Determination of the relaxation time spectrum from dynamic moduli using an edge preserving regularization method

For the numerical determination of a continuous relaxation time spectrum from rheological data so-called regularization methods are necessary. The regularization method based on Tikhonov regularization and commonly used in rheology assumes the relaxation time spectrum to be smooth. Accordingly, this method is not able to properly resolve spectra containing edges or at least large curvatures as proposed in the literature. In order to reconstruct such spectra a novel edge preserving regularization (EPR) method was developed which extends the properties of the commonly used method. In order to demonstrate the efficiency of EPR it is compared with the commonly used regularization method by means of simulated and experimental data. This reveals that EPR is able to prove whether or not the theoretically predicted edge containing spectra for high-molecular-weight, monodisperse polymers are compatible with experimental data. Received: 11 June 1999/Accepted: 1 September 1999     

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.     

The viscoelastic constitutive differential operator law in terms of the relaxation and retardation spectra

The case of a linear viscoelastic medium is considered. The Carson transforms of the relaxation and retardation functions are expressed in two different ways, taking on the one hand the differential operator form of the constitutive equation, and on the other hand the generalized mechanical models. By identification we deduce general explicit expressions for the constant coefficients of the differential operator law, in terms of the discrete relaxation and retardation spectra.     

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.     

A nonlinear regularization method for the calculation of relaxation spectra

It is well known that the relaxation spectrum characterizing the linear viscoelastic properties of a polymer melt or solution is not directly accessible by an experiment. Therefore, it must be calculated from data for a material function. With Tikhonov regularization the relaxation spectrum in the terminal and plateau region can be calculated from data for a material function in the corresponding region. Serious difficulties arise however, if the spectrum should be determined in a larger range. These difficulties are caused by the considerably different contributions at short and long relaxation times. We show that these difficulties can be avoided by a nonlinear regularization method.     

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.     

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.     

Some inverse problems in rheology leading to integral equations

Two inverse problems of the integral type, which are of the general importance to rheology, are discussed. The first of them is the possibility of calculating the molecular weight distribution (MWD) from the flow curve and the second one is the interrelation between creep and relaxation functions. It was shown that the first problem is incorrect and any solution is unstable in respect to minor experimental errors. It means that the general solution of this problem is impossible in principle and only estimations of the width of unimodal MWD can be received from the curvature of the flow curve. The possibility of the correct calculation of the creep function exists in case the relaxation curve being approximated by the sum of exponential members. But the approximation of the relaxation curve within the experimental accuracy is the necessary, but not sufficient condition for the correct solution of this integral inverse problem, because not every mode of approximation leads to the satisfactory prediction of creep function.Delivered as the Courtaulds Lecture at the Golden Jubilee Conference of the British Society of Rheology and Third European Rheology Conference, Edinburgh, 3–7 September, 1990.     

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.     

Simple linear viscoelastic models of dilute solutions of polymer molecules and emulsion droplets

The complex viscosity of microemulsions shows relaxation processes of which the largest relaxation time is about 10^–5 s or less. This time can be attributed to relaxation of stresses in the surface of emulsion droplets pertaining to interfacial tension. Superimposed on a spherical droplet surface shape fluctuations can occur due to thermal energies. Our aim is to show the influence of thermal shape fluctuations on the complex viscosity of emulsions. The method used in the derivation has also been applied to inflexible rods to demonstrate its feasibility by showing the formal rheological equivalence of in length thermally fluctuating rods and Rouse's simple model of polymers. The emulsion results have been applied to a dilution series of a non-ionic microemulsion.     

An intermediate model method for obtaining a discrete relaxation spectrum from creep data

A convenient method is described for obtaining a discrete stress relaxation spectrum from linear viscoelastic creep data by means of a three-stage process. In stage one, a discrete retardation spectrum is fitted to the creep data using a least squares procedure, subject to the constraint that the discrete spectrum must be a specified order of polynomial function of the retardation time. In stage two, the resulting generalised Voigt model is solved numerically for an imposed step in strain, to determine the stress relaxation modulus function of time. In stage three, a discrete relaxation spectrum is fitted to the calculated stress relaxation modulus function. Although three stages are involved instead of the usual two, the procedure has been found to have certain practical advantages. These advantages make it suitable for the generation of relaxation spectra needed in viscoelastic stress analyses of solids, for example by the finite element method. In order to illustrate the proposed procedure it is applied to both artificial data and experimental creep data for poly(methyl methacrylate) at 70°C and at the glass transition.     

