Fractal Structure of Hematite Aggregates

ROSE AMAL, J U D Y A. RAPER, AND T. D A V I D W A I T E *'l

University of New South Wales, School of Chemical Engineering, P.O. Box 1, New South Wales 2033, Australia,
and *Australian Nuclear Science and Technology Organization (A.N.S. ~ 0.), Private Mail Bag 1, Menai,
New South Wales, Australia
Received December 15, 1989; accepted April 18, 1990

The structure of hematite aggregates, considered to behave as fractal objects, is studied using static
light scattering methods. The fractal dimension obtained from the scattering exponent is found to be
dependent on the aggregationmechanism and it ranges from 2.3 for rapid (diffusion limited) to 2.8 for
slow (reaction limited) aggregation. Polydispersityand restructuring of aggregates do not affect the re-
lationship between scatteringexponentand fractal dimension in these aggregates.Excellentcorrespondence
over a range of temperatures and ionic strengths is obtained between results of experiments usingdynamic
light scattering to determine aggregationkinetics and those predicted using a modified Smoluchowski
model incorporating fractal dimensions. © 1990AcademicPress,Inc.

INTRODUCTION structures of oxide materials. Oxides occur

The structure of solid materials has impor-
tant implications in many natural and com-
mercial processes. Physical parameters of solid
materials such as size and porosity are deter-
mined by structure as are chemical parameters
such as solubility and reactivity. Highly struc-
tured materials such as crystalline solids can
readily be grouped according to their sym-
metries. However, such groupings are not ap-
propriate for randomly formed materials such
as aggregates. This lack of apparent symmetry
has greatly impeded the progress in under-
standing random morphologies. However, in
the last few years, the study of materials with
random structures has reemerged due to the
efforts of Benoit Mandelbrot, who described
the complex patterns in nature in terms of
fractal geometry ( 1 ). The random structures
described by Mandelbrot are both macro-
scopic (e.g., clouds, coastlines), and micro-
scopic (e.g., aggregates, polymers). This in-
vestigation is concerned with the microscopic
1To whom correspondenceshould be addressed.
widely in nature and form the basis of many
ceramic and catalyst preparations.
In previous work (2), dynamic light scat-
tering has been used to study the aggregation
kinetics of hematite particles. The results ob-
tained were compared with a model based on
theoretical considerations accounting for dif-
fusion, interparticle repulsive forces, and the
nature of packing within the aggregated ma-
terial (and referred to below as the "modified
Smoluchowski" model). Successful prediction
of rapid (diffusion limited) aggregation kinet-
ics was obtained assuming that the resultant
aggregates behaved as fractals with a fractal
dimension of 2.3. A somewhat higher fractal
dimension appeared to be appropriate for ag-
gregation under ionic conditions where a re-
pulsion barrier exists (reaction limited aggre-
gation ) (see Fig. 1 ). While the connection be-
tween kinetics and structure for colloidal
aggregates is not universally established (3),
our results for hematite indicate that the fractal
dimension depends on the aggregation kinetics
and hence must be determined a priori in or-
der to be used in predictive models of aggregate
growth.

