Bartosz

Journal of Chemical Tylkowski,and

Technology Iren Tsibranska50, 1, 2015, 3-12
Metallurgy,

OVERVIEW OF MAIN TECHNIQUES USED

FOR MEMBRANE CHARACTERIZATION
Bartosz Tylkowski 1,2, Iren Tsibranska 2

1
Universitat Rovira i Virgili, Received 01 October 2014
Departament de Enginyeria Química, Accepted 04 December 2014
Av. Països Catalans, 26 - 43007 Tarragona, Spain
E-mail: bartosz.tylkowski@urv.cat
2
Institute of Chemical Engineering,
Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria

ABSTRACT

The main force of membrane technology is the fact that it works without the addition of chemicals, with relatively low
energy consumption and easy and well-arranged process conductions in a compact module design. Although a good num-
ber of articles and books are available on membrane separation processes, many of which are of excellent quality within
their scope, most of them present research-oriented approaches of higher levels, thus making them good references in the
specific field of recent membrane processes applications. This publication is focused particularly on the main techniques
used for membrane characterization with supporting review of the literature and comparative discussion.
Keywords: porous membrane characterization, active pore size, pore size distribution, charaterization techniques.

INTRODUCTION mainly give information on membrane morphology and

Membrane technologies have been established as
an effective and commercially attractive option for
separation and purification processes in the chemical
and its allied industries dealing with fuel cell [1, 2],
gas separation [3], food chemistry [4], pharmaceutical
industry and medicine [5, 6], water treatment [7], con-
centration/separation of extracts [8 - 10] , etc. No doubts,
the membranes are now competitive for conventional
techniques, with a wide variety of applications, both
industrial and scientific.
The aim of this article is to provide a comprehen-
sive yet concise overview of main techniques used for
membrane characterization.
Characterisation techniques can be classified into
static and dynamic techniques. The static techniques
structure, chemical and physical properties. The dynamic
techniques are of fundamental importance when inves-
tigating membrane performance. Some characterisation
techniques are destructive for the membrane, while the
non-destructive ones are applied also to monitor the
membrane performance during its use. Except for bub-
ble pressure all other reported techniques have not yet
been standardized or harmonized. This fact often causes
confusion and can be misleading. Publications, aimed
to classify and comparatively discuss the advances in
membrane characterization techniques have appeared
recently [11]. Table 1 shows the main characterization
tests.
Bubble pressure
This method was initiated by Bechhold in 1908 [12]
and is based on the fact that the pressure (P) necessary to

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 Journal of Chemical Technology and Metallurgy, 50, 1, 2015

Table 1. Main characterization test.

Method Characteristic Typology M P

dynamic
Bubble pressure Maximum pore size non x x
destructive
dynamic
Gas and liquid displacement
Pore size distribution non x x
methods (GLDP-LLDP
destructive
statistic
Mercury porosimetry (MP) Pore size distribution x
destructive
Top layer thickness
Scanning Electron Microscopy
Surface porosity
(SEM), statistic
Pore size distribution x
Transmission Electron destructive
Qualitative structure
Microscopy (TEM)
analysis
static
Atomic force microscopy
Surface porosity non
(AFM)
destructive
dynamic
Flux and retention Permeability,
non x
measurements Selectivity, MWCO
destructive
static
Gas adsorption/desorption
Pore size distribution non x
(GAD)
destructive
dynamic
Permporometry Pore size distribution non x x
destructive
SEM + X-Ray microanalysis Chemical analysis static
(EDS) Surface studies destructive
X-Ray photoelectron Chemical analysis static
spectroscopy Surface studies destructive
Functional group
Infrared Spectroscopy (FT-IR, static
analysis
ATR, Photoacustic) destructive
Surface studies
non
Contact angle measurement Surface studies
destructive
Stress-Strain measurements distructive

blow a gas through a liquid-filled capillary is inversely
proportional to the capillary radius (r). The pore size can
be calculated using the Cantor equation (1):
2 ⋅g
P= ⋅ cos θ (1)
r The main advantages of this test are:
where q is a contact angle and g is a surface tension.
The bubble point test is a measure of the radius of
the largest pore, since, according to Cantor equation,
the gas will pass through it first. For air-water system
where the surface tension (g) is 72 mN/m and complete
wetting (the contact angle is equal zero) the pore size
has to be calculated from the equation (2):
1.4
r ( µm) = (2)
P(bar )
● non-destructive method,
● very simple procedure and apparatus,
● very useful for integrity test.
Unfortunately the test does not give information
on the membrane pore size distribution and because of

