A phase-field model for quasi-incompressible solid–liquid transitions

According to a unified thermodynamic scheme, we derive the general kinetic equation ruling the phase-field evolution in a binary quasi-incompressible mixture for both transition and separation phenomena. When diffusion effects are negligible in comparison with source and production terms, a solid–liquid phase transition induced by temperature and pressure variations is obtained. In particular, we recover the explicit expression of the liquid–pressure curve separating the solid from the liquid stability regions in the pressure–temperature plane. Consistently with physical evidence, its slope is positive (negative) for substances which compress (expand) during the freezing process.     

Structural changes without stable intermediate state in inelastic material. Part II. Applications to displacive and diffusional–displacive phase transformations,strain-induced chemical reactions and ductile fracture

A number of simple examples demonstrate the applicability of the general theory developed in Part I of this paper to various structural changes in solids, namely to displacive and generalized second-order phase transformations, twinning and reorientation of crystal lattice, ductile fracture, and strain-induced chemical reactions. The theory is extended to diffusional-displacive phase transitions. The following problems for elastic and elastoplastic materials are solved analytically: displacive and diffusional–displacive phase transitions in a spherical particle inside the space under external pressure, martensitic phase transition and twinning in ellipsoidal inclusion under applied shear stress, spherical void nucleation, crack propagation in a similar framework to the Dugdale model for a plane stress state. In most cases explicit expressions for the thermodynamic and kinetic conditions for structural changes and the geometric parameters of the nucleus are obtained and analyzed. The following typical cases in the determination of the geometric parameters of nucleus are found: solely from the principle of the minimum of transformation time and the kinetic equation without any constraints or with thermodynamic constraint; from the principle of the minimum of transformation mass and the thermodynamic criterion of structural changes (thermodynamically admissible nucleus); as an interatomic distance. For diffusional–displacive phase transformations, additional variants are related to the necessity to consider the diffusion equation (for the diffusion-controlled transformation) and constraints related to the maximum and minimum possible volume fraction of solute atoms. The nucleation kinetics for various nucleus geometries is compared.     

Nonequilibrium thermodynamics of pseudoelasticity

Solid-solid phase transitions often exhibit hystereses, and a hysteresis indicates energy dissipation. Pseudoelasticity refers to a hysteretic loadingunloading characteristic observed in the stress-induced martensitic transformation of shape memory alloys.This paper describes the thermodynamic model ofideal pseudoelasticity, a largely schematized adaptation of the experimental observations, and it reviews the works of other authors on thermodynamics of pseudoelasticity. Different approaches vary widely and we have chosen to put them into perspective by contrasting their assumptions and predictions against those of ideal pseudoelasticity.Ideal pseudoelasticity receives support from the experimental results of Fu [1] and its thermodynamic properties have been exploited by Huo [2]. The model makes use of an analytical ansatz proposed by Müller [3] in which the hysteresis is assumed to be due to the presence of a coherency energy in solid phase mixtures. This model permits the study of stability of the equilibrium states and the calculation of the energy dissipation or entropy production during the phase transition: The equilibrium states of a phase mixture are found to be unstable in load-controlled processes and the dissipated energy is related to the coherency coefficient.We also discuss some open problems concerning the states inside the hysteresis loop and the formation of interfaces.     

Stability of a two-phase process in an elastic solid

This work investigates the linear stability of an antiplane shear motion which involves a steadily propagating normal planar phase boundary in an arbitrary element of a family of non-elliptic generalized neo-Hookean materials. It is shown that such a process is linearly unstable with respect to a large class of disturbances if and only if the kinetic response function—a constitutively supplied entity which relates the normal velocity of a phase boundary to the driving traction which acts on it—is locally decreasing as a function of the appropriate argument. This result holds whether or not inertial effects are taken into consideration, demonstrating that the linear stability of the relevant process depends entirely upon the transformation kinetics intrinsic to the kinetic response function. The morphological evolution of the interface is then, in an inertia-free setting, tracked for a short time subsequent to the perturbation. It is found that, when the kinetic response function is non-monotonic, the phase boundary can evolve so as to qualitatively resemble the plate-like structures which are found in displacive solid-solid phase transformations.     

