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.     

A comparative study of kinematic hardening rules at finite deformations

Kinematic hardening models describe a specific kind of plastic anisotropy which evolves with the deformation process. It is well known that the extension of constitutive relations from small to finite deformations is not unique. This applies also to well-established kinematic hardening rules like that of Armstrong-Frederick or Chaboche. However, the second law of thermodynamics offers some possibilities for generalizing constitutive equations so that this ambiguity may, in some extent, be moderated. The present paper is concerned with three possible extensions, from small to finite deformations, of the Armstrong-Frederick rule, which are derived as sufficient conditions for the validity of the second law. All three models rely upon the multiplicative decomposition of the deformation gradient tensor into elastic and plastic parts and make use of a yield function expressed in terms of the so-called Mandel stress tensor. In conformity with this approach, the back-stress tensor is defined to be of Mandel stress type as well. In order to compare the properties of the three models, predicted responses for processes with homogeneous and inhomogeneous deformations are discussed. To this end, the models are implemented in a finite element code (ABAQUS).     

A large deformation framework for compressible viscoelastic materials: Constitutive equations and finite element implementation

For modeling the constitutive properties of viscoelastic solids in the context of small deformations, the so-called three-parameter solid is often used. The differential equation governing the model response may be derived in a thermodynamically consistent way considering linear spring-dashpot elements. The main problem in generalizing constitutive models from small to finite deformations is to extend the theory in a thermodynamically consistent way, so that the second law of thermodynamics remains satisfied in every admissible process. This paper concerns with the formulation and constitutive equations of finite strain viscoelastic material using multiplicative decomposition in a thermodynamically consistent manner. Based on the proposed constitutive equations, a finite element (FE) procedure is developed and implemented in an FE code. Subsequently, the code is used to predict the response of elastomer bushings. The finite element analysis predicts displacements and rotations at the relaxed state reasonably well. The response to coupled radial and torsional deformations is also simulated.     

The effect of annealing on the viscoplastic response of semicrystalline polymers at finite strains

A constitutive model is developed for the viscoplastic behavior of a semicrystalline polymer at finite strains. A solid polymer is treated as an equivalent heterogeneous network of chains bridged by permanent junctions (physical cross-links, entanglements and lamellar blocks). The network is thought of as an ensemble of meso-regions linked with each other. In the sub-yield region of deformations, junctions between chains in meso-domains slide with respect to their reference positions (which reflects sliding of nodes in the amorphous phase and fine slip of lamellar blocks). Above the yield point, this sliding process is accompanied by displacements of meso-domains in the ensemble with respect to each other (which reflects coarse slip and disintegration of lamellar blocks). To account for the orientation of lamellar blocks in the direction of maximal stresses and formation of micro-fibrils in the post-yield region of deformations (which is observed as strain-hardening of specimens) elastic moduli are assumed to depend on the principal invariants of the right Cauchy–Green tensor for the viscoplastic flow. Stress–strain relations for a semicrystalline polymer are derived by using the laws of thermodynamics. The constitutive equations are determined by six adjustable parameters that are found by matching observations in uniaxial tensile tests on injection-molded isotactic polypropylene at elongations up to 80%. Prior to testing, the specimens were annealed at various temperatures ranging from 110 to 163 °C. Fair agreement is demonstrated between the experimental data and the results of numerical simulation. The effect of annealing temperature on the material parameters is studied in detail.     

