Journal of Colloid and Interface Science 221, 114–123 (2000)
Article ID jcis.1999.6565, available online at http://www.idealibrary.com on
Fractal Morphology and Breakage of DLCA and RLCA Aggregates
S. Tang,∗,1 J. M. Preece,† C. M. McFarlane,† and Z. Zhang†
∗ Department of Chemical Engineering and Chemical Technology, Imperial College, London SW7 2BY; and †School of Chemical Engineering, University
of Birmingham, Birmingham B15 2TT, United Kingdom
Received June 29, 1999; accepted September 30, 1999
Latex aggregates, formed in 1 M McIlvaine buffer solution and
0.2 M NaCl solution, have been characterized in terms of aggre-
gate size distribution and fractal morphology. This was achieved
using three sizing techniques (image analysis, laser scattering, and
electrical sensing) in which size distributions and fractal properties
of the aggregates were measured. Estimates of fractal dimensions
were made using the two-slope method based on dimensional anal-
ysis and the small-angle light scattering method. Aggregate suspen-
sions were prepared using both water and a mixture of heavy water/
water as the solvent. The latter essentially eliminated sedimenta-
tion, which was observed after one day of aggregation when water
alone was used as a solvent. Latex aggregates formed by diffusion-
limited colloid aggregation (DLCA) and reaction-limited colloid
aggregation (RLCA) had fractal dimensions close to 1.8 and 2.1, re-
spectively. As observed through image analysis, DLCA aggregates
possessed a loose tenuous structure, whereas RLCA aggregates were
more compact. Disruption of both DLCA and RLCA aggregates
has been investigated in laminar flow and turbulent capillary flow.
The shear forces introduced by a laminar shear device with a shear
rate up to 1711 s−1 were unable to bring about aggregate breakup;
shearing facilitates aggregate growth in the case of DLCA. However,
latex aggregates were significantly disrupted after passage through
a turbulent capillary tube at 95209 s−1 . °C 2000 Academic Press
Key Words: fractal morphology; breakage; latex aggregates; size
distribution.
INTRODUCTION
Understanding aggregation has been a main goal in the field
of colloid chemistry for many years as colloidal aggregation is
widely used in many industrial processes, such as water treat-
ment, mineral recovery, paper manufacturing, and enhanced
oil recovery, and as an analytical tool in biotechnological and
biomedical sciences (1). In most industrial applications, the
shape, structure, and strength of aggregates play an important
role, since many characteristics of the suspensions (such as
the electrical, optical, magnetic, and adsorptive properties) are
mostly dependent upon the morphology, size distribution, and
strength of the aggregates.
1 To whom correspondence should be addressed. E-mail: s.tang@ic.ac.uk.
0021-9797/00 $35.00
Copyright ° C 2000 by Academic Press
All rights of reproduction in any form reserved.
For aggregation due to Brownian motion, two well-defined
regimes of irreversible colloid aggregation have been identi-
fied, those of diffusion-limited colloid aggregation (DLCA) and
reaction-limited colloid aggregation (RLCA) (2). The regimes
are determined by the collision mechanisms, i.e., a sticking prob-
ability (between monomers) equal to one leads to the DLCA,
while values much small than one give rise to the RLCA. The
addition of electrolytes into suspensions results in a decrease in
the repulsive force between the particles and an increase in the
sticking probability (3). DLCA occurs when there are negligible
repulsive forces between the colloid particles, causing particles
to stick upon contact and form highly tenuous structures. In con-
trast to DLCA, a substantial repulsive force remains between
particles during RLCA, so that the particles may collide many
times before sticking and the sticking probability approaches
zero.
The structures of colloidal aggregates formed by Brownian
motion exhibit dilation symmetry, and thus they are well de-
scribed as fractals (4, 5). Experiments have shown a universality
with respect to the aggregate fractal nature and the reaction kinet-
ics in the regimes of DLCA and RLCA. Theory and computer
simulations predict that the fractal dimensions (D3 ) of aggre-
gates are close to 1.8 for DLCA and 2.1 for RLCA (6); the
average aggregate mass should grow linearly in time (t) with
R ∝ t 1/D3 for DLCA and exponentially with R ∝ e0t for RLCA
during the initial stage of growth (7), where R is the hydrody-
namic radius of the aggregate and 0 depends on the experimental
conditions.
Despite Brownian motion taking place, shear and differential
sedimentation could also lead to particle collisions necessary to
produce aggregates, although in practice for a given situation
only one of these coagulation mechanisms is assumed to dom-
inate, depending on particle size, temperature, and shear rate
(8). Brownian motion is generally acknowledged to be impor-
tant only for small particles (≤1 µm); both shear and differen-
