Colloids and Surfaces

A: Physicochemical and Engineering Aspects 165 (2000) 79 – 93

www.elsevier.nl/locate/colsurfa

Diffusional deposition of colloidal particles: electrostatic

interaction and size polydispersity effects
Micha Semmler a,b, Jaroslav Rička b, Michal Borkovec c,*
a
Swiss Federal Institute of Technology, ETHZ-ITO, Grabenstrasse 3, 8952 Schlieren, Switzerland
b
Institute of Applied Physics, Uni6ersity of Bern, Sidlerstrasse 5, 3012 Bern, Switzerland
c
Department of Chemistry, Clarkson Uni6ersity, Potsdam, NY 13699 -5814, USA

Abstract

In the deposition process of charged nanosized particles onto oppositely charged planar substrates two effects are
being discussed: (1) The maximum surface coverage sensitively depends on the repulsive electrostatic particle – particle
interactions. The ionic strength of the particle suspension defines the magnitude of the electrostatic repulsion between
the particles, which in turn modifies the maximum surface coverage. The maximum surface coverage decreases with
decreasing ionic strength, a trend that can be well described by an effective hard-sphere model based on random
sequential adsorption (RSA), where the effective radius is estimated from the repulsive screened Coulomb potential.
Measured radial pair-distribution functions also reveal ideal hard-sphere behavior as compared to RSA simulations
for monodisperse disks. The magnitude of the interaction, however, is overestimated with the simple electrostatic
model. (2) Particle size polydispersity does also influence strongly the deposition process. Small particles may fill voids
left by larger particles such that the maximum surface coverage increases significantly. The size distribution of the
deposited particles on the surface changes with time, whereby the small particles are adsorbed preferentially. These
trends are observed experimentally and confirmed by computer simulation. © 2000 Elsevier Science B.V. All rights
reserved.

Keywords: Diffusional deposition; Electrostatic interactions; Polydispersity; Random sequential adsorption; Atomic force mi-
croscopy; Amidine latex

1. Introduction two areas. First, the evaluation of the initial depo-

Deposition of colloidal particles onto surfaces
is not only of substantial importance in numerous
applied disciplines, but also offers many interest-
ing aspects from the fundamental point of view.
The latter developments have mainly focussed on
* Corresponding author.
E-mail address: borkovec@clarkson.edu (M. Borkovec)
sition flux to the surface for various geometries
has received much attention [1,2]. These studies
show that the initial particle flux is well predicted
by theory in the regime of attractive particle–wall
interactions (favorable deposition), while the the-
ory fails in the regime of repulsive interactions
(unfavorable deposition). Second, much work was
done in the later stages of the favorable deposi-
tion regime, where repulsive particle–particle in-

