水蒸汽驱动高聚物形状记忆效应的力学模拟

部分形状记忆高聚物在相对湿度较高的环境中会从其临时形状恢复到永久形状,这种效应被称之为水蒸汽驱动形状记忆效应。由于不需要升高温度就可实现形状恢复,水蒸汽驱动的形状记忆效应在多个领域都有着潜在的应用价值。本文拟建立一个热-力-化学多场耦合的理论模型来模拟非晶态高聚物的水蒸汽驱动形状记忆行为。该理论模型采用自由体积的概念来模拟玻璃态转变,采用Fick定律来模拟水蒸汽在高聚物基体中的扩散行为。相关有限元模拟结果表明,该模型能定性地描述文献中观察到的恢复温度、相对湿度以及溶剂分子扩散速度对形状恢复行为的影响,也能模拟复杂变形条件下水蒸汽驱动的形状记忆效应。     

显式方法精确模拟形状记忆聚合物热力学行为

通过构建一个热耦合的多轴可压缩应变能函数，得到应力-应变、应力-温度和应变-温度之间的函数关系，建立形状记忆聚合物的本构方程.本文引入三个基于对数应变的不变量使得模型（i）可以模拟可压缩情况；（ii）适用于单轴拉伸和等双轴拉伸至少两个基准实验；（iii）多轴有效.通过显式方法（i）给出自由能和熵的具体表达，证明模型热力学定律；（ii）给出应变-应力，温度-应力以及，温度-应变的形函数具体表达.多轴模型在特定的情况下可以自动退化到各自的单轴情况. 通过调节形函数的参数，最终得到的模型结果和实验结果能够精确匹配.新方法建立的本构模型得到的结果能更加准确地指导形状记忆聚合物的工程设计。     

显式方法精确模拟形状记忆聚合物热力学行为

通过构建一个热耦合的多轴可压缩应变能函数,得到应力-应变、应力-温度和应变-温度之间的函数关系,建立形状记忆聚合物的本构方程.本文引入三个基于对数应变的不变量使得模型（i）可以模拟可压缩情况;（ii）适用于单轴拉伸和等双轴拉伸至少两个基准实验;（iii）多轴有效.通过显式方法（i）给出自由能和熵的具体表达,证明模型热力学定律;（ii）给出应变-应力,温度-应力以及,温度-应变的形函数具体表达.多轴模型在特定的情况下可以自动退化到各自的单轴情况. 通过调节形函数的参数,最终得到的模型结果和实验结果能够精确匹配.新方法建立的本构模型得到的结果能更加准确地指导形状记忆聚合物的工程设计。     

形状记忆聚合物力学行为及其物理机制

形状记忆聚合物是一类环境响应主动形变智能软材料,是智能材料与结构领域的新兴研究内容之一。宏观概括其物理和力学行为的研究热点,主要包括三个方面：材料与环境之间的信息交换（如热量、能量等）,主动形变控制（如驱动方法、形变行为本构建模等）,软材料及其结构力学（如相变/转变热力学、复合材料设计等）。形状记忆聚合物的记忆效应源于分子链段本征结构的热运动,受外场激励影响,是分子链段结构（包括构型和构象）松弛行为的宏观表象,遵循Arrhenius定律。本文从物理和力学两方面讨论了形状记忆聚合物的分子链段热力学行为及其熵弹效应、分子结构松弛力学行为、环境效应记忆行为的物理和力学机制,系统地对形状记忆聚合物分子结构本征属性及其物理机理、记忆效应转变机制及其力学内涵、温度记忆效应、多场耦合效应响应行为等热点和难点问题进行了分析和讨论。最后,论文展望了形状记忆聚合物力学行为研究的未来发展方向。     

纳米单晶NiTi合金单程形状记忆效应的分子动力学模拟

采用基于第二近邻修正型嵌入原子势的分子动力学方法研究了纳米单晶NiTi合金的单程形状记忆效应，详细阐明了温度诱发马氏体相变和应力诱发马氏体重定向过程中纳米单晶的变形行为和微结构演化，进一步分析了加/卸载速率对NiTi合金单程形状记忆效应的影响。结果表明，NiTi纳米单晶在应力加载过程中发生马氏体重定向，卸载后存在残余应变；当加热到奥氏体转变结束温度以上时，马氏体逆相变为奥氏体相，残余应变逐渐减小，但未完全回复；随着应力加载速率的增加，重定向临界应力和模量逐渐增加；再次降温过程中不同加载速率下的原子结构演化各不相同。     

电子封装钎料合金耦合损伤的多轴时相关低周疲劳失效研究

基于63Sn-37Pb钎料合金材料的多轴时相关循环变形行为及疲劳失效行为,提出了耦合损伤的多轴时相关理论模型及疲劳失效模型,模型引入了损伤演化方程,考虑了时相关效应及非比例路径效应,能较好地模拟材料在不同非比例加载路径下的循环变形行为及疲劳失效行为,较准确地预测多轴疲劳寿命.     

