Effect of solids concentration in dense suspensions of silica-iron(III) oxide and water

The rheological properties of dense suspensions, of silica, iron (III) oxide and water, were studied over a range of solids concentrations using a viscometer, which was modified so as to prevent settling of the solid components. Over the conditions studied, the material behaved according to power—law flow relationships. As the concentrations of silica and iron(III) oxide were increased, an entropy term in the flow equation was identified which had a silica dependent and an iron (III) oxide dependent component. This was attributed to a tendency to order into some form of structural regularity. A, A, B, C pre-exponential functions (K Pa^–n s^–1) - C _ox volume fraction iron (III) oxide - Q activation energy (kJ mol^–1) - R gas constant (kJ mol^–1 K^–1) - R _v silica/water volume ratio - T temperature (K) - n power-law index - H enthalpy (kJ mol^–1) - S entropy change (kJ mol^–1 K^–1) - shear strain rate (s^–1) - shear stress (Pa)     

Flow mechanisms in dense silica-metal oxide-water suspensions

The rheological properties of dense silica in water suspensions (approx. 50% solids by volume) containing additions of metal oxides were examined. Metal oxides used were ferric, zinc and stannic. To prevent settling, testing was performed in a rheometer which was modified to provide for continual stirring of the materials. Relatively small oxide additions had the effect of thickening the mixtures and making them non-Newtonian. Different rate-limiting steps for flow were identified depending on the particular mixture, testing temperature and shear strain rate. Flow could be described using empirical equations which are identical to those often used to describe plastic flow in solid crystalline materials.     

Different behaviors of concentrated polysaccharide systems in large-amplitude oscillating shear fields

Two series of oscillatory flow tests were carried out on two concentrated polysaccharide systems (hydroxyethyl guar gum and scleroglucan) in order to evaluate the possibilities offered by large-deformation techniques for the discrimination between different classes of macromolecular systems (i.e., entanglement networks and weak gels). Frequently and strain sweeps, as well as combined steady and oscillatory shear tests were performed to analyze the influence of strain amplitude and of the superposed parallel shear rate on the dynamic properties of these materials.     

The rheology of a smectic main-chain polymer

The rheology of a smectic main-chain polymer shows that the activation energy is high (275 kJ mol^–1) and that the viscosity is more than two orders of magnitude higher than in the isotropic phase. The recoverable strain in the smectic phase is largely due to the reformation of the smectic layers after cessation of shear.     

Linear rheology of viscoelastic emulsions with interfacial tension

Emulsions of incompressible viscoelastic materials are considered, in which the addition of an interfacial agent causes the interfacial tension to depend on shear deformation and variation of area. The average complex shear modulus of the medium accounts for the mechanical interactions between inclusions by a self consistent treatment similar to the Lorentz sphere method in electricity. The resulting expression of the average modulus includes as special cases the Kerner formula for incompressible elastic materials and the Oldroyd expression of the complex viscosity of emulsions of Newtonian liquids in time-dependent flow.     

Pure liquids described as concentrated cluster dispersions

The Fulcher-Tammann-Hesse-Vogel equation, ln = A + B/(T – T ₀ ), is shown to be equivalent to the general viscosity-composition relationship, ln _r =k f /(1 – f ), for binary mixtures. The Cailletet-Mathias law of the Rectilinear Diameter is rearranged to represent a density mixture formula for two components. Temperature-independent viscosities and densities can then be calculated for dense, solid cluster fractions, dispersed in a low-density, low-viscosity non-clustered continuous phase. The cluster fraction decreases with temperature. The value ofT ₀ is shown to be related to the liquid- or solid-like behavior of the clusters. For liquids with a vapor pressure < 1 mm Hg at the melting point, the calculated cluster volume fraction suggests close packing of clusters, ranging in shape from monodisperse spheres to polydisperse non-spherical particles. Examples are given for molecular liquids, molten metals, and molten salts. The size of the clusters is estimated from the heat of evaporation.     

The role of short chain molecules for the rheology of polystyrene melts.

