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6 (1976) 1’73~-200 @ Elsevier Scientific Rlblishing Company, Amsterdam - Printed in The Netherlands

173

RHEOLOGY

OF CONCENTRATED

DISPERSIONS

J. MEWIS Katholreke Universltert te Leuven, Leuven (Belgium) A.J.B SPAULL Brunel Unrwersity, Uxbridge (Gt. Britain)

CONTENTS A. Introduction ....................... B. Rheological behaviour of concentrated dispersions ........... (i ) Viscous phenomena ................... (ii) Plartlc phenomena .................... (iii) Elastic phenomena ................... C. Parameters in dispersion mechanics ............... (i) Hydrodynamic effects ............. (a) Spherical particles ................. ................ (b) Nonspherical part&es ................... (Ii) Brownian movement ................... (iii) Attractive forces (iv) Repulsion and stability .................. (a) Electric repulsion ................... (b) Steric repulsion .................... (c) Rheological effects of repulsion .............. D. Structure and rheology .............. (i) Interparticulate bonds in dis~er~on~ : ............. (Ii) Structure ....................... (iii) Elasticity in concentrated dispersions - _ _ .................... (iv) Flow phenomena (v) Relation with other physical properties ............ E. Summary ........................ References ......................... 174 175 175 177 176 180 181 181 185

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189 190 . 192 194 195 195 196

ABSTRACT Concentrated dispersions constitute an important class of materials, not only in science but also in technology, yet complete analysis of their rheological behaviour is still lacking. Available experimental data clearly underline the very general nature of the mechanical response encountered in eoneentrated dispersions. Thus, dispersions could be useful in fundamental rheological studies of the various constitutive equations. The analysis of diipersion mechanics in terms of underlying phenomena is sufficiep.ly advanced to show a strong interrelationship between rheology and colloidal statiility. The variety of structcres found links both. On the one hand, colloidal effects determivie the interpartiele forces

during deformation and consequently the variable structure and the rheological characterbtics. On the other hand, suitable rheological measurements, which may usefully be supplemented with those obtained using other techniques, can elucidate forces and structures involved as shown by analyses in terms of variable spectra and other basic visco-

elaalic measurements_

A. INTRODUCTION

This review deals with the mechanical

behaviour of heterogeneous

systems

containing solid particles having a size or size distribution, at least in one direction, within the range defined as the colloidal subdivision of matter, i.e., between 1 pm and 1 nm [l] _ The terminology recommended by IUPAC [l]

has been followed as far as possible. In view of the present discussion, the following concepts are defined explicitly. (1) Suspension: a heterogeneous two-phase system, of buoyant particulate solid, not colloidal, distributed in a continuous liquid. (2) Dispersion: a two-phase solid in liquid system, the particles of which are colloidal. In this manner, we discriminate between suspensions and dispersions. (3) Aggregate: a tight cluster of particles, strongly held together, so that it cannot be separated in a given rheological esperiment. (4) Floe or flocculate: a loose, thermodynamically metastable, structure from colloidal particles. A floe may be destroyed, to a greater or lesser extent, by the application of stresses in a given rheological experiment and may reform when these stresses are removed. Some authors discriminate further between weak, open structures, floccules, and tight but weak structures, agglomerates. For the present purpose such a distinction is not essential, as all weak structures can be discussed in common_ The concentrations considered here are such that particle interactions become predominan!, in the resistance to flow and deformation. The lower concentration limit will be governed by the particular systems under consideration but can be as low as 1%. Aqueous and nonaqueous systems are dealt with, but more attention is paid to the latter. Emphasis is given to the general aspects of the mechanical behaviour of disperse systems, not just viscosity, and their relationship with the physical phenomena that govern flow, the models of colloidal stability being included_ In comparison with those recently published, the present review differs in its--scope and points of importance. On the one hand, Brenner [Z] and Batchelor [3] focused attention on the theoretical rheology of dilute suspensions; emulsions have been dealt with by Barry in this journal [ 41. Mason gives a bibliography of his work on the microrheology of simple suspensions [ 51; viscous flow of dispersions has been treated by Goodwin [ 63 _ On the other hand, Ottewill [7a], Sonntag and Strenge [ 7b], and Lyklema [ 7c ] stress the developments in the theoretical models of stability_ This review puti dispersion rheology at the crossing of continuum mechanics and stability theory, which together provide the essentiaI elements in understanding and

in describing the rheology of such systems_

a

viscous. It can be solid-like or liquid-like. (i) Viscous phenomena When a constant shear rate is applied to a concentrated dispersion. a single sample may even show a combinatiqn of all these distinct responses f 8 J. 1. RHEOLOGICAL BEHAVIOUR OF CONCENTRATED DISPERSIONS Before an attempt is made to quantify or explain some data. In Fig.7 s-l). This higher level is illustrated in Fig. the relative viscosities even surpass the values represented in Fig. 3. including those often associated with polymeric components. but they do not affect the present discussion. 1. TiOz (0. Hence an apparent viscosity can be defined for this liquid-like behaviour. 1 by orders of magnitude If compared at identical concentrations [ 121. plastic or elastic. there are limitations to the simple test described [9]. Average curve for suspensions of spheres [lo]. in that the stress level is consistently higher than expected from suspension rheology. . This response does not fit any of the simple classes of continua.B. the available information about the general nature of the mechanical response in dispersions is surveyed. Probably all rheological effects known can be produced with dispersions of Hookean solids in Newtonian liquids. where an average result for spherical suspensions [lo] is compared with some selected data for two series of dispersions containing more or less spherical particles. Increased stress levels in flowing dispersions as compared with suspensions. 1.1 pm) Enstand oil (4 + 0) [ 111. Under suitable conditions. In the case of concentrated dispersions. Carbon black in mineral oil (4 = 0. the resulting shear stress usually tends to a constant value. 2.

