Shear Stress Relaxation Modulus Research Articles

Detailed dynamics of discrete Gaussian semiflexible chains with arbitrary stiffness along the contour.

We revisit a model of semiflexible Gaussian chains proposed by Winkler et al., solve the dynamics of the discrete description of the model, and derive exact algebraic expressions for some of the most relevant dynamical observables, such as the mean-square displacement of individual monomers, the dynamic structure factor, the end-to-end vector relaxation, and the shear stress relaxation modulus. The mathematical expressions for the dynamic structure factor are verified by comparing them with results from Brownian dynamics simulations, reporting an excellent agreement. Then, we generalize the model to linear polymer chains with arbitrary stiffness. In particular, we focus on the case of a linear polymer with stiffness that changes linearly from one end of the chain to the other, and we study the same dynamical functions previously presented. We discuss different approaches to check whether a polymer has constant or heterogeneous stiffness along its contour. Finally, we provide expressions for the Lagrangian multipliers for Gaussian chains with variable stiffness and bond length, as well as for chains with torsion-like interactions. Overall, this work presents a new insight into a well-known model for semiflexible chains and provides tools that can be exploited to explore a much broader class of polymers or compare the predictions of the model with simulations of coarse-grained semiflexible polymers.

Experimental and numerical research of stress relaxation behavior of magnetorheological elastomer

The paper presents experimental research and viscoelastic modeling of stress relaxation response of isotropic magnetorheological elastomer (MRE). The isotropic MRE has been prepared based on silicone matrix filled by magnetically micro-sized carbonyl iron particles. Effects of constant strain level and external magnetic field on the stress relaxation behavior of the MRE were carefully investigated by single- and multi-step relaxation tests in shear mode using double-lap shear specimens. Results revealed that the stress relaxation response of the MRE was dependent on the applied constant strain and external magnetic field. The relaxed stress and modulus of the MRE increased with increasing the constant strain level. In addition, the values of absolute stress and modulus in the relaxation periods enhanced with the rise of magnetic flux density. A four-parameter fractional derivative viscoelastic model was used to describe the stress relaxation behavior of the MRE. The studied model was fitted well to experimental data of the MRE in both single- and multi-step relaxation tests. The fitting of shear-stress relaxation modulus for the MRE is in a very good agreement with the experimental one. Effects of applied constant strain and magnetic field intensity on the fitted parameters were discussed. Moreover, the model can be applied to predict accurately the long-term relaxation behavior of the MRE.

Dynamics and Viscoelasticity of Disordered Melts of Symmetric Diblock Copolymers

Simulations of coarse-grained models are used to study relationships among chain motion, composition fluctuations, and stress relaxation in unentangled melts of symmetric diblock copolymers. Measurements of the dynamic structure factor S(q,t) are reported as a function of wavenumber q, time t, and χN, where χ is the Flory–Huggins interaction parameter and N is degree of polymerization. The function S(q,t) is found to be a nearly exponential function of time, S(q,t) ∝ e–t/τ(q), for wavenumbers similar to or less than the wavenumber q* at which the static structure factor S(q) ≡ S(q,t=0) is maximum. The relationship between the decay time τ(q) and S(q) is used to define an effective wavenumber-dependent diffusivity D(q) for fluctuations of wavenumber q. The function D(q) is shown to change very little with changes in χN and to be a monotonically decreasing function of the nondimensional wavenumber qRg, where Rg is polymer radius of gyration. The linear shear stress relaxation modulus G(t) is inferred from measurements of the shear stress autocorrelation function. At low values of χN, far from the order–disorder transition (ODT), the modulus G(t) agrees with predictions of the Rouse model. Near the ODT, G(t) develops an additional slowly decaying feature arising from slow decay of composition fluctuations with q ∼ q*. The behavior of G(t) near the ODT is predicted nearly quantitatively by a modified version of the model of Fredrickson and Larson (FL), in which the prediction of the FL theory for the slowly decaying component is added to the prediction of the Rouse theory for contributions arising from single-chain relaxation, using the independently measured behavior of S(q,t) as an input to the theory.

