Rheological behavior of concentrated suspensions as affected by the dynamics of the mixing process

The rheological characterizations of concentrated suspensions are generally carried out assuming “well-mixed” suspensions. However, the variation of the concentration distributions of the ingredients of the formulation, i.e., the “goodness of mixing”, the size and shape distributions of the particle clusters and the rheological behavior of the suspension all depend on the thermo-mechanical history that the suspension is exposed to during the mixing process. Here, various experimental tools are used for the characterization of the degree of mixedness (concentration distributions) of various ingredients along with the characterization of rheological material functions, wall slip behavior and the maximum packing fraction of a graphite/elastomer suspension. The degree of mixedness values of the ingredients of the suspensions processed using batch and continuous processes and under differing operating conditions were characterized quantitatively using wide-angle X-ray diffraction and thermo gravimetric analysis and were elucidated under the light of the electrical properties of the suspension as affected by the mixing process. Upon achieving better homogeneity of the graphite particles and the binder and decreases in the size and breadth of the size distributions of particle clusters (as inferred from electrical measurements and maximum packing fraction values), the elasticity (storage modulus) and the shear viscosity (magnitude of the complex viscosity from small-amplitude oscillatory shear and shear viscosity from steady torsional and capillary rheometry) of the suspension decreased significantly and the wall slip velocity values increased. These findings demonstrate the intimate relationships that exist between the rheological behavior of concentrated suspensions and the thermo-mechanical history that they are exposed to during the processing stage and suggest that the preparation conditions for suspensions should be carefully selected and well documented to achieve reproducible characterization of rheological material functions.     

Rheo-PIV analysis of the slip flow of a metallocene linear low-density polyethylene melt

The continuous extrusion of a metallocene linear low-density polyethylene through a transparent capillary die with and without slip was analyzed in this work by rheometrical measurements and particle image velocimetry (PIV). For this reason, a comparison was made between the rheological behaviors of the pure polymer and blended with a small amount of fluoropolymer polymer processing additive. Very good agreement was found between rheometrical and PIV measurements. The pure polymer exhibited stick-slip instabilities with nonhomogeneous slip at the die wall, whereas the blend showed stable flow. The slip velocity was measured directly from the velocity profiles and was negligible for the pure polymer before the stick-slip but increased monotonously as a function of the shear stress for the blend. The flow curves and the slip velocity as a function of the shear stress deviated from a power law and were well fitted by continuous “kink” functions. Comparison of PIV data with rheometrical ones permitted a direct proof of the basic assumption of the Mooney theory. Finally, the analysis of the velocity profiles showed that there is a maximum in the contribution of slip to the average fluid velocity, which is interpreted as the impossibility for the velocity profile to become plug like in the presence of shear thinning.     

Determination of the wall slip velocity in the flow of a SBR compound

Rubber compounds are known to exhibit slip at the wall in particular flow conditions. The slip velocity is usually determined by using the classical Mooney method. The rheological behavior of a styrene butadiene rubber (SBR) compound was studied with three different rheometers. Biconical rotational, capillary and slit die rheometers were used to define the true viscous behavior of the compound and the slip velocity. It was shown that it was impossible to apply the Mooney method to our experimental data. New characterizations were thus developed for both capillary and slit die experiments. They were based on the dependency of the slip velocity on the local flow gap. Contrarily to the Mooney method, they provided physically acceptable results and led to a power-law relationship between wall slip, wall shear stress and local geometry of the flow.     