) in dispersions. the viscosity is nearly independent of shear rate. 2.176 each case. The fact that their rheological properties can be affected by changing the colloidal characteristics provides additional justification for such an * approach. Changes in the shape of the rheogram at increasing concentration (Particle concentration increases from 1 to 6. The viscosity of the Newtonian region at low shear rates is more sensitive to concentration than that at high shear rates.141 and dilute suspensions of nonspherical particles [ 14. and represents qualitatively the average effect of concentration on the rheogram. Similar rheograms are encountered with polymers [ 13. Apart from the magnitude of the shear stress. separating two Newtonian regions. the stress levels clearly differ from suspension data. Quite often a region develops Fig. the zone extending to lower shear rates with increasing concentration. 2. A synthesis of published data on various systems 1s @en in Fig. At low concentrations. its change with shear rate is important. Consequently. As the concentration increases. The majority of disperse systems show pronounced non-Newtonian behaviour.151. . A cross-section through the possible patterns is obtained if the particle concentration is systematically increased. there are sources of resistance to flow in dispersions. Only at the lower limit of the concentration range of interest here can Newtonian fluid properties he found. a shear-thinning zone develops. the existence of which indicates the need to treat them as a separate class of materials in rheological studies.

antithixotropy or rheopexy. A rheogram represents only the equiltbrium behaviour under shear. effects due to ageing are excluded from the discussion. One of the features of concentrated dispersions is the appearance of considerable transients upon instantaneous changes in the kinematics of the flow. 177 where the viscosity decrease is inversely proportional to the shear rate (Fig. above which the material behaves in a shear-thinning or a Newtonian manner again. often around 40% for near spherical particles [ 16-181. will reflect flow anomalies of the continuous and the disperse phases. Reversible decrease of viscosity under shear is usually called thixotropy [ 241. and therefore there is no need to introduce new concepts for time dependency. a Newtonian region must exist at low shear rates. Some materials behave like solids under small stresses and then the viscosity tends to infinity at zero shear rate [8].23. the shear stress becomes independent of shear rate. curves 5 and 6).28]. consequently. Plasticity is more closely related to a model .27]. The relative viscosity seems to follow qualitatively the same evolution as in Newtonian media [ 221. 2. Dintenfass has discussed some of the possible flow curves for such systems [23].. Particular systems might deviate in one way or another from the general pattern outhned above. Thixotropy is attributed to a reversible breakdown of structure under shear and is encountered frequently in dispersions [13. an upper limit for dilatancy has been encountered by several investigators [17-211. It becomes steeper with increasing concentration. Tne viscosity changes described here are reversible. Most often a sudden application of shear or a sudden increase in shear rate causes an initial overshoot in stress. however. for the moment. is less common 1241 and is often confused with shear thickening. However.19. Viscosity measurements usually become impossible before the upper concentration limit of closest packing is reached. it seems useful to introduce the concepts of thixotropy and antithixotropy wherever the emphasis is on time effects. followed by a progressive decrease towards the equilibrium value. the physical reality of antithixotropy has been proved beyond doubt [19.26. It could be argued that on the one hand shear thinning and thixotropy and on the other hand shear thickening and antithixotropy emanate from the same changes in structure. a shear-thickening or dilatant region develops at higher shear rates. Starting from a critical concentration. The global viscosity. A reversible increase of viscosity with time under shear. If the dispersion is a real liqutd. Nevertheless. (ii) Plastic phenomena The viscous phenomena could be discussed with little reference to idealized rheological constitutive equations.24. Slightly different definitions of this concept are discussed by Reiner and Scott-Blair 1251. When measurements have been extended to sufficiently high shear rates. One obvious group consists of dispersions in non-Newtonian media. This plastic region will be discussed below. resulting in complex rheograms.

[8. It can be concluded that plastic flow is a special and limiting case of viscous flow. as can be seen by suitable experiments [8. the shear stress remains at the critical value irrespective of the shear rate applied. A critical strain corresponds to a critical stress of a plastic material. Few investigators have attempted to make measurements under low and constant values of shear stress in order to prove a no-flow condition. The maximum or overshoot value of the transient shear stress. It is only a model parameter of the flow curve and is not a direct measure of the stress limit for flow. some change of shear stress with shear rate is taken into account [29]. after a sudden application of shear. -r__ . the overshoot technique cannot be used to prove the presence of a plastic-yield value. Elasticity. there are few systematic studies of this parameter [ 31). Its value varies considerably according to the kind and the concentration of the components. The more concentrated ones show a solid-like behaviour at low stresses and strains for which an elasticity or a shear modulus can be determined [ 8. it is vrry small. implies the means to store mechanical energy reversibly during deformation. Although helpful in describing the behaviour of the material.36]. It constitutes an important parameter in industrial dispersions. including ro. More specific is the existence of a yield stress. It is an important parameter in understanding the deformation mechanism in concentrated dispersions. the yield stress. Some plastic dispersions are thixotropicas well.32-341 which complicates the measurements.. Under flow. This constancy of shear stress under plastic flow is identical with a viscous flow. In various papers. (iii) Elastic phenomena From an energetic point of view. . on the contrary. 10m3 or lower. Then the model parameters of the flow curve might depend on the kinematic history.35. 7. viscous phenomena result from dissipative processes. They proved solid-like behaviour below a critical stress in real systems. Nevertheless. It has been mentioned above that various dispersions approach this kind of behaviour.30]. In low viscous media. over a limited range of shear rates. to the fundamental properties of a colloidal system. A material is considered ideally plastic if it does not flow as long as the shear stress is below a critical value rO.178 description. is often called the apparent yield value. where the apparent viscosity decrease is inversely proportional to the shear rate. In models for non-ideal plastic materials. The presence of macromolecules is not necessary to cause dispersions to behave elastically. The different physical interpretations of “absolute” and “apparent” yield stresses should be kept in mind if one wants to relate r. Often. Such a value of r. A notable exception is the work of Rehbinder and his associates [ 81. is often assumed to provide a value for the yield stress. as seen in the flow curve. values between 10 and 10’ NmD2 have been recorded. is calculated by fitting part of the flow curve to one of the models for plastic behaviour.

