nonporous
symmetric membranes, microporous membranes,
integral asymmetric membranes, and composite
asymmetric membranes. All of them can be
processed in the form of at sheets or hollow
bers (Bungay et al. 1986; Mulder 1996; Baker
2004). Nonporous symmetric membranes consist
of a dense lm where the selective transport of
gases is governed by a solution/diffusion mecha-
nism. Microporous membranes have a rigid,
highly voided structure with randomly distrib-
uted, interconnected pores of different shapes
and sizes from 0.01 to 10 mm in diameter
depending on the preparation process. Asymmet-
ric membranes, rst developed by Loeb and
Sourirajan in 1963 (Loeb 1981), consist of two
layers: a dense and nonporous symmetric active
skin layer with thickness ranging from 0.1 to
50 mm and a relatively thick porous support layer
with thickness between 50 and 500 mm. The over-
all performance of the membrane is governed by
the top dense layer, while the porous sublayer
provides mechanical strength to the membrane.
When the material of the top layer and porous
sublayer are the same, the membrane is called an
integral asymmetric membrane and when com-
posed of different materials known as asymmetric
composite membranes.
The packaging and arrangement of the mem-
branes play a fundamental role in the development
of MBOs. Efcient packaging of large surface
areas of membrane into small volume devices
lead to MBOs of high gas transfer rates and low
priming volumes. Furthermore, the blood ow
path must be carefully designed. While disrupting
the blood-side mass transfer boundary layer will
lead to higher gas transfer efciencies, it also
leads to increased shear stresses on the blood
cells. Damage to blood cells depends both on the
applied shear stress and on the time for which the
shear stress is applied (Zydney 1985). Thus, while
mixing on the blood side is desirable, it is essential
Extracorporeal Blood Oxygenation Devices, Membranes for
to ensure that the blood cells and blood compo-
nents are not damaged.
Early microporous MBOs contained up to
5.5 m2 of membrane surface area (Von Segesser
1987), so, in order to overcome slow gas transfer
rates due to the high blood-side mass transfer
resistance, modern MBOs have utilized secondary
ow effects to disrupt the blood-side concentra-
tion boundary layer and hence reduce the mem-
brane surface area and priming volume. In the
case of at sheet MBOs, such as the Cobe CML
30 (Cobe Cardiovascular, Arvada, Colorado,
USA) (Voorhees and Brian 1996), the membrane
surface area has been reduced to between 2.5 and
3.0 m2, whereas for hollow ber designs with
extraluminal blood ow such as the Cobe Optima
(Medtronic Maxima, Medtronic, Anaheim, Cali-
fornia, USA) (Ulrich 1990), the membrane sur-
face has been reduced to between 1.7 and 2.3 m2.
In developed countries, the rate of growth of
the elderly population is exceeding the growth
rate of the rest of the population, and this means
that in the near future cardiac surgery will be
performed on older and less healthy patients,
some of which may even need to undergo more
than one operation (Voorhees and Brian 1996).
This changing patient population as well as clin-
ical and economic factors will demand improved
MBOs. Designing improved and novel MBOs is a
complex procedure given the interdependence of
the important design variables as described
below:
Maximizing the gas transfer per unit priming
volume of the device is essential. In the past,
the patients body temperature was lowered by
cooling the blood during CPB, thus reducing
the oxygen requirement. In current practice,
there is a trend toward normothermic coronary
perfusion which increases the oxygen require-
ment (Galletti 1993). In addition, the need to
minimize the transfusion of donated blood due
to possible transmission of pathogens will
drive module design toward lower priming
volumes (Voorhees and Brian 1996).
Minimizing the membrane surface area of the
device has clinical and economic benets. Dur-
ing CPB surgery, hematological and immune
Extracorporeal Blood Oxygenation Devices, Membranes for
responses are observed as a result of contact
between the blood and oxygenator surfaces.
While these side effects are relatively minor
in healthy patients, they are of concern for
older and less healthy patients. An increased
gas transfer efciency would allow a reduction
in membrane surface area and hence a reduc-
tion in the average contact time between the
blood and foreign surfaces. Since the mem-
brane is often the most expensive component
in a MBO, minimizing the membrane surface
area will reduce manufacturing costs.
The blood ow path must be carefully
designed. While disrupting the blood-side
mass transfer boundary layer will lead to
higher gas transfer efciencies, it also leads to
increased shear stresses on the blood cells.
Damage to blood cells depends both on the
applied shear stress and the time for which
the shear stress is applied (Kolff et al. 1944).
Thus, while mixing on the blood side is desir-
able, it is essential to ensure that the cells are
not damaged.
In the last decade, rather than focusing on the
research of novel blood oxygenation membranes,
most researchers have been concerned with blood
ow congurations for mass transfer enhance-
ment in hollow ber MBOs. Extraluminal blood
ow may be concurrent, crosscurrent, or counter-
current to the ow of gas within the bers, and all
these ow patterns have been studied. Some
researchers demonstrated that a hollow ber mod-
ule, in which the hollow bers are perpendicular
to the blood ow, is the most efcient as it pro-
motes the disruption of the momentum and con-
centration boundary layer on the blood side. The
subsequent decrease of the resistance to gas mass
transfer leads therefore to the increase of oxygen
transfer rates (Mockros and Leonard 1985; Yang
and Cussler 1986, 1986; Rajasubramanian
et al. 1997; Wickramasinghe and Han 2005).
However, this blood ow arrangement compli-
cates the design of oxygenators because of
the complex blood ow path and the
non-applicability of conventional mass transfer
correlations. As a consequence, many studies of
momentum and mass transfer in MBOs have been
745
carried out (Vaslef et al. 1994; Gabelman and
Hwang 1999; Wickramasinghe and Han 2002;
Taskin et al. 2010). Nagase et al. (2005a, b) have
thoroughly investigated the relationship between
the oxygen transfer rate and hollow ber arrange-
ment and found better mass transfer performance
in parallel ow hollow bers. This was due to the
fact that in the hollow ber module with blood
perpendicular ow, the hollow bers in the front
layer conceal those in the rear layer at the cross-
E
over point, and this decreases the mass transfer
rates. Furthermore, the membrane surface areas of
these parallel modules were larger than the ones in
the other modules. Other studies show that high
gas transfer rates can be obtained when micropo-
rous hollow ber membranes are arranged in an
orderly way in cross-laid double layer mats at an
optimal membrane angle (Catapano et al. 2001).
The MBOs used in ECMO for long-term lung
support system applications in infants and adults
account for a very small part of the MBOs used
worldwide. The at sheet coil-type modules are
generally composed of a nonporous, dense at
sheet reinforced silicone rubber membrane enve-
lope in a spiral coil around a polycarbonate spool.
The blood ows between turns of the envelope in
a thin lm, and oxygen from the gas compartment
diffuses through the membrane into the blood-
stream. At the same time, carbon dioxide diffuses
through the membrane into the gas compartment
and is ushed from the oxygenator by the oxygen
ow. More recent oxygenators aimed for long-
term ECMO usage are based on hollow ber
silicone-based membranes with extraluminal
blood ow (Kawahito et al. 2002a, b; Motomura
et al. 2003).
Hollow ber and at sheet MBOs have almost
equivalent hemocompatibility and gas exchange
performance. However, the gross air handling is
different due to differences in the packing density
dened by the total available membrane surface
area per unit volume. Gu et al. (2000) compared
at sheet and hollow ber MBOs in terms of
pressure drop, shear stress, and activation of leu-
kocytes or white blood cells. They found that both
congurations displayed similar gas transfer per-
formance. However, the pressure drop along the
blood ow path of the at sheet MBOs was higher
746 Extracorporeal Blood Oxygenation Devices, Membranes for
than that for hollow ber MBOs. Moreover, acti-
vation of leukocytes in at sheet MBOs was
greater. De Somer et al. (1996) compared at
sheet and hollow ber MBOs in terms of hemoly-
sis, shear stress, and white blood cell and platelet
counts and found that although they have important
differences in pressure drop and shear stress, no
statistical differences were found in hemolysis gen-
eration or other tormented blood elements. There-
fore, pressure drop as a single element may not be
considered to inuence hemocompatibility.