tial sedimentation have been suggested as predominating in the
coagulation of particles into larger aggregates. As fluid shear
changes the trajectories of the colliding particles and applies
forces on the aggregates, the clusters are subject to fragmenta-
tion, eventually leading to a breakup of the aggregates (9).
Previous studies of latex aggregation have been done either
on the aspect of size distributions (10–13) or on fractal natures
114
 FRACTAL MORPHOLOGY AND BREAKAGE OF AGGREGATES
(6, 9, 14). No result on disruption of latex aggregates by tur-
bulent capillary flow has been reported yet. The aim of this
work was to characterize the dynamic processes of aggrega-
tion/disruption of DLCA and RLCA latex aggregates by moni-
toring the changes in the size distribution and fractal dimension
of the aggregates, as well as to investigate the breakage of latex
aggregates in laminar and turbulent capillary flows. Three meth-
ods, image analysis, light scattering, and electrical sensing, were
used for measuring aggregate sizes in suspensions. The fractal
dimensions of latex aggregates were determined using the two-
slopes method (14–16) and a small-angle light scattering method
(17).
MATERIALS AND METHODS
Materials
The surfactant-free zwitterionic polystyrene latex particles
(batch 560) used in this work were purchased from the Interfa-
cial Dynamics Corporation, Portland, Oregon, USA. The diam-
eter of single particles was 1.28 µm ± 4.8% (data provided by
the manufacturer). The surface charge of the latex particles is
dependent on the pH of the medium. The isoelectric point (i.e.p.)
of the latex particles was known to be about 3.8.
Aggregation
The latex stock sample was placed in an ultrasonic bath (T-9,
L&R Manufacturing Company, New Jersey, USA) for about
20 min prior to aggregation, in order to break up doublets in
the suspensions (18). The latex aggregates were prepared by
mixing a 4.0% w/w suspension of latex with the appropriate
electrolyte. For DLCA, the initial volume fraction was φ0 =
1.9 × 10−5 and aggregation was induced by the addition of 1 M
McIlvaine buffer solution (19), which both neutralized the sur-
face charge and decreased the screening length. For RLCA,
φ0 = 7.6 × 10−5 and 0.2 M NaCl solution was added, decreasing
the screening length. The final solutions were gently mixed using
a blood tube rotator (SB1, Stuart Scientific Co. Ltd, UK). The
McIlvaine buffer solutions were composed of sodium hydrogen
orthophosphate (Na2 HPO4 ), citric acid (H3 C6 H5 O7 ), and potas-
sium chloride (KCl). The latter maintained the suspensions at
pH 3.8 with an ionic strength of 1 M. The final suspensions
were then kept at 25◦ C. The measurement of the sample was
taken at 20 min after initial preparation of the latex aggregate
solutions.
Shear Devices
The laminar shear device used was a double concentric cylin-
der (Rheomat 30, Contraves AG, Schaffhauserstrasse 580, CH-
8052, Zurich), consisting of two fixed cylinders mounted on a
base plate and a third rotating cylinder which was introduced
from the top into the gap between the fixed cylinders; a shear
rate up to 1711 s−1 could be generated. The turbulent capillary
flow apparatus used in this work consisted of a pump, a holding
115
flask, and a capillary test section connected into the loop with
wide-bore silicone tubing (20). The capillary tube had an inter-
nal diameter of 1.1 mm and a length of 22 mm. The flow rate
through the capillary tube was set at 3.9 × 10−6 m3 s−1 , in order
to produce turbulent flows (Re > 3500).
Particle Sizing
The image analysis system (Quantimet 600, Germany) was
used to measure aggregate diameters and cumulative size dis-
tributions in terms of length, the latter being required for the
two-slopes method for measuring fractal dimension. The im-
age analysis system consisted of a microscope (Leica DMR,
Germany) and a CCD-video camera (Sony, Japan). Images from
the CCD-video camera focused through the microscope were fed
to a personal computer for image analysis (21).
Size distributions based on solid volume and aggregate di-
ameters were measured using a Coulter Multisizer II (Coulter
Electronics Limited, UK) equipped with a 30-µm-orifice tube.
The conductive electrolyte used was Isoton II diluent (Coulter
Electronics Limited). All of the electrolytes were filtered with
a 0.45-µm cellulose acetate membrane filter prior to use. Data
from the Coulter Counter were transferred to a personal com-
puter for further data analysis using the Multisizer AccuComp
1.19 software provided by Coulter Limited.
A Malvern Mastersizer S (Malvern Instruments, UK) was
used to measure the aggregate diameters and the scattering an-
gular dependence of the scattered intensity of aggregates. The
Mastersizer employs a Reverse Fourier Optics configuration,
consisting of a laser light source (5 mW He–Ne laser with a
wavelength of 632.8 nm), an optic lens (300RF), and 45 photo-
sensitive detectors which allow the collection of light scattered