An icing physics study by using lifetime-based molecular tagging thermometry technique

An experimental investigation was conducted to quantify the unsteady heat transfer and phase changing process within small icing water droplets in order to elucidate underlying physics to improve our understanding of the important micro-physical process of icing phenomena. A novel, lifetime-based molecular tagging thermometry (MTT) technique was developed and implemented to achieve temporally-and-spatially resolved temperature distribution measurements to reveal the time evolution of the unsteady heat transfer and dynamic phase changing process within micro-sized water droplets in the course of icing process. It was found that, after a water droplet impinged onto a frozen cold surface, the liquid water at the bottom of the droplet would be frozen and turned to solid ice rapidly, while the upper portion of the droplet was still in liquid state. As the time goes by, the interface between the liquid phase water and solid phase ice was found to move upward continuously with more and more liquid water within the droplet turned to solid ice. Interestingly, the averaged temperature of the remaining liquid water within the small icing droplet was found to increase, rather than decrease, continuously in the course of icing process. The temperature increase of the remaining liquid water is believed to be due to the heat release of the latent heat during solidification process. The volume expansion of the water droplet during the icing process was found to be mainly upward to cause droplet height growth rather than radial to enlarge the contact area of the droplet on the test plate. As a result, the spherical-cap-shaped water droplet was found to turn to a prolate-spheroid-shaped ice crystal with cusp-like top at the end of the icing process. The required freezing time for the water droplets to turn to ice crystals completely was found to depend on the surface temperature of the test plate strongly, which would decrease exponentially as the surface temperature of the frozen cold test plate decreases.     

On the longitudinal impact of two phase transforming bars. Elastic versus a rate-type approach. Part II: The rate-type case

We study the propagation of phase transformation fronts induced by the longitudinal impact of two shape memory alloy bars modeled by a general form of a rate-type approach to non-monotone elasticity. We illustrate that such a rate-type law should be seen like a kinetic law for phase transformation. This investigation continues in a comparative way the analysis of the dynamic theory of elastic bar considered in Part I in relation with a viscosity criterion. We focus here on mathematical, thermodynamical and experimental aspects related with the wave structure which accompanies both the forward and reverse transformation. We analyze the propagation of disturbances in a pure phase near and far from their sources, that is the instantaneous waves and the delayed waves as well as the traveling wave solutions and the accompanying dissipation. In the numerical experiments one focuses on the influence of the impact velocity on the way the phase boundary propagates and on the results which can indicate indirectly the existence of a phase transformation like the time of separation, the velocity–time profile at the rear end of the target and the stress history at the impact face.     

Interfacial energy and dissipation in martensitic phase transformations. Part I: Theory

A model of evolving martensitic microstructures is formulated that incorporates the interfacial energy and dissipation on three different scales corresponding to the grain boundaries attained by martensite plates, the interfaces between austenite and martensite plates, and the twin interfaces within martensite plates. Three different time scales are also considered in order to clarify the meaning of rate-independent dissipation related to instabilities at more refined temporal and spatial scales. On the slowest time scale, the process of deformation and martensitic phase transformation is investigated as being composed of segments of smooth quasi-static evolution separated by sudden jumps associated with creation or annihilation of interfaces. A general evolution rule is used in the form of minimization of the incremental energy supply to the whole compound thermodynamic system, including the rate-independent dissipation. Close relationship is shown between the evolution rule and the thermodynamic condition for stability of equilibrium, with no a priori assumption on convexity of the dissipation function. It is demonstrated that the extension of the minimum principle from the first-order rates to small but finite increments requires a separate symmetry restriction imposed on the state derivative of the dissipation function. Formulae for the dissipation associated with annihilation of interfaces are proposed that exhibit limited path-independence and satisfy that symmetry requirement. By exploiting the incremental energy minimization rule with the help of the transport theorems, local propagation conditions are derived for both planar and curved phase transformation fronts. The theory serves as a basis for the algorithm for calculation of the stress-induced evolution of martensitic microstructures along with their characteristic dimensions and related hysteresis loops in shape memory alloys; the examples are given in Part II of the paper.     