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PII: S 0 9 2 7 - 7 7 5 7 ( 9 9 ) 0 0 4 3 8 - 0
80 M. Semmler et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 165 (2000) 79–93
teractions lead to surface blocking and to the
formation of structured particle monolayers on
the surface. This random sequential adsorption
(RSA) regime was studied for monodisperse hard
spheres theoretically in much detail [3 – 9].
Indeed, simple RSA in two dimensions agrees
with the experiment surprisingly well: it explains
the comparatively low surface coverage and the
pronounced spatial correlations within a layer
quantitatively [10 – 12]. The flow pattern and
shape of the surface does also influence the nature
of the deposit. For example, for non-spherical
particles shadowing effects may even induce or-
dering within the deposited layer [13]. In practical
situations, however, the case of hard-core interac-
tions in a monodisperse system is rather the ex-
ception than the rule. Actually, it is not easy to
find realistic systems, which represent the hard-
sphere case to a good degree of approximation.
Blocking phenomena are typically complicated by
the following factors. (i) Particle – particle interac-
tions in colloidal systems are seldom hardcore
like; (ii) particles are often polydisperse; and (iii)
in some cases the deposition process results in the
formation of surface-aggregates or formation of
multilayers (ripening). While the whole concept of
RSA can be extended to multilayers, RSA was
mainly compared with experiments for monolay-
ers. In the latter situation, however, the effects (i)
and (ii) modify substantially the predictions of
simple RSA for monodisperse hard spheres. These
complications which are particularly relevant for
applications, will be discussed in this paper in
more detail.
The most straightforward way to tune particle–
particle interactions is by adjusting the particle
charge or the ionic strength of the suspension.
The higher the charge and the lower the ionic
strength, the stronger the repulsion. This effect is
very important for the deposition of particles, and
leads to a pronounced decrease of the maximum
surface coverage with decreasing ionic strength.
This phenomenon has been observed for a num-
ber of systems [10,14 – 21]. For small and highly
charged particles at low ionic strength, the maxi-
mum surface coverage can be as low as 0.05
[20,21], which is about a factor of ten lower than
the jamming limit of 0.547 for hard spheres
[22,23]. While this difference is clearly due to the
overlap of the diffuse double layers of the parti-
cles, proper quantitative understanding of the ef-
fect is lacking. A simple screened Coulomb-type
potential model based on an effective hard-sphere
picture predicts much lower coverages than ob-
served experimentally.
The other important effect is size polydisper-
sity. While model particles are often of excellent
monodispersity, most colloidal particles in practi-
cal applications are more or less polydisperse. For
example, generation of particles by a random
process such as aggregation, milling or shattering
leads to substantial polydispersities, and the re-
sulting size distributions typically follow power-
laws. Such wide particle size distributions are also
very common in natural environments [24–26].
As found in some recent theoretical studies, ef-
fects of particle size polydispersity on the struc-
ture of the surface layer are very pronounced
[27–31]. The key observation is that in a polydis-
perse system smaller particles do adsorb preferen-
tially. This size selection results as a combination
of two mechanisms. (i) Already a small surface
concentration of small particles may block the
entire surface for larger particles. (ii) Adsorption
of small particles is possible even when the surface
is blocked by the larger particles, since small
particles can adsorb into the interstices between
the large particles. An interesting conjecture was
made by Brilliantov et al. [32,33]. These authors
show that if the original particle size distribution
of the incoming particles has a power-law tail for
small particle radii, the particle size distribution of
the adsorbed particles on the surface will also
scale as a power-law, but with a negative expo-
nent. Moreover, such a mechanism does lead to
the formation of fractal surface deposits, which
are similar to the so-called froth figures known in
metallurgy [34,35]. In addition, the kinetics of the
deposition process is very different from its
monodisperse counterpart.
The present paper focuses on effects of repul-
sive particle–particle interactions and particle size
polydispersity. We first analyze some data on the
deposition of monodisperse charged particles, and
discuss measured and calculated pair correlation
functions on the surface. Then we discuss com-
 M. Semmler et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 165 (2000) 79–93
puter simulations and experimental data in a
polydisperse system of charged particles at low
ionic strengths. The results are shown to be in
reasonable agreement. However, this comparison
does remain preliminary, as in our current experi-
mental setup the time window is too short to
reach the interesting regime of the late stages of
the polydisperse deposition process.
2. Methods
2.1. Atomic force microscopy of particle deposits
In our studies we use highly charged
polystyrene latex spheres with amidine surface
head groups (Interfacial Dynamics Corporation,
Portland OR). The number averaged radii of the
three batches used as determined by transmission
electron microscopy (TEM) are 24, 55, and 97
nm, with a coefficient of variation (CV) of 0.37,
0.15 and 0.02, respectively. In our polydisperse
study we have mixed the first two types of parti-
cles in a volume-ratio of 1:10. This mixture has a
broad size distribution with a long small particle
tail with a number averaged radius of 49 nm and
CV of 0.26.
The particles are deposited on freshly cleaved
mica (muscovite) sheets, which are immersed for a
certain time into a suspension of known particle
number concentration, ionic strength, and pH.
The sheets are removed from the beaker, carefully
rinsed with water (nanopure quality), and dried
for at least 24 h. We image the samples with an
atomic force microscope (AFM) Nanoscope IIIa
(Digital Instruments, Santa Barbara CA) oper-
ated in tapping mode in air with standard Si tips.
In order to measure the time evolution of the
surface deposit, for each data point an individual
sample has to be prepared. Further details on the
procedure are given elsewhere [21].
2a. In the polydisperse case, the optimal
An AFM image is an array of 512×512 pixels,
where the image size represented by one pixel can
vary from 2 A, up to a few 100 nm. With a
resolution of 1 nm, one detects on average less
than ten particles per image even at the longest
deposition time, a number which is far too low for
statistically reliable results. We have to enlarge
81
the detected area on the expense of the resolution,
though we have to be careful not to miss the
smallest particles. We select the size of the square
image to be 2.5 mm which leads to a horizontal
resolution of 5 nm. In this way we detect 120–170
particles per image. In the polydisperse situation,
the total number of detected particles typically
ranges from 800 to 2500, which involves analysis
of 5–20 separate images. Note that the horizontal
extent of an observed particle involves a convolu-
tion with the tip. However, the height provides an
accurate measure of the particle size, which is
conveniently obtained as the gray value of an
eroded particle in an image analysis software.
Depending on the sample, we reach a height
resolution of between 0.5 and 1.4 nm, which is of
the same order of magnitude as the surface rough-
ness of the mica substrate as determined by AFM.
2.2. Computer simulations
Random sequential adsorption (RSA) is a
purely two-dimensional model, where one only
considers the normal projection of each particle.
Particles of various shapes have been studied, but
here we restrict ourselves to circular disks. A
typical RSA algorithm starts by selecting a ran-
dom position to place a disk onto a plane. If there
is no overlap with any preadsorbed disks, the
position of the disk is accepted, otherwise it is
rejected. The same procedure is repeated. Once
placed, disks are completely immobile. In the
polydisperse case, the radii of the disks to be
placed are chosen according to a predefined size
distribution. The algorithm can be substantially
accelerated by subdividing the simulation plane
into square cells. Depending on the size distribu-
tion there are different reasonable choices of the
cell size. For monodisperse disks of radius a, the
optimal choice of the cell size is slightly larger
than
disk size is related to the size of the largest disks
amax. In our simulations we have used a cell size of
4amax.
The reliability of our computer program has
been checked by comparison with a known result
for monodisperse disks. We have carried out ten
independent RSA simulations on a square area of
82 M. Semmler et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 165 (2000) 79–93
unit size and with disks of radius 0.005. We
obtain a jamming fractional surface coverage u=
0.54719 0.0012 after 1.6× 109 attempts per unit
area (in dimensionless units). Extrapolating to
long times leads to an estimate of the jamming
limit of ujam =0.5477 90.0018, which is in excel-
lent agreement with previously published results
[22,23].
3. Electrostatic interactions
Electrostatic particle – particle interactions play
an important role in the understanding of the
deposition of colloidal particles onto solid sub-
strates. Here we consider the case where the elec-
trostatic interactions are the dominant ones, and
we neglect other contributions such as hydrody-
namic effects or van-der-Waals attraction. The
assumption is justified for highly charged parti-
where LB = be 2/(4pee0) is the Bjerrum length
(b − 1 = kT is the thermal energy, LB # 0.72 nm in
water). Eq. (2) applies only at sufficiently high-
salt concentrations, but is entirely adequate for
present considerations. In the high salt regime, the
presence of the counterions of the colloidal parti-
cles is neglected.
The maximum surface coverage can be esti-
mated by adopting an effective hard-sphere
model. One again assumes that the maximum
surface coverage is defined by the RSA jamming
limit, but one uses an effective hard-sphere block-
ing distance bij between two particles i and j,
which is estimated from the electrostatic particle–
particle repulsion [10]. This effective blocking dis-
tance bij is determined by the overlap of the
diffuse double layers surrounding the particles
and can be defined through the relation [10]
&
b 2ij = 2

