The Motion and Precipitation of Suspensoids in Divergent Electric Fields

Herbert A. Pohl

Citation: Journal of Applied Physics 22, 869 (1951); doi: 10.1063/1.1700065
View online: http://dx.doi.org/10.1063/1.1700065
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JOURNAL OF APPLIED PHYSICS
VOLUME 22. NUMBER 7 JULY. 1915
The Motion and Precipitation of Suspensoids in Divergent Electric Fields
HERBERT A. POHL *
Naval Research Laboratory, Anacosta, D. C.
(Received November is, 1950)
The motion of suspensoid particles relative to that of the solvent resulting from polarization forces pro-
duced by an inhomogeneous electric field is defined as "dielectrophoresis." It is analogous to the related
phenomenon of electrophoresis, in which motion of suspensoid particles is produced by the action of an
electrostatic field on the charged particles.
From a consideration of theoretical calculations and from experimental observations it is concluded that
the phenomena of "dielectrophoresis" and "dielectro-precipitation" can be observed under rather ideal
conditions, though it is ordinarily often difficult to do so because of the presence of the more easily produced
electrophoresis or ion-type migration of charged particles.
The usefulness of die1ectrophoresis (and/or electrophoresis) for removing suspended solid particles from
polymer solutions during analysis is described.
T
HE application of highly inhomogeneous, strong,
electric fields to suspensions of solids or of
liquids in fluids has been found helpful in coagulating
and precipitating finely dispersed material for analysis.
The phenomenon seen in the relative motion of sus-.
pensoid and medium resulting from polarization forces
produced by an inhomogeneous electric field is defined
as "dielectrophoresis;" and when this leads to co-
agulation, the process may be called "dielectro-
precipitation. "
Dielectrophoresis does not require ionized particles
but rather depends on asymmetrical induction and
attraction of displacement charges within the particles,
and further that the resultant motions be different for
solvent and solute. Migration in either alternating or
direct current fields is observed to take place. Figure 1
diagrammatically shows the effect of an inhomogeneous
field on a discrete particle lying in the field. The un-
equal field force acting on all permanent or induced
dipoles causes them to be constrained to move towards
the region of highest field density.
When the polarizability of the suspensoid is greater
than the solvent, the asymmetric field forces accelerate
the suspensoid particles more than the solvent, giving
rise to an increased concentration of the suspensoid
near the center of high field strength. The suspensoid
particles are then more prone to collision and coagula-
tion. Agglomerations of suspensions may therefore fre-
quently be accomplished with this technique using
simple apparatus.
The following equations are included to show the
relative importance of the factors involved. The force
on a small particle in a non-uniform field is expressed
to a good first approximation by
j=PiJE/iJr (1)
=E'E'iJE/iJr (2)
= (k-1) EiJE/47riJr= (k-1) 'iJ(Jtl)/87riJr, (3)
* Based on research at the Naval Research Laboratory, Ana-
costa, D. C. Present address: Du Pont Experimental Station,
Wilmington, Delaware.
where j=force per unit volume, P=polarization=EE,
E = field strength, E = proportionality factor of polariza-
bility, and k=dielectric constant = 1+ 47rE.
The excess force on the suspensoid of dielectric
constant, kl' over that on the solvent of dielectric
constant, k2' is
t:.j= (EI- E2)iJ (Jtl)/iJr = (k
l
- k
2
)iJ(Jtl)/47riJr. (4)
This relation says that the motion of the suspensoid
under the influence of the inhomogeneous field will be
proportional to the absolute value of the electric field
strength applied, to its divergence, and to the differ-
ences in dielectric constant of suspensoid and solvent.
The motion will be in the direction of the greatest field
strength and independent of field direction.
The force of the field on the particle will cause mo-
tion opposed by viscous drag; hence, the force on the
particle is given by
F= (volume of particle) 67ra?]v, (5)
using Stoke's equation and assuming spherical par-
ticles, giving
v= 2 a
2
a
2
(k
l
- k
2
) EiJE/187r?]iJr, (6)
where F=force on the particle, a=radius of particle
in cm, ?]=viscosity of medium in poises, v=velocity
in cm/sec.
In the interesting case of the divergent field formed
in the liquid between two infinitely long concentric
cylinders, we have
E=iJV /iJr= 2q/kr,
V1- V2= (2q/k) In h/rl),
V
1
- V = (2q/k)ln(r/rt),
iJ(Jtl)/iJr=4q2/rk2,
(7)
(8)
(9)
(10)
where V = potential in statvolts at r cm from the center,
V
1
- V
2
=potential in statvolts applied across the elec-
trodes, q=charge per cm on the inner conductor,
k=dielectric constant of the mixture.
869
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870
HERBERT A. POHL
v
FIG. 1. Diagram of forces operating on dipoles and suspended
particles in an inhomogeneous electric field.
