Nonlinear rheology of concentrated spherical silica suspensions: 3. Concentration dependence

Nonlinear rheology was examined for concentrated suspensions of spherical silica particles (with radius of 40 nm) in viscous media, 2.27/1 (wt/wt) ethylene glycol/glycerol mixture and pure ethylene glycol. The particles were randomly and isotropically dispersed in the media in the quiescent state, and their effective volume fraction φ_eff ranged from 0.36 to 0.59. For small strains, the particles exhibited linear relaxation of the Brownian stress σ_B due to their diffusion. For large step strains γ, the nonlinear relaxation modulus G(t,γ) exhibited strong damping and obeyed the time-strain separability. This damping was related to γ-insensitivity of strain-induced anisotropy in the particle distribution that resulted in decreases of σ_B/γ. The damping became stronger for larger φ_eff. This φ_eff dependence was related to a hard-core volume effect, i.e., strain-induced collision of the particles that is enhanced for larger φ_eff. Under steady/transient shear flow, the particles exhibited thinning and thickening at low and high γ˙, respectively. The thinning behavior was well described by a BKZ constitutive equation using the G(t,γ) data and attributable to decreases of a Brownian contribution, σ_B/γ˙. The thickening behavior, not described by this equation, was related to dynamic clustering of the particles and corresponding enhancement of the hydrodynamic stress at high γ˙. In this thickening regime, the viscosity growth η₊ after start-up of flow was scaled with a strain γ˙t. Specifically, critical strains γ_d and γ_s for the onset of thickening and achievement of the steadily thickened state were independent of γ˙ but decreased with increasing φ_eff. This φ_eff dependence was again related to the hard-core volume effect, flow-induced collision of the particles enhanced for larger φ_eff. Received: 26 June 1998 Accepted: 9 December 1998     

A convenient way of interpreting steady shear rheo-optical data of semi-dilute polymer solutions

Rheo-mechanical and rheo-optical investigations were carried out with the aim of determining the influence of deformation and orientation or disentangling of polymer coils on the flow behavior in the non-Newtonian region of the flow curve, for a moderately concentrated network solution. To avoid the influence of polydispersity this was done on a series of narrowly distributed polystyrene standards (dissolved in toluene). By using steady state shear flow measurements it was possible to detect qualitatively a reduction in the entanglement density within the non-Newtonian flow region. Birefringence experiments were able to show that deformation of the polymer coils also occurs in the Newtonian flow region, which has no effect on the flow behavior in this range, whereas in the non-Newtonian flow region the increase in deformation is lower than in the Newtonian range. The flow birefringence and its orientation can be described over the whole range of the flow curve with a newly developed equation system (Eq. 8 and 14) derived from the stress states of a sheared solution using the stress-optical rule. Starting from these equations, it could be shown, that in the Newtonian flow region a mastercurve in form of a reduced birefringence Δn′/η₀=f(γ˙) and a reduced orientation φ= f(γ˙/γ˙ _crit) can be plotted, independent from concentration and molar mass. A comparison of the experimentally determined orientation angle and birefringence curve form with theoretical deformations and orientations of polymer coils in a solution state, without intermolecular interactions, was able to demonstrate that the flow behavior of a moderately concentrated network solution is determined decisively (approximately to 85%) by the disentanglement. Received: 8 May 2000 Accepted: 12 September 2000     

Elastic properties of a dilute surfactant solution in the shear induced state

The first normal stress differences N ₁ of a highly dilute cationic surfactant solution are investigated in a cone-and-plate rheometer. In continuation of a previous paper (Nowak 1998), where the buildup of a shear induced structure in such a solution was attained after a reduced deformation, the N ₁ turned out to be in proportion to the square of the shear rate γ˙ reduced by a critical value γ˙ _c in a first range above γ˙ _c . At higher shear rates the N ₁ tend to lower values than predicted by this relation. Relaxation experiments were performed in the same geometry to determine the characteristic time scales of the shear induced state's decay. In the lower range above &γdot; _c the stress decay is a monoexponential process, while a second time constant has to be introduced to describe the relaxation in that range, where the N ₁ deviate from the parabolic dependence of the reduced shear rate. Received: 10 May 1999 Accepted: 15 November 2000     