Wall slip of mayonnaises in viscometers

The shear flow of mayonnaise is generally characterized by an apparent yield stress, shear thinning in steady flow, stress overshoots upon inception of flow and other time-dependent effects. These observations are usually understood to be the result of structural rearrangement within the material. Additionally and separately, the possibility that emulsions may exhibit apparent wall slip on a microscopic scale at a solid-liquid boundary has been reported by some researchers. Thus, observed rheological behavior is likely to be the result of the interplay between these two phenomena. In the present work, it is demonstrated that when measurements are sought to be made on mayonnaise using rotational viscometers visible wall slip occurs, rendering such instruments ineffective for the purpose of making viscosity measurements even at shear rates as low as 10^–3s^–1. The factors that influence the onset and extent of slip are investigated with the help of parallel plate viscometers, and it is concluded that the observed “yielding” of mayonnaise is actually an artifact of the onset of macroscopic slip. Slip effects are also found in capillary flow but are ameliorated with increasing shear rate. To circumvent these problems, it is proposed that extensional viscometry be employed for determining the flow behavior of mayonnaises. Received: 18 August 1997 Accepted: 1 April 1998     

Obtaining the steady shear rheological properties and apparent wall slip velocity data of a water-in-oil emulsion from gap-dependent parallel plate viscometry data

A two-stage Tikhonov regularisation procedure has been used to obtain rheological properties for a high internal phase emulsion from gap-dependent steady-state parallel plate shear data. This method is beneficial in that it can convert the steady shear data into rheological property functions. The built-in regularisation parameters of the method are able to keep noise amplification under control. The two-stage method is able to obtain not only the shear stress–shear rate function but also the apparent slip velocity as a function of wall shear stress. The method is such that it obtains the rheological functions over the maximum range of shear rate covered by the data. The results obtained using the new method are compared to those obtained using the vane geometry with good agreement being observed.     

Slip at the interface between immiscible polymer melts I: method to measure slip

Slip at the interface between immiscible polymer melts remains poorly understood. A method that relies solely on rheological measurements to obtain the interfacial slip velocity uses the slip-induced deviation in the flow variables. To use the method, accurate estimates of the flow variables under the assumption of no-slip are necessary. Although such estimates can be easily derived under some cases, in general, this is not straightforward. Therefore, methods to determine the interfacial slip velocity without using estimates for the flow variables under no-slip conditions are desirable. In this work, we focus on investigations of slip at the interface between two immiscible polymer melts undergoing two-phase coaxial flow. To enable such investigations, we have adapted the Mooney method, usually used to investigate wall slip, to investigate polymer/polymer interfacial slip. Using this method, we have measured the slip velocity at the interface between polypropylene and polystyrene as a function of the interfacial stress. To determine the validity of the modified Mooney method, we also determine the slip velocity using the slip-induced deviation in the flow variables. To enable this determination, we use polypropylene and polystyrene with almost identical shear rate-dependent viscosities over a range of shear rates. The slip velocity obtained from the modified Mooney method displayed excellent agreement with that determined using the deviation from no-slip. In agreement with prior work, the dependence of the slip velocity on the interfacial stress is a power-law. Our investigation spans a sufficiently wide range of interfacial stress to enable the direct observation of two power-law regimes and also the transition between the two regimes. We also find that the power-law exponent of approximately 3 at low stresses decreases to approximately 2 at high stresses.     

Simultaneous determination of shear and extensional viscosities and wall slip by on-line rheometry with parameter fitting: an application to EPDM rubber

