Polarizability Effects in the Electrostatic Repulsion

between Charged Colloidal Particles

JOHAN KIJLSTRA
Department of Physical and Colloid Chemistry, Wageningen Agricultural University, Dreijenplein 6,
6703 HB Wageningen, The Netherlands

Received November 13, 1991; accepted February 5, 1992

The electrostatic interaction between two colloidalsphereswith a fixedsurfacechargedensity is calculated
in order to determine the influence of the polarizability of the spheres on the repulsive electrostatic force.
The linearized form of the Poisson-Boltzmann equation is used in combination with the Laplace equation,
which enables us to construct an exact solution in terms of a multipole expansion. The calculations
show clearly how the electrostatic force decreases with the polarizability of the particle, the decrease
becoming larger with stronger double layer overlap, whereas it is relatively insensitive to Ka. This insensitivity is a consequence of tangential screening effects inside the particles, as illustrated by a comparison
of the exact solution with a Derjaguin-type approximation in which the possibilityof tangential screening
is not included. It is pointed out that for slowly coagulating dispersions of particles with a fixed surface
charge density, the stability ratio W is sensitive to the polarizability of the particle. 1992Academic
Press, Inc.

1. INTRODUCTION
The stability o f hydrofobic colloidal suspensions is determined by the interparticle
forces. In the D L V O theory, two types o f forces
are distinguished, the attractive Van der Waals
force and the repulsive electrostatic force,
present when overlapping o f diffuse double
layers occurs. F r o m these forces, the energy o f
interaction as a function o f the interparticle
distance can be deduced, which in turn is necessary to c o m p u t e the stability ratio W ( 1 ).
Usually the P o i s s o n - B o l t z m a n n equation
is solved to calculate the electrostatic repulsion
between two h y d r o p h o b i c colloidal particles,
and m a n y papers devoted to this subject have
appeared in the literature. The solution o f this
equation depends not only on the geometry
o f the system, to which m u c h attention has
been paid ( 1-4 ), but also on the distribution
o f the surface charge density. Regarding this
distribution, an assumption has to be made.
Verwey and Overbeek (1) already distinguished two limits o f interaction between par-

ticles, the constant (surface) charge and the

constant (surface) potential case. The first case
applies when the timescale o f particle interaction is too short for the surface charge to
adjust. If, on the other hand, desorption of
surface charge is very fast c o m p a r e d to the
a b o v e m e n t i o n e d timescale, equilibrium between the surface charge and the ions in solution will be maintained continually. For the
latter case Verwey and Overbeek assumed the
surface potential to be independent o f the interparticle distance. This assumption has been
shown to be not very realistic for systems such
as oxides. In these systems the potential is determined by a charge regulation mechanism,
which, in c o m p a r i s o n with either the constant
charge or the constant potential case, m a y give
rise to large differences in the colloidal stability
(5, 6). In the regulation model the double layer
is always in equilibrium and the surface
charge, as well as the surface potential, is adjusted during particle interaction. The adjustm e n t o f both these parameters is caused by
the entropic contribution o f the surface charge
30

0021-9797/92 $5.00
Copyright 1992 by Academic Press, Inc.
All rights of reproduction in any form reserved.