Shear-stress relaxation in free-standing polymer films

Using molecular dynamics simulation of a polymer glass model we investigate free-standing polymer films focusing on the in-plane shear modulus $\mu$ and the corresponding shear-stress relaxation modulus $G(t)$ as functions of temperature $T$, film thickness $H$ (tuned by means of the lateral box size $L$) and sampling time $\Delta t$. Various observables are seen to vary linearly with $1/H$ demonstrating thus the (to leading order) linear superposition of bulk and surface properties. In agreement with recent studies on three-dimensional polymer glass-formers, $\mu$ and $G(t)$ are found to decrease continuously with $T$. A jump-singularity is not observed. Confirming the time-translational invariance of our systems, the $\Delta t$-dependence of $\mu$ is traced back to $G(t)$.

Slip Spring-Based Mesoscopic Simulations of Polymer Networks: Methodology and the Corresponding Computational Code.

In previous work by the authors, a new methodology was developed for Brownian dynamics/kinetic Monte Carlo (BD/kMC) simulations of polymer melts. In this study, this methodology is extended for dynamical simulations of crosslinked polymer networks in a coarse-grained representation, wherein chains are modeled as sequences of beads, each bead encompassing a few Kuhn segments. In addition, the C++ code embodying these simulations, entitled Engine for Mesoscopic Simulations for Polymer Networks (EMSIPON) is described in detail. A crosslinked network of cis-1,4-polyisoprene is chosen as a test system. From the thermodynamic point of view, the system is fully described by a Helmholtz energy consisting of three explicit contributions: entropic springs, slip springs and non-bonded interactions. Entanglements between subchains in the network are represented by slip springs. The ends of the slip springs undergo thermally activated hops between adjacent beads along the chain backbones, which are tracked by kinetic Monte Carlo simulation. In addition, creation/destruction processes are included for the slip springs at dangling subchain ends. The Helmholtz energy of non-bonded interactions is derived from the Sanchez–Lacombe equation of state. The isothermal compressibility of the polymer network is predicted from equilibrium density fluctuations in very good agreement with the underlying equation of state and with experiment. Moreover, the methodology and the corresponding C++ code are applied to simulate elongational deformations of polymer rubbers. The shear stress relaxation modulus is predicted from equilibrium simulations of several microseconds of physical time in the undeformed state, as well as from stress-strain curves of the crosslinked polymer networks under deformation.

Shear-stress fluctuations and relaxation in polymer glasses.

We investigate by means of molecular dynamics simulation a coarse-grained polymer glass model focusing on (quasistatic and dynamical) shear-stress fluctuations as a function of temperature T and sampling time Δt. The linear response is characterized using (ensemble-averaged) expectation values of the contributions (time averaged for each shear plane) to the stress-fluctuation relation μ_{sf} for the shear modulus and the shear-stress relaxation modulus G(t). Using 100 independent configurations, we pay attention to the respective standard deviations. While the ensemble-averaged modulus μ_{sf}(T) decreases continuously with increasing T for all Δt sampled, its standard deviation δμ_{sf}(T) is nonmonotonic with a striking peak at the glass transition. The question of whether the shear modulus is continuous or has a jump singularity at the glass transition is thus ill posed. Confirming the effective time-translational invariance of our systems, the Δt dependence of μ_{sf} and related quantities can be understood using a weighted integral over G(t).

Shear Modulus and Shear-Stress Fluctuations in Polymer Glasses.

Using molecular dynamics simulation of a standard coarse-grained polymer glass model, we investigate by means of the stress-fluctuation formalism the shear modulus μ as a function of temperature T and sampling time Δt. While the ensemble-averaged modulus μ(T) is found to decrease continuously for all Δt sampled, its standard deviation δμ(T) is nonmonotonic, with a striking peak at the glass transition. Confirming the effective time-translational invariance of our systems, μ(Δt) can be understood using a weighted integral over the shear-stress relaxation modulus G(t). While the crossover of μ(T) gets sharper with an increasing Δt, the peak of δμ(T) becomes more singular. It is thus elusive to predict the modulus of a single configuration at the glass transition.

Numerical determination of shear stress relaxation modulus of polymer glasses.

