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Find out moreAP 1, 119–127 (1998)

**THE EUROPEAN PHYSICAL JOURNAL
**

APPLIED PHYSICS

c EDP Sciences 1998

**Rheological modelling of complex ﬂuids. I. The concept of eﬀective volume fraction revisited
**

D. Quemadaa

Laboratoire de Biorheologie et d’Hydrodynamique Physico-chimique, case 7056, Universit´ e Paris VII, 2 place Jussieu, 75251 Paris Cedex 05, France Received: 24 March 1997 / Accepted: 9 September 1997 Abstract. Number of complex ﬂuids (as slurries, drilling muds, paints and coatings, many foods, cosmetics, bioﬂuids...) can approximately be described as concentrated dispersions of Structural Units (SUs). Due to shear forces, SUs are assumed to be approximately spherical in shape and uniform in size under steady ﬂow conditions, so that a complex ﬂuid can be considered as a roughly monodisperse dispersion of roughly spherical SUs (with a shear-dependent mean radius), what allows to generalize hard sphere models of monodisperse suspensions to complex ﬂuids. A rheological model of such dispersions of SUs is based on the concept of the eﬀective volume fraction, φeﬀ which depends on ﬂow conditions. Indeed, in competition with particle interactions, hydrodynamic forces can modify (i) S , the number fraction of particles that all SUs contain, (ii) both SUs arrangements and their internal structure, especially the SU’s compactness, ϕ. As a structural variable, S is governed by a kinetic equation. Through the shear-dependent kinetic rates involved in the latter, the general solution S depends on Γ , a dimensionless shear variable, leading to φeﬀ (t, Γ ; ϕ). The structural modelling is achieved by introducing this expression of φeﬀ into a well-established viscosity model of hard sphere suspensions. Using the steady state solution of the kinetic equation, Seq (Γ ), allows to model non-Newtonian behaviors of complex ﬂuids under steady shear conditions, as pseudo-plastic, plastic, dilatant ... ones. In this model, the ratio of high shear to low shear limiting viscosities appears as a key variable. Diﬀerent examples of application will be discussed. PACS. 82.70.-y Disperse systems – 83.10.Ji Fluid dynamics (nonlinear ﬂuids) – 83.20.Bg Macroscopic (phenomenological) theories

Introduction

Complex ﬂuids (as drilling muds, paints and coatings, concrete, many foods, cosmetics, bioﬂuids, etc.) used for industrial applications have rheological properties under steady and unsteady conditions which show strong similarities in comparison with those of concentrated dispersions. As one of the more remarkable characteristics of these ﬂuids, such similarities are evidenced by using dimensionless variables that promotes disappearing of almost all the diﬀerences due to eﬀects of time and space scales, so that, dimensional analysis should play a very important role. Logically, these similarities must be interpreted as resulting from some generic characteristics of these systems, in spite of their large diversity. It is widely recognized that these shared properties are due to both the existence of internal structures (very often called the microstructure, although they are observed at all length scales) and shear-induced changes of these structures.

a

During the two last decades, number of studies have shown that the structure of any concentrated dispersion cannot be characterized by only its microstructure: small elements (as individual particles or primary ﬂocs) forms larger groups (as clusters, aggregates, ﬂocs, clusters of ﬂocs,...) up to an (eventual) sample spanning structure. These groups, herein call Structural Units (SUs), have a size which obviously depends on the applied shear through the hydrodynamic stress acting on the SUs, leading to the concept of the shear-dependent structure. For example, Figure 1 shows the structural interpretation of shearthinning behavior (due to progressive rupturing of large clusters present at low shear, as the shear rate is increased), which changes into a plastic behaviour if a sample spanning network can form at very low shear, i.e. if the particle volume fraction is high enough. Therefore, structural models, i.e. models which involve such structural changes, should be the most suitable for rheological characterization of these materials. Moreover, as complex ﬂuids are multi-component systems, it appears irrelevant to try to take this complexity into account in rheological modelling for practical purposes. In order to obtain a correct characterization of the system,