The role of the mathematical mean value theorem (MVT) in rheometry: an easy way to convert apparent flow curves into correct ones

The mean value theorem of integral calculus guarantees that the apparent viscosity η _a can easily be converted into the correct viscosity η. For ordinary liquids there is a direct identity between η _a and η but the apparent shear rate (or apparent shear stress) has to be shifted to the representative shear rate γ˙^ (or representative shear stress τ^). A model free approximation scheme is introduced which implies a constant shift factor. The corresponding approximation for η is acceptable for liquids most commonly encountered. For plastic fluids the relation between η and η _a is more complex since it involves a function depending upon α; the yield stress relative to the maximum stress within the viscometer. Using the same approximation scheme as before the shift factor will involve α as well. The corresponding approximation of η is shown to be acceptable for the whole range of α. Received: 7 February 2000/Accepted: 15 February 2000     

Rheology of lyotropic and thermotropic lamellar phases

We investigate the steady-state rheological behaviour of the lamellar phase of a lyotropic system (CpCl, hexanol, brine) and of a thermotropic system (8CB). Power laws characterize the behaviour of the imposed stress as a function of the measured shear rate and similarities are observed for both systems; the same regime γ˙∼σ ^m with m≈1.7 is obtained at low shear stresses corresponding to a texture of oily streaks oriented in the direction of the flow, as shown by microscopic observations. The “onion state” only exists in the case of dilute samples of the lyotropic lamellar phase; the stress then varies as γ˙∼σ ^m with m≈4.8, as already observed by other groups with different systems. Rheological measurements at different temperatures allow determination of different activation energies relating to the still badly understood processes involved in the different rheological regimes. We propose a model which reproduces the experimental power laws and which is based on an analogy with the theory of high-temperature creep in metals and alloys. Received: 19 October 1999/Accepted: 1 November 1999     

Rheological properties and dispersion stability of magnetorheological (MR) suspensions

In the present article, the rheological responses and dispersion stability of magnetorheological (MR) fluids were investigated experimentally. Suspensions of magnetite and carbonyl iron particles were prepared as model MR fluids. Under an external magnetic field (H ₀) and a steady shear flow, the yield stress depends upon H ₀ ^3/2. The Yield stress depended on the volume fraction of the particle (φ) linearly only at low concentration and increased faster at high fraction. Rheological behavior of MR fluids subjected to a small-strain oscillatory shear flow was investigated as a function of the strain amplitude, frequency, and the external magnetic field. In order to improve the stability of MR fluid, ferromagnetic Co-γ-Fe₂O₃ and CrO₂ particles were added as the stabilizing and thickening agent in the carbonyl iron suspension. Such needle-like particles seem to play a role in the steric repulsion between the relatively large carbonyl iron particles, resulting in improved stability against rapid sedimentation of dense iron particles. Furthermore, the additive-containing MR suspensions exhibited larger yield stress, especially at higher magnetic field strength. Received: 4 April 2000 Accepted: 6 November 2000     

The second-law analysis of mixed convection in rectangular ducts

 The rate of entropy generation, S˙ ^′ _G[W/mK], is examined both theoretically and numerically for forced and mixed convection in a rectangular duct heated at the bottom. Under fully-developed flow conditions S˙ ^′ _G is expressed in terms of relevant non-dimensional hydrodynamic and thermal parameters. Numerically, it is demonstrated that S˙ ^′ _G is a single, effective parameter to examine both thermal and hydrodynamic fields and their variations. Received on 22 November 1999     