both increase with decreasing particle size [42.2.39-411. the moduli become larger if the concentration of the disperse phase is increased [ 32. and in particular in the plateau region.383. . The curve resembles that of cross-linked polymers [ 38 1. At higher concentrations. 4244]. the apparent yield value and the shear modulus are affected in a similar way by concentration changes [31. while the plateau of the medium also appears in the dispersion (higher plateau). Transient and oscillatory tests indicate that dispersions combine elastic and viscous elements and produce a viscoeiastic response. two typical results are shown in Fig. carbon black in mineral oil [ 391. Formation of one or two plateau regions in the mo$ulun-frequency curves for dispersions in Newtonian (1.42. Again a plateau develops. 3.) media (-G . the reason being that a three-dimensional structure exists in both cases. For dispersions. 3.. Curve 1 represents data taken on a system having a Newtonian fluid as the medium. owing to the dispersed phase (lower plateau).C ). It has been used extensive. . as is the case with viscosity (section (i)). carbon black in polystyrene solution [-IO].46 1. Often. . Such behaviour can be completely described either by a spectrum of relaxation times or the time or frequency function of the modulus [ 37. Mechanical spectral analysis is extremely useful in analyzing the structure of matter.36. The viscoelasticity resides completely within the structure of the dispersed phase. and an increasing number of results on concentrated emulsions are becoming available [ 4 1. the increase in moGuli becomes steep.43]. In general. ly on polymers [ 381. In addition.) and viscoelastic (2. 1.45. 3 has been obtained on a dispersion in a viscoelastic medium. The presence of a plateau region has been demonstrated repeatedly in solid-like disperse systems [3.179 rog kw) Fig. Curve 2 of Fig.

elasticity reveals itself by normal stress differences.531 and from the time dependency of nonlinear vihrations [40. The latter are determined by the physicochemical bulk and surface properties of the components. The plateau modulus changes between wider limits in dispersions and depends more strongly on concentration. Structurized dispersions show considerable normal stress differences. Destruction of the structure results in nonlinear oscillatory behaviour [39. in most cases. which increase faster with concentration than the shear viscosity. liquid-like dispersions. C.40. at least qualitatively. With dispersions. they are often difficult to measure. at least under certain conditions [8. the effect of network stticture becomes less important in this frequency region. As a result.491. however. as seen from the changing viscoelastic spectrum 140.411. Thixotropy and elasticity can exist simultaneously in dispersions.50]. Clearly.180 though shifted in level. thus extending the time scale over -which transient and thixotropic effects are noticeable. Thixotropic dispersions have been shown to be viscoelastic. the difference between the two kinds of dispersion becomes smaller [ 39.52]. between disperse and polymer systems. As soon as the dispersion structure is completely broken down. In some cases. Under steady-state shear flow. beyond the structural plateau. increasing the nonlinearity of the mechanical response. The few available data nevertheless provide a picture consistent with oscillatory experiments [ 11.481. while the loss tangent increases or goes through a maximum [ 44. the moduli decrease with increasing amplitude. As is to be expected. Eydrodyn&Gc effects result from the mere presence of solid particles in the flowing medium. The rates of structural changes are normally much slower than in polymer systems. but supporting evidence is still lacking. the stress amplitude depends on strain. the viscosity and normal stress curves are parallel to those of the medium [ 111. The difference can be explained on the basis of of structural kinetics. For non-structurized. the stress pattern is strongly distorted. The resulting perturbation of the flow . At higher shear rates. It can be concluded that there is a considerable similarity. but the moduli still increase with concentration. the highfrequency moduli of dispersions in viscoelastic media change less with concentration than the low-frequency moduli [47]. the normal stresses approach the values for the continuous phase. The quantitative differences stem from the divergent nature of the structure in both types of material [ 521. structure is also more fragile.50]. where the structure is more broken down. At higher frequencies. It is particularly difficult in these experiments to avoid instrumental artifacts. The viscoelastic properties will then depend on the kinematic history. but the periodic change remains sinusoidal [51]. the lower plateau is missing.49. PARAMETERS IN IXSPERSION MECHANICS Distinction is made between hydrodynamic and colloidal stability effects. The structure can also be destroyed by use of oscillations with an amplitude above the critical value.

54].. As with other non-Newtonian systems.551 for the relative viscosity TJ.181 field causes an increase in energy dissipation as expressed by a modification of the bulk rheological properties. The most recent and complete analysis by Batchelor and Green [ 571 gives a value of 7. It is estimated that truncation at the c? term is valid for concentrations up to 10%. however. The higher-order factors k.e. and . for various reasons. the results of suspension rheology can be applied to dispersions. there is no effect of absolute size on the hydrodynamic behaviour. For a monodisperse system. The continuous phase affects the flow through its viscosity qm. their relative concentration and the flow field. (1) The factor k. and so the discrepancy is not surprising. Spherical particles The spherical shape is more tractable than any other and has been covered more extensively.: t7r = 17hm = 1 + klc + k2c2 + k3c3 + . (i) Hydrodynamic effects The average stress in a flowing suspension depends on the geometrical and mechanical characteristics of the components. Therefore. determines the linear concentration range where there is no interaction between particles. Its value has been calculated by Einstein to be 2. shear. Experimental values of k2 are usually above the theoretical value [10. the densities must be considered. At low shear rates. Detailed calculations are available for the c* term only [ 541.5 1561. The theoretical aspects of suspension rheology have been reviewed recently by Brenner [2] and by Batchelor [3]. they provide information about some factors affecting the flow of more concentrated systems. Most factors that could affect this experimental determination would tend to overestimate k2 . colloidal effect. Brownian movement is a size-dependent. size distribution and shape. It has been pointed out by Batchelor that there is no theoretical evidence that concentration effects should be most suitably expressed in such a way [3]. a. compression. The available analyses deal with lower concentrations than those of interest here.6. . which is also dealt with. extensional. one might expect effects from shear rate and from the type of flow. in suspension rheology. If inertia effects have to be included. the shear viscosities cannot be generalized as such to other flow fields [Z&3]. As soon as particle interactions control viscosity. i. Nevertheless. a complete description of their mechanical response. are often explained as representing the additional effect of simultaneous collisions of n particles at increasing concentration. without giving. the rigid particles through their concentration.. the dependence of Newtonian viscosity on volumetric concentration c is usually presented by a power series expression [ 54.

