On thermodynamic potentials in thermoelasticity under small strain and finite thermal perturbation assumptions

Expressions for thermodynamic potentials (internal energy, Helmholtz energy, Gibbs energy and enthalpy) of a thermoelastic material are developed under the assumption of small strains and finite changes in the thermal variable (temperature or entropy). The literature provides expressions for the Helmholtz energy in terms of strain and temperature, most often as expansions to the second order in strain and to a higher order in temperature changes, which ensures an affine stress–strain relation and a certain temperature dependence of the moduli of the material. Expressions are here developed for the four potentials in terms of all four possible pairs of independent variables. First, an expression is obtained for each potential as a quadratic function of its natural mechanical variable with coefficients depending on its natural thermal variable that are identified in terms of the moduli of the material. The form of the coefficients’ dependence on the thermal variable is not specified beforehand so as to obtain the most general expressions compatible with an affine stress–strain relation. Then, from each potential expressed in terms of its natural variables, expressions are derived for the other three potentials in terms of these same variables using the Gibbs–Helmholtz equations. The paper provides a thermodynamic framework for the constitutive modeling of thermoelastic materials undergoing small strains but finite changes in the thermal variables, the properties of which are liable to depend on the thermal variables.     

Representation of the glass-transition in mechanical and thermal properties of glass-forming materials: A three-dimensional theory based on thermodynamics with internal state variables

In the vicinity of the glass transition, glass-forming materials exhibit pronounced frequency-dependent changes in the mechanical material properties, the thermal expansion behaviour and the specific heat. The frequency dependence becomes apparent under harmonic stress, strain or temperature excitations. The Prigogine-Defay ratio is a characteristic number which connects the changes in magnitude of these quantities at the glass transition. In order to represent the thermoviscoelastic properties of glass-forming materials in continuum mechanics, a three-dimensional approach which is based on the Gibbs free energy as thermodynamic potential is developed in this article. The Gibbs free energy depends on the stress tensor, the temperature and a set of internal variables which is introduced to take history-dependent phenomena into account. In the vicinity of an equilibrium reference state, the specific Gibbs free energy is approximated up to second order terms. Evaluating the Clausius-Duhem inequality, the constitutive relations for the strain tensor, the entropy and the internal variables are derived. In comparison with other approaches, the entropy, the strain tensor and the internal variables are functionals not only of the stress tensor but also of the temperature. Applying harmonic temperature- or stress-controlled excitations, complex frequency-dependent relations for the specific heat under constant stress, for the thermal expansion coefficients as well as for the dynamic mechanical compliance are obtained. The frequency-dependence of these quantities depicts the experimentally observed behaviour of glass-forming materials as published in literature. Under the assumption of isotropic material behaviour, it is shown that the developed theory is compatible with the Prigogine-Defay inequality for arbitrary values of the material parameters.     

Thermomechanical material modelling based on a hybrid free energy density depending on pressure,isochoric deformation and temperature

In order to represent temperature-dependent mechanical material properties in a thermomechanical consistent manner it is common practice to start with the definition of a model for the specific Helmholtz free energy. Its canonical independent variables are the Green strain tensor and the temperature. But to represent calorimetric material properties under isobaric conditions, for example the exothermal behaviour of a curing process or the dependence of the specific heat on the temperature history, the temperature and the pressure should be taken as independent variables. Thus, in the field of calorimetry the Gibbs free energy is usually used as thermodynamic potential whereas in continuum mechanics the Helmholtz free energy is normally applied. In order to simplify the representation of calorimetric phenomena in continuum mechanics a hybrid free energy density is introduced. Its canonical independent variables are the isochoric Green strain tensor, the pressure and the temperature. It is related to the Helmholtz free energy density by a Legendre transformation. In combination with the additive split of the stress power into the sum of isochoric and volumetric terms this approach leads to thermomechanical consistent constitutive models for large deformations. The article closes with applications of this approach to finite thermoelasticity, curing adhesives and the glass transition.     