Shear and extensional viscosities and wall slip are determined simultaneously under extrusion processing conditions using an on-line rheometer. Because it is not possible to independently control flow rate and temperature, classical methods for interpretation of capillary data cannot be used with on-line rheometry. This limitation is overcome using computational optimization to fit parameters in a flow model. This consists of three parts, representing shear viscosity, extensional viscosity, and wall slip. Three-parameter, power law forms, based on local instantaneous deformation rates and including temperature dependence, are used for each, and analytic solutions applied for entry flow and flow in the capillary. For entry flow, the Cogswell–Binding approach is used, and for developed flow in the capillary a solution incorporating wall slip is derived. The rheometer, with interchangeable capillaries, is mounted in place of the die on a rubber profile extrusion line. Pressure drops and temperatures for extrusion of an EPDM rubber through 2 mm diameter capillaries of length 0, 2, 3, 4, and 5 mm are logged and flow rates determined for a range of extruder speeds (5 to 20 rpm). Pressures ranged from 60 to 75 bar and temperatures from 86 to 116 °C. Mean flow velocity in the capillaries was between 5 × 10⁻³ and 5 × 10⁻¹ m s⁻¹. The nine material parameters are optimized for best fit of the analytic pressure drops to experimental data, using about 100 data points, with the Levenberg–Marquardt method. It is concluded that flow is dominated by extension and wall slip. Shear flow appears to play little part. The slip model indicates that slip velocity increases much more rapidly than the wall shear stress (in the range 0.5–1 MPa) and decreases with temperature for a given stress level. Results for the (uniaxial) extensional viscosity represent an engineering approximation to this complex phenomenon at the high strains (approximately 200) and high extension rates (up to 800 s⁻¹) applying in the extrusion. Results indicate a slight extension hardening and a decrease with temperature. Results are put into the context of the available studies in the literature, which, particularly with regard to wall-slip and extensional flow, consider conditions far removed from those applying in industrial extrusion. The present methods provide a powerful means for flow characterization under processing conditions, providing data suitable for use in computer simulations of extrusion and optimization of die design.     

New measurements of the flow-curves for Carbopol dispersions without slip artefacts

The thickening properties of many commercial thickeners are difficult to measure because of wall slip artefacts. Here we report a series of experiments on a typical thickener where these artefacts have been successfully eliminated. As a result, complete, steady-state flow-curves of aqueous Carbopol 980 (the toxicologically preferred version of the older and more well-known Carbopol 940) dispersions are reported for a range of concentrations of 0.045–1.0 wt%. The vane-and-basket flow geometry was used to avoid slip problems at low shear stress, with the geometry housed in a TA AR1000-N controlled-stress rheometer, whilst a Haake RV2 viscometer with an SV2P and MV2P concentric-cylinder geometries were used at higher shear rates. The flow-curves obtained show a smooth but steep transition from a very high Newtonian viscosity at low shear stress to a much lower viscosity at high shear stress. No real yield stresses were detected, but the higher shear rate results can be fitted to the Herschel-Bulkley model, which assumes an apparent yield stress. The various model parameters are displayed as a function of Carbopol concentration. Received: 29 November 2000/Accepted: 26 February 2001     

Cessation of Newtonian circular and plane Couette flows with wall slip and non-zero slip yield stress

We solve analytically the cessation flows of a Newtonian fluid in circular and plane Couette geometries assuming that wall slip occurs provided that the wall shear stress exceeds a critical threshold, the slip yield stress. In steady-state, slip occurs only beyond a critical value of the angular velocity of the rotating inner cylinder in circular Couette flow or of the speed of the moving upper plate in plane Couette flow. Hence, in cessation, the classical no-slip solution holds if the corresponding wall speed is below the critical value. Otherwise, slip occurs only initially along both walls. Beyond a first critical time, slip along the fixed wall ceases, and beyond a second critical time slip ceases also along the initially moving wall. Beyond this second critical time no slip is observed and the decay of the velocity is faster. The velocity decays exponentially in all regimes and the decay is reduced with slip. The effects of slip and the slip yield stress are discussed.     

Rheological characterization of a solder paste for surface mount applications

Solder pastes used in surface mount soldering techniques (SMT) are very complex suspensions containing high volumes of metallic powder in a carrier fluid. The rheological complexity results largely from the carrier fluid itself, which is a suspension of colloidal particles. In this work, we have characterized the rheological properties of a typical carrier fluid and its solder paste containing 64 vol.% metallic powder. A six-blade vane geometry was used to avoid wall slip and sample fracture. All measurements were carried out following pre-shearing and rest time in order to obtain reproducible results. Steady shear experiments showed that the solder paste was highly shear-thinning and thixotropic. In oscillatory shear, the linear viscoelastic domain was found to be very narrow for both the suspending fluid and the paste. Frequency sweep tests in the linear domain revealed a gel-like structure with a nearly constant G′ for the suspending fluid and a slightly increasing G′ for the solder paste. From creep experiments, a yield stress of about 40 Pa was determined for the suspending fluid at temperatures between 25 and 40°C, and of 100 Pa at 4°C. A much larger yield stress, 480 Pa, was determined for the solder paste at 25°C.     

