A model of traps for yield in amorphous glassy polymers

Summary  Constitutive equations are derived for the viscoelastic and viscoplastic behavior of amorphous glassy polymers at isothermal loading with small strains. The model is based on the trapping concept: a disordered medium is treated as an ensemble of plastic flow units (with the characteristic size of micrometers), which, in turn, consist of a number of cooperative rearranging regions (with the characteristic length of nanometers). The viscoelastic response is described by rearrangement of relaxing regions, whereas the viscoplastic behavior is modeled as irreversible deformation of plastic units. Adjustable parameters are found by fitting observations for aromatic polyesters, nylon-66, polycarbonate block copolymers and an epoxy glass. Fair agreement is demonstrated between experimental data and results of numerical simulation. Received 17 November 1999; accepted for publication 23 March 2000     

A model for the viscoelastic behavior of polymers at finite strains

Summary A constitutive model is derived for the isothermal nonlinear viscoelastic response in polymers, which do not possess the separability property. The model is based on the concept of transient networks, and treats a polymer as a system of nonlinear elastic springs (adaptive links), which break and emerge due to micro-Brownian motion of chains. The breakage and reformation rates for adaptive links are assumed to depend on some strain energy density. The viscoelastic behavior is described by an integral constitutive equation, where the relaxation functions satisfy partial differential equations with coefficients depending on the strain history. Adjustable parameters of the model are found by fitting experimental data for a number of polymers in tension at strains up to 400 per cent. To validate the constitutive relations, we consider loading with different strain rates, determine adjustable parameters at one rate of strains, and compare prediction of the model with observations at another rate of strains. Fair agreement between experimental data and results of numerical simulation is demonstrated when the rates of strains differ by more than a decade. Received 1 July 1997; accepted for publication 7 October 1997     

Modelling of the elasto-viscoplastic damage behaviour of glassy polymers

Constitutive equations are proposed in order to describe the elasto-viscoplastic damage behaviour of polymers. The behaviour is well accounted for by a modified Bodner–Partom model comprising hydrostatic and void evolution terms. The true stress–strain and volumetric strain behaviour of typical rubber-toughened glassy polymers (RTPMMA and HIPS) were experimentally determined at constant local true strain rate by using a video-controlled technique. Successful agreement is obtained between experimental results and the proposed model.     

The relaxation of linear flexible polymers which are slightly poly-disperse

The relaxation of slightly poly-disperse linear flexible polymers has been expressed in a simplified blending rule which is presumed to be a weighted linear superposition of the relaxation spectra of mono-disperse components which constitute the blend. Discrete components are characterized by their molecular weight M _i,weight fraction w _i,and relaxation time spectrum H _i(). ). In contrast to broadly distributed blends in which the small molecules mobilize the large ones and vice versa, we introduce the term slightly polydisperse for blends with molecular weight distributions narrow enough to have very little change in the longest relaxation times of each molecular weight component. The properties of this blending rule are analyzed and dynamic data is calculated for slightly poly-disperse polystyrene. As an application, the blending rule is used to determine the characteristic mono-disperse parameters (BSW parameters) of two materials, poly (vinyl methyl ether) and polycarbonate, for which we could not determine their BSW parameters directly since they were not available in nearly monodisperse form. The proposed blending rule can only be applied to systems in which all components are above the entanglement molecular weight, i.e. M _iM _c.Dedicated to the memory of Professor Tasos C. Papanastasiou     

On the analytic expression of the free energy in linear viscoelasticity

Two definitions of free energy for a linear viscoelastic material, due to Graffi and to Coleman and Owen, are considered, and the compatibility of these definitions with some expressions of the free energy proposed in the literature is examined. For the expressions of Staverman and Schwarzl and of Breuer and Onat, the two definitions are proved to be equivalent, and the set of all relaxation functions for which the two expressions are indeed free energies is determined. Two more expressions, proposed by Volterra and Graffi and by Morro and Vianello, are taken into consideration. For them, only the classes of relaxation functions for which they are free energies according to the first definition, is completely characterized. All results are established under regularity assumptions weaker than those usually made in the literature.     