at angles from 0.03◦ to 46.4◦ . It has an accessible size range,
0.05–878.7 µm by employing the optic lens.
Fractal Dimension
The two-slopes method was used for fractal dimension mea-
surements (14–16). Particle size can be described using a size
distribution function n(L), defined by d N = n(L) d L, where d N
is the number of particles per unit volume with size in the range L
to L + d L. The characteristic length L can be any scale measure
of size, e.g., diameter, volume, and maximum or average length.
The cumulative size distribution N (L) is commonly used, de-
fined as the number concentration
R∞ of particles larger than a given
size L; i.e., N (L) = L n(L) d L. According to the definition,
cumulative size distributions in terms of aggregate length and
solid volume are equal for a given population of aggregates (16).
Based on this derivation, the fractal dimension D3 was then cal-
culated from the two slopes of the cumulative size distributions
in terms of maximum length and solid volume using (14–16)
D3 =
S(l)
, [1]
S(V )
116
where S(l) and S(V ) are exponents of the cumulative size distri-
butions N (l) = Al l S(l) , and N (V ) = A V V S(V ) based on aggregate
maximum length l and solid volume V , respectively, where Al
and A V are empirical constants.
The fractal dimension of aggregates was also measured us-
ing small-angle laser light scattering. The scattering intensity
I (Q) of the waves scattered from the aggregates obeys a power
law in the magnitude of the wave number Q (at a given scatter-
ing angle one probes fluctuations of Fourier spatial frequency)
(5, 17),
I (Q) ∝ Q −D3 ,
where Q is a function of the scattering angle θ and the wave-
length of laser light λ, Q = (4π n/λ) sin(θ/2) where n is the
refractive index of the medium. The fractal dimension D3 was
then obtained from the slope of the plot of log(I (Q)) against
log(Q).
RESULTS AND DISCUSSION
A Comparison of Different Sizing Techniques
The three sizing methods used in this work (image analysis,
Malvern Mastersizer, and Coulter Counter) measure different
properties of a particle, and thus they provide values for di-
ameters representing different kinds of averages (22). As the
difference between these diameters is small only if the stud-
ied system is of low polydispersity (18), standards must be
spherical for comparison between techniques. The surfactant-
free polystyrene latex particles having uniform size and shape
were chosen for this purpose.
Figure 1 shows the typical size distributions of single la-
tex particles measured using the three sizing techniques. The
number-based equivalent diameter distributions of a typical sus-
FIG. 1. Size distributions of single latex particles measured using the im-
age analysis system (IA), the Malvern Mastersizer (Malvern), and the Coulter
Counter (Coulter).
TANG ET AL.
[2]
FIG. 2. Effect of stirrer speed on the volume mean diameter of latex aggre-
gates formed in 1 M McIlvaine buffer solution using vortex mixing.
pension sample were estimated to be 1.08 ± 0.25, 1.14 ± 0.20,
and 1.16 ± 0.13 µm (mean ± standard deviation [SD]) for the
image analysis system (IA), Malvern Mastersizer, and Coulter
Counter, respectively. These data show consistency with the
value 1.28 ± 4.8% µm, which was provided by the manufac-
turer. At least 10 repeated measurments were carried out us-
ing each method in order to predict the reproducibility of the
techniques for sizing single latex particles; the average number
mean diameters D[1, 0] were determined to be 1.08 ± 0.01,
1.18 ± 0.01, and 1.19 ± 0.01 µm (±standard error [SE]), re-
spectively. The essentially identical results and measured size
distributions having similar shapes imply that these three tech-
niques give consistent results for size distribution measurements
and that such latex particles are a good standard to check the rel-
ative accuracy of different techniques.
Effects of Measurement Methods
Careful sampling should be made during measurements, as the
latex aggregates formed are very fragile. The shear history of the
aggregates during measurements is very important because the
aggregates could be broken up by the methods of measurement
themselves. In order to assess the effect of measurement meth-
ods on the aggregates, an easy mixing method was used in which
0.1% w/w latex aggregates were formed by mixing a 4.0% w/w
suspension of latex in distilled water with a 1 M McIlvaine
buffer solution at pH 3.8 using a vortex mixer for 3 s. All mea-
surements were undertaken 10 min after suspension mixing.
In measurements using the Malvern Mastersizer, a stirred
sampling unit is used to aid the flow of suspension into the
measurement cell inside the main unit. The stirrer speed of the
sampling unit was found to have a significant effect on the vol-
ume mean diameter D[4, 3] of latex aggregates formed in 1 M
McIlvaine buffer solution (Fig. 2). The lowest speed required to
keep the suspensions circulated is about 700 rpm. The measured
 FRACTAL MORPHOLOGY AND BREAKAGE OF AGGREGATES 117