4
 Bartosz Tylkowski, Iren Tsibranska
the very high air-water surface tension high pressure
(which can cause membrane compression) is needed for
gas permeation through small pores (in fact the lower
limit of the measurable pore diameter is about 13 nm)
[13]. For instance, the bubble points method was used
for three hollow fiber polyphenylsulfone membranes
in iso-propanol to determine the maximum pore size
[13], ranging from 53 to 237 nm at pressures between
9 and 2 bar. Close to the lower limit of detection of the
method are the results with semi-crystalline poly(ether
ether ketone) hollow fiber membrane in water, where
the largest pore was about 15 nm at applied pressure
4792 kPa [14].
Liquid-liquid displacement porosimetry
The liquid-liquid porosimetry (LLDP) is a method
that can be used to provide information on the pore
size distribution of membranes with small pores. The
procedure is based on the same principles of the air-
liquid displacement or extended bubble point technique,
both methods using the correlation between the applied
pressure and the pore radius rp open to flux as given by
Washburn [15]:
2g cos θ
∆p = (3)
rp
g being the surface tension and q the contact angle
between the permeating interface and the pore material.
The high potentiality of this technique in order to
evaluate the active pores in the nano- and subnanometer
range (usually dp > 1 nm) makes it a very promising
technique to study the pore size distribution of ultra-
filtration (UF) and nanofiltration (NF) membranes
because of the relatively low applied pressures which
do not cause membrane compaction. Results with
polymer membranes with pore sizes from 0.4 μm to 8
nm have proved the usefulness of the LLDP method for
optimizing membrane making conditions and accurate
estimation of performance related capabilities [16]. The
advantages of LLDP can be viewed in several directions:
● it tests the membrane in the wet state, so can give
information very close to the normal operating condi-
tions of the membrane,
● it also evaluates only the open pores, not any
closed or bottle ended ones,
● it does not use too high pressures, thus avoiding
mechanical over-stress of the membrane during the
test that could result in membrane damage or structure
collapse;
● it operates quickly which makes analysis simple
and easily manageable.
A pair of immiscible liquids with low interfacial
tension are used which means that pore sizes can be
measured at relatively low pressures. The procedure
consists in filling the membrane with the wetting liquid,
and then displacing it with the other one. By monitoring
the pressure and the flow through the membrane, the
corresponding pore radius opened at a given applied
pressure can be calculated using the Cantor equation,
provided that contact angle between the liquid-liquid
interface and the membrane material can be assumed
to be zero:
2g
∆p = (4)
r
By increasing the applied trans-membrane pressure
stepwise, corresponding pore radius and flow values,
represented as the permeability of the membrane, are
obtained. Thus a pore size distribution of permeability
contributions can be evaluated. Assuming cylindrical
pores, the Hagen-Poiseuille equation can be used to
correlate the volume flow, JV, and the number of pores
per surface unit, N, having a given pore radius, r. For
each pressure step, Δpi, the corresponding volume flow
measured is correlated with the number of pores thus
opened by [6]:
i
N k π rk4 ∆pi
JVi = ∑ (5)
k =1 8ηδ
where η is the dynamic viscosity of the displacing
fluid, Nk is the number of pores in the class kth per
unit membrane surface and δ is the pore length. This
could be used to estimate size distributions in num-
ber of pores. It should be remembered that Hagen-
Poiseuille´s law in that simple form only holds for
flow through cylindrically shaped straight pores. Thus,
the so obtained pore size distributions should be more
model-dependent.
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 Journal of Chemical Technology and Metallurgy, 50, 1, 2015
Liquid and air permeability
Permeability of a membrane for a certain liquid
can be considered as a characteristic parameter; often
the so-called hydraulic radius is calculated from the
measured fluxes. In such an analysis, the permeability
is determined, the porosity E, the tortuosity z and the
membrane thickness 1 are estimated (or preferably deter-
mined) and subsequently the pore size can be calculated
from the Hagen-Poiseuille equation (5).
It is obvious that such an approach depends largely
on the model as well as on the estimated values used.
Also, the model cannot discriminate between a system
with few large pores and one with a large number of
small pores.
The method can be improved by using gas as
permeating medium instead of liquid. As the transport
mechanism for gases is dependent on the overall pressure
in the system the pore size discrimination between fine
and coarse porous media is possible when the perme-
ability at different pressures is measured.
Both gas and solute permeation techniques have
been used for pore size determination in polymeric
hollow fibers [17], giving similar trends in the observed
mean pore size, but the gas permeation has advantages
