Progress in Organic Coatings 40 (2000) 111117

Rheology of sterically stabilized dispersions and latices

Jan Mewis , Jan Vermant
Department of Chemical Engineering, de Croylaan 46, Katholieke Universiteit Leuven, 3001 Leuven, Belgium

Abstract Steric stabilization is a method that is often used to properly disperse small particles. It can be applied in aqueous as well as non-aqueous media. The rheological properties of sterically stabilized dispersions are discussed here. The various controlling parameters and the physical mechanisms involved are reviewed. Brownian hard spheres are used as a reference. Scaling relations are presented that make it possible to reduce data sets and to predict properties. Viscosity, yield stress, shear thickening and viscoelasticity are included. The rheological properties are also related to the fundamental colloidal properties of the dispersions under consideration. Quantitative results are available for monodisperse spherical particles, although the effects of particle size distribution can sometimes be predicted also quite well. In other cases the procedures presented here can be used qualitatively to predict viscosities. 2000 Elsevier Science S.A. All rights reserved.
Keywords: Rheology; Latex; Suspensions; Steric stabilization; Viscosity predictions; Viscosity scaling; Dynamic moduli

1. Introduction Because of the presence of small particles most liquid coatings can be considered colloidal suspensions. The colloidal stability of the system then determines whether the particles will remain well dispersed or whether they will occulate. When occulation is not desirable stability can be induced by electrostatic repulsion between the particles, its application is mainly restricted to aqueous media. Steric repulsion between layers attached to the particle surface can provide stability in any suspending medium. Electrostatic stabilization is very effective but makes the structure and the rheology sensitive to variations in pH or ionic strength. Steric, or polymeric, stabilization is not affected by these parameters but, if the suspending medium is not a good solvent for the stabilizer molecules, the stability might change with temperature. Steric stabilization is frequently used as a suitable and robust way of ensuring proper dispersion of the particles. The stabilizer layer can be chemically grafted on the particle surface or, more often, physically adsorbed. The formulation of such materials would obviously be accelerated if the rheology could be predicted or estimated rather accurately on the basis of the composition. This is the problem which is addressed here. Only stabilizer layers of grafted polymers and adsorbed blockcopolymers or surfactants are considered, not homopolymers or statistical copolymers as such. In the latter case the stabilizer layer consists of a complex

mixture of tails and loops of the stabilizing polymer, whereas only tails are present in the other two cases. The suspending medium can be aqueous or non-aqueous. 2. Brownian hard spheres Various parameters affect the rheology of stable colloidal suspensions. In the limiting case of spheres without any interparticle interactions, only Brownian (thermal) forces and hydrodynamic forces affect the ow behaviour. The case of Brownian hard spheres is quite well documented, experimentally and theoretically, at least for monodisperse particles (e.g. Ref. [1]). At sufciently low shear rates Brownian motion will dominate the convective motion caused by the ow. Under these conditions the equilibrium structure of the particles that exist at rest is preserved during ow. As a result the viscosity does not change with shear rate and the contribution of the Brownian forces to the viscosity is at its maximum. When increasing the shear rate the Brownian motion will, at a certain stage, become slower than the convective motion. From then on the contribution of the Brownian motion to the viscosity will gradually decrease with increasing shear rate, whereas the hydrodynamic contribution remains relatively constant. This causes the viscosity to drop; a shear thinning region develops. At still higher shear rates the Brownian contribution levels off and becomes negligible, but an increase in hydrodynamic effects can either compensate the decrease, causing a pseudo-Newtonian high shear plateau, or overcompensate, producing a shear thickening zone [2].

