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Abstract
The dynamic behavior of concentrated suspensions (up to a solids volume fraction of 20%) of non-spherical particles is investigated
theoretically by coupling a rheological law to a population balance model accounting for coagulation and fragmentation of the detailed
particle size distribution. In these suspensions, the immobilization of matrix liquid renders the viscosity dependent on the particle
aggregation state. The e5ect of initial solids volume concentration and shear rate on the transient behavior of particle size distribution
and suspension viscosity is examined. Power law correlations for the equilibrium 6ow curves of aggregating suspensions are deduced
and compared to experimental data. Steady-state or equilibrium particle size distributions are found to be self-preserving with respect to
solids volume fraction and shear rate.
? 2003 Elsevier Science Ltd. All rights reserved.
0009-2509/03/$ - see front matter ? 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0009-2509(03)00133-7
2894 G. Barthelmes et al. / Chemical Engineering Science 58 (2003) 2893 2902
suspensions of polystyrene latex. They pre-sheared the sus- The >rst two terms of the right-hand side (RHS) describe
pensions at high shear rate for complete deaggregation and the birth of aggregate particles of section i by coagulation
then reduced sharply the shear rate resulting in a pronounced of smaller aggregates, the next two RHS terms account for
viscosity increase and later on in a shear rate-dependent the death of aggregates of section i by coagulation with
equilibrium viscosity. other aggregates, while the last two RHS terms describe
Here, the dynamic behavior of suspensions of polydis- death and birth, respectively, of aggregates in this section
perse particles is examined accounting for shear-driven by breakage.
coagulation and fragmentation by population balances. The i; j is the so-called collision kernel of particles or
Fluid and particle dynamics are coupled by replacing the aggregates. The collisions can be caused by the ever-present
solids concentration in material laws with an e5ective thermal motion (Brownian motion) or by shear deformation
solids volume fraction which includes the immobilized of the 6uid (Smoluchowski, 1917). Here, only particles of
6uid (Wolthers, van den Ende, Duits, & Mellema, 1996). at least micron size are considered where the in6uence
That way it overcomes the limitations of the earlier mod- of thermal motion is negligible compared to shear. This
els of de Rooij et al. (1993, 1994) that were con>ned to collision rate i; j of Sa5man and Turner (1956) for ho-
monodisperse particle suspensions and of Kramer and Clark mogeneous, isotropic turbulence with spherical particles
(1999) that assumed constant viscosity. The suspension smaller than the Kolmogorov microscale (for which par-
dynamics are investigated at various initial solids fractions ticle inertia can be neglected) was extended by Flesch,
and shear rates and the transient behavior of representative Spicer, and Pratsinis (1999) to account for the aggregate
macroscopic quantities (mass mean diameter, e5ective con- structure:
centration, viscosity) is studied. Special focus is placed on
the equilibrium state, particularly on a sensitivity analysis 1=Df 1=Df 3
i; j = 0:31 G vp (xi + xj ) ; (3)
of various model parameters on the 6ow curves, which are
compared to experimental data. where G is the so-called shear rate, i.e. the spatially aver-
aged velocity gradient that is constant and homogeneous.
The symbol G is utilized for both, laminar and turbulent
2. Theory shear. Possible e5ects of viscous retardation, van der Waals
attraction or particle repulsion are neglected, although at-
2.1. Sectional population balance model tractive and repulsive forces are usually not fully compen-
sating and the collision eOciency is depending on shear rate
The evolution of aggregate size distributions undergoing (cf. Vanni & Baldi, 2002). Here, completely destabilized
simultaneous coagulation and fragmentation is described suspensions are assumed where all collisions are successful.
by the population balance equation (Blatz & Tobolsky, This assumption of a collision eOciency of unity appears re-
1945). To solve this equation, Spicer and Pratsinis (1996a) alistic as the streamlines of 6ow only penetrate the outmost
extended the sectional model of Hounslow, Ryall, and layers of compact aggregates (Veerapaneni & Wiesner,
Marshall (1988) to account for fragmentation of aggregates. 1996). Therefore the primary particle density in the outer
They used a sectional spacing factor Vi =Vi1 = 2, where Vi regions of the aggregates must be suOciently large to ob-
is the mass-equivalent volume of an aggregate in section i, tain collisions of primary particles when the aggregates
i.e. the volume of a fully coalesced aggregate that consists start to overlap. The slight penetration of 6ow into the ag-
of xi = 2i1 spherical monodisperse primary particles of gregate reduces, however, hydrodynamic repulsion found
diameter dp : in squeezing 6ow between two approaching solid spheres
(see e.g. Happel & Brenner, 1973 or Kim & Karrila, 1991),
Vi = d3i = xi vp = xi dp3 : (1)
6 6 which would have decreased the collision eOciency.