Change in the structure of a polymer solution in a longitudinal hydrodynamic field

There are two qualitatively different conditions for the stretching of liquid fibers formed by moderately concentrated polymer solutions [1]. If the longitudinal gradient of the drawing rate is rather small the structure of the solution remains unchanged. If this gradient exceeds a certain critical value, some of the solvent is expressed from the solution in and the liquid filament is converted into a slightly swollen fiber. The solvent released settles as droplets on the filament surface. This effect is of very great importance for a number of industrial processes pertaining to the production of filaments and films from polymer solutions. In addition, as was reported in [1], the drawing of a liquid filament, accomapnied by orientational formation of the solid phase, can serve as a most simple imitation of the formation of silk and gossamer filaments in nature.This paper presents a qualitative theory for this phenomenon, based on investigation of the thermodynamic stability of a polymer solution in a longitudinal hydrodynamic field.In conclusion the author thanks S. Ya. Frenkel for kindly providing information about the experiments conducted in his laboratory.     

Long-term trends in fog and boundary layer characteristics in Tianjin,China

Long-term trends in fog episodes,vertical variations of atmospheric boundary structure,and air pollutant concentrations during two different heavy fog events in the Tianjin area were analyzed.The total amount of fog has increased since 1980 due to the stability of the boundary layer and an increase of pollutant emissions.The variation in the characteristics of the boundary layer and air pollutant concentrations were significantly different between the two fog processes(fog 1 and fog II).The onset of fog I was accompanied by a temperature inversion in the low atmosphere,and the average kinetic energy showed a clear diurnal trend and vertical variation,which increased with height.The dissipation of fog I was mainly due to turbulence.However,the atmospheric stratification was not stable in the lower layer before the onset of fog II.The diurnal and vertical changes in kinetic energy were very small,in which turbulent momentum at each measurement height tended to be zero.In the dissipation process of fog II,wind speed increased significantly.Surface PM_(2.)5 concentrations decreased,but the ratio of PM_(2.5) to PM_(10)increased from 0.66 to 0.82 until fog I dissipated.However,the concentration of PM2.5 did not decrease at the early stage of fog II,but the ratio of PM_(2.5) to PM_(10) PM_(2.5)/PM_(10) decreased to 0.21 when fog II dissipated.This study showed that there was a clear difference in the evolution of pollutant concentration for different pollutants and in different developing stages during the fog events.PM2.5 concentration accumulated faster than those of SO_2 and NO_x,and the PM_(2.5) cumulative rate was greater in the mid-term of the fog process.     

Mechanics and chemical thermodynamics of phase transition in temperature-sensitive hydrogels

This paper uses the thermodynamic data of aqueous solutions of uncrosslinked poly(N-isopropylacrylamide) (PNIPAM) to study the phase transition of PNIPAM hydrogels. At a low temperature, uncrosslinked PNIPAM can be dissolved in water and form a homogenous liquid solution. When the temperature is increased, the solution separates into two liquid phases with different concentrations of the polymer. Covalently crosslinked PNIPAM, however, does not dissolve in water, but can imbibe water and form a hydrogel. When the temperature is changed, the hydrogel undergoes a phase transition: the amount of water in the hydrogel in equilibrium changes with temperature discontinuously. While the aqueous solution is a liquid and cannot sustain any nonhydrostatic stress in equilibrium, the hydrogel is a solid and can sustain nonhydrostatic stress in equilibrium. The nonhydrostatic stress can markedly affect various aspects of the phase transition in the hydrogel. We adopt the Flory-Rehner model, and show that the interaction parameter as a function of temperature and concentration obtained from the PNIPAM-water solution can be used to analyze diverse phenomena associated with the phase transition of the PNIPAM hydrogel. We analyze free swelling, uniaxially and biaxially constrained swelling of a hydrogel, swelling of a core-shell structure, and coexistent phases in a rod. The analysis is related to available experimental observations. Also outlined is a general theory of coexistent phases undergoing inhomogeneous deformation.     