FIG. 3. Effect of stirrer speed on the fractal dimension of latex aggregates FIG. 4. Volume and number mean diameters of latex aggregates formed in
formed in 1 M McIlvaine buffer solution using vortex mixing. 1 M McIlvaine buffer solution measured using the Coulter Counter at different
flow speeds.
diameter kept almost constant until stirrer speed reached about
1000 rpm; thereafter it decreased rapidly with increasing stirrer particles into the aggregate takes places, since they collide with
speed. The decrease in volume mean diameter with increasing the aggregate exterior and stick there.
stirrer speed implies that the larger aggregates had been broken For the RLCA aggregates formed in 0.2 M NaCl solution,
up into smaller aggregates. Figure 3 shows the effect of stirrer calculations based on the classical DLVO theory (23) predicted
speed on the fractal dimension of the latex aggregates. The frac-
tal dimension of the aggregates started to increase when the stir-
rer speed was greater than 1000 rpm, indicating that the aggre-
gates become more compact under high stirrer speeds. Therefore
a low stirrer speed (not more than 1000 rpm) should be chosen so
as to minimize the aggregate damage by the stirrer sampling unit.
Coulter Counter operations were found to have no signifi-
cant effect on size distribution measurements. Both volume and
number mean diameters of the latex aggregates formed in 1 M
McIlvaine buffer solution were found to be consistent even at
different flow speeds of aggregates through the 30-µm-orifice
tube fitted inside the Coulter Counter (Fig. 4). This implied that
no crucial damage occurred to the aggregates.