A tremendous amount of research, as
evidenced by the numerous scientic articles and
patents, has been devoted to the design of the
MBOs available today. In 1999, the total BO
market was worth about $460 million and by
2001 had risen to over $500 million (Hanft
2002). In 2008, an estimated 1.4 million MBOs
were used worldwide for acute surgical CPB,
corresponding to a consumption of approximately
3 million km2 of oxygenation membranes (Wiese
2009).
Presently, most of the MBOs sold worldwide
contain hydrophobic microporous membranes,
and more than 95 % of them are composed of
extraluminal ow microporous hollow ber mem-
branes with pore sizes below 0.1 mm, outer diam-
eters between 300 and 500 mm, and surface areas
of approximately 2 m2. The hollow ber mem-
branes are assembled into carefully spaced cross-
laid double layer woven mats which provide uni-
form extraluminal ow channels for the blood
(Hanft 2002). The main polymers used in the
production of the blood oxygenation membranes
are polyolens such as polypropylene (PP), poly-
ethylene (PE), and poly-4-methylpentene (PMP)
and, at a smaller scale, polyvinylidene uoride
(PVDF) and silicone rubber (Wiese 2009).
Current Problems
Extracorporeal membrane blood oxygenators
(MBOs) used in the medical eld to substitute
the respiratory function of the lung have at their
very core membranes that act as a bloodgas
barrier and ensure oxygen delivery and carbon
dioxide removal from the patients bloodstream.
In order to be technologically feasible, the MBOs,
with minimal membrane surface area, have to
comply with two main properties: (i) be efcient
gas exchangers and provide physiological oxygen
and carbon dioxide transfer rates of approximately
250 cm3 per minute and 200 cm3 per minute,
respectively, at standard temperature and pressure
conditions and (ii) be hemocompatible.
The majority of current MBOs are made of
hollow bers of microporous hydrophobic mate-
rials with pore sizes below 0.1 mm. The resistance
of these membranes toward the respiratory gases
is very low as the gas exchange between the blood
side and the gas side is performed by diffusion and
convection of oxygen and carbon dioxide via the
open pores. MBOs with these types of membranes
have high gas permeabilities and are routinely
used to provide temporary cardiopulmonary
bypass (CPB) during open-heart surgery and are
also occasionally used for extracorporeal life sup-
port (ECLS) to substitute short-term cardiopulmo-
nary function in patients with respiratory failure.
One of the drawbacks of microporous hydropho-
bic membranes is plasma breakthrough which
occurs when plasma protein layers are formed at
the membrane surface and grow through the mem-
brane pores increasing the surface energy of the
pore, allowing plasma to leak through from the
blood side to the gas side (Montoya et al. 1992).
Another main concern that has troubled the
membrane industry for the past 30 years and to
date remains a serious issue is the blood compat-
ibility or hemocompatibility of the oxygenation
membranes. The denition of biocompatibility
has been updated for over 20 years and can be
considered as being the bodys acceptance of the
material, i.e., the ability of an implant surface to
interact with the cells and uids of the biological
system and to cause exactly the reactions which
the analogous body tissue would bring about
(Ratner 1993; Williams 2008). Presently, the bio-
materials community has been unable to more
accurately assign the term blood compatible to
a given biomaterial in spite of 50 years of inten-
sive research on the subject. There is no clear
consensus as to which materials are blood com-
patible as blood material interactions are com-
plex and involve multiple factors including
Extracorporeal Blood Oxygenation Devices, Membranes for
surface chemical composition, charge, exibility,
wettability, and conditions of blood ow
(Cazenave 1987). Furthermore, unlike biocom-
patibility assays, there are no standardized
methods to assess blood compatibility (Ratner
2007). Labarres (2010) tentative denition of a
blood compatible surface is a surface able to
keep under control coagulation and inammation
processes at its interface with normal blood, in
given hemodynamic conditions. According to
Ratner, we still do not have truly blood compatible
surfaces after 60 years of intense research of blood
compatibility and after numerous approaches
have been tried (Ratner 2007). The hemo-
compatibility of biomaterials is known to be
dependent on various surface properties such as
surface morphology, surface chemical composi-
tion, surface charge, surface wettability, and sur-
face topography. The overall blood-contacting
surfaces must avoid damage to the blood cells
and components but also to avoid stagnation and
localized clotting.
To improve blood compatibility of transport
surfaces such as the ones in MBOs, researchers
have focused mainly on surface modication
techniques and producing hemocompatible sur-
face coatings. Minimization of blood/material
interactions can be achieved through chemical
modication; however, these methods are still
far from perfect. Surface chemical modication,
besides requiring rather complex experimental
procedures and involving high costs, still does
not offer surfaces with long-term stability and
leads to potential complications downstream
(Klee and Hcker 2000). Most manufacturers
have focused on the development of
anticoagulant-based coatings for the entire bypass
circuit including the oxygenation membranes.
This approach led to the commercialization of
microporous-coated membranes and bypass-
coated circuits. Various manufacturers claim
that the added layer of material provides a
blood-surface interaction with improved
hemocompatibility compared to that seen for
the bulk ber materials. For example, heparin is
known to have good blood compatibility
properties and has been used as a coating on
several commercialized products. Unfortunately,
747
heparin-based coatings are inherently expensive
and complex due to the use of sodium heparin, a
complex, costly, and fragile biologically derived
substance. The Carmeda Bioactive Surface
(Medtronic, Inc.) uses a polymer primer coat
followed by covalent attachment of heparin to
primary amino groups present in the primer coat
(Stenach et al. 1992; Spiess et al. 1998). The
Durao Bonded Heparin Surface (Baxter, Inc.)
uses a heparin-polymer blend-based coating that
E
is intended to achieve similar results (Toomasian
et al. 1988; Mottaghy et al. 1989). Other heparin-
based coatings intended to improve blood com-
patibility are available from other medical device
manufacturers such as Terumo (Fukasawa 1983),
3M Sarns (Zacour 1988; Fried and Bell-Thomson
1992), etc.
Despite these developments, in order to pre-
vent in-circuit thrombosis, or clotting, when
subjected to extracorporeal blood oxygenation
using any of the MBOs available on the market,
patients still require the administration of antico-
agulant drugs that often lead to major hemorrhag-
ing and blood transfusions.
Another approach to improve the hemo-
compatibility of membranes destined for MBOs
focuses on the development of novel blood oxy-
genation membranes made from materials
different to the polyolens mentioned before.
Polyurethanes (PUs) rst found a niche in bio-
medical applications mainly because of their
unique mechanical properties, particularly fatigue
resistance, tensile strength, and abrasion (Szycher
and Poirier 1983; Szycher et al. 1983; Graig 1983;
Gogolewski 1989; Hepburn 1992; Furukawa
1997), but also because of their good bio- and
hemocompatibility properties (Boretos 1980;
Wang and Cooper 1983; Yoon and Ratner 1988;
Gogolewski 1989). PU membranes are a good
candidate for blood oxygenation devices as the
type, length, ratio, and crystallinity of the different
monomers as well as the method of membrane
preparation determine the bulk properties respon-
sible for the nal mass transfer properties (Yilgr
and Yilgr 1999; Hoshi et al. 2000; Jonquires
et al. 2002) and the surface properties that affect
bio- and hemocompatibility (Yoon and Ratner
1988; Gogolewski 1989).
748
Blood Compatibility and Membrane/Blood
Interfaces
In 2007, an estimated 250 million polymeric
devices contacting the bloodstream were used in
humans. All of these blood-contacting devices
exhibited thrombosis problems, and all cardiovas-
cular device procedures, both short term and long
term, required signicant anticoagulation, at high
cost and with considerable risk to the patient
(Geckeler et al. 1997). The number of blood-
contacting medical devices used worldwide is
increasing every day, but their hemocompatibility
properties still remain far from ideal.
To this date, there is no consensus denition of
blood compatibility. In 2007, Buddy Ratner
labeled as a catastrophe the fact that the scien-
tic community has still not been able to accu-
rately assign the term blood compatible to a
biomaterial in spite of 50 years of intensive
research on the subject (Geckeler et al. 1997;
Ratner 2007). While the denition of biocompat-
ibility is generally accepted as the ability of a
material to perform with an appropriate host
response in a specic application (Williams
1987), blood compatibility or hemocompatibility
has received different denitions by various
authors. From a clinical point of view, a biomate-
rial can be considered as blood compatible when
its interaction with blood does not provoke either
any damage of blood cells or any change in the
structure of plasma proteins. Only in this case can
it be concluded that this material fullls the main
requests of biocompatibility (Gurland 1987).