The influence of dewetting in filled elastomers on the changes of their mechanical properties

Summary The changes of mechanical properties of filled polymers and their dependence on deformation history are the subject of this paper. For most of filled polymers in practical use, the theory of linear viscoelasticity cannot be applied, even at small deformations. In this work, samples of glass bead filled polybutadiene rubber with different filler levels were investigated at small strains (<10%). The evolution of the relaxation modulus and Poisson's ratio was observed in cyclic experiments, which were also applied in inducing a defined deformation history for the succeeding relaxation experiments. In these experiments, the relaxation modulus and Poisson's ratio were measured as functions of time, with strain, strain rate, filler level and the preceeding deformation history as parameters. The results indicate dewetting as the main reason for the changes of the mechanical properties of the filled materials.The financial support of this work by the Deutsche Forschungsgemeinschaft (DFG) is gratefully acknowledged.     

Ageing and rejuvenation in glassy amorphous polymers

Physical ageing of amorphous polymers well below their glass transition temperature leads to changes in almost all physical properties. Of particular interest is the increase in yield stress and post-yield strain softening that accompanies ageing of these materials. Moreover, at larger strain polymers seem to rejuvenate, i.e. aged and non-aged samples have identical stress-strain responses. Also, plastically deforming an aged sample seems to rejuvenate the polymer. In this work we use molecular dynamic simulations with a detailed force field suitable for macromolecular ensembles to simulate and understand the effects of ageing on the mechanical response of these materials. We show that within the timescales of these simulations it is possible to simulate both ageing and rejuvenation. The short range potentials play an important role in ageing and rejuvenation. A typical yield drop exhibited by glassy polymers is a manifestation of a sudden relaxation in the short range structure of an aged polymer. Moreover, the aged polymers are known to be brittle. We show that this is intimately related to its typical stress-strain response which allows it to carry arbitrarily large mean stresses ahead of a notch.     

A generalized coupled viscoplastic-viscodamage-viscohealing theory for glassy polymers

A thermodynamic consistent, small-strain, non-unified model is developed to capture the irregular rate dependency included in the strain controlled inelastic responses of polymers at the glassy state. The model is considered as a generalized Frederick-Armstrong-Philips-Chaboche (FAPC) theory proposed by [Voyiadjis and Basuroychowdhury, 1998] and [Voyiadjis and Abu Al-Rub, 2003] which is based on a von Mises and Chaboche isotropic hardening type viscoplasticity formulation. Using the proposed model, different experimental results are simulated and the range of viscoplastic related material constants are obtained through a parametric study. The thermodynamic framework is used to incorporate the effect of coupling between viscodamage and viscohealing phenomena into the inelastic deformation of glassy polymers. This coupling effect is crucial for polymeric based self healing systems in which different damage mechanisms are active and the efficiency of the healing processes are highly dependent on the damage. The computational aspect for general coupled inelastic-damage-healing processes together with the required solution algorithms are elaborated and the inelastic-damage-healing response of a polymeric based self-healing system is simulated. The proposed viscoplasticity theory constitutes a physically consistent approach to model the irregular mechanical responses of glassy polymers and the viscodamage model provides an exquisite predicting tool to evaluate the ductile damage associated with the large inelastic deformation and low cycle fatigue in polymeric based material systems. In conclusion, a well structured viscohealing theory is formulated for polymeric based self healing systems.     

Predicting the nonlinear hereditary viscoelasticity of polymers

A mathematical model for the nonlinear hereditary viscoelasticity of polymer materials is proposed to predict deformation processes of various complexity — from simple relaxation and simple creep to complex deformation-relaxation and reverse relaxation processes with alternative loading and unloading. __________ Translated from Prikladnaya Mekhanika i Tekhnicheskaya Fizika, Vol. 48, No. 6, pp. 147–157, November–December, 2007.     

A constitutive equation of elastic-visco-plasticity for polymers

The rheological behavior and a constitutive relationship of elastic-visco-plasticity for polymers are investigated in this paper. Several sets of experiments have been carried out to determine the material constants and to test the validity of constitutive formulation. It is shown that the theoretical profiles are in good agreement with experimental results. The rheological characteristic and the strain-rate effect of model are analyzed by computer simulation.The project is supported by the National Natural Science Foundation of China     

Torsion and normal force responses of glassy polymers in the sub-yield regime

While there is a major body of literature relating the non-linear response of both elastomers and polymer melts with the molecular structure and topology of the chains, the same cannot be said of the non-linear response, especially that below the yield point, for polymer glasses. Here we take an approach that uses ideas of finite deformation elasticity and apply them to the isochronal response of glassy polymers in torsional deformations. We find that, while the torsional (shear) responses are similar for different molecular structures, there seems to be a strong effect of side group relaxations on the normal forces. The results are discussed in terms of the strain energy density function and the opportunities for future research.     

