Floc Structure and Growth Kinetics for Rapid Shear Coagulation

of Polystyrene Colloids

FRANCISCO E. TORRES, WILLIAM B. RUSSEL, 1

AND WILLIAM R. SCHOWALTER*
Department of Chemical Engineering, Princeton University, Princeton, New Jersey 08544-5263 and *Department of
Chemical Engineering, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801
Received July 5, 1990; accepted September 13, 1990
Colloid coagulation in a flowing suspension is governed by floc structure and by the colloidal and
hydrodynamic interactions between the aggregates. We have investigated both the internal structure and
growth rate of rigid flocs formed by rapid coagulation in a linear shear flow, examining structure by
static light scattering and measuring sizes by dynamic light scattering. Comparison of the results for
sheared suspensions with Brownian coagulation data reveals a similar structure for the two modes; in
both cases the flocs exhibit characteristics ofa fractal with dimension d = 1.8 _+0.1, and for both modes
the average number of nearest neighbors is approximately the same. In contrast, the growth kinetics are
inherently different, as expected. To model growth in a shear flow, we treat a porous floc as a body with
a hydrodynamic radius which is smaller than the capture radius corresponding to floc-floc contact, and
we also find it necessary to invoke a criterion for the maximum size a floc can obtain at a given shear
rate. Necessary structural details are provided by the static light scattering results. We compare kinetics
predicted by this model with data at several shear rates and find qualitative agreement. © 1991Academic
Press, Inc.

1. INTRODUCTION structure and dynamic light scattering to mea-

At the appropriate conditions, particles in
a colloidal suspension undergoing shear co-
agulate to form flocs containing a large num-
ber of the individual particles connected into
complex structures. As two such flocs ap-
proach, they experience hydrodynamic and
colloidal interactions, and these interactions
both govern the structure of any larger floc
formed and depend on the structure of the
coagulating flocs. Therefore, there is a basic
interdependence between the structure and the
hydrodynamic and colloidal forces. To help
provide a better understanding of this process,
we present an experimental study of the in-
ternal structure and coagulation kinetics for
rigid flocs formed by rapid coagulation in a
linear shear flow. This study is limited to dilute
suspensions, and it relies on static light scat-
tering to extract information about the internal
To whom correspondence should be addressed.
sure floc size.
Much of the previous fundamental work on
colloid coagulation in a flow field has dealt
with two solid spheres or, in some studies, two
nonspherical particles, but relatively few in-
vestigators have ventured beyond the doublet
formation step. Basic questions about the hy-
drodynamic and colloidal forces experienced
by porous flocs remain unanswered, and al-
though some data on floc structure for shear
coagulation have been reported (1-3), con-
clusions about general behavior are not avail-
able. However, many factors that influence the
coagulation process have been identified (see,
e.g., (2, 4-7 )). For example, the interparticle
forces, particle size, shear rate, and particle
surface characteristics can affect whether co-
agulated particles rotate freely relative to one
another, with rotation observed for bonding
within a secondary minimum in a DLVO-type
potential and rigid bonds (as desired in our