If the frequency is systematically increased. the particle interactions might depend on frequency and amplitude. At high frequencies. Little experimental infcfmation about this region is available. Packing and interlocking provide some explanation for it. The possibility of a much closer packing as compared with monodisperse systems shifts the critical concentration to higher values and reduces the relative viscosity at fixed values of c. Interparticle forces can give rise to structure formation. even in suspensions. as they will influence the interactions and consequently the higherorder terms. one must rely cn experiments. An average curve is shown in Fig. using the viscosity of the mixture of . Rutgers and Sherman have reviewed the earlier work [54.5. The concentration affects not only the Newtonian viscosity but also causes non-Newtonian behaviour. particles are close enough for weak dispersion effects to become noticeable.61. the particle movement eventually lags behind that of the medium and causes a phase shift for the stress. preventing the suspension from flowing. However. The data of Hellinckx and Mewis on dispersions support the picture given [47]. shear thickening can appear. This results in a viscoelastic response that depends on size [63]. cat. Except for steady-state shear flow.59] or by analyzing near-contact hydrodynamics [60]. The drop is particularly pronounced in bimodal mixtures of large and small particles where the smaller particles fit in be&ween the larger [67691.40. The crowding of par%les around that concentration results in an interlocking. The oscillatory flow mode can also be used to investigate inertia effects. the viscosity-concentration curve will consequently be flatter than in Fig. stability effects seem to dominate [ 16--181. In concentrated suspensions. A similar result holds for inertia effects under steady-state flow [ 641.sing the viscosity to increase [ 3. 182 transient. the absolute size enters the calculations only in case of inertia. the relative viscosity can be obtained by multiplying the relative viscosity of the fractions rjr.. Empirical and semi-empirical relations have been suggested in great number.55]. The two main features are an increasing sensitivity of qr to c and a tendency for viscosity to rise towards infinity when c reaches about 0. In the rheology of monodisperse suspensions containing large spherical particles. time-dependent types of flow show some ‘-ities.70. 4. from which empirical relationships have also been derived. For dispersions.62]. They can be illustrated by means of oscillatory flow. For higher concentrations. With a known mixture. where the interaction is minimal. attempts have been made to approximate the complex interactions either by using cell models [58. As their accuracy is as yet unknown. The data show considerable scatter. at high concentrations. The latter is explained by the existence of a maximum packing for spheres in that range. 4. In contrast.i. in heterodisperse systems the distribution of particle size can be of primary importance because it determines collisions and packing [65. interesting pecuL. Shear thinning owing to volumetric effects in suspensions of spherical particles is not very pronounced and has not been studied systematically [ 31. For values of c greater than approximately 0. particularly at high values of c.66].

Jeffrey’s wvorkhas heen extended and experimentally verified by Anczurowski and Mason. Orientation can be expressed by orientational distribution functions. The relative viscosity should be independent of the medium... (ii) Brownian movement Small particles distributed in a fluid undergo a statistical movement. Anisometry tends to increase alignment in the flow direction.22 J_ (b) Nonspherical partictes In addition to size and concentration.69 ] 77.that spheroids rotate around an axis perpendicular to the plane of shear. This effect was predicted theoretically by Batchelor [78] and verified experimentally by Mewis and Metzner [ 79 1. at least for suspensions in Newtonian media. = nit7r. the rheological nature of the medium has been shown to have an effect on the distribution function and consequently on the viscosity [77]. that effectively acts as a dispersive mechanism. Theoretical work has been mainly confined to the case of dilute suspensions of axisymmetric particles. It has an effect such that geometry and interaction are not completely determined by the relative position of the particles alone. III extensional flow. for fiber-like particles. Jeffrey presented the solution for spheroids [?O] He concluded. even at low concentrations. it also seems to promote alignment. which reduces the energy dissipation. their orientation must also be allowed for. if the aspect ratio is large enough. Viscoelastic media have been considered in a few investigations. which remain unexplained [ 6.01 for this number is sufficient to markedly affect the flow pattern./I)m in which L is the length of the particle and pm the medium density. translational and rotational. . They included transient behaviour and cstahlished the effect of collisions on orientation distribution functions [ 'il--731.From t!~ calculated orientation distribution function. i. shape becomes a factor now. some differences are found.77].e. The presence of particles increases their viscosity and normal stress [ 11. Inertial effects work in the opposite direction [76. qualitatively in a similar manner as in Newtonian media. Quantitatively. A last variable is the medium. = L2?P. (3) Re. A value of 0. Increasing the shear improves the alignment in the dlrection of shear.221.183 smaller size fractions as the medium viscosity for the next fraction [ 68. The particles spend more time with their largest axis parallel to the flow direction than perpendicular to it.75]. Hydrodynamic particle interaction appears at lower concentration with nonspherical particles. They are governed by a particle Reynolds number Re. interaction becomes pronounced. the result is less pronounced. (2) For the continuous size distributions. the viscosity and the normal stress differences can be computed [74. Finally.

82.* and a2 are the quadratic mean displacement and rotation and t is time. It entails a tendency towards more random radial and orientational distribution functions. T the absolute temperature and R the radius of the spheres. Thus for spheres Dt = kT/67rq0R. and D. One of the main reasons why Brownian movement is considered in suspension rheology is the fact that it makes the equilibrium distribution functions and (5) . of spherical inclusions in the absence of other than volumetric effects. Brownian movement introduces particular properties in a dispersion. 4) also makes a direct contribution to the stress [ 51. Brenner S*asrecently discussed Brownian movement effects in translation and rotation with axisymmetric particles [80]. F rom the point of view of rheology.R3 where k is the Boltzmann constant. Average viscosity-concentration curve for spherical suspensions. showing the effect This action is determined by the diffusion coefficients tion and rotation. for transla- (4) where ‘. which in turn will af<ect the stress.. 4. Results on particles of general shape will be published [ 811. The diffusion coefficients express the Brownian movement as a balance between the acting thermal movement and the viscous resistance..184 Fig. respectively [56b] --2 x =D.t D. The additional angular velocity (Fig.C and e2 =D. = kT/8nr). D.