158
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 STRUCTURE OF HEMATITE AGGREGATES
1200
=E
.S • • DLA rote
1000
800
/ • -#/ j~.1
'~ 600 t / ~ / ~ ' ~ ' / ~ ~ J ~ J• J J ~
~" 400 lJ &/~f"
/ " j ~ Q intermediate rate
~>, //'~" --
200 ~ 1 - - - model dF=2.3
,i,
0 10 20
Time (min)
FIG. 1. Comparison of hematite aggregate size mea-
surements obtained using dynamic light scattering with
size predicted using Smoluchowski's kinetic equation in-
corporating an assumption of fractal geometry of the ag-
gregate. Model results in a fractal dimension (dE) of 2.3
for the diffusion limited case and dr of 2.3 and 2.4 for the
reaction limited case are shown.
In this work static light scattering is used to
study the structure of colloidal hematite par-
ticles induced to aggregate at different rates by
altering solution conditions (electrolyte con-
centration and temperature). The aggregates
are considered to possess a fractal structure
and the fractal dimension is measured at dif-
ferent electrolyte concentrations and over a
range of temperatures.
THEORY
A fractal object is a rugose object whose ru-
gosities show up at any length scale and is thus
considered self-similar (i.e., the structure of
the object is invariant to a change of scale).
In the general theory of fractals, the fractal
dimension is defined as a n u m b e r which has
no special reason to be an integer and which
quantitatively measures the more or less ru-
gose aspect of the object.
M a n y more specific definitions of the fractal
dimension exist. One of them, the Bouligand
definition (4), consists of trying to cover all
the matter of the object, using the m i n i m u m
number of overlapping spheres of given radius,
r, then reproducing the operation with smaller
and smaller spheres. The variation of the min-
imal n u m b e r of spheres, N~, when r tends to
0 is studied. For a line, Nr grows as r-1; for a
159
smooth surface, Nr grows as r-2; etc. A fractal
--- model dF=2.3 dimension, dr, of a fractal object can then be
defined as
/
Nr oc r -dr, [1]
where 1 < dv < 3.
model dF=-2,4
The concept of fractal dimension is only
properly defined when using an asymptotic
50 40 limit to infinitely small lengths. However,
practically, when considering real physical
objects, there always exists a lower limiting
characteristic length below which the object
can not be described as a fractal. In particular,
when considering aggregates, the natural lower
cut off is simply the radius of the primary par-
ticle, r0.
Scattering experiments give access to the
position correlations between particles in the
aggregate and consequently appear to be a very
useful tool to measure the fractal dimension
(4). In a scattering experiment, a beam of light
of intensity, I0, is directed onto a sample and
the scattered intensity (photoncounts) is mea-
sured as a function of an angle O to the inci-
dent direction. The incident and scattered
beam are characterized by the m o m e n t u m
transfer Q (5), with
47rn s i n ( O / 2 )
Q = IQI = , [2]
X0
where X0 is the wavelength in the vacuum,
and n is refractive index of medium.
The intensity scattered ( I ~ ) from a single
fractal aggregate of mass M can be related to
two factors that describe the aggregate struc-
ture (6),
1~ ~ M 2 p ( Q ) S ( Q ) , [3]
where P ( Q ) is the form factor, and S ( Q ) the
interparticle structure factor.
The form factor is related to the shape of
the particle and the contrast. The contrast is
defined as p(r) - p0, the difference between
the scattering properties of the particles, as
measured by the microscopic n u m b e r density
p(r) at the point r, and the equivalent quantity
po of the solvent. In light scattering this density
Journal of Colloid and Interface Science, Vol. 140, No. 1, N o v e m b e r 1990
160
is identified as the refractive index (7). For a
monodisperse system with particles of radius
r0 and density p, the form factor is given as
P ( Q ) = (p - po) 2
× (3 sin(Qro) - Qrocos(Qro)] 2
(Qr~ ].
At small Q, when QRg < 0.5, the above equa-
tion can be simplified to the Guinier approx-
imation (8),
P ( Q ) ~ ( P - P°)2exp
where Rg is the radius of gyration of a sphere,
ro/Rg = ( 5 ~ . At Q large, averaging the
form factor, P ( Q ) , by assigning sin(x)
= cos(x) = V(1/2), gives the general Porod
law (4), and Eq. [ 4 ] becomes
9(p - p0) 2
P(Q)- 2(Qro) 4
The interparticle structure factor, S(Q), which
takes into account the interparticle correla-
tions and describes the spatial arrangement of
the particles, is given by
S(Q) = 1 + uo f [g(r)- II
× exp(iQ.r)dr,
where Np is the number density of particles
and g(r) is the pair correlation function rep-
resenting the probability of finding a particle
at a distance r from a particle situated at the
origin. For fractal objects within an isotropic
system, Chen and Teixeira (9) derived the
structure factor equation introducing a cut off
value (~) to describe the behavior of g(r) at
large r in order to avoid a divergence in the
evaluation of S(Q) (6). The cut off value (~)
generally represents the characteristic distance
above which the mass distribution does not
follow the fractal law and it is related to the
radius of gyration by Rg = V(dv(dv + 1 )/2)
× ~. The structure factor can then be expressed
by (9)
Journal of Colloid and Interface Science, Vol. 140, No. 1, November 1990
AMAL, RAPER, AND WAITE
S(Q) = 1
dFP(dv - 1 )sin((dv - 1 )tan-l(Q~))
+
(Qro)dF(1 + 1/Q2~2) av-~/2 ,
[7b]
where P(x) is the gamma function o f x .
[4]
At large Q ( Qro >>1 ), S( Q) is approximately
equal to 1 and only the scattering due to in-
dividual particles is seen, i.e., I ( Q ) oc P ( Q ) .
At Q small compared to l /r0, but large com-
pared to 1/R ( 1 / R .~ Q ~ 1/ro), P ( Q ) ~ (p
- o0)2, hence I ( Q ) depends only on its struc-
3 , [5] ture factor. Equation [7b] can then be sim-
plified to
S ( Q ) oc O-av [8]
when R is much larger than ro. The above
equation which only applies in the range 1/R
Q ~ 1/r0 is often used to analyze the scat-
tered intensity by a fractal object.
To interpret scattering curves it is necessary
[61 to distinguish between object and surface
scattering. In systems without distinct surfaces,
the fractal dimension dv relates mass, M, to
radius of gyration, R, by (5)
M ( R ) ~ R dv. [91
Objects obeying Eq. [9] are called mass or
volume fractals (10) and typically include
polymers, diffusion limited aggregates, and
[7a] percolation clusters. In contrast, objects that
are uniform, such that no scattering occurs
from the bulk and only from the surface, are
called surface fractals. For this case, Bale and
Schmidt ( 11 ) have shown that,
S ( Q ) ~ QdS-6 [10]
where ds is the surface fractal dimension which
relates surface area, A, to size,
A ( R ) ~ R ds, [11]
and 2 < ds < 3. In a porous and ramified sam-
ple, where both the object and its surface can
be thought of as having ffactal structure, the
scattering follows a Q-dr law at low Q, while
at larger values of Q, the scattered intensity
exhibits a Qas-6 dependence (12). In principle
 STRUCTURE OF HEMATITE AGGREGATES 161