cles. The opposite charge of particles and the
substrate ensures that the particles adsorb irre-
versibly. However, for particles and substrates
with charge of equal sign the situation is quite
different [36,37].
3.1. Effecti6e hard-sphere model
A pair of charged colloidal particles interacts
with a screened Coulomb potential [2,38]. At
sufficiently large center-to-center separations r,
the interaction potential between two colloidal
particles with radii ai and aj is given by
uij(r)=
ZiZje 2 exp[k(ai +aj)] n
exp( − kr)
4pee0 (1 +kai)(1 +kaj) r
where Zi and Zj are the effective charges in units
of the elementary charge e, ee0 is the dielectric
permittivity of water, and k − 1 is the Debye
screening length. For low surface charge densities,
the effective charge corresponds to the real (bare)
charge of the particle. For high charge densities,
the effective charge saturates at a constant value.
Within the Poisson – Boltzmann approximation,
this saturation value is given by [39]
Zi = (ai/LB)(4kai +6)
r[1− gij(r)]dr (3)
0
where gij(r) is the pair distribution function. In
the low-density expansion we have gij(r)= exp[−
buij(r)]. With the interaction potential given by
Eq. (1), bij can be evaluated numerically from Eq.
(3). A similar approach [2] defines the effective
blocking distance by comparing the interaction
energy with the thermal energy kT, and one solves
the relation lbu(bij)= 1, with l being an appro-
priate constant of order unity. An iterative solu-
tion of Eq. (1) leads to the second-order result
bij # k − 1 ln(A/ln A) with A=lZiZjkLB exp-
[k(ai + aj)](1+ kaj) − 1. Taking l= 2.8 this analyti-
(1)
cal approximation agrees well with the results
obtained from Eq. (3) [21].
For monodisperse particles, one can drop all
indices. An effective radius is assigned to every
particle by aeff = b/2. In this special case, the
maximum surface coverage has the simple form
umax = ujam(a/aeff)2,where ujam # 0.547 is the hard-
disk jamming limit and a the particle radius in the
monodisperse suspension. For the polydisperse
case, it turns out that if the two particle radii do
not differ too much, the effective blocking dis-
tance bij is in good approximation the sum of the
two effective radii calculated for monodisperse
(2) spheres of radius ai and aj.
 M. Semmler et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 165 (2000) 79–93
3.2. Charged nanoparticle deposits at low ionic
strength
A typical AFM image for adsorbed nanoparti-
cles at the maximum coverage is shown in Fig. 1
along with the corresponding RSA simulation
with an effective radius aeff. The image is taken at
low ionic strength ( 10 − 5 M), and therefore the
surface coverage is low, the particles are isolated
and nicely distributed over the surface.
To determine the maximum surface coverage
umax, we have measured the time evolution of the
coverage u for different deposition times, and
different bulk particle concentrations. The results
are shown in Fig. 2 for particles of radius 97 nm
). The dotted lines represent diffusion-lim-
Fig. 1. (a) Representative AFM image at the maximum ob-
served coverage for particles with radius 97 nm at an ionic
strength 10 − 5 M (no salt added). (b) Corresponding RSA
simulation based on the effective hard-sphere model assuming
charge saturation.
83
Fig. 2. The surface coverage u as a function of time t for
particles with radius 97 nm at an ionic strength 10 − 4 M and
pH 4.5 for different bulk number particle concentrations:
5 × 1011 cm − 3 (); 1011 cm − 3 ( ); 1.5×1010 cm − 3 (); and
2.5 × 109 cm − 3 (
ited adsorption calculated with the diffusion coefficient D =
2.30 ×10 − 8 cm2 s − 1, as measured by dynamic light
scattering.
at an ionic strength of 10 − 4 M.
The coverage increases with time according to
diffusion-limited deposition until a plateau level is
reached. The fact that all curves level off at the
same plateau value indicates that the maximum
surface coverage indeed has been reached. The
dotted lines in Fig. 2 is the prediction for the
surface coverage from the deposition by pure
diffusion. For monodisperse particles of radius a
one expects [40] that u= cbulka 2(4pDt)1/2, where
cbulk is the particle number concentration in the
bulk and D the bulk diffusion coefficient mea-
sured by dynamic light scattering. Clearly, the
prediction of diffusion limited deposition is con-
sistent with the experimental data. Only for the
lowest number particle concentration, the trans-
port to the surface is enhanced, most probable
due to convective currents which are generated by
small thermal gradients.
The approach to the maximum coverage is
substantially faster than predicted by RSA. This
model predicts a very slow approach to saturation
with time t, namely umax − u(t)  t − 1/2, as the
probability for choosing a potential gap decreases
[4,5]. Our findings are in line with recent results,
which also suggest that umax can be approached
more quickly, particularly in the presence of soft-
84 M. Semmler et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 165 (2000) 79–93
Fig. 3. The maximum surface coverage umax as a function of
the screening parameter ka for charged particles deposited
onto an oppositely charged substrate. The different symbols
denote experimental data for the particle radii: 24 nm (
); 55 measure of the maximum surface coverage umax is
nm (); and 97 nm (). These measurements incorporate the
actual particle size distribution on the surface as determined
by AFM. Solid lines are calculations based on an effective
hardsphere model with charge saturation. The electrostatic
interparticle repulsion decreases umax in comparison to the
RSA hard-sphere jamming limit, ujam # 0.547, indicated by the
dotted line.
Fig. 4. The radial pair-distribution function g(r) at low ionic
strength (  10 − 5 M) for particle radii 55 nm ( ) and 97 nm
