基于Rietveld无标样定量研究HMX的β→δ等温相变动力学

以Rietveld无标样定量方法为基础,利用原位X射线粉末衍射技术(XRD)研究了奥克托今(HMX)的β→δ等温相变动力学.描述了不同温度下HMX的转变进度-时间曲线,求得Avrami指数n约为0.6,建立了相关的等温相变动力学方程.采用Arrhenius方程定量表示了速率常数k与温度T的关系,计算的活化能Ea约为151 kJ/mol,指前因子lnA为36.2.结果表明:实验温度是影响相变的主导因素,HMX发生β→δ相变时,δ相近似于1维随机成核长大.     

温度对冲击相变波传播的影响

冲击加载下,相界面的传播是一热力耦合过程。相变波阵面不仅是力学和物质间断面,也是温度界面。为考虑温度对相变波传播的影响,本文首先建立了相界面上的热传导方程和热力耦合的相变本构方程,然后采用一维特征线理论和有限差分数值计算相结合的方法,分析了温度界面和相变波的基本相互作用规律,进而给出了连续温度梯度下和绝热冲击下相变波传播规律。结果表明,温度对相变波传播的作用主要体现在两个方面,一方面是作为温度界面将与各类间断面相互作用,另一方面冲击相变波阵面后区域热力学状态变化影响卸载波结构。其原因在于相变方式（可逆、不可逆）和相变阈值应力具有强烈的温度相关性。     

斜波压缩下HMX晶体的弹塑性行为

开展了（010）、（011）晶向HMX晶体的斜波压缩实验,获得了约15 GPa压力下的速度响应剖面。实验结果表明,HMX单晶存在明显弹塑性转变行为,且速度波形有下降趋势,这是材料的黏性效应导致,材料的弹性极限随着样品厚度增加而变化,不同晶向的材料动力学特性存在差异。结合Hobenemser-Prager黏弹塑性本构关系和三阶Birch-Murnaghan物态方程开展了HMX晶体斜波压缩物理过程的数值模拟,计算结果可以很好地描述HMX晶体的弹塑性转变这一物理过程。     

烤燃条件下HMX/TATB基混合炸药多步热分解反应计算

采用多步热分解反应动力学模型,描述单质炸药热分解反应,提出了多组分网格单元计算方法,对以HMX/TATB为基的多元混合炸药在烤燃条件下的热反应过程进行了计算。通过炸药烤燃实验测量了炸药内部温度,获得了炸药点火时间,验证了计算的准确性。分析了混合炸药组成比例的变化对炸药热反应性能的影响。在HMX/TATB混合炸药热反应阶段,主要是HMX发生分解反应释放热量,TATB的反应量很少,随着混合炸药中TATB含量的增多,炸药的点火时间逐渐增长,点火温度逐渐增高,炸药热安全性增强。     

马氏体相变过程中形核、失稳及多界面微结构的动力学模拟

材料发生相变的过程中会出现失稳、滞后回线及多界面的微结构等复杂现象，而稳定性的丧失使其动力学方程的求解十分困难。对于形状记忆合金中的马氏体相变，相变过程中材料的等效杨氏模量变为负值，使得传统的动力学方程成为病态的，无法直接求解，必须要进行正则化。而相变的滞后回线与微结构的出现也说明经典的弹性理论不再适用，必须要引入新的能量项以能刻画这些现象。本文在非线性弹性理论的框架下，引入应变梯度界面能和位移非均匀能，利用变分原理建立了材料相变的一维动力学模型。高阶项的引入极大地改善了方程的性质，使数值求解成为可能。计算结果表明，该模型确能较有效地描述相变时的失稳与微结构。     

破碎岩体非等温渗流的非线性动力学研究

分别从固体及流体导热的能量方程出发,导出破碎岩体非等温渗流的能量本构方程, 结合渗流的连续性方程、运动方程、状态方程等建立了破碎岩体非等温渗流的一维非线性动力学方程组;结合Mathcad软件计算得到了系统的无量纲化平衡态, 利用逐次亚松弛迭代法分析了对应于不同参数时平衡态的稳定性;指出非等温渗流系统存在鞍结分岔及折叠突变, 与等温渗流相比, 考虑温度场的破碎岩体渗流动力系统更容易发生渗流突变.      

具有体膨胀和剪切效应的结构陶瓷相变塑性细观本构模型:Ⅰ.非比例加载历史

本文在对结构陶瓷的四方至单斜(t→m)马氏体相变进行细观力学、热力学和微观机制分析的基础上,导出了在非比例加载条件下考虑材料的体膨胀和剪切效应的相变塑性细观本构模型。作者首次采用 Mori-Tanaka 方法以自洽的方式导出了材料构元的 Helmho-ltz 自由能及余能函数的解析表达式,它是外加宏观应力(或应变)、温度、相变夹杂体积分数以及夹杂内平均相变应变的函数,其中夹杂体积分数和平均相变应变为描述材料构元微结构变化的内变量。最后按 Hill-Rice 本构理论框架导出相变塑性屈服面方程及增量本构关系。     