e-mail: quemada@lbhp.jussieu.fr

Among these variables.M. pertinent variables which should have a clear physical signiﬁcance. as a master curve ηr = ηr (Pe). constant shear. He showed that the relative viscosity ηr should take the general form ηr = η = ηr (φ. same speciﬁc mass than the solid material) and with only hydrodynamic interactions. (d) . De → 0 and equation (1. ˙ = P´ eclet number. All structural models involve at least four essential ingredients: one has to (a) . (b) . Pe. large SUs break down into smaller and smaller ones. releasing an increasing amount of the suspending ﬂuid immobilized in the inside of SUs. see Figure 2.determine shear-dependences of kinetic constants involved in kinetic equations. 1. (ii) to start. 2A = @E KJA IOIJA I $πη. using characteristic shear stress σc and rate γ ˙ c. as a more or less pronounced shear thinning interrupted by shear thickening occuring in an intermediate shear rate domain.2. respectively.1) . (c) .1) is reduced to ηr = ηr (φ. describing the ﬂow induced rupturing and restoring of the structure. 1 Some recalls (showing the essential contribution of I. the development of a structural approach thus requires: (i) to be able to select the minimum number of parameters as a set of dimensionless. with a ﬁnite and an inﬁnite viscosity at zero shear. De) ηF (1. leading to a very strong repulsion between particles: the interaction is thus very close to that of Hard Spheres (HS).deﬁne a set of (dimensionless) structural variables [S ]. to enlarge its eﬀectiveness in modelling simple non-Newtonian behavior. ). Pe). Krieger to this ﬁeld) 1. π where φ = 43 N a3 = volume fraction of particles.= ! γ = γ ? 6 γ $πη=! $π=! σ = γ σ= 6 6 σ? Fig.choose the kinetic equations which governs [S ].2) (with γ ˙ = shear rate. extending its deﬁnition.3] is composed of monodisperse silica particles coated with a dense layer of short polymer chains grafted to the surface. tEx = duration of the experiment). suspended in a Newtonian ﬂuid (viscosity ηF . these two last numbers depending on the Brownian diﬀusion time of particles in the suspending ﬂuid tBr = a2 6πηF a3 = DT KT (1. characterizing the structure. Structural interpretation of shear-thinning and plastic behaviors. as much as possible.select an explicit form of the viscosity-structure relation η ([S ]). An excellent experimental model of such suspensions [2.e. T = absolute temperature. already well-described. the eﬀective volume fraction (EVF) of the disperse phase has been proved to be one of the more essential for structural modelling. Under steady conditions (i. number density N ). Dimensional Analysis was ﬁrst applied by Krieger [1] to the simplest case: a suspension of small rigid monodisperse spheres (radius a. 2. K = Boltzmann constant.1. The aim of the present paper is to re-examine the EVF concept and. colloidal dispersions play a unique role. which can be represented at φ = cst. As the shear rate in increased. A second part of this work will be devoted to apply this new EVF concept of φeﬀ to model more realistic non-Newtonian behaviour. in the presence of the other forces acting on particles. either σ/σc or γ/ ˙ γ ˙ c . in order to be able to generalize well-established relations. Γ . De = tBr /tEx = Deborah Pe = tBr γ number. what in principle will allow physical interpretations of the involved variables: in this aim. from dimensional analysis.120 CLEI? IEJO The European Physical Journal AP HA =JELA LEI? IEJO =?H IJHK?JKHA ≈ AJM H ( at the scale of the sample) ηH E?H IJHK?JKHAI (single particles) ? KIJAHI B AI IJHK?JKHAI ηH∞ AI IJHK?JKHAI I = B ?I " CIDA=H H=JA " 2A γ ? J? ≈ =! ? ?A JH=JA@ IOIJA I 2A ≅ Fig. 1. Master curve ηr = f (Pe). suspended in a (good solvent) non-polar liquid. constants which should be expressed in terms of a dimensionless shear variable. from models of simple systems.

4) has been veriﬁed in several experiments carried out on colloidal suspensions of spherical particles.5) φ φm −q (1. Γ 1 and Γ 1). The condition (1.5. leads to a non-Newtonian viscosity ηeq = f (Seq . equation (1. Early studies on latex suspensions [9] veriﬁed (1. 1. unacceptable for rigid spheres (theoretical value [η ] = 2. Moreover. that results to η0 following (1. respectively3 .5) is required in order to recover the Einstein viscosity. An expression of the same type than (1. (in practice. 1. gov˙ = g (S. q ) at very low and very high shear: (0. it would give φm = 0. For these dependences η (φ). ηr = 1 + [η ]φ.5) at φ → 0 should not be maintained (with [η ] = 2. in the case of a repulsive potential (either the abrupt steric potential or the smooth electrostatic one.72 for η∞ and very similar values of φm have been found for other suspensions of monodisperse silica spherical particles with diﬀerent radii [11].4. the limit (1. hence diﬀerent from the equation (1. This solution can be written in the general form ηr = 1 − where q = [η ]φm (1.5) is not satisﬁed. Einstein’s coeﬃcient [η ] –which quantiﬁes the (long range) hydrodynamic perturbation due to the presence of an isolated particle imbedded in the suspending ﬂuid. Seq = Seq (Γst ). q = 2. it is possible to introduce an eﬀective radius aeﬀ which deﬁnes the equivalent HS radius: it is the HS approximation which permits to apply the relation (1.96 and 1.71. as φ → 0. The relation (1. depending on the interaction potential.5 for a suspension of spheres). an unacceptable value since > 0. Measurements on latex suspensions in non-aqueous media [10] led to the following pair values for the two limits (φm . it seems rather unjustiﬁed to require the existence of a relation between. would correspond to [η ] close to 3.5) these q -values.74 (the Face Centered Cubic packing). However.3. from equation (1. in the limits Γ → ∞ and Γ → 0. requiring that the relation η (φ) takes at low concentration (for instance. the Einstein’s limit in very diluted media ([η ] = 2.4) remains valid. which mainly depend on lubrication interactions between close particles)– and.93. From equation (1.1 and 2. Later.7. forming doublets by Brownian collisions.63. the equilibrium value.a viscosity-structure relation. the divergent behavior of the zero shear viscosity η0 was studied theoretically [12] from a scaling analysis of the Brownian stress: if the range of interparticle forces is comparable to the particle size.68 instead of 2. As an example. these limits correspond to relative viscosities which are only functions of φ. simplest models used (i) only one (scalar) variable S .5).57. 1 eﬀects. Γst ) = F (Γst ). Γ. φm is observed close to the Random Close Packing φRCP = 0. the formation of which is governed by “chemical” kinetics .a reduced shear stress Γ = σ/σc ≈ a3 σ/KT . Krieger et Dougherty [6] gave the correct solution of Mooney’s approach [7]2 . Krieger-Dougherty model [5] describes the shear thinning behavior of suspensions of small spherical particles.5) seems to argue that such a constraint would hold only at φ → 0. but with q = 1.4) with q = 2 and φm close to φRCP . solution of the kinetic equation g (Seq . often superposed to an attractive potential which reduces the interaction range).3) to concentrated suspensions. 1.52) and (0.68. contrary to Mooney’s assumption.82). giving respectively [η ] = 2. η (S.3) 1+Γ where η∞ and η0 are respectively the limiting steady state viscosities. assumed linear in S . such as1 η0 − η∞ η = η∞ + (1.67 and 2.80. For steady ﬂow conditions. Obviously.96) for η0 and (0. not to the theoretical value φFCC = 0. 3 .4).4) with q = 2 by data ﬁtting of Ree-Eyring model.4) is the product of φm .4) after changing φ into Note that the limit (1. . was obtained [8] from a minimum principle applied to the energy dissipated by viscous Notice that applying (1. characterized by Γ = Γst .5.e.93) for η∞ . 2 Which is based on calculation of the viscosity of a suspension containing φ2 particles after adding an amount φ1 of particles: this procedure is not equivalent to adding φ2 to a suspension containing φ1 as Krieger claimed. the above-cited experimental models of HS systems allowed to make very precise veriﬁcations of equation (1. the hydrodynamic contribution to the stress scales as the Brownian stress4 . Based on the general frame proposed by Cheng and Evans [4] for modelling thixotropy of complex ﬂuids. The second case led to φm = 0. Γ ). Quemada: Eﬀective volume fraction of complex ﬂuids 121 1.63 for η0 and φm = 0. the maximum packing) by the intrinsic viscosity [η ].4): comparable quality in data ﬁtting was obtained in two cases: by using either φm and q as open variables or a ﬁxed value. say a very dilute suspension of doublets and absence of multiplets. 1. However.637. q and φm –parameters which command the viscosity behavior in the vicinity of the maximun packing (hence. appear to contradict K−D’s model assumptions. It is well-known that real (stabilized) suspensions are only approximately described as HS systems. on one hand.a structural variable S proportional to the number of doublets. t) = 0. t) erned by a kinetic equation of the form S and (ii) a viscosity-structure relation. the maximum volume fraction (i.1).4). The former case led to the pair of values (φm . on the other hand. In practice. q = 2. 1. however with a ﬁxed value.74). and only φm open. performed in many works. Γst .D. 4 In the case of very strong repulsive forces between particles. The only way to maintain equation (1. More recently. q ) = (0. 1. by using: . below a percolation threshold?) a form compatible with Einstein viscosity.