Influence of NaClO3 on the rheological behaviour of a micellar solution of CPCl

It is now well know that a small addition of salt to a micellar solution often increases the zero-shear viscosity η₀ of the solution, the understanding of the behaviour at high salt content is more questionable. In this situation, addition of more salt induces a decrease of η₀. In this experimental work we investigate the linear and non-linear rheological behaviour of a new micellar system: CPCl (surfactant)/NaClO₃ (salt). Studies of the evolution of η₀ as well as G₀ (the elastic modulus) or τ_R (the relaxation time) are in agreement with the hypothesis of a diminution of the mean micellar length when, after the maximum η₀, the salt content increases. In the non-linear behaviour (non-Newtonian viscosity) the evolution of γ˙ _c, (which defines the occurrence of the shear thinning) with salt concentration C_S is also in agreement with such a hypothesis. Received: 29 March 1999/Accepted: 20 March 2000     

The Dilute Rheology of Swimming Suspensions: A Simple Kinetic Model

A simple kinetic model is presented for the shear rheology of a dilute suspension of particles swimming at low Reynolds number. If interparticle hydrodynamic interactions are neglected, the configuration of the suspension is characterized by the particle orientation distribution, which satisfies a Fokker-Planck equation including the effects of the external shear flow, rotary diffusion, and particle tumbling. The orientation distribution then determines the leading-order term in the particle extra stress in the suspension, which can be evaluated based on the classic theory of Hinch and Leal (J Fluid Mech 52(4):683–712, 1972), and involves an additional contribution arising from the permanent force dipole exerted by the particles as they propel themselves through the fluid. Numerical solutions of the steady-state Fokker-Planck equation were obtained using a spectral method, and results are reported for the shear viscosity and normal stress difference coefficients in terms of flow strength, rotary diffusivity, and correlation time for tumbling. It is found that the rheology is characterized by much stronger normal stress differences than for passive suspensions, and that tail-actuated swimmers result in a strong decrease in the effective shear viscosity of the fluid.     

The effect of mixing particles of different size on the electrorheological response under steady shear flow

 The effect of mixing particles of different sizes on the electrorheological response of suspensions under steady shear flow was investigated. Two sizes, 15 μm and 50 μm, of monodisperse spherical sulfonated poly(styrene-co-divinylbenzene) particles were used. Several electrorheological fluids were made containing different proportions of small and large particles dispersed in silicone oil, but with constant overall particulate concentration. It was found that the mixed size system produced the highest electrorheological response under the shear rates used (10 s⁻¹ to 500 s⁻¹), which is the opposite trend to previous studies of bimodal systems with larger size ratios. Received: 21 December 2000 Accepted: 29 March 2001     

A procedure to determine the viscosity function from experimental data of capillary flow

The accurate calculation of the viscosity η as function of the shear rate &γdot; from capillary viscometry is still a matter of debate in the literature. In fact, this problem involves the inversion of an integral equation, which leads to multiple solutions due to the unavoidable noise present in the experimental data. The purpose of this work is to develop an efficient procedure to determine the viscosity function from experimental data of capillary flow without presenting the difficulties inherent in other methods discussed previously in the literature. The system identification procedure is used here to estimate the parameters of a viscosity model, which is appropriately selected for the fluid under study through preliminary calculations involving the apparent shear rate – shear stress data. Once the model is chosen by satisfying criteria for the fit goodness and its parameters are evaluated, a smooth and continuous function η(γdot;) is obtained in the range of experimental shear rates. The procedure proposed is also applicable to fluids in shear flow that present two Newtonian plateaus, as it is typically found in macromolecular dilute solutions. The mean value theorem of continuous functions is used to reduce significantly the computational time. Received: 15 November 1999 Accepted: 7 November 2000     

An automated single-particle tracker: application to characterization of non-azimuthal motion in Couette flows at low Reynolds number

