Chemical Engineering Science 58 (2003) 2893 – 2902

Particle size distributions and viscosity of suspensions undergoing
shear-induced coagulation and fragmentation
G. Barthelmesa , S. E. Pratsinisa;∗ , H. Buggischb
a Particle Technology Laboratory, Department of Mechanical and Process Engineering, Sonneggstrasse 3, ML F25, ETH Z!urich,
CH-8092 Z!urich, Switzerland
b Institut f!
ur Mechanische Verfahrenstechnik und Mechanik, Universit!at Karlsruhe (TH), D-76128 Karlsruhe, Germany
Received 23 September 2002; received in revised form 13 December 2002; accepted 21 February 2003


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.

Keywords: Particles; Fractals; Self-preserving; Population balance; Modeling; Rheology

1. Introduction increase the e5ective solids volume fraction in the sus-
pension and its viscosity (Graham, Steele, & Bird, 1984;
Simultaneous coagulation (or aggregation) and fragmen- Tsutsumi, Yoshida, Yui, Kanamori, & Shibata, 1994).
tation by 6uid shear is encountered in processes involving Increasing the viscosity increases the shear stresses that
polymerization (Blatz & Tobolsky, 1945), liquid–liquid dis- enhance breakage of aggregates. The structure of the ag-
persion (Coulaloglou & Tavlarides, 1977), emulsi>cation gregates and, thus, the rheology strongly depends on the
(Danov, Ivanov, Gurkov, & Borwankar, 1994), 6occula- applied shear stresses.
tion (Ives, 1978) and even diesel soot formation (Harris & Aggregating suspensions show shear thinning behavior
Maricq, 2002). At low particle concentrations the 6uid even with Newtonian matrix liquids. At low shear rates
and particle dynamics can be decoupled, facilitating thus their viscosity–shear rate correlation can be approximated
the description of the suspension dynamics (e.g. Spicer & by power laws (Doi & Chen, 1989; Chen & Doi, 1989). A
Pratsinis, 1996a). variation of the primary particle concentration (Chen & Doi,
At high solids concentrations, however, the state of parti- 1989; Folkersma, van Diemen, Laven, & Stein (1999)) or
cle aggregation can a5ect the rheology as has been encoun- interparticle forces (Kurzbeck, Kaschta, & MBunstedt, 1996)
tered in polymer slurry processing (Horn & Patterson, 1997), leads to a parallel shift of the 6ow curves in the low shear
metallic alloy solidi>cation (Barb@e, Perez, & Papoular, rate region. At higher shear rates, the 6ow curves level o5
2000), food processing (Weipert, Tscheuschner, & Wind- to a Newtonian plateau, which is the state of a deaggre-
hab, 1993) and even blood circulation (Schmid-SchBonbein, gated suspension where the aggregates can no longer break
Gallasch, Gosen, Volger, & Klose, 1976). Aggregates im- (Snabre & Mills, 1996). Rheological studies on aggregating
mobilize part of the matrix 6uid inside them and therefore suspensions mainly consider equilibrium, when the aggre-
gate structure is fully developed and in steady state. de Rooij,
∗ Corresponding author. Tel.: +41-1-632-2510; fax: +41-1-632-1595. Potanin, van den Ende, and Mellema (1994), in particu-
E-mail address: (S. E. Pratsinis). lar, studied the transient rheological behavior of aggregating

0009-2509/03/$ - see front matter ? 2003 Elsevier Science Ltd. All rights reserved.

Here. i. 1994) that were con>ned to collision rate i. They pre-sheared the sus. This assumption of a collision eOciency of unity appears re- 1945). the fractal dimension is a constant dt 2 j=1 though it can depend on shear rate. coagulation and fragmentation by population balances. 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.g. e5ective con. j Nj diameter dc. while the last two RHS terms describe Here. Theory shear. only particles of 6uid (Wolthers. isotropic turbulence with spherical particles (1999) that assumed constant viscosity. Therefore the primary particle density in the outer They used a sectional spacing factor Vi =Vi−1 = 2. 1991) imax  1=Df − Si Ni + i. and shear rates and the transient behavior of representative Spicer. Spicer & Pratsinis. of thermal motion is negligible compared to shear. at least micron size are considered where the in6uence That way it overcomes the limitations of the earlier mod. and layers of compact aggregates (Veerapaneni & Wiesner. i−1 Ni−1 range of 2. The collision   − Ni 2j−i i. laminar and turbulent 2. 1917).7. 1992). Vi = d3i = xi vp = xi dp3 : (1) 6 6 which would have decreased the collision eOciency. 2002). other aggregates. j of Sa5man and Turner (1956) for ho- monodisperse particle suspensions and of Kramer and Clark mogeneous. the dynamic behavior of suspensions of polydis. 1996). 1996). completely destabilized simultaneous coagulation and fragmentation is described suspensions are assumed where all collisions are successful. 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.. where Vi regions of the aggregates must be suOciently large to ob- is the mass-equivalent volume of an aggregate in section i. by the population balance equation (Blatz & Tobolsky. (1993.e. Barthelmes et al. however. and Pratsinis (1999) to account for the aggregate macroscopic quantities (mass mean diameter. 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. respectively. 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. shear history (Spicer et i−1 imax −1 al. & Mellema. To solve this equation. With this sectionalization. j Ni−1 Nj + i−1. 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. Spicer and Pratsinis (1996a) alistic as the streamlines of 6ow only penetrate the outmost extended the sectional model of Hounslow. j Sj Nj : (2) dc. 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.1–2. The i. j = 0:31 G vp (xi + xj ) . 