Journal of Colloid and lnterface Science, Vol. 153, No. 1, October 1, 1992

ELECTROSTATIC REPULSION
determining ions to the free energy, which
generally corresponds to a nonlinear function
of the surface charge density. Consequently,
both charge and potential may vary along the
particle surface. Obviously, this will also be
the case if the timescales of interaction and
surface charge relaxation are of the same order,
resulting in disequilibration of the surface
charge during interaction.
Apart from the limiting situation of a constant surface potential, all cases have in common that an electric field will be present inside
the particles during interaction. In principle,
this field has to be taken into account in calculating the electrostatic repulsion. However,
Gauss's law suggests that the influence of this
field on the electrostatic force can probably be
neglected in the case of low values of the ratio
between the dielectric constants of the particle
(e2) and the electrolyte solution (el). For many
aqueous dispersions this is probably true and
therefore the approximation is often applied
in the literature (7, 8 ). An example of a wellknown colloidal system for which this approximation is very poor is a rutile suspension.
Depending on the optic axis, rutile has two
dielectric constants, 86 and 170 (9). The
quality of the approximation depends not only
on e2/el, but also on the geometry of the system. For the interaction between two parallel
plates of finite thickness with constant surface
charge density on both sides, Ohshima (10)
showed how the correctness of the approximation improves with decreasing value of e2/
El, as well as with increasing value of Kd, with
K-1 and d being the double layer and plate
thickness, respectively. In his analytical theory
for the interaction between two spherical particles with constant surface charge density
( 11 ), he neglects the tangential component of
the electric field inside the particle. However,
according to Dukhin and Lyklema (12), this
component is the most important one and
therefore they conclude that the geometrical
parameter of importance for spheres is
O( ~
instead of O(Ka), with a the particle
radius. This geometrical parameter and the
distance between the two particles, which gives

31

the degree of double layer overlap, determine

together primarily the gradient in the surface
potential and thus the electric field strength
inside the particle.
In this paper, the validity of the approximation of neglecting the electric field inside
the particle will be tested for the interaction
between two identical spherical particles with
a fixed homogeneous surface charge distribution. A simple model is invoked in order to
determine in which range of Ka and particleparticle distance the influence of the particle
polarizability on the electrostatic force is significant. We assume the particles to have one
dielectric constant, irrespective of the optic
axis. The electrostatic repulsion is calculated
by solving the differential equations for the
electric field inside and outside the spheres.
The linearized form of the Poisson-Boltzmann equation is used in combination with
the Laplace equation, which enables us to
construct an exact solution in terms of a multipole expansion. Tangential screening effects
are therefore all taken into account. The Poisson-Boltzmann equation and the Laplace
equation are coupled at the particle surface by
Gauss's law. Consequently, a nondiffuse part
of the double layer, for example a Stern layer,
is assumed to be absent. In systems where the
nondiffuse part of the double layer is important, the model has to be extended for accurate
quantitative calculations. The multipole expansion of the linearized Poisson-Boltzmann
equation has been used before to check the
Derjaguin approximation (7) and to calculate
the effect of surface charge relaxation on the
force between two particles (e2 = 0) at a fixed
distance (8).
Generally, by using the Derjaguin approximation, one neglects the field inside the particle. It is, however, possible to take, on the
same level of approximation, the effect of this
field into account by using the theory of
Ohshima (10) for the interaction between two
parallel plates of finite thickness. The results
of the exact solution will therefore be compared with the combination of the Derjaguin
approximation with Ohshima's theory. In this
Journal of Colloid and lnleffiwe Science, Vol. 153, No. 1, October 1, 1992

32

JOHAN KIJLSTRA

approach, in contrast to the exact method,

tangential screening effects are not incorporated.

The general solution of [ 2.1 ] for two identical

interacting spherical particles, using polar coordinates, is given by (13)

2. THEORY

co

Consider two identical interacting spherical

particles (phase 2) in a symmetric electrolyte
solution (phase 1 ). For low potentials the
electrostatic potential 4'1 in the electrolyte solution is governed by the linearized PoissonBoltzmann equation
~'24' 1 =

(Ka)24'l

[2.1]

with K-1 the Debye length. Throughout this

section, dimensionless parameters are used,
the potential 4' scaled on k T / e and lengths
scaled on the particle radius a, with e the elementary charge and k T the Boltzmann temperature. Linearization of the PB equation is
justified if z4'~ < 1, with z the charge of the
ions. The potential 4'2 inside the sphere, where
the charge density equals zero, is governed by
the Laplace equation
V24'2 = 0.