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The viscosity curves for all suspensions with monodisperse Brownian hard spheres of a given volume fraction can be reduced to a single curve [3]. For that purpose the viscosity has to be divided by the medium viscosity m , i.e. the relative viscosity r is used, thus scaling for the hydrodynamic effects of the suspending medium which are proportional to m . The shear rate has to be substituted by a dimensionless stress r , which expresses the ratio between convective and Brownian effects, r = a 3 (1) kT where a is the particle radius, k the Boltzmanns constant and T the absolute temperature. The resulting representation scales for the effects of particle size, medium viscosity and temperature. The limiting relative Newtonian viscosities at low and high shear rates depend only on the volume fraction. These relations are well documented by now [1]. The hydrodynamic and Brownian contributions can be separated theoretically and experimentally [2,4]. A characteristic of the hydrodynamic forces is that they drop instantaneously to zero when the ow stops, the other contributions decay over a nite time scale [5]. At very high volume fractions the situation becomes more complicated as the details of the surface now become important. These effects show up in the viscosities as well as in the frequency dependence of the storage moduli [4]. Computer simulations are also difcult for such systems because of the divergence of hydrodynamic forces between particles when the interparticle distance goes to zero [6]. Experimentally, a sudden shear thickening can be observed in very concentrated suspensions, at least when the particles are not too small. At the moment it is still not quite clear to what extent the detailed surface conditions of the particles affect the results. 3. Viscosity curves The viscosity curves for sterically stabilized suspensions of monodisperse, spherical particles are similar to those of suspensions of Brownian hard spheres (see Fig. 1). There is however a quantitative difference. This is most easily seen when the limiting Newtonian viscosities are plotted as a function of volume fraction. When the stabilizer layer is either relatively thin with respect to the particle radius or relatively rigid, the viscosity curves still coincide with those of Brownian hard spheres, provided the stabilizer layer is included in the particle volume. The effect of the stabilizer can then be expressed by means of an effective volume fraction eff , which can be calculated from the core volume fraction of the particles themselves, c , the particle radius a and the thickness of the stabilizer layer eff = c 1 + a
3

Fig. 1. Viscosityshear rate curves for sterically stabilized PMMA suspensions (a = 42 nm) at different volume fractions, data from [7].

With a known, e.g. from transmission electron microscopy, the layer thickness can be deduced from intrinsic viscosity measurements or from dynamic light scattering data. Such a value is called the hydrodynamic layer thickness. Other measures for this parameter will be discussed later. When the stabilizer layer becomes thicker and/or softer, the previous procedure is not adequate anymore and results in overestimation of the viscosity, especially at higher volume fractions [8,9]. This is illustrated in Fig. 2, where the limiting viscosities at high shear rates are compared for a number of sterically stabilized PMMA suspensions with varying particle radius but similar thickness of the stabilizer layer and silica suspensions with different layer thicknesses [10]. The lack of superposition could be expected. Indeed, the stabilizer molecules are dissolved by the suspending medium and do not form a rigid layer. This layer will be compressed whenever particles approach each other with a certain force. In some cases the effective volume

(2)

Fig. 2. Limiting high shear viscosities for various sterically stabilized PMMA and silica dispersions [10].

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fraction becomes even larger than unity, which is clearly physically meaningless (see Fig. 2). The compression of the stabilizer layer is determined by the molecular structure of the layer, including molecular weight, grafting/adsorption density of the stabilizing polymer and its solubility in the suspending medium. A discussion on the molecular level is outside the scope of the present discussion. The softness of the stabilizer layer can be expressed by a potential for the particle interaction force. It is important to note that steric stabilization normally results in rather steep repulsion potentials, meaning that the softness of the layer is limited. Because of the relatively rigid nature of the stabilizer layer the viscosity curves still could possibly be treated approximately on the basis of an hard sphere approach. For such an approach to be useful it should reduce somehow the viscosities of different systems to a single curve that reects hard sphere behaviour. The viscosity curves of sterically stabilized suspensions, e.g. those in Fig. 2, denitely differ in the limiting volume fraction of the particles at which the viscosity goes to innity, i.e. in the maximum effective packing eff,max , at low as well as at high shear rates. To compare the intrinsic shape of the viscosityconcentration curves, the viscosities can be plotted versus the ratio eff / eff,max . As illustrated in Fig. 3 this procedure can often superimpose curves for different dispersions. For very soft particles the evolution of the viscosity with concentration should be more gradual than for rigid particles. Clearly, in Fig. 3 the slopes of the curves at the origin cannot be identical anymore as they were made to coincide in the representation of Fig. 2. Yet, the major part of the curves superimposes reasonably well. It is concluded that some degree of similarity with hard sphere suspensions still exists, provided a suitable measure for the volume fraction is used. This can be obtained in several ways. The maximum packing could be used for this purpose as shown in Fig. 3. Alternatively, a critical concentration for phase transition could be used [11]. Below, a