Molecular origin of viscoelasticity and chain orientation of glassy polymers

Dynamic birefringence and dynamic viscoelasticity of poly(4-methyl styrene) and poly(4-t-butyl styrene) were measured to investigate the molecular origin of viscoelasticity around the glass transition zone. The data were analyzed with a modified stress-optical rule: The birefringence and the stress were separated into two component functions of different molecular origins. One component is related to the orientation of the main chain axis and the other one to the rotation of the repeating units about the main chain axis. The strain dependence of the two characteristic orientation functions in the glassy zone was estimated and the orientation mechanism of repeating units was discussed.Dedicated to Prof. John D. Ferry on the occasion of his 85th birthday.     

Nonisothermal two‐ and three‐dimensional flow simulations of inelastic and viscoelastic fluids by a finite‐volume method

This paper applies the finite‐volume method to computations of steady flows of viscous and viscoelastic incompressible fluids in complex two and three‐dimensional geometries. The materials adopted in the study obey different constitutive laws: Newtonian, purely viscous Carreau–Yasuda as also Upper‐Convected Maxwell and Phan‐Thien/Tanner differential models, with a Williams–Landel–Ferry (WLF) equation for temperature dependence. Specific analyses are made depending on the rheological model. A staggered grid is used for discretizing the equations and unknowns. Stockage possibilities allow us to solve problems involving a great number of degrees of freedom, up to 1 500 000 unknowns with a desk computer. In relation to the fluid properties, our numerical simulations provide flow characteristics for various 2D and 3D configurations and demonstrate the possibilities of the code to solve problems involving complex nonlinear constitutive equations with thermal effects. Copyright © 2009 John Wiley & Sons, Ltd.     

A predictive model for impact response of viscoelastic polymers in drop tests

We show for the first time that a classical Hookean viscoelastic constitutive law for rubbery materials can predict the impact forces and deflections measured with a commercial drop tester when a mass, or tup with a flat impacting surface is dropped onto a flat pad of commercial impact-absorbing rubber. The viscoelastic properties of the rubber, namely the relaxation times and strengths, are obtained by a standard rheological linear-oscillatory test, and the equation of momentum transfer is then solved, using these measured parameters, assuming a uniaxial deflection of the pad during the impact. Good agreement between measured and predicted forces and deflections is obtained for a series of various drop heights, tup masses, impact areas, and pad thicknesses, as long as the deflection of the pad relative to its thickness is small or modest (<50% or so), and as long as the area of the pad is less than or equal to that of the tup. When the pad area is greater than the tup, forces are higher than predicted, unless an empirical factor is introduced to account for the nonuniaxial stretching of the ring of material that extends outside of the impact area. These results imply that the impact-absorbing properties of a rubbery polymeric material can be assessed by simply examining the material's linear viscoelastic spectrum.     

Effects of strong anchoring on the dynamic moduli of heterogeneous nematic polymers

We focus on the linear viscoelastic response of heterogeneous nematic polymers to small amplitude oscillatory shear, paying special attention to the macroscopic influence of strong plate anchoring conditions. The model consists of the Stokes hydrodynamic equations with viscous and nematic stresses, coupled to orientational dynamics and structure driven by the flow gradient, an excluded-volume potential, and a two-constant distortional elasticity potential. We show that the dynamical response simplifies when plate anchoring is either tangential or homeotropic, recovering explicitly solvable Leslie–Ericksen–Frank behavior together with weakly varying order parameters across the plate gap. With these plate conditions, we establish “model consistency” so that all experimental driving conditions (plate-controlled velocity [strain] or shear stress, imposed oscillatory pressure) yield identical dynamic moduli for the same material parameters and anchoring conditions, eliminating the culpability of device influence in scaling behavior. Two physical predictions emerge that imply significant macroscopic elastic and viscous effects controlled by plate anchoring relative to flow geometry: (1) The storage modulus is enhanced by two to three orders of magnitude for homeotropic relative to parallel anchoring, across all frequencies. (2) The loss modulus exhibits enhancement of a factor of two to three for homeotropic over tangential anchoring, restricted to low frequencies. We further deduce a scaling law for the dynamic moduli versus anisotropy of the distortional elasticity potential.

