A simplified cooperative model of stress relaxation and other consolidation processes in solids

This paper explores the properties of a relaxation function derived from a differential equation mimicking the distribution mechanism of Bose-Einstein statistics in the time domain. Within a significant portion of the process, the relaxation quantity n decreases linearly with log time. The relation between dn/dt and n is an exponential one. In this respect, the present approach produces results largely equivalent to those obtained using the hypothesis of stress-dependent thermal activation or a box-like spectrum of relaxation times, . The spectrum of the model proposed here is discrete, with integer valued fractions of a characteristic -centering the equations.     

Evaluation of the dynamic-mechanical properties of solids from a cooperative model for stress relaxation

For many solid materials the stress relaxation process obeys the universal relationF = – (d/d lnt)_max = (0.1 ± 0.01) ( ₀ — _i ), regardless of the structure of the material. Here denotes the stress,t the time, ₀ the initial stress of the experiment and _i the internal stress. A cooperative model accounting for the similarity in relaxation behaviour between different materials was developed earlier. Since this model has a spectral character, the concepts of linear viscoelasticity are used here to evaluate the corresponding prediction of the dynamic mechanical properties, i.e. the frequency dependence of the storageE () and lossE () moduli. Useful numerical approximations ofE () andE () are also evaluated. It is noted that the universal relation in stress relaxation had a counterpart in the frequency dependence ofE (). The theoretical prediction of the loss factor for high-density polyethylene is compared with experimental results. The agreement is good.     

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.     

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     

The influence of surface friction on the calculation of stress relaxation parameters for processed cheese

The stress relaxation-time behaviour of processed cheese has been studied after compression by 5–20%. Data were corrected for surface friction effects, since it is only that part of the registered force which actually compresses the samples that relaxes exponentially. The method of successive residuals and an empirical normalization linearization procedures were used to analyse the data. In both cases it was found that several of the calculated rheological parameters, at any selected compression, were significantly higher after correcting for surface friction. The initial compression also influenced the magnitude of the rheological parameters.     

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.     

Using regularization methods for the determination of relaxation and retardation spectra of polymeric liquids

The application of Tikhonov regularization to the determination of relaxation and retardation spectra of viscoelastic fluids is discussed using simulated and real experimental data. It is thereby shown that with this method consistent results for relaxation and retardation spectra can be obtained from experimental data for different material functions. Furthermore, the differences between the most frequently used variants of Tikhonov regularization and the maximum entropy method are discussed. For most calculations the program FTIKREG has been used, which is an especially fast and reliable implementation of Tikhonov's regularization method.     

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.     

Determination of discrete relaxation and retardation time spectra from dynamic mechanical data

A powerful but still easy to use technique is proposed for the processing and analysis of dynamic mechanical data. The experimentally determined dynamic moduli,G() andG(), are converted into a discrete relaxation modulusG(t) and a discrete creep complianceJ(t). The discrete spectra are valid in a time window which corresponds to the frequency window of the input data. A nonlinear regression simultaneously adjust the parametersg _i , _i ,i = 1,2, N, of the discrete spectrum to obtain a best fit ofG, G, and it was found to be essential that bothg _i and _i are freely adjustable. The number of relaxation times,N, adjusts during the iterative calculations depending on the needs for avoiding ill-posedness and for improved fit. The solution is insensitive to the choice of initial valuesg _i,0, _i,0,N ₀. The numerical program was calibrated with the gel equation which gives analytical expressions both in the time and the frequency domain. The sensitivity of the solution was tested with model data which, by definition, are free of experimental error. From the relaxation time spectrum, a corresponding discrete set of parametersJ ₀,, J _d,i and _i of the creep complianceJ(t) can then readily be calculated using the Laplace transform.This paper is dedicated to Professor Hanswalter Giesekus on the occasion of his retirement as Editor of Rheologica Acta.     

Rheological properties of skim milk gels at various temperatures; interrelation between the dynamic moduli and the relaxation modulus

The rheological properties of rennet-induced skim milk gels were determined by two methods, i.e., via stress relaxation and dynamic tests. The stress relaxation modulusG _c (t) was calculated from the dynamic moduliG andG by using a simple approximation formula and by means of a more complex procedure, via calculation of the relaxation spectrum. Either calculation method gave the same results forG _c (t). The magnitude of the relaxation modulus obtained from the stress relaxation experiments was 10% to 20% lower than that calculated from the dynamic tests.Rennet-induced skim milk gels did not show an equilibrium modulus. An increase in temperature in the range from 20° to 35 °C resulted in lower moduli at a given time scale and faster relaxation. Dynamic measurements were also performed on acid-induced skim milk gels at various temperatures andG _c (t) was calculated. The moduli of the acid-induced gels were higher than those of the rennet-induced gels and a kind of permanent network seemed to exist, also at higher temperatures. G storage shear modulus,N·m^–2; - G loss shear modulus,N·m^–2; - G _c calculated storage shear modulus,N·m^–2; - G _c calculated loss shear modulus,N·m^–2; - G _e equilibrium shear modulus,N·m^–2; - G _ec calculated equilibrium shear modulus,N·m^–2; - G(t) relaxation shear modulus,N·m^–2; - G _c (t) calculated relaxation shear modulus,N·m^–2; - G ^*(t) pseudo relaxation shear modulus,N·m^–2; - H relaxation spectrum,N·m^–2; - t time,s; - relaxation time,s; - angular frequency, rad·s^–1. Partly presented at the Conference on Rheology of Food, Pharmaceutical and Biological Materials, Warwick, UK, September 13–15, 1989 [33].     