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.     

Relaxation time spectra from short frequency range small-angle dynamic rheometry

In this work, the influence of the experimental frequency range over the relaxation time spectrum is studied. The relaxation time spectra were calculated from dynamic moduli, a well-known ill-posed problem, using a regularization method. The method solves the ill-posed problem by simultaneous minimization of the regularized standard deviation and a restriction function. The solution was validated using a simulated spectrum. Truncated moduli data generated from simulated spectra were used to evaluate the method for smaller frequency range data. Finally, experimental data of a wormlike micellar system mixed in aqueous solution with a zwitterionic copolymer were used to validate the method. It was possible to obtain relaxation time spectra from short frequency range data if the relaxation time range is allowed to be higher than the inverse of the highest and lowest experimental frequencies. These spectra can be used qualitatively to describe complex systems when no time-temperature superposition experiments are feasible.     

The effect of molecular weight distribution on the elongational properties of linear polymers

The elongational properties of a series of six polypropylene and two polystyrene samples have been studied at constant rate of strain. A Wagner-type constitutive equation has been used to fit the experimental data, and the shape of the damping function has been correlated with the polydispersity index of the samples. As the memory function or relaxation function of linear viscoelasticity may be derived from the molecular-weight distribution using either molecular or phenomenological models, it is therefore possible to calculate the stress growth function of a linear polymer in elongation from its molecular-weight distribution.     

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.     

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.     

From dynamic modulus via different relaxation spectra to relaxation and creep functions

The main goal of the paper is to compare predictive power of relaxation spectra found by different methods of calculations. The experimental data were obtained for a new family of propylene random copolymers with 1-pentene as a comonomer. The results of measurements include flow curves, viscoelastic properties, creep curves and rubbery elasticity of copolymer melts. Different relaxation spectra were calculated using independent methods based on different ideas. It lead to various distributions of relaxation times and their “weights”. However, all of them correctly describe the frequency dependencies of dynamic modulus. Besides, calculated spectra were used for finding integral characteristics of viscoelastic behaviour of a material (Newtonian viscosity, the normal stress coefficient, steady-state compliance). In this sense all approaches are equivalent, though it appears impossible to estimate instantaneous modulus. The most crucial arguments in estimating the results of different approaches is calculating the other viscoelastic function and predicting behaviour of a material in various deformation modes. It is the relaxation and creep functions. The results of relaxation curve calculations show that all methods used give rather similar results in the central part of the curves, but the relaxation curves begin to diverge when approaching the high-time (low-frequency) boundary of the relaxation curves. The distributions of retardation times calculated through different approaches also appear very different. Meanwhile, predictions of the creep curves based on these different retardation spectra are rather close to each other and coincide with the experimental points in the wide time range. Relatively slight divergences are observed close to the upper boundary of the experimental window. All these results support the conclusion about a rather free choice of the relaxation time spectrum in fitting experimental data and predicting viscoelastic behaviour of a material in different deformation modes. Received: 15 March 2000 Accepted: 18 September 2000     

Estimation of the relaxation spectrum from dynamic experiments using Bayesian analysis and a new regularization constraint

The relaxation spectrum is estimated from dynamic experiments using Bayesian analysis and a new regularization constraint. In the Bayesian framework, a probability can be calculated for each estimate of the spectrum. This offers several advantages; (1) an optimal estimate of the relaxation spectrum may be calculated as the mean of a large number of estimates, and (2) reliable errors for the optimal estimate can be provided using the deviation of all estimates from the mean. Furthermore, the Bayesian approach (3) gives an estimate of the overall noise level of the experiment, which is usually an important but unknown parameter for the calculation of relaxation spectra from dynamic experiments by indirect methods (determining the regularization parameter), and finally, (4) the information content in a given set of experimental data can be quantified. The validity of the Bayesian approach is demonstrated using simulated data.     

The concept of a rotational rheometer with helical screw impeller

The paper is concerned with the development of an on-line rheometer for suspensions with settling particles. A new concept of a rotational rheometer with helical screw impeller is discussed. On the basis of model considerations a procedure for the flow curve determination of the investigated fluid has been proposed. Contrary to previous attempts, in the developed procedure no calibration of the instrument is necessary. The preliminary experimental verification of the developed approach proved its applicability.