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Polyelectrolyte Adsorption
of
p\ ',
\\
1 \?
( I
compensation
1.5
r=O .O1 5
0.5
----_
nl
0.04
0.08
0.12
0.16
0.2
0.08
0.251
'\\
/-,
- /
I
\
I
\
r=0.015
0.04
C-01 M
n
"
0
0
0.2
0.6
0.4
0.8
12
16
20
layer
Figure 1. (a, top left) Effect of segment charge T on the adsorption of a fully dissociated polyelectrolyte of 100 segments on an
oppositely charged surface (-0.01 C/m2) as a function of the 1:l electrolyte concentration cI (M).The adsorbed amount r is given
in equivalent monolayers. (b, top right) Adsorbed amount r as function of the segment charge T at four different salt concentrations.
The limiting (dashed) curve represents the adsorbed amount necessary for charge compensation. (c, bottom left) Essentially the same
graph as Figure lb, with different scales for both axes, the adsorbed amount r as a function of the segment charge T at two different
M. Other parameters are given
salt concentrations. (d, bottom right) Volume fraction profile for various segment charges, c8 =
in Figure la.
For the nonelectrostatic interaction of a polymer segment P and a solvent molecule 0 with the surface S,similar
Flory-Huggins parameters can be defined. Throughout
this paper, however, we will use the adsorption energy
parameters xs, defined by Silberberg20as -(UA - uo)/kT,
where U A is the adsorption energy of a polymer segment
or a salt ion and uo that of a solvent molecule, k is
Boltzmann's constant, and T the absolute temperature.
Thus, xs is positive if A adsorbs preferentially from the
solvent. The relation between the Flory-Huggins parameters XAS and xos, and xs is xs = XI(XAS - xos), since
only a fraction, XI (0.25 in a hexagonal lattice), of an
adsorbed segment is in actual contact with the surface, so
u d k T = X ~ X A Sand uo/kT = hlxos. In our calculations xs
for the solvent and for the salt ions was zero. In the last
section, where we will investigate the effect of specific
adsorption of counterions, the xs of the salt cation was
larger than zero. To distinguish between the adsorption
energy parameter of counterions C+ and that of polymer
segments, we use xScand xs, respectively.
Pure Electrosorption. In order to obtain a good
insight into the effect of the electrostatic interaction, both
the attraction between polyelectrolyte and surface and
the repulsion between the segments, we first examine the
adsorption r (expressed in equivalent monolayers) of a
polyelectrolyte which has only electrostatic interactions
with the surface ( x s = 0). The effects of the salt
concentration and the segment charge T are shown in
Figure la. The adsorbed amount at very low salt concentration, ro, is always higher than the adsorbed amount
(20) Silberberg, A. J . Chem. Phys. 1968,48,2835.
Polyelectrolyte Adsorption
----------.
1.2
C/m2
'+l
\
0.8
\
'\
>\
0.4
\
\\
-0.001 C/m'
--
-0.01 Cim2
1
.
\,
\
\
\\\
17u01Q:
(1)
K~
0.04
0.08
0.12
0.16
0.2
'\
1
0
0
10
layer
Q:
or c,,
0:
TU^)^^/^^
(2)
KtOt,k!!'
=re (x, + h,x
- xsc)
(3)
Polyelectrolyte Adsorption
0.24 I
0.18
x =0.35
//
t.,i=o.oo;\
I .J
/
/
/
=0.29
_/
0.12 p
---z
0.06
\
,
-4
-3
-2
\t(I;
-1
0.
0.00
-5
0.0
-5
-4
log c
charge compensation
IL
k
0
1\
\. =
-1
xs=o6
screenino reduced
for
xs=o.6
10
layer
(3a)
Now, the exponent is 2 instead of 10/11. Hence, eq 3 does
not correctly describe the displacement by salt studied
here. The assumption that only electrostatic interactions
in the first layer need to be considered is probably not
justified. Yet, Evers found a fairly good agreement
between eq 3 and his numerical calculations. The reason
for this is that he used highly charged (T = 1) polyelectrolytes and X , = 1. From Figures Id, 2c, and 3b it can
be seen that a high segment charge, higher surface charge
density, and a not too small nonelectrostatic affinity for
the surface (xl > 0) promote a flat conformation of the
adsorbed polyelectrolyte. So, in Evers calculations, all
the segment-surface interactions are indeed short range.
The difference of a factor K~ between Evers and Wiegels
analysis, or, equivalently the factor K ~ between
/ ~ ~ the
analyses of Evers and Muthukumar, is due to the neglect
of adsorbed polyelectrolyte segments that interact with,
but do not touch, the surface.