We describe an experiment that allows us to record 3-dimensional trajectories of single particles in Couette shear flows, at low Reynolds number. The core of the apparatus is a Couette cell with transparent contra-rotating cylinders. Fluorescent spherical particles are used as tracers. A single tracer is imaged onto a webcam, equipped with a home-made autofocus system. For a given average shear rate, tracking of an individual tracer is performed automatically by driving the amount of contra-rotation between both cylinders and the position of the webcam. The performance of the tracker is illustrated through examples of trajectories of neutrally buoyant tracers in a Newtonian fluid. The setup is mostly aimed at characterizing complex flows in non-colloidal concentrated suspensions and wet granular materials. We show examples of 3d trajectories in a dense suspension of 200 μm spherical grains, revealing details of the short-scale diffusive-like particle motion, together with flow localization and large-scale non-azimuthal flow patterns.     

On the elastic properties of model suspensions as investigated by creep recovery measurements in shear

 The elastic properties of model suspensions with spherical monodisperse hydrophilic glass spheres that were dispersed in a Newtonian liquid were determined in creep and creep recovery measurements in shear with a magnetic bearing torsional creep rheometer. The creep and creep recovery measurements were performed depending on the applied level of shear stresses ranging from 0.19 Pa to 200 Pa. Since the recoverable creep compliances of the chosen suspending medium (i.e. a low molecular weight polyisobutylene) were far below the lower limit of the resolution of the creep rheometer it can be considered to behave as purely viscous. By applying a large shear stress in the creep tests the investigated suspensions with a volume fraction of Φ _t =0.35 behave as Newtonian liquids, too. For these suspensions no significant recoverable creep compliances could be detected, as well. In contrast to the Newtonian state of suspensions at high shear stresses, where a shear induced ordering of the particles can be expected, a non-Newtonian behaviour arises by applying a very low shear stress in the creep test. In this state large recoverable creep compliances were detected for the suspensions. The magnitude of the recoverable creep compliances of the suspensions exceeded the largest creep compliances of polymer melts that are reported in the literature by more than two decades. From the results obtained by creep recovery measurements with a magnetic bearing torsional creep rheometer it can clearly be concluded that the particle structure present in the chosen model suspension gives rise to a pronounced elasticity. Received: 21 November 2000 Accepted: 12 July 2001     

Characterization of the flow properties of sodium carboxymethylcellulose via mechanical and optical techniques

Sodium carboxymethylcellulose (NaCMC) in solution represents a complex rheological system, since it forms aggregates and associations and hence higher-level structures and, depending on the synthesis, is only found in a molecularly dispersed form in exceptional cases. Rheo-mechanical investigations of the viscoelasticity showed that the Cox-Merz rule is not fulfilled. The aim was therefore to examine whether rheo-optics could be employed to provide more detailed conclusions about the parameters that influence the flow behavior of NaCMC than has hitherto been available with mechanical methods. The flow birefringence, Δn ^′, rises as the degree of polymerization increases, and exhibits the same dependence on molar mass as does the viscosity: Δn ^′∝M _w ^3.4. As the degree of polymerization increases while the shear rate remains constant, the polymer segments become more distinctly aligned in the direction of shear. Hence increasing the degree of polymerization also affects the solution structure, i.e. the interaction of the molecules with one another. The stress-optical rule only applies to a limited extent for this system. The stress-optical coefficient, C, is almost independent of the shear rate, but is strongly influenced by the concentration and attains a limiting value of 3 × 10⁻⁸ Pa⁻¹. C was determined for a polymer in dilute solution and the curve obtained also enabled transitions in the solution structure to be recognized. Received: 1 May 1998 Accepted: 5 October 1998     

Hydrodynamic formation of stable anisotropic structures in Couette flow of dilute suspensionFormation hydrodynamique pour structures anisotropiques stables dans un flux de Couette d'une suspension diluée

