Anisotropic conduction of heat in a flowing polymeric material

In this paper a theory is presented which relates the thermal conductivity tensor of an amorphous polymeric material to the history of deformation of the material. The basis of the theory is formed by the network theory for polymeric materials. It will be shown that the results obtained here are in good agreement with experimental results on rubber. The effect of anisotropic heat conduction on the flow of a polymeric material will be demonstrated by the simple example of viscous heating in shear flow.Presented at the Golden Jubilee Conference of the British Society of Rheology and Third European Rheology Conference, Edinburgh, 3–7 September, 1990.     

Anomalous steady flows in a tube

Tube flow of a viscoelastic liquid of the multiple integral type driven by periodic forcing is investigated. It is shown that mean longitudinal and secondary flows exist, independently of the explicit form of the constitutive functions, due to frequency cancellation when the forcing oscillates around a zero mean. Closed form expressions are given for these non-trivial flows at the lowest order of the algorithm where nonlinear effects appear.Presented at the Third European Rheology Conference, Edinburgh, UK, Sept. 3–7, 1990.     

Gelation of a radiation crosslinked model polyethylene

A radiation crosslinked model linear low-density polyethylene (LLDPE) exhibits power-law relaxation,G(t) =St ^–n at its gel point (GP). The relaxation exponent has a value of about 0.46. The relaxation behavior is dominated by power laws, not only directly at GP, but in a very broad vicinity of GP and in a frequency window, which narrows with distance from the gel point. The power law exponent decreases with increasing radiation dose (increasing extent of crosslinking). Independent measurements of the gel fraction and the molecular-weight distribution of the radiated samples' soluble fraction support the rheological observations.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.     

Relaxation dynamics of selected polymer chain segments and comparison with theoretical models

Simultaneous measurement of infrared dichroism and birefringence is used to study selected polymer segment dynamics in isotopically labeled block copolymers. Two different polymers were studied: polybutadiene and poly (ethylene propylene). The first type consisted of a triblock with a short middle block labeled and a diblock with a short end block labeled, while the second type consisted of a triblock with three equal blocks and the end blocks labeled. Results of step strain experiments at –10°C for polybutadiene and at room temperature for poly(ethylene propylene) indicated that segments located at chain ends relax faster than segments located at chain centers. These experimental data were compared to the predictions of two molecular models: the bead-spring model of Rouse and the tube model of Doi and Edwards, and it was found that both models correctly predict the qualitative features of segmental relaxation. However, the tube-model predictions were closer to the experimental results. In addition, when the effects of orientational coupling interactions between segments in the melt were incorporated into this model, its predictions quantitatively agreed with the experimental results. The orientational coupling coefficient for poly(ethylene propylene) was 0.45 as measured from previous work, and for polybutadiene it was found to be 0.4.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.Dedicated to Prof. R.S. Stein, University of Massachussets at Amherst, USA, on the occasion of his 65th birthday.     

Shear and extensional flow of polyacrylamide solutions

As part of an EEC Science Stimulation programme on extensional viscosity two major conferences were organised on the subject. The second of these was devoted to the results obtained on a standard fluid, M 1. The data obtained in shear flow was remarkably consistent from laboratory to laboratory. Extensional flow results presented quite a different picture. Using a series of nonequilibrium techniques such as the spinline rheometer, opposing jet, falling drop and converging flow, extensional viscosity results were obtained which differed by as much as two to three orders of magnitude. Nevertheless, it was apparent that consistancy did exist between similar techniques. It is in the context of this information that the measurements described below have been made.The shear and extensional flow properties of partially ionised polyacrylamide in solution at concentrations ranging from 5 ppm were measured. The method of solution preparation was found to have a profound effect on the behaviour of the solutions in shear flow. The influence of salt concentration and pH was investigated and is discussed in the context of molecular shape in solution.Extensional flow measurements, using the spinline rheometer, show that the solutions are strongly strain thickening even at concentrations as low as 5 ppm. These results are considered in the light of polymer entanglement and association in the strong flow field.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.     