Effect of Specific Adsorption of Segments. In the
previous section we have seen that only the screeningreduced adsorption regime is found if the interaction
between polyelectrolyteand surface is merely electrostatic.
The screening-enhanced adsorption regime emerges when
a nonelectroetaticinteraction (%) is introduced,as is shown
in Figure 3a. It is more difficult to desorb the polyelectrolyte with salt if x8 > 0, even for very small x8, since a
nonelectroetatic attraction is added to the electric attraction. The effect of added salt is already nearly eliminated
for the curve in the middle (xs = 0.29); at first the
adsorption increases a little with increasing salt concenC,,
-2
log cs
0.02
-3
a (TQo)
,
0
0.04
,
0.08
0.12
0.16
0.2
--.
-...'.
-0.1 Ci"
L------'.l
1
T
',
'
0.5
0 C/.d
01
-5
-4
-3
-2
-1
0.02
0.06
0.04
0.08
0.1
0 (C/&
0
log cs
11
x =0.6
screening enhanced
n-
0.02
0.04
0.06
0.08
0.1
oo ( C i m ' )
0.5
screening enhanced
m
screening reducec
0.02
0.04 0.06
o0 ( C i m ' )
0.08
0.1
Figure 6. (a, top) Values for r and a0 for xB= 0.29 where the
Polyelectrolyte Adsorption
0.75
11
0.5 .
0.5
-5
-4
-3
-2
-1
-3
t = O . l , ~
-2
log cs
It now becomes clear why the screening-reduced adsorption regime was not found in earlier calculations based
on the mean field m0de1.~~61~
Only the influence of the salt
concentration for highly charged polyelectrolytes ( 7 = -1)
and xs > 0 (usually xs = 1)had been calculated. We also
understand better why, in experimental systems, the
adsorption is more often than not found to increase with
increasing salt concentration. Many experiments are done
with highly charged polyelectrolytes. The screeningreduced adsorption regime for such a system would only
be found if the attraction between polyelectrolyte and
surface is (almost) purely electrostatic, and it is rather
likely that at least some nonelectrostatic affinity between
polyelectrolyte and surface exists.
Specific Adsorption of Counterions. So far we have
considered the salt ions as solvent molecules, except for
their charge. However, it is well-known that salt ions may
adsorb specifically, which, in terms of this model, implies
that their xs is larger than zero. We will investigate the
effect of specifically adsorbing salt ions having the same
charge as the polyelectrolyte, namely the counterions. The
most interesting effect can be expected for the screeningenhanced adsorption regime, since the trend for the
screening-reduced adsorption regime will not change when
the salt ions have adsorption energy (the decrease of the
adsorption with increasing salt concentration will only be
more pronounced). Since the xs of the polyelectrolyte is
positive, the adsorbed amount will initially increase with
increasing salt concentration. Then, at higher salt concentration the salt cations win the competition and start
displacing the polyelectrolyte. The result of these two
trends is a maximum in the adsorbed amount as a function
of the salt concentration (Figure 7). The larger the
nonelectrostatic interaction of the salt cations, C, with
the surface (the more positive their xsc) the more effective
they act as displacers, so that the maximum becomes less
pronounced and moves toward lower concentrations. A
maximum in the adsorbed amount as a function of salt
concentration has occasionallybeen found experimentally.
For instance by B ~ n e k a m for
p ~polylysine
~~~
on silica, by
Lindstrdm and Wigberg31 and Tanaka et al.25 for respectively cationic polyacrylamides and polyDMDAAC (dimethyldiallylammonium chloride) on cellulose fibers.
Recently, we compared the adsorption of cationic amylopectin on microcrystalline cellulose with our theoretical
calculations, taking into account specific adsorption of
counterions. The experimental results showed also a
(31)Lindstrbm, T.; Wigberg, L. Tappi J . 1983,66, 83-86.
-1
log cs
",'"
-3
-2
-1
log c
Conclusions
Although it has been emphasized more than once that,
a t low salt concentration, polyelectrolytes adsorb in a flat
conformation and that the adsorption increases with
increasing salt concentration, we have shown this picture
to be incomplete. We propose to distinguish two regimes
based on the adsorption behavior of the polyelectrolyte
upon increasing salt concentration, the screening-enhanced
(32)van de Steeg, H. G. M.; de Keizer, A,; Cohen Stuart, M. A.;
Bijsterbosch, B. H.Submitted for publication in Colloids Surf.