Images of DLCA and RLCA Aggregates

Figure 5 shows the images of typical DLCA and RLCA latex
aggregates, taken using the image analysis system at 400× mag-
nification of the objective with a resolution of 0.165 µm. The
binary images contain masks of the two-dimensional projections
of the aggregates.
DLCA aggregates were made in 1 M McIlvaine buffer solu-
tions at their isoelectric point (pH = 3.8). At this pH, both the
surface charges of latex particles have become neutralized, and
the electric double layers are almost completely suppressed by
the high concentration of electrolytes; the electrical repulsive
forces between particles are negligible, and thus the particles
stick upon contact to form highly tenuous structures as shown
in Fig. 5 (top). The formation of such a highly tenuous structure
can be considered to be due to a very sticky particle moving FIG. 5. Images of typical DLCA and RLCA latex aggregates taken using
in a “random walk” to the aggregate surface. No penetration of image analysis (magnification ×400).
118 TANG ET AL.
that substantial repulsive forces remain between the latex parti-
cles, so that the attachment probability approaches zero, and that
particles may collide many times before sticking, allowing par-
ticles to penetrate the aggregate exterior to form a more compact
cluster as shown in Fig. 5 (bottom).
Size Distributions of DLCA and RLCA Aggregates
Figure 6 shows a typical size distribution of the DLCA la-
tex aggregates with an initial volume fraction φ0 = 1.9 × 10−5
formed in 1 M McIlvaine buffer solution at pH 3.8. The prob-
ability densities, used in the plot to present the frequency of
aggregate diameter, were obtained by dividing the number per-
centage of aggregates in a certain range of bin size by the width
of the bin size. A larger probability density represents a higher
frequency in aggregate diameter. The shapes of the size distri-
bution curves as measured by the three techniques were slightly
different although they covered similar size ranges. The distri-
bution from the Coulter Counter had the highest peak, and there
were two modes in the distribution measured using image anal-
ysis. For the typical suspension sample, the size distributions in
terms of number were estimated to be 1.71 ± 1.12, 1.51 ± 0.88,
and 1.40 ± 0.92 µm (mean ± SD) by image analysis, Malvern,
and Coulter, respectively.
A similar trend in size distribution was found for the RLCA
latex aggregates with an initial fraction volume φ0 = 7.6 × 10−5
formed in 0.2 M NaCl solution at pH 5.5, as shown in Fig. 7. The
size distributions based on the number of a typical RLCA suspen-
sion sample were 1.91 ± 0.87, 1.69 ± 0.83, and 1.59 ± 0.75 µm
(mean ± SD) as obtained from image analysis, Malvern, and
Coulter, respectively. The differences in the shapes of the dis-
tribution curves as determined by the three techniques for both
DLCA and RLCA aggregates may be due to the polydispersity
of the aggregates and the different sampling points for differ-
ent methods. These differences can be significant if the studied
FIG. 6. A typical size distribution of DLCA latex aggregates formed in
1 M McIlvaine buffer solution at pH 3.8.
FIG. 7. A typical size distribution of RLCA latex aggregates formed in
0.2 M NaCl solution at pH 5.5.
suspensions are of a broad size distribution, like the aggregates
here (18); the number of aggregates being selected for each mea-
surement are in the order 105 > 103 ∼ 104 > 103 for the Coulter
Counter, Malvern Mastersizer, and image analysis system, re-
spectively.
The average values of the number mean diameter D[1, 0]
and standard error (SE) for both DLCA and RLCA latex aggre-
gates, measured using the three different techniques, are listed
in Table 1. Each number mean diameter reported here is the av-
erage of at least six repeated measurements of size distribution.
The mean diameters measured using the different techniques
are obviously different for DLCA or RLCA aggregates, respec-
tively, even taking the standard errors into account. For both
kinds of aggregates, the magnitude of the number mean diame-
ters decreased in the order IA > Malvern > Coulter, which can
be explained in terms of different parameters being measured by
the three techniques. The equivalent circle diameter is converted
from a two-dimensional aggregate projected area in image anal-
ysis, resulting in an overestimate in determining aggregate size
as the aggregates are not of spherical. The Coulter Counter mea-
sures the solid volume of aggregates and gives lower equivalent
spherical diameters for aggregates. In contrast, the fundamental
size distribution derived from laser diffraction in the Mastersizer
is encased volume based, including the volumes of the aggre-
gates themselves and of water inside the aggregate pores.
TABLE 1
Number Mean Diameters of Latex Aggregates as Obtained
with the Three Techniques
DLCA aggregates RLCA aggregates
Techniques D[1, 0] SE D[1, 0] SE
IA 1.68 0.08 1.87 0.05
Malvern 1.42 0.04 1.66 0.08
Coulter 1.39 0.04 1.58 0.03
 FRACTAL MORPHOLOGY AND BREAKAGE OF AGGREGATES 119

Fractal Dimensions of DLCA and RLCA Aggregates

Fractal dimension, the most important numerical parameter
in the concept of fractal geometry, is used to describe the spatial
structures of fractals. The magnitude of the fractal dimension of
aggregates is related to the aggregate morphology, as the fractal
dimension characterizes how aggregate properties change with
size. Aggregates tend to become more porous with increasing
size (24), resulting in fractal dimensions (D3 ) that are less than
3 (the value for a Euclidean spherical object). The lower D3
indicates that aggregates are more amorphous and less compact,
whereas aggregates that are more compact should have higher
fractal dimensions.
The two-slopes method based on size distributions was used
to determine the fractal dimension for latex aggregates. Figure 8
shows the cumulative size distributions of DLCA latex aggre-
gates formed in 1 M McIlvaine buffer solution at pH 3.8 in terms
of maximum length measured using the image analysis system
(top) and of solid volume measured using the Coulter Counter
(bottom). Two parameters required by Eq. [1], S(l) = 1.49 and
S(V ) = 0.82, were obtained from the slopes of the log–log plots
of cumulative number versus maximum length and solid vol-
ume, respectively. Hence, the fractal dimension of DLCA ag-

FIG. 9. Cumulative size distributions of RLCA latex aggregates formed in

0.2 M NaCl solution in terms of maximum length measured using the image
analysis system (top) and of solid volume measured using the Coulter Counter
(bottom).

