Thermodynamic admissibility of the extended Pom-Pom model for branched polymers

The thermodynamic consistency of the eXtended Pom-Pom (XPP) model for branched polymers of Verbeeten et al. [W.M.H. Verbeeten, G.W.M. Peters, F.P.T. Baaijens, Differential constitutive equations for polymer melts: the extended pom-pom model, J. Rheol. 45 (4) (2001) 823–843; W.M.H. Verbeeten, G.W.M. Peters, F.P.T. Baaijens, Differential constitutive equations for polymer melts: the extended pom-pom model (vol 45, pg 823–843, 2001), J. Rheol. 45 (6) (2001) 1489] as well as its modified version [J. van Meerveld, Note on the thermodynamic consistency of the integral pom-pom model, J. Non-Newtonian Fluid Mech. 108 (1–3) (2002) 291–299] is investigated from the perspective of non-equilibrium thermodynamics, namely the General Equation for Non-Equilibrium Reversible–Irreversible Coupling (GENERIC) framework. The thermodynamic admissibility of the XPP model is shown for both its original and modified form. According to the GENERIC formalism, the parameter α introduced by Verbeeten et al. to predict non-zero second normal stress in shear flows must fulfill the condition 0 ≤ α ≤ 1.     

The mathematical representation of driven thermodynamic systems

A general framework for the treatment of driven systems in nonequilibrium thermodynamics is discussed for two selected theories and a simple model system. The framework is based upon the of modeling and control of general physical systems proposed by van der Schaft and co-workers. The crucial concept is the notion of a Dirac structure representing the dynamical equations of motion as well as the power conserving interconnection structure of the system. We applied the framework to two existing theories and a very simple model system. The two selected theories are the “General Equation for the Non-Equilibrium Reversible-Irreversible Coupling” (GENERIC) formalism of Grmela and Öttinger and the Matrix model of Jongschaap; the model system is a viscous gas in a cylinder and an externally driven piston. It is shown that the new approach provides not only a common framework for both theories, but also useful extensions, in particular, an extended GENERIC treatment of driven systems.     

Application of melt flow index for rheological characterization of branched and linear polymers

A procedure for evaluating rheological characteristics, such as the master curves log/ ₀ vs. log % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xd9Gqpe0x% c9q8qqaqFn0dXdir-xcvk9pIe9q8qqaq-xir-f0-yqaqVeLsFr0-vr% 0-vr0db8meaabaqaciGacaGaaeqabaWaaeaaeaaakeaaieGaceWFZo% Gbaiaaaaa!3B59!\[\dot \gamma \] ₀ and flow curves, using the melt flow index is described for branched and linear polymers. Experimental data on the melt flow index and branching degree are needed for this purpose, as well as some polymer constants, i.e. coefficients of the ₀ vs. MFI relation and coefficients of fluidity dependence on molecular characteristics. An example is given for bisphenol A polycarbonate.     

Primitive chain network simulations for branched polymers

We present simulations of branched polymer dynamics based on a sliplink network model, which also accounts for topological change around branch points, i.e., for branch-point diffusion. It is well-known that, with the exception of stars, branched polymers may show a peculiar rheological behavior due to the exceptionally slow relaxation of the backbone chains bridging branch points. Though Brownian simulations based on sliplinks are powerful tools to study the motion of polymers and to predict rheological properties, none of the existing methods can simulate the relaxation of the bridge chains. The reason for that is lack of a rule for network topology rearrangement around branch points, so that entanglements between bridge chains cannot be renewed. Therefore, we introduce in this paper one possible branch-point mobility rule into our primitive chain network model. For star polymers, diffusion coefficients were calculated and compared with experiments. For both star and H-shaped polymers, diffusion was simulated both with and without the new rule, and the effect on linear viscoelasticity was also determined in one case.     

Measurements of the first normal-stress difference in a new Rheo-dilatometer for molten polymers: Triple-step-shear-strain tests for all K-BKZ constitutive equations

Following the 3rd of a triple-step-shear-strain sequence, the relaxation of the first normal-stress difference,N ₁ (t), has been measured for a sample (IUPAC A) of low-density polyethylene at 150 °C over a range of shear-strain magnitudes up to 28 shear units. A new cone-plate Rheodilatometer was used, giving sample volume change data as well as thrust and torque data during cone rotation. At 130 °C, prior measurements (described elsewhere) gave an upper limit of 0.001% for the volume change with IUPAC A; this gave an estimated error of only 1.7% in determiningN ₁(t) from time-dependent thrust data. Wagner's network-rupture model (based on a postulated strain-induced irreversible network disentanglement process) gave quantitative agreement withN ₁(t) data for IUPAC A at 150 °C over some of the ranges of time and shear-strain investigated. Wagner's earlier constitutive equation (of K-BKZ type) gave no quantitative agreement. Using a special choice of strain magnitudes in which the 3rd is half that of the 1st and 2nd, it is shown that a critical test of all K-BKZ equations can be made on the basis ofN ₁ (t) data only. This test excludes all K-BKZ equations for IUPAC A under the conditions here used. In all the present investigations, the 1st and 3rd shears had the same sign while the 2nd had the opposite sign.     

On the dynamics of grafted branched polymers—a Monte Carlo simulation study

A simplified model of grafted branched polymers was designed and investigated. The model consisted of star-branched chains constructed on a simple cubic lattice. The star polymers were built of three arms of equal lengths. The chains were attached to an impenetrable flat surface with one arm’s end. The arm attached to the surface (a stem) was built of segments different from those in two remaining arms (branches). During the Monte Carlo simulation of the system, the conformation of each chain was modified according to the metropolis sampling algorithm with local changes of chain conformations. The simulations were performed for different chain lengths and the temperature of the system (solvent conditions). The structure of a polymer film formed on the grafting surfaces depended strongly on the temperature and the low temperature films consisted of two separate layers with the insoluble layer located near the grafting surface. The short-time relaxation of the branches and stems of chains was also investigated. The analysis of the dynamics of the model system shows the influence of the structure of the system on relaxation times of various parameters. Paper presented at the AERC 2005 held on April 21–23, 2005 in Grenoble, France.     