A tentative denition, by Labarre (2010), of a
blood compatible surface is a surface able to
keep under control coagulation and inammation
processes at its interface with normal blood, in
given hemodynamic conditions.
The contact between the blood and the surface
of a biomaterial often leads to different degrees of
clot formation, as a consequence of the
nonspecic protein adsorption and adhesion and
activation of blood cells (Horbett 1986; Courtney
et al. 1994). Within the rst few seconds after
blood contacts, material surface plasma proteins
are deposited. The extent of protein adsorption
depends on the properties of the foreign surface,
namely, the wettability, charge, roughness,
Extracorporeal Blood Oxygenation Devices, Membranes for
chemical composition, etc. This protein layer con-
trols further reactions of the other blood compo-
nents and cell system. Additionally, the adsorbed
proteins are subject to conformational changes as
well as exchange processes with other proteins
(Ziats et al. 1988). The competitive adsorption
behavior of proteins at the material surface deter-
mines the pathway and the extent of intrinsic
coagulation and adhesion of platelets. Platelets
play a fundamental role in hemostasis. Following
the protein adhesion to the surface of the bioma-
terial, coagulation is initiated by platelets adher-
ing to specic binding sites exposed by the plasma
proteins. The activated platelets swell, grow spiky
extensions known as pseudopodia, and release the
contents of their secretory granules, which contain
a variety of substances which include ADP, sero-
tonin, and thromboxane A2, which stimulate fur-
ther platelet adhesion and activation and enhance
the coagulation process. A large variety of clotting
factors take part in a series of chemical reactions
that eventually create a mesh of brin bers. Each
of the clotting proteins has a very specic func-
tion, and the three main ones are prothrombin,
thrombin, and brinogen. Thrombin promotes
the conversion of brinogen into long insoluble
bers or threads of another protein brin. Fibrin
threads wind around the platelets forming an
interlocking network of bers and a framework
for the clot. This net of bers traps and helps hold
platelets, blood cells, and other molecules tight to
the material surface, forming a blood clot also
referred to as a thrombus.
It has long been established, in the eld of
biomaterials, that bio- and hemocompatibility is
mainly governed by the surface properties of the
material that contacts the blood (Cooper 1982;
Lelah and Cooper 1986; Schamberger and
Gardella 1994). Predictions about the interactions
between the biomaterial surface and the adsorbed
proteins can only be formulated by having an
exact knowledge of the structure of the biomate-
rials surface and the conformation of the
adsorbed proteins. These interactions are deter-
mined both by the hydrophobic/hydrophilic,
charged/uncharged, and polar/nonpolar parts of
the proteins and the properties of the polymer
surface such as chemical composition,
Extracorporeal Blood Oxygenation Devices, Membranes for 749

morphology, charge, wettability, and topography Hb released  Hb negative control

(Dawids and Bantjes 1986; Williams and Wil- HI  100
Hb positive control  Hb negative control
liams 1989; Stamm 2008).
(1)
Hemocompatibility properties of surface
materials can be evaluated following the
where [Hb]released is the concentration of Hb in the
ISO10993-4 (Biological evaluation of medical
supernatant solution and [Hb]negative control and
devices, Part 4: Selection of tests for interactions
[Hb]positive control are the concentrations of Hb in
with blood. Geneva, Switzerland: International
the negative and positive controls, respectively.
Organization for Standardization; 2002) guide-
According to ASTM F-756, materials can be
lines in terms of protein adsorption, hemolysis,
labeled nonhemolytic when the HI is between E
platelet adhesion and platelet activation, whole
0 and 2, slightly hemolytic when HI is between
blood clotting time, and clinical coagulation
2 and 5, and hemolytic when HI >5.
times.
Thrombosis can be evaluated through an assay
Hemocompatibility properties of surface mate-
based on the determination of the thrombus mass
rials can be evaluated in vitro according to the ISO
formed on the surface of the membranes after
10993-4:2002 standard (ISO standard) guidelines
contact with static, recalcied blood, based on a
in terms of hemolysis, thrombosis, platelet adhe-
modication of the gravimetric assay proposed by
sion and activation, protein adsorption, and clini-
Imai and Nos (1972) and Allmr et al. (1990).
cal coagulation times. The three categories of
Samples of each membrane are cut into pieces
effects on blood most commonly evaluated are
with a surface area of 4 cm2, and 250 mL of
hemolysis, thrombosis, platelet adhesion, and
blood are carefully placed on top. The clotting
activation (Imai and Nose 1972; Goodman
process is then started by addition of 25 mL of
et al. 1989; Allmr et al. 1990; Haycox and Ratner
0.10 M CaCl2 to the blood drop on the sample.
1993; Tze-Man et al. 1993; Bahulekar et al. 1999;
The clotting process is stopped at different time
ASTM International 2000).
periods by addition of distilled water. The throm-
Damage to the membrane of red cells, as a
bus formed at the surface of the membrane is xed
result of blood exposure to foreign materials, can
with formaldehyde and then washed with water.
be evaluated by the hemolysis test. Hemolysis can
The thrombus mass is determined after drying the
be assessed by quantication of released hemo-
thrombus at 37  C until a constant weight was
globin (Hb) after contact between blood and sam-
reached. The results are expressed as a percentage
ple, according to the ASTM F 756-00 standard.
of the thrombus mass formed on glass (positive
The Hb concentration can be determined by col-
control). A pre-weighted lter paper disk that
orimetry at 540 nm, with a UV/VIS spectropho-
followed the above procedure in parallel, but in
tometer. In the cyanmethemoglobin method
the absence of a membrane sample and of blood,
(Moore et al. 1981; Van Assendelft et al. 1996;
was used as a blank. From the thrombus mass
Zwart et al. 1996), blood samples with a plasma
formed on each sample, a thrombosis degree is
Hb concentration below 2 mg/mL are diluted in
calculated as a percentage of the thrombus mass
PBS in order to obtain blood with a total Hb
formed on the positive control after subtracting
concentration of 10
1 mg/mL. The contact
the blank from each thrombus mass. A thrombosis
between diluted blood and membranes with an
degree of 100 % is assigned to the positive
area of at least 7 cm2 is maintained for at least
control;
4 h of static incubation at 37  C, and after which
the blood is centrifuged, the supernatants are ana- mmembrane  mnegative control
Thrombosis %  100
lyzed for their Hb content. Two controls are com- mpositive control  mnegative control
monly used: distilled water (positive control) and
PBS solution (negative control). The hemolysis The interaction between platelets and the surface
degree is expressed through the hemolytic index of the membranes can be evaluated by a technique
(HI), calculated as follows: often used by researchers based on the analysis of
750
Extracorporeal Blood Oxygenation Devices, Mem-
branes for, Fig. 3 Diagram of the platelet spreading
process divided into ve shape categories for analysis
and correlation between platelet categories and planimet-
rically determined platelet spread area. From left to right,
the stages of spreading are dened as follows: stage I
round or discoid: no pseudopodia present; stage
scanning electron microscopy (SEM) images
(Goodman et al. 1989; Haycox and Ratner 1993;
Tze-Man et al. 1993; Bahulekar et al. 1999).
Platelet-rich plasma (PRP) is prepared by centri-
fugation of the pooled blood and is incubated with
the membrane samples for 30 min at 37  C. After
incubation, the samples are xed with glutaralde-
hyde post xed with osmium tetroxide (OsO4).
After xation the samples are dehydrated through
a graded ethanol series to 100 % and dried by
critical point drying. The dry samples are then
observed by SEM. Quantitative and morphology
analysis of platelets adhered to the surface of the
membranes is carried out by imaging software.
In order to ensure the presence and activity of the
platelets, glass is generally used as positive control
for in vitro platelet response to foreign materials as
it promotes enhanced adhesion and activation of
platelets (Park et al. 1991; Amiji 1998).