2) where φeﬀ > φ since ϕ < 1.7) in which φeﬀ is the whole volume fraction of clusters [20–22. in shape. it appears more and more obvious that these clusters may form groups.4) have been obtained with suspensions of particles of very diﬀerent kind. φeﬀ was taken as the EVF of fractal aggregates in colloidal dispersions and was used in equation (1. it seems better to rewrite (2. If this SU is composed of n particles of radius a. Note that the form of equation (1. On the contrary. As the evaluation of φeﬀ is very often diﬃcult to carry out in complex ﬂuids. the maximum packing is not known.7) Many works ([13–15].6) is required every time a relation established for HS systems is taken into account. the cluster compactness) and packing characteristics of clusters in the sample. not for s = (0.7) –very often in the form of Krieger equation (i. The needs to take the structure formation at any scale into account has been underlined in the previous section. In many circumstances. if the cluster’s shape is very diﬀerent (for instance in the case of clusters composed of ﬁbers having a very large axis ratio). one may deﬁne a mean compactness. however without considering the consequence for the EVF concept.7) ηr = 1 − φeﬀ φm −q (2. as shown by clay suspensions for instance. what leads to a simple description of these ﬂuids as suspensions of SUs.4) is interesting since it contains only one unknown parameter. what corresponds to [η ] ∼ = 3.5 (2.4) after changing φm into an eﬀective maximum packing φPK = ϕφm (2.25]). however the limit (1.4) is unchanged if one uses φeﬀ in place of the ratio φ/φm .122 The European Physical Journal AP an Eﬀective Volume Fraction (EVF) φeﬀ = 4π 3 N a3 eﬀ = (aeﬀ /a) φ 3 −q (1. Extension of the HS Approximation to complex ﬂuids directly results from including the formation of SUs in the model. limiting referred papers to the more recent ones) currently used (1. when the dispersion should be described as a suspension of clusters. (1. Moreover. φPK . as those of Brinkman [16] or Roscoe [17]. leading to generalize the equation (1. the compactness of which is deﬁned by the ratio ϕn of the solid volume inside the SU to its total volume. especially of non-spherical particles [27]. a ﬂowing complex ﬂuid can be considered as a roughly monodisperse dispersion of roughly spherical SUs. [23]. i.6).4) with either q = 2 (in Ref.6) is not suﬃcient in the presence of a attractive potential strong enough to promote particle clustering. Fair data ﬁtting of equation (2. In some recent works.74)−1 . For the suspension of (roughly identical) SUs as a whole. Therefore. For instance. Nevertheless.74)−1 or s = 1 according to the system is composed of monodisperse or wholly polydisperse particles. The viscosity of the dispersion considered as a suspension of SUs should take the same form than equation (1. The size distribution of SUs. the factor s only depending on the size distribution of particles. this last author established the relation ηr = (1 − φeﬀ )−2.26]. the expression (2.5) which involves both packing characteristics of individual particles in clusters (i. The EVF deﬁnition (2.4) thus becomes ηr = 1− φeﬀ φm . however equation (1. It is worth noting that using equation (1.e. Then. assemblies of any scale. noticely during its .) or q = [η ]φm (in Refs.e. e. likely rather broad in the rest state. Note that such multiscaled structures. is however expected to be narrowed under ﬂow conditions and centered on a mean size R(Γ ) as resulting from shear forces acting on SUs.5). were early introduced by Michaels and Bolger [18] and by Firth and Hunter [19] in their studies of clay suspensions. is satisﬁed for s = 1. Some amount of suspending ﬂuid is immobilized inside any SU.g. its effective radius is Reﬀ = (na3 /ϕn )1/3 . and the total EVF is thus related to true volume fraction φ by φeﬀ = φ/ϕ (2.3) as a function of the true volume fraction. ϕ. these forces and collisions between particles promote the formation of SUs more or less spherical where φm is the maximum packing fraction of SUs. Such a structural feature leads to an important change in the above-deﬁned EVF concept as it will be discussed in the next section. opened the EVF concept towards eﬀects of polydispersity. Particle size and shape distributions mainly contribute to cluster compactness.3) a value close to RCP packing. [24. It could be evaluated from the sedimentation volume if SU restructuring does not occur during settling.1) with φeﬀ = sφ. in concentrated systems.3) 2 Generalization of the hard sphere model and the EVF concept revisited Some pioneer works.e.4. that is seldom the case. thus only taking the (steric or electrostatic) barrier of the stabilizing potential into account. clusters under shear forces are broadly spherical in shape that allows to use for φm in equation (2. although not included in number of even recent approaches. It takes the values s = (0.2) may however appear rather too restrictive: the SU formation generally results from regrouping smaller elements –not necessarily the primary particles but small irreducible aggregates formed at the higher shear applied to the sample. φ ηr = 1 − φ φPK −q (2. with q = [η ]φm )– with φeﬀ deﬁned from (1.6) equation (1.