Back to the thermodynamic admissibility of creep-relaxation functions in linear viscoelasticity

The recent discussion on admissibility criteria for the kernels of linear viscoelastic liquids is completed by the results for viscoelastic solids. The necessary and sufficient conditions of thermodynamic admissibility are established. The class of thermodynamically admissible creep-relaxation functions is proved to be wider than it is usually supposed, including as well numerous nonmonotone and even locally negative functions. These nontraditional viscoelasticity kernels find applications in physics of heterogeneous materials, like for instance in mechanics and theology of composites.     

An evaluation of the Larson-Doi model for liquid crystalline polymers using recoil

The mesoscopic models for the rheological properties of liquid crystalline polymers proposed by Larson and Doi in 1991 and Kawaguchi and Denn in 1999 are based on phenomenological expressions that describe the evolution of the defect density and the contribution of the “texture” to the stress. In the present work, we attempt to assess some of these assumptions by monitoring how the energy stored in the texture of liquid crystalline materials evolves during shear flows. For that purpose, strain recovery is measured as a function of the applied strain for flow reversal and intermittent flow. Solutions of poly-benzylglutamate in m-cresol, hydroxypropylcellulose in water and a nematic surfactant solution are used as model systems. Although the behaviour is described qualitatively by the model, discrepancies between the predictions and the experiments are observed, especially when the shear history includes rest periods. Received: 14 July 1999 /Accepted: 30 August 1999     

On the application of branched operator continued fractions for a boundary problem of linear viscoelasticity

In solving linear viscoelastic problems for composite materials, the problem arises of representing a multivariable operator function. To resolve this problem, the method of operator continued fractions is generalized to the case of a multivariable operator function. The method is based on the theory of branched continued fractions. Branched operator continued fractions are considered. Using the convolution theorem, fractions can be represented in terms of operators of basic class. This representation makes it possible to effectively solve boundary problems of linear viscoelasticity Published in Prikladnaya Mekhanika, Vol. 42, No. 1, pp. 133–143, January 2006.     

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 ?ttinger 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.     

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     

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 hierarchical algorithm for predicting the linear viscoelastic properties of polymer melts with long-chain branching

The hierarchical model proposed earlier [Larson in Macromolecules 34:4556–4571, 2001] is herein modified by inclusion of early time fluctuations and other refinements drawn from the theories of Milner and McLeish for more quantitative prediction. The hierarchical model predictions are then compared with experimental linear viscoelastic data of well-defined long chain branched 1,4-polybutadienes and 1,4-polyisoprenes using a single set of parameter values for each polymer, which are obtained from experimental data for monodisperse linear and star polymers. For a wide range of monodisperse branched polymer melts, the predictions of the hierarchical model for monodisperse melts are very similar to those of the Milner–McLeish theories, and agree well with experimental data for many, but not all, of the branched polymer samples. Since the modified hierarchical model accounts for arbitrary polydispersity in molecular weight and branching distributions, which is not accounted for in the Milner–McLeish theories, the hierarchical algorithm is a promising one for predicting the relaxation of general mixtures of branched polymers.     

A constitutive theory for shape memory polymers. Part II: A linearized model for small deformations

A constitutive theory is developed for shape memory polymers. It is to describe the thermomechanical properties of such materials under large deformations. The theory is based on the idea, which is developed in the work of Liu et al. [2006. Thermomechanics of shape memory polymers: uniaxial experiments and constitutive modelling. Int. J. Plasticity 22, 279-313], that the coexisting active and frozen phases of the polymer and the transitions between them provide the underlying mechanisms for strain storage and recovery during a shape memory cycle. General constitutive functions for nonlinear thermoelastic materials are used for the active and frozen phases. Also used is an internal state variable which describes the volume fraction of the frozen phase. The material behavior of history dependence in the frozen phase is captured by using the concept of frozen reference configuration. The relation between the overall deformation and the stress is derived by integration of the constitutive equations of the coexisting phases. As a special case of the nonlinear constitutive model, a neo-Hookean type constitutive function for each phase is considered. The material behaviors in a shape memory cycle under uniaxial loading are examined. A linear constitutive model is derived from the nonlinear theory by considering small deformations. The predictions of this model are compared with experimental measurements.     

A finite deformation fractional viscoplastic model for the glass transition behavior of amorphous polymers

The stress response of amorphous polymers exhibits tremendous change during the glass transition region, from soft viscoelastic response to stiff viscoplastic response. In order to describe the temperature-dependent and rate-dependent stress response of amorphous polymers, we extend the one-dimensional small strain fractional Zener model to the three-dimensional finite deformation model. The Eyring model is adopted to represent the stress-activated viscous flow. A phenomenological evolution equation of yield strength is used to describe the strain softening behaviors. We demonstrate that the stress response predicted by the three-dimensional model is consistent with that of one-dimensional model under uniaxial deformation, which confirms the validity of the extension. The model is then applied to describe the stress response of an amorphous thermoset at various temperatures and strain rates, which shows good agreement between experiments and simulation. We further perform a parameter study to investigate the influence of the model parameters on the stress response. The results show that a smaller fractional order results in a larger yield strain while has little effect on the yield stress when the temperature is below the glass transition temperature. For the stress relaxation tests, a smaller fractional order leads to a slower relaxation rate.     

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.     

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