554
0021-9797/91 $3.00
Copyright © 1991 by Academic Press, Inc.
All rights of reproduction in any form reserved. Journal of Colloid and Interface Science, Vol. 142, No. 2, March 15, 199-1
 SHEAR-INDUCED COLLOID COAGULATION
experiments) observed for primary minimum
coagulation (8, 9). Thus, rearrangement and
breakup can be influenced by these factors,
and studies by Lindsay, et al. (10) and Sonntag
and Russel (11 ) provide some experimental
results.
Regarding the current understanding of floc
hydrodynamics, Wiltzius and co-worker ( 12,
13) report experimental work on the hydro-
dynamic behavior of fractal flocs, and Chen
et aI. (14) compare these data with computer
simulations reported in a different context
earlier ( 15 ). Also, Pusey et al. (16) discuss the
effect of floc size polydispersity on the mea-
surements reported by Wiltzius. Taken to-
gether, these papers and comments appear to
bring the experiments and simulations into
reasonable accord, but the assumptions in-
voked need further study. The above authors
all report their results in terms of the ratio of
the floc hydrodynamic radius RH to the radius
of gyration Re, where RH is defined as the
radius of a sphere having the same Stokes drag
as the given floc, and they find/3 = R H / R a
has a value between 0.72 and approximately
1.0, independent of size for large flocs. In an-
other investigation, Rogak and Flagan (17)
calculate approximate values of/3 for various
geometries, providing some insight into the
effect of structure on drag. However, a detailed
understanding of the hydrodynamics of two
interacting flocs is lacking, even for flocs
treated as equivalent spheres. Consequently,
the present analysis relies on simple descrip-
tions of the hydrodynamics which capture the
essential features expected for two porous
bodies.
At the doublet formation level, coagulation
rates due to Brownian motion, flow, and cer-
tain combinations thereof have been calcu-
lated by utilizing known hydrodynamic func-
tions and colloidal force equations, and to-
gether with experimental data these results
provide a basis for predicting two sphere be-
havior in detail (of. (4, 5, 7 )). Because these
results form a framework for our studies, we
briefly review relevant points, beginning with
the differential equation governing the initial
555
coagulation rate within a random suspension
of uniform spheres:
dnl
= - K i l n 2. [1.1]
dt
The term nl is the number concentration of
singlets, and Kll is the rate constant.
In his pioneering study of colloid coagula-
tion, Smoluchowski (18) derived equations for
Kll for both flow- and Brownian motion-in-
duced coagulation. In the former case, he as-
sumed particles follow streamlines undis-
turbed by other particles except at contact,
giving
KII = K0 = X ( a l q- a2)3q/ [1.2]
for linear flows with a strain rate ,) and par-
ticles of radii al and a2. The constant x de-
pends on the type of flow and equals 4 for
simple shear flows, the type of interest here.
The Smoluchowski result K0 often provides a
useful estimate of the actual coagulation rate
K, and we adopt the convection of expressing
K in terms of the stability ratio
K0
W K " [1.3]
Later investigators included hydrodynamic
interactions and colloidal forces in predicting
W for particles and studied a range of Peclet
numbers
67r#a32/
Pe- kBT ' [1.4]
providing information on the interaction of
Brownian motion and shear flow. In particu-
lar, for purely flow-induced coagulation van
de Ven and Mason (8) and Zeichner and
Schowalter (19) calculated trajectories of two
spheres with different interaction potentials to
obtain collision cross sections, and Feke and
Schowalter (20) extended the infinite Peclet
number results to large but finite values
through a regular perturbation expansion of
the trajectory equations in Pe-l. Interestingly,
the latter investigators found rather large ef-
fects for small amounts of Brownian motion.
These analyses centered on the equation for
Journal of Colloid and Inter-face Science, Vol. 142, No. 2, March 15, 1991
556 TORRES,
the relative velocity of two spheres in a linear
flow field, which can be written as (20)
v=ft×r+E-r
+ A(r,X)7~+B(r,X ) I-
C(r, X)
+--Fc-D(r,X)'Vlnp2.
6rqzal
The functions A(r, X), B(r, X), and C(r, X)
are hydrodynamic functions whose detailed
tabulation made the trajectory approach pos-
sible. Other variables are the center-to-center
particle separation r, the ratio of the particle
radii X, the vorticity vector ft and rate of strain
tensor E of the bulk flow, the colloidal force
Fo, the tensor D characterizing mutual diffu-
sion of two spheres, and the pair distribution
function P2 whose gradient drives a Brownian
velocity (21 ). Note that the Smoluchowski re-
sult given by [ 1.2 ] follows from [ 1.5 ] by setting
A(r, X), B(r, X), Fc, and Vp2 equal to
zero (19).
Thus, the two-particle studies mentioned
above demonstrate the role of hydrodynamic
and colloidal forces in coagulation, and to an-
alyze floc coagulation the importance of these
interactions for aggregates must likewise be
assessed. Floc interactions, however, depend
on the floc structure, an important factor
which the two sphere results do not address.
On the other hand, previous investigators of
rapid Brownian coagulation ( e.g., (22-26))
studied floc structure and detected fractal-like
configurations with a fractal dimension d
= 1.8 + 0.1 for nonrearranging flocs, in good
agreement with simulations (27, 28 ).
To learn more about shear-induced aggre-
gation of colloidal flocs, we have conducted
an experimental study of the internal structure
arising from both shear- and Brownian mo-
tion-induced rapid coagulation, and we have
measured the growth rate for the former, ap-
plying new results for dynamic light scattering
from flocs. These experiments are the subject
of this paper. The colloidal suspensions con-
tained high NaCI concentrations to realize the
rapid coagulation conditions (i.e., with neg-
Journal of Colloid and Interface Science, Vol. 142, No. 2, March 15, 1991
RUSSEL, A N D S C H O W A L T E R
ligible interparticle repulsion), and to obtain
a model system for which flocs undergo little
rearrangement, we study particles that appear
to form strong and rigid primary-minimum
bonds. Examining the structure and kinetics
.E.r
together, we demonstrate that the kinetics can
be described by a model which combines three
features: the structural information inferred
[1.5]
from the first set of experiments, a simple de-
piction of floc hydrodynamics, and an ap-
proximate criterion for the maximum floc size
attainable at a given shear rate. Insofar as our
structure results lead to a reasonable kinetics
model, we conclude that the proposed de-
scription of the aggregation process is consis-
tent.
The next section describes the experiments
performed to examine structure and coagu-
lation rates. A discussion of the static light
scattering results follows in Section 3, after
which we discuss the rate data obtained by
dynamic light scattering in Section 4. The
calculations of the floc growth process are
presented and compared with our data in
Section 5.
2. E X P E R I M E N T A L DESCRIPTION
2.1. Particle Synthesis and Characterization
The particles used in our experiments were
monodisperse polystyrene latexes purchased
from Interfacial Dynamics Corporation (batch
7-108-7), who synthesized the particles by
surfactant-free emulsion polymerization. The
manufacturer reports a surface charge density
of 1.16 ~tC/cm2 for these IDC particles, equiv-
alent to 1378 A2 per charge group, with the
charge arising predominantly from sulfate
groups generated by the initiator for the po-
lymerization. The reported mean diameter,
determined by transmission electron micros-
copy, is 0.098 #m, with a coefficient o f vari-
ation equal to 10.9%. Our dynamic light scat-
tering measurements give an intensity aver-
aged diameter equal to 0.108 gm in a 10-3M
HC1 glycerol/water solution (36.0 wt% glyc-
erol), in reasonable agreement with the mi-
croscopy results; the HC1 concentration was
 SHEAR-INDUCED
chosen to minimize diffuse double layer effects
without inducing coagulation.
2.2. Flocculation Studies
Using these particles, both Brownian and
shear coagulation experiments were carried
out at ~b = 1.00 X 10 -6 in 36.0 wt% glycerol
solutions, the glycerol added to raise the vis-
cosity. These conditions slow Brownian co-
agulation to levels that permit shear coagula-
tion and sampling in reasonable times. At
these conditions and T = 25°C, the charac-
teristic time for doublet formation by Brown-
ian motion,
67r~a 3
IBR = chkBT' [2.1]
is 30 rain, allowing sufficient time for mixing,
shearing, and sampling. Since tBR ~ R 3 for
fiocs with hydrodynamic radius RH, the
Brownian times for the coagulated suspensions
greatly exceed 30 rain, providing sufficient
time for light scattering measurements after
sampling as well. The sheared suspensions
contained 1.0 M NaC1 to eliminate double
layer repulsion, putting all experiments in the
rapid coagulation regime. Furthermore, the
suspensions contained 2.5 X 10 - 4 M HC1 to
associate weak acid surface groups, but this
step is not expected to be crucial. The re-
mainder of the solvent was deionized water.
Prior to adding particles, we passed all of the
solvents at least twice through 0.22-#m Mil-
lipore GS filters to eliminate dust, a term
which refers to any unwanted particles,
fibers, etc.
Because the particles start to coagulate im-
mediately in a 1.0 M NaC1 solution, we pre-
pared two solutions for each experiment, one
containing the NaC1 and HC1, and the other
containing the particles. Both contained 36.0
wt% glycerol, with the exact contents listed in
Table I together with the contents and prop-
erties of the final test suspension. At the be-
ginning of an experiment, equal volumes of
each were mixed in a 250-ml Erlenmeyer flask
by swirling gently approximately 12 times at
1 rotation per s, and for shear coagulation
COLLOID COAGULATION 557
TABLEI
Properties of test suspension
36.00 _+ 0.05 wt% glycerol
5.20 -+ 0.01 wt% NaC1
58.80 ± 0.12 wt% H20, deionized
2.5 X 10-4 M H C I
q~ = 1.00 X 10 -6 _+ 1%, I D C particles
a = 0.05 # m
# = 3.12 _+ 0.06 cP at 25°C
= 2.79 _+ 0.05 cS at 2 5 ° C
o = 1.12 g / c m 3 at 22.8°C
no = 1.3872 at 2 5 ° C (Xo = 538 nm)
Properties of precursor solutions A and B ~
Solution A Solution B
36.00 _+ 0.05 wt% glycerol 36.00 -+ 0.05 wt% glycerol
64.0 _+ 0.1 wt% H20, deion. 10.10 _+ 0.02 wt% NaC1
~h = 2.00 × 10 -6 ± 1% 5.0 X 10-4 M H C I
53.9 +_ 0.1 wt% H20, deion.
p - 1.09 g / c m 3 at 2 5 ° C p = 1.15 g / c m 3 at 2 5 ° C
= 2.67 +_0.01 cP at 2 5 ° C
a E q u a l v o l u m e s o f s o l u t i o n s A a n d B a r e m i x e d to o b -
tain the test suspension for the coagulation experiments.
experiments the final solution was then slowly
poured into a concentric cylinder apparatus,
the entire preparation taking less than 2 to 4
min. After shearing for a predetermined time,
we would remove a sample for analysis. For
the Brownian coagulation experiments, we
placed the mixed solution directly in a light
scattering cell and followed coagulation in situ.
We maintained the temperature at 25.0
_+ 0.1 °C for all light scattering measurements
and the Brownian coagulation experiments,
while shearing was done at 25.0 _+ 1.7°C. Since
the characteristic time for shear coagulation is
inversely proportional to +q~ and the strain
rate + is less than 50 s -1 during careful mixing
and pouring, the low value of q~ ensures min-
imal shear coagulation during these steps in
addition to guaranteeing minimal Brownian
coagulation as stated above. Note, however,
that raising 4~to 10 -5 or decreasing the particle
radius by a factor of 2 would cause Brownian
coagulation to occur during the few minutes
of mixing and pouring.
We performed shear experiments at rates
between 780 and 1590 s -1 for shearing times
between 5 and 30 min _+5 s, and at these shear
Journal of Colloid and InterfaceScience, Vol. 142, No, 2, March 15. 1991
 558 TORRES, RUSSEL, A N D S C H O W A L T E R

