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.     

Thermomechanics of shape memory polymers: Uniaxial experiments and constitutive modeling

Shape memory polymers (SMPs) can retain a temporary shape after pre-deformation at an elevated temperature and subsequent cooling to a lower temperature. When reheated, the original shape can be recovered. Relatively little work in the literature has addressed the constitutive modeling of the unique thermomechanical coupling in SMPs. Constitutive models are critical for predicting the deformation and recovery of SMPs under a range of different constraints. In this study, the thermomechanics of shape storage and recovery of an epoxy resin is systematically investigated for small strains (within ±10%) in uniaxial tension and uniaxial compression. After initial pre-deformation at a high temperature, the strain is held constant for shape storage while the stress evolution is monitored. Three cases of heated recovery are selected: unconstrained free strain recovery, stress recovery under full constraint at the pre-deformation strain level (no low temperature unloading), and stress recovery under full constraint at a strain level fixed at a low temperature (low temperature unloading). The free strain recovery results indicate that the polymer can fully recover the original shape when reheated above its glass transition temperature (T_g). Due to the high stiffness in the glassy state (T < T_g), the evolution of the stress under strain constraint is strongly influenced by thermal expansion of the polymer. The relationship between the final recoverable stress and strain is governed by the stress–strain response of the polymer above T_g. Based on the experimental results and the molecular mechanism of shape memory, a three-dimensional small-strain internal state variable constitutive model is developed. The model quantifies the storage and release of the entropic deformation during thermomechanical processes. The fraction of the material freezing a temporary entropy state is a function of temperature, which can be determined by fitting the free strain recovery response. A free energy function for the model is formulated and thermodynamic consistency is ensured. The model can predict the stress evolution of the uniaxial experimental results. The model captures differences in the tensile and compressive recovery responses caused by thermal expansion. The model is used to explore strain and stress recovery responses under various flexible external constraints that would be encountered in applications of SMPs.     

Constitutive modeling of shape memory polymer based self-healing syntactic foam

In a previous study, it was found that the shape memory functionality of a shape memory polymer based syntactic foam can be utilized to self-seal impact damage repeatedly, efficiently, and almost autonomously [Li G., John M., 2008. A self-healing smart syntactic foam under multiple impacts. Comp. Sci. Technol. 68(15–16), 3337–3343]. The purpose of this study is to develop a thermodynamics based constitutive model to predict the thermomechanical behavior of the smart foam. First, based on DMA tests and FTIR tests, the foam is perceived as a three-phase composite with interfacial transition zone (interphase) coated microballoons dispersed in the shape memory polymer (SMP) matrix; for simplicity, it is assumed to be an equivalent two-phase composite by dispersing elastic microballoons into an equivalent SMP matrix. Second, the equivalent SMP matrix is phenomenologically assumed to consist of an active (rubbery) phase and a frozen (glassy) phase following Liu et al. [Liu, Y., Gall, K., Dunn, M.L., Greenberg, A.R., Diani J., 2006. Thermomechanics of shape memory polymers: uniaxial experiments and constitutive modeling. Int. J. Plasticity 22, 279–313]. The phase transition between these two phases is through the change of the volume fraction of each phase and it captures the thermomechanical behavior of the foam. The time rate effect is also considered by using rheological models. With some parameters determined by additional experimental testing, the prediction by this model is in good agreement with the 1D test result found in the literature. Parametric studies are also conducted using the constitutive model, which provide guidance for future design of this novel self-healing syntactic foam and a class of light-weight composite sandwich structures.     

A finite deformation thermomechanical constitutive model for triple shape polymeric composites based on dual thermal transitions

Shape memory polymers (SMPs) have gained strong research interests recently due to their mechanical action that exploits their capability to fix temporary shapes and recover their permanent shape in response to an environmental stimulus such as heat, electricity, irradiation, moisture or magnetic field, among others. Along with interests in conventional “dual-shape” SMPs that can recover from one temporary shape to the permanent shape, multi-shape SMPs that can fix more than one temporary shapes and recover sequentially from one temporary shape to another and eventually to the permanent shape, have started to attract increasing attention. Two approaches have been used to achieve multi-shape shape memory effects (m-SMEs). The first approach uses polymers with a wide thermal transition temperature whilst the second method employs multiple thermal transition temperatures, most notably, uses two distinct thermal transition temperatures to obtain triple-shape memory effects (t-SMEs). Recently, one of the authors’ group reported a triple-shape polymeric composite (TSPC), which is composed of an amorphous SMP matrix (epoxy), providing the system the rubber-glass transition to fix one temporary shape, and an interpenetrating crystallizable fiber network (PCL) providing the system the melt-crystal transition to fix the other temporary shape. A one-dimensional (1D) material model developed by the authors revealed the underlying shape memory mechanism of shape memory behaviors due to dual thermal transitions. In this paper, a three-dimension (3D) finite deformation thermomechanical constitutive model is presented to enable the simulations of t-SME under more complicated deformation conditions. Simple experiments, such as uniaxial tensions, thermal expansions and stress relaxation tests were carried out to identify parameters used in the model. Using an implemented user material subroutine (UMAT), the constitutive model successfully reproduced different types of shape memory behaviors exhibited in experiments designed for shape memory behaviors. Stress distribution analyses were performed to analyze the stress distribution during those different shape memory behaviors. The model was also able to simulate complicated applications, such as a twisted sheet and a folded stick, to demonstrate t-SME.     