Focusing on simulated polymer glasses well below the glass transition, we confirm the validity and the efficiency of the recently proposed simple-average expression [Formula: see text] for the computational determination of the shear stress relaxation modulus G(t). Here, [Formula: see text] characterizes the affine shear transformation of the system at t = 0 and h(t) the mean-square displacement of the instantaneous shear stress as a function of time t. This relation is seen to be particulary useful for systems with quenched or sluggish transient shear stresses which necessarily arise below the glass transition. The commonly accepted relation [Formula: see text] using the shear stress auto-correlation function c(t) becomes incorrect in this limit.

Marginally compact hyperbranched polymer trees.

Assuming Gaussian chain statistics along the chain contour, we generate by means of a proper fractal generator hyperbranched polymer trees which are marginally compact. Static and dynamical properties, such as the radial intrachain pair density distribution ρpair(r) or the shear-stress relaxation modulus G(t), are investigated theoretically and by means of computer simulations. We emphasize that albeit the self-contact density diverges logarithmically with the total mass N, this effect becomes rapidly irrelevant with increasing spacer length S. In addition to this it is seen that the standard Rouse analysis must necessarily become inappropriate for compact objects for which the relaxation time τp of mode p must scale as τp ∼ (N/p)5/3 rather than the usual square power law for linear chains.

Shear-stress fluctuations in self-assembled transient elastic networks.

Focusing on shear-stress fluctuations, we investigate numerically a simple generic model for self-assembled transient networks formed by repulsive beads reversibly bridged by ideal springs. With Δt being the sampling time and t_{☆}(f)∼1/f the Maxwell relaxation time (set by the spring recombination frequency f), the dimensionless parameter Δx=Δt/t_{☆}(f) is systematically scanned from the liquid limit (Δx≫1) to the solid limit (Δx≪1) where the network topology is quenched and an ensemble average over m-independent configurations is required. Generalizing previous work on permanent networks, it is shown that the shear-stress relaxation modulus G(t) may be efficiently determined for all Δx using the simple-average expression G(t)=μ_{A}-h(t) with μ_{A}=G(0) characterizing the canonical-affine shear transformation of the system at t=0 and h(t) the (rescaled) mean-square displacement of the instantaneous shear stress as a function of time t. This relation is compared to the standard expression G(t)=c[over ̃](t) using the (rescaled) shear-stress autocorrelation function c[over ̃](t). Lower bounds for the m configurations required by both relations are given.

Simple average expression for shear-stress relaxation modulus

Focusing on isotropic elastic networks we propose a simple-average expression G(t)=μ_{A}-h(t) for the computational determination of the shear-stress relaxation modulus G(t) of a classical elastic solid or fluid. Here, μ_{A}=G(0) characterizes the shear transformation of the system at t=0 and h(t) the (rescaled) mean-square displacement of the instantaneous shear stress τ[over ̂](t) as a function of time t. We discuss sampling time and ensemble effects and emphasize possible pitfalls of alternative expressions using the shear-stress autocorrelation function. We argue finally that our key relation may be readily adapted for more general linear response functions.

Shear-strain and shear-stress fluctuations in generalized Gaussian ensemble simulations of isotropic elastic networks

Shear-strain and shear-stress correlations in isotropic elastic bodies are investigated both theoretically and numerically at either imposed mean shear-stress $\tau$ ($\lambda=0$) or shear-strain $\gamma$ ($\lambda=1$) and for more general values of a dimensionless parameter $\lambda$ characterizing the generalized Gaussian ensemble. It allows to tune the strain fluctuations $\mu_{\gamma\gamma} \equiv \beta V \la \delta \gamma^2 \ra = (1-\lambda)/G_{eq}$ with $\beta$ being the inverse temperature, $V$ the volume, $\gamma$ the instantaneous strain and $G_{eq}$ the equilibrium shear modulus. Focusing on spring networks in two dimensions we show, e.g., for the stress fluctuations $\mu_{\tau\tau} \equiv \beta V \la \delta\tau^2 \ra$ ($\tau$ being the instantaneous stress) that $\mu_{\tau\tau} = \mu_{A} - \lambda G_{eq}$ with $\mu_{A} = \mu_{\tau\tau}|_{\lambda=0}$ being the affine shear-elasticity. For the stress autocorrelation function $c_{\tau\tau}(t) \equiv \beta V \la \delta \tau(t) \delta \tau(0) \ra$ this result is then seen (assuming a sufficiently slow shear-stress barostat) to generalize to $c_{\tau\tau}(t) = G(t) - \lambda \Geq$ with $G(t)$ being the shear-stress relaxation modulus.