then, it should be possible to distinguish be-
tween surface and mass fractals from the re-
sults of a scattering experiment ( 10 ). However,
as noted by Teixeira (12), the crossover be-
tween the two regimes is not distinct if dE is
between 2 and 3.
EXPERIMENTAL
Samples of nearly spherical hematite par-
ticles were prepared by the forced hydrolysis
of a homogeneous iron salt solution under
strictly controlled conditions ( 13, 14). He-
matite samples were diluted to 1.95 X 1 0 - 4 M
(approx. 2.25 × 101° particles/ml) in order
to avoid multiple scattering.
The mean hydrodynamic diameter and
scattered intensity (in terms ofphotoncounts)
of the aggregates were measured with the Mal-
vern 4700 PCS system, utilizing a 15-mW,
633-nm H e - N e laser. As described in detail
elsewhere (2), the mean hydrodynamic di-
ameter (which is related to the translational
diffusion coefficient of the aggregate) is readily
obtained from the slope of the logarithm
transformed autocorrelation function of scat-
photoncount rates throughout the static light
scattering experimental period.
RESULTS AND DISCUSSION
The effects of ionic strength and tempera-
ture on variation in aggregate size with time
are shown in Figs. 2a and b. At 50 m M KC1,
the repulsion barrier is still significant, so the
aggregation rate increases markedly with tem-
perature since it affects both the repulsive en-
ergy as well as the rate of particle diffusion.
Previous modelling of the effect of temperature
on the aggregation process indicated close
correspondence between experiment and the-
ory with the major influence of temperature
being on the repulsive energy of interaction
and hence on the stability ratio (15). Indeed,
for 50 m M KC1, the stability ratio is on the
order of 103 at 25°C and decreases to 102 and
1 for increases in temperature to 35 and 55°C
respectively. The change in aggregation rate
1500
E
c a. [KCI] = 50raM
• 25°C
I 55°C

tered light. Aggregation and scattering exper- 10o0!