A three-dimensional model of the thermomechanical behavior of shape memory alloys

A new macro-scale model of shape memory alloys is developed within the framework of generalized standard materials with internal constraints [Moumni, Z., 1995. Sur la modélisation du changement de phase à l’état solide. Ph.D. Thesis, École Nationale Supérieure des Ponts et Chaussées]. It is shown that the introduction of two state variables: the martensite volume fraction and the martensite orientation strain tensor, is sufficient to account for several effects exhibited by SMAs subject to thermomechanical loading, namely: self-accommodation, orientation and reorientation or martensite, as well as superelasticity and one-way shape memory. These phenomena are simulated using the same set of constitutive equations and evolution laws. A simple procedure for identifying the parameters of the model is described in detail and a validation against experimental data is conducted. The model is then used to analyze a 3D SMA structure representing a superelastic stent. Cyclic loading and other pertaining phenomena like training and two-way shape memory are considered in the second part of this paper.     

Thermomechanical behavior of thermoset shape memory polymer programmed by cold-compression: Testing and constitutive modeling

Programming is a key process for thermally activated stress or strain recovery of shape memory polymers (SMPs). Typically, programming requires an initial heating above the glass transition temperature (T_g), subsequent cooling below T_g and removal of the applied load, in order to fix a temporary shape. This work adopted a new approach to program thermoset SMPs directly at temperatures well below T_g, which effectively simplified the shape fixing process. 1-D compression programming below T_g and free shape recovery of a thermoset SMP were experimentally investigated. Functional stability of the shape fixity under various environmental attacks was also experimentally evaluated. A mechanism-based thermoviscoelastic-thermoviscoplastic constitutive model incorporating structural and stress relaxation was then developed to predict the nonlinear shape memory behavior of the SMP trained below T_g. Comparison between the prediction and the experiment showed good agreement. The structure dependence of the thermomechanical behavior of the SMP was further discussed through a parametric study per the validated constitutive model. This study validates that programming by cold-compression is a viable alternative for thermally responsive thermoset SMPs.     

NiTi形状记忆合金裂纹尖端热力耦合行为研究

本文对NiTi形状记忆合金I型裂纹尖端热力耦合行为进行了数值仿真分析和实验验证。建立了包含相变和热力耦合的本构模型,通过有限元计算得到了裂纹尖端附近的纵向应变、马氏体体积分数和温度场分布,依据马氏体相变情况对裂纹尖端有效应力强度因子进行了修正,揭示了加载速率对形状记忆合金裂纹尖端有效应力强度影子的影响规律。参数研究表明,随着加载频率的增加,裂纹尖端附近温度逐渐升高,马氏体相变区域逐渐缩小,有效应力强度因子呈下降趋势,形状记忆合金表现出增韧效应,有助于减缓裂纹扩展。本研究结果对于揭示热力耦合作用下超弹性形状记忆合金疲劳裂纹扩展规律具有重要参考意义。     

Bubbles in liquids with phase transition

In the forthcoming second part of this paper a system of balance laws for a multi-phase mixture with many dispersed bubbles in liquid is derived where phase transition is taken into account. The exchange terms for mass, momentum and energy explicitly depend on evolution laws for total mass, radius and temperature of single bubbles. Therefore in the current paper we consider a single bubble of vapor and inert gas surrounded by the corresponding liquid phase. The creation of bubbles, e.g. by nucleation is not taken into account. We study the behavior of this bubble due to condensation and evaporation at the interface. The aim is to find evolution laws for total mass, radius and temperature of the bubble, which should be as simple as possible but consider all relevant physical effects. Special attention is given to the effects of surface tension and heat production on the bubble dynamics as well as the propagation of acoustic elastic waves by including slight compressibility of the liquid phase. Separately we study the influence of the three phenomena heat conduction, elastic waves and phase transition on the evolution of the bubble. We find ordinary differential equations that describe the bubble dynamics. It turns out that the elastic waves in the liquid are of greatest importance to the dynamics of the bubble radius. The phase transition has a strong influence on the evolution of the temperature, in particular at the interface. Furthermore the phase transition leads to a drastic change of the water content in the bubble. It is shown that a rebounding bubble is only possible, if it contains in addition an inert gas. In Part 2 of the current paper the equations derived are sought in order to close the system of equations for multi-phase mixture balance laws for dispersed bubbles in liquids involving phase change.     