具有体膨胀和剪切效应的结构陶瓷相变塑性细观本构模型:Ⅰ.非比例加载历史

本文在对结构陶瓷的四方至单斜(t→m)马氏体相变进行细观力学、热力学和微观机制分析的基础上,导出了在非比例加载条件下考虑材料的体膨胀和剪切效应的相变塑性细观本构模型。作者首次采用 Mori-Tanaka 方法以自洽的方式导出了材料构元的 Helmho-ltz 自由能及余能函数的解析表达式,它是外加宏观应力(或应变)、温度、相变夹杂体积分数以及夹杂内平均相变应变的函数,其中夹杂体积分数和平均相变应变为描述材料构元微结构变化的内变量。最后按 Hill-Rice 本构理论框架导出相变塑性屈服面方程及增量本构关系。     

斜波压缩下锡的相变和层裂行为

获取不同热力学路径下锡的动态响应实验数据,是深入研究其相变和损伤物理过程的基础.利用小型磁驱装置CQ-4完成了金属锡的斜波加载实验,获取了锡含有相变和层裂损伤物理信息的实验数据.实验结果显示,在加载段锡依次经历了弹塑性转变和β-γ相变两种物理过程,屈服强度约0.194 GPa,相变压力随着锡厚度的增加从7.54 GPa减小到7.14 GPa.在卸载段出现了明显的层裂损伤,层裂强度约1.1 GPa,与相同加载压力下冲击实验结果有巨大差异,层裂片厚度约0.38 mm.结合由锡的多相Helmholtz自由能计算的多相状态方程、Hayes相变动力学方程和损伤度理论,对斜波压缩实验过程进行一维流体动力学数值模拟,计算结果可以很好描述锡的弹塑性转变、相变和层裂三个物理过程.     

冲击作用下炸药热点形成的3维离散元模拟

为了探讨非均质炸药在冲击作用下的细观响应特性,分别对以HMX为基的PBX塑料粘接炸药和含孔洞的HMX炸药在活塞推动下热点的形成过程进行了3维离散元模拟(未考虑化学反应)。结果表明,塑料粘接炸药中的热点集中在炸药晶体与粘结剂的结合部,晶体温升低于粘结剂,且晶体边界温升高于内部。对于含孔洞炸药,热点温度与孔洞的尺寸和形状有关,大孔洞塌缩形成的热点温度高于小孔洞塌缩形成的热点温度,球形孔洞塌缩形成的热点温度高于立方体孔洞塌缩得到的热点温度。     

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。     

A micromechanical model of phase boundary movement during solid–solid phase transformations

Summary  Understanding the kinetics of phase boundary movement is of major concern in e.g. martensitic transformation in related engineering applications. The main goal of this paper is to develop such kinetics on the basis of thermodynamic principles at the material microlevel. After a short literature survey in the introduction, the jump condition and thermodynamic force on the interface are discussed based on laws of conservation and thermodynamics. This leads to a relation for the driving force of the transformation front. In particular, the propagating front of a phase-transforming sphere within an elastic-plastic medium is considered. Due to density change, which is implicitly expressed in the transformation volume strain, strains and accompanying stresses are induced which hamper the propagation and influence the transformation kinetics. Together with the latent heat, the heat due to plastic dissipation occurs as a source term in the heat conduction equation. Since kinetics are influenced by temperature, the heat conduction equation and the kinetics equation are coupled. Using Green's function techniques, an integral equation is derived and solved numerically. The results of a parameter study are discussed. Received 10 February 2000; accepted for publication 18 October 2000     

Phase transition and dynamics of iron under ramp wave compression

The ramp wave compression experiments of iron with different thicknesses were performed on the magnetically driven ramp loading device CQ-4. Numerical simulations of this process were done with Hayes multi-phase equation of state (H-MEOS) and dynamic equations of phase transition. The calculated results of H-MEOS are in good agreement with those of shock phase transition, but are different from those under ramp wave compression. The reason for this is that the bulk modulus of the material in the Hayes model and the wave velocity are considered constant. Shock compression is a jump from the initial state to the final state, and the sound speed is related to the slope of the Rayleigh line. However, ramp compression is a continuous process, and the bulk modulus is no longer a constant but a function of pressure and temperature. Based on Murnaghan equation of state, the first-order correction of the bulk modulus on pressure in the Hayes model was carried out. The numerical results of the corrected H-MEOS agree well with those of pure iron in both ramp and shock compression phase transition experiments. The calculated results show that the relaxation time of iron is about 30 ns and the phase transition pressure is about 13 GPa. There are obvious differences between the isentropic and adiabatic process in terms of pressure–specific volume and temperature–pressure. The fluctuation of the sound speed after 13 GPa is caused by the phase transition.     