1983). van der Waals attraction or particle repulsion are neglected. The symbol G is utilized for both. The slight penetration of 6ow into the ag- of xi = 2i−1 spherical monodisperse primary particles of gregate reduces. by (cf. Possible e5ects of viscous retardation. Here. j Nj − Ni i. (3) of various model parameters on the 6ow curves. / Chemical Engineering Science 58 (2003) 2893 – 2902 suspensions of polystyrene latex. Happel & Brenner. In i−2 dNi  j−i+1 1 2 sheared suspensions the fractal dimension is typically in the = 2 i−1.1. van den Ende. 1998) and on aggregate size (Oles. 1973 or Kim & Karrila. As they exhibit fractal-like properties they can be char- acterized by a fractal dimension Df (Mandelbrot. the volume of a fully coalesced aggregate that consists start to overlap.e. Matsoukas & Friedlander. tain collisions of primary particles when the aggregates i. This els of de Rooij et al. structure: centration. Duits. Marshall (1988) to account for fragmentation of aggregates. 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. i = dp xi : (4) j=i . the spatially aver- aged velocity gradient that is constant and homogeneous.2894 G. Here. 1991). j is the so-called collision kernel of particles or Fluid and particle dynamics are coupled by replacing the aggregates. particularly on a sensitivity analysis 1=Df 1=Df 3 i. Special focus is placed on the equilibrium state. which are compared to experimental data. hydrodynamic repulsion found diameter dp : in squeezing 6ow between two approaching solid spheres   (see e. of aggregates in this section perse particles is examined accounting for shear-driven by breakage. where G is the so-called shear rate. 1996a): size. viscosity) is studied. death and birth. although at- 2. Vanni & Baldi. Ryall.

So they are ruptured more sidered easily as in Spicer and Pratsinis (1996a). G. / Chemical Engineering Science 58 (2003) 2893 – 2902 2895 The smaller the Df . while m = 0:6 is used here as an average. di ˙ Vi1=3 = (xi vp )1=3 . It is a measure of the aggregate strength: the larger the ∗ . 2. How. (5) and (6) shows that ∗ can be related to A by where vc. aggregates with identical collision diameter but lower consistent with photographic observations by van de Ven fractal dimension are more porous. a one-parameter viscosity function is chosen that de- product of viscosity and strain rate which is proportional scribes polydisperse suspensions of hard spheres (Quemada. the less susceptible to breakage are the particles at a In this equation. 1977). the volume of the ni . i . The fragmentation parameter A and The viscosity of suspensions with fractal-like aggregates the exponent q are determined experimentally (Spicer & corresponds to that of suspensions of solid spheres with the Pratsinis.69 (Lee. the approach of Kramer and Clark (1999) who utilized the Here. (13) dp ni This is consistent with Pandya and Spielman (1982) who where the geometric mean diameter is de>ned by proposed S ˙ V m where the exponent m is determined  experimentally (for their data: m = 0:33). the shear rate is replaced by 1996). & Yang. So. where kb = 1 cm−1 s−1 is used to match the dimensions of The fragment distribution function i. with 1:6. 1998): volume fraction of the aggregates. (7) A (Wolthers et al. This is similar to volume fraction and suspension viscosity (Quemada. The m is the maximum volume concentration at kb which the viscosity diverges to in>nity. From the data of Oles (1992) the fraction of fragments produced in section i. j in Eq. with increasing porosity of the aggregates. 1999). where the viscosity is con- stant. & Shiu.e. (5). (5). i ni (ln di − ln dgn )2 Si ˙ vp : (8) ln gn =  . As porosity is ni ln di ln dgn =  : (14) independent of the primary particle size. (2) gives both sides of the equation. Therefore. i = (=6) d3c. the mass equivalent diameter di is replaced by the collision diameter dc. i is the collision volume of the ag-  1=q gregates. the less compact the aggregate is and primary particles is distinguished from the relative aggregate the larger is its collision diameter. (5). Here only binary breakage (or Pratsinis (1996a) extracted A = 0:0047 cm−1 sq−1 and q = “aggregate splitting”) is considered. With the viscosity of water  = 10−3 Pa s. Introducing Eqs. (5) In dilute suspensions ( → 0). Barthelmes et al. As the disrupting shear forces are acting on the collision i. tot is the e5ective or total volume concen- certain shear stress: tration of the aggregates:  q G imax  Si ˙ : (6) tot = Ni vc.. i in Eq. 1996) to 0. The dimension. (11) ∗ i=1 A comparison of Eqs.58 ∗ = . 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. size. There is a variety of correlations between particle the external shear stress in the suspension. 2001). particle bonds per aggregate volume and their strength is Splitting into more than two daughter fragments can be con- lower (Tang. Spicer and aggregate of section j breaks. (9) nicely where Si is proportional to the mass-equivalent diameter reduces to Eq. j = (12) 0 else: diameter of the aggregate. this results  in a characteristic shear stress ∗ = 0:0285 Pa. gn is given by (Hinds. Thus they contain less (1989) and simulations by Higashitani and Iimura (1998). 1999)  3=Df  1=2 1=3 dc. ranging from 0. and for spherical particles (Df = 3). A characteristic shear 0 stress ∗ is introduced to non-dimensionalize the shear stress (tot ) = : (10) (1 − tot =m )2 term. This splitting into two roughly equally sized fragments is ever. The shear stress 1977) or of “structural units” like clusters or aggregates is proportional to viscosity that depends on the e5ective (Quemada. to the shear stress in simple shear 6ows. j = i + 1. i. Since the aggregates are actually ruptured hydrodynamic diameter of the aggregates (Snabre & Mills. 1996a). when an for an aqueous dilute polystyrene suspension. easily by shear forces. the linear dependency on The width of the aggregate size distribution can be de- the aggregate collision diameter can be replaced by a power scribed by a number-based geometric standard deviation gn law so the breakage rate increases with decreasing fractal or by a volume based geometric standard deviation gv . Eq. i S i = kb vp : (9) & Spielman. 1983) ∗ dp Si = A G q Vi1=3 . Ma. by the forces acting upon them. (6)–(8) in Eq.