Fluctuation-dissipation relation between shear stress relaxation modulus and shear stress autocorrelation function revisited

The shear stress relaxation modulus G(t) may be determined from the shear stress after switching on a tiny step strain γ or by inverse Fourier transformation of the storage modulus G′(ω) or the loss modulus G″(ω) obtained in a standard oscillatory shear experiment at angular frequency ω. It is widely assumed that G(t) is equivalent in general to the equilibrium stress autocorrelation function which may be readily computed in computer simulations (β being the inverse temperature and V the volume). Focusing on isotropic solids formed by permanent spring networks we show theoretically by means of the fluctuation-dissipation theorem and computationally by molecular dynamics simulation that in general G(t) = Geq + C(t) for t > 0 with Geq being the static equilibrium shear modulus. A similar relation holds for G′(ω). G(t) and C(t) must thus become different for a solid body and it is impossible to obtain Geq directly from C(t).

Shear-stress relaxation and ensemble transformation of shear-stress autocorrelation functions.

We revisit the relation between the shear-stress relaxation modulus G(t), computed at finite shear strain 0<γ≪1, and the shear-stress autocorrelation functions C(t)|(γ) and C(t)|(τ) computed, respectively, at imposed strain γ and mean stress τ. Focusing on permanent isotropic spring networks it is shown theoretically and computationally that in general G(t)=C(t)|(τ)=C(t)|(γ)+G(eq) for t>0 with G(eq) being the static equilibrium shear modulus. G(t) and C(t)|(γ) thus must become different for solids and it is impossible to obtain G(eq) alone from C(t)|(γ) as often assumed. We comment briefly on self-assembled transient networks where G(eq)(f) must vanish for a finite scission-recombination frequency f. We argue that G(t)=C(t)|(τ)=C(t)|(γ) should reveal an intermediate plateau set by the shear modulus G(eq)(f=0) of the quenched network.

Density dependence of the stress relaxation function of a simple fluid

We present accurate molecular dynamics calculations of the shear stress relaxation modulus of a simple atomic fluid over a wide range of densities. The high accuracy of the data enables us to study changes in the functional form of the shear relaxation modulus, and the properties that are derived from it, as the density is increased from the ideal gas limit to the upper limit of the fluid range. We show that the shear relaxation modulus of a dilute atomic fluid can be accurately described with a simple functional form consisting of a Gaussian plus a single exponential, whereas the dense fluid exhibits a more complicated relaxation function. The infinite-frequency shear modulus, the zero-shear viscosity, and the zero-shear first normal stress coefficient are calculated from the stress autocorrelation function. The ratio of the first normal stress coefficient to the viscosity is used to calculate the viscoelastic relaxation time. While the viscosity and the infinite-frequency shear modulus both increase monotonically with increasing density, the first normal stress coefficient and the viscoelastic relaxation time both decrease to a minimum at intermediate densities before increasing again. Our results for the viscosity and the first normal stress coefficient in the low-density limit both agree well with the predictions of kinetic theory.

Correlation of cooperatively localized rearrangement on the “fluidized domain” in glass substances (or polymers) to their fragility III: Theory of dynamic fragility at isochoric state