considering the influence of the polymer concentration.
The latter greatly decreases the water solution flux, but
has little influence on gas permeability and the value of
the measured effective surface porosity over pore length
value [18]. Gas permeation technique has proved to be
useful in characterization of the thin layer in asymmet-
ric membranes, but it does not give any insight into the
remaining membrane pore size structure [19].
Nitrogen adsorption/desorption (pore size dis-
tribution)
In this method the pore size distribution is deter-
mined by the adsorption/desorption isotherms of a gas
(usually nitrogen) subjected to adsorption and capillary
condensation in the pores. The nitrogen adsorption
BET analysis is very useful for determining surface
area and pore size distribution of ceramic membranes
usually in the micro- and meso-size pore range. For
conventional dense polymer membranes (considered
as “nonporous”) the BET analysis is rarely used. It has
6
found application in structures like glassy polymers
(examples are known in the study of PIOFG polymers
[20], characterization of the support membrane in case
of thin film composite OSN membranes [21], as well as
in the characterization of micro- and mesopore materials
as composite amorphous (ex. TiO2–ZrO2–organic) [23]
or semi-crystalline polymer (ex. poly(ether ether ketone)
PEEK [22] membranes.
Permporometry (pore size distribution)
This technique was initiated by Eyraud and modified
by Katz et al. [24, 25]. The method is based on the fact
that the vapour pressure at the surface of a liquid depends
on its curvature. The vapour is capillary-condensed in
membrane pores thus blocking the permeation of the
non-condensable gas in the feed. The pore filling occurs
according to the Kelvin equation:
−4vσ cos θ
dK =
RT ln( P / PS ) (6)
in pores smaller than the Kelvin diameter dK. The latter
is proportional to the vapour pressure (P) of the con-
densable gas and related to the true pore diameter dp by
the thickness t of the adsorbed layer (t): dP= dk+t. The
rest of the parameters in eq. (6) are the contact angle
(q), the surface tension (s) and the molar volume (v),
the temperature (T).
By measuring the permeability of the non-condensa-
ble gas as a function of relative pressure, P/Ps (0 to 1), it
is possible to estimate the pore size distribution.
Using this method, the closed pores are said to be
excluded, and the pore size distribution of only the active
pores is determined. So, permporometry is considered
as a method able to determine accurately the active pore
size distribution. The nanopermporometry, based on
the capillary condensation of vapor (water or hexane)
and blocking of the permeation of a non-condensable
gas (N2), has found numerous applications for charac-
terization of organic/inorganic hybrid membranes with
pores ranging from 1 to several nanometers and used for
nanofiltration of organic solutions [23, 26].
Electron microscopy
The aim of this method is to acquire visual infor-
mation of the membrane structure and porosity through
magnification by scanning electron microscope (SEM)
 Bartosz Tylkowski, Iren Tsibranska
or a transmission electron microscope (TEM).
However, the high electron beam energy used to
observe the specimen at the highest magnification can
damage the surface of a polymeric membrane. The
procedure for specimen preparation is relatively simple.
The surfaces of the membranes can be observed directly
while the cross-sections are obtained by a simple cold
(liquid N2) fracture. The SEM observation does not give
a deeper insight on finer porosity since it has a lower
resolution (≈ 10-20 nm) than TEM.
The TEM has a much higher resolution (0.2 nm) than
SEM and is therefore particularly useful for studying
the very thin skin layer of asymmetric membranes. The
procedure for the preparation of TEM cross-sections is
difficult and tedious (drying, embedding into epoxy, cold
ultramicrotomy) since samples thin enough (50 nm or
less) for electrons to penetrate must be prepared. Using
this kind of microscopy the membrane surface cannot
be directly observed. The procedure for preparing the
so-called surface replica is also difficult and tedious the
risk of producing artifacts is very high.
Membrane characterization by SEM is a common
technique for analysis, used for polymeric hollow
fibers [27], in order to characterize the predominant
morphology of polymeric asymmetric and mixed ma-
trix membranes [19, 28 - 32], used in organic solvent
nanofiltration, to measure the thickness of the top- and
the support layers and their role in the control of the
membrane mass-transport rates, as well as eventual
changes in the membrane before and after nanofiltration
[4, 9]. The limits of traditional microscopy techniques
were enlarged in direction 3D characterization of po-
rous membranes by incorporating other modifications.
An example is the X-ray ultramicroscopy, based on
integration with TEM, with a resolution of 100 nm and
capability to characterize membrane samples in both
dry and wet states [11].
Stress - strain property
Most materials are subjected to stress and the ac-
companying deformation during processing and use. The