2 t*=0.7 relative mass fraction. i.25 t*=0. 5)  rate G.1 3. the suspension has reached steady state (t ∗ = t G 0 = 0:5) with a low collision cross-section and or equilibrium between particle coagulation and fragmenta- thus a slow growth. the distribution curves aggregates have a larger collision volume than the sum of undergo signi>cant changes in shape by the presence of a the collision volumes of their predecessors. 1992. di5er- over di . di/dp was evaluated >rst for dilute suspensions ( → 0) of spher- ical particles with Df = 3 at the conditions of Oles (1992).e. the self-preservation is no longer valid as has been shown . The latter is consistent with results of Spicer and G — Pratsinis (1996a) for dilute suspensions. tured by the ongoing shear forces. Particle growth accelerates when larger tion. particles. 8) shear rates. 9) the decomposition of aggregates into primary particles. When these are plotted External as a function of a normalized aggregate size.2896 G. Dynamics of aggregate size distributions 0 1 10 102 103 104 Table 1 shows the parameters employed here. all distribution   0:01 (Figs: 1–3) curves collapse to one line. (ni Vi)/φ0 and (14). 2).1. Nordenswan. This hump grows rapidly and moves to lations of Silbert. of the dp 2:0 m 5:1 m 0 10−3 Pa s 24 × 10−3 Pa s mass-equivalent aggregate diameter di of the aggregates divided by the mass mean diameter dmm . (13) t*=0.e. i.. 4. Fig. around t ∗ = 0:7).15 lations (10)–(12) is solved numerically using the VODPK solver (Byrne. >rst small aggregates of Df = 2:3 are formed t ∗ = 2:1 and 21). Particle size distribution at increasing dimensionless time The evolution of the detailed size distribution and the mass t ∗ =t G 0 and Df =2:3 in a moderately concentrated suspension (primary mean particle diameter as well as the attainment of equilib. 7 and 8 size distributions is independent of the initial solids vol- ume fraction or shear rate (Fig. This mode of the large aggregate mode. After about t ∗ = 2:1. Parameters used for simulation of >gures (unless otherwise noted) The shape of the steady-state or equilibrium particle Parameter Figs.17 0:1 (Figs: 4. 4–6) ∗ 16 Pa (Fig. The model relative aggregate diameter.g.3 2. starting with a completely deaggregated rium size distribution were identical to that of Spicer and suspension. Self-preservation  1 s−1 (Fig: 3)  here means that particles attain a size distribution of which Model the shape is invariant with respect to 0 and G even though Df 2. 1 shows the Therefore. Netlib. Initially aggregate-free suspensions of particles of dp = 2 m and 0 = 0:01 are considered. 9) aggregate size distributions are self-preserving with re-   spect to both.3 the actual size changes.05 3. This holds however only as long q 4 4 as the fraction of primary particles is negligible. resulting in the signi>cant fraction of primary particles and the appearance large-aggregate mode in the size distribution. 2. / Chemical Engineering Science 58 (2003) 2893 – 2902 The volume-based geometric standard deviation gv is 0. Melrose. and Rosenholm (2001) explained also their experimental results on the shear history dependence of aggregating sus- Table 1 pensions using the concept of transient gelation. 0. This indicates that steady-state 0 0. The observation of the very can be observed after some time (t ∗ = 0:7) as a hump in large aggregates or superclusters is in agreement with simu- the distribution. 1–6 and 9 Figs. 2. 2001).5 obtained likewise by replacing ni by ni Vi in Eqs. 2001). 1. they are disrupted by the increasing shear forces evolution of the dimensionless aggregate mass distribution from the increasing viscosity. who calculated smaller sizes (t ∗ = 0:8) because the large aggregates have a a transient particle gel network that is subsequently rup- high porosity and thus a low strength (Tang et al.1 The sectional population balance equation (2) for imax =40 t*=21 and the above-de>ned kernels (3) and (9) and the corre- 0. and Ball (1999). initial solids volume fraction 0 and shear  10 s−1 (Figs: 1. Barthelmes et al. 0. Gustafsson. Starting with the initial monodisperse primary ences in distribution curves can no longer be discerned (cf. when fragmentation dominates resulting in 0:01 Pa (Figs: 3. Fig. Results and discussion 0.8 t*=2. At high   0:1 Pa (Figs: 1. Pratsinis (1996a). particle concentration 0 = 0:01). fractal-like aggregates are formed since the newly formed Transiently (e.