Dielectrophoresis.
Combining Eqs. (8) and (9) and substituting in
Eq. (6), we get
v=a
2
(k
1
-k
2
)(V
1
- V
2
)2j1811"?)r In(r2/rl)' (11)
In a system, e.g., where 11 = 10 mils= 1.27X lQ-2 em, '2=5 em,
and Vl- V
2
=1()o1 volts=33.3 statvolts, and '1=1Q-2 poise (tolu-
ene, etc.), we have
(12)
E.g., if a= 101'= 10-
8
em, r= 1 em, k
1
-k
2
'i= 108 as for a graphite
or Ni sol in toluene, then we have V= 55(10-
3
)2108= 0.055 em/sec,
which is a reasonably determinable velocity in the laboratory.
However, for a very fine suspension of particles of not too
different dielectric constant we might observe, e.g., where a= 11'
= 10-
4
em, r= 1 em, kl -k2'i= 10; as for a polymer suspended in
toluene:
v=55(1Q-4)210=5.5X10-
6
em/sec, which is in the order of
magnitude of diffusional velocities. The migration in this case
would be quite difficult to observe.
A calculation due to J. A. Wheeler of the time re-
quired to sweep out a cell by dielectrophoresis is given
below:
dt=dr/(ar/at) = dr/v = const rdr, (13)
since rlr.
Hence, the time in seconds is
t(sec) = 911"?)r4[ln(r/rl)]2/2a
2
(k
1
-k
2
) (V1- V
2
). (15)
E.g., in the above apparatus [see Eq. (12)J, we have
t = ,4/220a
2
(kl - k
2
).
For the case of the graphite or Ni sol described,
t= 103108/220103=4.55 sec, which is a reasonably short experi-
mental period.
For the polymer suspension described
t= lQ410
4
/22010=4.55 I()o1 sec= 12.6 hr.
In the absence of disturbing influences such as con-
vection, the weight, w, of material migrating to the
central electrode in time, t, will be
W=c(vol. swept out)=ch(1I"r,2)i
hence, we have,
W = !hca[(V 1- V 2)/ln(r2/rl)][211"(k1- k
2
)/?)]lt
1
,
where c=conc of sol in grams/cm
3
, h=height of cylin-
drical cell, and rt=radius swept clean in time t.
At this point it is well to sum 'up our expectations
about the occurrence of dielectrophoresis and compare
it with the related phenomenon of electrophoresis.
Dielectrophoresis, arising because of the tendency
of matter to become polarized and move into regions
of highest field strength,
1. Produces motion of the particles in which the direction of
motion is independent of the direction of the field; Le., either dc
or ac voltages can be employed.
2. Should be observable most readily in relatively coarse sus-
pensions (e.g., particle diameter
3. Requires highly divergent fields. No motion should be ob-
served in the nondivergent field between centers of parallel plates.
4. Requires relatively high field strengths, e.g., 10,000 v across
a 5-cm cell.
5. Would be most apparent in fluids of low viscosity (thin
liquids, gases).
6. Generally requires a large difference in dielectric constant
between solvent and (k
l
- k2) > 10-100.
7. Will deposit weights of sol in direct proportion to the voltage
applied in equal times of deposition.
Electrophoresis, arising from the electrostatic attrac-
tion of charged electrodes for charged particles,
1. Produces motion of the particles in which the direction of the
motion is dependent on the direction of the field. Reversal of the
field reverses the direction of travel. Care must be taken in the
application of this rule for distinction between electro- and
dielectrophoresis as motion of charged particles towards a sharp
electrode can occur even in alternating fields of high strength
because of the occurrence of partial rectification effects making
the applied alternating voltage cause predominantly direct current.
For example, a milky 20 percent suspension of Hycar rubber in
methyl ethyl ketone was readily precipitated to form a thick
adherent coat on parallel electrode plates 5 cm apart by dc but
not by ac voltage of 2000 to 6000 v. This shows the suspension
to consist mainly of charged particles capable of deposition fol-
lowing electrophoresis. The suspension was also precipitated at
the wire of the wire and sheet pair by either dc or 6O-cycle ac
voltage as above. The latter observation by itself might at first
sight be considered as caused by dielectro-precipitation; however,
the further consideration shows this cannot be the case as the
dielectric constant of the medium (18.4) exceeds that of the sus-
pended particles (ca 15). This leaves deposition following electro-
phoresis as the more probable explanation with the assumption
that partial rectification of the ac occurred.
2. Is observable with particles of any molecular size.
3. Operates in either divergent or uniform fields.
4. Requires relatively low voltages.
5. Requires relatively small charges per unit volume of the
particles.