gregates was estimated to be 1.81 ± 0.02 (±SE) by dividing

FIG. 8. Cumulative size distributions of DLCA latex aggregates formed in
1 M McIlvaine buffer solution in terms of maximum length measured using the
image analysis system (top) and of solid volume measured using the Coulter
Counter (bottom).
S(l) by S(V ); the standard error was calculated from the six re-
peated measurements. Using the same procedure for DLCA, two
slopes of S(l) = 2.39 and S(V ) = 1.16 and hence fractal dimen-
sions of D3 = 2.06 ± 0.03 (±SE) were obtained for RLCA latex
aggregates formed in 0.2 M NaCl solution at pH 5.5. The two
typical cumulative size distributions based on maximum length
and solid volume are presented in Fig. 9.
Small-angle laser light scattering was also used to determine
the fractal dimension of latex aggregates. Figure 10 shows the
scattering intensities as a function of wave number Q for DLCA
and RLCA latex aggregates formed in 1 M McIlvaine buffer
solution and 0.2 M NaCl solution, respectively; measured using
the Malvern Mastersizer. The scattering curves display a linear
relationship on a double logarithmic plot over at least two or-
ders of magnitude of the Q range, which is a “signature” of the
scattering from a mass fractal object (4). The fractal dimensions,
D3 = 1.82 ± 0.01 and D3 = 2.06 ± 0.01 (±SE), were obtained
from the slopes of log (intensity)–log (wave number) plots for
DLCA and RLCA latex aggregates, respectively. Both fractal di-
mensions are identical to those measured for the same DLCA and
RLCA suspension samples with the two-slopes method (Figs. 8
and 9).
120 TANG ET AL.
FIG. 10. Scattering intensities of DLCA and RLCA latex aggregates formed
in 1 M McIlvaine buffer solution and in 0.2 M NaCl solution, respectively,
measured using the Malvern Mastersizer.
The magnitude of all values for D3 was significantly smaller
than the value of D3 = 3 expected for Euclidean spherical ob-
jects and is experimental evidence of the fractal structure of both
types of latex aggregates. The fractal dimensions obtained for
these latex aggregates further support the evidence that there is
a universality of the fractal dimension for aggregates formed by
Brownian motion (6), i.e., the magnitude of the fractal dimen-
sion is independent of the type of colloid (the detailed chemical
nature of the colloid), and the fractal dimensions are D ∼ 1.8 and
D ∼ 2.1 for diffusion-limited colloid aggregation and reaction-
limited colloid aggregation, respectively.
Kinetics of DLCA and RLCA
DLCA and RLCA are recognized as fast aggregation and slow
aggregation in colloidal chemistry. Aggregation kinetics are sub-
ject to flocculation conditions, such as particle charge and con-
centration and flocculant type (10, 25). The trajectory of the ki-
netics of aggregation plays an important role in the formation of
aggregates, hence dominating aggregate morphology. Because
DLCA and RLCA are limited to Brownian motion, contribu-
tion from differential sedimentation, arising from a difference
in the density between latex particle and electrolyte, is undesir-
able. In order to eliminate particle sedimentation, aggregations
were carried out in a mixture of deuterium oxide (54%)/water
(46%)/electrolyte having a density of 1.055 g cm−3 identical to
latex particles.
Although lower particle concentrations reduce the likelihood
of particle sedimentation, it also results in unacceptably long ex-
perimental runs. An initial latex volume fraction of 1.9 × 10−5
was chosen for DLCA experiments, and the aggregation took
place over an 8-day period. Figure 11 shows the volume mean
and number mean diameters of DLCA latex aggregates formed
in 1 M McIlvaine buffer solution under nonisopycnic and isopy-
cnic conditions (HW). Both volume mean and number mean di-
ameters remained essentially constant during the first 2 h. This is
the reason that measurements for DLCA aggregates were made
within half an hour. The volume mean diameters increased lin-
early with time after 1 day, which was a consequence of the
formation of large aggregates; number mean diameters decayed
slightly. This would suggest that only a relatively small propor-
tion of aggregates are contributing to the observed increase in
the D[4, 3]. No significant differences in both mean diameters
of aggregates were detected between the systems with water as
solvent and those with a mixture of heavy water and water, al-
though obvious particle sedimentation was observed after 1 day
in those samples without heavy water. This may suggest that sed-
imentation leads to larger aggregates being broken up, resulting
in a decrease in the volume mean diameter; on the other hand,
some of broken-up aggregates may collide with each other again
to form large aggregates which compensate for the decrease in
the mean diameter.
Similar experiments were carried out for RLCA aggregates.
A slightly higher initial volume fraction of 7.6 × 10−5 was em-
ployed to provide a higher collision probability for the particles.
This ensured the formation of aggregates under reaction-limited
conditions, in which latex particles collide more times before
they stick to each other in 0.2 M NaCl solution as there are sub-
stantial repulsive forces remaining between the latex particles.
As can be seen in Fig. 12, both volume mean and number mean
diameters increased with time before reaching a plateau value
after 1 day; for this reason, all samplings of RLCA aggregates
took place after 24 h of aggregation. Obvious sedimentation
was observed after 29 h in the absence of heavy water. The data
are more scattered under nonisopycnic conditions than they are
under isopycnic conditions, which can be attributed to the sedi-
mentation.
The effect of sedimentation on aggregation was also eluci-
dated in terms of the fractal character of aggregates. Figure 13
FIG. 11. Number mean D[1, 0] and volume mean D[4, 3] diameters of
DLCA latex aggregates, formed in 1 M McIlvaine buffer solution in the presence
and absence of heavy water (HW), as a function of aggregation time, measured
using the Malvern Mastersizer.
 FRACTAL MORPHOLOGY AND BREAKAGE OF AGGREGATES 121