.£ OO
iments were conducted at a zeta potential of E O0
48 + 2 mV (corresponding to a suspension of 500
OOO •
o &A&
pH 3) at temperatures of 25, 35, and 55°C,
and salt (KC1) concentrations of 50, 60, and A
80 m M . For each temperature and salt con- 0
20 40 60
centration, the variation in mean hydrody- Time (rain)

namic diameter with time was determined by

dynamic light scattering measurements every 1500
2-3 min for up to 1 h. The intensity (photon- b. [KCl3 = 8 0 ~ M
vc • 25°C
counts) of scattered light was measured at an- • 55°C

gles ranging from 15 to 90 ° and for 5 s at each ~5

1000
• 0O •
.u
angle. In order to comply with conditions 0 A •
governing the relation of scattering exponent
g 50o • OAOOA
and fractal dimension (discussed further be- =>,
low), these static light scattering experiments g
were carried out when the aggregates, con- 0 i
5 10 15 20
taining a large number of primary particles, Time (rain)

were typically about 1 #m in diameter. At this

stage, the rate of growth of the aggregates was
slow, and significant settling (sedimentation)
did not occur. This was indicated by stable
FIG. 2. Effect of temperature on aggregation of hematite
particles (a) under reaction limited conditions ([KC1] = 50
m M ) , and (b) under diffusion limited conditions ( [ KC1]
= 80 raM).
Journal of Colloid and Interface Science, Vol. 140, No, 1, November 1990
162 AMAL, RAPER, AND WAITE

attributable to temperature dependence of dif- TABLEI

fusion was found to be minor. At 80 m M K C 1 , Scattering Exponents (_+1~) Obtained from Static Light
attractive van der Waal forces dominate and Scattering Studies of Hematite at Different Ionic Strengths
the temperature affects diffusion only with a and Temperatures
resultant relatively insignificant effect on ag- KCI concentration
gregation rate. Temperature
The plots of scattered intensity (photon- (°C) 50 m M 60 m M 80 m M

count) as a function of angle for 50, 60, and

25 2.86 + 0.05 2.55 +_0.06 2.33 _+0.06
80 m M KC1 at different temperatures are 35 2.56 +_0.06 2.36 _+0.04 2.30 _+0.07
shown in Fig. 3a, b, a n d c, respectively, with 55 2.37 _+0.07 2.32 -+ 0.04 2.31 4- 0.03

0 the slopes of the graphs representing the fractal

0 25°C, slope=-2,86 dimension. The fractal dimensions obtained
8 • 35°C, slope=-2.56
(and summarized for comparative purposes
6 55°C, slope=-2.37
in Table I) vary with aggregation mechanism.
For example, at 25°C, for slow ("reaction
o 0
limited") aggregation (50 m M KC1) the fractal
0
8 dimension, dF, is 2.86 +_ 0.05; for aggregation
approaching the diffusion limited regime (60
a, [KCI] = 50mM m M ) , dF is 2.55 + 0.06, while for diffusion
,
0.003 Q ( n m - 1 ) 0'010 limited aggregation (80 r a M ) , dF is 2.33
+ 0.06. The fractal dimension obtained here
0 by static light scattering in the diffusion limited
• 0 25°C, slope=-2.55 case is close to the value of 2.3 previously
Ex 0 • 35°C, slope=-2.36
found to give good agreement between the
0 LX 55°C, slope=-2.32
modified Smoluchowski aggregation model
d 0
gg zx • 0 and experimental data obtained by dynamic
g 0 light scattering (2).
?_ A 0
At the slow rate of aggregation in which the
a.
W
0 probability of sticking is low, the aggregating
b. [KCE] : 6omu ~ clusters will have the opportunity to explore
A
0.003 0,010
a large n u m b e r of possible mutual configu-
Q (rim - 1 ) rations, which leads to some interpenetration,
and therefore denser aggregates. In contrast,
0 25°C, slope=--2.33 in diffusion limited aggregation, the interior
• 35°C, slope=-2.30 of the clusters is effectively screened from
LX 55°C, slope=-2,31
m
penetration since approaching particles readily
adhere to other particles (high sticking prob-
U
=
o
A ability) resulting in a more tenuous structure.
"6 zx The marked decrease in packing density on
"E'
ZX changing from aggregation under diffusion
a limited conditions to conditions under which
c [KCE] = 80ram