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SUSPENSO IDS IN DIVERGENT ELECTRIC FIELDS 871
With these guides for examination of particle motion
in electric fields, it is instructive to examine some of
the experimental facts available. Hatschek and Thorne
l
studied nickel sols in anhydrous toluene in which rubber
acted as a protective colloid. As electrodes, they used
small parallel plates having sharp edges. They observed
equal quantities of precipitate forming at each elec-
trode, with considerable rubber present in the pre-
cipitate. The sol precipitated in quantities proportional
to the first power of the applied voltage during equal
times. This, they concluded, was a principal reason for
interpreting the results as electrophoretic and not di-
electrophoretic, since they expected first-power de-
pendence in the first and second-power dependence in
the second instance. The present theory indicates that
first power dependence on voltage for the weight de-
posited would be expected for cells of cylindrical sym-
metry, an approximation of the field at the sharp edge
of the parallel sheet electrodes.
Hatschek and Thorne found several contradictory
phenomena in their interesting study. For one, alter-
nating potential did not cause coagulation (migration
was not studied) as did static voltage in their large
apparatus, an observation which led them to interpret
the phenomenon in this instance to be electrophoresis.
On the other hand, in a smaller cell used on their
microscope stage they observed the particles in the
middle of the field between two narrow parallel plates
to be unaffected by the field. Further, particles away
from the exact middle, which were caused to migrate
under the influence of the field, did not reverse their
direction of travel on changing the field direction. The
last two observations cannot easily be explained as
electrophoresis but can easily be interpreted as typical
examples of dielectrophoresis. It would seem that both
electrophoresis and dielectrophoresis were being ob-
served in their experiments despite their conclusion that
only electrophoresis was present.
Soyenoff2 noted the coalescence of coal dust in
toluene occurring at over 5000 volts/em to be equally
effective by dc or ac voltage. This he attributed to
dielectric pohtrization, remarking that " ... any sus-
pensoid body of higher conductivity or dielectric con-
stant than the medium (is caused) to move toward the
region of highest field intensity."
Reising,S in a study of the migration of pigment
particles in paint vehicles observed in several cases
that roughly equal quantities of precipitate collected
on his relatively narrow electrodes. He used static
voltages. Whether or not this is an instance of dielectro-
phoresis is not certain from the descriptions given.
1 E. Hatschek and P. C. L. Thorne, Kolloid-Z. 23, 1 (1923).
2 B. C. Soyenoff, J. Phys. Chern. 35, 2993 (1931).
S J. A. Reising, Ind. Eng. Chern. 29, 565 (1937).
Winslow' produced rotary migration and alignment
of elongated semiconducting particles suspended in
media of low dielectric constant (e.g., moist silica gel
particles suspended in kerosene), and also observed
migration of particles under the influence of field gradi-
ents. The latter seems describable as dielectrophoresis.
Studies in our laboratory have been concerned prin-
cipally with the use of dielectrophoretic technique to
aid in polymer analysis. It proved difficult, e.g., to
remove carbon-black filler from polyvinyl chloride
samples by other means such as filtration or centrifuga-
tion; but removal was rapidly and simply accomplished
in a powerful, divergent electric field. For example, a
one-gram sample of the polymer sample was taken up
in 50 ml of di-isopropyl ketone with the aid of gentle
heating, then placed in the coagulation cell. The cell
consisted of a Petri dish of ca lO-cm diameter containing
the electrodes. A lO-mil tungsten wire formed the
central electrode and dipped vertically into the liquid.
A band of tinfoil 8 rum high resting on the inner wall
of the cell formed the outer electrode. A high voltage,
either dc or ac of 10,000 volts, was then applied. The
liquid immediately underwent considerable action, small
ripples formed, and the carbon particles underwent
rapid migration toward the central wire to form a
coating. The solution of polymer became water clear in
a few minutes of what was very likely dielectro-pre-
cipitation and was then removed for further analysis.
Similar results were obtained with polyvinyl chloride-
polyvinyl acetate copolymers .When parallel plates,
with carefully rounded edges to avoid high field gradi-
ents, were used instead of the wire and sheet combina-
tion, no precipitation was observable with either dc or
ac. This adds confirmation to the conclusion that di-
electrophoresis occurred under these conditions.
Similar results were obtained with suspensions of
coal dust or of charcoal dust in toluene.
It is concluded that the phenomenon of dielectro-
phoresis can be observed, though it is often difficult
to do so because of the presence of the more easily
produced electrophoresis or ion-type migration of
charged particles. Calculations of the magnitudes of the
effects of various variables on it show that dielectro-
phoresis, to be observed, requires rather ideal condi-
tions. A number of experiments are cited as examples
of these conclusions. The usefulness of dielectrophoresis
(and/ or electrophoresis) for polymer analysis is de-
scribed.
The author wishes to acknowledge the many helpful
suggestions and criticisms made by Drs. Maurice B.
Hall, Harold F. Ring, and John A. Wheeler.
4 W. M. Winslow, J. App\. Phys. 20, 1137 (1949).
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