高熵合金强韧化理论建模与模拟研究进展

高熵合金因其优异的性能受到广泛关注，如高强度、高硬度、高韧性、高耐磨、高耐辐照、高耐腐蚀、高电阻、高耐热等，有望应用于核能、航天航空等重要领域和重大装备。从高熵合金制备、组织结构以及性能表征等方面开展的实验研究表明其独特的性质依赖于高熵合金高熵效应、晶格畸变和扩散迟滞。在微观尺度以及宏观尺度, 理论模型和数值模拟为研究高熵合金微观机理和力学特性提供了一种方法。建立从高熵合金的微观结构与变形机理到宏观独特力学性能的联系是一个多尺度的科学问题。最近，基于实验观察结果，采用多尺度的理论与模拟方法（第一性原理、分子动力学、离散位错动力学、晶体塑性有限元、微结构依赖的理论模型），研究了高熵合金层错能、弹性模量、扩散系数以及相稳定性，揭示了高熵合金变形与强韧化机制。本文综述多尺度计算在高熵合金力学性能和变形行为方面的研究进展，并对高熵合金在原位变形实验、高通量技术以及机器学习方面的研究进行简要展望。     

活性材料冲击释能行为研究进展

活性材料是一种具备释能特性的新型材料,其在冲击导致的高压/高温作用下可以发生化学反应,释放大量的化学能,因此在破片、聚能破甲战斗部等军事领域有广泛的应用潜力。为了实现对活性材料释能过程的设计与控制,推进活性材料武器化应用进程,就必须解答活性材料冲击释能行为中所包含的一系列复杂的力-热-化耦合问题。近40年来,对活性材料的冲击释能行为已开展了大量研究,本文在此基础上系统梳理了活性材料的冲击诱发化学反应机理、动力学以及相关效应的研究现状,重点关注活性材料的冲击释能实验表征技术、冲击诱发化学反应理论模型以及考虑力-热-化耦合的冲击压缩数值模拟方法等3方面的研究进展。总结认为,对活性材料冲击释能行为的研究已经具有一定的积淀,但目前对实验中超快化学反应行为的实时诊断研究还缺乏更加丰富、精细、直观的表征与探索,相关理论与数值模拟研究尚未建立能够完整描述活性材料冲击释能行为的力-热-化理论模型,缺乏能够从宏观尺度描述冲击释能行为的有效方法。因此,超快化学反应实验表征技术、宏观角度的力-热-化机理与模型建立及其数值模拟应用以及具备可调性能的活性材料制备新工艺3方面研究内容将是推进活性材料未来军事化应用的重点关注对象。     

聚氨酯高聚物注浆材料剪切测试与有限元模拟

通过扭转试验对高聚物注浆材料剪切性能进行试验研究,并在扫描电子显微镜(scanning electron microscope, SEM)下观测了试件断面处胞体形状破坏特征,在此基础上通过有限元数值模拟,对其剪切变形力学响应特征及剪应力分布规律进行了研究。结果表明:密度对高聚物材料的剪切强度及剪切模量影响显著,且随着高聚物材料密度的增加,其剪切强度和剪切模量被显著提升;高聚物材料胞体分布遵循能量最低原理,密度越大,胞体表面积越小,表面能越小,体系越稳定;面心立方体堆砌模型可以较好模拟材料剪切变形行为,且密度越大,拟合效果越好。     

SHEAR TEST AND FINITE ELEMENT SIMULATION OF POLYURETHANE POLYMER GROUTING MATERIALS1)

通过扭转试验对高聚物注浆材料剪切性能进行试验研究,并在扫描电子显微镜(scanning electron microscope, SEM) 下观测了试件断面处胞体形状破坏特征,在此基础上通过有限元数值模拟,对其剪切变形力学响应特征及剪应力分布规律进行了研究。结果表明：密度对高聚物材料的剪切强度及剪切模量影响显著,且随着高聚物材料密度的增加,其剪切强度和剪切模量被显著提升;高聚物材料胞体分布遵循能量最低原理,密度越大,胞体表面积越小,表面能越小,体系越稳定;面心立方体堆砌模型可以较好模拟材料剪切变形行为,且密度越大,拟合效果越好。     