Micromechanics of ferroelectric domain switching behavior: Part II: Constitutive relations and hysteresis

A constitutive relation is developed to describe the nonlinear behavior of ferroelectric ceramics subjected to external stress and electric field. The theoretical development considers each domain as an inclusion. The Helmholtz and Gibbs free energy of the constituent element are derived by using a micromechanics approach. They are functionals of the orientation distribution function (ODF) that represents the domain distribution patterns. By applying the internal variable theory and expanding ODF in Fourier series, the yield condition, evolution of ODF, and constitutive relation are obtained. Theoretical results agree with experiments.     

A model for twinning

The modelling of twins in crystals with strain gradient theories provides interesting problems both in thermodynamics and in the calculus of variations. Here, Dunn and Serrin's thermomechanical theory of interstitial working is used to obtain a variational principle that governs the equilibria of materials with non-convex Helmholtz free energy. In some geometries, this principle reduces to a novel calculus of variations problem; an example is described in which symmetry-related uniform equilibrium states can be connected by nonconstant extremals which realiselocal minima of the free energy. Certain implications of different definitions of local minima are also discussed.     

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.     

PETN、RDX和HMX炸药爆轰参数的数值模拟

用吉布斯自由能最小原理,通过解化学平衡方程组,求解PETN、RDX和HMX炸药爆轰产物系统的平衡组分,计算结果与用BKW和LJD方法计算的结果相近。用自编的程序从碳的石墨相、金刚石相、类石墨液相和类金刚石液相4种相态中确定出炸药爆轰产物中游离碳更可能存在的相态,并用此相态计算碳的吉布斯自由能。以WCA状态方程作为爆轰气相产物的物态方程,对PETN、RDX和HMX炸药爆轰参数作了预言,爆轰CJ点的爆速、爆压和爆温的计算结果与实验值吻合得很好。     

Thermomechanical modeling of nonlinear internal hysteresis due to incomplete phase transformation in pseudoelastic shape memory alloys

This paper presents a thermomechanical model for pseudoelastic shape memory alloys (SMAs) accounting for internal hysteresis effect due to incomplete phase transformation. The model is developed within the finite-strain framework, wherein the deformation gradient is multiplicatively decomposed into thermal dilation, rigid body rotation, elastic and transformation parts. Helmholtz free energy density comprises three components: the reversible thermodynamic process , the irreversible thermodynamic process and the physical constraints of both. In order to capture the multiple internal hysteresis loops in SMA, two internal variables representing the transition points of the forward and reverse phase transformation, \(\phi _s^f\) and \(\phi _s^r\), are introduced to describe the incomplete phase transformation process. Evolution equations of the internal variables are derived and linked to the phase transformation. Numerical implementation of the model features an Euler discretization and a cutting-plane algorithm. After validation of the model against the experimental data, numerical examples are presented, involving a SMA-based vibration system and a crack SMA specimen subjected to partial loading–unloading case. Simulation results well demonstrate the internal hysteresis and free vibration behavior of SMA.

     

A thermodynamic theory of damage in elastic inorganic and organic solids

This contribution presents the foundations of a thermodynamic theory of damage in elastic solids, developed in collaboration with the late J. Kestin and with E. Honein and T. Honein. The theory is rooted in the so-called conservative or conventional thermodynamics of irreversible processes, where the concept of a local thermodynamic state plays a prominent role. An elastic body prone to damage is regarded as a thermodynamic system characterized by a set of extensive variables that can be defined in both equilibrium and nonequilibrium states and assigned approximately the same values in both the physical space and the abstract state space (i.e., the Gibbsian phase space of constrained equilibria). The extensive variables introduced include internal parameters which describe the damaged state of the body and whose conjugate intensive variables, or affinities, constitute a generalization of Eshelby’s concept of a “force on an elastic singularity”. The local state approximation is applied by assigning to the entropy and temperature in physical space local values which can be calculated in the Gibbsian phase space by the well-established methods of equilibrium thermodynamics. This leads to an explicit expression for the entropy production. The rate equations for the damage are then postulated in such a way as to conform to the second part of the second law of thermodynamics. The resulting theory captures many features of real inorganic material behavior in which no mass loss is sustained. By contrast, damage of organic materials, such as compact bone subject to osteoporosis, is accompanied by bone mass loss. This feature can be accommodated in the theory proposed by a suitable adjustment of the expression of the Gibbs free energy.     