4) compatible with equation (3. in addition to IFs. the P´ eclet number can be generalized by replacing into the above expression of tBr the viscosity of the suspending ﬂuid. equation (2. tA and tD . γ ˙ (very often approximated by a power law).9) that led to introduce the concept of a shear-dependent maximum packing φPK (Γ ) [20. Γ = (γ/ ˙ γ ˙ c ). it seems rather improbable that all the IFs are included in SUs. and where S0 and S∞ are the limits of S at very low and very high shear.4) requires to use now φPK = φm /[1 + CS ] (2. Quemada: Eﬀective volume fraction of complex ﬂuids 123 J. respectively. using characteristic shear rate 1 γ ˙ c = t− and shear stress σc . Dynamical equilibrium under steady conditions (at given Γ ) between Individual Flocs and Structural Units of mean radius R(Γ ). some of IFs have to remain free. In terms of the structural variable.6) 1 −1 with κA = t− A and κD = tD as shear-dependent kinetic constants of formation and rupturing of SUs.e. it is assumed that. As a consequence.6). especially in colloidal dispersions [30]. respectively.2) when γ ˙ → ∞ and γ ˙ → 0.8) Note that from equation (2.Γ J )Γ are supposed to be relaxation processes with mean relaxation times. the kinetic processes involved in formation and breakdown (or reduction) of SUs where tc is a characteristic time required for dimensional homogeneity. In the latter case this value has some theoretical background [31]. (3. deﬁned as the “aggregated” fraction (i.29].e. It is worth noting that θ can be expressed as a simple function of a dimensionless shear variable. the exponent p should be < 1 in order to make equation (3.7) (2. (2. In the case of complex ﬂuids in which. Therefore. The steady state (dS/dt = 0) solution of equation (3. respectively. preparation–. 3 Structure kinetics and non-Newtonian behavior Still for the sake of simplicity. the c simplest modelling will be obtained by using the experimentally applied shear. considering that any Brownian particle is embedded in the whole suspension as an eﬀective medium.1) Fig. S = φA /φ. the above-deﬁned number fraction of aggregated particles. indiﬀerently written in terms of either the shear rate. From its deﬁnition (3.4).D. For dilute colloidal dispersions of spherical particles of radius a. Due to the non-linear variation of σ vs. Γ = (σ/σc ). Γ . Ci )–. elements which will be herein called Individual Flocs (IFs). the generalized Pe number is proportional to the product η γ ˙ . is governed by: K IJHK?JKHA@ IJ=JA IJHK?JKHA@ IJ=JA =J CELA Γ dS = κA (S0 − S ) − κD (S − S∞ ) dt (3.4) Ci Si φ. by some eﬀective value. Pe = tBr γ ˙ . φeﬀ can be written φeﬀ = [1 + CS ]φ where C = ϕ−1 − 1 (2. thus depends linearly on shear stress. In fact. the EVF of SUs will be φAeﬀ = φA /ϕ. Let φA and φI = φ − φA to be the volume fractions of particles contained in all the SUs and IFs. S . close to the suspension viscosity. Moreover. Γ 1 and Γ 1. as illustrated on Figure 3. ηF . respectively. tc is necessarily closely related to at least one of the relaxation times tA and tD . leading to deﬁne the EVF of the suspension as a whole by φeﬀ = φI + φAeﬀ . where tBr ∼ = ηF a3 /KT is the Brownian diﬀusion time5 . i. characterized by Γ . the alternate form (2. For concentrated systems. From equation (2. one may identify several classes of SUs –each of them characterized by the pair (Si . . θ(γ ˙ ) = κD /κA = tA /tD = (tc γ ˙ )p (3. once again for the simplest modeling. either γ ˙ or σ.6) can easily be generalized in the form φeﬀ = 1+ i This solution corresponds to the equilibrium structure the system reaches under constant shear. or the shear stress. 3. one expects a non-linear dependence θ in γ ˙ . as an independent 1 1 5 Using relaxation times κ− ˙ −1 and κ− D ≈ γ A = tBr for breaking down and building up the structure.2). ϕ. dimensional analysis allows to identify θ to the P´ eclet number. in concentrated systems. directly related to the mean compactness of SUs. Assuming that the ﬂow makes the SUs roughly homogeneous in shape and size. η .3) is a “compactness factor”.2) θ = κD /κA = f (Γ ). respectively.2) to a suspension composed of SUs and IFs in dynamical equilibrium under steady ﬂow conditions.1) is given by Seq = where θ is deﬁned by S0 + S∞ θ 1+θ (3. ηeﬀ . It is therefore possible to generalize the deﬁnition (2. In other words. what leads to θ ∝ σ. Note that the value of p has been very often found experimentally close to 1/2. the total number density of primary particles contained in all the SUs).