The problem of rotary motion of rigid axially symmetric elongated particles in the Couette flow of dilute suspension with anisotropic carrier fluid is solved. It is shown that the stable stationary solutions of the dynamical set of ordinary differential equations describing the particles rotary motion are possible in the case of forming the stationary anisotropy in the carrier fluid of the suspension. It allows us to detect the stationary orientation of suspended particles and formation of stable anisotropic liquid-crystalline structures in the considered suspension under the action of hydrodynamic forces. The study of rheological properties of such a structured suspension shows that it behaves as a viscoelastic quasi-Newtonian anisotropic liquid medium. To cite this article: E.Yu. Taran et al., C. R. Mecanique 332 (2004).     

Shear-banding structure orientated in the vorticity direction observed for equimolar micellar solution

 The non-monotonic shear flow of a viscoelastic equimolar aqueous surfactant solution (cetylpyridinium chloride-sodium salicylate) is investigated rheologically and optically in a transparent strain-controlled Taylor Couette flow cell. As reported before, this particular wormlike micellar solution exhibits first a shear thinning and then a pronounced shear-thickening behavior. Once this shear-thickening regime is reached, a transient phase separation/shear banding of the solution into turbid and clear ring-like patterns orientated perpendicular to the vorticity axis, i.e., stacked like pancakes, is observed (Wheeler et al. 1998; Fischer 2000). The solution exhibit several unique features as no induction period of the shear induced phase, no structural build-up at the inner rotating cylinder, jumping pancake structure of clear and turbid ringlike phases, and oscillating shear stresses appear once the pancake structure is present. According to our analysis this flow phenomenon is not purely a mechanical or rheological driven hydrodynamic instability but one has to take into account structural changes of the oriented micellar aggregates (flow induced non-equilibrium phase transition) as proposed by several authors. Although this particular flow behavior and the underlying mixture of shear induced phases and mechanical instabilities is not fully understood yet, some classification characteristics based on a recent theoretical approach by Schmitt et al. (1995) and Porte et al. (1997) where a strong coupling between the flow instability (non-homogeneous flow profile due to the bands) and the structural changes causes the observed transient phenomena can be derived. In reference to the presented model the observed orientation of the rings is typical for complex fluids that undergo a spinodal phase separation coupled with a thermodynamic flow instability. In contrast to other shear banding phenomena, this one is observed in parallel plate, cone-plate, and Couette flow cell as well as under controlled stress and controlled rate conditions. Therefore, it adds an additional aspect to the present discussion on shear banding phenomena, i.e., the coupling of hydrodynamics and phase transition of rheological complex fluids. Received: 8 January 2001 Accepted: 15 May 2001     

Rheological and mechanical properties of silica colloids: from Newtonian liquid to brittle behaviour

Rheological and mechanical properties of aqueous mono-disperse silica suspensions (Ludox? HS40) are investigated as a function of particle volume fraction (ϕ _p ranging from 0.22 to 0.51) and water content, using shear rate tests, oscillatory methods, indentation and an ultrasonic technique. As the samples are progressively dried, four regimes are identified; they are related to the increasing particle content and the existence and behaviour of the electrical double layer (EDL) around each particle. For 0.22 ≤ ϕ _p ≤ 0.30), the suspensions are stable due to the strong electrostatic repulsion between particles and show Newtonian behaviour (I). As water is removed, the solution pH decreases and the ionic strength increases. The EDL thickness therefore slowly decreases, and screening of the electrostatic repulsion increases. For 0.31 ≤ ϕ _p ≤ 0.35, the suspensions become turbid and exhibit viscoelastic (VE) shear thinning behaviour (II), as they progressively flocculate. For 0.35 ≤ ϕ _p ≤ 0.47, the suspensions turn transparent again and paste-like, with VE shear thinning behaviour and high elastic modulus (III). At higher particle concentration, the suspensions undergo a glass transition and behave as an elastic brittle solid (IV, ϕ _p = 0.51).     