Non-Newtonian flow in microporous structures under the electroviscous effect

Single phase non-Newtonian microporous flow combined with the electroviscous effect is investigated in the pore-scale under conditions of various rheological properties and electrokinetic parameters. The lattice Boltzmann method is employed to solve both the electric potential field and flow velocity field. The simulation of commonly used power-law non-Newtonian flow shows that the electroviscous effect on the flow depends on both the fluid rheological behavior and pore surface area ratio significantly. For the shear thinning fluid with power-law exponent n < 1, the fluid viscosity near the wall is smaller and the electrovicous effect plays a more important role compared to the Newtonian fluid and shear thickening fluid. The high pore surface area ratio in the porous structure increases the electroviscous force and the induced flow resistance becomes important even to the flow of Newtonian and shear thickening fluids.     

Numerical simulation of the transition from adhesion to slip with friction in generalized Newtonian Poiseuille flow

The axisymmetric Poiseuille flow of a purely viscous generalized Newtonian fluid under rate of flow controlled conditions is studied with a change in the boundary conditions at a transition point from an adhesive to a slip condition with friction at the wall. The friction law used originates from an experimental study by (J.M. Piau and N. El Kissi, J. Non-Newtonian Fluid Mech. 54 (1994) 121–142) using a capillary made of steel and a silicone fluid, and is based also on a molecular dynamics theory by (Yu. B. Chernyak, A.I. Leonov, Wear, 108 (1986) 105–138). It gives a non-linear multivalued dependance of the wall shear stress to the velocity at the wall. Moreover, wall shear stress values may become smaller than values obtained when adhesion prevails in the capillary. The shear stress must over-step some limiting stress level to trigger the wall slip. After checking slip boundary condition implementation for the case of Poiseuille flow with slip along the entire wall, the convergence and the validity of the computation was studied. Important morphologic changes of the flow field and the stress field appear around the transition point from adhesion to slip boundary condition. Slip at the wall allows the principal stress difference to be drastically reduced, except in the vicinity of the transition point where this difference is maximum. A peak in shear stress located upstream of the transition, and a peak in elongational stress located downstream of the transition, are observed at the wall. Fully developed near plug-like flows are obtained within about 1D only downstream of the transition point. It is concluded that the effect of slip on extrudates distorsion should appear clearly even when the exit slippery zone is reduced to 1D.     

Pipe flow of suspensions

This study shows that fully developed pipe flow of a particulate suspension is defined by four dimensionless parameters of particle-fluid interactions in addition to the Reynolds number. Effects accounted for include the Magnus effect due to fluid shear, electrostatic repulsion due to electric charges on the particles, and Brownian or turbulent diffusion. In the case of a laminar liquid-solid suspension, electrostatic effect is negligible but shear effect is prominent. Solution of the basic equations gives the density distribution of particles with a peak at the center (Einstein, Jeffery) or at other radii between the center and the pipe wall (Segré et al) depending on the magnitudes of the various flow parameters. In the case of a turbulent gas-solid suspension, the Magnus effect is significant only within the thickness of the laminar sublayer. However, charges induced on the particles by the impact of particles at the wall produce a higher density at the wall than at the center of the pipe. The velocity distribution of particles is characterized by a slip velocity at the wall and a lag in velocity in the core from the fluid phase. These results are verified by earlier measurements.     

