Linear viscoelastic models: Part IV. From molecular dynamics to temperature and viscoelastic relations using control theory

Viscoelasticity and temperature dependences are explained using molecular dynamics and control theory. We have previously (Borg and Pääkkönen, 2009 [1], [2], [3]) applied control theory to model the relationship between the relaxation modulus, dynamic and shear viscosity, transient flow effects, power law and Cox–Merz rule related to the molecular weight distribution (MWD), and here these topics are discussed more generally. In this paper we show the direct simple relation to molecular dynamics using structural models comprising dumb-bells (Bird et al., 1987 [4]) with internal viscosity and elasticity in a statistical tube. The dumb-bell model is used to obtain the linear relation to the elasticity P′ value of function P′(ω) and the relation to the viscosity P″ value of function P″(ω) from chain friction. The applied principle is also valid for the relaxation modulus or shear viscosity. A new principle is presented for obtaining absolute values such as zero viscosity by modelling, which is first used to obtain absolute values for a target point at a high rate for unentangled chains (since close relaxed states of chain topology are much more complicated). An analytical model for the temperature dependency of viscoelastic flows is presented, which is many times more accurate than WLF or Arrhenius equations. Control theory and variations of tube diameter as a function of temperature gives linear relation between chain dynamics and viscoelastic properties. New compact formulas are presented to simultaneously model different polymer flows and temperatures. We have also found that the MWDs computed from the relaxation modulus or complex and the shear viscosity are not temperature sensitive, in contrast to what time–temperature superposition (TTS) suggests, although absolute viscoelastic values make them appear very temperature-dependent. TTS is verified for thermorheologically simple materials, and the reasons for it not holding are explained.     

Linear viscoelastic models: Part I. Relaxation modulus and melt calibration

Constitutive models for the linear viscoelasticity of polymers are presented for the relation between the relaxation modulus and the molecular weight distribution (MWD). We also compute the MWD from a simulated relaxation modulus curve by first obtaining the rheologically effective distribution (RED) as a function of time, and converting this into the MWD by melt calibration; that is, the relation between timescale and the molecular weight. This procedure has similarities with the widely used universal calibration with solved polymers. The main principles of our technique are applied here to familiar relaxation modulus data, for which we present two models: (1) an analytical model derived from control theory, which is known capable of modelling partially observed system and (2) a practical characteristic model for obtaining usable results. No relaxation time or spectrum procedures are used to model the process of linear viscoelastic relaxation. The use of relative calculations and melt calibration dispenses with the need to know the real chain structures such as branching and entangled chain dynamics, and the model remains useful for future investigations of polymer chain structures and dynamics, such as using tube theory.     

Dynamic bulk and shear moduli due to grain-scale local fluid flow in fluid-saturated cracked poroelastic rocks: Theoretical model

Grain-scale local fluid flow is an important loss mechanism for attenuating waves in cracked fluid-saturated poroelastic rocks. In this study, a dynamic elastic modulus model is developed to quantify local flow effect on wave attenuation and velocity dispersion in porous isotropic rocks. The Eshelby transform technique, inclusion-based effective medium model (the Mori–Tanaka scheme), fluid dynamics and mass conservation principle are combined to analyze pore-fluid pressure relaxation and its influences on overall elastic properties. The derivation gives fully analytic, frequency-dependent effective bulk and shear moduli of a fluid-saturated porous rock. It is shown that the derived bulk and shear moduli rigorously satisfy the Biot-Gassmann relationship of poroelasticity in the low-frequency limit, while they are consistent with isolated-pore effective medium theory in the high-frequency limit. In particular, a simplified model is proposed to quantify the squirt-flow dispersion for frequencies lower than stiff-pore relaxation frequency. The main advantage of the proposed model over previous models is its ability to predict the dispersion due to squirt flow between pores and cracks with distributed aspect ratio instead of flow in a simply conceptual double-porosity structure. Independent input parameters include pore aspect ratio distribution, fluid bulk modulus and viscosity, and bulk and shear moduli of the solid grain. Physical assumptions made in this model include (1) pores are inter-connected and (2) crack thickness is smaller than the viscous skin depth. This study is restricted to linear elastic, well-consolidated granular rocks.     