Later Df=2. 4a and b) at high initial volume fractions (e. di /dmm tal dimension.5 Df=3. G = 1000 s−1 ).2 2. At Df = 3. 1996b). 1 only when the suspension is at rest. & Casamitjana.2 (here: 0 = 0:01) for Df = 2:3.01 relative mass fraction. Folkersma et al. Dickinson. At high shear rates (e. 3 the number-based geometric standard deviation 0 gn (squares) and the volume-based geometric standard de- 0. 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. The scaling of the dynamics of shear-induced 6occulation of suspensions with t ∗ = t G 0 geometric standard deviation σg 2 has been found in dilute systems also (Oles. 2. 1) results in a short overshoot of the dmm (Fig. Therefore. G.. volume based: gv . i 1=(D −3) ˙ 0 f : (15) fractal dimension Df dp Fig. of dilute suspensions where increasing particle concentra- tions give larger steady-state size distributions (Spicer & by Spicer. 1997). Pratsinis.0 and on the shear rate as has been shown amply with dilute suspensions (Oles.62 for the (symbols): ratio of particle mass in one section to total particle mass. & Stein.1 1 normalized aggregate diameter. dence on 0 is more pronounced. and Meesters (1996) for Pratsinis. 3. however. Serra et al. van Diemen..2 for Df = 3 to Fig. so they are not φ0=0.5 ter depending on the initial primary particle concentration relative mass fraction. The transient formation of large particles (Fig. (ni Vi)/φ0 φ0=0. With this scaled volume−based σgv time. The increased fragility 0. i. to establish a space->lling particle network (Folkersma. The inset shows the normalized at higher tot enhancing fragmentation. In Fig.4 2. no overshoot in average aggregate size can be observed as The inset of Fig.3 on the dmm reaches asymptotically an equilibrium diame- Df=2.1 The peak of the distribution curve is sharpened and shifted to smaller sizes for decreasing Df . 4 shows the dmm evolution as a function of dimen- sionless time t ∗ = t G 0 for various initial volume frac- number−based σgn tions 0 (a) and various shear rates (b).g. same Df ). the ag- steady-state particle size distribution by coagulation and fragmentation of gregates become even smaller than at rest and the depen- concentrated suspensions of 0 = 0:01– 0.1 −1 self-preserving with respect to Df . Fig. squares. ni vi/φ0 1. 0.g. / Chemical Engineering Science 58 (2003) 2893 – 2902 2897 0. 3 shows the equilibrium or steady-state the high shear stresses cause high fragmentation rates even particle size distributions normalized by dmm for Df =2:3–3. 1999.8 to 1.6 2. 1998. the initial aggregation kinetics coincide regardless of 0 (Fig.5 and 3.5 the narrowing of the distributions in the inset of Fig. .g. Geometric standard deviations (number based: gn . 1997). Laven. Trennepohl. of small aggregates. 2000). 0. of Spicer and Pratsinis (1996a) for binary fragmentation as it is used here. dilute suspensions undergoing shear-induced 6occulation. This result contrasts that 2. Normalized particle size distribution for various initial solids 1:64 for Df = 2:1.2 with 0 =0:01 and G =1 s−1 .1 1 10 viation gv (triangles) are plotted as a function of the frac- normalized aggregate diameter. This can be achieved. Serra.8 3 dc. the viscosity increases a function of fractal dimension Df . 1992. 1992.05 of large aggregates at low Df may dominate over the en- hanced collision cross-section narrowing the distributions. G 6 10 s−1 ). di/dmm 10 the cluster size scales with (Varadan & Solomon. The fractal ag- gregates tend to occupy as much space as possible. van der Plas. 2001): 2 2. These normalized steady-state φ0=0. whereas the dependence of gv on Df is volume fractions at G = 10 s−1 (lines) and various shear rates at 0 = 0:1 less pronounced (only a decrease from 1. 4a) or G (Fig. Barthelmes et al. 0 ¿ 0:01) and low shear rates (e.e. Colomer. triangles) of the steady-state particle size distributions as In sheared concentrated suspensions. The gn decreases from 2. Under such conditions.001 distributions broaden with increasing Df . 4b). 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). The decrease in gn with lower Df re6ects 2. 3.