Phenomenological nonlinear modelling of glassy polymers

Compared with the numerous works into the constitutive equations for the mechanical behaviour of metals, very little attention has been devoted to those of polymers. However, a model is required to describe both the complex shape of the stress–strain curves and strain rate sensitivity of glassy polymers. In this Note, a unified viscoelastic-viscoplastic model is presented in which the nonlinear pre-yield behaviour, the strain softening and the strain hardening are described by internal variables, in analogy with the models developed for metals. In order to check the predictive capability of the model, the numerical results are compared with the experimental data (monotone, creep and relaxation tests) of a typical amorphous glassy polymer. To cite this article: F. Zaïri et al., C. R. Mecanique 333 (2005).     

Rheology of polydisperse polymers: relationship between intermolecular interactions and molecular weight distribution

An expression of the relaxation function of linear polydisperse polymers is proposed in terms of intermolecular couplings of reptative chains. The relaxation times of each molecular weight are assumed to be shifted according to a tube renewal mechanism accounting for the diffusion of the surrounding chains. The subsequent shift is applied to the relaxation function of each molecular weight obtained from an analytical expression of the complex compliance J ^*(). Therefore the complex shear modulus G ^*() is derived from the overall relaxation function using the probability density accounting for the molecular weight distribution and four species-dependent parameters: a front factor A for zero-shear viscosity, plateau modulus G _N ⁰ , activation energy E and characteristic temperature T . All the main features of the theology of polydisperse polymers are described by the proposed model.     

On the damping function of shear relaxation modulus for entangled polymers

Published data of the damping function of the shear relaxation modulus, h(), are reviewed. This is the ratio of the relaxation modulus measured at a finite magnitude of shear, , to that at the limit of = 0. Majority of the data are in accord with the universal function of the Doi-Edwards tube model theory, in which the damping or the decrease of h() is attributed to the contraction along the tube of extended polymer chains. The weaker damping seems to be attributed to 1) comb-branching such as in LDPE; 2) lack of entanglement in too short chains; 3) bimodal molecular weight distribution. However, a star-branching does not cause a deviation from the tube model theory and a broadness of molecular weight distribution is not a major origin of a weaker damping. A star-branched polystyrene with 15 arms exhibits no strain dependence: h() = 1. For highly entangled systems with more than 50 entanglement points per molecule, the strain dependence is stronger than that of the Doi-Edwards theory. This could be due to a slip or an instability of deformation in the material.     

A molecular network model to describe the nonlinear viscoelastic behavior of polymers

A transient molecular network model is built to describe the nonlinear viscoelasticity of polymers by considering the effect of entanglement loss and regeneration on the relaxation of molecular strands. It is an extension of previous network theories. The experimental data on three thermoplastic polymers (ABS, PVC and PA6) obtained under various loading conditions are used to test the model. Agreement between the theoretical and experimental curves shows that the suggested model can describe successfully the relaxation behavior of the thermoplastic polymers under different loading rates by using relatively few relaxation modes. Thus the micromechanism responsible for strain-rate dependence of relaxation process and the origin of nonlinear viscoelasticity may be disclosed. The project supported by the National Natural Science Foundation of China and Doctorial Fund     

The “decaying springs” model for irreversibility in polymer melts

In this work, entanglements in a polymer melt are modeled as a system of parallel springs which form and decay spontaneously. The springs are assumed to be nonlinear, and a certain fraction of them is torn apart by a certain strain.Based on these assumptions, a model of behavior in simple shear is developed. This model is shown to predict a behavior comprising that of a Wagner fluid, and is generalized to a tensorial model of single integral type. The integrand depends on a product of a material function, modeling reversible behavior, and a material functional which takes irreversible processes into account.Irreversibility of network disentanglement, which may occur when deformation changes or reverses direction, can be modeled in this way. It is shown that the two well-known Wagner constitutive equations with and without irreversibility assumptions are special cases of the model developed. In case of a deformation which does not change directions, the new material function and the material functional are multiplied to yield Wagner's damping function.When the rate of spring formation is a function of temperature, the developed model is shown to predict thermorheologically simple behavior. A constitutive equation for non-isothermal flow of polymers is developed with this assumption.