Simulation of strain-induced anisotropy for polymers with weighting functions

The alignment of polymer chains is a well-known microstructural evolution effect due to straining of polymers. This has a drastic influence on the macroscopic properties of the initially isotropic material, such as a pronounced strength in the loading direction of stretched films. For modeling the effect of strain-induced anisotropy, a macroscopic constitutive model is developed in this paper. Within a thermodynamic framework, an additive decomposition of the logarithmic Hencky strain tensor into elastic and inelastic parts is used to formulate the constitutive equations. As a key idea, weighting functions are introduced to represent a strain-softening/hardening effect to account for induced anisotropy. These functions represent the ratio between the total strain rate (representing the actual loading direction) and a structural tensor (representing the stretched polymer chains). In this way, we introduce material parameters as a sum of weighted direction-related quantities. The numerical implementation of the resulting set of constitutive is used to identify material parameters based on experimental data, exhibiting strain-induced anisotropy. In the finite-element examples, we simulate the cold-forming of amorphous thermoplastic films below the glass transition temperature subjected to different re-loading directions.     

Nonisothermal flow of polymer melts

The Curtiss-Bird theory for polymer melts is modified to allow the temperature to be a function of time. The resulting constitutive equation involves integrals over the temperature history of the polymer. The predictions of this constitutive equation for the inception of uniaxial elongation with simultaneous cooling at a constant rate are calculated and compared with the experimental data of Matsumoto and Bogue. Qualitative agreement between the theory and the data is obtained when the link tension coefficient in the Curtiss-Bird theory is not equal to zero, but such agreement cannot be obtained when this coefficient is equal to zero. The extension of the theory to include spatially varying temperature is also discussed.     

Incorporation of polymer diffusivity and migration into constitutive equations

Given a general one-particle constitutive equation for the stress tensor, we discuss how to incorporate the additional effects of polymer diffusivity and migration into that constitutive equation within the framework of continuum mechanics. For the example of an upper-convected Maxwell model representing the polymer contribution to the stress tensor of a dilute polymer solution, we describe i) how to modify the constitutive equation for the stress tensor to include diffusion and migration effects, ii) how to formulate a balance equation for the polymer mass density in order to describe the nonhomogeneous composition of the polymer solution resulting from migration, and iii) how to close the extended set of coupled equations by means of further constitutive equations for the migration velocity and the diffusion tensor. In order to guarantee the material objectivity for all equations, we formulate them in the body tensor formulation of continuum mechanics (and then translate them into Cartesian space). The proposed equations are compared to results of a recent kinetic-theory approach.Dedicated to Professor Arthur S. Lodge on the occasion of his 70th birthday and his retirement from the University of Wisconsin.     

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.     

An unsymmetric constitutive equation for anisotropic viscoelastic fluid

A continuum constitutive theory of corotational derivative type is developed for the anisotropic viscoelastic fluid–liquid crystalline (LC) polymers. A concept of anisotropic viscoelastic simple fluid is introduced. The stress tensor instead of the velocity gradient tensor D in the classic Leslie–Ericksen theory is described by the first Rivlin–Ericksen tensor A and a spin tensor W measured with respect to a co-rotational coordinate system. A model LCP-H on this theory is proposed and the characteristic unsymmetric behaviour of the shear stress is predicted for LC polymer liquids. Two shear stresses thereby in shear flow of LC polymer liquids lead to internal vortex flow and rotational flow. The conclusion could be of theoretical meaning for the modern liquid crystalline display technology. By using the equation, extrusion–extensional flows of the fluid are studied for fiber spinning of LC polymer melts, the elongational viscosity vs. extension rate with variation of shear rate is given in figures. A considerable increase of elongational viscosity and bifurcation behaviour are observed when the orientational motion of the director vector is considered. The contraction of extrudate of LC polymer melts is caused by the high elongational viscosity. For anisotropic viscoelastic fluids, an important advance has been made in the investigation on the constitutive equation on the basis of which a series of new anisotropic non-Newtonian fluid problems can be addressed. The project supported by the National Natural Science Foundation of China (10372100, 19832050) (Key project). The English text was polished by Yunming Chen.     