Linear viscoelastic model for elongational viscosity by control theory

Flows involving different types of chain branches have been modelled as functions of the uniaxial elongation using the recently generated constitutive model and molecular dynamics for linear viscoelasticity of polymers. Previously control theory was applied to model the relationship between the relaxation modulus, dynamic and shear viscosity, transient flow effects, power law and Cox–Merz rule related to the molecular weight distribution (MWD) by melt calibration. Temperature dependences and dimensions of statistical chain tubes were also modelled. The present study investigated the elongational viscosity. We introduced earlier the rheologically effective distribution (RED), which relates very accurately and linearly to the viscoelastic properties. The newly introduced effective strain-hardening distribution (RED_H) is related to long-chain branching. This RED_H is converted to real long-chain branching distribution by melt calibration and a simple relation formula. The presented procedure is very effective at characterizing long-chain branches, and also provides information on their structure and distribution. Accurate simulations of the elongational viscosities of low-density polyethylene, linear low-density polyethylene and polypropylene, and new types of MWDs are presented. Models are presented for strain-hardening that includes the monotonic increase and overshoot effects. Since the correct behaviour at large Hencky strains is still unclear, these theoretical models may aid further research and measurements.     

Analytic derivation of the Cox�CMerz rule using the MLD ��toy�� model for polydisperse linear polymers

A general constitutive formalism, the ??na?ve?? polydisperse MLD model, has been developed by Mead et al. (Macromolecules 31:7895?C7914, 1998) and Mead (Rheol Acta 46:369?C395, 2007) at both the tube coordinate level and the mathematically simplified ??toy?? level independent of the tube coordinate. The model includes constraint release generated by convection-driven chain retraction (which is equivalent to ??convective constraint release?? (CCR)), reptation, and tube contour length fluctuations. The properties of the mathematically simplified na?ve polydisperse ??toy?? MLD model are explored in linear and nonlinear steady shear flows where we analytically derive the Cox?CMerz rule relating the steady shear viscosity to the modulus of the linear viscoelastic dynamic viscosity. The Cox?CMerz rule relating the linear viscoelastic material properties and the nonlinear material properties is shown to be a direct consequence of convective constraint release. The specific feature of CCR that leads to this result is that the relaxation rate due to convective constraint release is proportional to the shear rate, $\dot{{\gamma }}$ , independent of molecular weight. The viability of this well-known empirical relationship is a direct consequence of a coincidence in the mathematical structure of the linear viscoelastic material properties and convective constraint release. There is no physical analogy or relationship between the molecular relaxation mechanisms operative in linear (diffusive relaxation) and nonlinear (convective relaxation) flow regimes. The polydisperse MLD model predictions of the individual molecular weight component contributions to the flow curve, and interpretations thereof, are effectively identical to those first postulated by Bersted (J Appl Polym Sci 19:2167?C2177, 1975, J Appl Polym Sci 20:2705?C2714, 1976). Following the theoretical developments, a limited experimental study is executed with a commercial polydisperse polystyrene melt. Nearly quantitative agreement between the polydisperse MLD theory and experimental measurements of steady-shear viscosity and dynamic moduli is achieved over a wide range of shear rates.     

Waterhammer modelling of viscoelastic pipes with a time-dependent Poisson's ratio

Poisson's ratio in viscoelastic materials is a function of time. However, recently developed waterhammer models of viscoelastic pipes consider it constant. This simplifying assumption avoids cumbersome calculations of double convolution integrals which appear if Poisson's ratio is time-dependent. The present research develops a mathematical model taking the time dependency of Poisson's ratio into account for linear viscoelastic pipes. Poisson's ratio is written in terms of relaxation function and bulk modulus which is assumed to be constant. The relaxation function is obtained from creep function given as the viscoelastic property data of pipe material. The results obtained from the present waterhammer model are compared with the experimental data for two different flow rates. The comparison reveals that with the application of the time-dependent Poisson's ratio and unsteady friction, the viscoelastic data of mechanical tests can directly be used for waterhammer analysis with less need for the calibration of the flow configuration. It was also shown that the creep curve calibrated based on the present model is closer to the actual creep curve than that calibrated based on previous models.     