TABLE 2
DLCA Latex Aggregates in a Laminar Shear Device

Before shearing After shearing

Sample D[4, 3] D[1, 0] D3 D[4, 3] D[1, 0] D3

1 5.10 1.33 1.73 5.58 1.61 1.79

2 5.50 1.42 1.75 5.64 1.66 1.80
3 5.07 1.31 1.75 5.50 1.69 1.81
4 5.30 1.41 1.73 6.06 1.59 1.81
5 5.26 1.43 1.78 5.92 1.63 1.80
Mean 5.25 1.38 1.75 5.74 1.64 1.80
SE 0.08 0.03 0.01 0.11 0.02 0

creasing number of collisions, before a “steady stage” in terms

FIG. 12. Number mean D[1, 0] and volume mean D[4, 3] diameters of
RLCA latex aggregates, formed in 0.2 M NaCl solution in the presence and
absence of heavy water (HW), as a function of aggregation time, measured
using the Malvern Mastersizer.
shows the fractal dimensions of DLCA and RLCA aggregates
under both nonisopycnic and isopycnic conditions, which were
determined using the laser light scattering method. For DLCA,
the fractal dimensions of aggregates were almost consistent un-
der isopycnic conditions, but they decreased under nonisopy-
cnic conditions after 1 day, after which serious sedimentation
occurred. The decrease in fractal dimension after 1 day of ag-
gregation implied that aggregates collided with each other and
formed aggregates with more loose tenuous structures under the
shear influence introduced by sedimentation. For RLCA, fractal
dimensions steadily increased during the first 1 day, thereafter
reaching a plateau value which was then maintained over 7 days.
This indicated that aggregates with loose structures formed dur-
ing the early stages tended to become more compact with in-
of mean diameters and fractal dimension was achieved. A dif-
ference in D3 is seen between aggregates generated with heavy
water/water and water only as solvent, with the latter giving
higher D3 values.
Breakage of Aggregates in Laminar Flow
Breakage experiments on latex aggregates generated through
DLCA and RLCA mechanisms in 1 M McIlvaine buffer solution
and 0.2 M NaCl solution, respectively, were made 20 min and
24 h after aggregate generation since after these time periods
aggregates were considered to have reached an initial “steady
stage.” Measurements were carried out immediately using a
Malvern Mastersizer after 3 min shearing in a double concentric
cylinder shear device at a shear rate of 1711 s−1 (maximum rate
possible); results for DLCA and RLCA aggregates are listed in
Tables 2 and 3, respectively.
In the case of DLCA, the volume mean diameter D[4, 3],
number mean diameter D[1, 0], and fractal dimension D3 in-
creased slightly after shearing. The increase in aggregate mean
size is a consequence of the formation of large aggregates under
shearing; at this time, shearing facilitates latex aggregation (24).
The increase in D3 suggests that the presence of more compact
aggregates resulted from restructuring of the aggregates under
shearing.
By taking the standard errors over five repeated experiments
into account, no significant changes in D[4, 3], D[1, 0], or

TABLE 3
RLCA Latex Aggregates in a Laminar Shear Device

Before shearing After shearing

Sample D[4, 3] D[1, 0] D3 D[4, 3] D[1, 0] D3

1 3.01 1.60 2.05 2.78 1.67 2.05

2 2.70 1.55 1.99 3.08 1.55 1.98
3 2.92 1.58 2.04 2.69 1.60 1.96
4 2.52 1.45 1.97 2.60 1.67 2.00
5 2.82 1.40 2.03 2.51 1.38 2.05
FIG. 13. Fractal dimensions of DLCA and RLCA latex aggregates in the
Mean 2.80 1.52 2.02 2.73 1.57 2.01
presence and absence of heavy water (HW), as a function of aggregation time,
SE 0.08 0.04 0.01 0.10 0.05 0.02
measured using small-angle light scattering.
122 TANG ET AL.