third method will be presented that is based on the particle interaction potential. Varying temperature and medium viscosity can be taken into account for sterically stabilized suspensions by means of the scaling procedure used for Brownian hard spheres [12]. When changing the suspending medium its solubility for the stabilizer molecules could then change as well, thus affecting the thickness of the layer. As this factor is not covered by the scaling for Brownian hard spheres, it should be accounted for separately. When working with media which are on the edge of solubility for the stabilizer molecules the viscosity could become very sensitive to temperature because of weak occulation setting in. Such a situation is obviously not desirable in practice. When the volume fraction reaches the maximum packing value for zero shear rate the limiting low shear viscosity diverges and a yield stress appears. As the viscosity it depends on volume fraction and the colloidal characteristics of the system. This will be discussed together with the dynamic moduli in the next section.

4. Dynamic moduli Oscillatory measurements, in particular on concentrated colloidal dispersions, can provide detailed information about the material under consideration. In such experiments the viscous and elastic contributions can be separated in, respectively, the loss (G ) and storage (G ) moduli. In Brownian hard spheres the Brownian motion is responsible for the elastic part, whereas the high frequency limit of G measures the pure hydrodynamic contribution in the equilibrium structure. In concentrated, sterically stabilized, systems the stabilizer layers overlap and G measures the interaction forces between layers on neighbouring particles during the oscillatory motion. This requires the frequency to be high enough to avoid particle diffusion, caused by Brownian motion, during an oscillation. G should become independent of frequency if this condition is satised. The critical frequency at which this happens, i.e. the relaxation frequency, depends on particle mobility, exactly as the critical shear rate does in the viscosity curves. These two parameters are therefore linked to each other as well as to the zero shear viscosity which also depends on particle mobility, of which particle diffusivity is the fundamental measure. The modulusfrequency curves can also be scaled in a similar fashion as the viscosityshear rate curves. The overlap of neighbouring layers and the resulting interaction forces will depend on the relative distance between particles, which will decrease with increasing volume fraction. Hence, the change in moduli with volume fraction can be used to probe the change of interaction potential with distance. The ZwanzigMountain equation, derived in the framework of molecular dynamics, relates the plateau modulus G to the interaction potential and the distribution function g(r) of interparticle distances r [13]

Fig. 3. Scaling the viscosityvolume fraction curves using the maximum packing, numbers indicate diameters (PMMA data of Fig. 2) [8].

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of the stabilizer layer and provides the means to calculate the limiting viscosities. Empirically it has also be found that the ratio between yield stress and plateau modulus is between 0.02 and 0.04 for many suspensions, irrespective of stabilizer softness, particles size or volume fraction [8]. Hence these two parameters are affected in the same fashion by the stabilizer layer.

5. Viscosity predictions based on dynamic moduli The particle interaction potential, as for instance determined from the plateau values of the storage moduli, can be used to estimate the viscosities. Provided the particles are not too soft, a perturbation theory, based on small deviations from hard sphere behaviour can be applied. As was the case for the expression of the plateau moduli, it is borrowed from molecular dynamics theory. In essence it replaces the real, steep, interaction potential by a hard sphere potential (i.e. vertical line) at a suitable distance from the particle surface (see Fig. 5). This distance provides another measure for the effective thickness of the stabilizer layer, which is smaller than the hydrodynamic value. The ratio between the new value, hs , and the hydrodynamic layer thickness from Eq. (2) depends on the shape of the interaction potential, i.e. the softness of the stabilizer layer. An approximate expression for the resulting particle diameter is used 2(a + hs ) =
0

Fig. 4. Interaction potentials as a function of interparticle distance for two PMMA dispersions and two aqueous latices, calculated from plateau storage moduli (after Ref. [16]).