rates the characteristic time for shear coagu- by a Brookhaven Instruments BI-2030AT
lation, digital correlator, and the results were stored
71" on an AT-clone personal computer for later
rs 4+4' [2.21
analysis. We verified alignment of the appa-
ranges from 8.2 to 16.8 min. The shearing de- ratus by examining the light scattered from
vice (29) is a chrome-plated apparatus with the silicone oil used as a bath for the light scat-
the outer cylinder rotating to prevent Taylor tering cell, and over the full range of angles
instabilities, and it has a gap with an outer the results behaved as expected for a Rayleigh
r a d i u s Rcouett e = 6.417 X 10 -2 ___ 4.0 X 10 s scatterer within <2.3%. After alignment, all
m and width h = 1.55 X 10 - 3 ± 1.2 X 10 - 4 experiments took place without further ad-
m. The sample volume is approximately 150 justment to permit accurate comparison. We
ml. Sampling at approximately 0.5 m l / s measured the static light scattering for the co-
through a valve with a diameter of 2.5 X 10-3 agulated suspensions at 12 ° , 15 ° , 20 ° , 30 ° ,
m assured no significant shear coagulation oc- 60 ° , 90 ° , 125 ° , 140 ° , and 160 ° , while auto-
curred during this step, and, prior to each correlation functions were measured and an-
sampling, we collected and discarded 2 to 3 alyzed at the three larger angles. The scattering
ml of solution. Furthermore, we performed volume at 90 ° is estimated to be 18-32 X 106
all experiments well below a conservative es- ~m 3 based on dynamic light scattering mea-
timate of the critical Reynolds n u m b e r given surements discussed elsewhere (31 ).
by For all the measurements, dust proved to
be a~major source of error and often made it
wRcouetteh
Reont- - 1500, [2.3] necessary to repeat experiments. When ~b
2v = 10 - 6 for 0.1-~zm diameter particles in an
which corresponds to the onset of turbulence aqueous suspension, the scattering intensities
for the above geometry (see (30, p. 591 )). In are small, making cleanliness crucial. Conse-
[2.3 ], w is the device angular velocity and u is quently, in addition to passing all solvents
the suspension kinematic viscosity. twice through 0.22-#m filters, the shearing de-
We measured light scattering with a Brook- vice and all glassware were critically cleaned
haven Instruments dynamic light scattering prior to use. The cleaning procedure consisted
goniometer and 514.5 n m light from a Lexel of soaking the items in Micro cleaner and
Argon ion laser, providing data for scattering thoroughly rinsing with deionized water, fol-
angles from 12 ° to 160 ° . This range corre- lowed by a thorough rinsing with filtered
sponds to deionized water and covering the items to pre-
vent contamination. Dust problems still oc-
3.54 # m -1 ~< q = - ~ 0 sin curred despite these steps; hence, we discarded
any experiment for which the intensities were
~< 33.37 # m -1, [2.4] abnormally high. Additionally, in the later ex-
0 being the scattering angle, no being the sol- periments we checked the NaC1 solutions by
vent refractive index, and Xo being the wave- light scattering prior to use, and the NaCl-free
length of the incident light in vacuum, with particle solution precursors were likewise
the incident light polarized perpendicular to checked immediately prior to adding the par-
the scattering plane. Since the scattering vol- ticles.
ume varies with scattering angle as 1 /sin 0 for 3. STATIC L I G H T S C A T T E R I N G
this instrument, all intensities are multiplied The intensity of light scattered from a floc
by sin 0 before analysis, and all intensities re- at a given angle depends on the structure of
ported here have been corrected in this m a n - the floe and is most sensitive to structural de-
ner. The autocorrelation function and average tails on the length scale q-l; therefore, static
intensity of the scattered light were compiled light scattering data covering a range of q pro-
Journal of Colloid and Interface Science, Vol. 142, No. 2, March 15, 1991
 SHEAR-INDUCED COLLOID COAGULATION
vide a useful fingerprint of the floe. In addition,
this spectrum can be analyzed in a straight-
forward m a n n e r for weak scattering, making
the technique a useful tool for our purposes.
Before discussing our results, we briefly review
the theory for scattering from a floc based on
the Rayleigh-Gans-Debye approximation and
discuss our procedure for examining data.
3.1. Theory
For a floc containing M identical particles,
the static light scattering in the Rayleigh-
G a n s - D e b y e approximation is
I = So ~i=1 M sin(qArij)
j=l qArij [3.1]
where I0 is the scattered intensity correspond-
ing to an independent particle, Arij is the cen-
ter-to-center distance between particles i and
j, and the double sum represents a summation
over all particle pairs (32). The above sum is
sensitive to the floc structure (i.e., the config-
uration of particles in the floe) because the
structure determines which Arij are included
in the sum. Furthermore, the s u m m a n d in
[3.1] changes most for q-1 ~ Arij, resulting
in a strong dependence on the distribution of
Arij nearest q 1.
To elaborate on the behavior of [3.1], in
Fig. 1 we present a sketch of a static light scat-
tering plot over a large range o f w a v e n u m b e r s
q for a hypothetical suspension of flocs con-
sisting of identical particles. To emphasize the
floc configuration dependence in favor of par-
ticle size effects, we divide the intensity by
P(aq), the single particle form factor. At qRo
1, RG being the aggregate radius of gyration,
the length scales probed exceed the aggregate
size and, consequently, any Ar 0. As a result,
the s u m m a n d is approximately one for all
particle pairs, and in the low q limit the spec-
t r u m asymptotes to a value proportional to
nlolo<N)w, [3.2]
the sum of the scattering from the individual
particles multiplied by the weight averaged
n u m b e r of particles in a floe. Likewise, in the
559
n 1 o Id <N>w -
2
nlol d - .f,,
I I I I I I
log (air g) 1
Log (a'q)
FIG. i. Static light scattering for a fraetal-likeaggregate
with dimension d. The intensity is divided by the single
panicle form factor P(aq), where a is the particle radius.
The small aq asymptotereflectsthe flocsize, and the linear
portion represents the internal structure, nl0 is the total
number concentration of individual particles, regardless
of whether they are part of an aggregate,and [d is the zero-
angle limit of the scattering intensity from a singlet mul-
tiplied by an instrument-dependent factor that accounts
for the scattering volume, detector efliciencies, etc.
high angle limit where aq ,> 1 and therefore
qAr o ~> 1 unless i = j, only the i = j terms in
[3.1] contribute significantly, and the spec-
t r u m becomes independent of floc structure
and size, asymptoting to the value expected
for a suspension ofuncoagulated independent
particles. Since we divide the intensity by
P(aq), this asymptote is a horizontal line. In
the intermediate region, the spectrum has a
shape that reflects the internal structure; for
Fig. 1 the intermediate region is a straight line
with slope - d as would be expected for a frac-
tal floc with dimension d (22). We will ex-
amine the value of a fractal description for
floes formed by rapid coagulation in the fol-
lowing sections.
The static light scattering spectra reported
in this investigation cover the domain 0.177
< aq < 1.67, corresponding to the conditions
cited above. In addition, the data are all pre-
sented as log(I/P(aq)) vs log(aq) for the rea-
sons cited above. To demonstrate the sensi-
tivity to floc structure, calculated spectra based
Journal of Colloid and lnlerface Science, Vol. 142, No. 2, M a r c h 15, 1991
 560 TORRES, RUSSEL, AND SCHOWALTER

on [3.1] are shown in Fig. 2 for various ag- 5.50

gregate structures. The line drawn through the

diamond symbols in Fig. 2 represents a typical 5.00
set of data, and the figure compares this curve
with spectra for a BCC floc with a radius equal
4.50
to t6 particle radii, a linear chain of 10 par-
tides, a doublet, and a singlet. The most im-
portant aspects of this figure are the large, eas- " ~ 4.0O
ily discernible differences between these curves o
over the range o f l o g ( a q ) examined in our ex-
3.50
periments. Also, at aq > 1 the curves should
all approach the singlet line in an oscillatory
m a n n e r (31 ), and this asymptotic behavior 3.00 H H ' ' H I [ ' ' ' ' I IIHllH HH''IIHI HH' IIHH I IH II'IHH H I,,,,,,,H I
-1.00-0.80-0.60-0.40-0.20 0.00 0.20 0.40
begins to appear at the larger aq. The curve Log (aq)
for the BCC floc is based on calculations at
relatively few aq values shown as solid circles; FIG. 3. Static light scattering for a sample sheared 17.5
min at ~/= 1170 s -~. The data represent internal structure
nevertheless, the curve drawn through these since the small aq asymptote depicted in Fig. 1 does not
points shows more oscillations than the other affect these data.
curves, a consequence of the long-range reg-
ularity. For log(aq) < 0.2, the BCC curve has
an average slope of ~ - 3 . The linear chain
the beginning o f an oscillation; the horizontal
spectrum is roughly linear with a slope of ~ - 1
portion indicates the light scattering probes
and starts to turn up at the highest aq. The
length scales larger than the doublet size for
spectrum for the doublet is horizontal over
these lower values of aq. Just as the structures
m u c h of the low aq values and exhibits a min-
of these various types of aggregates differ, so
i m u m at a point above aq = 1, presumably
do the static light scattering spectra in the range
of aq studied, justifying the assertion that our
measured spectra are sensitive to structure in
%00
a practical sense.
6.00
3.2. Results and Discussion
doto
5.00
linear ~ _ Experiments at shear rates of 780, 1170,
t~ 1350, and 1590 S - 1 w e r e performed for shear
4.00 o:22 ,
times varying between 5 and 30 min.
~a 3.00 Data for 17.5 min of shearing at + = 1170
O
s ~ are displayed in Fig. 3, with the scatter
2.00 resulting from the small scattering volume and
the corresponding low scattering intensities,
1.00
the low diffusivity of the large floes, and small
amounts of dust contamination floating in and
0"00--1.2'0.... '--'0
~8'0.... '---b~4~..... 0.dd ..... o.4{) '
out of the scattering volume. The points at
Log (aq)
log(aq) -- 0.18, 0.20, 0.22 are for measure-
FIG. 2. Calculated staticlight scattering for various hy- ments averaged over 300 to 400 s, whereas the
pothetical aggregate structures compared with typicaldata measurements at lower aq are averaged over
from our expcrimcnts (~). BCC: Particleson a body-cen-
60 to 100 s. Also, the data are roughly linear
tcrcd-cubic latticeextending to R = 16a, with the actual
calculated points (@) connected by a spline fit.Linear: for log(aq) < 0 and go through a m i n i m u m
Chain of I0 particlesin a straight line. at larger aq. The slope of the linear portion is
Journal of Colloid and Interface Science, Vol. 142, No. 2, March 15, 1991
 SHEAR-INDUCED COLLOID COAGULATION 561

a 5.50 : b 5.50
shear time: shear time:
~. (-10 min
I5 rain 5.00 ~ . ~ 22.5 r a i n
5.00
5.00 n ~ 26.2r5nin
5 mi
" •4.50 4.50

4.00 O~O4 . 0 0
,--1
3
-- 20 r a i n
S.60 ~25 rain 3.50 ~--.~--
_J30 rain

3.00 i i . . . . . . i i i 11 i l l i i i i i l l i i l l i l l l l l l i 1 1 1 1 I I I I I I I I I I I l l I I S l l l l l I I I I I I I I I l
-~.00-0.50-0.50-0.40-0.~0 0.00 0 . ~ 0 0.40 --1.00 -0.80 -0.60 -0.40 --0.20 0.00 0.20 0.40
Log (~q) Log (aq)

F~O. 4. ( a ) Static light scattering for shearing at ~/ = 1170 s -~ for various shear times. (b) Static light
scattering for shearing at + = 780 s -~ for various shear times.