A set of universal equations on the reduced stress relaxation modulus with K-W-W stretched exponential function has been derived from the dynamics of α and β structural relaxation processes. In the present work, the K-W-W decay function is used to define the three types of relaxations (single α, single β relaxation and α-β co-relaxation), then their average times of relaxation are theoretically calculated from the reduced shear stress relaxation modulus and the relaxation time spectrum function H(τ). When the average time of co-relaxation, the reference temperatures (ficitive T f and glass transition T g ) and the isostructural parameter achieved from the conditions of isostructural glass state are introduced into the reduced shear stress relaxation modulus (G T ) under the equilibrium state, a set of correlations between isochoric fragility index (m να , m νβ and m ναβ ) and the coupling strength (α and β) under the reference temperatures are derived from the exact definition of isochoric fragility. So the theory of dynamic fragility for glass substances at isochoric state is developed. The theory can predict the following main features of structural relaxations and behavior of isochoric fragility: the temperature dependence of peak relaxation frequency exhibits a bifurcation with a pair of single α and single β relaxations; the temperature dependence of Stickel equation on 1/T exhibits two crossovers with VFTH(1) and VFTH(2) at the temperatures of T f and T g regime; there are two linear correlations between isochoric fragility index (m να and m νβ ) and the coupling strength. Fine agreements between the theoretical calculation and experimental results are obtained.

A new interpretation for the dynamic behaviour of complex fluids at the sol–gel transition using the fractional calculus

We propose to analyse power law shear stress relaxation modulus observed at the sol–gel transition (SGT) in many gelling systems in terms of fractional calculus. We show that the critical gel (gel at SGT) can be associated to a single fractional element and the gel in the post-SGT state to a fractional Kelvin–Voigt model. In this case, it is possible to give a physical interpretation to the fractional derivative order. It is associated to the power law exponent of the shear modulus related to the fractal dimension of the critical gel. A preliminary experimental application to silica alkoxide-based systems is given.

Thermodynamic, Transport, and Viscoelastic Properties of PBX-9501 Binder: A Molecular Dynamics Simulations Study

Atomistic molecular dynamics simulations were performed on a low-molecular-weight nitroplasticized Estane® mixture representative of the binder used in PBX-9501. Pressure-volume-temperature (PVT) behavior over a wide range of pressures and temperatures above the order-disorder temperature (ODT) of Estane was determined and represented with the empirical Tait and Sun equations of state. The effect of temperature, pressure, and plasticization on transport properties of the mixture was also examined. A combination of molecular dynamics simulations and theoretical reptation models was used to predict the shear stress relaxation modulus G(t) of PBX-9501 binder at 473 K and 1 atm pressure. Data obtained from simulations of the model PBX-9501 binder presented here can be utilized to predict the temperature and pressure dependence of the shear stress relaxation modulus for temperatures above the ODT.

A critical evaluation of step strain flows of entangled linear polymer liquids

A critical evaluation of step strain flow experiments on entangled, linear polymer liquids is performed. Roughly one-half of the published shear stress relaxation modulus data for these systems are consistent with the predictions of the well-known tube model. A model of step strain flow experiments is developed to determine whether the remaining published data, which are qualitatively different from tube model predictions, are simply artifacts caused by slip, an imperfect strain step strain history, or transducer compliance. Modeling results suggest that these factors are capable of producing the types of behavior observed in experiments deemed anomalous. New criteria based on the retraction time τR, or longest Rouse relaxation time, for avoiding anomalies caused by imperfect strain step strain history and transducer compliance are proposed. These simple criteria are, in a majority of cases, found to be capable of predicting the type of observed stress relaxation behavior for 60 published step strain experiments on entangled, linear polymer liquids.

Evaluation of rheological constitutive equations for branched polymers in step shear strain flows

The pom-pom rheological constitutive equation for branched polymers proposed by McLeish and Larson is evaluated in step shear strain flows. Semianalytic expressions for the shear-stress relaxation modulus are derived for both the integral and approximate differential versions of the pom-pom model. Predictions from the thermodynamically motivated differential pompon model of Ottinger are also examined. Single-mode integral and differential pom-pom models are found to give qualitatively different predictions, the former displays time–strain factorability after the backbone stretch is relaxed, while the latter does not. We also find that the differential pompon model gives quantitatively similar predictions to the integral pom-pom model in step strain flows. Predictions from multimode integral and differential pom-pom models are compared with experimental data on a widely characterized, low-density polyethylene known as 1810H. The experiments strongly support time–strain factorability, while the multimode pom-pom model predictions show deviations from this behavior over the entire range of time that is experimentally accessible.