0,003 0.010
a repulsion barrier to aggregation is present,
Q (nm - 1 ) is clearly seen in the transmission electron mi-
FIG. 3. Effectof temperature on scatteringexponent for croscope prints in Fig. 4.
hematite aggregatesformed in (a) 50, (b) 60, and (c) 80 At higher temperatures, the fractal dimen-
mM KC1. sions of the aggregates in 50 and 60 m M KC1
Journal of Colloid and Interface Science, Vol. 140, No. I, November 1990
 STRUCTURE OF HEMATITE AGGREGATES
FIG. 4. Transmission electronmicroscope(TEM) plates of hematite aggregatesformed at 25°C in (a) 50
and (b) 80 mM KC1.
are significantly lower than at 25 °C (see Table
I). As temperature increases, the repulsion
barrier decreases and the sticking probability
increases, resulting in much less penetration
to the interior of the clusters with resultant
formation of more tenuous aggregates. As ex-
pected in the absence of significant interpar-
ticle (or interaggregate) repulsion, temperature
has little effect on the fractal dimension of ag-
gregates formed under diffusion limited con-
ditions (80 m M KC1) with values of dv at 25,
35, and 55°C all about 2.3. Similar effects of
temperature on aggregate structure have re-
cently been reported by Tang et al. (16) in
studies of fractal structure of silica aggregates.
As discussed previously (2), the fractal di-
mension of 2.3 obtained here under diffusion
limited aggregation conditions (no repulsion
barrier) is only slightly less than the value of
2.53 expected from theoretical considerations
for aggregates growing via particle-cluster dif-
fusion limited aggregation (DLA) ( 17, 18 ). In
163
DLA, clusters grow purely from monomers,
which approach the cluster with a random
walk trajectory. The random-walk nature of
the approaching m o n o m e r favors growth on
the extremities of the cluster, and thus, open,
ramified geometries develop. Cluster-cluster
aggregation (CA) is a variation of DLA where
clusters grow from existing clusters as well as
from monomers. In CA, dv is reduced sub-
stantially because two fractals are extremely
unlikely to penetrate without contact. Widely
spread, loosely packed structures are produced
in cluster-cluster aggregation. Fractal dimen-
sions on the order of 1.75 are to be expected
where cluster-cluster aggregation is the dom-
inant mechanism (19, 20). The fractal di-
mensions of dv > 2.3 obtained here are con-
sistent with reaction limited particle-cluster
aggregation. These values are generally con-
siderably higher than results reported by other
workers for aggregates of silica and gold for
which cluster-cluster aggregation appears to
Journal of Colloid and Interface Science, Vol. 140, No. 1, November 1990
 164
be a more appropriate model (21, 22, 3 ), pre-
sumably because of the low particle densities
used in studies reported here.
Restructuring within the aggregate following
initial coalescence with a resultant increase in
fractal dimension over time has been observed
for silica (23) but does not appear to be im-
portant in the case of the hematite aggregates
considered here. No systematic change in
scattering exponent with time was observed
once the aggregates had reached approxi-
mately one micron diameter and before sig-
nificant gravity settling occurred. However, it
should be recalled that the approximation
S(Q) oc Q-dr (Eq. [81) is only valid for 1/R
Q ~ 1/ro and R >> r0; i.e., the cluster size
must be large compared to the primary particle
size (at least an order of magnitude larger) for
Eq. [ 8 ] to hold. Outside of these conditions,
the slope of a log (scattered intensity) vs log
Q plot cannot be considered equivalent to the
fractat dimension of the aggregate and may
well change with size and time. Indeed, as
shown in Table II, the slopes of log-log plots
for hematite aggregates of increasing size over
time (at 60 m M KC1) increase from - 1 . 8 9 to
-2.54. The effect of cluster size on light scat-
tering can be obtained from theory using the
interparticle structure factor expression pre-
sented previously (Eq. [ 7 ] ). Calculated scat-
tered intensities as a function of scattering
function, Q, for aggregates of various sizes and
fractal dimensions, dF, of 2.3, 2.5, and 2.8 are
shown in Figures 5a, b, and c, respectively.
From these figures, it is clear that the scattered
intensity is essentially linear on a log-log plot
in the range 1/R <~ Q <~ 1/ro. However, as
stressed above and is apparent from Table III,
Effectof Cluster Size on the Scattering Exponent Obtained for Hematite Aggregates
with dF = 2.54 (t = 25°C, [KC1]= 60 mM)
Cluster diameter (nm) 190
Scattering exponent - 1.89
Standard deviation 0.04
Journal of ColloM and Interface Science, Vol. 140, No. 1, November 1990
AMAL, RAPER, AND WAITE
the slopes of these plots within this Q range
correspond to fractal dimension estimates for
large cluster size only. The requirement that
R ,> ro is particularly severe at lower fractal
dimensions.
The fact that scattering occurs from a broad
distribution of particle sizes (i.e., a polydis-
perse system) could possibly mislead the de-
termination of dv from the scattering expo-
nent. To compute the effect of polydispersity,
the single particle intensity (IM is approxi-
mately equal to MaS(Q), since P(Q) is con-
stant for the range studied) must be averaged
over the number distribution of particles
N(M) (10, 24), i.e.,
I ~ f MaN(M)S(Q)dM, [12]
where M i s the mass and S ( Q ) is the structure
factor described earlier. The number distri-
bution may range in form from a bell-shaped
curve (Gaussian distribution), to a very broad
power-law decay. If the distribution is narrow
(as in the case for a bell-shaped curve), it will
not change the asymptotic fractal behavior
S(Q) ~ Q--dF(10) but this may not be the
case for power-law polydispersity. Here, the
number distributions of masses can be written
generally, for fixed time, in the form (24-26)
N(M) ~ M-Tf(M/Mc), [13]
where ~-is termed the polydispersity exponent,
Mc is some characteristic cluster mass, and
f(M/Mo) is a large-mass scaling (or cutoff)
function for the number distribution where
f ( x ) must decay faster than a power law for
x >> 1 and is a simple constant for x ~ 1. An
exponentially decaying function satisfies these
TABLE II
320 400 485 710 800 1100
-2.10 -2.13 -2.18 -2.31 -2.35 -2.54
0.07 0.03 0.12 0.03 0.05 0.06
 STRUCTURE OF HEMATITE AGGREGATES 165