- 1.8 _+ 0.1, indicating a similarity to a frac- negligible for smaller shear times. Analogous
tal of dimension d = 1.8. data for -~ = 780 s -1 shown in Fig. 4b resemble
Figure 4a displays results for all shear times that in Fig. 4a.
at -~ = 1170 s -1, the curves being smooth fits Additionally, comparing the results for four
to the data with the actual points excluded to shear rates at constant +t = 1.05 × 106 in Fig.
minimize clutter. (The scatter for the different 5 shows that the data for at least the three
shear times is comparable to that in Figs. 3 higher shear rates are independent of shear
and 5.) At shear times less than 17.5 min, the rate. The data for 780 s -~ appear to be system-
spectra change with shear time at lower aq be- atically lower than the other sets, but the de-
cause the flocs for these shear times are small viation is certainly within the scatter observed
enough for the low aq asymptote to be affecting
the data. As the shear time increases, the
5.50
curves approach the 17.5-min curve and the
intensity becomes less dependent on the floc A

size, the spectra for these longer shear times 5.00

being representative of the internal structure.
Floc size data discussed in Section 4 support
4.50
this assertion. Above t = 17.5 rain, the curves
retain their shape while assuming lower po-
sitions in intensity, but we do not believe this 4.00
change reflects a further change in structure 0
,-.1
because the type of structural evolution which 3.50
would cause such a shift is rather unlikely. In-
stead, this drop probably results from a com-
bination of effects including possible multiple 3.00

scattering and loss of particles due to floc sed- Log (aq)

imentation or coagulation on the walls of the
FIG. 5. Static light scattering for shearing at various
shear device. Conversely, the occurrence of shear rates for ~,t = 1.05 × 106. The data correspond to
this shift only for shear times greater than 17.5 + = 1590 s -1 (C3), -~ = 1350 s - ' ( ~ ) , -~ = 1170 s -~ ( . ) ,
rain indicates that these effects are probably a n d "~ = 780 s -~ ( © ) .

Journal of Colloid and Interface Science, Vol. 142, No. 2, March 15, 1991
562
for these experiments. Thus, the internal
structure of the flocs formed by shear coagu-
lation apparently does not depend strongly on
shear rate over the range of rates examined.
The data in Figs. 3 through 5 imply the in-
ternal floc structure is independent of shear
rate, at least at the shear rates examined, but
complementary data in Fig. 6 supports a more
general conclusion. This figure compares scat-
tering intensities for shear coagulation with
those for Brownian coagulation, and as with
the different spectra for shear coagulation, (he
two spectra in ibis figure are indistinguishable
with respect to both shape and magnitude.
Since previous experimental studies of flocs
formed by rapid Brownian coagulation dem-
onstrate the structure to be approximately
fractal with d = 1.8 + 0.1, it follows that the
flocs formed by shear coagulation may also
have fractal characteristics. (Also, this knowl-
edge about the behavior of Brownian flocs
gives us confidence that the small deviations
at the lowest aq in Fig. 6 result from experi-
mental scatter of the Brownian data.) In both
cases, we report measurements at coagulation
times long enough that the data become in-
dependent of floc size, assuring the spectra
represent the internal structure, but we also
avoid floc sizes for which multiple scattering
5.50
0 namely,
~4.50
4.00
3.50
3.00 , ,,, .... , ....
-1.00 2518'0'-0.60 -0.40 -0.20 0.00
, ....
Log (aq)
FIG. 6. Comparison of the static light scattering spectra
for shear-induced ( • ) and Brownian motion-induced ((?)
coagulation.
Journal of Colloid and Interface Science, Vol. 142,No. 2, March 15, 1991
TORRES, RUSSEL, A N D S C H O W A L T E R
may be significant. The strong similarity of
the internal structure for Brownian and shear
flocs is quite interesting, as well as being un-
expected. The shear coagulation process may
feasibly approach scale invariance with respect
to structural evolution as the flocs grow to sizes
much larger than the particle radius, thereby
eliminating the natural length scale; thus, a
fractal structure for these flocs would not be
unreasonable. However, the static light scat-
tering results indicate that both the dimension
of the scale invariant structure and the density
are approximately the same for the two modes
of coagulation, which means the flocs pro-
duced by the two modes not only exhibit a
fractal-like structure but also exhibit nearly the
same apparent scale invariance.
3.3. Data Fitting
To further investigate the static light scat-
tering spectra, we fit the data for t = 17.5 min
at ~, = 1170 s -1 using
N(r)= l+2t~(r - 2 a ) . B ( r ) d, [3.3]
where N ( r ) equals the number of particle cen-
ters within a radius r of a given particle in a
floc, and Y ( r - 2a), the Heaviside step func-
tion, accounts for the excluded volume. From
[3.3] one can derive the corresponding spher-
ically averaged pair distribution func.t.io~
02(r) = ~¢~(r - 2 a ) - - -
47rr 3
2dB
+ 6(r- 2a) 16~ra2. [3.41
The first term in [ 3.4 ] is the power-law decay
with an excluded volume contribution, and
¢
the second term is the nearest neighbor con-
tribution. The function 6 (x) is the Dirac delta
function. We choose a power-law dependence
, ....
0.20
~ .... ,
0.40 characteristic of fractals and fit this particular
set of data because it represents internal struc-
ture.
Using the above pair distribution function
for d = 1.8--chosen to match the slope of the
 S H E A R - I N D U C E D COLLOID C O A G U L A T I O N
6.00
B a higher value of log (aq) and a lower intensity.
0.80
0.68
5.50 0.62
0.57
0.46
0.34
,~5.00 0.23
~ 4.80
~ 4.00
3.50
8.00 ..,,.,,i.,.,,..i.,...,,i.,..,,,i..
-1.20 --0.80 --0.40 0.00
Log (aq)
FIG. 7. Calculated static light scattering corresponding
to [3.4] for d = 1.8 and various values of B.
low aq d a t a - - a n d various values of the coef-
ficient B, we calculated the family of static
light scattering curves shown in Fig. 7. These
curves have all been normalized using the
measured scattering intensity for uncoagulated
IDC particles, thereby accounting for the scat-
tering from a single particle, the scattering
volume, and the optics of the detection system.
Specifically, we measured the scattering inten-
sity as a function of aq for particles suspended
in a salt-free solution and corrected the inten-
sities using Rayleigh-Gans-Debye theory to
account for the actual particle concentration
and refractive index of the sheared suspension.
As a reference, Figs. 7 and 8 show the single
particle scattering determined in this manner
as horizontal lines at log(I/P(aq)) = 3.67
+0.03. For small log(aq), the calculated
curves have values significantly higher than
this line and asymptote to lines with slope
-1.8, each curve displaced an amount depen-
dent on the value of B. However, the curves
all cross the single particle line at the same
point, as required by the form of[ 3.3 ]. Figure
8 shows a fit to the data corresponding to B
= 0.62 (chosen "by eye"), and this curve is
seen to cross the single particle line near where
the data approach this line. The calculated fit
does not capture the upturn in the data at
log(aq) > 0, but it does have a minimum at
563
Consequently, we conclude that the simple
power-law fit outlined above reasonably rep-
resents the internal structure at larger length
scales but not near contact.
With the fitted values for B and d, one can
estimate some characteristic floc parameters.
First, these values correspond to an average of
2.2 nearest neighbors for a particle, which im-
plies the floc does not have a tightly packed
structure. Consistent with the number of
nearest neighbors, a plausible description of
floc-floc bonding for rapid coagulation might
0.40
incorporate interpenetration of two flocs until
a particle in one contacts a particle in the other,
at which point a bond forms. For our exper-
imental conditions, the attractive forces be-
tween particles are expected to dominate only
at small separations and, as mentioned earlier,
the bonds are believed to be rigid; hence, for
two flocs to form multiple bonds these contacts
would have to occur at almost the same time,
an unlikely possibility. Thus, it is reasonable
to expect two flocs to form a new floc by
bonding at only one point in most coagulation
events.
In addition to the number of nearest neigh-
bors, one can estimate porosities by approxi-
5.80
8.00
"• 4.00
¢~ 4.00
3.50
Log (a,~
FIG. 8. Fit based on [3.4] of the data in Fig. 3. The
chosen values of B and d are B = 0.62 and d = 1.8. The
horizontal line represents the scattering for uncoagulated
particles.
Journal of Colloid and Interface Science, VoL I42, No. 2, March 15~ 1991
564 TORRES,
mating the number of particles in a floc with
outer radius Rci a s
i=B +1,
withB=0.62andd= 1.80,
B and d being the values obtained from the
fit in Fig. 8 and R~i defined as the radius of
the smallest sphere containing all particle cen-
ters of an /-particle floc. The power-law de-
pendence o f [3.5] is chosen to be the same as
that for N ( r ) without the excluded volume
term, and the factor 1 is added to give reason-
able behavior for i = 2 and i = 1; nonetheless,
the choice of [3.5] is ad hoc, as is [3.3]. For
R~i = 10a, [3.5 ] yields a solids volume fraction
4~o~ of 0.04.
To summarize, the flocs formed by rapid
shear coagulation of particles that form strong,
rigid bonds appear to be porous, tenuous ag-
gregates with ~ 2.2 nearest neighbors for each
particle on average. The structure is remark-
ably similar for Brownian motion- and shear-
induced coagulation at these conditions and
appears to be independent of shear rate. The
2.2 nearest neighbors, the porous structure,
and the similarity between shear and Brown-
tan results are indications that there is little
rearrangement, as desired for our studies.
4. DYNAMIC LIGHT SCATTERING
Unlike the structure, the rates correspond-
ing to shear- and Brownian motion-induced
coagulation differ substantially, and measure-
ments on the former mode at the conditions
of interest are lacking. In order to obtain data
for a characterized model system, we measured
average floc sizes by dynamic light scattering
for the shear coagulated suspensions described
above. Specifically, we calculated floc hydro-
dynamic radii from the initial decay of the
intensity, or second order, autocorrelation
functions. This calculation requires a theory
describing the initial decay in terms of the size,
and for single spheres it is known that the de-
cay follows a simple exponential in t/a (33).
For a floc, though, the decay is more compli-
Journal of Colloid and Interface Science, Vol. 142, No. 2, March 15, 1991
RUSSEL, AND SCHOWALTER
cared. Even if one assumes the floc to be
spherical, rotational motion affects the auto-
correlation function. Lindsay and co-workers
(34-36) addressed this problem for a fractal
structure by numerically evaluating the au-
[3.5] tocorrelation function of simulated flocs at aq
< 1 and all values of qRc, and they later pre-
sented an approximate method; however, we
will apply an alternate methodology that ad-
dresses the behavior at aq >~ 1 by examining
the differential equations governing dynamic
light scattering.
4.1. Theory Accounting for Rotations
Consider a collection of a large number of
flocs c~ = 1, 2 . . . . . n~, with centers at R,.
Each floc contains Ms particles located at b~
(m = 1. . . . . M,) relative to its center. The
electric field scattered from a floc at a given
scattering vector q follows
M~
E~(t) "~ E 0 . e iq'x%~t~ ~ e iq'b~"~t~, [4.1]
m=l
where E0 is the incident electric field assumed
to be polarized perpendicular to the scattering
plane. Therefore, the intensity autocorrelation
function defined by
G2(q, t) = (I(q, t)I(q, 0 ) ) , [4.2]
an ensemble average over all floc positions and
orientations, can be written as
G2(q,t)= C( ~ exp{iq.[R~(0)
cq/~,3,,6= 1
- l i e ( 0 ) + R~(t) - li~(t)])
× ~] exp{ iq. Ibm(0) - b ~ ( 0 )
l,m,n,p=l
+ b.~(t)- b~t)])5. [4.3]
The constant C multiplying the right-hand side
of [4.3 ] is not important insofar as data anal-
ysis is concerned. If one assumes the flocs dif-
fuse independently and rotational diffusion is
independent of translational diffusion, the en-
semble averaging eliminates most of the terms
in the summations of [4:3], and terms cor-
 SHEAR-INDUCED COLLOID COAGULATION 565