Coarse-grained simulation of molecular mechanisms of recovery in thermally activated shape-memory polymers

Thermally actuated shape-memory polymers (SMPs) are capable of being programmed into a temporary shape and then recovering their permanent reference shape upon exposure to heat, which facilitates a phase transition that allows dramatic increase in molecular mobility. Experimental, analytical, and computational studies have established empirical relations of the thermomechanical behavior of SMPs that have been instrumental in device design. However, the underlying mechanisms of the recovery behavior and dependence on polymer microstructure remain to be fully understood for copolymer systems. This presents an opportunity for bottom-up studies through molecular modeling; however, the limited time-scales of atomistic simulations prohibit the study of key performance metrics pertaining to recovery. In order to elucidate the effects of phase fraction, recovery temperature, and deformation temperature on shape recovery, here we investigate the shape-memory behavior in a copolymer model with coarse-grained potentials using a two-phase molecular model that reproduces physical crosslinking. Our simulation protocol allows observation of upwards of 90% strain recovery in some cases, at time-scales that are on the order of the timescale of the relevant relaxation mechanism (stress relaxation in the unentangled soft-phase). Partial disintegration of the glassy phase during mechanical deformation is found to contribute to irrecoverable strain. Temperature dependence of the recovery indicates nearly full elastic recovery above the trigger temperature, which is near the glass-transition temperature of the rubbery switching matrix. We find that the trigger temperature is also directly correlated with the deformation temperature, indicating that deformation temperature influences the recovery temperatures required to obtain a given amount of shape recovery, until the plateau regions overlap above the transition region. Increasing the fraction of glassy phase results in higher strain recovery at low to intermediate temperatures, a widening of the transition region, and an eventual crossover at high temperatures. Our results corroborate experimental findings on shape-memory behavior and provide new insight into factors governing deformation recovery that can be leveraged in biomaterials design. The established computational methodology can be extended in straightforward ways to investigate the effects of monomer chemistry, low-molecular-weight solvents, physical and chemical crosslinking, different phase-separation morphologies, and more complicated mechanical deformation toward predictive modeling capabilities for stimuli-responsive polymers.     

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.     

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.     

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.     

On the evolution law for the frozen fraction in linear theories of shape memory polymers

Shape memory properties of thermally responsive polymeric materials are due mainly to a phase transition from the rubbery phase above the transition temperature (glass transition or melting temperature) to the glassy or semicrystalline phase below this temperature. Within constitutive models of shape memory polymers (SMPs), this phase transition is mathematically accounted for by the frozen volume fraction for which a suitable evolution law must be postulated or derived. In this paper, the evolution laws that have been proposed in the literature are examined both from the experimental and from the theoretical point of view. It is found that the predictive capabilities of the phenomenological laws may be improved by admitting involved material constants to depend on parameters such as pre-strain, rate of heating and cooling, and other quantities characterizing thermomechanical cyclic tests. It is next shown that for a wide class of linear constitutive models of SMPs, the evolution law for the frozen volume fraction may be derived in a systematic way from strain and stress profiles experimentally obtained in the standard thermomechanical test.     

Finite deformation thermo-mechanical behavior of thermally induced shape memory polymers

Shape memory polymers (SMPs) are polymers that can demonstrate programmable shape memory effects. Typically, an SMP is pre-deformed from an initial shape to a deformed shape by applying a mechanical load at the temperature T_H>T_g. It will maintain this deformed shape after subsequently lowering the temperature to T_L<T_g and removing the externally mechanical load. The shape memory effect is activated by increasing the temperature to T_D>T_g, where the initial shape is recovered. In this paper, the finite deformation thermo-mechanical behaviors of amorphous SMPs are experimentally investigated. Based on the experimental observations and an understanding of the underlying physical mechanism of the shape memory behavior, a three-dimensional (3D) constitutive model is developed to describe the finite deformation thermo-mechanical response of SMPs. The model in this paper has been implemented into an ABAQUS user material subroutine (UMAT) for finite element analysis, and numerical simulations of the thermo-mechanical experiments verify the efficiency of the model. This model will serve as a modeling tool for the design of more complicated SMP-based structures and devices.     

Confined thin film wrinkling on shape memory polymer with hybrid surface morphologies

Acta Mechanica Sinica - With appropriate stimuli, such as heat, humidity, or magnetic field, shape memory polymers (SMPs) can recover to their original shapes from temporary, programmed states....