(
) as a function of the center-to-center distance r. The data
for the smaller particles represent an average of 2000, for the
larger ones 3600 particles. The solid lines denote a fit to the
data with the g(r) for hard-spheres (shown in the inset as
determined from the simulation up to the jamming limit for
monodisperse disks) convoluted with the Gaussian exp( − r 2/
2s 2). The position if the first maximum and the width s are
339 and 62.8 nm for the 55 nm particles, the corresponding
numbers are 533 and 62.7 nm for the 97 nm particles.
repulsive potentials [12] or if particle diffusion
along the surface [41] is taken into account. Quite
recently, this fast approach to the maximum cov-
erage was explained by Adamczyk et al. [42].
The saturation coverages umax obtained in this
way are shown as symbols in Fig. 3 as a function
of ka for different particle radii. The coverages
are calculated according to umax =
pa 2surfrmaxrmax, where rmax is the number den-
sity of particles in the saturation limit and a 2surf
the second moment of the size distribution on the
surface as directly measured by AFM. Here we
exploit the advantage of the AFM to measure
each adsorbed particle individually and to obtain
the particle size distribution of the deposited par-
ticles on the surface. In this way, a very reliable
obtained. From Fig. 3, one observes that umax can
be much smaller than the jamming limit for hard
spheres ujam # 0.547, and it decreases
monotonously with decreasing ka. At low salt
concentration and for the smallest particles used,
we have umax # 0.05 for ka # 0.25. The large hori-
zontal error bars indicate that these low ionic
strengths are difficult to estimate reliably. The
solid lines in Fig. 3 are calculated values for umax
obtained with the effective hard sphere model
using saturation values of Z given by Eq. (2). The
two different curves correspond to the particle
radii a= 20 nm and a= 100 nm. The dependence
on the particle size is very weak, and one may
therefore consider an almost universal relation
between u and ka.
We have also calculated the radial pair-distribu-
tion function g(r) from images at the saturation
level for two different radii, 55 and 97 nm. No
salt was added, which corresponds to an ionic
strength around 10 − 5 M. The results are shown in
Fig. 4. The inset shows the g(r) for hard spheres,
which we derived from RSA simulations of
monodisperse disks. Our simulation results agree
well with the calculations of Hinrichsen et al. [6].
The simulated hard-sphere g(r) was convoluted
with a Gaussian exp(− r 2/2s 2) and fitted to the
experimental data. For the width s we obtained
62.8 and 62.07 nm for the smaller and the larger
particles, respectively. This spread could indicate
some softness of the interaction potential, how-
 M. Semmler et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 165 (2000) 79–93
ever, the magnitude of s can be attributed to the
instrumental resolution, since these values are
consistent with the lateral resolution of our image
analysis: our data is collected into bins with a
width of 50 nm, and the position of each particle
is known to an accuracy of 20 nm. The position
of the first maximum in g(r), which is the most
probable distance to the nearest neighbor, was
found to be 339 nm for a =55 and 533 nm for the
a= 97 nm particles. From the experiment one
extracts effective radii aeff of 169 and 267 nm,
respectively. The simple effective hard-sphere
model gives radii about a larger factor of two.
3.3. Discrepancies with the effecti6e hard sphere
model
As shown in Fig. 3 the maximum surface cover-
age umax decreases with increasing ka, and this
trend is reasonably well captured by the simple
effective hard-sphere model. In an earlier study
[21], we have compared our data with those found
in literature for various planar surfaces and parti-
cles [10,14,20] and more complicated geometries
[15–19]. The general trend is rather universal
irrespective of the deposition mechanism, includ-
ing the impinging jet flow [10,20], flow through
packed columns of fibers [15] or glass beads
[16,17,19], or other diffusional deposition experi-
ments [14,18].
While at moderate ka the quantitative agree-
ment between experiment and theoretical model
shown in Fig. 3 is rather good, for low ka,
substantial deviations are present. The hard-
sphere model predicts surface coverages, which
are about an order of magnitude smaller than
measured in experiment. The solid lines in Fig. 3
were obtained with saturation values of the sur-
face charge Z given by Eq. (2); these values
correspond to the maximum possible repulsion
and thus to the lowest possible umax at a given ka.
We have also calculated umax using the appropri-
ate effective charges corresponding to a surface
charge density of 50 mC m − 2, a value that is fully
consistent with measured electrophoretic mobili-
ties of the particles. The resulting deviations to
the theoretical curves are barely visible on the
scale of Fig. 3. Therefore, the use of the actual
85
effective charge fails to explain the discrepancies
between model and experiment at low ka, and
other reasons must be sought.
One may also suspect that the reason for the
discrepancies is an enhanced surface coverage due
to lateral diffusion. In the RSA algorithm, each
disk makes only a single attempt, while in the real
situation each particle that is not adsorbed on the
first approach wanders around above the surface
and may adsorb on the surface in the vicinity of
the first attempt. This so-called diffusional RSA
has been investigated for hard spheres by Senger
et al. [43]. Their analysis showed that the resulting
coverages and the structure on the surface in the
jamming limit are indistinguishable from simple
RSA [43]. This finding can be understood by