The indicators of platelet adhesion used are
platelet deposition (PD) and platelet coverage
(PC), which are the number of adhered platelets/
10,000 mm2 of membrane surface area and the
Extracorporeal Blood Oxygenation Devices, Membranes for
II dendritic or early pseudopodial: one or more pseudo-
podia with no evident attening; stage III spread den-
dritic or intermediate pseudopodial: one or more
pseudopodia attened, hyaloplasm not spread between
pseudopodia; stage IV spreading: hyaloplasm spread
between pseudopodia; and stage V fully spread: hyalo-
plasm extensively spread, no distinct pseudopodia
percentage of the membrane surface area covered
by platelets, respectively. The platelets are either
passively attached and remain discoid and singu-
lar or may be activated subsequently. In the latter
case, they progressively release their granule con-
tents, thereby attracting further platelets, showing
a typical shape change with attening, formation
of pseudopodia, and increasing area of contact.
Scanning electron microscopic images of adhered
platelets with magnications of 1,000 or
2,000 magnication have been used by several
authors for the quantitative analysis of platelet
material interaction. The extent of platelet spread-
ing is examined by categorizing platelet shapes
into ve morphological forms describing increas-
ing activation stages (IV). These are discoid or
round (stage I), dendritic or early pseudopodial
(stage II), spread dendritic or intermediate pseu-
dopodial (stage III), spreading or late pseudopo-
dial (stage IV), and fully spread (stage V). The
spreading stages and respective platelet areas are
shown in Fig. 3 and dened in the legend (Allen
et al. 1979; Goodman et al. 1984, 1989).
Extracorporeal Blood Oxygenation Devices, Membranes for
References
Allen RD, Zacharski LR, Widirstky ST, Rosenstein R,
Zaitlin LM, Burgess DR (1979) Transformation and
motility of human platelets: details of the shape change
and release reaction observed by optical and electron
microscopy. J Cell Biol 83:126142
Allmr K, Hilborn J, Larsson PH, Hult A, Rnby B (1990)
Surface modication of polymers. V. Biomaterial appli-
cations. J Polym Sci A Polym Chem 28:173183
Alpha D, King E, Bicknell DA (1986) Clinical evaluation
of the extracorporeal Maxima hollow ber membrane.
Proc Am Acad Clin Perfusion 7:3234
American Society for Testing of Materials (ASTM) Prac-
tice for assessment of hemolytic properties of materials
(2000) ASTM International. http://www.astm.org/
DATABASE.CART/HISTORICAL/F756-00.htm
Amiji MM (1998) Platelet adhesion and activation on an
amphoteric chitosan derivative bearing sulfonate
groups. Colloids Surf B: Biointerfaces 10:263271
Bahulekar R, Tamura N, Ito S, Kodama M (1999) Platelet
adhesion and complement activation studies on
poly(N-alkyl mono and disubstituted) acrylamide
derivatives. Biomaterials 20:357362
Baker R (2004) Membrane technology and applications.
West Sussex, England
Bartlett RH, Gazzaniga AB, Jefferies MR, Huxtable RF,
Haiduc NJ, Fong SW (1976) Extracorporeal
membrane oxygenation (ECMO) cardiopulmonary
support in infancy. Trans Am Soc Artif Intern Organs
22:8093
Bartlett RH, Andrews AF, Toomasian JM, Haiduc NJ,
Gazzaniga AB (1982) Extracorporeal membrane oxy-
genation for newborn respiratory failure: forty-ve
cases. Surgery 92:425433
Bartlett RH, Roloff DW, Custer JR, Younger JG, Hirschl
RB (2000) Extracorporeal life support: the University
of Michigan experience. JAMA 283:904908
Bergdahl ME, Bergdahl LA (1989) A comparison of at-
sheet and hollow-ber membrane oxygenators: the
Shiley M-2000 vs. the Bentley BOS-CM 40. Tex
Heart Inst J 16:2731
Boretos JW (1980) Past, present and future role of poly-
urethanes for surgical implants. Pure Appl Chem
52:18511855
Bramson ML, Osborn JJ, Main FB, OBrien MF, Wright
JS, Gerbode F (1965) A new disposable membrane
oxygenator with integral heat exchange. J Thorac
Cardiovasc Surg 50:391400
Bungay PM, Lonsdale HK, de Pinho MN (1986) Synthetic
membranes science, engineering, and applications.
Published in cooperation with NATO Scientic Affairs
Division by D. Reidel
Cahn RP, Li NN (1974) Separation of phenol from waste
water by the liquid membrane technique. Sep Sci
9:505519
Calaore AM, Glieca F, Marchesani F, Troise G,
Santarelli G, Possati F (1987) A comparative clinical
assessment of a hollow-bre membrane oxygenator
751
(Capiox II) and a bubble oxygenator (Harvey 1500).
J Cardiovasc Surg (Torino) 28:633637
Catapano G, Papenfuss HD, Wodetzki A, Baurmeister U
(2001) Mass and momentum transport in extra-luminal
ow (ELF) membrane devices for blood oxygenation.
J Membr Sci 184:123135
Cazenave JP (1987) Blood surface interactions: biological
principles underlying haemocompatibility with articial
materials. Elsevier Science. http://www.bn.com/w/blood-
surface-interactions-j-p-cazenave/1013930926
Chalwin RP, Tiruvoipati R, Peek GJ (2008) Fatal throm-
bosis with activated factor VII in a paediatric patient on
extracorporeal membrane oxygenation. Eur E
J Cardiothorac Surg 34:685686
Clowes GH, Hopkins AL, Neville WE (1956) An articial
lung dependent upon diffusion of oxygen and carbon
dioxide through plastic membranes. J Thorac Surg
32:630637
Cooper SL (1982) Biomaterials: interfacial phenomena
and applications. American Chemical Society, Wash-
ington, DC, USA
Courtney JM, Lamba NM, Sundaram S, Forbes CD
(1994) Biomaterials for blood-contacting applications.
Biomaterials 15:737744
Dawids S, Bantjes A (1986) Martinus Nijhoff Publishers a
member of the Kluwer Academic Publishers Group,
Dordrecht, The Netherlands
De Somer F, Foubert L, Vanackere M, Dujardin D,
Delanghe J, Van Nooten G (1996) Impact of oxygena-
tor design on hemolysis, shear stress, and white blood
cell and platelet counts. J Cardiothorac Vasc Anesth
10:884889
DeWall RA, Naja H, Roden TA (1966) Hard-shell
temperature-controlling disposable blood oxygenator
use in clinical open-heart surgery. JAMA
197:10651068
Dorson W, Baker E, Hull H (1968) A shell and tube
oxygenator. Trans Am Soc Artif Intern Organs
14:242249
Dutton RC, Mather FW, Walker SN, Lipps BJ, Rudy LW,
Severinghaus JW, Edmunds LH (1971) Development
and evaluation of a new hollow-ber membrane oxy-
genator. Trans Am Soc Artif Intern Organs 17:331336
Edmunds LH (2004) Cardiopulmonary bypass after
50 years. N Engl J Med 351:16031606
Edmunds LH, Colman RW (2006) Thrombin during car-
diopulmonary bypass. Ann Thorac Surg 82:23152322
Elgas RJ, Gordon TM (1984) Blood oxygenator. http://
www.google.com/patents/US4451562
Fox S (2007) Human physiology. McGraw-Hill Science/
Engineering/Math, New York, USA
Fried DW, Bell-Thomson J (1992) Oxygen transfer perfor-
mance of a new Sarns membrane oxygenator. Perfusion
7:263271
Fukasawa H (1983) http://www.google.com/patents/
US4374802
Furukawa M (1997) Hydrolytic and thermal stability of
novel polyurethane elastomers. Die Angewandte
Makromolekulare Chemie 252:3343
752
Gabelman A, Hwang S-T (1999) Hollow ber membrane
contactors. J Membr Sci 159:61106
Galletti PM (1993) Cardiopulmonary bypass: a historical
perspective. Artif Organs 17:675686
Gassman CJ, Galbraith GD, Smith RG (1987) Evaluation
of three types of membrane oxygenators and their suit-
ability for use with pulsatile ow. J Extracorporeal
Technol 19:297304
Geckeler KE, Rupp F, Geis-Gerstorfer J (1997) Interfaces
and interphases of (bio)materials: denitions, struc-
tures, and dynamics. Adv Mater 9:513518
Ghosh S, Falter F, Cook DJ (2009) Extracorporeal mem-
brane oxygenation. Cambridge University Press.