G =

2 2 15

g(r)

d dr

r4

d dr

dr

(3)

with the particle number density. Eq. (3) has been used for electrostatically as well as sterically stabilized suspensions. In electrostatically stabilized systems the particles can order in a crystal-like lattice order in which the distance between nearest neighbours has a well-dened value [13]. In sterically stabilized systems often a less ordered glassy structure exists during ow, but using suitable estimates for the average distance still makes it possible to calculate the interparticle potentials [8,14,15]. Some results for non-aqueous PMMA suspensions and for aqueous latex suspensions with adsorbed stabilizer are given in Fig. 4 [16]. Three of the four systems in this gure have stabilizer layers with an hydrodynamic thickness of about 10 nm, which is typical for industrial dispersions. In the case of adsorbed blockcopolymers or surfactants, steric stabilization is provided by the moiety of the stabilizer molecule that is not adsorbed on the particle but is extended in the suspending medium. Increasing the molecular weight of this moiety obviously increases the layer thickness of the stabilizer layer and consequently the repulsion force at a given interparticle distance (compare the two latices in Fig. 4). This does not imply that the dispersion becomes more stable under all conditions, at least for adsorbed layers. Changing the relative size of the adsorbed and non-adsorbed moieties affects the strength of the adsorption. The change that apparently increases the stability will actually reduce the adsorption strength. At high shear rates this could result in an irreversible, shear-induced, occulation. Such a behaviour has actually been observed in the latex system of Fig. 4 when increasing the length of the hydrophylic part of the stabilizer molecules. It is obvious that the relation between plateau storage modulus and volume fraction is an important characteristic of a sterically stabilized suspension. It reects the softness

1 exp

kT

dr

(4)

With Eq. (4) a value for the effective volume can be calculated, hs , which is relevant in the case of non-dilute suspensions. Using this value superimposes the limiting viscosity curves of various stericially stabilized dispersions, as demonstrated in Fig. 6 [8,9]. Fig. 6 provides a rational basis for the effective hard sphere approach in the case of sterically stabilized suspensions, with either grafted or adsorbed stabilizer layers. It also connects the rheological properties with the colloidal parameters of the material and allows viscosities to be predicted over a wide range of conditions, at least for model

Fig. 5. Steric interaction potential (dotted line) and corresponding hard sphere potential (full line).

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Fig. 6. Superposition of viscosity curves using the corrected volume fraction hs , PMMA and latex suspensions (numbers indicate diameter) [16].

Fig. 7. Illustration of predictions for the viscosity in binary mixtures (25% 3 m and 75% 127 nm diameter particles) [16].

systems. In practical formulation problems fundamental characteristics as interaction potential and particle diffusivity are often not known in sufcient detail, although some molecular scaling arguments could still be used. Nevertheless, the present approach can always be followed at least in a semi-quantitative manner. Also, the results suggest that measuring, e.g. the maximum packing is an adequate measure to characterize a given stabilizer layer and to predict its effect on the viscosity curves at various particle concentrations.

the power three, Eq. (3), particle size distributions can give rise to a very broad shear thinning region (Fig. 8). The whole discussion has been limited to spherical particles. In all other cases the shape has to be considered, e.g. the aspect ratio (length over diameter) for axisymmetric particles. For large particles the main effect is a reduction in maximum packing. For smaller ones the relations given above cannot be applied quantitatively but qualitatively similar strategies can often still be followed.

6. Particle size distribution In real life systems the particles, even if they are spherical, are seldom monodisperse. The particle size distribution can have a pronounced effect on the rheology. For large, non-colloidal particles various mixing rules are available, as reviewed by Utracki [17]. They can give reasonable predictions for the viscosity. As could be expected from the discussion of the previous paragraph, the maximum packing is still the governing characteristic parameter. A mixture of different sizes can be packed more densely than monodisperse particles, which increases the maximum packing. For large particles the latter can be derived from geometrical arguments. In colloidal suspensions the situation becomes more complex. The contribution of Brownian motion has to be considered, which introduced a different size dependence. It reduces the efciency of packing small particles between larger ones. For mixtures of colloidal and non-colloidal particles mixing rules have been proposed that take the said phenomenon into account [1820]. An example of such a prediction for the limiting viscosity is shown in Fig. 7, where measured and predicted limiting viscosities are compared for mixtures of latex (a = 63 nm) and polystyreen (a = 1545 nm) particles [16]. With each size a shear rate region for shear thinning can be associated. As the dimensionless stress contains the particle radius to