mechanical properties of the membranes characterised
by stress-strain tests are needed to confirm the potential
suitability of this membrane in applications like: nano-
filtration [33], the appropriate chemical treatment in
coating polymeric hollow fiber membranes in view of
their mechanic properties [27], in connection with the
abrasive resistance of flat sheet membranes [33], etc.
Stress (σ) is the internal force (F) per unit area
experienced by the material (So) while strain (ε) is the
unit change in deformation of the material (100 Δl/lo).
σ=F/So (7)
The stress-strain relationships can then be used to
establish the compressive or tensile yielding strength,
the modulus of elasticity and the ultimate strength.
Fig. 1 presents a typical stress-strain curve for a
structural mild steel specimen subjected to tensile test
under normal conditions. The specimen elongation is
plotted along the horizontal axis and the corresponding
stresses are indicated by the ordinates of the curve 0 A
B C D. This diagram will be used to explain some of
the following nomenclature.
In the region 0A, the stress and the strain are propor-
tional and the stress at A is the proportional limit. If upon
removal of the stress (load), the strain in the specimen
returns to zero as the stress goes to zero, the material is
said to remain perfectly elastic.
The constant of proportionality in the straight-line
region 0A is called the modulus of elastic or Young’s
modulus (E). Geometrically, it is equal to the slope of
the stress-strain relationship in the region 0A.
σ
E= (8)
ε
Upon loading beyond the proportional limit, the
elongation increases more rapidly and the diagram
Fig. 1. Typical stress-strain curve.
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 Journal of Chemical Technology and Metallurgy, 50, 1, 2015
Fig. 2. Water drop behavior and contact angle values at solid of different hydrophobicity.
becomes curved. At point B, a sudden elongation of the
specimen takes place without significant increase in the
applied load and the material has yielded. The value of
stress at point B is called yield stress or yield strength.
The deformation of the material prior to reaching the
yield point creates only elastic strains, which are fully
recovered if the applied load is removed. However,
once the stress in the material exceeds the yield stress,
permanent (plastic) deformation begins to occur. The
strains associated with this permanent deformation are
called plastic strains. When the material has passed
through the yielding point, stress continues to increase
with strain, but at a slower rate than in the elastic range,
until a maximum value is reached which is termed the
ultimate strength (point C). The increase in stress upon
yield stress is due to material strain hardening. Beyond
point C, the stress decreases until the specimen ruptures
at point D.
Yield strain and tensile strain are defined differently
in polymers than in metals and the degree of plastic
deformation varies with polymer type and concentra-
tion. For instance results with PAN membranes show
that tensile strength and elongation can be enhanced
by reasonably increasing PAN concentration. The me-
chanical properties of the membranes depend on their
microstructure. Greater tensile strength and elongation
are observed when cellular-like pores in comparison
with sheet- or needle-like pores [34].
Contact angle
The hydrophobic/hydrophilic characteristics of sol-
ids plays a key role in many processes such as: wetting,
WA σ LV (1 + cos θ )
=
flotation, enhanced oil recovery, cleaning technologies,
superhydrophobicity, liquid spreading, plants protec-
tion, etc. Hydrophilicity and hydrophobicity are general
8
terms introduced to describe relative affinity of solids
to water spreading on their surfaces. Wettability is due
to unbalanced molecular interactions when at least two
materials are brought in a contact. A measure of this
unbalance of forces is the contact angle (θ). Its value
is related to surface energy values of the materials. It
is generally, but rather arbitrarily assumed that for θ
< 90° indicates that the solid is partially wetted by a
liquid (for example water). Surfaces characterized by
the contact angle of water smaller than 90° are usually
termed hydrophilic. Hydrophilic means literally „water
preferring”, and drops of water placed at such surfaces
should spread spontaneously forming a thin water film
at the surface when θ ≈ 0° (Fig. 2). The contact angle
θ > 90° indicates non-wetting. Such surfaces are called
hydrophobic. Drops of water tend to form „beads” on
hydrophobic („water rejecting”) solid surfaces. Surfaces
on which the water contact angle is above 140° are
termed superhydrophobic and can be obtained from the
hydrophobic ones by appropriate modifications such as
roughening, micro patterning, machining or etching.
Water spreading and forming drops of various con-
tact angles is showed in Fig. 2. On the other hand, if the
contact angle of water is higher than zero, then the work
of spreading, WS, is negative.
WS = W A − WC
(9)
where WA is the work of adhesion and WC is the work
of cohesion. The works of adhesion and cohesion are
related to solution surface tension as follows:
(10)
WC = 2σ LV (11)
 Bartosz Tylkowski, Iren Tsibranska
where σ LV is the liquid/vapor surface energy. Hence:
WS = σ LV (1 + cos θ ) − 2σ LV = σ LV (cos θ − 1) (12)
The first approach to characterize the equilibrium
in a solid/liquid/vapor system was introduced by Young
(1805) and his equation describes the mechanical bal-
ance at the line of the three phase contact (TPC) on an
ideal (smooth, homogeneous, rigid and insoluble) solid
surface as:
σ=
SV σ SL + σ LV cos θ (13)
where σSL is the solid/liquid surface energy, and σSV is the
solid/ vapor surface energy. The fundamental problem
associated with the equilibrium contact angle is related
to the structure and topography of the solid surface, as
the real solids are rough. Surface roughness can affect
strongly wettability and values of the apparent contact
angles. To characterize the geometrical non-ideality of
a surface, roughness parameter r was introduced and
defined as:
Areal
r= (14)
Ageometrical
where (Areal) and (Ageometrical) are the real and geometrical
areas of the surface. For r > 1 Young equation was modi-
fied by Wenzel. The Wenzel equation:
cos θ W = r ⋅ cos θ (15)
is a generalization of the Young’s equation, where θW is
the Wenzel contact angle. The Wenzel equation refers to
Fig. 3. Water drop behavior and contact angle on smooth and rough hydrophobic surface.
so-called homogeneous wetting regime [35] i.e. when
the liquid completely penetrates scratches, grooves and
cavities (Fig. 3). Another situation, when air is entrapped
inside the grooves underneath the liquid, is termed the
heterogeneous wetting (see Fig.3.2C), and is described
by the Cassie-Baxter equation:
cos
= θCB rf ' f ' cos θ + f ' − 1
(16)
where θCS is the Cassie-Baxter contact angle, f’ is the
fraction of the projected area that is wet by a liquid and
rf’ is the roughness ratio of the wet area. When f’ = 1
then rf’ is equal r and Cassie-Baxter equation (16) simpli-
fies to Wenzel equation (15). As recently discussed [36,
37], the phenomenon of higher values of contact angle
on modified (roughened, micro patterned, machined or
etched hydrophobic surfaces is caused by inhibition
of the liquid spreading into grooves, scratches and/or
cavities on the rough surface. Moreover, a spreading of
such drop can be “arrested” by the edges of the grooves.
Contact angle is a widely used analysis for char-
acterization of membrane hydrophilic/hydrophobic
behaviour [31], the effect of chemical modification like
cross-linking on the latter [38] or by introducing hydro-
philic or hydrophobic solvent stable polymeric materi-
als as support membranes in the search of optimal flux
without sacrificing selectivity [22]. It is observed that
contact angle and thickness of the hollow-fiber decrease
similarly against air gap distance. Contact angle is re-
lated to the roughness parameter of the outer membrane
surfaces [18]. It is considered as key feature for deeper
understanding of other techniques like permporometry,
related to the sorption layer thickness [11].
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 Journal of Chemical Technology and Metallurgy, 50, 1, 2015
CONCLUSIONS
The field of membrane technology is currently
enjoying a great deal of interest and its field of appli-
cation is expanding rapidly. Every day, both in public
laboratories (universities, research centers, etc) and in
private ones (R&D centers of industrial companies)
variety of techniques and approaches are routinely used
for characterizing the physical and chemical properties
of membranes.
Concerning the applications of porous membranes in
separation processes the importance of reliable characteri-
zation of pore sizes and distributions requires: increased
measurement resolution and capability to define the active
part of the pore structure, which really contributes to the
permeability; discrimination between artefacts induced
by the characterization technique itself, swelling effects,
etc.; dealing with pronounced asymmetric pore-size dis-
tributions, including bimodal ones; characterization of
three dimensional morphology of porous membranes. In
the scope of the actual problematic of depth profile ex-
amination, non-destructive sample preparation, wet-state
characterization, etc., recent standard methods for char-
acterizing membrane surfaces, cross-section and porosity
are presented and discussed. This review is motivated by
the improvement of researchers’ ability to evaluate the
role(s) of membrane properties in determining membrane
performance, preferably for a wide range of applications
with accent on examples with porous polymeric mem-
branes. In the focus are conducting and interpreting results
from bubble pressure, liquid-liquid porosimetry, nitrogen
adsorption/desorption, permporometry, scanning electron
microscope, transmission electron microscope, contact
angle and permeability methods. Porosity and pore size
distributions studies together with factors as tortuosity,
pore shape and connectivity give link to recent devel-
opments (including 3D morphology characterization)
important to the performance of membranes in various
applications areas.
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