Steady viscoelastic film flow over 2D topography: I. The effect of viscoelastic properties under creeping flow

Two-dimensional, steady flow of a viscoelastic film over a periodic topography under the action of a body force is studied. The exponential Phan-Thien and Tanner (ePTT) constitutive model is used. The conservation equations are solved via the usual mixed finite element method combined with a quasi-elliptic grid generation scheme in order to capture the large deformations of the free surface. The constitutive equation is weighted using the SUPG method and solved via the polymeric stress splitting EVSS-G technique. First, the code is validated by verifying that in isolated topographies the periodicity conditions result in fully developed viscoelastic film flow at the inflow/outflow boundaries and that its predictions for Newtonian fluids over 2D topography under creeping flow conditions coincide with those of previous works. Since the lubrication approximation is not invoked here, the topographical features can have wall segments that form any angle with the main flow, but only slight smoothing of the convex corners assists in reducing the stress singularity there. Thus, steady-state solutions are computed accurately up to high Deborah numbers, resulting in large deformations of the free surface. The magnitude of the capillary ridge in the film before the entrance to a step down of the substrate and of the capillary depression before a step up is increased as De increases up to ～0.7 due to increased fluid elasticity. Above this value they decrease, because increasing De increases also the shear and elongational thinning, which eventually affect them more. Increasing the ratio of solvent to polymer viscosities, β, the elongational parameter, ? and the molecular slip parameter, ξ, monotonically increases their magnitudes and especially that of the capillary ridge, but the mechanisms leading to these changes are different as explained in the text.     

Modelling of stress softening in elastomeric materials: foundations of simple theories

This work is concerned with formulation of constitutive relations for materials exhibiting the stress softening phenomenon (known as the Mullins effect) typical observed in elastomeric and other amorphous materials during loading–reloading cycles. It is assumed that microstructural changes in such materials during the deformation process can be represented by a single scalar-valued softening variable whose evolution is accompanied by microforces satisfying their own law of balance, besides the classical laws of mechanics underlying macroscopic deformation of a material. The constitutive equations are then derived in consistency with thermodynamics of irreversible processes with the restriction to purely mechanical theory. The general form of the derived constitutive equations is subsequently simplified through introduction of additional assumptions leading to various models of the stress softening phenomenon. As an illustration of the general theory, it is shown that the so-called pseudo-elastic model proposed in the literature may be derived without an ad hoc postulate of the variational principle.     

Finite viscoelasticity and viscoplasticity of semicrystalline polymers

Observations are reported on low-density polyethylene in uniaxial tensile and compressive tests with various strain rates and in tensile and compressive relaxation tests with various strains. A constitutive model is developed for the time-dependent response of a semicrystalline polymer at arbitrary three-dimensional deformations with finite strains. A polymer is treated as an equivalent network of chains bridged by junctions (entanglements between chains in the amorphous phase and physical cross-links at the lamellar surfaces). Its viscoelastic behavior is associated with separation of active strands from temporary junctions and merging of dangling strands with the inhomogeneous network. The viscoplastic response is attributed to sliding of junctions between chains with respect to their reference positions. Constitutive equations are derived by using the laws of thermodynamics. The stress–strain relations involve 6 material constants that are found by matching the observations.      

Extended thermodynamics of molecular ideal gases

The objective of extended thermodynamics of molecular ideal gases is the determination of the 17 fields ofmass density, velocity, energy density, pressure deviator, heat flux, intrinsic energy density and intrinsic heat flux. The intrinsic energy represents the rotational or the vibrational energy of the molecules. The necessary field equations are based upon balance laws and the system of equations is closed by constitutive relations which are characteristic for the gas under consideration. The generality of the constitutive relations is restricted by theprinciple of material frame indifference, and by the entropy principle. These principles reduce the constitutive coefficients of all fluxes to the thermal and caloric equation of state of the gas and provide inequalities for the transport coefficients. The transport coefficients can be related to the shear viscosity, the heat conductivity, and the coefficients of self-diffusion and attenuation of sound waves, so that the field equations become quite specific. The theory is in perfect agreement with the kinetic theory of molecular gases. It is shown that in non-equilibrium the temperature is discontinuous at thermometric walls. The dynamic pressure and the volume viscosity, are discussed and it is shown how extended thermodynamics and ordinary thermodynamics are related.     