Atactic polystyrenes of narrow molar mass distribution with average molar masses larger than the critical molar massM _c were mixed with similar polystyrenes of molecular masses lower thanM _c . Linear viscoelastic melt properties of these binary blends were measured with a dynamic viscometer of the concentric cylinder type. One of the experimental findings is that the time-temperature shift factorsa _T are dependent on the composition of the samples. This can be understood, if free volume due to chain-ends is taken into account. A computer-fitted WLF-equation being modified in a proper way leads to the following results: At the glass-transition-temperature the fraction of free volume in polystyrene of infinite molar mass is only 0.015. At a temperature of 180 °C the mean value of the free volume at a chain end is 0.029 nm³ for the polystyrene investigated.     

The effect of dissolved polymers on the rheological properties of coating colours

Coating colours used for the coating of paper and board consist mainly of a mineral pigment, which is very often clay, a synthetic binder such as a styrenebutadiene latex, dispersion agents and water retention aids. The latter are often water soluble polymers. These polymers have a very strong influence on the rheological properties of the coating colours, both on the strain rate dependence of the apparent viscosity and on the viscoelasticity. The effects of two different grades of carboxymethylcellulose (CMC) and one grade of hydroxyethylcellulose (HEC), on the rheological properties at room temperature of a clay-based coating colour at pH 8, have been investigated. It is concluded that the high values of the dynamic modulus of the colours are due to interactions between the cellulose derivatives and the solid particles, i.e. mainly the clay particles. For HEC this interaction is associated with adsorption of the polymeric molecules on the clay particles. In the case of CMC, the adsorption is strongly retarded by the presence of the dispersant (a polyacrylate salt). It is suggested that the marked elasticity of the CMC-containing colour in addition to a possible polymer adsorption may be due to charge interactions and/or depletion flocculation. The effect of CMC and HEC on the water-retention properties of the colour is also discussed.     

Effect of processing and particulate fillers on the rheology of a nematic polymer melt

Processing of a nematic HBA/HNA polymer melt increases the capillary diameter dependence of the viscosity and induces structural changes which are evident in oscillatory shear, but cannot be characterized by DSC. The effect of 6-m calcium carbonate particulate fillers is to increase the viscosity uniformly. Low concentrations of sub-micron carbon black particles cause an unexplained viscosity minimum in a large (30-mil) capillary.     

An adaptation of finite linear viscoelasticity theory for rubber-like viscoelasticity by use of a generalized strain measure

In this paper a simplified three-dimensional constitutive equation for viscoelastic rubber-like solids is derived by employing a generalized strain measure and an asymptotic expansion similar to that used by Coleman and Noll (1961) in their derivation of finite linear viscoelasticity (FLV) theory. The first term of the expansion represents exactly the time and strain separability relaxation behavior exhibited by certain soft polymers in the rubbery state and in the transition zone between the glassy and rubbery states. The relaxation spectra of such polymers are said to be deformation independent. Retention of higher order terms of the asymptotic expansion is recommended for treating deformation dependent spectra.Certain assumptions for the solid theory are relaxed in order to obtain a constitutive equation for uncross-linked liquid materials which exhibit large elastic recovery properties.Apart from the strain energyW(I₁,I ₂), which alternatively characterizes the long-time elastic response of solids or the instantaneous elastic response of elastic liquids, only the linear viscoelastic relaxation modulus is required for the first-order theory. Both types of material functions can be obtained, in theory, from simple laboratory testing procedures. The constitutive equations for solids proposed by Chang, Bloch and Tschoegl (1976) and a special form of K-BKZ theory for elastic liquids are shown to be particular cases of the first-order theory.Previously published experimental data on a cross-linked styrene-butadiene rubber (SBR) and an uncross-linked polyisobutylene (PIB) rubber is used to corroborate the theory.     

Rheology of brown coal-water suspensions

Techniques for measuring the fundamental flow properties of as-mined Victorian brown coal suspensions are developed. Flow properties are presented for Morwell, Yallourn and Loy Yang coals as a function of concentration for fixed particle size distribution. Even at the relatively low solids concentration of 20 to 30 percent by weight, the suspensions exhibit complex non-Newtonian characteristics. Generally at high concentration, the suspensions are thixotropic with a shear rate dependent viscosity and exhibit a yield stress. The inherent thixotropy of the coals can be exploited and it is technically but perhaps not economically feasible to transport the as-mined coals in a pipeline. The power requirement to pump the coals in a pipeline is found to be 10 to 30 times that required to pump black coal in the Black Mesa pipeline in the U.S.A. The differences in the rheological properties of the three coals is related to the surface properties of the coal particle — expressed in terms of carboxylate and inorganic cation content, and to differences in the pore volume of the coals. The flow characteristics of one coal can be converted to that of another simply by varying either the carboxylate or ionic content of the suspension.     