responding to translation factor from those for To derive an equation for F(q, t, bl, bp,
rotation (see similar arguments in (34, 33 pp. 01p), we examine P(b, t; b(0)), the probability
62-64)). Assuming for simplicity that the that a particle in a floc starting at b(0) at t = 0
translational diffusion coefficients of all flocs resides at b at time t. This probability is the
are identical, we then obtain solution of the initial value problem (37)
G2(q, t) = G0exp { -2q2Dt} OP
- - = Ob2V~P [4.7.1]
nT Me Ot
× E [~ (exp{iq.(b;(0)-bp(t))})
a,B4~o~ Lp ~ 1 t.C.:P=6(b-b(0)) att=0. [4.7.2]
M~ The operator V2~--the angular part of the
× ~ (exp{-iq'(b~m(O)-h~(t))})] + G~ divergence operator--is defined as V~
m,n ~ l
= Vb~" Vb~, where Vb~ = (I - bb/b2) • V, and
[4.4]
the rotational diffusion coefficient O governs
when the scattering volume contains a large how quickly the rigid body changes its orien-
number of flocs, a condition met in our ex- tation due to Brownian motion. The ensemble
periments. Equation [4.4] has a baseline G~ average in [4.5 ], the defining equation for F(q,
and a time dependent part which depends on t, bl, bp, Olp), is similar to a Fourier transform
the diffusion coefficients of interest. Thus, the of P; hence, an initial value problem describ-
problem of determining the dynamic light ing F(q, t, bt, bp, 0lp) can be obtained from
scattering from a floc with a given structure Eqs. [4.7] by applying methods similar to
reduces to solving for those invoked to Fourier transform the three-
F( q, t, bz, bp, Otp) dimensional diffusion equation. Working
through the details yields
=(exp{iq.[b,(0)-bp(t)]}) [4.5]
for two points at bl and bp in a rigid body which - q2b2F- b2ff-~ [4.8.1]
undergoes rotational diffusion independent of
its translational diffusion. The independent sin(qs)
variable Ozprepresents the angle between bt and I.C.:F--- att=0. [4.8.2]
qs
bp, the vectors whose magnitudes are bl and
In Eqs. [4.8], b can equal the magnitude of
bp, respectively.
either bl or bp, and s = [bz(t) - bp(t)[. One
The function F(q, t, bl, bp, Olp) describes
method of solving Eqs. [4.8] involves applying
the correlation between the electric field scat-
separation of variables to obtain
tered from the point bt at time t = 0 and that
scattered from the point bp at time t, with the
F = ~ (2n + 1 ) e x p { - n ( n + 1)Or}
brackets denoting an ensemble average over n-0
all orientations at time t = 0. As a result of
the averaging over all orientations, F depends × jn(qbt)jn(qbp)Ln(cos Olp); [4.9]
on bl and bp only in terms of their magnitudes
then this series can be summed over all particle
and the angle Otp,as reflected in the functional pairs, each pair (l, p) corresponding to specific
form given above. Once F( q, t, bt, bp, Otp) is
values for bl, bp, and 0tp, to obtainf(q, t). (In
obtained, one can determine
[4.9],jn(x) is the nth spherical Bessel function
M . M~
of the first kind and Ln(x) is the nth Legendre
f(q, t) = ( Z Z F(q, t, bl, bp, Ozp)> [4.6] polynomial.) However, this procedure can be
/=I p=l
quite cumbersome for all but the simplest
for a given floc structure. The brackets in [4.6] structures. In addition, it requires knowledge
represent an average over an ensemble offlocs, of the structure in terms of the number of par-
replacing the outer summation in [4.4]. ticle pairs in a floc corresponding to a partic-
Journal o f Colloid and lnterface Science, Vol. 142, No. 2, March 15, 1991
 566 TORRES, RUSSEL, A N D S C H O W A L T E R

ular set of values for bl, bp, and 01p.Thus, we
utilize an approach which circumvents the
need for a priori knowledge of the structure at
this point in the derivation.
To proceed, we convert G2(q, t) to the first-
order autocorrelation function Gl(q, t)by
subtracting the baseline G~ from G2 ( q, t) and
taking the square root, yielding
G~(q, t) = A e x p { - q 2 D t ) f ( q , t).
The time derivative of Gl(q, t) at t = 0 is
Gl(q, o)
Therefore, the contribution to Of(q, t)/Ot at
t = 0 from the self-correlation term in [4.13 ]
becomes
-O(N)qZRg. [4.16]
In a manner analogous to the derivation of
[ 4.16 ], we substitute the initial condition for
F(q, t, bl, bp, 0lp) into the governing differ-
[4.10] ential equation [4.8.1] to provide an equation
for F at t = 0, and we sum the result over all
pairs of distinct particles to give the pair cor-
relation term in [ 4.13 ]. Equivalently,

of
=A{-q2D.f(q,O)+-~t=o }. [4.11] f dblpf(b,) f ds p2(S; bl)F(t = 0) [4.17]