obviously results into η (Seq ) = η (Γ ).6) has been found to predict very well both the shear thinning behavior and the φdependences of the η∞ and η0 limits: very fair agreement was obtained by ﬁtting the model to steady state viscosity data of spherical particle suspensions and some complex ﬂuids [20. deﬁned by φ∞ = φm 1 + CS∞ and φ0 = φm · 1 + CS0 (3.2) leads to ηr = 1− 1+ C (S0 + S∞ θ) φ 1+θ φm −2 4 Prediction of simple non-Newtonian behaviors under steady conditions The steady state viscosity (3. or shear thickening. which describes the non-Newtonian viscosity under steady conditions. such a generalization leads to enlarge the physical meaning of the characteristic time involved in the reduced shear rate. χ given in equation (3. where WI is the particle interaction energy. a further generalization of Pe to more complex systems was obtained [32. as Pe can also be expressed as the ratio WH /KT where WH is the energy dissipated by viscous ﬂow.10) into equation (2. depending on the values of the limiting viscosities. shear-thickening if χ > 1 and shows a discontinuous viscosity if χ < 0. η = f (S ). in relation with corresponding values of volume fractions. especially one should obtain . (3.6) Table 1. the model is completely deﬁned by equation (3. Table 1 collects these features.7) rheological index 0<χ<1 1<χ<∞ χ=0 −∞ < χ < 0 χ=1 depends on the limiting maximum packings at Γ → ∞ and Γ → 0. respectively.9) Alternatively. Moreover. Diﬀerent rheological behaviors.6).7) works as a rheological index: indeed. as clay suspensions. From η = η (φeﬀ ) and φeﬀ = φeﬀ (S ).8) These packings are involved in the corresponding steady state limiting viscosities η∞ and η0 η∞ = ηF 1 − φ φ∞ −2 rheological behavior PSEUDOPLASTIC DILATANT PLASTIC (CASSON) DISCONTINUOUS VISCOSITY (NEWTONIAN) range of volume fraction φ < φ0 < φ∞ φ < φ∞ < φ0 φ = φ0 φ ∞ < φ < φ0 φ0 = φ∞ η0 = ηF 1 − φ φ0 −2 · (3.4. η∞ and η0 . WH /WI . η0 → ∞ and η0 < η∞ . The last step in modelling. it depends only on the limiting viscosities.4). shear-thinning if χ < 1.33] by changing this ratio into a new one. very large in comparison with KT in the case in stabilized dispersions. Up to now. (3. using the steady state solution Seq = S (Γ ) of the kinetic equation. which can easily be written in the form (with θ = Γ p ) η = η∞ In equation (3.29] 1 −1 φ− PK = φ∞ + 1 −1 φ− 0 − φ∞ · p 1+Γ (3. for instance). A second way to model plastic behavior. as simple shear thinning. a one-to-one relation is automatically obtained. the sheardependent maximum packing φPK (S ) should verify the following relation [20. The viscosity model (3. 2. with χ given by equation (3. involves the more original part in using the new EVF concept. such an origin can be forgotten: indeed. associated with the value of the rheological (structural) index. ˙ . in spite of using a diﬀerent formalism.3. As WH ≈ σa3 ≈ ηeﬀ a3 γ ˙ . written as either γ/ ˙ γ ˙ c or σ/σc . respectively. its value controls the behavior of the suspension.6). from equations (3. to deﬁne (a fortiori to measure) a “volume fraction” in such complex ﬂuids. This is generally true.33–36]. even impossible. it is important to remark that although the present structural model was originally developed for concentrated dispersions. Indeed. the domain of application of the model can be enlarged to complex ﬂuids (at least those for which the above-introduced structural concepts may be accepted. it has been admitted that no diﬀerence can result from using the reduced shear variable. by putting tc γ tc ≈ ηeﬀ a3 /WI . 2. i. which is Newtonian if χ = 1. 3. plastic. Γ . using equation (3. More precisely.10) Notice that the behavior described by equation (3. although it would be very diﬃcult. in direct association with the relation η (φ).e. Γ = cst.6) is also obtained after putting equation (3. η0 > η∞ .7). Therefore.124 The European Physical Journal AP variable: the choice between these two forms of Γ will be dictated by the type of rheometer used in measurements.29. and through these relations.9). which allows physical interpretation of model variables.6) the ratio χ = χ(φ) = 1 − φ/φ0 ≡± 1 − φ/φ∞ η∞ η0 1/2 1 + Γp χ + Γp 2 · (3. which concerns the relation between viscosity and structural variable. An example of such data ﬁtting is shown in Figure 4. for p = 1/2–. see equations (2. More precisely.5) Finally. diﬀerent kinds of “pure” non-Newtonian behaviors. plastic if χ = 0 –identical to the Casson behavior.6) presents a monotonic variation.2.