10.1017/CBO9780511635564
Gibbon JH (1937) Articial maintenance of circulation
during experimental occlusion of pulmonary artery.
Arch Surg 34:11051131
Gibbon JH Jr (1954) Application of a mechanical heart and
lung apparatus to cardiac surgery. Minn Med
37:171185
Gogolewski S (1989) Selected topics in biomedical poly-
urethanes. A review. Colloid Polym Sci 267:757785
Goodman SL, Lelah MD, Lambrecht LK, Cooper SL,
Albrecht RM (1984) In vitro vs. ex vivo platelet depo-
sition on polymer surfaces. Scan Electron Microsc
Pt. 1:279290
Goodman SL, Grasel TG, Cooper SL, Albrecht RM
(1989) Platelet shape change and cytoskeletal reorga-
nization on polyurethaneureas. J Biomed Mater Res
23:105123
Graig RG (1983) Transactions of the ninth annual meeting
of the society for biomaterials. http://www.docstoc.
com/docs/88308470/Annual-Meeting-of-the-Society-
for-Biomaterials-Birmingham
Grenvik A, Ayres SM, Holbrook P, Shoemaker W (1999)
Textbook of critical care. Elsevier Science Health Sci-
ence. http://www.ecampus.com/textbook-critical-care-
4th-grenvik-ake/bk/9780721672465
Gu YJ, Boonstra PW, Graaff R, Rijnsburger AA,
Mungroop H, van Oeveren W (2000) Pressure drop,
shear stress, and activation of leukocytes during cardio-
pulmonary bypass: a comparison between hollow ber
and at sheet membrane oxygenators. Artif Organs
24:4348
Guidoin RG, Awad JA, Domurado D, Haggis GH
(1978) Thrombus formation in a staged capillary mem-
brane oxygenator associated with a microaggregate
blood lter: a scanning electron microscope study.
J Biomed Mater Res 12:255269
Gurland H (1987) Uremia therapy. Springer, New
York, http://www.bn.com/w/uremia-therapy-h-j-gurland/
1000920138
Hammon JW (2008) Extracorporeal circulation: the
response of humoral and cellular elements of blood to
extracorporeal circulation. Card Surg Adult 3:370
Hanft SC (2002) Key medical membrane devices for the
new millennium. BCC Research, Wellesley, MA, USA
Haworth WS (2003) The development of the modern oxy-
genator. Ann Thorac Surg 76:22162219
Extracorporeal Blood Oxygenation Devices, Membranes for
Haycox CL, Ratner BD (1993) In vitro platelet interactions
in whole human blood exposed to biomaterial surfaces:
insights on blood compatibility. J Biomed Mater Res
27:11811193
Hepburn C (1992) Polyurethane elastomers. Dordrecht,
Netherlands
Hill JD (1977) Acute pulmonary failure: treatment with
extracorporeal oxygenation. Med Instrum 11:198201
Hill JD, Aguilar MJ, Baranco A, de Lanerolle P, Gerbode
F (1969) Neuropathological manifestations of cardiac
surgery. Ann Thorac Surg 7:409
Ho WS, Sirkar KK (1992) Membrane handbook. Van
Nostrand Reinhold, New York
Horbett TA (1986) Interaction of the blood with natural and
articial surfaces. J Biomed Mater Res 20:411412
Hoshi M, Ieshige M, Saitoh T, Nakagawa T (2000) Sepa-
ration of aqueous phenol through polyurethane mem-
branes by pervaporation. III. Effect of the methylene
group length in poly(alkylene glycols). J Appl Polym
Sci 76:654664
Hsu LC (1997) Biocompatibility in cardiopulmonary
bypass. J Cardiothorac Vasc Anesth 11:376382
Iatridis A, Chan T, Thompson R (1985) Experimental and
clinical trials with the extracorporeal hollow bre lung.
Proc Am Acad Clin Perform 6:4750
Imai Y, Nose Y (1972) A new method for evalution of
antithrombogenicity of materials. J Biomed Mater Res
6:165172
ISO International Organization for Standardization.
ISO10993-4 Biological evaluation of medical
devices, Part 4: selection of tests for interactions
with blood. http://www.iso.org/iso/iso_catalogue/cata
logue_tc/catalogue_detail.htm?csnumber=32086
Iwahashi H, Yuri K, Nos Y (2004) Development of the oxy-
genator: past, present, and future. J Artif Organs 7:111120
Janvier G, Baquey C, Roth C, Benillan N, Blisle S, Hardy JF
(1996) Extracorporeal circulation, hemocompatibility,
and biomaterials. Ann Thorac Surg 62:19261934
Jonquires A, Clment R, Lochon P (2002) Permeability of
block copolymers to vapors and liquids. Prog Polym
Sci 27:18031877
Kawahito S, Maeda T, Motomura T, Takano T, Nonaka K,
Linneweber J, Ichikawa S, Ishitoya H, Hanazaki K,
Glueck J, Sato K, Nos Y (2002a) Feasibility of a new
hollow ber silicone membrane oxygenator for long-
term ECMO application. J Med Invest 49:156162
Kawahito S, Motomura T, Glueck J, Nos Y (2002b)
Development of a new hollow ber silicone membrane
oxygenator for ECMO: the recent progress. Ann
Thorac Cardiovasc Surg 8:268274
Kay PH, Munsch CM (1992) Techniques in extracorporeal
circulation. 4th Ed, Arnold, London
Kirklin JK, Westaby S, Blackstone EH, Kirklin JW,
Chenoweth DE, Pacico AD (1983) Complement and
the damaging effects of cardiopulmonary bypass.
J Thorac Cardiovasc Surg 86:845857
Klee D, Hcker H (2000) Polymers for biomedical appli-
cations: improvement of the interface compatibility.
Biomed Appl Polym Blends 149:157
Extracorporeal Blood Oxygenation Devices, Membranes for
Kolff WJ (1954) Dialysis in treatment of uremia: articial
kidney and peritoneal lavage. AMA Arch Intern Med
94:142160
Kolff WJ, Balzer R (1955) The articial coil lung. Trans
Am Soc Artif Intern Organs 1:3942
Kolff WJ, Watschinger B (1956) Further development of a
coil kidney; disposable articial kidney. J Lab Clin
Med 6:969977
Kolff WJ, Berk HTJ, Welle NM, Ley AJ, Dijk EC,
Noordwijk J (1944) The articial kidney: a dialyser
with a great area. Acta Medica Scand 117:121134
Kolff WJ, Efer DB, Groves JK, Peereboom G, Moraca PP
(1956a) Disposable membrane oxygenator (heart-lung
machine) and its use in experimental surgery. Cleve
Clin Q 23:6997
Kolff WJ, Watschinger B, Vertes V (1956b) Results in
patients treated with the coil kidney (disposable dialyz-
ing unit). J Am Med Assoc 161:14331437
Kolobow T, Bowman RL (1963) Construction and evalu-
ation of an alveolar membrane articial heart-lung.
Trans Am Soc Artif Intern Organs 9:238243
Kolobow T, Spragg RG, Pierce JE, Zapol WM
(1971) Extended term (to 16 days) partial extracorpo-
real blood gas exchange with the spiral membrane lung
in unanesthetized lambs. Trans Am Soc Artif Intern
Organs 17:350354
Kramme R (2011) Medizintechnik: Verfahren- Systeme-
Informationsverarbeitung. Gabler Wissenschaftsverlage,
Heidelberg, Germany
Kremesec VJ (1981) Modeling of dispersed-emulsion sep-
aration systems. Sep Purif Rev 10:117157
Labarre D (2010) Improving blood-compatibility of poly-
meric surfaces. Trends Biomater Artif Organs 15(1):13
Le Gallois JJC (1812) Experiments on the principle of life,
and particularly on the principle of the motions of the
heart, and on the seat of this principle: including the
report made to the rst class of the Institute, upon the
experiments relative to the motions of the heart. http://
www.archive.org/details/2561017R.nlm.nih.gov
Lee WH, Krumhaar D, Fonkalsrud EW, Schjeide OA,
Maloney JV (1961) Denaturation of plasma proteins
as a cause of morbidity and death after intracardiac
operations. Surgery 50:2939
Lee WH, Miller W, Rowe J, Hairston P, Brady MP
(1969) Effects of extracorporeal circulation on person-
ality and cerebration. Ann Thorac Surg 7:562
Lelah MD, Cooper SL (1986) Polyurethanes in medicine.