聚合物熔体本构关系的研究进展

总结和评述了聚合物熔体本构关系的研究成果,并着重介绍分子链缠结动力学的结构网络本构理论．      

Thermally actuated shape-memory polymers: Experiments, theory, and numerical simulations

With the aim of developing a thermo-mechanically coupled large-deformation constitutive theory and a numerical-simulation capability for modeling the response of thermally actuated shape-memory polymers, we have (i) conducted large strain compression experiments on a representative shape-memory polymer to strains of approximately unity at strain rates of 10⁻³ and 10⁻¹ s⁻¹, and at temperatures ranging from room temperature to approximately 30 °C above the glass transition temperature of the polymer; (ii) formulated a thermo-mechanically coupled large-deformation constitutive theory; (iii) calibrated the material parameters appearing in the theory using the stress-strain data from the compression experiments; (iv) numerically implemented the theory by writing a user-material subroutine for a widely used finite element program; and (v) conducted representative experiments to validate the predictive capability of our theory and its numerical implementation in complex three-dimensional geometries. By comparing the numerically predicted response in these validation simulations against measurements from corresponding experiments, we show that our theory is capable of reasonably accurately reproducing the experimental results. As a demonstration of the robustness of the three-dimensional numerical capability, we also show results from a simulation of the shape-recovery response of a stent made from the polymer when it is inserted in an artery modeled as a compliant elastomeric tube.     

A differential constitutive equation for polymer melts

A modification of the Giesekus constitutive equation is derived by incorporating (approximately, via the Peterlin approximation) the finite extensibility of polymer molecules into dumbbell kinetic theory along with the anisotropic hydrodynamic drag suggested by Giesekus. The constitutive equation that is obtained retains much of the simplicity of Giesekus' constitutive equation, but it involves terms that are cubic in the stress as well as those that are quadratic. It is shown that the constitutive equation quantitatively describes the steady elongational viscosity of the IUPAC polymer melt A (including the strain softening of the melt), but it cannot describe the elongational and shear viscosities simultaneously. It is also shown that the constitutive equation satisfies the Lodge-Meissner relation for shear strains less than unity.     

Multi-mechanism anisotropic model for granular materials

By representing the assembly by a simplified column model, a constitutive theory, referred to as sliding–rolling theory, was recently developed for a two-dimensional assembly of rods subjected to biaxial loading, and then extended to a three-dimensional assembly of spheres subjected to triaxial (equibiaxial) loading. The sliding–rolling theory provides a framework for developing a phenomenological constitutive law for granular materials, which is the objective of the present work. The sliding–rolling theory provides information concerning yield and flow directions during radial and non-radial loading. In addition, the theory provides information on the role of fabric anisotropy on the stress–strain behavior and critical state shear strength. In the present paper, a multi-axial phenomenological model is developed within the sliding–rolling framework by utilizing the concepts of critical state, classical elasto-plasticity and bounding surface. The resulting theory involves two yield surfaces and falls within the definition of the multi-mechanism models. Computational issues concerning the solution uniqueness for stress states at the corner of yield surfaces are addressed. The effect of initial and induced fabric anisotropy on the constitutive behavior is incorporated. It is shown that the model is capable of simulating the effect of anisotropy, and the behavior of loose and dense sands under drained and undrained loading.     

液晶高分子各向异性粘弹性流体本构方程理论

将液晶高分子－各向异性流体的本构方程,建立在Oldroyd随体导数观点基础上。推广上随机Oldroyd B流体模型,提出共转OldroydB流体模型,同时将微观结构的影响通过宏观参数表示出来,使在宏观理论中包含微观结构的贡献,即引入取向物质函数,非线性各向异性黏度函数和各向异性松弛时间及推迟时间等,表征取向运动对黏度和松弛及推迟现象的影响,在此基础上开展了一类新的液晶高分子－Oldroyd型本构方程理论,由该类型本构方程得出的物质函数,液晶高分子流体的第一、第二法向应力差与实验结果一致,解释了液晶高分子溶液的第一、第二法向应力差的特殊流变学行为。     

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.     

A unified model for polystyrene–nanorod and polystyrene–nanoplatelet melt composites

We present a unified constitutive model capable of predicting the steady shear rheology of polystyrene (PS)–nanoparticle melt composites, where particles can be rods, platelets, or any geometry in between, as validated against experimental measurements. The composite model incorporates the rheological properties of the polymer matrix, the aspect ratio and characteristic length scale of the nanoparticles, the orientation of the nanoparticles, hydrodynamic particle–particle interactions, the interaction between the nanoparticles and the polymer, and flow conditions of melt processing. We demonstrate that our constitutive model predicts both the steady rheology of PS–carbon nanofiber composites and the steady rheology of PS–nanoclay composites. Along with presenting the model and validating it against experimental measurements, we evaluate three different closure approximations, an important constitutive assumption in a kinetic theory model, for both polymer–nanoparticle systems. Both composite systems are most accurately modeled with a quadratic closure approximation.     

Steady spinning of the Oldroyd fluid B II: Experimental results

Isothermal fiber-spinning results have been obtained for an 1850 ppm solution of polyisobutylene with a constant viscosity of 360 poise and a relaxation time of 0.824 s. The steady and dynamic shear properties of this Boger fluid are well described by the Oldroyd B constitutive equation for shear rates less than 10 s⁻¹. Velocity profiles and spinline stresses were measured for a variety of fiber drawdown ratios, spinline lengths and for shear rates within the range of applicability of the Oldroyd B model. The results are compared with the theory developed in Part I [4], and excellent agreement is obtained when the effects of gravity were propertly taken into account. Indeed, this is the first time that the correct stress levels in the extensional flow of a highly viscoelastic polymer solution have been predicted from a knowledge of viscometric data alone using a simple three-parameter constitutive equation.     