EFFECT OF WALL SLIP ON SQUEEZE FLOW OF RIGID-PLASTIC MEDIA BETWEEN PARALLEL DISK

The squeeze flow of a rigid-plastic medium between parallel disks is considered for small gaps with partial wall slip. The stress distribution and the squeeze force between parallel disks of a rigid-plastic medium with the following four different slip boundary conditions are obtained. (1) The Coulombic friction condition is applied, and the stress distribution on the wall is derived, which is linear or exponential distribution in the no-slip area or slip area. (2) It is assumed that the slip velocity at the disks increases linearly with the radius up to the rim slip velocity, with the stress distribution and the squeeze force gained. (3) The assumption that the slip velocity at the disks is related to the shear stress component is used, with the stress distribution and the squeeze force obtained, which is equivalent to the result given in (2). (4) Rational velocity components are introduced, and the stress distribution is satisfied.     

Strain stiffening of non-colloidal hard sphere suspensions dispersed in Newtonian fluid near liquid-and-crystal coexistence region

Concentrated hard sphere suspensions often show an interesting nonlinear behavior, called strain stiffening, in which the viscosity or modulus starts to increase at critical strain amplitude. Sudden increase of rheological properties is similar to shear thickening; however, the particle dynamics in the strain stiffening under oscillatory shear flow does not necessarily coincide with the mechanism of shear thickening under step shear flow. In this study, we have systematically investigated the nonlinear rheology of non-colloidal (>1???m) hard sphere suspensions dispersed in Newtonian fluid near liquid-and-crystal coexistence region in order to better understand the strain stiffening behavior. The suspensions near liquid-and-crystal coexistence region are known to locally form the closed packing structure. The critical strain amplitude which is the onset of strain stiffening was different for the storage and loss modulus. But they converged to each other as the suspension forms a more crystalline structure. The critical strain amplitude was independent of medium viscosity, imposed angular frequency, and particle size, but was strongly dependent upon particle volume fraction. The onset of strain stiffening was explained in terms of shear-induced collision due to particle motion in the closed packing structure. Nonlinear stress wave-forms, which reflect the micro-structural change, were observed with the onset of strain stiffening. During the strain stiffening, enhanced elastic stress before and after flow reversal was observed which originates from changes in the suspension microstructure. Nonlinearity of the shear stress in terms of Fourier intensity was extremely increased up to 0.55. Beyond the strain stiffening, the suspension responded liquid-like and the nonlinearity decreased but the elastic shear stress was still indicating the microstructure rearrangement within a cycle.     

Pipe flow of suspensions

This study shows that fully developed pipe flow of a particulate suspension is defined by four dimensionless parameters of particle-fluid interactions in addition to the Reynolds number. Effects accounted for include the Magnus effect due to fluid shear, electrostatic repulsion due to electric charges on the particles, and Brownian or turbulent diffusion. In the case of a laminar liquid-solid suspension, electrostatic effect is negligible but shear effect is prominent. Solution of the basic equations gives the density distribution of particles with a peak at the center (Einstein, Jeffery) or at other radii between the center and the pipe wall (Segré et al) depending on the magnitudes of the various flow parameters. In the case of a turbulent gas-solid suspension, the Magnus effect is significant only within the thickness of the laminar sublayer. However, charges induced on the particles by the impact of particles at the wall produce a higher density at the wall than at the center of the pipe. The velocity distribution of particles is characterized by a slip velocity at the wall and a lag in velocity in the core from the fluid phase. These results are verified by earlier measurements.     