7. Shear thickening At sufciently high volume fractions and shear rates shear thickening will occur in most suspensions. It normally limits the concentration and shear rates that can be used, but it also turns out to be important in understanding particle interactions and ow in concentrated suspensions. General

Fig. 8. Broad shear thinning zones in dispersions with two particle sizes [8].

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discussions on shear thickening are available [21]. This phenomenon is not restricted to colloidal systems, it occurs even more readily with larger particles. The shear rate or shear stress at which shear thickening sets in is considered as the most relevant parameter. When discussing shear thickening it is important to distinguish between two different types. At moderate concentrations a gradual increase of the viscosity with shear rate can often be noticed at high shear rates. No abrupt changes in structure seem to accompany this kind of shear thickening. Experimental as well as simulation results indicate that gradual shear thickening is normal rather than exceptional at the upper limit of the shear thinning region for suspensions with a liquid-like interparticle structure [2,22]. As mentioned earlier it is caused by a stronger increase with shear rate of the hydrodynamic contribution to the viscosity than the simultaneous decrease in Brownian contribution. The so-called high shear Newtonian plateau is actually a limiting case of such a gradual shear thickening region. Under more extreme conditions of volume fraction and shear rate a second type of shear thickening can be encountered. In motion-controlled rheometers it is difcult to study because often the sudden stress jump accompanying the increase in shear rate is too large to be measured. In stress-controlled devices it can be seen that, at the onset of sudden shear thickening, an increase in stress causes in fact a decrease in shear rate, after which the latter changes erratically (Fig. 9). When continuously increasing and decreasing the shear stress the transition between the two regimes shows an hysteresis. Both this and the erratic variations suggest that a statistical process governs the transition. The mechanisms responsible for the onset of shear thickening are still under debate. Most likely more than one mechanism is possible. Hoffman [23] was the rst to show that at least in some suspensions with monodisperse spheres, applying high shear rates caused the particles to order in layers with an hexagonal packing in each layer. This structure

would become unstable at a critical shear rate, signalling the onset of shear thickening. The latter would then correspond to an orderdisorder transition. The instability would occur because of hydrodynamic effects dominating the stabilizing effect of the interparticle repulsion. This approach was extended by Boersma and Laven [24] who proposed a scaling in which the critical shear rate for shear thickening would be proportional to the product T/m a2 . The existence of such a scaling has been conrmed in systematic experiments in which, however, not always an orderdisorder transition could be detected at the onset of shear thickening [25]. Rheo-optical studies on such sterically stabilized suspensions indicate a ow-induced, hydrodynamic aggregation to be responsible for shear thickening [26]. A similar result has been obtained in some computer simulations [22]. As mentioned earlier, hydrodynamic interactions are difcult to incorporate in such simulations and turn out to be extremely important [6]. It should be mentioned that in suspensions of relatively hard spheres the critical shear rate might scale with a3 rather than with a2 [25]. Polydispersity in particle size dramatically postpones shear thickening. It can still occur although it is unlikely that it would be preceded by shear layering. In bimodal dispersions of big and small particles a rst approximation of the critical shear rate can be obtained by plotting this parameter versus the volume fraction of the big particles alone [8]. This proofs at least the strong effect of particle size on shear thickening. Finally the effect of particle volume fraction should be considered. At moderate effective volume fractions, often to about 0.50, shear thickening sets in at a constant shear rate. At very high volume fractions the critical shear rate tends to drop drastically and it is rather the critical shear stress c which now becomes constant. In that region the product c a2 provides a scaling factor which takes into account particle size and volume fraction. The extent of the range in volume fractions over which the critical shear stress remains constant seems to be quite variable and to depend on the nature of the suspending medium.