CRC Press, Boca Raton, Florida, USA
Lillehei CW, Cohen M, Warden HE, Read RC, Aust JB,
DeWall RA, Varco RL (1955) Direct vision intracardiac
surgical correction of the tetralogy of fallot, pentalogy
of fallot, and pulmonary atresia defects. Ann Surg
142:418442
Loeb S (1981) The Loeb-Sourirajan membrane: how it
came about. Synthetic membranes, vol I, ACS Sympo-
sium Series 153. ACS, Washington, DC
Lund C, Sundet K, Tennoe B, Hol PK, Rein KA, Fosse E,
Russell D (2005) Cerebral ischemic injury and cogni-
tive impairment after off-pump and on-pump coronary
753
artery bypass grafting surgery. Ann Thorac Surg
80:21262131
Marx TI, Baldwin BR, Miller DR (1962) Factors inuenc-
ing oxygen uptake by blood in membrane oxygenators:
report of a study. Ann Surg 156:204213
McArdle WD, Katch FI, Katch VL (2005) Essentials of
exercise physiology. Lippincott Williams & Wilkins,
Baltimore
Mockros LF, Leonard R (1985) Compact cross-ow tubu-
lar oxygenators. Trans Am Soc Artif Intern Organs
31:628633
Montoya JP, Shanley CJ, Merz SI (1992) Plasma leakage
through microporous membranes. Role of phospho- E
lipids. ASAIO 38:399
Moore GL, Ledford ME, Merydith A (1981)
A micromodication of the Drabkin hemoglobin
assay for measuring plasma hemoglobin in the range
of 5 to 2000 mg/dl. Biochem Med 26:167173
Motomura T, Maeda T, Kawahito S, Matsui T, Ichikawa S,
Ishitoya H, Kawamura M, Shinohara T, Sato K,
Kawaguchi Y, Taylor D, Oestmann D, Glueck J, Nos
Y (2003) Development of silicone rubber hollow ber
membrane oxygenator for ECMO. Artif Organs
27:10501053
Mottaghy K, Oedekoven B, Pppel K, Bruchm uller K,
Kovacs B, Spahn A, Geisen C (1989) Heparin free
long-term extracorporeal circulation using bioactive
surfaces. ASAIO Trans 35:635637
Mulder J (1996) Basic principles of membrane
technology. Kluwer Academic Publishers, Dordrecht,
Netherlands
Nagase K, Kohori F, Sakai K (2005a) Oxygen transfer perfor-
mance of a membrane oxygenator composed of crossed
and parallel hollow bers. Biochem Eng J 24:105113
Nagase K, Kohori F, Sakai K, Nishide H (2005b)
Rearrangement of hollow bers for enhancing oxygen
transfer in an articial gill using oxygen carrier solu-
tion. J Membr Sci 254:207217
Niiya KY, Noble RD (1985) Competitive facilitated transport
through liquid membranes. J Membr Sci 23:183198
Nos Y (2001) The ICMT on articial organs, vol II, The
oxygenator. ICMT Press, Houston
Nos Y, Malchesky PS (2000) Therapeutic membrane
plasmapheresis. Ther Apher 4:39
Onorati F, Rubino AS, Nucera S, Foti D, Sica V, Santini F,
Gulletta E, Renzulli A (2010) Off-pump coronary artery
bypass surgery versus standard linear or pulsatile cardio-
pulmonary bypass: endothelial activation and inamma-
tory response. Eur J Cardiothorac Surg 37:897904
Park K, Mao FW, Park H (1991) The minimum surface
brinogen concentration necessary for platelet activa-
tion on dimethyldichlorosilane-coated glass. J Biomed
Mater Res 25:407420
Peek GJ, Clemens F, Elbourne D, Firmin R, Hardy P,
Hibbert C, Killer H, Mugford M, Thalanany M,
Tiruvoipati R, Truesdale A, Wilson A (2006) CESAR:
conventional ventilatory support vs extracorporeal
membrane oxygenation for severe adult respiratory
failure. BMC Health Serv Res 6:163
754
PlunkettSD(2002)Alkoxysilane/alkysilanecopolymercoating
of medical devices. http://www.docstoc.com/docs/
51355531/Alkoxysilanealkysilane-Copolymer-Coating-
Of-Medical-DevicesPatent-6395226
Rajasubramanian S, Nelson KD, Shastri P,
Constantinescu A, Kulkarni P, Jessen ME, Eberhart
RC (1997) Design of an oxygenator with enhanced
gas transfer efciency. ASAIO J 43:710714
Ratner BD (1993) New ideas in biomaterials science a
path to engineered biomaterials. J Biomed Mater Res
27:837850
Ratner BD (2007) The catastrophe revisited: blood compat-
ibility in the 21st century. Biomaterials 28:51445147
Roy BJ, Rycus P, Conrad SA, Clark RH (2000) The chang-
ing demographics of neonatal extracorporeal mem-
brane oxygenation patients reported to the
Extracorporeal Life Support Organization (ELSO) reg-
istry. Pediatrics 106:13341338
Schamberger PC, Gardella JA (1994) Surface chemical
modications of materials which inuence animal cell
adhesion a review. Colloids Surf B: Biointerfaces
2:209223
Scott W, Rode R, Castlemain B, Kessler R, Follis F,
Pett S, Wernly J (1992) Efcacy, complications, and cost
of a comprehensive blood conservation program for car-
diac operations. J Thorac Cardiovasc Surg 103:10011006
Segal H, Sheikh S, Kallis P, Cottam S, Beard C, Potter D,
Townsend E, Bidstrup BP, Yacoub M, Hunt BJ
(1998) Complement activation during major surgery:
the effect of extracorporeal circuits and high-dose
aprotinin. J Cardiothorac Vasc Anesth 12:542547
Skeggs LT (2000) Persistence. . . prayer: from the articial
kidney to the AutoAnalyzer. Clin Chem 46:14251436
Skeggs LT, Leonards JR, Heisler CR (1949) Articial kid-
ney. II. Construction and operation of an improved
continuous dialyzer. Proc Soc Exp Biol Med
72:539543
Spiess BD, Vocelka C, Cochran RP, Soltow L, Chandler
WL (1998) Heparin-coated bypass circuits (Carmeda)
suppress the release of tissue plasminogen activator
during normothermic coronary artery bypass graft sur-
gery. J Cardiothorac Vasc Anesth 12:299304
Stamatialis DF, Papenburg BJ, Girons M, Saiful S,
Bettahalli SN, Schmitmeier S, Wessling M (2008) Med-
ical applications of membranes: drug delivery, articial
organs and tissue engineering. J Membr Sci 308:134
Stamm M (2008) Polymer surfaces and interfaces. Char-
acterization, modication and application. Springer,
Heidelberg, Germany http://www.springer.com/
chemistry/polymer+science/book/978-3-540-73864-0
Stenach N, Korn RL, Fisher CA, Jeevanandam V,
Addonizio VP (1992) The effects of heparin bound
surface modication (Carmeda Bioactive Surface) on
human platelet alterations during simulated extracor-
poreal circulation. J Extra Corp Technol 24:97102
Suma K, Tsuji T, Takeuchi Y, Inoue K, Shiroma K,
Yoshikawa T, Narumi J (1981) Clinical performance
of microporous polypropylene hollow-ber oxygena-
tor. Ann Thorac Surg 32:558562
Extracorporeal Blood Oxygenation Devices, Membranes for
Szycher M, Poirier VL (1983) Synthetic polymers in arti-
cial hearts: a progress report. Ind Eng Chem Prod Res
Dev 22:588593
Szycher M, Poirier VL, Dempsey DJ (1983) Development
of an aliphatic biomedical-grade polyurethane elasto-
mer. J Elastomers Plast 15:8195
Tanishita K, Panol G, Richardson PD, Galletti PM
(1994) Gas transport in the intracorporeal oxygenator
with woven tubes. Artif Organs 18:797800
Taskin ME, Fraser KH, Zhang T, Grifth BP, Wu ZJ
(2010) Micro-scale modeling of ow and oxygen trans-
fer in hollow ber membrane bundle. J Membr Sci
362:172183
Toomasian JM, Hsu LC, Hirschl RB, Heiss KF, Hultquist
KA, Bartlett RH (1988) Evaluation of Durao II hepa-
rin coating in prolonged extracorporeal membrane oxy-
genation. ASAIO Trans 34:410414
Tze-Man K, Jui-Che L, Cooper SL (1993) Surface charac-
terization and platelet adhesion studies of plasma-
sulphonated polyethylene. Biomaterials 14:657664
Ulrich B (1990) Multilayer hollow ber wound body.
http://www.docstoc.com/docs/41159322/Multilayer-
Hollow-Fiber-Wound-BodyPatent-4940617
Vallely MP, Bannon PG, Bayeld MS, Hughes CF,
Kritharides L (2010) Endothelial activation after coronary
artery bypass surgery: comparison between on-pump and
off-pump techniques. Heart Lung Circ 19:445452
Van Assendelft OW, Buursma A, Zijlstra WG (1996) Sta-
bility of haemiglobincyanide standards. J Clin Pathol
49:275277
Vaslef SN, Mockros LF, Anderson RW, Leonard RJ
(1994) Use of a mathematical model to predict oxygen
transfer rates in hollow ber membrane oxygenators.