t G φ0 Fig. the extend of towards an equilibrium value. This parallel shift of the 6ow curves is consistent with direct numerical simulations of aggregating concen- 3. Viscosity and =ow curves trated suspensions (Chen & Doi. 0 was varied over some range typical for moderately concentrated suspensions (Fig. η(t)/η0 The correlation between viscosity and applied shear is ex- 102 φ0=0. 6].01 0. 1993) or from 3% to 21% (Folkersma et al. 5). relative viscosity. 1989. dmm(t)/d0 G=0. Barthelmes et al. the overshoot behavior of the mass mean diameter.001 10 ted against the applied shear rate. mass mean diameter. aqueous polystyrene latex suspensions (dp = 2:0 m) with crease in viscosity (Fig. t G φ0 (b) dimensionless time. / Chemical Engineering Science 58 (2003) 2893 – 2902 3 10 10 φ0=0. while the model predicts only an increase by a factor viscosity evolution after a step from high to low shear rate. Doi & Chen. The simulated 6ow curves are straight lines in the log–log plot in the range of low shear rates (here 1 0. Evolution of the mass mean diameter as a function of time for various (a) initial solids volume fractions (for G = 10 s−1 ) and (b) shear rates (for 0 = 0:1). the parallel shift is underpredicted by the model: The ex- gregates are >lling the available space gradually until the si. 4a.1 1 10 0. Potanin. creases from 2% to 10% (de Rooij.1 amined and the in6uence of various model parameters on the viscosity is elucidated.1s−1 −1 G=10s 2 10 φ0=0. and completely eOcient aggregate collisions. This quantity does not exhibit 0:5 M NaCl [cf. the fractal ag. Moudgil. 4. shear rates. Experimental ob. 5. inset in Fig. (1994) on the viscosity evo.1 1 10 (a) dimensionless time. lution of aggregating suspensions show moderate slopes of 1999). & Mellema.01 rheological properties is the so-called “6ow curve” where the suspension viscosity (or the relative viscosity) is plot- φ0=0. A common presentation of the φ0=0. mass mean diameter. To study the in6uence of the initial volume fraction on the 6ow curves. and El-Shall (1996) for aqueous silica suspensions a few of the large particles are formed.001 rel. and of Zaman.01 0. (1999) for The appearance of the large aggregates leads to an in. However.2898 G.2. A change of the primary particle Fig. Evolution of the relative viscosity for the same parameters as in concentration causes a parallel shift of the 6ow curves at low Fig. t G φ0 At high G the viscosity approaches the value of completely deaggregated suspensions. servations of de Rooij et al.1 1 10 G ∗ = 0 G=∗ 6 1) and can be approximated by power laws. but bends smoothly (dp = 1 m) with 0:03 M NaNO3 . dimensionless time. constant fractal dimension.01 3 −1 10 G=10 s φ0=0. of 3 when the solids concentration is increased from 1% to .01 0.. By coagulation. 6). van den Ende. perimental data show an increase of viscosity by more than multaneously increasing viscosity is leading to shear stresses one order of magnitude when the solids concentration in- that counteract growth by fragmentation. as only Fricke. 1989) and with experimental data of Folkersma et al.1 1 1 0. 103 The very rapid dynamics of viscosity evolution predicted by the model can be attributed to the model assumptions: ide- ally homogeneous shear >eld. dmm(t)/dp rel.

Bushell. for binary collisions without any in6uence of surrounding Selomulya.9 3 10 relative viscosity η/η0 Folkersma et al . the experimentally measured e5ective viscosity 13% H2O decreases and approaches a value (at G ¿ 1000 s−1 ) above 6% H2O the viscosity of a completely deaggregated suspension.7). aggregates and an increase of Df over time. Amal.7 on the 6ow curves for the system of Kurzbeck et al. 7 shows the e5ective suspension viscosity as a func.7) indicates that the apparent viscosity is not at various moisture contents. The ∗ is determined by matching 103 the model predictions and experimental results. (1996).7 0 = 0. φ0 =0. signi>cantly a5ected by the selection of Df . particles. 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 . 9 shows the e5ect of the fragmentation exponent q coagulation and thus the viscosity. In the range of values that is typical for sheared sus- 10 pensions (Df = 2:1–2. G. 1996). 7).(1999) 10 2 10 1 10−2 10−1 1 10 102 dimensionless shear rate G*=(G η0/τ*) Fig.01 φ0 =0.216 Df=2. / Chemical Engineering Science 58 (2003) 2893 – 2902 2899 104 3 10 Df=2. resulting in a compaction of 10%.5 relative viscosity η/η0 Df=2. A possible reason for this di5erence may be in the frag. At higher τ*=16 Pa τ*=8 Pa shear rates. (1996) of a suspension of a hydrophobic 1 molten wax at 50◦ C >lled with a volume fraction 0 =0:17 of 10−3 10−2 10−1 1 10 chromium oxide pigment particles (dp =5:1 m) at di5erent dimensionless shear rate. As 10 2 10 3 10 4 Df → 3. (1996) of a pigment-wax suspension at 50◦ C 2:1–2. 6ow curves in the low shear rate range (G ¡ 300 s−1 ) par- allel to higher viscosity.. Barthelmes et al. & Waite. 7). A variation of ∗ in the simulations leads to a parallel shift of the 6ow curves in the Fig.1 ← 0 = 0. Inset: experimental data adapted from plotted over the shear rate.001 of Kurzbeck et al. G*= (G η0/τ*) moisture content (points in Fig. on the e5ective viscosity as a function of G ∗ for q = 2– Fig. Parameters: ∗ = 16 Pa.216 (∇).2 Df = 2:1–2. Steady-state 6ow curves for various initial solids fractions or low shear rate range (Fig. (1999): 6ow curves for primary particle concentrations gation of the particles. Possible shear-induced restructuring. The relative viscosity η/η0 2 dry 10 highest applied shear stresses were apparently not suOcient to disintegrate the aggregates completely down to primary particles (Kurzbeck et al. Negligible in6uence of the fractal dimension in the typical range 10 φ0 =0. 1998. Only at fractal dimensions 1 close to Df = 3 the viscosity is reduced signi>cantly.1 φ0 =0. ∗ 16 Pa (solid line) by the present model as well as the data or Df ). which can lead to multiple collisions. 7. This property of q facilitates the estimation from .3 Df=2. can be ne- mentation kernel and that the coagulation kernel is derived glected for particles larger than 1 m (Spicer et al. 8. and eventually none at all for Df =3 . 7. So increasing the moisture shifts the from 0 = 0:031 () to 0. 8). 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. enhancing Fig. 6. 6. 2002).. otherwise as in Fig. The insensitivity of the 6ow curves to the fractal dimension Fig.031→ 102 Df=2. the aggregates become more compact and immobi- −1 shear rate G/s lize less matrix liquid. The moisture enhances the aggre- Folkersma et al. when the relative viscosity is primary particle concentrations. the fractal dimension Df has negligible in6uence on the slope of the 6ow curves of con- centrated suspensions (Fig.