Furthermore, at time t = 0, represents the summation over all pairs of dis-

tinct particles as a double integral, where pf(bl)
f(q, O) = ( ~ pZ sin(qS);qs/ , [4.12] is the probability density for a particle in a floc
1 to be at bl relative to the floc center and p2(s;
b/) is the pair probability density for a particle
which is just the static light scattering for the
to be at s relative to position b/given that there
floc divided by the single particle scattering.
is a different particle at bl. Assuming spherical
To analyze [4.11], we separate f ( q, t) into
symmetry of p2 (s; bl) with respect to s makes
self-correlation and pair correlation terms and
it possible to integrate [ 4.17 ] over all orien-
differentiate to obtain
tations of s to yield
df Mo
- ~ = ( E Fo( q, t, bi) )
i=1 87rq23 o [ f dblpf(bl)b~
M~ M~
+ ( ~ ~ F(q, t, bt, bp, Olp)}. [4.13]
l=1 p=l × f ds o2(s; b,)szSin(---qs)l. [4.18]
p#l qs j
The second term on the right-hand side of
[4.13 ] is a double sum over all distinct particle In making this assumption, we are focusing
pairs, distinguishing it from the sum in [4.6 ]. our attention on the behavior at qRG ~> 1,
The function F0 represents self-correlation and whereas at smaller qRG the outer boundary of
satisfies the initial value problem given by Eqs. the flocs would cause a dependence on the di-
[4.8] for s = 0, rection o f s . (Note that one must account for
the dependence o f / " on the orientation of s
10Fo _ q2bZFo _ ~b ( b2 OFoI relative to bl when performing this integra-
00t Ob ] [4.14.1] tion.) If one further assumes that 02(s; hi) is
independent of bl, [ 4.18 ] simplifies to
I.C.: Fo = 1 at t = 0. [4.14.2]
Upon substituting the initial condition for F0 87rq2 OR 2
into [4.14.1 ], one finds 3
OFo
Ot~-t=O = - O q Z b 2 " [4.15] - - s
qs )
2 . [4.19]

Journal of Colloid and Interface Science, Vol. 142, No. 2, March 15, 1991
 SHEAR-INDUCED
Our motivation for making this assumption
comes from its validity with fractal objects,
but the form of p2(s) is not restricted to be a
power of s, giving added generality. Again, in
making this assumption we are considering
wavenumbers satisfying qRG >> 1, rendering
the behavior ofp2(s; bl) at length scales com-
parable to Rc unimportant. Finally, recogniz-
ing that f ( q, 0) can be written as
f ( q , O) = ( N } + 47r
sin(qs)
× f dbtpAbl) f ds p2(s)s2 qs
= ( N ) { 1 + 47r f ds p2(s)s 2 sin(qs)}
qs
[4.201
using the same assumptions invoked to arrive
at [ 4.19 ], we obtain the result
rl __ (~1 (t = 0) { 2
G l ( t = 0 ) - q2 D + ~ 0 R 2 absent from their solution, but their results do
× ( 1+
2 f ( q , O)
)}
'
[4.21]
where F1 is the first cumulant of the first-order
autocorrelation function (33). Eq. [4.21] is
the desired equation relating the diffusion
coefficients to the autocorrelation function.
Note that the term
(N}
[4.22]
f ( q , O)
equals the ratio of the single particle baseline
to the scattered intensity and therefore can be
measured by static light scattering, and recall
that [ 4.21 ] was derived without explicitly in-
voking a power-law pair distribution function.
Also, note that the ratio of the pair correlation
term to the self-correlation term in [ 4.13 ],
2 ( N } - f ( q , O)
[4.23]
3 (N} ' 67r~zRH
COLLOID COAGULATION 567
becomes smaller as q becomes larger.
Because the pair correlation term in [ 4.13 ]
is small relative to the self-correlation term at
large q, the assumptions regarding 02 are not
expected to be important in this limit. Indeed,
[ 4.18 ] furnishes a basis for determining the
order of magnitude of the pair correlation term
even when the assumptions about 02 are not
strictly valid. In our experiments the ratio
given by [4.23] is not always negligible, but it
is small enough to provide confidence that the
assumptions about 02 do not lead to unac-
ceptable errors in the data analysis.
The only other analysis of dynamic light
scattering from flocs similar to the type seen
in this investigation is work reported by Lind-
say et al. (34, 35 ) and Lin et aL (36) for fractal
flocs with aq < 1. Comparing their results with
[4.21], one finds the term
1 (N}
[4.24]
2 f ( q , 0)
address the behavior for all qRG when aq ~ 1.
Equation [4.21], on the other hand, was de-
rived using assumptions for p2 which only
make sense ifqR~ >> 1. Although of theoretical
interest, the additional contribution from the
above term is comparable to the uncertainty
in our experimental data and therefore is not
crucial here. Nonetheless, our development
explicitly distinguishes the contributions of the
self and pair correlation terms.
4.2. Determining the Hydrodynamic
Radius of a Floc
In order to determine a floc radius using
[4.21], one must relate the diffusion coeffi-
cients to the radius. Unfortunately, exact
equations are not available. Consequently, we
follow the lead of previous investigators (e.g.,
(12, 34, 36)) and define an effective hydro-
dynamic radius RH according to
D - - -
kBT [4.25]
Journal of Colloid and Interface Science. Vol. 142, No. 2, March 15, 1991
 568 TORRES,
Also, Lindsay et al. (34) assumed
O- kBT
87r~R3n
and Chen et al. (14) reported /3 = RH/RG
= 0.875; hence, to be consistent with their re-
suits we adopt
2 0R 2
3
- - = 0.65.
D
Thus, our final working equation is
['1 = q 2 D 1 +0.65 1 +2f(q, 0)
Compared with the large qRG asymptote
I'1 1
q2----~= 1 + 2 7
reported by Lin et al. (36), our analysis differs
quantitatively only in the extra term given by
[4.24], a term which is important when aq
>~1.
To illustrate the expected behavior of r l/
q2D, Fig. 9 shows points calculated from
[4.28] based on our data (the necessary scat-
tering intensities were obtained from Fig. 3)
as well as a curve representing results from
L~ndsay et al. (35). As illustrated, [ 4.28 ] pre-
dicts behavior at aq >~ 1 that is not reported
by Lindsay et al. (34, 35) or Lin et al. (36),
while their results address behavior at qRG <~ 1
that our approach misses.
For our purposes, [ 4.28 ] together with scat-
tering intensity data provide an adequate
means for determining average floc hydrody-
namic radii. Alternatively, one could measure
I'1 and the static light scattering over a range
of q and plot I'1/q2 against the ratio given by
[4.22]; then O . R~ and D could be deter-
mined directly from the slope and intercept
by invoking [4.21]. Unfortunately, this pro-
cedure requires data at aq >~ 1 that are more
accurate than our measurements provide.
Journal of Colloid and Interface Science, Vol. 142, No. 2, March 15, 1991
RUSSEL, AND SCHOWALTER
2.50
[4.26] 2.00
J
~-~ 1.50
1.00 - -
[4.27]
0.50
0.1
, , , , , , , i
1
, , , , , , , ,
1'o
qRQ
" FIG. 9. FI/q2D as a function ofq/~ at Rda = 11.3.
The points (*) depict calculationsbased upon [4.28] for
[4.28] the data in Fig. 3, and the solidcurverepresentsthe results
from Lindsayet al. (35) for fractal flocs.The valueRG/a
= 11.3 followsfrom/3 = 0.875 and measurementsOfRn
correspondingto the experimentdepicted in Fig. 3.
[4.29]
4.3. Discussion of Results
Figure 10 shows a typical plot of G~(q, t)
at longer shear times for correlation times cor-
responding to the first 64 correlator channels.
To calculate G1 (q, t) from the measurements
of Gz(q, t), one needs a value for the baseline
G~, and the Brookhaven Instruments corre-
lator/computer determines this quantity by
two methods: from the total scattered intensity
and from six delay channels. The difference
between the two yields an uncertainty which
we include in the calculation of error bars. For
our purposes, we determined F1 by plotting
ln{ G1 (q, t) } vs t and graphically measuring
the initial slope; due to noise in the data, un-
certainty of the baseline, and a lack of a simple
equation describing the autocorrelation func-
tion at t > 0, more elegant methods would not
significantly increase the accuracy.
Figure 11 presents data for floc size scaled
by the particle radius as a function of time
scaled by ~-s, the characteristic shear time at t
= 0 (see [ 2.1 ]). Each point corresponds to
one shear experiment, and the error bars rep-
resent uncertainties of the baseline and differ-
ences between data collected at the three angles
 SHEAR-INDUCED COLLOID COAGULATION 569