Data ﬁtting giving the parameter values in equation (3.3) This agrees with the observed change of dilatancy into discontinuous viscosity if the volume fraction is high .. with an increasing yield stress σY given by equation (4. depending on the choice of the independent variable. very close to the value obtained from electronic microscopy.6) can be written in the form η = η∞ p σp + σC p σp − σY 2 (4. This point will be discussed in more detail in the second part of this paper. (4. calculation of the square a) In the former case. such a choice can be avoided since it is possible to ﬁnd the form of the kinetic equation using a method based on analysing. Note that in the Krieger and Dougherty’s model. Almost all of the previous structural models of the literature used for S either the number of links (e. though this model was generally applied in the literature with an (open) non-linear dependence in σ.6 and 3. S deduced from viscosity data [38].1) = η∞ tC 1/2 1/2 1/2 + η∞ γ ˙ (for χ = 0) in which precise expressions of both the Casson viscosity and the yield stress are obtained automatically ηCasson = η∞ and σY = η∞ /tC . of equation (3.9): φ0 = 0. in the frame of the present model. 33].629. the shear thinning behavior observed at φ < φ0 (σY does not exist there) abruptly changes at φ = φ0 (where σY = 0) then becomes a plastic behavior at φ > φ0 . b) Alternatively. γ ˙ 1/2 (4. in the second case.5) same values for the limiting viscosities. putting σY = (−χ)1/p σC . Quemada: Eﬀective volume fraction of complex ﬂuids 125 enough.2) However. see (1.4) Fig. as φ is increased.6) tends to zero [28]. a Moore-like equation. Moreover as η is always > η∞ (that requires the condition φ < φ∞ ).g. The kinetic equation was chosen from reaction kinetics or from relaxation kinetics (e. (1. Variations viscosity vs.D. It is worth noting that φ0 and φ∞ values are very close to the ones found later in dispersions of colloidal silica particles [2] and tC . another deﬁnition of σY can be deduced from equation (3. It is worth noting that this preliminary choice. 5 Discussion 5. particle volume fraction = 0. shear rate in a monodisperse suspension of latex particles (diameter = 0. p = 0.g. As γ ˙ increases. 4.5).. the same expression of the yield stress (Eq. θ depends linearly in σ. 5.155 µm [20. χ takes negative values if φ lies in the interval between the limitings packings φ∞ and φ0 . e. [37]) or. usually made for the sake of simplicity. that leads to 1 γ ˙ cr t− C 1 − φ/φ0 φ/φ∞ − 1 −1/p (for χ < 0) (4. suspending ﬂuid viscosity = 4.89 mPa. tBr (cf.3). the number of particles contained in the structured elements. shear rate or shear stress. However. Eq.1.155 µm.6.158 µm.4) with χ = 0.h.6) without any reference to the Casson law. that gives the possibility to observe viscosity discontinuities if the denominator in the r. In particular.10) of the sheardependent maximum packing and using the same shear stress-dependent kinetic model.2)) leads to a particle diameter 2a = 0. as follows: ˙ . Therefore. from equation (3. the present model provides two quite diﬀerent ways to describe the plastic behavior. Starting from the same deﬁnition (3.. the shear dependence of kinetic constants has been taken such as their ratio θ is a power law of the above-used dimensionless shear variable.5)) has been recently given and satisfactorily veriﬁed in several concentrated mineral suspensions [36]. Data from [10].g. φ∞ = 0. the characteristics of the time variation dS/dt vs. 2a = 0. For the simplest modelling.2. leads to the Casson equation (in the case p = 1/2) 1/2 σ1/2 = η 1/2 γ ˙ 1/2 = η∞ 1 + Γ −1/2 2 which exists only if φ > φ0 .7).986. Indeed. also herein used).716. expressed as [γ/ ˙ γ ˙ C ]p or [σ/σC ]p . However. the critical shear rate γ ˙ cr beyond which the viscosity diverges is obtained when Γ reaches the value (−χ)1/p . special attention is required if χ = 0 or χ < 0. (4. This critical stress σY appears as the yield stress since the viscosity diverges at σ = σY and should not exist if σ is lower than σY . 3. Γ = σ/σc .50). tC = 11 ms. in the case of a given value χ < 0. is more or less arbitrary. as in the present model. interpreted as the Brownian diﬀusion time. the expression of σY results as σY = σC φ/φ0 − 1 1 − φ/φ∞ 1/p (4. Γ . Γ = tc γ root of the shear stress from equations (3.s. equation (3.