A Classification of thermodynamical potentials for two-variable transition systems

We suggest here a possible classification of the thermodynamical potentials for phase transition systems with two state variables. Within each of the single-typed classes, the characters and typical diagrams of the internal energy, enthalpy, Helmholtz and Gibbs free energy are shown. Multivalued potentials appear to be the rules rather than the exceptions. Several known examples of phase transitions, e.g. van der Waals gas, Landau-Devonshire model, are studied within the framework of the present classification.

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Sommario II lavoro suggerisce una possibile classificazione dei potenziali termodinamici per sistemi con due variabili di stato soggetti a transizioni di fase e, per ogni classe individuata, mostra le caratteristiche e i diagrammi tipici dell'energia interna, l'entalpia, le energie libere di Helmholtz e Gibbs. Potenziali termodinamici a più valori appaiono essere la regola più che l'eccezione. Nell'ambito della classificazione trovata sono studiati vari esempi noti, come il gas di van der Waals e il modello di Landau-Devonshire.

     

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.     

Variational asymptotic homogenization of temperature-dependent heterogeneous materials under finite temperature changes

The variational asymptotic method is used to construct a thermomechanical model for homogenizing heterogeneous materials made of temperature-dependent constituents subject to finite temperature changes with the restriction that the strain is small. First, we presented the derivation for a Helmholtz free energy suitable for finite temperature changes using basic thermodynamics concepts. Then we used this energy to construct a thermomechanical micromechanics model, extending our previous work which was restricted to small temperature changes. The new model is implemented in the computer code VAMUCH using the finite element method for the purpose of handling real heterogeneous materials with arbitrary periodic microstructures. A few examples including binary composites, fiber reinforced composites, and particle reinforced composites are used to demonstrate the application of this model and the errors introduced by assuming small temperature changes when they are not necessarily small.     

Theoretical derivation of the conservation equations for single phase flow in porous media: a continuum approach

This paper deals with the theoretical derivation of the conservation equations for single phase flow in a porous medium. The derivation is obtained within the framework of the continuum mechanics and classical thermodynamics. The adopted procedure provides the conservation equations of mass, momentum, mechanical energy, total energy, internal energy, entropy, temperature, enthalpy, Gibbs free energy and Helmholtz free energy. The obtained results highlight the connection between the basic equations of fluid mechanics and of fluid flow in porous media, as well as the restrictions and the limitations of Darcy’s law and Richards’ equation.     

Thermo-Mechanically Coupled Thermo-Elasto-Visco-Plastic Modeling of Thermo-Induced Shape Memory Polyurethane at Finite Deformation

A series of mono tonic tensile experiments of thermo-induced shape memory polyurethane(TSMPU) at different loading rates were carried out to investigate the interaction between the internal heat production and the mechanical deformation. It is shown that the temperature variation on the surfaces of the specimens due to the internal heat production affects the mechanical properties of TSMPU remarkably. Then, based on irreversible thermodynamics, the Helmholtz free energy was decomposed into three parts, i.e., the instantaneous elastic free energy,visco-plastic free energy and heat free energy. The total deformation gradient was decomposed into the mechanical and thermal parts, and the mechanical deformation gradient was further divided into the elastic and visco-plastic components. The Hencky's logarithmic strain was used in the current configuration. The heat equilibrium equation of internal heat production and heat exchange was derived in accordance with the first and second thermodynamics laws. The temperature of specimens was contributed by the internal heat, production and the ambient temperature simultaneously, and a thermo-mechanic ally coupled thermo-elas to-visco-plastic model was established. The effect of temperature variation of specimens on the mechanical properties of the material was considered in this work. Finally, the capability of the proposed model was validated by comparing the simulated results with the corresponding experimental data of TSMPU.     