~"-.~ Average size (nm) terized by the appearnace of an "infinite"

\ ~.. -- -- 300 cluster at some finite time (10)).
~'-~ ~'.\ -- -- 500
"" ~\~.~. - - - lOOO Since the mass M is proportional to the
d ~ ' ~ ~.~ . . . . 1500
"~,~.
number of particles, n, in the aggregate, the
number distribution of particles, N ( M ) , can
--...~-~ be reexpressed in terms of n (5), i.e.,
o_
""-Z~'~.
N(n) ~ n-rf(x), [15]
a, d F = 2 . 3 --~-~_._
. ,
where f ( x ) is the scaling function defined
" ~
0.002 0,005 0.010 above. Theoretical number distributions for
Q (nm - 1 )
the cases studied here can be obtained using
Average size (nm)
the modified Smoluchowski model (2). For
~.~ 300 both diffusion limited and reaction limited
'~-.~.. 500
"~" ~."< ~ . . 1000
aggregation, the computed number distribu-
"~- ~-. 1500 tions are observed to be less polydisperse than
o: "~-~%. expected for power-law behavior. Under both
o ~ ~'~.~
~ ~.%. diffusion limited conditions and slow aggre-
o
"--.Q ~.~.
gation the computed number distributions
take on the nonmonotonic form (Fig. 6). This
a. d F = 2 . 5 , ~ ~
case can be described by the above scaling
0.002 0,005 0,010 form (Eq. [ 13 ] ) with 7- = 0 and a scaling func-
O (rim - 1 )
t i o n f ( x ) ~ 1 for x < 1 a n d f ( x ) < 1 for x
>> 1. Thus, under conditions considered here,
,;~ Average size (nm)
~-~ K~. - - - - 300 the polydispersity in aggregate size is not great
\\\. -- -- 500
enough to modify the fractal dimension esti-
z . . . lOOO.