(iii) A t trac tive forces Particles dispersed in liquids will be in an attractive field as a result of the van der Waals forces existing between them.185 independent of the initial conditions [2. and. The attraction between two particles can. Transient behaviour due to Brownian movement has been dealt with by Hinch and Leal [ 831. Sheraga has shown the extent of shear thinning that can be expected on this basis for spheroids of different aspect ratio [ 153. shear-thinning. The physical phenomena described until now suffice to explain qualitatively the various rheological phenomena encountered m dispersions.. Therefore.. i.e. in principle. The viscoelastlc response to be expected from Brownian movement has been calculated in steady-state shear flow. Their relative contributions are expressed by translational and rotational Ptklet numbers. In dispersion rheology. At higher shear rates. Available quantitative information is limited to dilute systems. but. even so. induced and instantaneous dipoles or some combination of these. the ordering effect of shear becomes systematically more important. which for spheres are [Z] (6) At low shear rates. Randomization of the distribution functions due to diffusion is a timedependent process. behaviour appears. The expression is a generic one describing the total attraction as a result of interaction arising between perma-. i. Theoretical results are available only for dilute suspensions.e. During flow. considerable differences between theory and experiment can be found (see section B). Krieger has made an attempt to apply some of these principles on more concentrated dispersions of spheres [ 84 1. normal stress differences [ 851 and under oscillatiops.3]. As a result non-Newtonian. The effects of multipolr? interaction other than between dipoles are small or negligible. In nearly all types of atoms and molecules.e. low P&let numbers. be calculated by summing up the contributions from all the atoms and molecules constituting the individual particles. with the exception of yield stress.. the effects of Brownian movement and shear are superimposed. i. riiffusion dominates and prevents any time-average alignment of anisometric particles with respect to the shear plane. nent. as such. dynamic shear modulus [ 821. It brings the dispersion dition. the route from interactions on an atomic and molecu- . serves as a “memory” back to a random equilibrium conto this reference situation. additional contributions to the internal stresses must be considered. Brownian movement is of direct importance due to the smaller diameter of the particles. Memory corresponds to elasticity In mechamcs. the greatest contribution to the total attraction arises through the interaction of instantaneous dipoles.

Longuet-Higgins and Widom [91] suggested that in liquids far from the critical point.186 lar level to their macroscopic effect being known. In a further extension. the attractive force depends on the medium: generally the following approximation is used . the effect of adsorbed layers could be allowed for [ 881. Apart from the distance dependency. = AIHg 11 (7) (8) where Ai is the interaction parameter and H. is the Hamaker constant for the particle material and x = d/D. under shear. viscoelasticity and thixo’tropy./* -AZ*)* (9) where A. The original theory of these interactions .. the factors that influence these forces should be considered: the geometry of the particles. the short-range repulsive forces (see below) determine the structure while the longer-range attraction forces merely provide an almost uniform background potential that holds the liquid together. The general expression for an arbitrary particle geometry. the species adsorbed on their surfaces. where d is the distance between the surfaces of the particles [ 871. can be thrown into the form V. Ai = (A. shear thinning. This idea can be extended to dispersions. when the inter-particle distance is not large. (iv) Repulsion and stability Interaction betw. As the rheological behaviour of concentrated dispersions depends on the interparticle attraction. the geometrical parameter. 7%~ attraction energy between two particles must be influenced by the presence of surrounding particles in a concentrated dispersion. with fluid surrounding the particles. is the Hamaker constant for the medium. Suffice it tosay that the attractive forces will oppose deformation. the potential energy will increase due to separation of the particles. Gosiewski attempted a calculation of interaction effects using a cell model technique [go]. The rheological consequences of the London-van der Waals forces are more efficiently discussed together with repulsive forces. which contains the effect of shape and interparticle distance. For a geometry of two spherical particles of equal size in vacuum. consisting of an attractive and a repulsive part. and the influence of the surrounding particles [ 7. Flocculation calculations based on floe diameter rather than on the diameter of the elementary particle results in erroneous stability predictions [ 891.?en colloidal particles is composite. Little is known about the changes induced in this manner. the potential energy of attraction V. These concepts will be used to explain high viscosities. the nature of the liquid medium. is given by va =-12 [ x*+2x 4 1 + X2 +2X+1 1 x* +2x f 2 In ( -42 +!2x+1 where A.861.

e_. This figure shows a deep primary minimum and a less pronounced secondary one. an electric double layer may be formed on the liquid side of the solid-liquid interface. showing two possible. the ions of which can be exchanged with those of the bulk. . thus limiting aggregation or flocculation and permitting a stable dispersion to exist. surface charge. one by Derjaguin and Landau 192 ] and the other by Verwey and Overbeek main development ing from electrical [ 931. The shape of the curve representing the total interaction energy between two particles as a function of distance depends on the values of the various parameters [7b]. A possible form of particular interest in rheology is given in Fig. The over the years has been to include with the repulsion arisinteraction that due to steric interaction [7a. or in some instances no charge. Potential mteraction energy between particles as a function of distance. 94 1.187 Fig.g. The interaction depends on a pumber of influences. it consists of two parts. interparticle distances.. stable. In a first approximation. 5. and their direct experimental determination was reviewed by Ottewill (a) Electric repulsion When a particle. Methods of caIculating the force between spheres have been given by Bell and Peterson [ 951. the shape of the particles. hence the term DLVO theory. having an electrostatic . is dispersed in a continuous liquid. one with strong and another with weak interaction forces. consisting of ions of different sign. The sum of London-van der Waals and repulsion energy equals the total potential energy. If the two particles are at a suitable distance. an inner part close to the surface of the particle and an outer diffuse part. separated by an energy barrier. was given in two publications. 5. interaction is strong enough to keep them at this distance. dielectric constant of th? bulk liquid and the concentration of electrolyte in the bulk. The opposing forces can counterbalance each other. corresponding to the potential wells.