4'1 = ~a f ~ [ K , ~ ( K a r ) P , , ( c o s O)
n=0
oo

+ ~

Bnm(Karsep)(2m + 1)

m=0

Im(Kar)P,.,,(cos 0)]

[2.3]

with the polar axis 0 = 0 coinciding with the

line connecting the centers of the two spheres,
r the radial coordinate, rsepthe center-to-center
distance, P, the Legendre polynomials, Im and
Kn the spherical modified Bessel functions of
the first and third kind, and f , the unknown
coefficients. The function B~m is defined as
Bnm( Karsep)
min(n,m)

AnmvKn+m_2v(Karsep)

[2.4]

[2.2]
with

Ant'ell)

r ( n - v + 1 / 2 ) P ( m - v + 1/2)P(v + 1/2)(n + m - v ) ! ( n + m - 2v + 1/2)

rrr(n + m - v + 3 / 2 ) ( n - v ) ! v ! ( m - v)!
[2.51

and P the gamma function. Solution [2.3]

satisfies the requirements of zero field at the
midplane and zero potential at infinity. For a
finite potential inside the sphere, the solution
of [2.2] is
oo

4'2 = ~ gnr"P,,(cos 0).

[2.6]

n 0

The coefficients f, and g~ can be determined

from the boundary conditions at the particle
surface. For the present case, where space
charges inside the particle and nondiffuse
double layer effects in the solution are supposed to be absent, the boundary conditions
are given by the continuity of the potential,
4'1 ]r=l = 4'21r=1,

[2.7]

and the law of Gauss,

Journal of Colloid and lnleffkweScience, Vol.

153, No. 1, October 1, 1992

~204'2
~1 Or r=l

04'1
Or r=l = ~'

[2.8]

with a the surface charge scaled on < k T / e a .

The importance of the first term on the lefthand side of [ 2.8 ], representing the polarizability of the particle, which has been neglected
in the literature, is now the point of discussion.
Combining Eqs. [2.3] and [2.6] with the
potential continuity equation [2.7] gives
& = fjKj(Ka)
co

+ ~ f ~ ( 2 j + 1)Bnj(Karsep)Ij(Ka).

[2.9]

n-0

By substituting the derivatives of the potentials

at the particle surface in Gauss's law, we get

ELECTROSTATIC REPULSION

Ka ~ f~{K'(Ka)P,(cosO)+ Z ( 2 m + 1)
n=0

m=0

B,m(Karsep)I'(Ka)Pm(COS O) }
o0

E2 Z g, nP~(cos 0) = - ~

[2.10]

33

techniques to compute the unknown coefficientsf.

For low potentials, the interaction force Fe
between two identical particles due to the osmotic pressure and the Maxwell stress has been
given as (7)

E1 n = 0

with the derivatives of the Bessel functions

taken with respect to the argument.
The method used to calculate the electrostatic interaction between two identical spheres
is not restricted to spheres with a constant surface charge density. It is also applicable to two
interacting spheres with an inhomogeneous
charge distribution, provided that the conditions of symmetry (axial symmetry around the
polar axis 0 = 0 and symmetry plane midway
between the spheres) are satisfied. The distribution of the surface charge density can then
be written as a series of Legendre polynomials

Fe = 7r

{ [(Ka)2~ 2 + E02 - E2]#

1

+ 2ErEo(1 - #2)]/2}d#

[2.14a]

with the electric field scaled on kT/ae, the

force on el(kT)Z/e 2, # = cos 0, and the integrand evaluated at any surface enveloping
the particle, for example at the particle surface.
The polar components of the electric field at
the surface Eo and Er are given by
of~

E~ = Ka ~ f~[K'(Ka)Pn(cos O)
n=0
oo

oo

a = ~ ajPficos 0).
j=o

[2.11]

+ ~ Bnm(Kar~ep)(2m + 1)
m=O

l"(Ka)Pm(cOs 0)]

In our limiting case of constant surface charge

density, we have

[2.14b]

O7)

Eo = - s i n 0 ~ f.[K~(Ka)P'(cos O)
~o = a, (rj>o = 0.