Direct laser-driven ramp compression studies of iron: A first step toward the reproduction of planetary core conditions

The study of iron under quasi-isentropic compression using high energy lasers, might allow to understand its thermodynamical properties, in particular its melting line in conditions of pressure and temperature relevant to Earth-like planetary cores (330–1500 GPa, 5000–8000 K). However, the iron alpha-epsilon solid–solid phase transition at 13 GPa favors shock formation during the quasi-isentropic compression process which can depart from the appropriate thermodynamical path. Understanding this shock formation mechanism is a key issue for being able to reproduce Earth-like planetary core conditions in the laboratory by ramp compression. In this article, we will present recent results of direct laser-driven quasi-isentropic compression experiments on iron samples obtained on the LULI 2000 and LIL laser facilities.     

Multiphase flow model developed for simulating gas hydrate transport in horizontal pipe

The hydrate formation or dissociation in deep subsea flow lines is a challenging problem in oil and gas transport systems. The study of multiphase flows is complex while necessary due to the phase changes (i.e., liquid, solid, and gas) that occur with increasing the temperature and decreasing the pressure. A one-dimensional multiphase flow model coupled with a transient hydrate kinetic model is developed to study the characteristics of the multiphase flows for the hydrates formed by the phase changes in the pipes. The multiphase flow model is derived from a multi-fluid model, while has been widely used in modelling multiphase flows. The heat convection between the fluid and the ambient through the pipe wall is considered in the energy balance equation. The developed multiphase flow model is used to simulate the procedure of the hydrate transport. The results show that the formation of the hydrates can cause hold-up oscillations of water and gas.     

The Experimental and Numerical Studies on Gas Production from Hydrate Reservoir by Depressurization

A set of experimental system to study hydrate dissociation in porous media is built and some experiments on hydrate dissociation by depressurization are carried out. A mathematical model is developed to simulate the hydrate dissociation by depressurization in hydrate-bearing porous media. The model can be used to analyze the effects of the flow of multiphase fluids, the kinetic process and endothermic process of hydrate dissociation, ice-water phase equilibrium, the variation of permeability, convection and conduction on the hydrate dissociation, and gas and water productions. The numerical results agree well with the experimental results, which validate our mathematical model. For a 3-D hydrate reservoir of Class 3, the evolutions of pressure, temperature, and saturations are elucidated and the effects of some main parameters on gas and water rates are analyzed. Numerical results show that gas can be produced effectively from hydrate reservoir in the first stage of depressurization. Then, methods such as thermal stimulation or inhibitor injection should be considered due to the energy deficiency of formation energy. The numerical results for 3-D hydrate reservoir of Class 1 show that the overlying gas hydrate zone can apparently enhance gas rate and prolong life span of gas reservoir.     

初始压力对多孔介质中气体水合物生成的影响

利用自制的一维天然气水合物生成与开采模拟实验系统,实验研究多孔介质中天然气水合物生成时不同初始压力对生成量、生成时间的影响.分别用相同气水比注入、相同注气量不同注水量、相同注水量不同注气量三种方式来控制初始压力.结果表明:在砂粒粒径300μm～500μm,盐水质量浓度2%,系统温度为2℃、初始压力为5MPa～9MPa的条件下进行水合物的等容生成实验时,初始压力越大,生成的水合物量越多,水合物开始生成的时间越早;但初始压力越大,实验系统中水合物生成最终稳定所需的时间越长.本实验系统采用的三种不同的控制初始压力的方式都可以得到上述结果.由此,可以为今后室内进行天然气水合物的生成实验提供科学指导.     