On the thermomechanical modeling of shape memory alloys

In this work, a general inelastic framework for the derivation of general three-dimensional thermomechanical constitutive laws for materials undergoing phase transformations is proposed. The proposed framework is based on the generalized plasticity theory and on some basic elements from the theory of continuum damage mechanics. More specifically, a new elaborate formulation of generalized plasticity theory capable of accommodating the multiple and interacting loading mechanisms, which occur during the phase transformations, is developed. Furthermore, the stiffness variations occurring during phase transformations are taken into account by the proposed framework. For this purpose, the free energy is decomposed into elastic and inelastic parts, not in a conventional way, but in one which resembles the elastic-damage cases. Also, a rate-dependent version of the theory is provided. The concepts presented are applied for the derivation of a three-dimensional thermomechanical constitutive model for Shape Memory Alloy materials. Numerical simulations to show qualitatively the ability of the model to capture the behavior of the shape memory alloys are also presented. Furthermore, the model has been fitted to actual experimental results from the literature.     

A thermodynamic finite-strain model for pseudoelastic shape memory alloys

A thermodynamic finite-strain model describing the pseudoelastic response of shape memory alloys is proposed. The model is based on a self-consistent Eulerian theory of finite deformations using the logarithmic rate. Purely elastic material response is derived from a hyperelastic potential. The mass fraction of martensite is introduced as internal state variable to indicate the thermomechanical state of the phase transforming material. The evolution of martensite is governed by a kinetic law which is derived from the Helmholtz free energy of the two-phase solid and takes the heat generated during phase transition into account. The material model is implemented into a finite element code in an updated Lagrangian scheme and calibrated to experimental data. Simulations under different loading conditions illustrate the characteristics of the model.     

RENEWAL OF BASIC LAWS AND PRINCIPLES FOR POLAR CONTINUUM THEORIES (Ⅳ)--SURFACE COUSERVATION LAWS

The purpose is to reestablish rather complete surface conservation laws for micropolar thermomechanical continua from the translation and the rotation invariances of the general balance law. The generalized energy-momentum and energy-moment of momentum tensors are presented. The concrete forms of surface conservation laws for micropolar thermomechanical continua are derived . The existing related results are naturally derived as special cases from the results proposed in this paper . The incomplete degrees of the existing surface conservation laws are clearly seen from the process of the deduction. The surface conservation laws for nonlocal micropolar thermomechanical continua may be easily obtained via localization .     

Phase proportioning in CuAlBe shape memory alloys during thermomechanical loadings using electric resistance variation

The microstructure of shape memory alloys changes with the thermomechanical history of the material. During thermomechanical loading, austenite, thermally-induced martensite or stress-induced martensite can be simultaneously present in the material. In applications integrating SMA parts, utilization conditions seriously affect the microstructure and can generate macroscopic strain or stress. Consequently, during thermomechanical loadings, it is important to be able to proportion the different phases and consequently to understand the kinetic transformation. This is very useful in the development of constitutive equations. This study shows, by a series of tests, that the proposed experimental method, based on the measurement of the variation of electric resistance of CuAlBe wires, permits to determine the volume fraction of the different phases present in the material (i.e., austenite, stress-induced martensite and thermally-induced martensite). The proposed method is applied to the most common thermomechanical behavior met in engineering applications of shape memory alloys: pseudoelasticity, pseudoplasticity, recovery-stress and stress-assisted two-way shape memory effect. The proportioning method based on a mixture law integrating the resistivity of pure phases present in the SMA is first performed on different two-phase mixture cases and then applied to a three phase mixture case.     

Differential and integrated form consistency in 1-D phenomenological models for shape memory alloy constitutive behavior