[2.12]

For an isolated sphere with a homogeneous

charge distribution, the charge-potential relation a = ff~( 1 + Ka) is valid, with ff~ the surface potential. By substituting [2.9 ] and [2.11]
into [ 2.10 ] and taking the inner product with
Pj(cos 0), we end up with the following set of
linear equations:
co

(Ka)fKj(Ka) + (Ka) Z f ~ ( 2 j + 1)
n=0
E2

B,j(Karsep)I~(Ka)---j{fKfiKa)
El

+ Z f ~ ( 2 j + 1)B~j(Kar~p)IfiKa)}
n=0

n=O
O9

+ ~ Bnm(Karsep)(2m + 1)
m=0

Im(Ka)P'(cos 0)]

[2.14c]

with the derivatives of the Bessel and Legendre

functions again taken with respect to the arguments. For further details on the expression
for the force in terms of Legendre and Bessel
functions, the reader is referred to Weaver and
Feke (8). For a discussion of the numerical
limitations of this method, see Glendinning
and Russel (7). The number of terms used in
the expansions was chosen in order to converge the force within 0.1%.

The Derjaguin Approximation

=-as-.

[2.13]

This set is solved by truncating the multipole

expansion and using standard numerical

An approximate method to calculate the

electrostatic force between two spherical particles from the knowledge of the interaction
Journal of Colh)id and lnte([ace Science. VoL 153, No. I, October 1, 1992

34

JOHAN

between two infinitely large parallel plates has

been given by Derjaguin (14). According to
his approximation, the electrostatic force FD
is expressed for low potentials by the integral

FD = -7rKa
T ~Ho' ~2 dH

KIJLSTRA

with the + and - signs referring to the first

and second case, respectively. If, at a given
surface charge density, a ~ 0, the integral in
[ 2.15 ] can be easily evaluated numerically in
combination with [ 2.17 ].

[2.151
3. R E S U L T S A N D C O N C L U S I O N S

with ~bm the potential midway between two

parallel plates (of finite thickness) at distance
H and Ho the closest distance between the surfaces of the spheres. For convenience, these
lengths are both normalized on g-l, the latter
being related to rsep through rsep = 2 + Ho/Ka.
Analytical expressions for ~km are available
for the linearized PB equation. In the case of
given surface potential $s, we have
ffm = c o s h ( H / 2 )

[2.16]

and in the case of constant surface density on

both sides of the plates, according to Ohshima
(10)
~m

0"*

l+a
a cosh(H/2) + sinh(H/2)
[2.17]

and
ce -

1 + (q/e2)Kd

[2.18]

Figures 1 and 2 show the ratio F(ez)/F(e2

= 0) as a function of the interparticle distance
for Ka values of 1 and 10, calculated by using
the exact solution [2.14]. For all graphs
shown, the surface potential of the isolated
particles (~s,r,ep=~ = 0.5) and the dielectric
constant of the electrolyte solutions (el = 80)
are fixed.
An important feature is that, even for not
too high values of E2 / E1, the ratio Fe(e2) / F e ( E2
= 0) decreases with diminishing interparticle
distance to values significantly less than 1. This
is the immediate consequence of the increase
Of~s in the interaction regime with decreasing
particle-particle distance and the concomitant
increase of the electric field strength inside the
particle. At constant a, the ratio F(e2)/F(e2
= 0) also decreases with increasing E2. This is
obvious because the higher e2, the lower the
electric field strength inside the particle. Such
a situation can only be accomplished if ~s decreases inside the interaction regime, whereas
it increases somewhere outside that regime (in

with or* the surface charge scaled on KelkT/e,

and e2 and d the dielectric constant and the
thickness of both plates, respectively. The dimensionless parameter a represents the importance of the electric field inside the plates
during interaction, present due to the difference in surface potentials on both sides of each
plate. In the limiting case of very low e2/el
a n d / o r very thick plates, the electric field inside the plates can be neglected, and a approaches zero. Analytical solutions of the integral in [2.15 ] are known for the constant
surface potential, as well as for the constant
charge case with a = 0,
e-Ho

FD = 27rKa~Ps2'H=~1 _+ e -H'

[2.191

Journal o[Colloid and Interface Science, Vol. 153, N o . 1, O c t o b e r 1, 1992

1.0

/,
.'