With this sectionalization, the population balance for the Aggregates are irregularly shaped with a void fraction or
number concentration Ni of aggregates in section i becomes inversely an aggregate density that depends on aggregate
(cf. Spicer & Pratsinis, 1996a): size. As they exhibit fractal-like properties they can be char-
acterized by a fractal dimension Df (Mandelbrot, 1983). In
i2
dNi ji+1 1 2 sheared suspensions the fractal dimension is typically in the
= 2 i1; j Ni1 Nj + i1; i1 Ni1 range of 2.12.7. Here, the fractal dimension is a constant
dt 2
j=1
though it can depend on shear rate, shear history (Spicer et
i1 imax 1 al., 1998) and on aggregate size (Oles, 1992). The collision
Ni 2ji i; j Nj Ni i; j Nj diameter dc; i of an aggregate of section i is related to the
j=1 j=i
number of primary particles xi of diameter dp in it, by (cf.
Matsoukas & Friedlander, 1991)
imax
1=Df
Si Ni + i; j Sj Nj : (2) dc; i = dp xi : (4)
j=i
G. Barthelmes et al. / Chemical Engineering Science 58 (2003) 2893 2902 2895
The smaller the Df , the less compact the aggregate is and primary particles is distinguished from the relative aggregate
the larger is its collision diameter. size. Introducing Eqs. (6)(8) in Eq. (5), it becomes
The fragmentation kernel Si is the rate of particle breakage q 3=Df
and is related to shear rate and aggregate size by (Pandya (tot ) G 1=3 dc; i
S i = kb vp : (9)
& Spielman, 1983) dp
0=0.1
1
self-preserving with respect to Df . This behavior of suspen-
0.15 G=1s 1
G=10s 1
sions with shear-induced aggregation and fragmentation is
G=100s similar to that of suspensions undergoing Brownian coagu-
lation in the continuum regime (Vemury & Pratsinis, 1995).
0.1
The peak of the distribution curve is sharpened and shifted
to smaller sizes for decreasing Df . The increased fragility
0.05
of large aggregates at low Df may dominate over the en-
hanced collision cross-section narrowing the distributions.
In Fig. 3 the number-based geometric standard deviation
0 gn (squares) and the volume-based geometric standard de-
0.1 1 10 viation gv (triangles) are plotted as a function of the frac-
normalized aggregate diameter, di /dmm
tal dimension. The gn decreases from 2.2 for Df = 3 to
Fig. 2. Normalized particle size distribution for various initial solids
1:64 for Df = 2:1, whereas the dependence of gv on Df is
volume fractions at G = 10 s1 (lines) and various shear rates at 0 = 0:1 less pronounced (only a decrease from 1.8 to 1.62 for the
(symbols): ratio of particle mass in one section to total particle mass, same Df ). At Df = 3, the size distribution and both geo-
as function of the mass-equivalent diameter of the aggregates divided by metric standard deviations closely coincide with the values
the mass mean diameter for Df = 2:3. of Spicer and Pratsinis (1996a) for binary fragmentation
as it is used here. The decrease in gn with lower Df re6ects
2.5 the narrowing of the distributions in the inset of Fig. 3.
Fig. 4 shows the dmm evolution as a function of dimen-
sionless time t = t G 0 for various initial volume frac-
numberbased gn tions 0 (a) and various shear rates (b). With this scaled
volumebased gv time, the initial aggregation kinetics coincide regardless of
0 (Fig. 4a) or G (Fig. 4b). The scaling of the dynamics of
shear-induced 6occulation of suspensions with t = t G 0
geometric standard deviation g
1.5 Df=3.0
and on the shear rate as has been shown amply with dilute
suspensions (Oles, 1992; Serra et al., 1997). The fractal ag-
gregates tend to occupy as much space as possible, i.e. to
establish a space->lling particle network (Folkersma, van
Diemen, Laven, van der Plas, & Stein, 1998; Folkersma et
al., 1999; Dickinson, 2000). This can be achieved, however,
1
only when the suspension is at rest. Under such conditions,
0.1 1
normalized aggregate diameter, di/dmm
10
the cluster size scales with (Varadan & Solomon, 2001):
3
10 10
0=0.001
rel. mass mean diameter, dmm(t)/dp
3 1
10 G=10 s
0=0.1
1 1
0.01 0.1 1 10 0.01 0.1 1 10
(a) dimensionless time, t G 0 (b) dimensionless time, t G 0
Fig. 4. Evolution of the mass mean diameter as a function of time for various (a) initial solids volume fractions (for G = 10 s1 ) and (b) shear rates
(for 0 = 0:1).