The rheology of powders

This paper studies the slow flow of powders. It is argued that since powders can flow like liquids, there must be equations similar to those of liquids. The phenomenon of a variable density, dilatancy, is described by an analogue of temperature called the compactivity X. Whereas, in thermal physicsT = E/S, powders are controlled byX = V/S. The equations for, v, T of a liquid are replaced by, v, X. An analogy for free energy is described, and the solution to some simple problems of packing and mixing are offered. As an example of rheology, it is shown that the simplest flow equations produce a transition to plug flow in appropriate circumstances.Delivered as a Gold Medal Lecture at the Golden Jubilee Conference of the British Society of Rheology and Third European Rheology Conference, Edinburgh, 3–7 September, 1990.     

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.     

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.     

Challenges in process rheometry

Process rheometers are useful as process sensors for on-line quality control as well as for process control. Unlike passive sensors for equilibrium properties, such as temperature and pressure, a rheometer must subject the material of interest to a controlled deformation while monitoring the resulting stress. To accomplish this in a compact, robust device suitable for use in a manufacturing environment is not straightforward. Problems that arise in processing applications include the need for frequent sample renewal without interference from the measurement or the process itself and the fact that the process stream is usually under pressure. Considerable ingenuity has been applied to developing rheometers to meet these requirements.However, there remain many potential applications for which presently available units are not suitable. In particular, special problems arise when a very fast response is required, when the fluid being processed is non-Newtonian or has a very high viscosity, and when it is a multiphase system, as for example in the case of mineral slurries. In addition, in food processing and fermentation applications, all the exposed surfaces of the rheometer must be sterilizable. Possible solutions to these problems are described.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.     

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.     

Characterization of yield stress fluids with concentric cylinder viscometers

The methods normally employed for shear rate calculations from concentric cylinder viscometer data generally are not applicable for fluids with a yield stress. In cylindrical systems with large radius ratios, as usually is the case with suspensions, the yield stress induces two possible flow regimes in the annulus. Unless the yield value is exceeded everywhere in the gap only part of the fluid can be sheared while the remaining region behaves like a solid plug. A correct calculation of the shear rate must take into account the presence of a variable effective gap width determined by the extent of the sheared layer. For time-independent yield stress fluids, a two-step procedure, which does not require any specific flow model, is proposed for analysing the experimental torque-speed data. Under the partially sheared condition, the shear rate can be computed exactly, whereas for the fully sheared flow the Krieger and Elrod approximation is satisfactory. The method is assessed by examining both semi-ideal data generated with a Casson fluid with known properties, and experimental data with an industrial suspension. A more complicated problem associated with characterization of time-dependent yield stress fluids is also identified and discussed. An approximate procedure is used to illustrate the dependence of the shear rate on time of shear in constant-speed experiments.     

The nonlinear strain measure of polyisobutylene melt in general biaxial flow and its comparison to the Doi-Edwards model

The nonlinear strain measure of a polyisobutylene (PIB) melt as determined by analysis of uniaxial, planar, ellipsoidal, and equibiaxial extensions is compared to the predictions of the molecular model of Doi and Edwards. It is found that the universal strain function of the Doi-Edwards model is unable to predict the nonlinear behavior of this polymer melt in general extensional flow. The qualitative agreement between predictions and experimental data for the strain dependence of shear stress and first normal stress difference in shear flow that was considered as powerful evidence for the correctness of the Doi-Edwards model seems to be accidental. The exaggerated strain dependence of the model suggests a need to reconsider the assumptions concerning the chain retraction process.Presented at the Golden Jubilee Conference of the British Society of Rheology and Third European Rheology Conference, Edinburgh, 3–7 September, 1990.Dedicated to Professor F.R. Schwarzl on the occasion of his 65th birthday     

On the relaxation of shear and normal stresses of viscoelastic fluids following constant shear rate experiments

By means of a cone and plate rheometer the relaxation of the shear stress and the first normal stress difference in polymer liquids upon cessation of a constant shear rate were examined. The experiments were conducted mostly in a high shear rate region of relevance for the processing of these materials. The relaxation behavior at these shear rates can only be measured accurately under extremely precise specifications of the rheometer. To determine under which conditions the integral normal thrust is a convenient measure for the relaxing local first normal stress difference the radial distribution of the pressure in the shear gap was measured. The shape of relaxation of both the shear stress and the first normal stress difference could be closely approximated for the entire measured shear rate and time range by a two parameter statistical function. In the range of measured shear rates, one of the parameters, the standard deviationS, is equal for the shear and the normal stress, and is independent of the shear rate within the limit of experimental error. The second parameter, the mean relaxation timet _50, of the shear stress andt _50, of the first normal stress difference, can be calculated approximately from the viscosity function and only a single relaxation experiment.     