called IFs). the exponents p and p should be different.4.3. 5. On the contrary. is generalized to complex ﬂuids. A model of hard sphere suspensions –a well-established relation η (φ) giving the viscosity vs. but a more complex one. (5. the compactness of the clusters. the model is able to predict viscosity discontinuities present at a φ-dependent critical shear rate as it has been experimentally observed in colloidal dispersions. any SU contains some amount of immobilized ﬂuid which depends on its compactness. Therefore. volume fraction relation.2).9). respectively.3).4) . Conclusive remarks and perspectives In this work.2) whatever the kinetic equation may be: indeed equation (1. the (true) volume fraction–. φeﬀ is used in place of φ in the viscosity relation η (φ). in order to obtain the non-Newtonian viscosity (3. it seems possible to apply the model to complex ﬂuids. arguing that clustering of particles is also present in hard sphere suspensions and may mask their diﬀerences from complex ﬂuids. in dynamical equilibrium under steady ﬂow conditions. more realistic deﬁnition of the eﬀective volume fraction (EVF). whereas plastic behavior results from taking χ = 0. there is nothing to assume but (i) the validity of a viscosity vs. what allows to discard from the present model the arbitrariness due to assuming a linear relationship η (S ). under an unsteady shear kinetic equation. mainly the broad particle distributions in size and in shape of the latter. as well as Cross model [37]. An example of such an extension of the present model is given by the shear induced ﬂocculation described by the following form of the kinetic constant for SUs’ formation. However. κA = κ0 [1 + (tF γ ˙ )s ]. Using the shear stress. leading to a shear-dependent EVF. However. A kinetic equation governs the time evolution of S under steady or unsteady shear conditions. from equation (5. On the contrary. (ii) it gives the possibility to model the thixotropy without additional assumption since a time-dependent viscosity directly results from insertion into equation (5.6) –and in spite of its very simple form–. the condition 0 ≤ S ≤ 1 holds in the whole domain ∞ > Γ > 0. ˆ(t)]−2 . with the help of φeﬀ .126 The European Physical Journal AP see [2]. the system being shear-thinning below this threshold.2). these experiments do not show a pure shear-thickening behavior as γ ˙ is increased. η (t) = η∞ [1 − (1 − χ)S (5. an assumption which necessarily leads to a viscosity expression of the form η = η∞ + (η0 − η∞ )S (Γ ) (5. i. due to the presence of large clusters in both concentrated suspensions and complex ﬂuids. Therefore. leads to the viscosity equation η (Γ ) ˆ(Γ )]−2 .6): φeﬀ is deﬁned as the whole EVF of IFs and SUs. It should be underlined that.5) (5. that requires using S∞ = 0 and S0 = 1 in equation (3. The domains 0 < χ < 1 and 1 < χ < ∞ correspond to shear-thinning and shear-thickening behavior. a φdependent plastic behavior is predicted above a threshold in volume fraction at which the yield stress vanishes.e.8) reduce to φ∞ = φm and φ0 = φm ϕ in agreement with equation (2. Γ (t)]. i.4) of the general (time-dependent) solution of the ˆ[t. for instance using the general form θ = Γ p f (Γ ). In this case. 2. with shear-thinning domains on where tF is a “ﬂocculation” time. complex ﬂuids are considered as mixtures of Structural Units (SUs) and individual elements (as primary particles or likely irreductible ﬂocs. the case of negative values of χ shows interesting features. 5. which now depends on two variables. as it was done usually in classical models. Finally. S Γ (t). depending on what is the independent shear variable taken in the model. see equation (2.4) is interesting since (i) it leaves open the precise dependence of S (Γ ). using the shear rate. (i) S . 5. the fraction of individual particles embedded in all the clusters. one of the prime interests of the present structural model seems to avoid any arbitrary choice of the relation η (S ).3) is just like this form. leading to a one-to-one relation η (S ). In fact. a more complicated dependence θ = θ(Γ ) could be introduced without limiting the improvement of the present model.3. it may be argued that clustering should hide the eﬀects of likely broad distributions of “particles” as disperse elements in complex ﬂuids: the main diﬀerence with concentrated suspensions comes from “particle” arrangement in clusters.6. any “pure” non-Newtonian behavior is obtained in a very simple way: the key parameter is χ which appears directly related to the ratio of the limiting viscosities at very high and very low shear rates. under steady conditions. holds for any kinetic equation. This approximate description leads to a new. The non-Newtonian behavior is thus automatically obtained through the shear dependence of φeﬀ .5. Combining equations cosity as a simple function of S (2. with f (0) = 1 and taking f (∞) in order to keep unchanged the power law behavior with p > 0. It will be discussed in the second part of this work.2) are satisﬁed.3) which varies from 0 (for fully broken structure) to 1 (for complete structure building up) allows to express the visˆ(Γ ). this relation has been generally supposed linear in most of shear thinning models. Obviously. η (Γ ) = η∞ [1 − (1 − χ)S Expression (5. with the only requirement that the limits of equation (3. In fact. (ii) a relaxation kinetics for the “aggregated” fraction. Therefore. (ii) ϕ.1) 5. As a group of IFs (or a cluster of these groups). Using a reduced structural variable ˆ(Γ ) = S (Γ ) − S∞ S S0 − S∞ (5.e. the limiting packings (3. However. thus from the cluster’s compactness.