A coupled theory of fluid permeation and large deformations for elastomeric materials

An elastomeric gel is a cross-linked polymer network swollen with a solvent (fluid). A continuum-mechanical theory to describe the various coupled aspects of fluid permeation and large deformations (e.g., swelling and squeezing) of elastomeric gels is formulated. The basic mechanical force balance laws and the balance law for the fluid content are reviewed, and the constitutive theory that we develop is consistent with modern treatments of continuum thermodynamics, and material frame-indifference. In discussing special constitutive equations we limit our attention to isotropic materials, and consider a model for the free energy based on a Flory-Huggins model for the free energy change due to mixing of the fluid with the polymer network, coupled with a non-Gaussian statistical-mechanical model for the change in configurational entropy—a model which accounts for the limited extensibility of polymer chains. As representative examples of application of the theory, we study (a) three-dimensional swelling-equilibrium of an elastomeric gel in an unconstrained, stress-free state; and (b) the following one-dimensional transient problems: (i) free-swelling of a gel; (ii) consolidation of an already swollen gel; and (iii) pressure-difference-driven diffusion of organic solvents across elastomeric membranes.     

A nonlocal strain gradient plasticity theory for finite deformations

Strain gradient plasticity for finite deformations is addressed within the framework of nonlocal continuum thermodynamics, featured by the concepts of (nonlocality) energy residual and globally simple material. The plastic strain gradient is assumed to be physically meaningful in the domain of particle isoclinic configurations (with the director vector triad constant both in space and time), whereas the objective notion of corotational gradient makes it possible to compute the plastic strain gradient in any domain of particle intermediate configurations. A phenomenological elastic–plastic constitutive model is presented, with mixed kinematic/isotropic hardening laws in the form of PDEs and related higher order boundary conditions (including those associated with the moving elastic/plastic boundary). Two fourth-order projection tensor operators, functions of the elastic and plastic strain states, are shown to relate the skew-symmetric parts of the Mandel stress and back stress to the related symmetric parts. Consistent with the thermodynamic restrictions therein derived, the flow laws for rate-independent associative plasticity are formulated in a six-dimensional tensor space in terms of symmetric parts of Mandel stresses and related work-conjugate generalized plastic strain rates. A simple shear problem application is presented for illustrative purposes.     

The molecular theory of viscoelasticity for thermoplastic elastomer SBS (SIS) at large deformations

A microstructure model for SBS and SIS triblock copolymers with hard domains as multifunctional reinforcing fillers is proposed. Based on this model and proposed mechanism of large deformations, the probability distribution function of the end-to-end vector for each constituent chain and the free energy of deformation for the total networks was calculated by the combination of statistical thermodynamics and kinetics. A new molecular theory of non-linear visco-elasticity for SBS and SIS at large deformations is presented. It is successful in relating the viscoelastic state to molecular constitution by three important parameters (C ₁₀₀,C ₀₂₀, andC ₂₀₀) of the networks. The relations of stress to strain for four types of deformation, the elastic modulus and the constitutive equation for the stress relaxation were derived from this theory. It provides a theoretical foundation for studying the relationships of multiphase network structures and mechanical properties at large deformations. An excellent agreement between the theoretical relationships and experimental data from the experiments and the reference was obtained.Project supported by the National Natural Foundation of China     