considering the fact that the diffusion coefficient
perpendicular to the surface decreases more
rapidly than the diffusion coefficient parallel to
the surface, and any later attempt samples basi-
cally a position which is not correlated to the
position of the previous attempt [44]. Therefore
we suspect that the diffusion process does not
alter the maximum surface coverage.
The most likely reason for the discrepancies is
probably related to the presence of a charged
wall, which may influence the particle–particle
interaction potential in its vicinity. It was shown
that an additional pairwise attraction between the
particles might occur in the vicinity of a charged
wall [45,46]. This many-body effect is most pro-
nounced at low ionic strengths [46]. Even on the
Poisson–Boltzmann level, the particle–particle in-
teraction potential of charged particles close to an
oppositely charged wall might differ substantially
from the bulk counterpart at sufficiently low ionic
strengths [12].
Our results on the radial pair-distribution func-
tion g(r) may be compared to the work of Woj-
taszczyk et al. [11]. These authors have
investigated the deposition of mm-sized particles
in the transition region between ballistic deposi-
tion, which is characterized by a strong influence
of gravity, and a region that is well described by
RSA. Their particles were large compared to the
Debye screening length k − 1, and these particles
could be treated as true hard spheres. According
to their analysis, our experiment is well within the
86 M. Semmler et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 165 (2000) 79–93
RSA regime. The low ionic strength in our exper-
iment leads to k − 1 #100 nm, which is in the same
order of magnitude as the particle radius. The
effective hard-sphere model seems to be adequate,
but a quantitative difference in the magnitude of
a0 is present: As mentioned above, the repulsive
particle–particle interaction potential is probably
weakened by the presence of the oppositely
charged wall.
The negligible influence of drying on our sam-
ples is noteworthy. Drying does not change the
circular disks distributed according to this size
distribution was studied recently; it was shown
that in the limit of large deposition times, the
particle size distribution on the surface also fol-
lows a power law, but with a negative exponent,
namely Psurf 8 a − a% − 1 with a%\ 0 [32,33]. This
result is remarkable, since it will become valid for
any size distribution that can be expanded into a
power-law for a“ 0. The exponent a% can be also
interpreted as the fractal dimension of the surface
pattern. Brilliantov et al. [33] have conjectured
total number of adsorbed particles [14], but capil-
lary forces may drive the particles to clusters
during the drying process [47]. However, the con-
vincing agreement between ideal hard-sphere be-
havior from the simulation and the experimental
data in the radial distribution function g(r) ob-
tained at very low salt conditions is a good indica-
tion, that if the particles are sufficiently separated
and the samples dried carefully, the general struc-
ture on the surface is not altered. The only hint to
an artifact could be a tiny peak at small center-to-
center distances for the 55 nm particles.
4. Deposition of polydisperse particles
So far, effects of polydispersity have been stud-
ied theoretically and by means of computer simu-
lations. Experimental studies are lacking. Here we
present some preliminary attempts to study the
time-evolution of the size distribution on the sur-
face, and show that a simple RSA model captures
the experimental results rather nicely.
4.1. Model distributions and simulations
As an illustration, consider first a few simula-
tion results. For the probability distribution for
the incoming particles onto the surface we follow
Brilliantov et al. [32,33] and use a truncated
power law distribution
Á a a − 1 a 5a
max
Pinc(a) 8 Í , (4)
Ä 0 a \ amax
where amax is the upper cutoff and a \0. RSA for
that for a“  the surface structure approaches
the so-called Appolonian packing, and a% #1.305
[48,49].
Our interest is the application to a realistic
situation. Rather than pushing the exponent to
the limits, we exploit three typical distributions.
An inverse power law (a= 1/2), uniform box dis-
tribution (a= 1), and moderately large exponent
(a= 4). For the comparison of these distributions,
amax has been chosen such that ainc is identical
for all three cases. Fig. 5 shows the evolution of
the size distribution on the surface for the three
different a. With increasing number of attempts,
small disks adsorb preferentially and the size dis-
tribution skews towards smaller particles. The
inset shows the resulting size distribution at the
end of the simulation in a doubly logarithmic
representation: The emerging power-law sets in
from above, and the exponents are in good agree-
ment with earlier simulations [33]. The pictures
illustrate the appearance of the disk- covered sur-
face in the power law regime at the end of the
simulation. Another way to quantify the evolution
of the size distribution on the surface is to evalu-
ate its moments. The results for the normalized
average radius is shown in Fig. 6. As expected,
asurf decreases monotonously, and the smaller
the exponent a the faster the decrease. Fig. 7
shows the number of placed objects and the sur-
face coverage u for different exponents a. The
results for the case of monodisperse RSA is
shown for comparison. Initially, the results for the
different distributions follow the monodisperse
situation rather well. Later, however the results
differ substantially, since the surface eventually
fills up completely. The smaller the exponent a,
 M. Semmler et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 165 (2000) 79–93 87