e. The deflocculation under shear will cause shear thinning. which can be broken down under the mechanical action of shear. the adsorbate layers undergo elastic deformation during collision. this is the secondary effect. The electric repulsive interaction by V. In that case repulsion occurs. theory is not available for the effect of movement of particles on their steric repulsive interaction.. The tertiary effect. Theory is mainly concerned with static situations. Usually two mechanisms are distinguished.94]. where- . A similar effect appears with steric repulsion [ 981. -L-vine and co-workers are attacking this problem using a cell model [ 861. This reversible mechanism entails a whole range of rheological effects. With high adsorbate concentration.188 [7a]. is outside the scope of this review. (b) Steric repulsion Particulate material dispersed in aqueous and nonaqueous media can be stabilized by the adsorption of polymers and surface-active agents as a result of what is called steric repulsion. If the adsorbate concentration is relatively low in the adsorption layer. the repulsive forces keep the particles further apart. Vincent has questioned the correctness of additivity of attractive and steric repulsion forces [ 88 1. ln[ 1 + exp(-Kc!)] /4 potential V. the surrounding particles must be taken into account in concentrated dispersions. $e the surface potential and K the Debye-Hiickel constant [7b]. i. During collision. (c)_Rheological effects of repulsion Three electroviscous effects are associated [ 655 ] with electric repulsion. constant surface charge has been applied instead of constant surface potential [ 96. mixing is less probable. The global result of any interparticle potential energy field must be to affect the interparticle distances. There are a number of problems that are of interest in rheology currently engaging the attention of colloid chemists. Different assumptions about the boundary conditions at the particle surface have been made for the calculation of the potential as the distance between the particles is varied. also causing repulsion. if there are potential wells (Fig. = ED@. Some recent reviews are available [7a. 5) these could be preferential distances under suitable energetic conditions. In particular. is given. The primary effect resalts from the distortion of the ionic atmosphere around the particles under flow. arising from changes in size and shape of flexible macromolecular ions. causing an increase in free energy. with qualification. particles can form flocculates. comparable with an apparent increase in particle size.971. As with London-van der Waals forces. increasing the viscosity. Of special importance to rheology is the secondary minimum. The presence of flocculates will necessitate large stresses during flow. If it exists. (10) where E is the dielectric constant of the medium. the layers can interpenetrate during the mutual approach of two particles.

Insufficient shielding of the primary minimum by an energy barrier inevitably leads to irreversible aggregation. knowledge of the shape of the potential energy curve permits calculation of the force or energy necessary to separate the particles to a distance where the interaction becomes small and thus where the direction of the interparticle forces can easily be changed by an applied external couple. the primary and the secondary.105] and the role of adsorbed surfactant and polymers [106-1081. If the floes throughout the sample unite into one structure. A large body of experimental work supports this conclusion. Although chemical bonds. From stability theory. It has been mentioned above that two energy minima are distinguished in colloidal science. the radial and orientational distribution functions can be consldered to describe “structure”. Systematic rheological studies useful in physicochemical research are relatively rare except for clay minerals [99. at least qualitatively. They force the system to a configuration having least potential energy. It must be concluded that stability theory provides the basic elements in understanding the rheological behaviour of concentrated dispersions. In concentrated systems. the potential energy must be overcome. for flow to occur. As an illustration. Some of the evidence suggests that the rheology can be explained only in terms of a bond having a reversible character with respect to stress . In some dispersions. may occur between particles. elastic behaviour is to be expected. the concept of bond can be used and defined on a physical. indicating the presence of real yield stresses. STRUCTURE (i) In terpartrculate bonds m dispersions The elements of the previous section can be combined cal behaviour through a physical picture of structure. The flocculation-deflocculation situation also will cause viscoelasticity in a way similar to the combined effect of Brownian motion and shear (section (ii)). it is concluded that this condition corresponds to well-defined interparticle distances. the predictions from potential-energy considerations [ 18. the dispersion becomes solid.100]. the interparticulate interactions thoroughly change the picture. The effect of electrolyte concentration has been found to follow. D. Further. yet which readily reforms when stress is removed.103]. the dielectric constant [104. potential basis. as evidence suggests that the physical bond dominates in the rheology of dispersions. Under small deformations. the same holds for the electrokinetic mobility [97. especially hydrogen bonds.189 as the subsequent reflocculation explains thixotropy. The existence of reversible structures seems to require the presence of a . they are not considered here. to approach rheologidispersions and ip dilute suspensions.one that stress destroys.102] .101. a few results of general interest are quoted. application of a shear causes the particles to surmount the barrier and reach the primary minimum [ 1091. Hence.

various intermediate situations might be expected. even if they are not affected by the shear stresses. Four are quoted [115-1181. Intuitively. a linear growth leading to chain-like structures. as in an outstretched necklace. In the following discussion. Structure formation carries a statistical effect. The most obvious method of detection is that of direct observation. the bonding In the aggregates remains unchanged during flow or deformation.119]. The changing structure can also be detected and analyzed by various physical techniques: electric conductivity [115. a detailed analysis of the data is not yet possible for concentrated dispersions. dielectric [116.190 secondary minimum and a suitable barrier to the primary one. For most techniques. but by comparison of rheological and other physical data it can be concluded that isolated structural elements of variabie size and shape exist in some cases and continuous elements (networks) in others. Other bonds might esist in the dispersion.114 3. Only above a critical concentration is flocculation observed. In particular. two possibilities suggest themselves. the depth of the energy well must amount to several kT units of thermal energy. Flocculation kinetics is somewhat similar . particles are understood to be the flow units that cannot be broken down under stress. These two shapes are to be considered extreme simplifications of reality. particle concentration is a necessary factor. which gives rise to a more spherically-shaped cluster of particles. its value may be used to determine the depth of the minimum in the potential energy interaction [llO]. In determining the stability of a dispersion. and to a frrst approximation. For this reason. size and properties of the flow units and cons lqently the global rheological behaviour 1113. they contribute to structure and rheological behaviour and interfere with the interpretation of rheological data. At high concentrations. in order to be physically meaningful the bond must be able to persist for some time. they are either elementary particles or aggregates. Chains could develop further into a network. the solid elements of the dispersed phase often consist. For the existence of flocculated structures. with or even without liquid between them 11111. In practice. It changes the shape. at least partially. many reported examples of powerful evidence exist. the possibility then exists for the formation of stable structures. and a random growth. This situation could arise as a result of an incomplete dispersion operation or insufficient stabilization of dispersed particulate material and is usually referred to as “degree of dispersion” [ 112 1. (ii) Structure If particles can form stable physical bonds. However. of aggregates of elementary particles strongly bound together.120] and optical [121] measurements. the difference between the two cases must disappear. In addition. which limits the regularity to be expected. This lack of regularity complicates the determination of the spatial arrangement of particles.