Influence of the formation of associations of macromolecules on the rheo-optical properties of their dilute solutions. II. Comparison with experimental results

The results of the theory presented in part I are compared to already published flow birefringence data obtained with dilute up to semi-dilute solutions of polyethylene oxide which have also shown shear thickening effects. The agreement with the theory is quite good so that the reversible formation of associations in flow seems to be a process which has to be taken in account for high molecular weight flexible macromolecules solutions in relatively poor solvents.     

Prediction of stress in a linear viscoelastic solid strained while cooling

A simplethermoelastic method is proposed, and justified, for predicting stresses arising during cooling of a linearviscoelastic solid. It is equivalent to representing the material by an array of spring-switch thermoelastic elements. The final stress resulting from an increment of strain is calculated using isochronal modulus data applying to the temperature at which the strain was applied, modified to accommodate temperature dependence of the limiting moduli. The method is exact for a material whose relaxation times and limiting moduli scale uniformly with change in temperature, with time-temperature shift factora _T obeying the Arrhenius equation, cooled such that reciprocal absolute temperature is linear in time. For other cooling sequences it is useful as an approximation. In particular, it assists the computational prediction of stresses arising during cooling in polymer processes.     

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.     

On the derivation of some fundamental expressions for the average stress tensor in systems of interacting particles

The so-called generalized Kramers-Kirkwood expression for the average stress tensor of a system of interacting point particles, derived by Bird and Curtiss on using a phase-space-kinetic formalism has been reconsidered from different points of view. First a derivation based upon volume averaging is discussed, and after that a derivation based upon a virtual work principle. The latter approach offers the possibility of distinguishing reversible (including thermodynamic and Brownian) and dissipative forces and stresses by using a projection operator, associated with the constraints of the system.     

Shrinkage effect on polyethylene based blends

An experimental study of the shrinkage effect in low density-high density polyethylene blends, high density-high density polyethylene blends and low density polyethylene-ethylene vinyl acetate copolymer blends is presented. Viscosity measurements are also included.The strain recovery is analysed as the addition of the interfacial tension effect and the elastic recoverable strain. The results are compared with those obtained for other polyolefin blends observing that in the case of compatible systems as low density-high density polyethylene and high density-high density polyethylene blends the strain recovery and the viscosity follow approximately the additive rule. In the case of more incompatible systems like polyethylene-ethylene vinyl acetate copolymer, polyethylene-polypropylene and others very large recoveries were observed. The formation of minifibres of the dispersed phase during the preparation of the samples is suggested as responsible for the obtained results.     

History-dependent dimensional stability of paper

History-dependent dimensional behavior of paper has been formulated within the framework of the general linear theory of viscoelasticity and the classical lamination theory. The effect of the drying history of the papermaking process was incorporated by introducing the residual stress in the reference configuration which was taken at the final drying stage in this study. This permits us to account for complex dimensional and form changes of paper in the converting and end use processes.In order to determine the prediction performance of the computer simulation model developed, in-plane and out-of-plane dimensional responses under cyclic humidity changes were predicted on the basis of hygroviscoelastic data of paper. The simulation examples demonstrated typical irreversible dimensional responses of paper both for the in-plane dimensional change and the curvature change (curl). The computer code can easily deal with the non-uniform distribution of 1) anisotropic viscoelastic properties, 2) hygrothermal properties, and 3) moisture and temperature through the thickness.     

Thermodynamics of relaxation processes in the glass transition region

Relaxation processes in the glass transition region, especially the recovery of the volume and the physical ageing of polymers, do not follow the common (linear) theory of relaxation. On the contrary, they show a development which depends on the previous history, may be non-monotonous and requires a relaxation time that may have negative values and a pole. These phenomena can be explained if the single relaxation time is replaced by a spectrum of relaxation times and the relaxation times are supposed to be subjected to a feedback via certain structure- and temperature-parameters (as, for instance, in the KAHR-theory).However, the feedback and a pole of the relaxation time arise already for a single internal degree of freedom by themselves, if, in the non-equilibrium thermodynamics, a dynamic and a static temperature are strictly differentiated. In the case of the relaxation of the diffusive translational motion of the molecules in the glass transition region the dynamic temperature is identical with the socalled fictive temperature introduced by Tool.With regard to the relaxation of the volume three different temperature regions must be distinguished: A fluid region at high temperatures where the relaxation is controlled by the free volume and complies with the linear theory at least approximately; a glass-like region at low temperatures where the relaxation is controlled by the thermal expansivity of the free volume and where, under certain conditions, the statements set up by Davies and Jones are valid; an intermediate region (the glass transition region) where the free volume as well as its coefficient of expansivity are decisive. In that region the effective relaxation time of the volume may have a pole and the dynamic temperature may approach its equilibrium value by discontinuous jumps or in a chaotic manner.Dedicated to Professor Dr. J. Meissner (ETH Zürich) on the occasion of his 60th birthday     

Finite rise time step strain modeling of nearly monodisperse polymer melts and solutions

The step shear strain experiment is one of the fundamental transient tests used to characterize the rheology of viscoelastic polymer melts and solutions. Many melts and solutions exhibit homogeneous deformation and stress relaxation; in these cases the transient dynamics can be modeled by completely ignoring momentum effects and imposing singular kinematics. Recently, however, it has been observed that there are certain classes of nearly monodisperse melts and solutions that exhibit anomalous nonhomogeneous deformation and stress relaxation (Morrison and Larson (1990), Larson, Khan, and Raju (1988), Vrentas and Graessley (1982), and Osaki and Kurata (1980)). We demonstrate that, for these classes, a finite rise time must be incorporated, some source of inhomogeneity must be present, and a small amount of added Newtonian viscosity is necessary. We examine five nonlinear and quasilinear models; the Johnson-Segalman, Phan Thien Tanner, Giesekus, White-Metzner, and Larson models. We determine which mathematical features of the models are necessary and/or sufficient to describe the observed experimental behavior.     

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.