Fig. 5. The evolution of the size distribution on the surface Psurf with increasing attempts per unit area n (in dimensionless units)
for three different truncated power law size distributions (Eq. (4)). Pinc is indicated with the arrow n = 0, and with each subsequent
line n increases by an order of magnitude. The inset gives Psurf in a doubly logarithmic representation at the end of the simulation
and indicates the corresponding exponent a. The upper row gives a visual impression of the disk-covered surface in this regime.

the faster the number of placed objects grows. quiescent suspension is well described by a simple
The behavior of the surface coverage is more diffusion equation with the appropriate boundary
complicated, which is due to our choice of the conditions. For monodisperse particles one has


second parameter of the size distribution amax by [40]
fixing the first moment ainc: for a smaller expo- dr D 1/2

nent or, amax is larger, and the surface coverage
grows faster for small number of attempts per
unit area n (in dimensionless units). On the whole,
however, the surface coverage is only slightly
affected by size polydispersity until jamming of
the corresponding monodisperse disks is reached.
4.2. Diffusional deposition flux
For a perfectly adsorbing surface the number of
particles per unit area r that reach the surface is
given by integrating the flux of incoming particles
j with respect to the time t. As shown earlier, the
deposition of particles onto a surface from a
j= = cbulk 8 cbulka − 1/2t − 1/2, (5)
dt pt
where cbulk is the bulk particle number concentra-
tion and D= kT(6pha) − 1, the bulk diffusion co-
efficient of the suspended particles, and h, the
viscosity of the suspension. In the polydisperse
situation, the incoming flux has to be considered
for each size class, and the particle flux density for
the particle radius a is proportional to the corre-
sponding concentration of these particles in the
bulk and to a 1/2 (cf. Eq. (5)). Based on this
argument one finds a simple relation between the
size distribution of the incoming particles Pinc and
the corresponding distribution in bulk Pbulk. The
result is
88 M. Semmler et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 165 (2000) 79–93

1
Pinc(a)8 Pbulk(a). (6)
a 1/2
In order to compare such diffusional experiments
with computer simulations, we integrate Eq. (5)
and arrive at the expression

n= cbulk
 
2kT 1/2
a − 1/2bulkt 1/2. (7)
3p 2h
This relation allows to match the experimental
time scale t with the number of attempts per unit
area n.