Comparison of linear viscoelastic constitutive equations for non-uniform polymer melts

Linear-viscoelastic properties of polydisperse and randomly-branched polymer melts were fit with several proposed relaxation functions by non-linear regression. Three polymer systems were investigated, including 1) crosslinked polyethylenes, 2) polydisperse linear poly(dimethylsiloxane)s, and 3) Marlex polyethylenes, which are polydisperse and probably contain long-chain branching. Four relaxation functions were evaluated, including the Rouse, reptation, stretched-exponential, and stretched-exponential-power-law (SEPL) relaxation functions. The SEPL best described each series of polymers, and therefore may be a general relaxation function for non-uniform polymer melts. The flow activation energy for crosslinked polyethylene may be coupled to a breadth-of-relaxation index, indicating that a coupling between a characteristic short relaxation time and longest relaxation time, as suggested by Ngai and Plazek (J. Polym. Sci. Polym. Phys. Ed. 1985, 23:2159–2180), may hold for some non-uniform polymers.     

Effect of secondary zone dimensions on melt fracture manifestations of high density polyethylene

An experimental study was performed on melt fracture phenomena in extrusion of high density polyethylene. The purpose of the work was to study the sensitivity of melt fracture driven roughness to the size of recirculation zones, viz. secondary zones. The experimental apparatus consists of a right angle die and a hypodermic needle used as a capillary. The position of the needle relative to the die was adjusted using a special fixture. The roughness of the extrudate was studied as a function of penetration depth. A developed procedure provides a comparison between profile lengths of extruded strands. The computed mean, median, and mode values for roughness were presented as a function of capillary position. A qualitative analysis was conducted for the force oscillations during extrusion with a separate set of dies, equipped with the fixed capillaries of identical lengths and different depths of penetration. It was observed that the oscillatory pattern is sensitive to the sizes of the secondary zones. This qualitative observation supports the conclusions from the quantitative analysis that the roughness of the extrudate can be controlled through an adjustment of the secondary zone sizes.Partly presented at the 58th Annual Meeting of the Society of Rheology, Tulsa, Oklahoma, October 20–23, 1986     

Parameter identification for viscoelastic materials

Starting from the general stress-strain relation for a linear Boltzmann-Volterra material, which is in agreement with the principle of inertia, a new identification procedure is proposed. Instead of running one long-range relaxation experiment, following asingle suitably specified deformation history, material characterization is done using the data ofn short relaxation experiments followingn different deformation histories. To interpret these data a direct non-iterative algorithm has been developed. Compared with other methods, for example curve fitting by using Gauss' method, this direct method is numerically stable and allows a simple direct evaluation of the error due to the scattering of experimental data. The method has been applied to the determination of the relaxation times of an unsaturated polyester material.     

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.     

Correlation between interfacial interactions and internal stresses in filled high density polyethylene

The stress relaxation and the creep behaviour of high density polyethylene (HDPE) filled with glass fibres, clay (plate-like particles) or CaCO₃ (particles with irregular shape) were measured in uniaxial extension at room temperature. It was observed that the addition of filler increased the internal stress level, as evaluated from stress relaxation data. This increase was larger than the corresponding increase in the (short-term) elastic modulus. This behaviour may be attributed to a reduced macromolecular mobility in the matrix material close to the filler surface, i.e. to formation of an interphase region in the HDPE-matrix. From the internal stress values, the thickness of this interphase region around each filler particle was estimated, assuming a uniform coverage of the particles. It was suggested that the amount of matrix material with reduced mobility (or the thickness of the interphase region) reflected the degree of adhesion between the filler and HDPE. The change in the internal stress level due to the incorporation of different fillers, which were surface treated in some cases, was also consistent with the observed creep behaviour.     

A note on the periodic motion of a visco-elastic fluid in a radially non-symmetric constricted tube

An approximate solution for the problem of fluid flow through a rigid tube with a mild constriction is given. It is assumed that the fluid is visco-elastic (Maxwell fluid) and the constriction is non-symmetric with respect to the radial distance. A theoretical result is given for the wall shear stress and numerical solutions are shown graphically for different values of the relaxation time and the shape parameter of the constriction profile.