Constitutive equation of co-rotational derivative type for anisotropic-viscoelastic fluid

A constitutive equation theory of Oldroyd fluid B type, i.e. the co-rotational derivative type, is developed for the anisotropic-viscoelastic fluid of liquid crystalline (LC) polymer. Analyzing the influence of the orientational motion on the material behavior and neglecting the influence, the constitutive equation is applied to a simple case for the hydrodynamic motion when the orientational contribution is neglected in it and the anisotropic relaxation, retardation times and anisotropic viscosities are introduced to describe the macroscopic behavior of the anisotropic LC polymer fluid. Using the equation for the shear flow of LC polymer fluid, the analytical expressions of the apparent viscosity and the normal stress differences are given which are in a good agreement with the experimental results of Baek et al. For the fiber spinning flow of the fluid, the analytical expression of the extensional viscosity is given. The project supported by the National Natural Science Foundation of China (19832050 and 10372100)     

Convection and diffusion of polymer network strands

A review of several important constitutive equations is herein conducted with an eye towards determining those most suitable for use in modelling polymer melt processing. General principles are invoked for a priori screening of the equations without needing detailed comparison of the model predictions with experimental data. These principles, which are derived from continuum mechanics, thermodynamics and molecular kinetic theory, and dela with convection and diffusion of entangled polymer strands during flow, are: (1) During sudden deformations, the stress is a unique function of the total strain. (2) The second law of thermodynamics holds for all deformations. (3) The constitutive equation can be derived from a plausible molecular model which describes the convection and diffusion. (4) The model parameters can be determined by a reasonable number of rheometric experiments. Based on these principles, it is concluded that separable free energy models are the most promising. These are either BKZ integral models with a kernel factorable into a time-dependent and a strain-dependent part. or sets of Maxwell-type differential equations that employ a generalized convected derivative, and that are linear in stress in the absence of flow.     

Multi-scale micromorphic theory for hierarchical materials

For the design of materials, it is important to faithfully model macroscopic materials response together with mechanisms and interactions occurring at the microstructural scales. While brute-force modeling of all the details of the microstructure is too costly, many of the current homogenized continuum models suffer from their inability to capture the correct underlying deformation mechanisms—especially when localization and failure are concerned. To overcome this limitation, a multi-scale continuum theory is proposed so that kinematic variables representing the deformation at various scales are incorporated. The method of virtual power is then used to derive a system of coupled governing equations, each representing a particular scale and its interactions with the macro-scale. A constitutive relation is then introduced to preserve the underlying physics associated with each scale. The inelastic behavior is represented by multiple yield functions, each representing a particular scale of microstructure, but collectively coupled through the same set of internal variables. The theory is illustrated by two applications. First, a one-dimensional example of a three-scale material is presented. After the onset of softening, the model shows that the localization zone is distributed according to two distinct length scale determined by the model. Second, a two-scale continuum model is introduced for the failure of porous metals. By comparing the theory to a direct numerical simulation (DNS) of the microstructure for a specimen in tension, we show that the model capture the main physics, and at the same time, remains computationally affordable.     

A thermo-mechanically coupled theory for fluid permeation in elastomeric materials: Application to thermally responsive gels

An elastomeric gel is a cross-linked polymer network swollen with a solvent, and certain gels can undergo large reversible volume changes as they are cycled about a critical temperature. We have developed a continuum-level theory to describe the coupled mechanical deformation, fluid permeation, and heat transfer of such thermally responsive gels. In discussing special constitutive equations we limit our attention to isotropic materials, and consider a model 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. We have numerically implemented our theory in a finite element program. We show that our theory is capable of simulating swelling, squeezing of fluid by applied mechanical forces, and thermally responsive swelling/de-swelling of such materials.     

一种黏弹塑性统一本构模型

经过对大量有关统一本构模型的文献资料分析，指出了现有统一本构模型存在的问题，并通过对材料实验数据的分析，指出了黏弹性现象在实验中的表现，并据此将黏弹性引入到弹性黏塑性统一本构模型之中，建立了黏弹塑性统一本构模型，通过模型的数值模拟证明：模型计算结果无论在变形趋势上，还是在数值精度上都与实验数据符合得很好，克服了此前统一本构模型存在的问题。黏弹塑性统一本构模型的产生将统一本构模型的产生将统一本构理论的内涵扩大到黏弹性范围，进而构造了一个黏弹塑性理论的新框架。