II

/
,t
t
t
r
t
i

0.5

t
.r
J
i'
I

( rse p - 2)~ca
FIG. 1. Ratio of exact force to exact force for e2 = 0. Ka
= 1, ~1 = 80, ( - - ) E2 = 10, ( - - - ) E2 = 30, ( - - - ) e2 = 50,
( ....

) C2 =

10 4.

ELECTROSTATIC REPULSION

35

1.5
1.0
J
It

/,
*

/.

1.0

/
t
.t

0.2

0.5 i .............
0

2
(rse p- 2)~a

) (2 =

0.8

0.9

cos 0

FIG. 2. Ratio of exact force to exact force for e2 = 0. ca

1 0 , ~1 = 8 0 , ( - - ) 2 = 1 0 , (- - -- - - ) E2 = 30, (---) ~2 = 50,

( ....

0.7

104.

c o m p a r i s o n w i t h t h e ~2 = 0 c a s e ) . T h i s has
b e e n i l l u s t r a t e d in Figs. 3 a n d 4, w h i c h are
results f r o m t h e e x a c t s o l u t i o n . F o r K a = 1 w e
see e v e n a slight i n c r e a s e o f 6~ w i t h e2 at t h e
" b a c k " o f t h e s p h e r e ( c o s 0 = - 1 ), in c o n t r a s t
t o t h e case o f r a = 10, w h e r e t h e m o s t signifi c a n t i n c r e a s e a p p e a r s j u s t a r o u n d t h e interaction regime. From the limited penetration
d e p t h o f t h e e l e c t r i c field i n t o t h e p a r t i c l e for
n o t t o o l o w Ka values, it c a n be c o n c l u d e d t h a t
its t a n g e n t i a l c o m p o n e n t i n s i d e t h e p a r t i c l e is
important.

FIG. 4. Surface potential distribution for the case of r a

= 10, a = 5.5, ~b~,r=p== 0.5, ej = 80, and (r~p - 2)Ka =
1. (--) ea = 0, ( - - - ) E2 = 10, (---) ez = 50, ( . . . . ) e2 =
l04.

The deviations of the Derjaguin force from

t h e e x a c t f o r c e are s h o w n in Fig. 5 for Ka =
20 a n d d i f f e r e n t ~ 2 values. T h e p o o r q u a l i t y o f
t h e D e r j a g u i n a p p r o x i m a t i o n for e2 = 0 has
b e e n n o t e d b e f o r e ( 7 ) a n d is d u e t o t h e prese n c e o f t a n g e n t i a l s c r e e n i n g effects in t h e diffuse d o u b l e layer. I n t r o d u c i n g a s e c o n d possibility o f lateral screening, b y t a k i n g t h e p o larizability of the particle into account, only
m a k e s t h e a p p r o x i m a t i o n worse.
I n t h e l i m i t o f E2 --~ oo, t h e i n t e r i o r o f t h e
p a r t i c l e will b e h a v e like a c o n d u c t o r , f o r c i n g

2.5
0.8
2.0

';

~s
V~

",

x ..

1.5

~'.

0.5
I

-0.5

0.5

1.0

"

I
0

COS 0

"x
",

%.