"g" --.~\\'4\ --. --1500 mates obtained from static light scattering
studies. This is no doubt attributable, to a large
extent, to the low particle densities used in
these studies.
--= ~ ~ ~.~.,~.
As mentioned earlier, we have previously
o, dF=2.8 . ,
used dynamic light scattering methods to study
0.002 0.005 0.010 the aggregation kinetics of hematite particles
Q (nm - 1 )
and have compared the results with a model
FIG. 5. Calculateddependencyof scatteredlightintensity based on theoretical considerations accounting
on scatteringfunction(Q) for aggregatesof increasingsize for diffusion, interparticle repulsive forces, and
and fractal dimension(dr) of(a) 2.3, (b) 2.5, and (c) 2.8. the nature of packing within the aggregated
material (2). G o o d correspondence between
theory and experiment was obtained for the
conditions and represents a suitable scaling
diffusion limited case for which R ~ t 1~at
function. With these definitions, it is easily
(with dF = 2.3) was appropriate. In accord
shown (24) that, for mass fractals,
with results for simulated clusters, an approx-
I ~ O -dF(3-r), 7" > 2 [14a] imate equivalence between hydrodynamic ra-
dius (Rh) and radius of gyration (Rg) was as-
I ~ Q--dF ~- < 2. [t4b]
sumed for the diffusion limited case. However,
Thus polydispersity only has an effect on scat- equivalence of Rh and Rg is generally not the
tering exponent when r is greater than 2 (the case with Rh/Rg being dependent on the nature
so-called "gelation" regime which is charac- of packing. For example, Chen a n d Meakin

Journal of Colloid and Interface Science, Vol. 140, No. 1, November 1990
166 AMAL, RAPER, AND WAITE

TABLE III
Effect of Cluster Size on the Theoretical Scattering Exponent for Aggregatesof Different
Fractal Dimension (Using Eq. [7])
Cluster size (tam)

dv 300 400 500 700 1000 1500

2.3 - 1.84 - 1.94 -2.06 -2.12 -2.19 -2.22

2.5 -2.10 -2.23 -2.28 -2.31 -2.48 -2.51
2.8 -2.63 -2.82 -2.89 -2.90 -2.85 -2.81

(28, 29) obtained values for Rh/Rg of 0.875 from the dynamic light sca~ering results) and
and 0.97 for simulated clusters with dv = 1.78 corresponding Rh/Rg ratios. Note that the
and 2.1 respectively and for a solid sphere (dr fractal dimensions obtained by the nonlinear
= 3), the Rh/Rg ratio becomes ~ . least square fitting (Table IV) are in good
While the dv values presented above have agreement with those obtained from the slopes
been obtained straightforwardly through the of the log transformed scattering data (i.e., Eq.
relationship S(Q) ~ QdF, nonlinear least [8], Table I). The increase in Rh/Rg with in-
square fitting of I ( Q ) = KP(Q)S(Q), where creasing packing density (increasing dr) is in
P(Q) and S(Q) are as expressed in Eqs. [6] agreement with the results for simulated clus-
and Eq. [ 7b ] and K is a constant, to the static ters (28, 29), but the magnitude of Rh/Rg is
light scattering data is possible and yields, in slightly lower. However,/~h//~g should not be
addition to fractal dimensions, estimates of the compared directly to the Rh/Rg value calcu-
average radius of gyration/~g over the period lated for a single fractal cluster, since/~h and
of analysis. Values of dE and/~g obtained by /~g reflect different m o m e n t s of the cluster
Q u a s i - N e w t o n nonlinear least squares anal- mass distribution (30). As can be seen from
ysis of the static light scattering data for he- Fig. 7, good correspondence between theory
matite aggregated to approximately steady and experiment is obtained when these values
state sizes in 50 m M KC1 and at temperatures of dv and Rh/Rg are used to obtain aggregate
of 25, 35, and 55°C are given in Table IV as size estimates using the modified Smolu-
are the m e a n hydrodynamic radii,/~h (obtained chowski model. This result is particularly sat-
isfying since the model predictions are ob-
tained quite independently of the experimental