(1999) (in text) 0.9 –5.25 Greek letters experimental data by regression of  at small G ∗ . the extracted q also vary over some range (q = 1:75– 6. and Dhont (1996): Table 1 0.56 2. j section number m maximum (concentration) 4.64 – 0. 14 0.75 4 x number of primary particles per aggregate Silbert et al.8– 6. 9. Similar values (1. reference .75 – 4. 2 0.71– 0. / Chemical Engineering Science 58 (2003) 2893 – 2902 104 uid within the aggregates. Two material parameters are in6uencing signif- icantly the predicted 6ow curves and need to be determined 1 by comparison with experimental results: the fragmentation −4 −3 −2 −1 2 10 10 10 10 1 10 10 exponent q and the characteristic shear stress ∗ . (1996): Fig.85). The equilibrium aggregate size 103 q=6 distributions are self-preserving with respect to the initial relative viscosity η/η0 solids volume fraction and shear rate.80 5.79 3. (1999): Fig.4 t time (s) v aggregate or particle volume (cm3 ) Simulated V mass equivalent volume (of fully coalesced sphere) Chen and Doi (1989): Fig.2– 6.5).5 kb dimension correction factor (1 cm−1 s−1 ) Kosmulski. (1993): Fig.4 – 4. As the negative 6ow curve exponents scatter  aggregate volume concentration signi>cantly (0. 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 expo- dimensionless shear rate G*=(G η0/τ*) nent q de>nes the sensitivity of the aggregates on the shear Fig. The correla- 10 tion between viscosity and shear rate can be described by a power law. In6uence of the fragmentation exponent q on the slope of the rate and is the only parameter with signi>cant in6uence on simulated 6ow curves. 6 0.3 Chen and Doi (1999): Fig. c collision i. the slope of the 6ow curves.55 – 0. 1 0.2– 6. and Rosenholm 0.84 6. Summary and conclusions mm mass mean p primary particle A sectional population balance model for shear-induced R relative coagulation fragmentation of concentrated suspensions is tot total developed accounting for the immobilization of matrix liq.67 3 (cm3 ) Silbert.85 3.0 N aggregate number concentration (cm−3 ) (1999): Fig. Melrose.43– 0.69 – 0.6) are Superscripts and subscripts reported by Serra and Casamitjana (1998) for dilute sus- pensions. and Ball (1997): Fig. There the  collision kernel (cm3 s−1 ) 6ow curves can be approximated by the following power  fragment distribution function law correlation:  dynamic viscosity (Pa s) 0 dynamic viscosity of matrix liquid (Pa s) R ˙ G (1−q)=q : (16) g geometric standard deviation of diameter (cm) Table 2 summarizes the analysis of 6ow curves in the ∗ characteristic shear stress (Pa) literature. Barthelmes et al. 2 Flow curves of suspensions of polydisperse particles (up 10 to 20% by solids volume) are calculated that are consis- tent with experimental data in the literature.4 G shear rate (s−1 ) Folkersma et al. 5 0. 3 0.84 2.2900 G.7 q fragmentation exponent Verduin. 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.77 1. 11 0. 0 initial. (1996): Fig. Gustafsson. de Gans.43– 0. The fractal dimension has little in6uence on the 6ow curves.84 2. 3 Kurzbeck et al.3 S fragmentation kernel (s−1 ) Zaman et al.