Simulation of the rheological properties of suspensions of oblate spheroidal particles in a Newtonian fluid

A simulation algorithm was developed to predict the rheological properties of oblate spheroidal suspensions. The motion of each particle is described by Jeffery’s solution, which is then modified by the interactions between the particles. The interactions are considered to be short range and are described by results from lubrication theory and by approximating locally the spheroid surface by an equivalent spherical surface. The simulation is first tested on a sphere suspension, results are compared with known experimental and numerical data, and good agreement is found. Results are then presented for suspensions of oblate spheroids of two mean aspect ratios of 0.3 and 0.2. Results for the relative viscosity η _r, normal stress differences N ₁ and N ₂ are reported and compared with the few available results on oblate particle suspensions in a hydrodynamic regime. Evolution of the orientation of the particles is also observed, and a clear alignment with the flow is found to occur after a transient period. A change of sign of N ₁ from negative to positive as the particle concentration is increased is observed. This phenomenon is more significant as the particle aspect ratio increases. It is believed to arise from a change in the suspension microstructure as the particle alignment increases.     

Stability of an Initially, Stably Stratified Fluid Subjected to a Step Change in Temperature

The onset of convective instability in an initially quiescent, stably stratified fluid layer between two horizontal plates is analyzed with linear theory. The bottom boundary is heated suddenly from below, subjected to a step change in surface temperature. The critical time t _c to mark the onset of Rayleigh-Bénard convection is predicted by propagation theory. This theory uses the length scaled by , where α denotes thermal diffusivity. Under the normal mode analysis the dimensionless disturbance equations are obtained as a function of τ(=αt/d ²) and ζ(=Z/), where d is the fluid layer depth and Z is the vertical distance. The resulting equations are transformed to self-similar ones by using scaling and finally fixing τ as τ_c under the frame of coordinates τ and ζ. For a given γ, Pr and τ_c, the minimum value of Ra is obtained from the marginal stability curve. Here γ denotes the temperature ratio to represent the degree of stabilizing effect, Pr is the Prandtl number and Ra is the Rayleigh number. With γ=0, the minimum Ra value approaches the well-known value of 1708 as τ_c increases. However, it is inversely proportional to τ_c ^3/2 as τ_c decreases. With increasing γ, the system becomes more stable. It is interesting that in the present system, propagation theory produces the stability criteria to bound the available experimental data over the whole domain of time. Received 5 November 2001 and accepted 29 March 2002 Published online: 2 October 2002 RID="*" ID="*" This work has been supported by both SK Chemicals Co. Ltd. and LG Chemical Ltd., Seoul under the Brain Korea 21 Project of the Ministry of Education. Communicated by H.J.S. Fernando     

On the Shear Number Effect in Stratified Shear Flow

The influence of the shear number on the turbulence evolution in a stably stratified fluid is investigated using direct numerical simulations on grids with up to 512 × 256 × 256 points. The shear number SK/ε is the ratio of a turbulence time scale K/ε to the shear time scale 1/S. Simulations are performed at two initial values of the Reynolds number Re _Λ= 44.72 and Re _Λ= 89.44. When the shear number is increased from small to moderate values, the nondimensional growth rate γ= (1/SK)dK/dt of the turbulent kinetic energy K increases since the shear forcing and its associated turbulence production is larger. However, a further increase of the shear number from moderate to large values results in a reduction of the growth rate γ and the turbulent kinetic energy K shows long-time decay for sufficiently large values of the shear number. The inhibition of turbulence growth at large shear numbers occurs for both initial values of the Reynolds number and can be explained with the predominance of linear effects over nonlinear effects when the shear number is sufficiently high. It is found that, at the higher initial value of the Reynolds number, the reduction of the growth rate occurs at a higher value of the shear number. The shear number is found to affect spectral space dynamics. Turbulent transport coefficients decrease with increasing shear number. Received 23 June 1998 and accepted 25 February 1999