A compressible single‐temperature conservative two‐phase model with phase transitions

A model for multidimensional compressible two‐phase flow with pressure and velocity relaxations based on the theory of thermodynamically compatible system is extended to study liquid–gas flows with cavitation. The model assumes for each phase its own pressure and velocity, while a common temperature is considered. The governing equations form a hyperbolic system in conservative form and are derived through the theory of a thermodynamically compatible system. The phase pressure‐equalizing process and the interfacial friction are taken into account in the balance laws for the volume fractions of one phase and for the relative velocity by adding two relaxation source terms, while the phase transition is introduced into the model considering in the balance equation for the mass of one phase the relaxation of the Gibbs free energies of the two phases. A modification of the central finite‐volume Kurganov–Noelle–Petrova method is adopted in this work to solve the homogeneous hyperbolic part, while the relaxation source terms are treated implicitly. In order to investigate the effect of the mass transfer in the solution, a 1D cavitation tube problem is presented. In addition, two 2D numerical simulations regarding cavitation problem are also studied: a cavitating Richtmyer–Meshkov instability and a laser‐induced cavitation problem. Copyright © 2014 John Wiley & Sons, Ltd.     

受热炸药的冲击起爆特征

设计了炸药驱动飞片起爆受热炸药的实验装置,该装置既能够对实验炸药进行均匀地加热,又能够避免高温对加载炸药的影响。利用设计的实验装置对PBXC10炸药（HMX/TATB复合炸药）进行了14、100、140、160和180 ℃等5种不同加热温度下的冲击起爆实验,测量了该炸药内部压力的成长历程。采用点火增长反应速率方程对PBXC10炸药冲击起爆进行了数值模拟。根据实验结果,标定了不同温度下PBXC10炸药的点火增长模型参数,并给出了模型参数随温度变化的关系式,获得了不同温度下炸药的Pop关系。研究结果表明:PBXC10炸药的冲击波感度随温度的升高而升高,但与HMX炸药相比,其冲击波感度对温度的敏感性明显降低,这是因为PBXC10炸药中的TATB具有较好的降感作用。     

Effect of chemical structure on the crosslinking behavior of bismaleimides: Rheological study

The effect of molecular structure on the cure characteristics of bismaleimides (BMIs) was investigated by rheological measurements. BMI resins of different chemical structures were used, prepared from diglycidyl ether of bisphenol A and N-(3-carboxy phenyl) maleimide or N-(4-carboxy phenyl) maleimide. Temperature dependence of the rheological data was correlated to the Arrhenius equation, from which the activation energy of crosslinking was calculated.Upon heating in dynamic curing, viscosity passed through a minimum then sharply increased due to increasing amount of the crosslinking reaction. The temperature at minimum viscosity increased as the chain length became longer. After passing the minimum point, viscosity increased much faster for meta BMIs (3BE1, 3BE2) than para BMIs, however, the difference in the chain length did not show any appreciable difference in the viscosity increase rate (dη^∗/dT). Nonetheless, the final viscosity was lower for longer chains, because their crosslinking density would be lower.In isothermal curing, the final crosslinking density was expected to increase with temperature, which was shown via the increase in the final viscosity. The gelation time decreased with temperature, and the activation energy of the crosslinking reaction was obtained. Using the reaction kinetics parameters obtained from dynamic scanning calorimeter and Arrhenius type equation, the viscosity change during the isothermal curing was simulated and compared with the measurements.     

Effect of the phase transition on intra-tow flow behavior and void formation in liquid composite molding

A model describing the microscopic isothermal flow inside a fiber bundle completely surrounded by a resin during a liquid molding process is developed. A distinguishing feature of this model is that it takes into account the liquid/vapor phase transition occurring in the gas entrapped inside the tow. In contrast to the existing void formation models which assume that the entrapped gas behaves as an ideal gas, in the present analysis, the condensation and vaporization processes inherent in the liquid/vapor system under high external pressures are simulated by using the Peng–Robinson equation of state. The numerical results show that the phase transition inside the fiber tow has strong effect on both the void dynamics and its size, thus indicating the need to account for this phenomenon in simulation of liquid composite molding processes.     

A shape memory alloy model by a second order phase transition

Motivated by the experimental results of the paper [1] and unlike the general theories of shape memory alloys (SMAs), in this paper we suggest for such materials a phase field model by a second order phase transition. So that, with this new system we obtain a simulation of phase dynamics very convenient to describe the natural behavior of these materials. The differential system is governed by the motion equation, the heat equation and the Ginzburg–Landau (GL) equation and by a constitutive law between the phase field, the temperature, the strain and the stress. The use of this new model is characterized by new potentials of the GL equation and by a new dependence on the temperature in the constitutive equation. Using this new model, we obtain simulations in better agreement with experimental data and respect to previous work [2].     

Transition to instability of a phase interface in a porous medium in the isothermal approximation

The stability of the phase interface in geothermal systems is considered in the isothermal approximation with allowance for capillary effects. The dispersion relation is obtained and the domains of stability and instability of steady-state vertical flows are found. Possible types of transition to instability, namely, transitions with the most unstable mode corresponding to zero and infinite wavenumbers or to all wavenumbers simultaneously, are described. In the first case the nonlinear Kolmogorov-Petrovskii-Piskunov equation describing the evolution of a narrow strip of weakly unstable modes on the stability threshold is derived. The effect of the parameters of the system on its stability is investigated.