ASAIO J 40:990996
Verrier ED, Boyle EM (1996) Endothelial cell injury
in cardiovascular surgery. Ann Thorac Surg
62:915922
Von Segesser L (1987) Determination of signicant differ-
ences in performance of the Bentley BOS-CM 40 hollow
bre membrane oxygenator and the polystan VT5000
venotherm bubble oxygenator. Perfusion 2:289295
Voorhees ME, Brian BF (1996) Blood-gas exchange
devices. Int Anesthesiol Clin 34:2945
Wang CB, Cooper SL (1983) Morphology and properties
of segmented polyether polyurethaneureas. Macromol-
ecules 16:775786
Weibel ER (2009) What makes a good lung? Swiss Med
Wkly 139:375386
Weissman MH, Mockros LF (1968) Gas transfer to blood
owing in coiled circular tubes. J Eng Mech Div
94(EM3):857872, paper 6007, American Society of
Civil Engineers. American Society of Civil Engineers
Weissman MH, Mockros LF (1969) Oxygen and carbon
dioxide transfer in membrane oxygenators. J Med Biol
Eng 2:169184
WHO World Health Organization (2011). The top
10 causes of death. WHO World Health Organization.
http://www.who.int/mediacentre/factsheets/fs310/en/
index.html
Extraction Index 755

Wickramasinghe SR, Han B (2002) Mass and momentum
transfer in commercial blood oxygenators. Desalina-
tion 148:227233
Wickramasinghe SR, Han B (2005) Designing micropo-
rous hollow bre blood oxygenators. Chem Eng Res
Des 83:256267
Wiese F (2009) Membranes for articial lung and gas
separation, membranes in medicine workshop. Lisbon
Wiese F (2010) Membranes for articial lungs. Membr Life
Sci 1:4968. Wiley-VCH. http://onlinelibrary.wiley.
com/. doi:10.1002/9783527631360.ch2/summary
Williams DF (1987) Denitions in biomaterials: proceed-
ings of a consensus conference of the European Society
for Biomaterials, Chester, England, March 35, 1986.
Elsevier, Amsterdam
Williams DF (2008) On the mechanisms of biocompatibil-
ity. Biomaterials 29:29412953
Williams RL, Williams DF (1989) The spatial resolution of
protein adsorption on surfaces of heterogeneous metal-
lic biomaterials. J Biomed Mater Res 23:339350
Yang M, Cussler EL (1986) Designing hollow-ber
contactors. AIChE J 32:19101916
Yilgr I, Yilgr E (1999) Hydrophilic polyurethaneurea
membranes: inuence of soft block composition on the
water vapor permeation rates. Polymer 40:55755581
Yoon SC, Ratner BD (1988) Surface and bulk structure of
segmented poly(ether urethanes) with peruoro chain
extenders. FTIR, DSC, and x-ray photoelectron spec-
troscopic studies. Macromolecules 21:23922400
Zacour RK (1988) Clinical evaluation of the sarns mem-
brane oxygenator. Perfusion 3:219224
Zapol WM, Snider MT, Hill JD, Fallat RJ, Bartlett RH,
Edmunds LH, Morris AH, Peirce EC, Thomas AN,
Proctor HJ, Drinker PA, Pratt PC, Bagniewski A, Miller
RG (1979) Extracorporeal membrane oxygenation in
severe acute respiratory failure. A randomized prospec-
tive study. JAMA 242:21932196
Ziats NP, Miller KM, Anderson JM (1988) In vitro and
in vivo interactions of cells with biomaterials. Bioma-
terials 9:513
Zwart A, van Assendelft OW, Bull BS, England JM, Lewis
SM, Zijlstra WG (1996) Recommendations for refer-
ence method for haemoglobinometry in human blood
(ICSH standard 1995) and specications for interna-
tional haemiglobinocyanide standard (4th edition).
J Clin Pathol 49:271274
Zydney AL (1985) Cross-ow membrane plasmapheresis:
an analysis of ux and hemolysis. Massachusetts Insti-
tute of Technology, Cambridge, MA
E
Extraction Index
Giuseppe Barbieri
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, Rende,
Italy
The extraction index is a measure of membrane
operation performance of extracting a desired spe-
cies from the feed/retentate side in order to have it
as permeate. It can be dened/evaluated for any
involved species. It gives an indication about the
real advantages offered by using a membrane unit
instead of conventional ones. The higher the var-
iable value, the higher the performance of the
membrane unit. It is dened as the ratio (Eq. 1)
of the permeate ow rate of the species permeated
through the membrane to that totally fed to the
membrane unit. Equation 1 shows different ways
for evaluating the extraction index:

Permeate flow ratei

Extraction Indexi
Feed flow ratei

Permeate flow rate Permeate molar fractioni

Feed flow rate Feed molar fractioni

Permeate flow rate Permeate Partial Pressurei

(1)
Feed flow rate Feed Partial Pressurei

Permeate flow rate Permeate concentrantioni

Feed flow rate Feed concentrantioni

Permeate flow rate Permeate mass fractioni

Feed flow rate Feed mass fractioni
756
The extraction index assumes a specic and more
interesting form when a chemical reaction takes
place inside the membrane unit such as in the
membrane reactors since a desired chemical can
Permeate flow ratei
Extraction Indexi
Feed flow ratei Production by Reaction for i  th
If the water-gas shift reaction is used as an example,
the extraction index can be dened as the ratio of
the H2 permeated through the membrane to that
H2 Extraction Index
Flow rateAvailable
Flow ratePermeate
in the MR
Flow rateFeed
H2
H2 O=CO feed molar ratio
a
1 per H2 O=CO feed molar ratio  1
The extraction index (Barbieri et al. 2008) takes into
account the hydrogen fed as H2 molecules and that
is contained in the feed stream in other chemicals
(e.g., H2O). The term (a ow rate CO feed) of the
Eq. 3 considers the maximum H2 extractable from
the chemicals (other than hydrogen) present in the
system. The coefcient (a) takes into account the
defecting reactant (CO or H2O) by means of the
feed molar ratio H2O/CO. It (a) is equal to the feed
molar ratio if the latter is lower than 1 (CO in defect
with respect to H2O). It (a) will be equal to 1 when
the CO exceeds the H2O. As dened, the extraction
index is determined by the membrane properties,
feed molar ratio, and CO conversion achieved in the
membrane reactor, at set operating conditions.
References
Barbieri G, Brunetti A, Tricoli G, Drioli E (2008) An
innovative conguration of a Pd-based membrane reac-
tor for the production of pure hydrogen. Experimental
analysis of water gas shift. J Power Sources
182(1):160167. doi:10.1016/j.jpowsour.2008.03.086
Extremophiles
be fed in it but also produced by reaction. In this
case, Eq. 1 has to take into account also the pro-
duction term:
(2)
totally available in the feed stream both as H2
molecules and also obtainable from other chemicals
(e.g., CO) by reaction, to the membrane unit (Eq. 3):
Flow ratePermeate
H2
H2
in the feed
H2
(3)
a  Flow rateFeed
CO
per H2 O=CO feed molar ratio < 1
Extremophiles
Chiara Schiraldi and Mario De Rosa
Department of Experimental Medicine, Section of
Biotechnology, Medical Histology and Molecular
Biology, Second University of Naples, Napoli,
Italy
The discovery of life in demanding environments
continues to challenge conventional concepts of
the growth-limiting conditions of many cellular
organisms. Extremophiles may have diverse fea-
tures; they may live at temperatures higher than
60  C (thermophiles) or prefer colder sites, being
able to grow between 5  C and 20  C; they may
need pH <4 or >9 (acidophiles or alkaliphiles,
respectively); or they can survive to high-salinity
environments such as salty lakes (halophiles).