Evaluation of wall slip effects in the lubricating grease/air two-phase flow along pipelines

Evaluation of wall slip phenomena during the horizontal pipeline flow of air/lubricating grease mixtures was investigated. With this aim, pressure drop measurements have been carried out along pipelines with different diameter and roughness. A modified Jastrzebski's equation for the slip velocity, based on the introduction of the relative roughness, has been used to correct wall slip effects for a lithium lubricating grease/air system. This expression has been introduced in the classical Rabinowitsch–Mooney treatment and applied to the superficial liquid velocity instead of the single-phase average velocity following a single-phase treatment analogy. Thus, the non-slip flow curve data for the two-phase mixture were obtained from roughened pipes and compared with those obtained from pipes with smooth internal surfaces. The effect of air on the extension of wall slip has been established as a function of air flow rate. Thus, the consideration of the reduction of the wetted pipe surface as air is injected allows an adequate explanation of this phenomenon, confirmed by the reduction of the effective slip contribution on the observed apparent shear rate. A power-law relationship between the slip velocity and the wall shear stress has been deduced, although this tends asymptotically to linearity as air flow rate is increased.     

Two-fluid non-linear model for flow in catheterized blood vessels

Blood flow through a catheterized artery is analyzed, assuming the flow is steady and blood is treated as a two-fluid model with the suspension of all the erythrocytes in the core region as a Casson fluid and the plasma in the peripheral region as a Newtonian fluid. The expressions for velocity, flow rate, wall shear stress and frictional resistance are obtained. The variations of these flow quantities with yield stress, catheter radius ratio and peripheral layer thickness are discussed. It is noticed that the velocity and flow rate decrease while the wall shear stress and resistance to flow increase when the yield stress or the catheter radius ratio increases while all the other parameters were held fixed. It is found that the velocity and flow rate increase while the wall shear stress and frictional resistance decrease with the increase of the peripheral layer thickness. The estimates of the increase in the frictional resistance are significantly very small for the present two-fluid model than those of the single-fluid Casson model.     

Dynamic properties of shear thickening colloidal suspensions

The transient shear rheology (i.e., frequency and strain dependence) is compared to the steady rheology for a model colloidal dispersion through the shear thickening transition. Reversible shear thickening is observed and the transition stress compares well to theoretical predictions. Steady and transient shear thickening are observed to occur at the same value of the average stress. The critical strain for shear thickening is found to depend inversely on the frequency at fixed applied stress for low frequencies (high strains), but is limited to an apparent minimum critical strain at higher frequencies. This minimum critical strain is shown to be an artifact of slip. Lissajous plots illustrate the transition in material properties through the shear thickening transition, and the energy dissipated by a shear thickening suspension is analyzed as a function of strain amplitude.     

Plane Couette flow of viscoplastic materials along a slippery vibrating wall

This study looks at the influence of slip at the wall on plane Couette flows of viscous and yield stress fluids with ultrasonic wall motion. These fluids are used in coating processes. A constant speed V at one wall creates the flow, and vibrations and slip take place at the other wall. Isothermal conditions and arbitrary (longitudinal or transverse) vibrations are considered, with negligible vibrational inertia.For the Bingham model, due to its nonlinearity, whatever the vibration direction and the wall slipperiness, significant decreases occur in the average stress as soon as moderate values of the dimensionless vibration velocity amplitude are involved. Such effects are associated with adherent or slippery walls, even with linear friction laws. They do not occur with linear viscous (Newtonian) models.Average stress reductions can reach nearly 100% for very high Oldroyd numbers, i.e. for stress values without vibration close to the yield limit. Slip velocity also decreases. The cost in terms of the power dissipated remains relatively less than in the Newtonian case, and may contribute to a change in the temperature field. Even when the flow without vibration is a pure slip one, large enough amplitude vibrations, either longitudinal or transverse, applied at the wall can reduce the average shear stress and slip velocity, giving rise to an average axial shear flow.Hence vibrations of moderate or high-velocity amplitude applied to adherent or slippery walls enhance plane Couette flow rates for viscoplastic materials. With moderate values of this amplitude, longitudinal vibrations may be 1.5–2 times more efficient than transverse vibrations with an equivalent cost. However, if for technological reasons transverse vibrations have to be preferred, they can also produce significant results. In any case, coating flows should benefit from an adequate application of ultrasound at the wall.