A model for the thermorheological behavior of viscoelastic fluids

Using a power-law ansatz for the temperature dependence of the shear modulus on the level of internal variables, the thermorheological behavior is modeled for viscoelastic fluids of a special group of rheological constitutive equations (rate-type models). The model parameter introduced characterizes thermoelastic contributions. The relation between the model parameter and the physical quantities appearing in deformation processes is discussed. Based on the chosen temperature dependence of the shear modulus, thermodynamically consistent equations like the nonlinear rheological constitutive equation and the temperature equation are derived. The special cases of entirely entropy and energy elastic fluids are also considered. The thermorheological behavior (exo-, - or endothermal processes) of a viscoelastic fluid in a stress-growth experiment followed by relaxation is analyzed with respect to the model parameter.     

A simple integral constitutive equation for polymeric liquids

An integral constitutive equation describing the strain history in terms of the Cauchy-Green and Finger tensors is presented. Its memory functions, which correspond to a flow-dependent continuous spectrum of relaxation times, depend on the invariants of the Cauchy-Green and Finger rate of strain tensors. Theoretical predictions resulting from this equation are compared with experimental data for some types of flow. Using the Laguerre polynomial expansion, the basic equation is generalized.     

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     

Rheological properties of service weathered road bitumens

A study was carried out of the rheological properties of service weathered bitumens and their properties were compared with road performance. Bitumen from 39 test sites was recovered from the uppermost layer of stone particles covering the road surfacing and tested under dynamic and transient loading. Dynamic testing was carried out under forced sinusoidal loading. Testing under transient loading was mainly with a viscosity test conducted at 45°C, but some creep testing in compression was conducted at 0°C. From the results of dynamic testing, master curves of modulus and loss angle were constructed, spanning over ten decades in loading frequency. The hyperbolic expressions of Dickinson and Witt successfully described the frequency dependence of bitumen modulus and loss angle. The Williams, Landel and Ferry (WLF) equation, with newly derived coefficients, described the temperature dependence of the shift factor (or Newtonian viscosity) for the temperature range –10 to 60°C. Attempts were made to compare the measured transient response with that calculated from dynamic results. The result of the viscosity test conducted at 45°C as an indicator of modulus at low temperatures was assessed. Surfacing distress increased as the bitumen viscosity or modulus increased, however service performance of the bitumens was best correlated with the modulus calculated at conditions representative of traffic stressing and lowest site temperature. The changes in the rheological properties of bitumens induced by weathering is discussed.     

Rheological properties of lightly crosslinked carboxy copolymers in aqueous solutions

The rheological properties of a series of lightly crosslinked carboxy copolymers in aqueous solutions have been evaluated in steady shear and dynamic oscillatory modes. Viscosity profiles and the behavior of storage modulus are related to the chemical composition of the copolymers and their crosslinking density. A maximum in viscosity and in storage modulus which depends on the type of crosslinking agent used is explained by a combination of a chain entanglement mechanism and a closely-packed spheres model. The recovery of viscosity and storage modulus after shearing is very fast and is related to the very fast rearrangement of the microgel structure as a function of time.     

Evolution of time constants during sol-gel transition

In developing a rheological constitutive equation for crosslinking polymers the determination and explanation of time constants are of great importance. For stoichiometrically balanced and imbalanced reactions of polydimethylsiloxane and polyurethane model polymers with appropriate cross-linkers, it is shown that the experimental data for the storage and loss moduli are well fitted within a large frequency range by a linear rheological constitutive equation with a truncated power law relaxation function.Special attention is given to the problem of estimating the different time constants. A method is proposed for the determination of the terminal relaxation time (in the case below the gel point) and a characteristic retardation time (in the case above the gel point) from the intersection points of the high and low frequency asymptotes of the storage modulus.     

New methods of determination of the molar weight distribution from rheological measurements

By assuming simplified hypotheses which result from the molecular analysis of Doi-Edwards, it is possible to propose rheological methods for characterizing molar weight distribution of entangled polymeric liquids. The generalized exponential distribution is especially concerned. Theoretical expressions of rheological parameters are derived, and their numerical values are calculated in special cases. A numerical method of discrimination and identification of these special distributions is proposed.     

On-line measurements of the rheological properties of fermentation broth

The paper is concerned with measurements of rheological properties of fermentation broth. An on-line rheometer, Rheohelix-1, based on the application of a helical screw impeller rotating in a draught tube has been constructed. The instrument was used for measurements of the rheological parameters of fermentation broth of Aspergillus niger in a submerged fermentation process. The results of rheological and some standard measurements have been compared and proved the applicability of the instrument.Presented at the Golden Jubilee Conference of the British Society of Rheology and Third European Rheology Conference, Edinburgh, 3–7 September, 1990.     