4.3. The polydisperse deposition experiment

The experimental size distribution in the bulk

Pbulk(a), as determined by transmission electron
microscopy TEM, is shown in Fig. 8. The distri-
bution is peaked at 56 nm and has a tail down to
small particles around 10 nm. The dotted line in
Fig. 8 is the best fit of the distribution with a
truncated triple-Gaussian. The fit is fairly insensi-
tive to the number of bins. The solid line is the
actual distribution of the incoming particles calcu-
lated according to Eq. (6).
Fig. 9 shows a typical AFM picture and a Fig. 7. (a) Total number of placed objects per unit area (in
corresponding simulation result for the polydis- dimensionless units) and (b) the surface coverage u as a
perse situation. The situation refers to the longest function of the number of attempts per unit area n (in dimen-
sionless units) for power law size distributions (Eq. (4)). The
experimental time t =1.0 × 106 s that could be
symbols are as in Fig. 6 with the monodisperse disk radius
equal to ainc.

Fig. 6. First moment of the surface size distribution normal-

ized to the average radius of the input power-law size distribu-
tion (Eq. (4)) as a function of number of attempts per unit Fig. 8. Experimental bulk size distribution of the suspended
area n (in dimensionless units) for a= 4 (
), a=1 ( ), and particles determined with TEM (dashed columns), and the
a= 1/2 (). amax has been chosen such that ainc is identical fitted bulk size distribution Pbulk with a triple-Gaussian (dot-
for all a. The dotted line indicates the case of monodisperse ted line). With Eq. (6) one obtains the flux distribution Pinc
disks. (solid line).
 M. Semmler et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 165 (2000) 79–93
achieved. The ionic strength in the suspension was
3× 10 − 4 M. In the AFM picture shown in Fig.
9a, the effect of electrostatic repulsion between
the particles is evident, as the particles are well
separated on the surface and each individual par-
ticle can be easily detected by AFM. It appears
that the drying process has not influenced the
position of the particles, as no clusters on the
surface were detected. Fig. 9b displays the corre-
sponding situation from simulation, where the
electrostatic repulsion has been incorporated by
the use of the effective blocking distances. The
particles appear larger in the AFM image due to
particle-tip convolution.
Fig. 9. (a) AFM image of polydisperse amidine latex particles
deposited onto a mica sheet. The size distribution of the
incoming particles Pinc is given by Fig. 8. The deposition time
has been t =1.0× 106 s, the ionic strength 3×104 M. (b)
Corresponding polydisperse RSA simulation with the effective
hard-sphere model, including the appropriate blocking dis-
tance to account for the electrostatic repulsion.
89
In Fig. 10 we show the evolution of the size
distribution of the deposited particles on the sur-
face with time. The graphs show the surface size
distribution for five experimental deposition
times: 1.2× 102, 2.4× 103, 2.2×104, 2.3×105,
and 1.0 × 106 s. The experimental data are de-
noted by the dark gray columns, while the simula-
tion results are shown as dashed columns. For
reference, the incoming particle distribution is
reproduced as well (solid line). The last graph
shows only a simulation result, that goes well
beyond experimentally accessible times with our
setup. This graph indicates that the kinetics of
these processes is extremely slow indeed.
One observes that the size distribution on the
surface shifts progressively towards smaller parti-
cles. At the end of our experiment after 106 s
deposition time, the number of particles with ra-
dius rB 30 nm have doubled, and the prominent
peak of particles around 56 nm has decreased by
roughly a factor of two. The simulation results
agree reasonably well with the experiment. The
height of the main peak is reproduced well, and
the doubling of the smallest particles in number
for the longest deposition time results in the simu-
lation, too. The number of attempts in the simula-
tion was converted to the experimental deposition
times with Eq. (7). Each size distribution shown
represents an average of five separate simulation
runs. The electrostatic repulsion has been incor-
porated into the simulations within the effective
hard-sphere model.
Fig. 11 shows the normalized average particle
radius on the surface asurf. Full circles are the
experimental data. These results are compared
with simulation results including the electrostatic
interactions, and with hard-core interactions only.
The monodisperse situation shows of course no
time dependence. While the experimental data
show strong scatter, the results agree reasonably
well with the model including electrostatic interac-
tions. Fig. 12 gives the total number of adsorbed
particles per unit area and the surface coverage as
a function of the deposition time. Experimental
data are denoted by symbols. Again we show the
simulation results for the polydisperse case with
and without the electrostatic interactions. For
comparison, the corresponding situation in the
90 M. Semmler et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 165 (2000) 79–93

Fig. 10. Experimental surface size distribution Psurf (dark gray columns) and corresponding simulations with the effective
hard-sphere model (dashed columns) for different adsorption times of diffusional deposition. The simulations represent and average
over five individual runs, the experimental data are from 800 – 2500 particles. The adsorption times t are indicated. The longest time
shows only the simulation result for 1 year of purely diffusional deposition, which is inaccessible in our experiment.