Viscoplasticity of agglomerated suspensions

This work is a theoretical study on the effects of agglomeration on the fluidity and plasticity of a suspension of neutrally buoyant particles in a Newtonian fluid. The dynamics of a cluster of permanently attached spherical particles in a simple shear field is analyzed. The viscous and plastic components of the drag force acting on each of the agglomerated particles is then calculated and found to depend on the size of the individual particle unit, its location being relative to the center of the cluster and the material properties of the engulfing fluid. This information in conjunction with the knowledge of the interparticle cohesive forces is used to establish criteria for the agglomerate size reduction during dispersive mixing. From the kinematics of the cluster movement and the forces acting on its particulate components the rate of energy dissipation is calculated and utilized to evaluate the viscosity and yield stress of the suspension. These rheological parameters depend on the volume fraction and architecture of the agglomerate, the number of fused particles per cluster, and the viscosity of the suspending fluid. The analysis is also extended to include the case of polydispersity of agglomerate sizes.     

Generalized Cole-Cole behavior and its rheological relevance

Starting from an analysis of the rheological behavior of the complex modulus predicted by the Cole-Cole formalism, a generalized Cole-Cole ansatz is suggested in order to overcome the related difficulties. The corresponding rheological constitutive equation with fractional derivatives belonging to the generalized Cole-Cole respondance is stated and the characteristic material functions of the linear viscoelasticity theory (like the dynamic modulus and compliance, the relaxation and ratardation functions, the spectra, etc.) are derived. Model predictions of these functions will be compared with experimental results from dynamical measurements and creep data on different polymer systems which show cooperative phenomena (polymeric glasses and gelling systems). One can see that the modified ansatz fits the data very well, in spite of its relative simplicity.     

Elongational rheology of polyethylene melts — temporary network constitutive laws

The uniaxial elongational properties of various polyethylenes have been evaluated using an elongational rheometer and a melt-strength apparatus. It is possible to derive the data obtained in elongation from the distribution of relaxation times obtained from oscillatory shearing measurements (linear viscoelasticity), using a Wagner constitutive equation. The effects of the molecular parameters of the samples have been studied, in particular the effect of polydispersity on the shape of the damping function.     

Transient stress responses predicted by the internal viscosity model in elongational flow

Predictions are made for the elongational-flow transient rheological properties of the dilute-solution internal viscosity (IV) model developed earlier by Bazua and Williams. Specifically, the elongational viscosity growth function _e ⁺ (t) is presented for abrupt changes in the elongational strain rate . For calculating _e ⁺, a novel treatment of the initial rotation of chain submolecules is required; such rotation occurs in response to the macroscopic step change of at t = 0. Representative are results presented for N = 100 (N = number of submolecules) and = 1000 f and 10000 f (where is the IV coefficient and f is the bead friction coefficient), using h ^* = 0 (as in the original Rouse model) for the hydrodynamic interaction. The major role of IV is to cause the following changes relative to the Rouse model: 1) abrupt stress jump at t = 0 for _e ⁺; 2) general time-retardance of response. There is no qualitative change from the Rouse-model prediction of unbounded il growth when exceeds a critical value ( ), and calculations of submolecule strains at various show that the unbounded- _e ^– behavior arises from unlimited submolecule strains when . However, the time-retardance could delay such growth beyond the timescale of most experiments and spinning processes, so that the instability might not be detected. Finally, _e ⁺ (t) and _e ( ) in the limit are presented for N = 1 and compared with exact predictions for the analogous rigid-rod molecule; close agreement lends support for the new physical approximation introduced for solving the transient dynamics for any N.     