Zz
.
0.004

0.005
\ data, i.e., no fitting parameters are required.

.£
TABLE IV
oo02 \
Ratio of Mean HydrodynamicRadius to Radius of Gy-
oNe
=E 0.001 \o\ ° ration of Hematite AggregatesFormed in 50 mM KCI and
Different Temperatures (Thus Different Fractal Dimen-
, -- - - e _ o ~ _ o _
sions)
0.000
200 400 600 800 1000
n particles/cluster Temperature (°C) dr /~b (nm) / ~ (nm) /~b/J~g

FIG. 6. Computed number distribution for hematite ag-

25 2.81 343.1 405.5 1.18 _+0.1
gregatesobtained using the modifiedSmoluchowskimodel
described in Ref. (2) under diffusion limited conditions 35 2.62 556.5 585.1 1.05 _+0.07
55 2.37 712.0 665.2 0.93 + 0.1
(t = 25°C, [KC1] = 80 mM).

Journal of Colloid and Interface Science, Vol. 140, No, l, November 1990
 STRUCTURE OF HEMATITE AGGREGATES
~1400
E Excellent correspondence over a range of
• 25°C
1200
• 35°C •
~I000 • 55°C ~ ~ .~.,,~..-.-~
o
~5
._o 800
E
600
o 400
~z
= 200
z~ 0
0 5 10 15 20 25
Time (rain)
FIG. 7. Comparison of aggregation kinetics for hematite
at 25, 35, and 55°C as determined by dynamic light scat-
tering with kinetics predicted using the modified Smolu-
chowski model described in Ref. (2). Model predictions
in which an equivalence of/~h and/~g is assumed are pre-
sented (---) as are predictions incorporating Rh/Rg ratios
where its Rg is determined by nonlinear least-squares fit-
tings ofEq. [7b] to static light scattering data (see Table
IV) ( - - ) .
CONCLUSION
In this work, the fractal dimension of he-
matite aggregates has been measured using
static light scattering techniques. Increasing
salt concentration was found to increase the
aggregation rate and the probability of adhe-
sion, yielding increasingly tenuous structures
and thus lower fractal dimensions. For ex-
ample, at 25°C scattering exponents of 2.86
_+ 0.05, 2.55 + 0.06, and 2.33 + 0.06 were
obtained for KC1 concentrations of 50, 60, and
80 m M , respectively, once the scattering
function (Q) was significantly greater than 1 /
R and R >> r0.
The effect of temperature on kinetics and
structure of aggregating hematite particles fol-
lows the expected trend. Increasing the tem-
perature increases the aggregation rate and
decreases the packing density of the aggregates.
The effect is more noticeable at salt concen-
trations (50 m M for this system) where both
diffusion and repulsion, which will both be af-
fected by temperature, are important contrib-
utors to the aggregation process. Restructuring
or polydispersity effects do not significantly af-
fect these fractal dimension estimates.
167
temperatures and ionic strengths is obtained
between aggregation kinetics as determined by
dynamic light scattering and kinetics predicted
using a modified Smoluchowski model incor-
porating fractal dimensions as determined by
static light scattering.
30 35 ACKNOWLEDGMENTS
The Australian Institute of Nuclear Science and Engi-
neering (AINSE) is thanked for the financial support to
one of the authors (R. Amal). In addition, the continuing
assistance provided by the Australian Water Research Ad-
visory Council (AWRAC) and the help of Mr. R. Blake
in transmission electron microscopy (TEM) are gratefully
acknowledged.
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