Journal of Colloid and Interface latex particles. M. Selomulya. V. J. H. 5271–5279. K. Simulation of aggregating colloids in shear Quemada. D. E5ect of the shear and volume in concentrated suspensions. D.. Harris.. Industrial & Engineering Chemistry Fundamentals. 54(4). Correlation viscosity of semi-solid mixtures.. (1998). 495–506. fraction on the aggregation and breakup of particles.. Particle clusters Serra. D. J. J.. & Tobolsky. Journal of Chemical Physics. L. C. & Mellema. D. J. Dickinson. J.. 7067–7077. Two-dimensional simulation of the Smoluchowski.. 37. (2002). van den Ende. 1(1). Dynamics of aerosol Coulaloglou. Doi. (1999).. Journal of Chemical Physics. Steady shear viscosity of weakly aggregating polystyrene latex suspensions: Theory and data processing strategy.Ch. & Chen.I.. Rheologica mechanisms of latex of di5erent particle sizes in a controlled shear Acta. Volger. R. J. Klinische Wochenschrift.. 549–555. (1978). H. New York: Wiley. A. Physical Review E. J. Blatz.. & MBunstedt. Graham. G. The role of fragmentation in Silbert. & Spielman. E. 446–457. E. A.. 209(1). C. S. / Chemical Engineering Science 58 (2003) 2893 – 2902 2901 Acknowledgements Hinds. 257–267. Journal of Colloid and Interface Science. Journal of Fluid Mechanics. R. R. 32(11). (1999). G. (1989). 1821–1832. Aerosol Technology (2nd ed. E. T. Colomer. 99(11). S. T. P. R. Science. & Spielman. P. The 6ow. (1996). 159–167. Lee. Rheologica Acta. P. B... 242(1). & Schmid-SchBonbein. Ryall. Netlib Repository at University of Tennessee and Oak Danov. dynamics: Pair-drag simulations of model-concentrated aggregated Leyden. (1992). J. M. 1974–1984. Potanin. A. A. M.. Microhydrodynamics. J. 23(4). I.E.. Aggregation and aggregation of anatase dispersions investigated by oscillation and low breakup of particles in a shear 6ow. (1999). A. 9213–9223. 187.-H. Rheology. A. R. A. van den Ende. G. B. Incorporation of aggregate breakup phenomena.. M. 1789–1797. R. C. 38(12).. London: Butterworth-Heinemann.. Higashitani. Oxford: of a >lled wax system. 90(2).. A discretized the Swiss Commission for Technology and Innovation (KTI. 77–80. Microstructure and Kosmulski. van Diemen. B. S. M. Journal of This research was supported partially by the Deutsche the American Ceramic Society. Gustafsson. L. A. A.2). M. Microstructure and viscosity of aggregating Mandelbrot.. Rheologica Acta. (1998). (1977). 323–356). in the sti5 ODE setting. Rheology of concentrated disperse systems. Journal of Chemical Physics. Grant No. from aggregated colloidal particles. Journal of Colloid and Interface Minimum energy dissipation principle and viscosity–concentration Science. R.. T. R. On the collision of drops in turbulent 45(5). 2567–2577. 33(6). M. & Tavlarides. 35. 225(1). 43(3). R. 82–89. & Rosenholm. processes in agitated liquid–liquid dispersions. Journal of Physics: Condensed between the zeta potential and rheological properties of anatase Matter. & Iimura. (1991). Pandya. systems. 12(12). (1998). 2–15. Floc breakage in agitated (1993).netlib. D. T. B. Aggregation Steady shear rheology of dilute polystyrene particle gels. A. (1976). J. & Borwankar. V. J. R. in the simulation of orthokinetic coagulation. L. aggregated colloids. Rheological behavior and Chen. E5ect on apparent gels during steady-shear. D.. 286–292... 2656–2663.. 2. X. M. Gurkov.. Thermally induced reversible coagulation in ceramic powder polymer liquid suspensions. E. & Ball.. E. Structure and rheology of simulated gels formed Quemada. 100(7). Rheological modelling of complex 6uids. (1999). II. S. N. J. viscosity of blood. S. D. Floc breakage in agitated Transient shear viscosity of weakly aggregating polystyrene latex suspensions: E5ect of agitation rate. Pragmatic experiments with Krylov methods Interface Science. Journal of Colloid and Interface Freeman. Langmuir. 44(8). M. (1994). New York: colloids under strong shearing force. URL: http://www. & Casamitjana. (1983). Journal of Colloid dispersions.. B.. 56(6).. concept of e5ective volume fraction revisited. dispersions. Journal of Colloid and Interface Science. & Maricq.-M. M.. J. & Waite. Amal. So. Bushell. L. (1989). X. Perez. Sa5man. Pandya.. A. Gladwell (Eds. Netlib. J. (1997). B. 3. Description of interaction agglomerate formation. D. S. J. G.. & Yang. Kinetic-model for the simultaneous processes of 6occulation Oles. Journal of Colloid and Interface Science. Bu485/21-1) and Hounslow. Low Reynolds number hydrodynamics. M. & Brenner. Horn. shear-induced 6occulation of fractal aggregates. 420–425. van Diemen. 34(11). D. 16(1).. 92.I. Visualization of the breakdown of dilute particle H. 1117–1140. J. & Klose. T. and Interface Science. 5773. Barthelmes et al. R. Journal of Chemical Physics. H. 82–94. & Marshall. & Patterson. Journal of Rheology. 116–126. (1998). & Doi. Shear-induced aggregation and breakup of polystyrene and coalescence in emulsion systems. Versuch einer mathematischen Theorie der breakup process of aggregates in shear and elongational 6ows. Note on the kinetics of 200–206. & Clark. J. 90(10). D. J.E. Melrose. European Physical Flesch. (1994). K. J.. 517–531.). relationship. M. (2000). G. Alphen aan den Rijn. (1999). 