Temperature evolution associated with phase transition from quasi static to dynamic loading

Thermo-mechanical coupling is an intrinsic property of first order martensitic transformation. In this paper, we study the temperature evolution during phase transition at a wider strain rates from quasi static to impact loading to reveal the thermodynamic nature of the strain rate effect of phase transition materials. Based on the laws of thermodynamics and the principle of maximum dissipated energy, a thermal-mechanically coupled model was proposed. The model shows that, in the quasi static case, the temperature profile grades around the moving phase boundary, while for the dynamic case, thermal response of the specimen can be reached homogeneously due to random nucleation. The predicted results of the model are in good agreement with the experimental results, suggesting that the interaction between the self-heating effect and the temperature dependence of phase transition behavior plays a leading role in the process of the transformation deformation mechanism associated with the loading rate.

     

On the structure of the Hugoniot relation for a shock-induced martensitic phase transition

The Hugoniot curve relates the pressure and volume behind a shock wave, with the temperature having been eliminated. This paper studies the Hugoniot curve behind a propagating sharp interface between two material phases for a solid in which an impact-induced phase transition has taken place. For a solid capable of existing in only one phase, compressive impact produces a shock wave moving into material, say, at rest in an unstressed state at the ambient temperature. If the specimen can exist in either of two material phases, sufficiently severe impact may produce a disturbance with a two-wave structure: a shock wave in the low-pressure phase of the material, followed by a phase boundary separating the low- and high-pressure phases. We use a theory of phase transitions in thermoelastic materials to construct the Hugoniot curve behind the phase boundary in this two-wave circumstance. The kinetic relation controlling the evolution of the phase transition is an essential ingredient in this process.      

Implicit finite element formulations for multi-phase transformation in high carbon steel

An anomalous plastic deformation observed during the phase transformation of steels was implemented into the finite element modeling. The constitutive equations for the transformation plasticity originally proposed by Greenwood and Johnson [Greenwood, G.W., Johnson, R.H., 1965. The deformation of metals under small stresses during phase transformation. Proc. Roy. Soc. A 283, 403] and further extended by Leblond et al. [Leblond, J.B., Mottet, G., Devaux, J.C., 1986a. A theoretical and numerical approach to the plastic behavior of steels during phase transformations, I. Derivation of general relations. J. Mech. Phys. Solids 34, 395–409; Leblond, J.B., Mottet, G., Devaux, J.C., 1986b. A theoretical and numerical approach to the plastic behavior of steels during phase transformations, II. Study of classical plasticity for ideal-plastic phases. J. Mech. Phys. Solids 34, 411–432; Leblond, J.B., Devaux, J., Devaux, J.C., 1989a. Mathematical modeling of transformation plasticity in steels, I: case of ideal-plastic phases. Int. J. Plasticity 5, 511–572; Leblond, J.B., 1989b. Mathematical modeling of transformation plasticity in steels, II: coupling with strain hardening phenomena. Int. J. Plasticity 5, 573–591] were modified to consider the thermo-mechanical response of generalized multi-phase steel during phase transformations from austenite at high temperature. An implicit numerical solution procedure to calculate the plastic deformation of each constituent phase was newly proposed and implemented into the general purpose implicit finite element program via user material subroutine. The new algorithms include efficient calculation of consistent tangent modulus for the transformation plasticity and application of general anisotropic yield functions without limitation to the isotropic yield function. Besides the thermo-elastic–plastic constitutive equations, non-isothermal transformation kinetics was characterized by the Johnson–Mehl–Avrami–Kolmogorov (JMAK) equation and additivity relationship for the diffusional transformation, while the model proposed by Koistinen and Marburger was used for the diffusionless transformation. Numerical verifications for the continuous cooling experiments under various loading conditions were conducted to demonstrate the applicability of the developed numerical algorithms to the high carbon steel SK5.     

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.