-0.60
of interest. The Brownian calculations are

-0.80

-1.00
<. based on the equation ( 11 )

RH
a - Y(2 -
(t/tBr) ~/a
1/d) "
In addition to Fig. 11, we present data for
[4.31]

floc size as a function of shear rate at constant

~ -1.20 "i,l = t.05 × 106 in Fig. 12. If there were no
breakup or rearrangement and no significant
-1.40 hydrodynamic or colloidal interactions, then
the data would all lie on a horizontal line be-
cause the shear rate' would only affect the time
-1.60 ......... f ......... ~ ......... = .........
O.OE+O00 1.0E+O03 2.0E+003 3.0E+003 4.0E+003 scale; however, we see that floc size does vary
time, /.t,s e c with the shear rate, being smallest at the high-
FIG. 10. First-order autocorrelation function G~(t) cal- est values. We discuss the possibility of this
culated from G2(t) measured at a scatteringangle of 140° effect arising from floc breakup in the next
for 15 min of shearing at ~/= 1170 s 1. section.

5. KINETICS CALCULATIONS
125 ° , 140 ° , and 160 ° . This figure shows results
for shear rates of 1170 and 780 s -1, and the To calculate shear coagulation kinetics we
scaling given by rs partially collapses the data use the equations (4)
for the two rates. As discussed in the following dNi_ 1 i~ 1
section, this time scaling is expected to be less dz 8 j=l ~ ( R j Jv Ri_j)3NjNi_j
effective at long shear times because breakup
of large flocs occurs. Note that the radii at t~ 1 o~ 1
rs < 1.5 for + = 1170 s -I are comparable to 4 j~ -~o (Ri + Rj)3NiNj [5.1.1]
the values o f ( a q ) -I at which the curves in Fig.
4a deviate from the 17.5-min curve, providing I.e. 1: N~ = 1 at r = 0 [5.1.2]
further evidence that the 17.5-rain curve rep-
resents the internal structure. A similar com-
l.C. 2 : N i = O , i > O , a t r = 0. [5.1.3]
parison can be made with Fig. 4b, but the The quantities N~ represent the n u m b e r con-
scatter makes the effect less obvious. centrations of flocs containing i particles di-
Another important aspect of these experi- vided by the initial n u m b e r concentration of
ments is the contribution of Brownian motion. singlets, r is the time scaled by rs, Ri = Rci/a
At the initial stages of the shearing when most is the capture radius of an/'-particle floc scaled
particles exist as singlets, the Peclet n u m b e r by a (a quantity discussed below), and Wa is
a t e / = 1170s - l i s the stability ratio for coagulation of an i-par-
ticle floc with a j-particle floc.
Pe = 2.15, [4.30]
The stability ratios W/j differ from unity due
and Brownian motion obviously contributes to hydrodynamic and colloidal interactions,
significantly. Note, however, that Pe ~ R 3 but these effects are expected to be small for
for a floc; hence, when RH = 6a, Pe = 465. the system investigated. As stated above, dou-
To compare the rates of shear and Brownian ble layer repulsions are negligible because the
coagulation at longer times, Fig. 11 shows the solvent has a high salt concentration, and the
calculated growth for Brownian coagulation, hydrodynamic and attractive dispersion forces
demonstrating that this mode is m u c h slower between the porous flocs are much weaker
than shear coagulation for most of the times than those for two solid bodies of comparable
Journal of Colloidand InterfaceScieuce, Vol. 142, No. 2, March 15, 1991
570 TORRES, RUSSEL, AND SCHOWALTER

25.00
and colloidal floc behavior at a level that is
appropriate to the current understanding.
20.00 To proceed, the hydrodynamic and capture
radii must be related to the number of particles
15.00
in a floc. Equation [ 3.5 ] suffices for Rci, and
an equation for RHi results from setting /3
= 0.875 as in Section 4 (14). In order to relate
10.00
Rri to i, we assume the distribution of particles
in a floc follows
5.00

0.00 ' ' ' ' l ' ' ' ' l ' ' ' ' ' ' ' ' l l l ' ' ' ' ' ' ' ' l ' ' ' ' ' ' ' ' ' t ' ' ' ' ' ' ' ' ' l
0.00 0.50 1,00 1.50 2.00 2.50
t/-r,
with B = 0.62, d = 1.8, and b equal to the
F~G. 11. Floe hydrodynamic radius vs r = t/zs for
distance from the center of the floc. This
shearing at + = 780 s -l ([])'and + = 1170 s -l (0). The
solid line ( ) represents kinetics calculations for + equation follows upon eliminating the nearest
= 1170 s -l with a maximum-floe-sizecriterion, and the neighbor term and excluded volume step
dashed line ( ..... ) represents calculations for Brownian function from [3.4 ], retaining the power-law
coagulation ( 11). dependence. (The former terms are necessary
in [3.41 but not in [5.2] .) Also, the 6(b) term
in [5.2] is added to maintain at least one par-
size. In fact, the latter two forces are only sig- ticle in the floc. F r o m [5.2] and the chosen
nificant very near contact. Taking these factors value of 13
into account, we develop a two-radius floc
model and use it to examine by what extent (i-1)d] °'5
W o. exceeds unity. RHi = 0.875 ~-~--_~2) ] Rci
The proposed two-radius model describes
the floc as a spherical body with both a capture for i >~ 2, [5.3]
radius Rc and a smaller hydrodynamic radius
RH. The latter describes the drag in a flow field
and is used to estimate the hydrodynamic 20.00
functions, whereas the former radius repre-
sents the distance within which another floc
must approach for coagulation to occur. Be- 15.00
cause two flocs bond according to our model
when they are separated by a distance (Rcl
+ Re2) that is greater than ( R m + RH2), lu-
brication forces will not exhibit a singularity
at contact, and as a consequence the form of
10.00
t
the equation invoked to describe attraction is
5.00
not as important as for two solid bodies. In-
deed, trajectory calculations suggest the at-
traction can be replaced with adhesion at con-
0.00
tact without significantly affecting the results. 50~ ~o . . . . . . io'od.~6 . . . . . 1'5~d.6d ..... ~o~d.oo
Our model also accommodates the expected •.f, sec -I