Shape memory alloys are being explored increasingly for developing smart structures and devices in aerospace, automotive and other application areas. The material behavior is highly nonlinear with coupled thermomechanical response involving temperature and/or stress induced phase transformations. Modeling the constitutive behavior of these materials poses several challenges and a few phenomenological models exist that provide a quick and reasonable approach to assess their behavior. Due to phenomenological approach, several assumptions are made in order to simplify the model and some of them introduce inconsistencies or anomalies into the model. In this paper, a frequently used approach, namely, Brinson [Brinson, L.C., 1993. One dimensional constitutive behavior of shape memory alloys: thermomechanical derivation with non-constant material functions and redefined martensite internal variable. J. Intell. Mater. Syst. Struct. 4(2), 229–242.] model, is investigated. The constitutive equation is usually expressed at the outset in the differential form and the integrated form of the same is obtained. It is shown that the two forms of equations are not consistent in the Brinson [Brinson, L.C., 1993. One dimensional constitutive behavior of shape memory alloys: thermomechanical derivation with non-constant material functions and redefined martensite internal variable. J. Intell. Mater. Syst. Struct. 4(2), 229–242.] model, given the assumed form of material functions. In the present work, the nature and implications of the inconsistency are highlighted. The cause of incompatibility is the inconsistent material definitions. A modified consistent constitutive model is proposed by redefining the material function which satisfies the compatibility condition. The advantages in using the proposed modified model are highlighted with numerical case studies involving hysteretic stress–strain behavior.     

A thermomechanical model for the analysis of light alloy solidification in a composite mould

A coupled thermomechanical model to simulate light alloy solidification problems in permanent composite moulds is presented. This model is based on a general isotropic thermoelasto-plasticity theory and considers the different thermomechanical behaviours of each component of the mould as well as those of the solidifying material during its evolution from liquid to solid. To this end, plastic evolution equations, a phase-change variable and a specific free energy function are proposed in order to derive temperature-dependent material constitutive laws.The corresponding finite element formulation and the staggered scheme used to solve the coupled non-linear system of equations are also presented. Finally, the temperature and displacement predictions of the model are validated with laboratory measurements obtained during an experimental trial.     

Micromechanical modeling of stress-induced phase transformations. Part 1. Thermodynamics and kinetics of coupled interface propagation and reorientation

The universal (i.e. independent of the constitutive equations) thermodynamic driving force for coherent interface reorientation during first-order phase transformations in solids is derived for small and finite strains. The derivation is performed for a representative volume with plane interfaces, homogeneous stresses and strains in phases and macroscopically homogeneous boundary conditions. Dissipation function for coupled interface (or multiple parallel interfaces) reorientation and propagation is derived for combined athermal and drag interface friction. The relation between the rates of single and multiple interface reorientation and propagation and the corresponding driving forces are derived using extremum principles of irreversible thermodynamics. They are used to derive complete system of equations for evolution of martensitic microstructure (consisting of austenite and a fine mixture of two martensitic variants) in a representative volume under complex thermomechanical loading. Viscous dissipation at the interface level introduces size dependence in the kinetic equation for the rate of volume fraction. General relationships for a representative volume with moving interfaces under piece-wise homogeneous boundary conditions are derived. It was found that the driving force for interface reorientation appears when macroscopically homogeneous stress or strain are prescribed, which corresponds to experiments. Boundary conditions are satisfied in an averaged way. In Part 2 of the paper [Levitas, V.I., Ozsoy, I.B., 2008. Micromechanical modeling of stress-induced phase transformations. Part 2. Computational algorithms and examples. Int. J. Plasticity (2008)], the developed theory is applied to the numerical modeling of the evolution of martensitic microstructure under three-dimensional thermomechanical loading during cubic-tetragonal and tetragonal-orthorhombic phase transformations.     

Engineering models for synthetic microvascular materials with interphase mass,momentum and energy transfer

New materials are being developed that consist of a solid matrix with pores or vessels through which a functional fluid phase may pass. The fluid can provide expanded functionality such as healing and remodeling, damage disclosure, enhanced heat transfer, and controlled deformation, stiffness and damping. This paper presents a class of engineering models for synthetic microvascular materials that have fluid passages much smaller than a characteristic structural length such as panel thickness. The materials are idealized as two-phase continua with a solid phase and a fluid phase occupying every volume. The model permits the solid and fluid phases to exchange mass, momentum and energy. Balance equations and the entropy inequality for general mixtures are taken from existing continuum mixture theory. These are augmented with certain definite types of solid–fluid interactions in order to enable adequately general, but workable, engineering analysis. The thermomechanical characteristics of this restricted class of materials are delineated. By demanding that the law of increase of entropy be satisfied for all processes, much is deduced about the acceptable forms of constitutive equations and internal state variable evolution equations. The paper concludes with a study of the uniaxial tension behavior of an idealized vascular material.     

A phenomenological description of shape memory alloy transformation induced plasticity

Transformation induced plasticity is defined as the plastic flow arising from solid state phase transformation processes involving volume and/or shape changes without overlapping the yield surface. This phenomenon occurs in shape memory alloys (SMAs) having significant influence over their macroscopic thermomechanical behavior. This contribution presents a macroscopic three-dimensional constitutive model to describe the thermomechanical behavior of SMAs including classical and transformation induced plasticity. Comparisons between numerical and experimental results attest the model capability to capture plastic phenomena. Both uniaxial and multiaxial simulations are carried out.