All mod& are based on simple assumptions about the sequence in which bonds rupture. Chain formation seems to have been underestimated m these simulation studies. (0)). from which it has been derived_ Initial aggregate size calculations were based on random collision between flow elements leading to a permanent union.(t) is also a function of shear stress. Van den Tempel’s treatment considered only the equilibrium structure under shear. The result is a time-dependent distribution function for size Iv. In order to explain shear thinning and thlxotropy. Weymann and Mercer [137. the total number of elementary particles. other than . The problem of particle arrangement within the aggregate has been tackled by computer simulation [ 1241. This probably stems from neglecting the effect of the shape of growing particles on the potential energy. He has shown the possibility of chain formation [125]. In chains.130J. they can be expressed as Nk(l) = &-l(f) [ lY] (12) where S. Difficulties arise due to the lack of information about the real structure of the flocculates and the corresponding susceptibility to rupture under shear. A bond strength distribution could be introduced 11391 or weak spots in the geometrical structure located [ 1401. all bonds are usually given equal probabSlity. it will induce breakdown of flocculates [ 128. and it can change the stability condltlons [ 19. Shear will affect the collision frequency (1271. In later studies.(t) = N. the other two studies contain in addition the transient distribution functions. Casson introduced an average length of rod-like flocculates as a function of shear rate 11341. It should be pointed out that Casson assumed flocculation to occur as a result of association in the primary minimum. mainly in rheological studies [135-1381. Chain-like structures have been dealt with by van den Tempel 11351 and by Ruckenstein and Mewis [136].(t) is the total number of flocculates and S.138] considered sphere-like flocculates.191 to aggregation kinetics.129]. the time necessary to reduce the total number of floes to half the original number (N.(0)(t/&)k-l/(l + t/t. Sutherland has produced some interesting results. the influence of shear rate on flocculation kinetics should be known. and also that the average shape of the aggregate is spheroid&l with an aspect ratio of thrse [ 1261. distribution functions under shear were calculated. For the Ruckenstein-Mewis model. S. All the models mentioned neglect specific changes in shape. First.)k+’ (11) where ATkis the number of aggregates containing I: particles and t. These assumptions were first applied by von Smoluchowski in his kinetic theory of rapid coagulation [ 1221. based on von Smoluchowski’s theory. Overbeek has discussed some improved versions of this theory [123]. only the number of bonds was considered [131--1331.

it can also reduce the interparticle repulsion. that different kinds of structure are encountered when a dispersion is subject to snear and when it is subsequently recovering at rest. this decrease in repulsion could lead to shear thickening and antithixotropy. A WLF reduction for temperature [33. even without shear. the fact that the shift factors are independent af concentration 11491 seems to indicate that elasticity . Indeed. Rehbinder [ 146 ] and Uchida [ 1473 put forward entropic mechanisms for elasticity. Available data turn out to be inconclusive [ 33.148].105]. In principle. [118] noticed a rearrangement of chain-like aocculates to a more spherical shape. It has been shown that the edges and the flat sides of these particles carry opposite charges. Neither can be eliminated a priori. Mason et al. Using these materials as a model. [ 1411 have shown. The chain-like geometry. Unfortuxtely. based on orientation of the plates.142-1441. behave as solids. a potential mechanism as defined from the DLVO theory will describe the elastic response. with which cardhouse structures for the flocculated system have been suggested [ 1453. at least under small deformations. L change in temperature could provide a solution. Thus. iavoured on an interaction-energy basis. Corresponding model calculations are available [ 32. potential and entropic mechanisms can be distinguished. the simplification seems reasonable. it is impossible to come to any definite conclusions. (iii) Elasticity in concentrated dispersions An important and as yet unanswered question is the seat of elasticity in concentrated dispersions that. which would increase particle interaction. suggesting similarity with polymer systems [381_ However. using rheological and dielectric measurements.192 those caused by simple changes of size. since polymers were present.45. In highly concentrated dispersions of spherical particles the deformation must be located mainly in the interparticle space. It is difficult to modify the controlling parameters separately and thus obtain conclusive evidence. Both mechanisms give reasonable values for the modulus. is forced into a form that is more favourable from a hydrodynamic point of view. experimental evidence that does not support this assumption has become available. The minor effect of temperature on the modulus for some aqueous systems could be interpreted as supporting the potential explanation. In addition Mewis et al.144.149] has been applied to some materials. Bearing in mind the difficulties in determining floe shape. a phenomenon they called structural hysteresis. Hence. Some clay minerals are in the form of flat plates. The physical reality of such a mechanism has been supported by dielectric [ 19 ] and by rheological measurements on systems with variable colloidal stability [ 17. From a thermodynamic point of view. Whereas the normal effect of shear is to break down structure.