F. Lebon. G´ en. 207 (1981). Gr. 29` eme Coll. J. Rheol. J. D.B. A. Rheol. J. J. . Physica A160. Quemada. 21.T. J. W. Cross. Hunter. Casas-Vasquez and G. De Rooij. Rheol. Van den Ende. 34. Appl. Acta 23. C. Rangel-Nafaile. 544 (1995). D. Proc IX Intl Congr. A. Phys. Sci. Frith.C. Mewis. Krieger. Rheol. 571 (1952). D.K. 12. I.. Cabane. 15. 5.. still using the new EVF concept. Magnin. J. Quemada. 16. R. 470.J. J.D. Soc. R. B.R. AIChE Journal 35. 1-10. 567 (1993). Y. 16. Rheol. 266 (1976). 24. Sci. 30` eme Coll. R. Coll. Quemada. 38.B. Michaels. Les Cahiers de Rh´ eologie XIII-1-2 (1994) pp.G. Evans.D.A.K. J.S. A. Bolger. de Kruif. E. 8. D. Watkins. Congr. J.E. 7. Chem. Trans.J. Unstable ﬂows of concentrated suspensions. I. 99. a more realistic model of such behavior [39.C.M. 39.40] will be discussed in the second part of this paper. C. J. Rheol. 571-582.G.C. Appl. Rheol. Williams. A. D. Phys. Phys. Chaﬀey C.G. 381 (1992). C. 31. Lapassin.B. Russel. Colloid Polym.E.M. 22. 24 (1962). 131. time-dependent solution S (t) in the viscosity relation. 20. As a similar complex behavior is also observed in suspensions in the presence of shear induced ﬂocculation. 6.B. JCIS 57.A. 1982) pp. 3. (Canada. Notes in Physics 164 (Springer-Verlag. 2.S. 205 (1989). Russel. Another feature of this model is the possible generalization to rheological behavior under unsteady conditions. Brady. J. Colloid Sci. J. Gr. 1996) p.H. 83. J. 33. D. Quemada. Rheol. Acta 31. 174 (1985). Chem. 210-247. Lect. Chem. Les Cahiers de Rh´ eologie XIV-1 (1995) pp. D. 20. 255 691 (1977). Kikic. 34. 256-265. De Kruif. D.Q. Krieger. Leary. Fran¸ c. R. I & EC Fundamentals 1. Acta 17. edited by B. Papir. Parker. Thixo-´ elasticit´ e des ﬂuides complexes : Mod´ elisation du ﬂuage et de l’hyst´ er´ esis m´ ecanique. 112 (1989). W. 40. Mooney. 30. Rheol. D. Colloid Interface Sci. 33. J.J. 23. Baravian. 20. J.M. D. 4. References 1. De Kruif.C. Quemada: Eﬀective volume fraction of complex ﬂuids 127 the both sides of the shear-thickening region. 201 (1989). 500 (1983). 26. D. Dhont. 13. Interf. J. Mod´ elisation structurelle du comportement rh´ eo´ epaississant des ﬂuides complexes in Application aux dispersions collo¨ ıdales. 99. Acta 34. Krieger. 3. P. Brinkman. Mexico (1984) pp. Van den Ende. i. J. Dougherty. Kataoka. T. 101 (1963). Rheol. J. M. Chang. 126 (1970). R. Mellema. 195 (1989). and Polym. Quemada. Quemada. 137 (1959). 643 (1978). Vrij. Rheol. J. H.A. Mewis. Fran¸ c. Firth.G.H. A. 82 (1977). 4717 (1985). 147. 267 (1952). Rheol.C. 415 (1989). C. Phys. Soc. η (S ). J. 19.R. Advan. 531 (1996). d’Haene. T. 17. D. 3. Duits. 41. 479 (1991). Shirota. Quemada. Phys. T. Piau. 28. 111 (1972).G. Acta 20. J. 11. Van der Werﬀ. Rheol.F. 25. Fang. Acta 16. Jones. B. Mena. Rheol. 40. C. Rev. Russel. J. Van der Werﬀ. 417 (1965). J. 40. in “Stability of Thermodynamic Systems”. Interf. Quemada. Persello. J. Fang. Boger. J. Wolthers.A. Brit. 79. Rheol. D. I. 9.C. Strivens. Sci.V.C. 18. 421 (1989). Potanin.N. W. 7. 3. Van Iersel. P. J. Buscall.M. Trans. D. D. 1599 (1965). Maron. Patel. B. Van der Werﬀ. W. J. Chem. D.G. Rheol. Podolsak.e. M.K. A. P.H. T. Texture Studies 27. 279. Krieger. G. Luo. 632 (1978). 799 (1996). Garcia-Rejon and C. edited by J. Brit.. Dhont. de Thermique Fr. 14. P. C. Berlin. 35.M. 27. Uhlherr. J. 9213 (1993). Roscoe. Colloid Interface Sci. 38.M. 627 (1984). Frith. Coll. 10. 32. Zhou. Rheol. a very simple one since it will result from using the general. 80 (1956). Colloid Sci.G. W. S.H. A. F. T.Z. A. Mellema. Quemada. Phys. 371 (1996). Structural modelling of shear-thickening in complex ﬂuids. I. T. Coll. Tiu. Pierce. W. 6. Quemada. T. 36. Acta 17.J. 162 (1951). C. M. M.-M. Quemada. Acta 22. Rheol. 11. J. De Kruif. Physica A160. Proc XII Intl. J. giving automatically a model of Thixotropy [41]. 29. Colloid Sci. Progr. Alessandrini. Wildemuth. J. Sci. I. Kitano. J. 37. 1845 (1994).

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