Rheological and drag reduction characteristics of xanthan gum solutions

The rheological and turbulent drag reducing characteristics of commercial and purified xanthan gum solutions of concentrations 50–500 ppm have been studied with and without addition of 100 ppm NaCl. The purification by soxlet extraction of xanthan gum using 95% ethanol is effective in removing low-molecular-weight impurities from xanthan. The increased content of higher molecular-weight xanthan in purified xanthan is evident from rheological and drag reduction behavior. The addition of 100 ppm salt to dilute solutions introduces semi-flexibility in xanthan gum solution without occurrence of self-association. The change in molecular behavior in the presence of salt is evident from rheological normal-stress and turbulent drag reduction behaviors.     

A photographic study of shapes of bubbles and coalescence in non-Newtonian polymer solutions

This communication reports (photographically) on the shapes of bubbles of different gases in several Newtonian and polymer solutions, encompassing a wide range of rheological behavior. Effects of a surface active agent are mentioned and bubble coalescence in viscoelastic solutions is visualized.     

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.     

Estimates of apparent elongational viscosity using the fibre spinning and “pure” methods

A comparison is made between elongational properties predicted by the FENE-P dumbbell rheological equation of state for fibre spinning and true values obtained from pure elongation. True values are found by using a constant elongation rate in the model and calculating the steady state values of the stresses. Two new averaging procedures are suggested for extracting elongational properties from fibre spinning experiments. It is suggested that a variety of flow conditions be used and care be taken when determining these properties. The rheological model is found to predict adequately shear and elongational flow properties of the polyacrylamide-type of Boger or ideal elastic fluid.     

Transient rheology in a new type of couette apparatus. Application to blood

By using our new air-bearing viscometer different types of transient flow can be studied; in the present work this viscometer was specifically applied to non-Newtonian blood suspensions. To observe the influence of both the aggregation and the deformation of red blood cells (RBCs), different concentrations of fibrinogen and dextran were used: the suspended RBCs were simply washed or rigidified with diamide. From the data three rheological parameters were determined, two of which are relative to the behavior at low and at high shear gradients, respectively. Their values were related to the theory of Taylor, and the internal viscosity of RBCs was estimated to be around 3 cp.     

Rheological properties of dilute polymer solutions: An extended thermodynamic approach

It is shown that extended irreversible thermodynamics can be used to account for the shear rate and frequency dependences of several material functions like shear viscosity, first and second normal stress coefficients, dynamic viscosity and storage modulus. Comparison with experimental data on steady shearing and small oscillatory shearing flows is performed. A good agreement between the model and experiment is reached in a wide scale of variation of the shear rate and the frequency of oscillations. The relation between the present model which includes quadratic terms in the pressure tensor and the Giesekus model is also examined.     

The shear modulus in the fiber direction of unidirectional fiber composites based on the concept of mesophase

A new and accurate relationship for the shear modulus in the fiber direction of unidirectional fiber composites is derived, based on the Kerner model concepts but not using its approximate relationships. Furthermore, this model is extended by taking into account the mesophase between the fiber and the matrix accomodating smoothly the mechanical properties between neighbouring phases. The introduction of the mesophase results in an improvement of the theoretical predictions, which now approach close to experimental values for the moduli of different fibrous composites.     

The squeezing flow of a model suspension fluid

The paper is concerned with the squeezing flow of a model suspension fluid. The numerical solution obtained by a time-dependent Boundary Element Method is compared to an asymptotic solution at large radius. It is found that the kinematics are Newtonian in character, and the fibres quickly align themselves radially. Consequently, the squeezing force is only weakly dependent on the initial orientations of the fibres and the device can be used for measuring the effective viscosity of the suspension. The effective viscosity found from the squeezing flow agrees surprisingly well with experimental data and numerical data derived from the falling sphere geometry at low volume fractions ( < 0.1).     