( rse p - 2 )Ka

FIG. 3. Surface potential distribution for the case of c a

= 1, a = 1, ~,.r~=oo = 0.5, E1 = 80, and (r~p - 2)ca = 1.
(--) ~2 = 0, ( - - - ) ~2 = 10, (---) ~2 = 50, ( . . . . ) ~2 =

FIG. 5. The ratio of the Derjaguin force to the exact

force in the case of ca = 20, el = 80. (--) E2 = 0, (- - -)

104 .

c2 =

10, (---)

c2 = 5 0 , ( . . . .

) e2 =

104

Journal of Colloid and lntelface Science, Vol. 153, No. 1, October 1, 1992

36

JOHAN KIJLSTRA
1.05

""

1.00

~"

0.95

II

0.90
O.

10

100

1000

04

FIG. 6. The ratio F,el(Ka)/Frej(Ka = 10) as a function

of 62, with F,,1 = Fe(ez)/Fe(e2 = 0) and (r~ep 2)Ka = 1.
(--) Ka = 20, (- - -) Ka = 30, (---) Ka = 40, ( . . . . ) Ka
= 50.
the p o t e n t i a l along the particle surface to be
c o n s t a n t d u r i n g interaction. T h e value o f this
p o t e n t i a l will exceed the surface p o t e n t i a l o f
a n isolated particle, b u t the difference decreases slightly with increasing Ka a n d thus
Fe(62 = oo )/Fe(62 = 0 ) d o e s too. H o w e v e r , at
n o t t o o high values o f 62, the radial screening
effects b e c o m e relatively less i m p o r t a n t t h a n
the t a n g e n t i a l ones. M o r e o v e r , the tangential
field a l o n g the surface d i m i n i s h e s with Ka a n d
the c o m b i n a t i o n o f these effects cause Fe(62)/
Fe (62 = 0) to increase with Ka. T h e c a l c u l a t e d
sensitivity o f F e ( 6 2 ) / F e ( 6 2 = 0) to Ka is, however, small, p r o v i d i n g a solid s u p p o r t for the
first o r d e r e s t i m a t e o f D u k h i n a n d L y l d e m a
( 1 2 ) . In m o s t cases, c h a n g i n g Ka will have a n
effect in the o r d e r o f o n l y a few percent, as is
s h o w n in Fig. 6.
In general, the a p p r o x i m a t i o n o f neglecting
the electric field inside the particle b e c o m e s
worse at s m a l l e r s e p a r a t i o n distances a n d
higher 62/61 values. F o r e x a m p l e , for a q u e o u s
suspensions, i f (rsep - 2)Ka < 1 a n d 6 2 > 30
the e r r o r in t h e electrostatic force a d d s u p to
m o r e t h a n t e n percent. A small change in the
electrostatic force, however, can have a large
effect o n the stability factor W. F o r slow coagulation, the stability factor W i s m a i n l y de-

Journal ~/'Colloid and lnter&ce Science. Vol. 153, No. 1, October 1, 1992

t e r m i n e d b y the net force at distances o f (rsep

- 2)Ka ~ 1, a region where the net force
is relatively small c o m p a r e d to its repulsive
a n d attractive c o m p o n e n t s . C o n s e q u e n t l y , a
change in the repulsive force o f 10% results in
a c h a n g e o f W w h i c h c a n be o n the o r d e r o f
one m a g n i t u d e or more. T h e relative size o f
the change is m o r e p r o n o u n c e d for large stability factors, for which the m a x i m u m in the
net force is l o c a t e d at s h o r t e r interparticle distances. F o r suspensions with 62/61 = O ( 1 ) ,
for e x a m p l e n o n a q u e o u s suspensions, it is
clear t h a t the electric field inside the particle
has to be a c c o u n t e d for. Especially for systems
with high Ka values, the calculations show t h a t
the t a n g e n t i a l c o m p o n e n t o f this field is i m portant.
ACKNOWLEDGMENT
The author thanks Dr. H. P. van Leeuwen for checking
the manuscript and for his useful suggestions.
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