104
3
10
Df=2.1
0 = 0.216 Df=2.3
Df=2.5
relative viscosity /0
Df=2.7
0 = 0.031 102 Df=2.9
3
10
relative viscosity /0
Folkersma et al .(1999) 10
2
10
1
102 101 1 10 102
dimensionless shear rate G*=(G 0/*)
2 dry
10 highest applied shear stresses were apparently not suOcient
to disintegrate the aggregates completely down to primary
particles (Kurzbeck et al., 1996).
In the range of values that is typical for sheared sus-
10
pensions (Df = 2:12.7), the fractal dimension Df has
negligible in6uence on the slope of the 6ow curves of con-
centrated suspensions (Fig. 8). Only at fractal dimensions
1 close to Df = 3 the viscosity is reduced signi>cantly. As
10
2
10
3
10
4
Df 3, the aggregates become more compact and immobi-
1
shear rate G/s lize less matrix liquid, and eventually none at all for Df =3 .
The insensitivity of the 6ow curves to the fractal dimension
Fig. 7. Comparison between model predictions for the e5ect of varied
particle interaction forces on 6ow curves (lines) and experimental results in the typical range for shear-induced aggregation (Df =
(dots) of Kurzbeck et al. (1996) of a pigment-wax suspension at 50 C 2:12.7) indicates that the apparent viscosity is not
at various moisture contents. signi>cantly a5ected by the selection of Df . Possible
shear-induced restructuring, resulting in a compaction of
10%. A possible reason for this di5erence may be in the frag- aggregates and an increase of Df over time, can be ne-
mentation kernel and that the coagulation kernel is derived glected for particles larger than 1 m (Spicer et al., 1998;
for binary collisions without any in6uence of surrounding Selomulya, Bushell, Amal, & Waite, 2002).
particles, which can lead to multiple collisions, enhancing Fig. 9 shows the e5ect of the fragmentation exponent q
coagulation and thus the viscosity. on the e5ective viscosity as a function of G for q = 2
Fig. 7 shows the e5ective suspension viscosity as a func- 6. The q changes the slope of the 6ow curve in contrast to
tion of shear rate for equal to 8 Pa (dotted line) and the parallel shift of R by the previous parameters (0 ,
16 Pa (solid line) by the present model as well as the data or Df ). This property of q facilitates the estimation from
2900 G. Barthelmes et al. / Chemical Engineering Science 58 (2003) 2893 2902
104 uid within the aggregates. This model describes the evolu-
q=2
q=3
tion of aggregate size distribution and the associated change
q=4 of the suspension viscosity. The equilibrium aggregate size
103 q=6 distributions are self-preserving with respect to the initial
relative viscosity /0
Table 2
Analysis of 6ow curves from literature
Author Negative
Notation
6ow curve Calculated
exponent q d diameter (cm)
Experimental Df fractal dimension
de Rooij et al. (1993): Fig. 3 0.64 0.84 2.8 6.4 G shear rate (s1 )
Folkersma et al. (1999): Fig. 2 0.69 0.85 3.2 6.5 kb dimension correction factor (1 cm1 s1 )
Kosmulski, Gustafsson, and Rosenholm 0.80 5.0
N aggregate number concentration (cm3 )
(1999): Fig. 3
Kurzbeck et al. (1996): Fig. 6 0.71 0.79 3.4 4.7 q fragmentation exponent
Verduin, de Gans, and Dhont (1996): Table 1 0.43 0.77 1.75 4.3 S fragmentation kernel (s1 )
Zaman et al. (1996): Fig. 1 0.55 0.84 2.2 6.4 t time (s)
v aggregate or particle volume (cm3 )
Simulated
V mass equivalent volume (of fully coalesced sphere)
Chen and Doi (1989): Fig. 14 0.56 2.3
Chen and Doi (1999): Fig. 11 0.67 3 (cm3 )
Silbert, Melrose, and Ball (1997): Fig. 5 0.75 4 x number of primary particles per aggregate
Silbert et al. (1999) (in text) 0.84 6.25
Greek letters
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