the elastic behaviour is essentially nonlinear. the reason being that rupture occurs readily and changes the pattern. Sherman discussed experimental evidence that proves a clear particlesize effect. Similarly. The latter result is not substantiated by the experiments which suggest a stronger change with c. Sherman got a similar dependence in the modulus equation. and selecting a convenient expression for the potential-energy field.143 1. A constant modulus is only to be expected in the limiting case of infinitely small deformations [ 321. illustrating the complexity of the situation. due to van den Tempel [142]. it must also depend on concentration. This conclusion agrees with the experimental data [f&32. its power is about 3 in all models. They have been used to calculate the Hamaker constant. The basic model. Nevertheless. sliding of the edges on the plates has .193 originated in the polymer. For particles having a shape between a sphere and a flat plate. its voids fiIled with liquid. starts from a network structure . In reality. yet the configuration they form extends throughout the whole of the available space. (13) through the expression for the potential energy. By introducing a more complex structure where the number of bonds changes inversely.33]. As the potential energy is not a second-order function of position.42. van den Tempel calculated the modulus from the second derivative of the potential energy to particle distance. Deviations have been reported [150]. the modulus is predicted to be proportional to the Hamaker constant and to the concentration. 1511.149. Such a structure satisfies two requirements: the particles are close together as a result of attractive forces. This statement seems difficult to reconcile with the available evidence. only undisturbed structures hsve been considered. his model provides the framework for the inclusion of nonlinear concentration effects. Sherman argued that there are persistent effects of particle size that obscure the picture 1451. With spherically-shaped particles. for which purely elastic models could be used. if the number of bonds depends on the particle size in a non-ideal network. The interparticle distance enters eqn. the material response is always viscoelastic.which are branched and interlinked to form a three-dimensional mesh. No effort has been made to explain the effect quantitatively. which illustrates the possible uses of rheological measurements to study structure and colloidal stability in dispersions [144]. the prediction is that the modulus is not particularly sensitive to their size { 32. The previous models predict the right order of magnitude of the modulus.a linear assembly of chains of particles placed close together . For cardhouse structures. the quantitative expression of which cannot accurately be determined.144. Using this model of structure. closer to a logarithmic relation [ 32. Up to now. Indeed. his relation is G = ~AcD~‘~/~~xc~-~ (13) where x0 is the equilibrium particle distance. The case in which a potential elasticity is plausible is important because it allows for a direct link between rheology and colloidal stability.

194 been suggested as a source of viscosity. At higher concentrations. An interesting elaboration of this theory which incorporates surface parameters has been published by Hunter et al. However. r. The predicted relation with zeta potential has been verified experimentally. Hunter and Friend concluded their data that the repulsive energy is determined by constantsharge rather than by constant potential conditiom and that the primary minimum conditions. Michaels and Bolger used the interaction energy during collision to calculate the shear viscosity of low concentration kaolinite dispersions [ 154 1. plastic viscosity and yield value change exponentially with concentration [ 42. This factor undoubtedly increases the resistance to flow. These flaw models are valid only at relatively low concentrations and high shear rates. whether it overshadows other partic!e interactions has not been proved. Van den Tempel presented an analysis that uses the interparticle forces to calculate the floe size.155]. are relevant in high shear calculations. For the apparent yield value they find 70 (141 I where < is the zeta potential. bonds rupture and subsequently reform. flow can occur.103].156].ructural changes j153]. the energy required to separate particles after collision for stable.103. A change in distance between two particles would necessitate flow in the pxpressions for flow of this type are available and can be intermediate liquid.erp(-Kcxo ) ] c2 . f*‘7. 151]. In general.42. first suggested by van den Tempel 11421 and !ater applied by l’akano [ 152 J to calculate a single relaxation time. I-Ie obtained a Bingham equation in which pla&ic viscosity and yield value change with the square of concentration.147]. instead of the secondary minimum. as calculated from the yield stress. d used in viscoelastic modelling [ 1431. Their results are rather similar to Takano’s. a region can be selected where the quadratic relation is valid [97. (iv) Flow phenomena A different situation develops if. lr202 1 12x0 _ 12ca ti -@l . was higher than calculated from stability theory. Thixotropic theories for this region ha1 e been developed. If rupture of bonds is possible. At lower concentrations. leading to a Max-Nell model (146. but their translation in rheological terms has been phenomenolog-ical instead of following a structural argument. slowly aggregating sysiems. changes with concentration in much the same way as the shear modulus [ 31. At lower shear rates the structure is more complex. Harris has given a phenomenological treatment of viscoelastic behaviour due to s’. Takano llas also applied his model to steady-state shear flow [ 152 1. They could explain the effect of some physical parameters on flow. the increased resistance to flow being uniquely attributed to immobilization of fluid in the floes [135]. during the measurement. This reversible change in structure leads to a different mechanism for viscoelasticity.

The increase of the low-frequency dielectric constant can be explained partly by the formation of floes with high-aspect ratios [120. In concentrated dispersions containing flocculates and aggregates. Important dif- . In this respect.164] because of their effect on the Maxwell-Wagner dispersion. Thus magnetic [ 1571 and electric fields [ 158. In dilute dispersions. opacity will be a measure of the variable structure [ 1621. However. a qualitative similarity with polymer systems becomes evident. surface conductivity seems to be an important factor [X66]. Magnetic [160]. No full analysis nor complete explanation is available. dcconductivity [115.1191 and dielectric [116. light scattering [161]. a search should be made for using these methods in attacking yet unsolved problems in colloid science through subtle concerts of techniques. The combination of dielectric and rheological measurements is a promising tool in the analysis of variable structure.SUMMARY Concentrated dispersions show complex rheological behaviour. More detailed information is available through dielectric me‘asurements [ 1631. electric [115) and optical [121] measurements can be used to supplement rheological data in detecting structure.159] can be applied to counteract the mechanical field. they provide information about the time scales of the different relaxation processes. the effective op. In addition. surface phenomena take part in the process 11651. it provides evidence of the presence of a structure that extends throughout the :nateriaI. a variety of physical techniques are avaiiable that may be used in translating the previous section into a global picture of the essentially variable structure of concentrated dispersions. the use of light scattering is limited to very low concentrations.195 (v) i(elation with other physical properties Besides mechanical routes. With conventional equipment and techniques. the system is characterized by a spectrum that changes with structure. Combination of varicus fields and detection methods gives rise to techniques known as electro-optical.157] properties have been shown u ‘ to depend on the state of flocculation. From its opacity. technical problems as well as interpretation difficulties often arise. both provide time and shear-rate dependent spectra [ 39. they have been proved useful in analyzing the shape and orientation of anisometric particles. Even in nonaqueous systems. As in viscoelasticity. rheo-electric and the like. Their dependence on different variables could lead to substantial progress in colloid science and dispersion rheology. plastic and elastic phenomena. rheo-optic‘al. The availability of high intensity laser sources removes the limitation somewhat [161]. conversely. snd if this changes with flocculation.t!cal cross section for the dispersion can be calculated. E.163 ] but are differently related to structure. In addition. DC-conductivity is a direct measure of a continuous structure of conductive elements in the nonconductive medium. opacity [162]. their response includes viscous.

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