Theoretical modeling of microstructured liquids: a simple thermodynamic approach

A new method is presented for accounting for microstructural features of flowing complex fluids at the level of mesoscopic, or coarse-grained, models by ensuring compatibility with macroscopic and continuum thermodynamics and classical transport phenomena. In this method, the microscopic state of the liquid is described by variables that are local expectation values of microscopic features. The hypothesis of local thermodynamic equilibrium is extended to include information on the microscopic state, i.e., the energy of the liquid is assumed to depend on the entropy, specific volume, and microscopic variables. For compatibility with classical transport phenomena, the microscopic variables are taken to be extensive variables (per unit mass or volume), which obey convection-diffusion-generation equations. Restrictions on the constitutive laws of the diffusive fluxes and generation terms are derived by separating dissipation by transport (caused by gradients in the derivatives of the energy with respect to the state variables) and by relaxation (caused by non-equilibrated microscopic processes like polymer chain stretching and orientation), and by applying isotropy. When applied to unentangled, isothermal, non-diffusing polymer solutions, the equations developed according to the new method recover those developed by the Generalized Bracket [J. Non-Newtonian Fluid Mech. 23 (1987) 271; A.N. Beris, B.J. Edwards, Thermodynamics of Flowing Systems with Internal Microstructure, first ed., Oxford University Press, Oxford, 1994] and by the Matrix Model [J. Rheol. 38 (1994) 769]. Minor differences with published results obtained by the Generalized Bracket are found in the equations describing flow coupled to heat and mass transfer in polymer solutions. The new method is applied to entangled polymer solutions and melts in the general case where the rate of generation of entanglements depends nonlinearly on the rate of strain. A link is drawn between the mesoscopic transport equations of entanglements and conformation and the microscopic equation describing the configurational distribution of polymer segment stretch and orientation. Constraints are derived on the generation terms in the transport equations of entanglements and conformation, and the formula for the elastic stress is generalized to account for reversible formation and destruction of entanglements. A simplified version of the transport equation of conformation is presented which includes many previously published constitutive models, separates flow-induced polymer stretching and orientation, yet is simple enough to be useful for developing large-scale computer codes for modeling coupled fluid flow and transport phenomena in two- and three-dimensional domains with complex shapes and free surfaces.     

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 constitutive theory for shape memory polymers. Part I: Large 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 modeling. 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.     

Column buckling with shear deformations—A hyperelastic formulation

Column constitutive relationships and buckling equations are derived using a consistent hyperelastic neo-Hookean formulation. It is shown that the Mandel stress tensor provides the most concise representation for stress components. The analogous definitions for uniaxial beam plane stress and plane strain for large deformations are established by examining the virtual work equations. Anticlastic transverse curvature of the beam cross-section is incorporated when plane stress or thick beam dimensions are assumed. Column buckling equations which allow for shear and axial deformations are derived using the positive definiteness of the second order work. The buckling equations agree with the equation derived by Haringx and are extended to incorporate anticlastic transverse curvature which is important for low slenderness, high buckling modes and with increasing width to thickness ratio. The work in this paper does not support the existence of a shear buckling mode for straight prismatic columns made of an isotropic material.     

Cyclic deformation of ternary nanocomposites: Experiments and modeling

Observations are reported on the mechanical response of a ternary composite (blend of polypropylene and a thermoplastic elastomer reinforced with montmorilonite nanoclay) at cyclic tensile deformations with relatively large amplitudes (up to the necking point). Constitutive equations for the viscoplastic behavior of hybrid nanocomposites are derived by using the laws of thermodynamics. Adjustable parameters in the stress–strain relations are found by fitting the experimental data. It is demonstrated that the model adequately predicts stress–strain diagrams of the nanocomposite under cyclic loading.     