monodisperse situation is shown as well. In spite
of the substantial scatter, the experimental data
are reasonably well bracketed by both polydis-
perse situations. A similar conclusion was already
reached in the previous section: The effect of
electrostatic interactions is overestimated by the
simple screened Coulomb potential model.
For the polydisperse systems, one might ques-
tion the concept of surface coverage based on a
two-dimensional projection, and rather consider a
three-dimensional description as being more ap-
propriate [27]. While in very polydisperse situa-
tions, the two dimensional picture becomes
obsolete due to layering effects, this is not yet the
case in our system. First of all the particles are
charged and every particle is surrounded by an
exclusion zone of two to four Debye lengths, and
secondly the experiment is not carried out to very
long deposition times. Unfortunately, the effects
of polydispersity observed in this study are mod-
erate, and for this reason the data are not fully
conclusive. These difficulties could be circum-
vented with an experiment with a higher convec-
tive flux towards the surface, as could be
achieved, for example, in impinging jet flow
[13,20]. However, with this technique hydrody-
namic scattering is an additional effect entering
into the problem [50]. Another difficulty is related
to the limited width of the particle size distribu-
tion. Our particles were not that much polydis-
perse, and more pronounced effects would be
present in a system with a more pronounced
polydispersity. The measurement of substantially
broader size distributions with the AFM repre-
sents a challenge as well.
5. Conclusion
Two effects in the deposition of colloidal parti-
cles onto solid surfaces were discussed, namely
 M. Semmler et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 165 (2000) 79–93 91

electrostatic interactions and particle size polydis-

persity. The focus has been on experimental inves-
tigations of the deposition of charged nanometer
sized particles onto an oppositely charged mica
surface at moderately low ionic strengths. The
findings have been interpreted with simple models
based on RSA.
Atomic force microscopy (AFM) has been used
to analyze particle deposits. Adsorbed particle can
be detected individually with this technique, and
the particles size distribution on the surface can
be determined unambiguously. This feature can
be used to estimate the maximum surface cover-
age umax accurately. With this method we find
that umax decreases strongly with decreasing ionic
strength and can be B 0.1 for screening parame-
ters ka B1. This effect originates from the inter-
particle repulsion, and can be understood as
random sequential adsorption (RSA) of hard-
spheres, whose effective radius is determined by
the range of the screened Coulomb potential.
The effective hard-sphere picture is confirmed
for monodisperse particles by measurements of
the pair-distribution function g(r) on the surface.
The experimental g(r) is well described within the
Fig. 12. (a) The total number of placed objects per unit area
and (b) the surface coverage u as a function of the adsorption
time t. Experimental data are denoted by symbols ( ). The
lines show corresponding RSA simulations for two cases: (i)
Electrostatic repulsion is included by the effective hard-sphere
model, assuming charge saturation; (ii) particles are treated as
hard-spheres with no electrostatic interaction. In each case, the
solid line represents a polydisperse simulation with Pinc (Fig.
10); the dotted line is the appropriate monodisperse RSA
simulation.

hard-sphere model, given one incorporates the

Fig. 11. Normalized first moment of the size distribution on
the surface as a function of the adsorption time t. The full
circles ( ) are experimental results, calculated from the size
distribution as obtained by AFM (cf.Fig. 10). Between six and
17 images contribute to each data point with a total of
800 – 2500 particles. The solid lines show corresponding RSA
simulations for two cases: (i) Electrostatic repulsion is included
by the effective hard-sphere model, assuming charge satura-
tion; (ii) particles are treated as hard-spheres with no electro-
static interactions.
finite instrumental resolution. The effective radius
(or the effective blocking distance for polydisperse
samples), however. is overestimated by the
screened Coulomb potential model. We suspect
that the particle–particle interaction potential is
modified due to the presence of the charged sur-
face. In conclusion, the effective hard-sphere
model validly describes the electrostatic interac-
tion, but the effective radius is overestimated.
The effects of size polydispersity were studied
with a similar deposition experiment with strongly
polydisperse latex spheres. The particle size distri-
92 M. Semmler et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 165 (2000) 79–93
bution of the particles on the surface shifts to-
wards smaller particles with time. This shift could
be well detected with the AFM and also explained
by computer simulations based on RSA. Unfortu-
nately, our idealized experiment is restricted.
Within the accessible time window polydispersity
effects can be seen, but they are moderate. A
better experimental setup would require a convec-
tion cell, where higher flux of the particles to the
surface could be achieved. However, with a con-
vection setup other complications arise, such as
issues of homogeneity of the convective flow field
or shadowing effects. Nevertheless, this experi-
mental approach seems most promising in order
to explore the interesting regime of long deposi-
tion times in polydisperse RSA.
Acknowledgements
During our stay at ETH Zürich, we had de-
lightful discussions with E.K. Mann, and would
like to thank R. Kretzschmar for the help with the
TEM work. Financial support by the Swiss Sci-
ence Foundation (NFP 36), and US National
Science Foundation (Grant CHE-9870965) are
gratefully acknowledged.
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