6ow. Journal of and microstructure of concentrated. 212(2).). D. 49. J. Kaschta.I. A. Rheologica Acta.Ch... Chemical Engineering Science. and aggregation. A.. Journal of Colloid and Interface shear rate viscometry. (1973).-D... H. Forschungsgemeinschaft (DFG. & Karrila. S. T. Laven. Oxford University Press. 8–17. & Papoular. Spicer. Journal of Colloid and Interface Science. J. Nordenswan. (1991). (1984). Laminar and turbulent Journal—Applied Physics. Zeitschrift f!ur Physikalische of Colloid and Interface Science. van der Plas. K. & Mellema. (2002).. 1114–1124. Steele. Ridge National Laboratory. Chemical Engineering 146(2). K. (1983). N. V. . Kurzbeck. & Turner. (2001)... 673–700. R. C. (1945). A. I.. Journal Koagulationskinetik kolloider LBosungen. Netherlands: Noordho5. Chen. D. Silbert. L. Matsoukas. Cash & I. The scientiEc basis of =occulation. The rheology de>ning the signature size distribution of diesel soot. Rheological behaviour Computational ordinary di@erential equations (pp. 154(2). R.. D. G.. Prediction of suspension viscosity. Science. Gustafsson.. J. C. (1988). (2000). 38. & Rosenholm. L. Journal. Redcell aggregation in blood 6ow. 91(4). 129–168. K. Netherlands: Sijtho5 & Noordho5. Journal of Aerosol Science. (1997). J. 351–358.. (1999). References Kim.. A. 1983–1992. J. 167(1)... Shear-induced Serra. systems manifesting simultaneous polymerisation–depolymerisation Kramer. (1997). (1956). Gosen. L. (1977). (1999).. W. TOP Nano21 Project No. (2001).. Folkersma. P. Gallasch.. Science. & Stein. de Rooij. 466–473. & Bird. 1(1). T. 16–30.. 1724–1730. & Doi. C. Chemie. 119–127. Barb@e. L. Ivanov. R. J.. 204. J.. Simulation of aggregating colloids in shear stability of concentrated silica suspensions. Journal of Colloid and Byrne.. E. Colloidal micro- Happel. Journal. Journal of Physical Chemistry. & Friedlander.E. The fractal geometry of nature. 935–942. (1992). 1289–1297. & Pratsinis. R. dispersions. A. A. J. environment. (1982). J. R. I. H. Folkersma. 18. V. 320–327. von (1917).. B. clouds. Stein. & Ball. Science. 43(5). J. Melrose. & Casamitjana.Ch. G. de Rooij. (1999). 80(7). Journal. In J. J. Potanin. 216(1). 5353–5360. population balance for nucleation. growth. Ives. Laven.

E. Rheology of weakly 6occulated Vanni. Journal of van de Ven. J. Bushell. G. (1998). 2918–2929. (2001). Journal de Physique III.. G.. P. T. 97. Spicer. & Windhab. S. E. E. & Mellema. 1049–1056... 17(10). 78(2).. & Meesters. 42(6). 45–57. 1811– particles in shear 6ow. & Meesters. Powder Rheological behavior of highly concentrated aqueous silica suspensions Technology. S. S.. & El-Shall. Self-preserving size distributions G.. A. M.. Spicer. 2947–2955. 175–185.. Journal of Rheology. Tsutsumi. L. 97(1–3). 165–172. C. structural changes in a gel-forming suspension studied by light Spicer. E. (1996). W. structure during 6occulation in stirred tanks. J. Rheologie der the time lag for attainment of steady state. de Gans. T. Shear-induced 6occulation: The Veerapaneni. E. G. H. & Dhont. London: Rheology. Chemistry Research. S. Colloidal hydrodynamics. (1996). J.. H... E. 3074–3080.. Yui. P.. (1989).I. Moudgil. & Wiesner. 26(4). & Shiu. Journal of Colloid and steady state.. 40(6).. A. H.. Shear viscosity behavior of 6occulated suspensions. A.. Tang.. 35(9). P. 1834. Ma. Trennepohl. Y. (1996). D. Advances in Colloid and Interface Science. Coagulation and fragmentation: The variation of shear rate and Weipert. D. & Pratsinis... Raper. Colloids and Surfaces A.. density. Verduin. D. & Shibata. P. Shear-induced microstructural Universal steady-state particle size distribution. & Mills. (2001). Germany: Behr’s. P. M. S. (1996b). (1994). M. Spicer. M. & Baldi. & Pratsinis. (1996a). 40(1). in a Couette 6ow. Coagulation and fragmentation: Varadan. .. in the presence of sodium nitrate and polyethylene oxide. Zaman. (1996). (1995). 1612–1620. and of agglomerates.. 6(12).2902 G. Tscheuschner. E5ect of shear schedule on particle size.. van den Ende. Wolthers. K. Barthelmes et al. 151–177. H. J. (1996). B. Water Research. M. J. S. (1993).. G. Shear induced 26–34. Pratsinis. Modelling the mechanical strength The viscosity and sedimentation of aggregating colloidal dispersions of fractal aggregates. S. T. & Pratsinis. P. Hamburg. A. Journal.. M.. A.. R. evolution of a thermoreversible colloidal gel. H. Journal of Aerosol Science. Industrial & Engineering Lebensmittel. Coagulation eOciency of colloidal suspensions of rigid particles. P. T. Pratsinis. 55–67. I. S. Hydrodynamics of fractal evolution of 6oc structure and the shape of the size distribution at aggregates with radially varying permeability.. M. Academic Press. 7–16. E. Langmuir. scattering and rheology. (2002). S.E. K. 177.Ch. Yoshida. T. Kanamori. G. M. / Chemical Engineering Science 58 (2003) 2893 – 2902 Snabre. Interface Science. 30(5). & Solomon. 1191–1210. 180(1–2). (1996). G. M. Amal. K.. R. Powder Technology. Vemury. Fricke. Langmuir. Duits. 12(12). B.