A simple mixture theory for ν Newtonian and generalized Newtonian constituents

This work presents the development of mathematical models based on conservation laws for a saturated mixture of ν homogeneous, isotropic, and incompressible constituents for isothermal flows. The constituents and the mixture are assumed to be Newtonian or generalized Newtonian fluids. Power law and Carreau–Yasuda models are considered for generalized Newtonian shear thinning fluids. The mathematical model is derived for a ν constituent mixture with volume fractions ${\phi_\alpha}$ using principles of continuum mechanics: conservation of mass, balance of momenta, first and second laws of thermodynamics, and principles of mixture theory yielding continuity equations, momentum equations, energy equation, and constitutive theories for mechanical pressures and deviatoric Cauchy stress tensors in terms of the dependent variables related to the constituents. It is shown that for Newtonian fluids with constant transport properties, the mathematical models for constituents are decoupled. In this case, one could use individual constituent models to obtain constituent deformation fields, and then use mixture theory to obtain the deformation field for the mixture. In the case of generalized Newtonian fluids, the dependence of viscosities on deformation field does not permit decoupling. Numerical studies are also presented to demonstrate this aspect. Using fully developed flow of Newtonian and generalized Newtonian fluids between parallel plates as a model problem, it is shown that partial pressures p _α of the constituents must be expressed in terms of the mixture pressure p. In this work, we propose ${p_\alpha=\phi_\alpha p}$ and ${\sum_\alpha^\nu p_\alpha = p}$ which implies ${\sum_\alpha^\nu \phi_\alpha = 1}$ which obviously holds. This rule for partial pressure is shown to be valid for a mixture of Newtonian and generalized Newtonian constituents yielding Newtonian and generalized Newtonian mixture. Modifications of the currently used constitutive theories for deviatoric Cauchy stress tensor are proposed. These modifications are demonstrated to be essential in order for the mixture theory for ν constituents to yield a valid mathematical model when the constituents are the same. Dimensionless form of the mathematical models is derived and used to present numerical studies for boundary value problems using finite element processes based on a residual functional, that is, least squares finite element processes in which local approximations are considered in ${H^{k,p}\left(\bar{\Omega}^e\right)}$ scalar product spaces. Fully developed flow between parallel plates and 1:2 asymmetric backward facing step is used as model problems for a mixture of two constituents.     

A unified residual-based thermodynamic framework for strain gradient theories of plasticity

A unified thermodynamic framework for gradient plasticity theories in small deformations is provided, which is able to accommodate (almost) all existing strain gradient plasticity theories. The concept of energy residual (the long range power density transferred to the generic particle from the surrounding material and locally spent to sustain some extra plastic power) plays a crucial role. An energy balance principle for the extra plastic power leads to a representation formula of the energy residual in terms of a long range stress, typically of the third order, a macroscopic counterpart of the micro-forces acting on the GNDs (Geometrically Necessary Dislocations). The insulation condition (implying that no long range energy interactions are allowed between the body and the exterior environment) is used to derive the higher order boundary conditions, as well as to ascertain a principle of the plastic power redistribution in which the energy residual plays the role of redistributor and guarantees that the actual plastic dissipation satisfies the second thermodynamics principle. The (nonlocal) Clausius-Duhem inequality, into which the long range stress enters aside the Cauchy stress, is used to derive the thermodynamic restrictions on the constitutive equations, which include the state equations and the dissipation inequality. Consistent with the latter inequality, the evolution laws are formulated for rate-independent models. These are shown to exhibit multiple size effects, namely (energetic) size effects on the hardening rate, as well as combined (dissipative) size effects on both the yield strength (intrinsic resistance to the onset of plastic strain) and the flow strength (resistance exhibited during plastic flow). A friction analogy is proposed as an aid for a better understanding of these two kinds of strengthening effects. The relevant boundary-value rate problem is addressed, for which a solution uniqueness theorem and a minimum variational principle are provided. Comparisons with other existing gradient theories are presented. The dissipation redistribution mechanism is illustrated by means of a simple shear model.     

A 3D finite strain phenomenological constitutive model for shape memory alloys considering martensite reorientation

Most devices based on shape memory alloys experience both finite deformations and non-proportional loading conditions in engineering applications. This motivates the development of constitutive models considering finite strain as well as martensite variant reorientation. To this end, in the present article, based on the principles of continuum thermodynamics with internal variables, a three-dimensional finite strain phenomenological constitutive model is proposed taking its basis from the recent model in the small strain regime proposed by Panico and Brinson (J Mech Phys Solids 55:2491–2511, 2007). In the finite strain constitutive model derivation, a multiplicative decomposition of the deformation gradient into elastic and inelastic parts, together with an additive decomposition of the inelastic strain rate tensor into transformation and reorientation parts is adopted. Moreover, it is shown that, when linearized, the proposed model reduces exactly to the original small strain model.