Flow birefringence and rheological measurements on shear induced micellar structures

Aqueous solutions of cationic surfactant systems with strongly binding counterions show the striking phenomenon of shear induced phase transitions. At low shear rates or angular frequencies, the solutions exhibit Newtonian flow. At high rates of shear, however, the rheological properties change dramatically. Above a well defined threshold value of the velocity gradient, a supermolecular structure can be formed from micellar aggregates. This shear induced structure (SIS) behaves like a gel and exhibits strong flow birefringence. The formation of the shear induced structure is very complicated and depends on the specific conditions of the surfactant system. In this paper we discuss new results which have been obtained from rheological measurements and from flow birefringence data. We examine the stability of the shear induced state as a function of temperature, surfactant concentration and salt concentration and we analyse the effect of solubilisation of alcohols and hydrocarbons. The results are interpreted in terms of a kinetic model which accounts for the observed behavior.Dedicated to the 60. birthday of Prof. H. Harnisch, Hoechst AGPartly presented at the 2nd Conference of European Rheologists, Prague, June 17–20, 1986     

Physiology,mechanics, and rheology

Biological systems possess rather specialized mechanical properties, acquired as part and parcel of the evolutionary development of the system as a whole. Their optimization permits the system to function physiologically in the context of a biologically essential, but mechanically often widely varying environment with adequate efficiency. The system's environment is its source of food and shelter; it represents the space in which it forages or preys on other creatures and in which it has to defend itself against still others. Thus, the system has to develop an adequately pliant, rheologically matched, energy-use efficient, mechanical interface between it and its surroundings. This must be an interface that both effectively excludes, but also effectively admits, the external. Internally, as well, it has to adapt the mechanical properties of cell and connective tissue to physiological function and the efficient performance of useful work. This will be illustrated by way of examples. Blood rheology is briefly discussed and put into the context of clinical hemorheology and epithelial protection; and function, by way of a mucus coating or a mucociliary clearance system, is reviewed in some detail. The importance of all aspects of rheological matching is demonstrated.Delivered as a Keynote Lecture at the Golden Jubilee Conference of the British Society of Rheology and Third European Rheology Conference, Edinburgh, 3–7 September, 1990.     

Driven torsion pendulum for measuring the complex shear modulus in a steady shear flow

To investigate the viscoelastic behavior of fluid dispersions under steady shear flow conditions, an apparatus for parallel superimposed oscillations has been constructed which consists of a rotating cup containing the liquid under investigation in which a torsional pendulum is immersed. By measuring the resonance frequency and bandwidth of the resonator in both liquid and in air, the frequency and steady-shear-rate-dependent complex shear modulus can be obtained. By exchange of the resonator lumps it is possible to use the instrument at four different frequencies: 85, 284, 740, and 2440 Hz while the steady shear rate can be varied from 1 to 55 s^–1. After treatment of the theoretical background, design, and measuring procedure, the calibration with a number of Newtonian liquids is described and the accuracy of the instrument is discussed.Notation a radius of the lump - A geometrical constant - b inner radius of the sample holder - c constant - C ₁, C ₂ apparatus constants - D damping of the pendulum - e _x , e _y , e _z Cartesian basis - e _r , e , e _z orthonormal cylindrical basis - E geometrical constant - E _t , ⁰ E _t , _t relative strain tensor - f function of shear rate - F _t relative deformation tensor - G (t) memory function - G ^* complex shear modulus - G Re(G ^* ) - G Im(G ^* ) - h distance between plates - H ^* transfer function - , functional - i imaginary unit: i ²= – 1 - I moment of inertia - J _exc excitation current - J ₀ amplitude of J _exc - k ^* = k – ik complex wave number - K torsional constant - K fourth order tensor - l length of the lump - L mutual inductance - M _dr driving torque - M _liq torque exerted by the liquid - ⁰ M _liq, _liq steady state and dynamic part of Mliq - n power of the shear rate - p isotropic pressure - Q quality factor - r radial position - R,R ₀, R _c Re(Z ^*, Z ₀ ^* , Z _c ^* ) - s time - t, t time - T temperature - T, ⁰ T, stress tensor - u velocity - U lock-in output - ₀ velocity - V _det detector output voltage - V _sig, V _cr signal and cross-talk part of V _det - x Cartesian coordinate - X , X ₀, X _c Im(Z ^*, Z ₀ ^* , Z _c ^* ) - y Cartesian coordinate - z Cartesian coordinate, axial position