Viscoelastic flow of polymer solutions around a periodic,linear array of cylinders: comparisons of predictions for microstructure and flow fields

Numerical simulation is used to investigate the flow of polymer solutions around a periodic, linear array of cylinders by using three constitutive equations derived from kinetic theory of dilute polymer solutions: the Giesekus model; the finitely extensible, nonlinear elastic dumbbell model with Peterlin's approximation (FENE-P); and the FENE dumbbell model of Chilcott–Rallison (CR). In the Giesekus model, intramolecular forces are described by a Hookean spring, whereas a finitely extensible spring whose modulus is given by the Warner approximation is used in both the FENE-P and CR models. Hydro dynamic drag on the beads is taken to be anisotropic for the Giesekus model and isotropic for the other two models. The CR and FENE-P models differ subtly in their approximate treatment of the nonlinear force law. The three models exhibit very similar rheological behavior in viscometric flow and steady elongational flow, with the notable exception that the viscosity for the CR model is shear-rate independent. Finite element simulations are performed by using two different formulations: the elastic-viscous split-stress gradient (EVSS-G) method and a new variant of this formulation, the discrete EVSS-G (DEVSS-G) formulation, in which the elliptic stabilization term is added only to the discrete version of the momentum equation, and the constitutive equation is solved directly in terms of the polymer contribution to the stress tensor. Calculations are performed for all models up to a Weissenberg number We, where the configuration tensor 〈QQ〉 loses positive definiteness. However, by locally refining the mesh in the gap region, the positive definiteness of 〈QQ〉 is recovered. The flow and stress fields predicted by the three constitutive equations are qualitatively similar. A `birefringent strand' of highly stretched polymer molecules, which appears to emanate from the rear stagnation point in the cylinder, strengthens as We is increased. Not surprisingly, the molecular extension computed for the Giesekus model is considerably larger than that of the two FENE spring models. The drag force on the cylinders differs for the FENE-P and CR models, because of the difference in the shear-thinning viscosity resulting from the different approximations used in these models.     

Velocity measurements for a turbulent nonseparated flow over solid waves

The laser-Doppler velocimeter was used to obtain measurements of the streamwise velocity over solid sinusoidal waves of small enough amplitude that a nonseparated flow existed. The measurements provide a critical test for Reynolds stress closure models since they are particularly sensitive to happenings in the viscous wall region (y ⁺ < 40), for which present theories are of uncertain accuracy. The results are compared with calculations that use an eddy viscosity model that successfully describes measurements of the wall shear stress along waves of small enough amplitude that a linear response is obtained. These calculations are in approximate agreement with measurements because they exactly account for inertia and viscous effects. However, there are significant differences which point to the inadequacy of turbulence models. In particular, non-linear effects and the amplitudes of the wave-induced velocity variations are underpredicted.     

A constant-contour-length reptation model without independent alignment or consistent averaging approximations for chain retraction

A reptation model for the primitive chain that does not assume independent alignment or consistent-averaging for the retraction process, or equilibrium relaxation for the reptation process is proposed and compared to the analytical expressions of Doi and Edwards in single-step, double-step strains and steady-state shear flow. The Doi and Edwards model with independent alignment approximation underpredicts the magnitude of the relaxation modulus by 25%, and consistently overpredicts the magnitude of the damping function; for steady shear flow, it predicts the correct shape for the steady-state viscosity and the first normal stress difference coefficient, although the magnitude is incorrect. The analytical expressions of Doi and Edwards without independent alignment approximation are excellent approximations to the damping function. In double-step strains, the expressions of Doi assuming consistent averaging, but no independent alignment, predict well the stress decay following the second strain. Linear response theory is found to be invalid for describing the stress relaxation following single-step strain for the models considered. Similar to the Doi and Edwards model, no overshoot for the first normal stress difference is observed for the simulation model. Unlike the Doi equation derived without the independent alignment approximation but restricted to double-step strains, the simulation model proposed here can be easily generalized to complex flow fields. No contour length fluctuation or constraint release is considered in this model, and chain retraction is assumed to be instantaneous.     

Surface rheology

This review article approaches the subject of surface rheology from a phenomenological point of view. Operational definitions are given for the four surface rheological parameters: modulus and viscosity in either dilation or shear. Results of recent measurements are discussed. Observed non-Newtonian or viscoelastic behaviour has in some cases been interpreted in terms of known relaxation processes. The surface rheological behaviour affects the flow of bulk liquid near the surface; coupling occurs through the tangential stress boundary condition.     

Influence of suspension viscosity on Brownian relaxation of filler particles

Brownian relaxation caused by Brownian movement of particles in suspensions can macroscopically be probed by small-amplitude oscillatory shear experiments. Phenomenological considerations suggest a direct proportionality between suspension viscosity and Brownian relaxation times. To verify this relation experimentally, a set of nanocomposite suspensions with viscosities varying over five decades is presented. The suspensions are chosen in a way to ensure that particle-particle interactions and average particle-particle distances are identical so that they can be used as a model system to study the mere influence of suspension viscosity on Brownian relaxation. The suggested linear relationship between suspension viscosity and Brownian relaxation time can be confirmed. Moreover, a verification of a recently introduced characteristic timescale for Brownian relaxation is presented.     