fluid flow within the outer portions of a porous FIG. 12. Floc hydrodynamic radius vs ~/for shearing at
floc. Thus, our simple description encom- +t = 1.05 × 106. The points ( e ) represent kinetics cal-
passes the basic features of the hydrodynamic culations incorporating a maximum-floc-size criterion.
Journal of Colloid and Interface Science, Vol. 142, No. 2, March 15, 1991
 SHEAR-INDUCED COLLOID COAGULATION
but this equation gives RHi < a for i = 2. This
discrepancy is not too important because our
investigation considers flocs containing many
particles, but to maintain a realistic value of
RH2 the factor 0.445a is added as an ad hoc
correction, yielding our working equation
((i- 1)all°5
RHi = 0.875 ~ + 2) ] Rci + 0.445a.
Single particles are assigned the values RHi
= R c i = a.
Comparison of the results of the kinetics
calculations with the dynamic light scattering
data also requires determining the intensity
averaged hydrodynamic radius ( R H ) , and as-
suming Ii is proportional to i as suggested by
the data for the larger scattering angles, this
average can be written as
(RH) = Z ~ I Nil
Combined with known hard-sphere hydro-
dynamic functions (21, 38-41), our model
can be used with [1.5] to calculate stability
ratios for two interacting flocs. The details are
presented elsewhere (31 ), but the result for
two equal-size flocs in the absence of Brownian
motion is
{ 1 -- 87]---
3~ f 27/i~ ( B1( r.~) ~'-?, ) ) r
Wff I:
× exp[-2 ~ig (B(F)
-1---A-~
- A(?) IF
ll
×exp[3~n~(B(-lr)-A(r)-_~-~ ,I ldr]
r [5.6]
with rh = Rci/RHi. Figure 13 illustrates that
the stability ratio W~ differs only moderately
from unity and does not depend strongly on
i. Further computations would provide all the
necessary W~j, but Wij = 1 is a reasonable ap-
proximation in view of Fig. 13, the uncertainty
in our data, and our intent to identify trends.
In addition, the neglect of Brownian motion
571
1.60
1.40
1.20
1.00
[5.41
0.80
0.60
, , , , ,,,,i
10
, , , , ,,1,1
100
, , , , ,,,11
1000
i
FIG. 13. Estimate of the stability ratio W. as a function
of i based on the two-radius floc model.
already limits our ability to calculate W~j ac-
curately. Thus, in the following calculations
we set Wo = 1.
When all the elements of the above model
. [5.5]
are put together and Eqs. [ 5.1 ] solved, the re-
sults predict floc growth that increases at a
continuously increasing rate, contrary to the
data in Fig. 11. Evidently the flocs cannot grow
to arbitrarily large sizes in the shear flows
studied, indicating breakup should be included
in our calculations. For the case of interest
two flocs likely coagulate at one particle-par-
ticle contact as discussed in Section 3, and
breakup occurs when the hydrodynamic force
pulling the flocs apart exceeds the attractive
force at the contact point. However, the hy-
drodynamic force changes as the flocs rotate
together in the fow; hence, to develop a
breakup criterion we assume that two flocs
which come into contact will separate if the
maximum hydrodynamic force acting to sep-
arate them exceeds the attractive force holding
two particles together. For stability between i-
and j-particle flocs, this criterion is
3
7 r # ( R H i -t- R H j ) 2 / y <. FAu [5.7]
for simple shear and small separation limits
of the appropriate hydrodynamic functions,
Journal of Colloid and InterfaceScience, Vol. 142,No. 2, March 15, 1991
572 TORRES,
with the extrema in the radial component of
the viscous force occurring at an angle of 45 °
relative to the bulk velocity (4, p. 301 ). Pri-
mary m i n i m u m attraction at a separation 6
with a Hamaker coefficient An yields
aAH 11/2
(RHi + R , j ) <~ 18--~-52 /
To evaluate [5.8 ] we simply choose 5 = 1 nm,
a value that corresponds to length scales at
which molecular structure, roughness, etc.,
become important, and we calculate A H for
polystyrene latexes in the solvent of interest
according to an approximation reported by
Russel et al. (4, Eq. [5.9.3]), obtaining AH
= 5.5 × l0 -21J. It is also likely that rearrange-
ment begins to play a role when the shear
forces are comparable to the bonding forces,
and a detailed analysis of the structure at
longer times should consider such effects. For
our purposes, however, the simple criterion
above captures the essential physics that limit
,further growth of aggregates.
Figure 11 shows the solution of Eqs. [ 5.1 ]
for ~ = 1170 s -1 using [3.5] and [5.4] for the
floc capture and hydrodynamic radii, [5.5] for
the intensity averaged hydrodynamic radius,
[5.8] for floc breakup, and Wij = 1. We per-
formed the integration using the routine
ODESSA (42-44) on a CONVEX vector pro-
cessor. Although the calculated curve and the
data differ somewhat, the agreement is good
considering the uncertainties in the data and
the approximations in the theory. In addition
to limiting the sizes at large times to values
consistent with measurements, the breakup
criterion causes the change in curvature of the
calculated growth curve at intermediate times.
To examine the size distribution at longer
shearing times, we show a representative plot
in Fig. 14, and this figure illustrates the de-
velopment of a peak at the maximum floc size,
as well as the broadening peak expected at
smaller sizes.
Figure 12 shows the prediction for shearing
at different shear rates with ~t = 1.05 × l06,
and although the predicted values are high,
Journal of Colloid and Interface Science, Vol. 142, No, 2, March 15, 199 !
RUSSEL, AND SCHOWALTER
1.0 E-1
1.0 E-2
z" 1.o ~.-s
[5.81
1.0 E - 4
l.O E - 5 .
1.0 E-6. ~-~
i
FIo. 14. Dimensionless number concentration N~vs i
calculatedfor r = 1.2 at -y = 1170 s-1. The peak at i = 390
correspondsto the maximum floc size at this shear rate.
the dependence on shear rate agrees nicely
with the data. Recognizing that the calcula-
tions would give a horizontal line in the ab-
sence of a breakup criterion, these results sup-
port the hypothesis that the force holding two
floes together is comparable to one particle-
particle bond. Furthermore, it is interesting to
note that the calculated curve would lie closer
to the data if stability ratios closer to those
given in Fig. 13 were used instead of Wij = 1.
Evidently, the two-radius floc model, struc-
tural information from our fit of the static light
scattering spectra, and the proposed floc
breakup criterion provide the necessary ele-
ments for describing the coagulation process
at a level of detail appropriate for our data.
Reconsidering the effects of shear on the floc
structure, recall that the two possible conse-
quences of large shear stresses are rearrange-
ment and breakup. As examples, L i n e t al.
(45) found rearrangement occurs without sig-
nificant breakup when fractal gold clusters
formed by Brownian aggregation experience
large shear stresses, whereas we propose the
stresses in our system restrict the flocs to a
maximum size. In the absence of breakup,
rearrangement of our floes would yield more
compact aggregates and slow the kinetics ac-
cordingly, but Figs. 11 and 14 suggest the ab-
 SHEAR-INDUCED COLLOID COAGULATION
sence of an upper limit on the n u m b e r of par-
ticles in a floc would still lead to m u c h larger
radii than observed. On the other hand, Eq.
[ 5.8 ] with AH(gold) = 3 × 10 -19 J (4, p. 148),
6 = a / l O , and a = 7.5 n m implies the Rr~
= 500 n m flocs studied by L i n e t al. (45) re-
main intact as long as ~+ < 280 N / m 2, and
the largest shear stress they report equals 90
N / m 2 ; therefore, [ 5.8 ] is consistent with their
conclusion that breakup does not occur. The
reason the gold aggregates restructure at length
scales between 100 and 500 n m while ours
apparently do not remains an interesting topic
for study.
6. SUMMARY
In a suspension undergoing rapid shear co-
agulation, polystyrene particles with a low
surface charge can form strong, rigid bonds
and aggregate into large, tenuous flocs. Static
light scattering detects an internal structure
which is independent of shear rate and indis-
tinguishable in our experiments from that as-
sociated with Brownian coagulation; namely,
both modes give a floc structure that can be
approximated as a fractal with d ~ 1.8 _+ 0.1.
Also, a fit to the static light scattering data sug-
gests an average of 2.2 nearest neighbors per
particle.
With results for the dependence of the first
cumulant on the rotational and translational
diffusion coefficients, we also examine floc size
as a function of shear rate and time by dy-
namic light scattering. To interpret these data,
we develop a two-radius floc model that de-
scribes the hydrodynamic behavior of our
tenuous aggregates. Analysis of the model
suggests hydrodynamic interactions can be
neglected in kinetics calculations and, further,
that a sticky-floc attraction suffices for our
purposes. Calculations based on this model
predict behavior consistent with our measure-
ments, but only when a m a x i m u m size crite-
rion is invoked.
To develop a size criterion, we assume two
flocs join at one particle-particle bond, a hy-
pothesis consistent with the number of nearest
573
neighbors inferred from the static light scat-
tering spectra. An approximate breakup cri-
terion then follows by equating the force hold-
ing two particles together to the m a x i m u m
hydrodynamic force acting to separate two
flocs near contact. Rearrangement without
breakup m a y also occur when these forces be-
come comparable, but we neglect this more
complicated possibility because it does not
appear to be capable of explaining our data.
A further paper will describe simulations
that provide complementary information on
the structure of flocs formed by shear coagu-
lation.
ACKNOWLEDGMENTS
The authors gratefully acknowledge NSF and the Ford
Foundation for graduate fellowship support (FET), IFPRI
for financial support, and Prof. Y. B. Kevrekidis and
H. S. Brown for assisting with the kinetics calculations
and providing access to the CONVEX computer.
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