TABLE 4 likely to have been the largest aggregates and to have represented
Effect of Passing DLCA Aggregates through a small proportion of the total aggregate population.
a Turbulent Capillary For RLCA aggregates, decreases in D[4, 3] and D[1, 0] after
the first pass through the capillary imply that larger aggregates
Before Pass 1 Pass 2 Pass 3 Pass 4
were disrupted into smaller ones. The value of D[4, 3] was not
D[4, 3] 4.91 3.32 2.72 2.65 2.60 reduced to that of single latex particles, indicating the presence
SE 0.24 0.25 0.06 0.14 0.13 of a small number of aggregates which were able to withstand
D[1, 0] 1.36 1.43 1.41 1.43 1.36 breakage after passage through the capillary. The D[1, 0] de-
SE 0.13 0.03 0.02 0.02 0.06
creased to 1.21 µm, close to that of single latex particles. The
D3 1.81 1.81 1.84 1.84 1.83
SE 0.03 0.02 0.02 0.02 0.03 fractal dimension of aggregates increased to ∼2.89, approaching
the value of 3 expected for Euclidean spherical objects, indicat-
ing the formation of single latex particles. Thus the majority
D3 have been found for RLCA latex aggregates before or af- of the aggregates were disrupted into primary particles after
ter shearing at a shear rate of 1711 s−1 . This would suggested one pass. On subsequent passes, no further changes in D[4, 3],
that the maximum shear force introduced by the double con- D[1, 0], and D3 were observed.
centric cylinder was not high enough to bring about aggregate For both DLCA and RLCA latex aggregates, significant ag-
growth, breakage, or restructuring (7). gregate breakage occurred in turbulent flows. These findings are
consistent with the prediction that aggregates can be disrupted
Breakage of Aggregates in Turbulent Flow when the Kolmogorov microscale of turbulence (here ∼5 µm)
is comparable with the aggregate size. It can be anticipated that
A turbulent capillary may provide much higher shear rates
aggregate disruption most likely takes place in a very small re-
than a laminar shear device. A high shear rate of 95209 s−1 and
gions close to the capillary wall where local energy dissipation
wall shear stress (=solvent viscosity × shear rate) of 85 Nm−2
rates could be higher (26).
were predicted in the capillary tube used in this work, assum-
ing the viscosity of water is 8.9 × 10−4 Pa s at 25◦ C, based on
calculations from a recommended model (20). The aggregate SUMMARY
suspensions were circulated around a flow loop, allowing their
passage through the capillary tube several times. Samples were The image analysis system (IA), Malvern Mastersizer, and
collected after each pass and introduced gently and promptly Coulter Counter can give consistent diameters for single latex
into the measurement cell of the Malvern Mastersizer for mea- particles but not for latex aggregates with wide size distributions;
surements of their size and fractal dimension. The results for the number mean diameters of latex aggregates measured using
DLCA and RLCA aggregates are listed in Tables 4 and 5, re- the three techniques are in the order IA > Malvern > Coulter.
spectively. All the results in the tables are based on three repeated Care should be taken during measurements to avoid the breakup
experiments. of aggregates by the techniques themselves.
For DLCA aggregates, the volume mean diameter D[4, 3] Latex aggregates formed under DLCA conditions had tenuous
of aggregates decreased significantly after the first two passes structures with lower fractal dimensions close to 1.8, while la-
through the capillary, implying that larger aggregates had been tex aggregates formed by RLCA possessed more compact struc-
broken up during shearing. No further decrease in D[4, 3] was tures with higher fractal dimensions close to 2.1. A mixture of
detected after the first two passes, indicating that the aggregates heavy water and water (54/46) instead of water alone as solvent
reached a minimum size and became resistant to the extent of minimized sedimentation, which occurred after about 1 day of
shearing. The relative consistency in the number mean diameter aggregation when water alone was used.
D[1, 0] and fractal dimension D3 suggests that those aggregates No disruption of either DLCA or RLCA aggregates was de-
which were broken up while passing through the capillary are tected after shearing with a laminar shear device at a shear rate
up to 1711 s−1 . Latex aggregates were found to be significantly
disrupted after passing through a turbulent capillary tube.
TABLE 5
Effect of Passing RLCA Aggregates through
a Turbulent Capillary ACKNOWLEDGMENT

Before Pass 1 Pass 2 Pass 3 Pass 4 Funding was provided by the BBSRC.

D[4, 3] 2.74 1.78 1.69 1.81 1.72

SE 0.15 0.09 0.12 0.11 0.09
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