They have been isolated in challenging biotopes
from terrestrial solfataric elds to marine volcanic
areas (Rothschild and Mancinelli 2001). The
Extremophiles
Extremophiles, Fig. 1 Electron micrograph of
Sulfolobus solfataricus MT4
phylogenetic assessment of the isolated species
widens between Archaea, Bacteria, and Eukarya.
There has been a steady increase in the isolation of
these microorganisms documenting the enormous
scientic effort in the last 30 years. Although
major advances have been made in the last
decade, our knowledge of the physiology, metab-
olism, enzymology, and genetics of this fascinat-
ing group of organisms is still limited. However
there is little doubt that extremophiles will supply
novel catalysts and will be a source of biomole-
cules with unique and biotechnologically relevant
properties. It has been argued that membranes of
extremophiles contain surfactants bearing unique
stability that can be used in pharmaceutical
and cosmeceutical formulations. Amylases,
pullulanases, and glycosidases from hyperther-
mophiles were studied and proved efcient in
starch biotransformation obtaining process
throughput enhancement (Burg 2003).
Trehalose-forming enzymes were found in
Sulfolobus shibatae and S. solfataricus isolated
in diverse solfatara elds worldwide (Fig. 1).
Also lipases and esterases from thermophilic
microorganisms and Archaea proved unique fea-
tures (Schiraldi et al. 2002). Compatible solutes,
of key importance for halophile survival, were
isolated from Halomonas and Marinococcus spe-
cies and thoroughfully characterized proving their
outstanding DNA/enzyme stabilization capacity;
their commercialization was pursued by a
757
specically founded company (bitop).
Alkaliphilic enzymes were found as natural deter-
gents, thus suggesting specic industrial interest.
Psychrophilic enzymes may also be of applicative
interest when biotransformations need to be car-
ried out at low temperature. Other innovative
products from extremophiles are cyclodextrins
and polyunsaturated fatty acids, for which
industrial applications are foreseen. Most of
these kind of microorganisms isolated to date
E
show specic needs to increase cell density.
Recent alternatives to technological applications
most commonly employed when the production
of extremocompounds is approached at a bioreac-
tor scale describe batch, fed batch, and continuous
or in situ product removal fermentations in
specically developed bioprocesses. However,
when large-scale production is needed for
commercialization of these novel compounds,
there is the need to bring together genetic and
bioreaction engineering with separation tech-
niques. The former prompted the development
of specic plasmids and vectors to obtain a
sound expression of extremophilic gene sequence
and thus enzymes into mesophilic hosts; these
recombinant strains are easier to cultivate, and
the whole strategy is in fact recommended
to solve the typical problems faced in
extremophile-based bioprocesses and will
serve to open up new opportunities for the devel-
opment of unexplored elds such as renewable
energies.
References
Burg BVD (2003) Extremophiles as a source for novel
enzymes. Curr Opin Microbiol 6:213218
Kristjansson JK, Hreggvidsson GO (1995) Ecology and
habitats of extremophiles. World J Microbiol
Biotechnol 11:1725
Rothschild LJ, Mancinelli RL (2001) Life in extreme envi-
ronments. Nature 409:10921101
Schiraldi C, Giuliano M, De Rosa M (2002) Perspectives
on biotechnological applications of archaea. Archaea
1(2):7586
Sellek GA, Chaudhuri JB (1999) Biocatalysis in organic
media using enzymes from extremophiles. Enzyme
Microb Technol 25:471482
758
Extremozymes
Chiara Schiraldi and Mario De Rosa
Department of Experimental Medicine, Section of
Biotechnology, Medical Histology and Molecular
Biology, Second University of Naples, Napoli,
Italy
The biocatalysts produced by extremophilic
microorganisms, so-called extremozymes, are
proteins with outstanding stability to temperature,
pH, and organic solvents, thus becoming excellent
candidates to improve industrial biotransforma-
tions (Schiraldi and De Rosa 2002). Polymer-
degrading enzymes from hyperthermophiles,
psychrophiles, and acidophiles may play an
important role in food, detergent, and pulp and
paper industry (e.g., amylases, pullulanases,
xylanases, proteases). Extremozymes also include
cellulases, proteases, pectinases, keratinases,
lipases, esterases, catalases, peroxidases, and
phytases. Owing to the unusual properties of
these classes of enzymes, they are expected to
ll the gap between biological and chemical
industrial processes (Taylor et al. 2011). Despite
this, actually few are the current processes based
on these biocatalysts, the most known of which is
the polymerase chain reaction (PCR) technology
that in fact is based on DNA-modifying enzymes
Taq polymerase isolated from Thermus aquaticus.
The use of this enzyme allowed the automation of
PCR with a great advantage for research labora-
tories and industries. Beside this, few biocatalysts,
used in diagnostics and starch liquefaction, are
commercially produced by several biotechnology
companies. Recently enzymes of interest in bio-
remediation have also been isolated from
extremophiles: a thermoalkaliphilic catalase,
which initiates the breakdown of hydrogen perox-
ide into oxygen and water, was isolated from
Thermus brockianus, found in Yellowstone
National Park, and operates over between 30  C
and 94  C (pH range 610). Its outstanding
Extremozymes
stability and wide operational range suggest appli-
cation in hydrogen peroxide removal in pulp and
paper bleaching, textile bleaching, food pasteuri-
zation, and surface decontamination of food pack-
aging (Thompson et al. 2003). Enzymes isolated
from psychrophiles, such as lipases, proteases,
and cellulases, have been used as additives for
the preparation of detergents working at low tem-
peratures or in frozen food preparations. Further-
more, thermophilic enzymes have been used for
the construction of optical nanosensors, stable and
nonconsuming analytes. These innovative devices
are based on the ability of thermophilic enzymes
to bind the substrate at room temperature, without
transforming it (de Champdor et al. 2007). The
binding of substrate to thermophilic enzyme is
monitored as uorescence variations of the
enzyme. Many of these isolated enzymes have
been cloned and expressed in mesophilic hosts
to overcome the issues of extremophilic microor-
ganisms cultivations, such as the unconventional
fermentation parameters, special construction
materials need, the low growth rates that are typ-
ical of most of these species, and the low biomass
yield (despite the good enhancement proved in
membrane bioreactors) (Schiraldi et al. 2001).
The recombinant enzymes (Cimini et al. 2008),
easily produced at high yield, may be commer-
cialized, and furthermore, modern techniques like
mutagenesis and gene shufing will lead to
in vitro tailored enzymes that are highly specic
for countless industrial applications.
References
Cimini D, De Rosa M, Panariello A, Morelli V,
Schiraldi C (2008) Production of a thermophilic
maltooligosyl-trehalose synthase in lactococcus lactis.
J Ind Microbiol Biotechnol 35(10):10791083
de Champdor M, Staiano M, Rossi M, DAuria S (2007)
Proteins from extremophiles as stable tools for
advanced biotechnological applications of high social
interest. J R Soc Interface 4(13):183191
Schiraldi C, De Rosa M (2002) The production of
biocatalysts and biomolecules from extremophiles.
Trends Biotechnol 20(12):515521
Extremozymes
Schiraldi C, Acone M, Giuliano M, Carten M, De Rosa M
(2001) Innovative fermentation strategies for the pro-
duction of extremophilic enzymes. Extremophiles
5(3):193198
Taylor MP, van Zyl L, Tufn IM, Leak DJ, Cowan DA
(2011) Genetic tool development underpins recent
759
advances in thermophilic whole-cell biocatalysts.
Microb Biotechnol 4(4):438448
Thompson VS, Schaller KD, Apel WA (2003) Purication
and characterization of a novel thermo-alkali-stable
catalase from Thermus brockianus. Biotechnol Prog
19:12921299