8. Conclusions Starting from the reference case of suspensions with Brownian hard spheres, the rheology of sterically stabilized suspensions can be quite well understood. The scaling laws for Brownian spheres can be used to predict the effect of temperature and medium viscosity in sterically stabilized systems as well. The stabilizer layer increases the effective volume of the particles which results in a viscosity rise. This could lead to overestimated values for the viscosity, especially at higher volume fractions, as the stabilizer layer is partially deformable. This deformability is expressed by the interparticle potential, which can be used to calculate a more suitable measure of the effective volume for non-dilute suspensions. The interparticle potential is normally not

Fig. 9. Sudden shear thickening in a sterically stabilized PMMA suspension (a = 170 nm, eff = 0.636) [8].

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known, but can be derived from the storage moduli obtained in oscillatory experiments. On the whole, the rheology of well characterized suspensions can be explained in terms of fundamental colloidal parameters such as interparticle potential and particle diffusivity. A distribution of particle sizes reduces the viscosities, especially in more concentrated suspensions. For bimodal distributions some suitable mixing laws seem to be available. Scaling relations have also be proposed for the onset of shear thickening. Medium viscosity, temperature and particle size can be taken into account. These relations do not describe all possible conditions but can nevertheless be used to estimate the effect of changing the composition. References
[1] W.R. Russel, D.A. Saville, W.R. Schowalter, Colloidal Dispersions, Cambridge University Press, Cambridge, 1989. [2] J.W. Bender, N.J. Wagner, J. Colloid Interf. Sci. 172 (1995) 171. [3] I.M. Krieger, Trans. Soc. Rheol. 7 (1963) 101. [4] R.A. Lionberger, W.B. Russel, J. Rheol. 41 (1997) 399. [5] M.E. Mackay, B. Kaffashi, J. Colloid Interf. Sci. 174 (1995) 117.

[6] R.C. Ball, J.R. Melrose, Adv. Colloid Interf. Sci. 59 (1995) 19. [7] W.J. Frith, Ph.D. Thesis, Katholieke Universiteit Leuven, Leuven, Belgium, 1986. [8] P. DHaene, Ph.D. Thesis, Katholieke Universiteit Leuven, Leuven, Belgium, 1992. [9] J. Mewis, Ann. Trans. Nordic Soc. Rheol. 1 (1993) 5. [10] G. Biebaut, Ph.D. Thesis, Katholieke Universiteit Leuven, Leuven, Belgium, 1999. [11] S.E. Phan, et al., Phys. Rev. E 54 (1996) 6633. [12] J. Mewis, et al., AIChE J. 35 (1989) 415. [13] R. Buscall, et al., J. Chem. Soc., Faraday Trans. 78 (1982) 2889. [14] R. Buscall, J. Chem. Soc., Faraday Trans. 87 (1991) 1365. [15] L. Raynaud, et al., J. Colloid Interf. Sci. 181 (1996) 11. [16] L. Raynaud, Ph.D. Thesis, Katholieke Universiteit Leuven, Leuven, Belgium, 1997. [17] L.A. Utracki, in: A.A. Collier, D.W. Clegg (Eds.), Rheological Measurements, Elsevier Applied Science, Barking, 1993, p. 479. [18] B.E. Rodriguez, E.W. Kaler, Langmuir 8 (1992) 2382. [19] R.F. Probstein, et al., J. Rheol. 38 (1994) 811. [20] P. DHaene, J. Mewis, Rheol. Acta 33 (1994) 165. [21] H.A. Barnes, J. Rheol. 33 (1989) 329. [22] J.F. Brady, Curr. Opinion Colloid Interf. Sci. 1 (1996) 472. [23] R.L. Hoffman, Etrans. Soc. Rheol. 16 (1972) 155. [24] W.B. Boersma, J. Laven, AIChE J. 36 (1990) 321. [25] W.J. Frith, et al., J. Rheol. 40 (1996) 531. [26] P. DHaene, et al., J. Colloid Interf. Sci. 156 (1993) 350.