Second gradient viscoelastic fluids: dissipation principle and free energies

We consider a generalization of the constitutive equation for an incompressible second order fluid, by including thermal and viscoelastic effects in the expression for the stress tensor. The presence of the histories of the strain rate tensor and its gradient yields a non-simple material, for which the laws of thermodynamics assume a appropriate modified form. These laws are expressed in terms of the internal mechanical power which is evaluated, using the dynamical equation for the fluid. Generalized thermodynamic constraints on the constitutive equation are presented. The required properties of free energy functionals are discussed. In particular, it is shown that they differ from the standard Graffi conditions. Various free energy functionals, which are well-known in relation to simple materials, are generalized so that they apply to this fluid. In particular, expressions for the minimum free energy and a more recently introduced explicit functional of the minimal state are proposed. Derivations of various formulae are abbreviated if closely analogous proofs already exist in the literature.     

Thermomechanical constitutive equations for the dynamic response of ceramics

The behavior and failure of brittle materials is significantly influenced by the existence of inhomogeneities such as pores and cracks. The proposed constitutive equations model the coupled micro-mechanical response of these inhomogeneities through evolution equations for scalar measures of porosity, and a “density” function of randomly oriented penny-shaped cracks. A specific form for the Helmholtz free energy is proposed which incorporates the known Mie–Grüneisen constitutive equation for the nonporous solid. The resulting thermomechanical constitutive equations are valid for large deformations and the elastic response is hyperelastic in the sense that the stress is related to a derivative of the Helmholtz free energy. These equations allow for the simulation of the following physical phenomena exhibited by brittle materials: (1) high compressive strength compared with much lower tensile strength; (2) inelastic deformation due to growth and nucleation of cracks and pores instead of due to dislocation dynamics associated with metal plasticity; and (3) loss of integrity (degradation of elastic moduli) due to damage accumulation. The main features of the model are demonstrated by examples of cyclic loading in homogeneous deformation and by a simulation of a dynamic plate-impact experiment on AD85 ceramic. The theoretical predictions of the model are in excellent agreement with the dynamic experimental data.     

分析力学方法在平衡态热力学中的应用:分析热力学

分析热力学乃是用分析力学的方法来研究平衡态热力学。本文用较简单的方法证明了“熵最大”变分原理与“Gibbs自由能最小”变分原理或“Helmholtz自由能最小”变分原理是等价的;以这三个Gibbs变分原理为出发点,导出了平衡态热力学的正则方程。由平衡态热力学中的正则方程,可以证明热力学基本Poisson括号成立。本文的另一主要任务是借助于Gibbs变分原理,讨论平衡态热力学中热力学量的正则变换。可以得到热力学正则变换的四种形式。在分析(平衡态)热力学中也可提出“化准Hamiltonian为压强或容积的正则变换技术”。作为应用正则变换的实例,讨论了理想气体并得到了简明的结果。     

A micromechanics constitutive model for pure dilatant martensitic transformation of ZrO2-containing ceramics

A new micromechanics constitutive model for pure dilatant transformation plasticity of structure ceramics is proposed in this paper. Based on the thermodynamics, micromechanics and microscalet→m transformation mechanism analysis of the TZP and PSZ ZrO₂-containing ceramics, an analytic expressions of the Helmholtz and complementary free energy of the constitutive element for the case of pure dilatant transformation is derived for the first time in a self-consistent manner. By the analysis of energy dissipation in the forward and reverse transformations, the micromechanics constitutive law is derived in the framework of Hill-Rice's internal variable constitutive theory. The project is supported by the National Natural Science Foundation of China.