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     

Structure and linear viscoelasticity of flexible polymer solutions: comparison of polyelectrolyte and neutral polymer solutions

The current state of understanding for solution conformations of flexible polymers and their linear viscoelastic response is reviewed. Correlation length, tube diameter, and chain size of neutral polymers in good solvent, neutral polymers in θ-solvent, and polyelectrolyte solutions with no added salt are compared as these are the three universality classes for flexible polymers in solution. The 1956 Zimm model is used to describe the linear viscoelasticity of dilute solutions and of semidilute solutions inside their correlation volumes. The 1953 Rouse model is used for linear viscoelasticity of semidilute unentangled solutions and for entangled solutions on the scale of the entanglement strand. The 1971 de Gennes reptation model is used to describe linear viscoelastic response of entangled solutions. In each type of solution, the terminal dynamics, reflected in the terminal modulus, chain relaxation time, specific viscosity, and diffusion coefficient are reviewed with experiment and theory compared. Overall, the agreement between theory and experiment is remarkable, with a few unsettled issues remaining.     

A class of linear viscoelastic models based on Bessel functions

In this paper we investigate a general class of linear viscoelastic models whose creep and relaxation memory functions are expressed in Laplace domain by suitable ratios of modified Bessel functions of contiguous order. In time domain these functions are shown to be expressed by Dirichlet series (that is infinite Prony series). It follows that the corresponding creep compliance and relaxation modulus turn out to be characterized by infinite discrete spectra of retardation and relaxation time respectively. As a matter of fact, we get a class of viscoelastic models depending on a real parameter \(\nu > -1\). Such models exhibit rheological properties akin to those of a fractional Maxwell model (of order 1/2) for short times and of a standard Maxwell model for long times.     

Constitutive relationships for polymeric materials with power-law distributions of relaxation times

The linear relaxation modulus of polydisperse polymer melts and solutions can often be approximated by a power law,ct ^–m over some range of time,t. If, in addition, the nonlinear rheology is given by a separable integral equation, with a strain-dependent factor typical of those observed experimentally, then some commonly observed empirical rules and equations can be readily derived as approximations, namely the Cox-Merz relationship between complex viscosity and steady-state shear viscosity, Bersted's predictions of steady shear stress and first normal-stress difference from a truncated spectrum of linear relaxation times, and the observation of Koyama and coworkers that the ratio of the nonlinear to the linear time-dependent elongational viscosity is independent of strain rate, over a range of strain rates outside the linear regime.     

Viscoelasticity of low molecular weight polymers and the transition to the entangled regime

The viscoelasticity of unentangled polystyrene melts has been investigated in terms of terminals parameters: zero-shear viscosity, steady-state compliance and relaxation spectrum. The Rouse model applies well for molecular weights lower than the average molecular weight between entanglements, providing that one takes into account the proper variations of the radius of gyration. Moreover, local motions at the scale of Kuhn segments have to be considered in order to describe correctly the relaxation modes intermediate between the terminal zone and the glassy plateau. On the other hand, reptation models are commonly used for describing the entangled regime. We propose an expression of the shear modulus which accounts not only for the terminal modes (reptation, tube length fluctuations and tube renewal), but also for the relaxation modes responsible for the plateau zone and the transition of the glassy plateau. A crossover region between the unentangled and untangled regimes is located around . When the molecular weight increases, a shift transfer of Rouse modes towards reptation modes occurs. That leads to a continuity of the expression of the shear modulus over the entire range of molecular weights. Received: 29 December 1997 Accepted: 27 July 1998     

Computation of strongly swirling confined flows with cubic eddy‐viscosity turbulence models

An investigation on the predictive performance of four cubic eddy‐viscosity turbulence models for two strongly swirling confined flows is presented. Comparisons of the prediction with the experiments show clearly the superiority of cubic models over the linear k–εmodel. The linear k–εmodel does not contain any mechanism to describe the stabilizing effects of swirling motion and as a consequence it performs poorly. Cubic models return a lower level of Reynolds stresses and the combined forced‐free vortex profiles of tangential velocity close to the measurements in response to the interaction between swirl‐induced curvature and stresses. However, a fully developed rotating pipe flow is too simple to contain enough flow physics, so the calibration of cubic terms is still a topic of investigation. It is shown that explicit algebraic stress models require fewer calibrations and contain more flow physics. Copyright © 2003 John Wiley & Sons, Ltd.