On some nearly viscometric flows of viscoelastic liquids

Superposition of oscillatory shear imposed from the boundary and through pressure gradient oscillations and simple shear is investigated. The integral fluid with fading memory shows flow enhancement effects due to the nonlinear structure. Closed-form expressions for the change in the mass transport rate are given at the lowest significant order in the perturbation algorithm. The elasticity of the liquid plays as important a role in determining the enhancement as does the shear dependent viscosity. Coupling of shear thinning and elasticity may produce sharp increases in the flow rate. The interaction of oscillatory shear components may generate a steady flow, either longitudinal or orthogonal, resulting in increases in flow rates akin to resonance, and due to frequency cancellation, even in the absence of a mean gradient. An algorithm to determine the constitutive functions of the integral fluid of order three is outlined.Nomenclature A _n Rivlin-Ericksen tensor of order . - A _k Non-oscillatory component of the first order linear viscoelastic oscillatory velocity field induced by the kth wave in the pressure gradient - d Half the gap between the plates - e _x, e _z Unit vectors in the longitudinal and orthogonal directions, respectively - G(s) Relaxation modulus - G History of the deformation - Stress response functional - I() Enhancement defined as the ratio of the frequency dependent part of the discharge to the frequencyindependent part of it at the third order - I ^*() Enhancement defined as the ratio of the increase in discharge due to oscillations to the total discharge without the oscillations - k Power index in the relaxation modulus G(s) - k _i ^–1 Relaxation times in the Maxwell representation of the quadratic shear relaxation modulus (s ₁, s ₂) - m _i ^–1, n _i ^–1 Relaxation times in the Maxwell representations of the constitutive functions ₁(s ₁,s ₂,s ₃) and ₄ (s ₁, s ₂,s ₃), respectively - P Constant longitudinal pressure gradient - p Pressure field - _mx ,⁽³⁾ _nz ,⁽³⁾ Mean volume transport rates at the third order in the longitudinal and orthogonal directions, respectively - ₀,⁽³⁾, ₁,⁽³⁾ Frequency independent and dependent volume transport rates, respectively, at the third order - s = t- Difference between present and past times t and      

Newtonian stratified flow through an abrupt expansion

The present paper is devoted to the numerical simulations of stratified generalized Newtonian flow. The main feature of the algorithm is to include the coordinates of the interface as primitive unknowns of the flow problem together with the nodal velocity components and pressures calculated on a deformable finite element mesh. Newton-Raphson's iterative method is used for solving the non-linear problem. Special attention is given to the location of the intersection between the interface and a solid boundary, when it is unknown at the outset. The method is applied to the creeping stratified flow of two Newtonian fluids through a one-to-four abrupt expansion; the results remain valid for the contraction problem. It is found that, under appropriate conditions, the small Newtonian corner vortex can increase by a large factor, both in size and intensity; the degrees of freedom of the simulation are the ratios of flow-rate and of viscosity of the fluids.     

A thermodynamic approach to non-linear viscoelasticity

We show that Extended Irreversible Thermodynamics (EIT) may be regarded as a unifying thermodynamic scheme which generates a variety of non-linear viscoelastic equations of state. In particular, we show how the so-called eight-constants Oldroyd model, with all its invariant properties, may be derived from the postulates of EIT. It is also shown that the structure of the thermodynamic based rheological equations of state is in complete agreement with that of the representation theorems formulation of constitutive relationships originally proposed by Rivlin and Ericksen. We discuss how more complex rheological models can be derived from higher order approximations of the theory. Finally, the connections between our approach and other related works are briefly discussed.     

Fragile networks and rheology of concentrated suspensions

Suspensions consisting of particles of colloidal dimensions have been reported to form connected structures. When attractive forces act between particles in suspension they may flocculate and, depending on particle concentration, shear history and other parameters, flocs may build-up in a three-dimensional network which spans the suspension sample. In this paper a floc network model is introduced to interpret the elastic behavior of flocculated suspensions at small deformations. Elastic percolation concepts are used to explain the variation of the elastic modulus with concentration. Data taken from the suspension rheology literature, and new results with suspensions of magnetic -Fe₂O₃ and non-magnetic -Fe₂O₃ particles in mineral oil are interpreted with the model proposed.Non-zero elastic modulus appeared at threshold particle concentrations of about 0.7 vol.% and 0.4 vol.% of the magnetic and non-magnetic suspensions, respectively. The difference is attributed to the denser flocs formed by magnetic suspensions. The volume fraction of particles in the flocs was estimated from the threshold particle concentration by transforming this concentration into a critical volume concentration of flocs, and identifying this critical concentration with the theoretical percolation threshold of three-dimensional networks of different coordination numbers. The results obtained indicate that the flocs are low-density structures, in agreement with cryo-scanning electron micrographs. Above the critical concentration the dynamic elastic modulus G was found to follow a scaling law of the type G ( _f - _f ^c ) ^f , where _f is the volume fraction of flocs in suspension, and _f ^c is its threshold value. For magnetic suspensions the exponent f was found to rise from a low value of about 1.0 to a value of 2.26 as particle concentration was increased. For the non-magnetic a similar change in f was observed; f changed from 0.95 to 3.6. Two other flocculated suspension systems taken from the literature showed a similar change in exponent. This suggests the possibility of a change in the mechanism of stress transport in the suspension as concentration increases, i.e., from a floc-floc bond-bending force mechanism to a rigidity percolation mechanism.