锆基非晶合金的动态弛豫机制和高温流变行为

非晶合金的动态弛豫机制对于理解其塑性变形, 玻璃转变行为, 扩散机制以及晶化行为都至关重要. 非晶合金的力学性能与动态弛豫机制的本征关联是该领域当前重要科学问题之一. 本文借助于动态力学分析(DMA), 探索了Zramorphous alloy,dynamic mechanical analysis,high temperature deformation,structural relaxation,quasi-points defects,1)国家自然科学基金(51971178);陕西省自然科学基金(2019JM-344);中央高校基本科研业务费专项资金(3102019ghxm007);中央高校基本科研业务费专项资金(3102017JC01003)2020-01-062020-04-10非晶合金的动态弛豫机制对于理解其塑性变形, 玻璃转变行为, 扩散机制以及晶化行为都至关重要. 非晶合金的力学性能与动态弛豫机制的本征关联是该领域当前重要科学问题之一. 本文借助于动态力学分析(DMA), 探索了Zr$_{50}$Cu$_{40}$Al$_{10}$块体非晶合金从室温到过冷液相区宽温度范围内的动态力学行为. 通过单轴拉伸实验, 研究了玻璃转变温度附近的高温流变行为. 基于准点缺陷理论(quasi-point defects theory), 对两种力学行为的适用性以及宏观力学行为变化过程中微观结构的演化规律进行描述. 研究结果表明, 准点缺陷理论可以很好地描述非晶合金损耗模量$\alpha$弛豫的主曲线. 基于非晶合金的内耗行为, 玻璃转变温度以下原子运动的激活能$U_\beta$为0.63 eV. 与准点缺陷浓度对应的关联因子$\chi $在玻璃转变温度以下约为0.38,而在玻璃转变温度以上则线性增大. Zr$_{50}$Cu$_{40}$Al$_{10}$块体非晶合金在玻璃转变温度附近, 随温度和应变速率的不同而在拉伸实验中显示出均匀的或不均匀的流变行为. 非晶合金的高温流变行为不仅可以通过扩展指数函数和自由体积理论来描述, 还可以通过基于微剪切畴(shear micro-domains, SMDs)的准点缺陷理论来描述.     

非晶态固体的结构可以决定性能吗?

晶态固体的力学性能与塑性变形主要由结构缺陷,比如位错的运动决定.而在非晶态固体中结构如何决定性能,仍然是固体力学、材料学和凝聚态物理学共同关心但尚未解决的核心问题之一.传统材料学研究的经典范式为"结构决定性能".遵循这一信条,已经有大量的实验表征与理论、模拟研究,尝试将非晶态固体的某种结构特征与性能建立一一对应关系.但是,科学界对于非晶固体结构-性能关系成立与否,以及背后隐藏的规律知之甚少.本文针对非晶态固体的变形机制以及其微结构特征,基于分子动力学模拟,定量评估短程简单结构与中长程复杂结构在决定非晶态固体动力学性能方面的效用.通过海量抽样每种具体玻璃结构的激活能(标识激发难易程度),尝试将结构参数与激活能建立定量关系,从而揭示出非晶态固体结构-性能关系的隐藏主控因素为结构的空间关联,受限比几何结构本身更关键.只有某种结构在空间上呈现亚纳米级的空间关联长度,这种完备结构才有可能有效地决定非晶态固体的力学性能,而短程简单结构则无效.进一步,给出了评价非晶态固体结构预测性能有效性的普适定量方法,为建立广义无序物质的结构-性能关系提供了筛选准则.     

非晶态固体的结构可以决定性能吗?

晶态固体的力学性能与塑性变形主要由结构缺陷, 比如位错的运动决定. 而在非晶态固体中结构如何决定性能, 仍然是固体力学、材料学和凝聚态物理学共同关心但尚未解决的核心问题之一.传统材料学研究的经典范式为"结构决定性能". 遵循这一信条, 已经有大量的实验表征与理论、模拟研究, 尝试将非晶态固体的某种结构特征与性能建立一一对应关系. 但是, 科学界对于非晶固体结构-性能关系成立与否, 以及背后隐藏的规律知之甚少. 本文针对非晶态固体的变形机制以及其微结构特征, 基于分子动力学模拟, 定量评估短程简单结构与中长程复杂结构在决定非晶态固体动力学性能方面的效用. 通过海量抽样每种具体玻璃结构的激活能(标识激发难易程度), 尝试将结构参数与激活能建立定量关系, 从而揭示出非晶态固体结构-性能关系的隐藏主控因素为结构的空间关联, 受限比几何结构本身更关键. 只有某种结构在空间上呈现亚纳米级的空间关联长度, 这种完备结构才有可能有效地决定非晶态固体的力学性能, 而短程简单结构则无效. 进一步, 给出了评价非晶态固体结构预测性能有效性的普适定量方法, 为建立广义无序物质的结构-性能关系提供了筛选准则.      

ORIGIN OF HEAT EFFECTS AND SHEAR MODULUS CHANGES OF A Cu-BASED AMORPHOUS ALLOY 1)

剪切模量在非晶合金黏性流动、扩散及结构弛豫等行为中起着重要作用. 宏观剪切弹性决定非晶合金热流变化.探索非晶合金在结构弛豫和玻璃转变过程中宏观力学性能与热流的关联有助于理解其力学行为起源. 本研究基于自间隙理论对Cu$_{49}$Hf$_{42}$Al$_{9}$非晶合金热流、剪切模量及黏度进行研究,建立剪切模量与热流之间的关联. 通过测量剪切模量精确测定自间隙缺陷浓度演化规律.从能量角度出发,通过激活能图谱探索自间隙缺陷浓度对非晶合金热力学性能的影响. 借助于动态力学分析仪研究非晶合金从室温到过冷液相区的动态弛豫行为,探索物理时效引起的结构弛豫以及内耗演化规律. 研究结果表明,自间隙理论可准确描述非晶合金的弛豫动力学、剪切软化及结构弛豫诱导的力学行为. 结合热流数据可以很好描述铸态和弛豫态非晶合金剪切模量随温度演化过程,激活能图谱直观表述了单位激活能可激活的自间隙缺陷浓度. 自间隙缺陷在结构弛豫中湮灭,表现为玻璃体系结构向更稳定状态迁移.在玻璃化转变过程中,缺陷浓度显著升高伴随热吸收,表现为原子大规模协同运动和剪切软化. 物理时效诱导非晶合金内耗和原子移动性降低. 过冷液相区内原子移动性高至消除了结构弛豫影响.     

锆基非晶合金的动态弛豫机制和高温流变行为

非晶合金的动态弛豫机制对于理解其塑性变形,玻璃转变行为,扩散机制以及晶化行为都至关重要.非晶合金的力学性能与动态弛豫机制的本征关联是该领域当前重要科学问题之一.本文借助于动态力学分析(DMA),探索了Zr_(50)Cu_(40)Al_(10)块体非晶合金从室温到过冷液相区宽温度范围内的动态力学行为.通过单轴拉伸实验,研究了玻璃转变温度附近的高温流变行为.基于准点缺陷理论(quasi-point defects theory),对两种力学行为的适用性以及宏观力学行为变化过程中微观结构的演化规律进行描述.研究结果表明,准点缺陷理论可以很好地描述非晶合金损耗模量α弛豫的主曲线.基于非晶合金的内耗行为,玻璃转变温度以下原子运动的激活能U_β为0.63 eV.与准点缺陷浓度对应的关联因子χ在玻璃转变温度以下约为0.38,而在玻璃转变温度以上则线性增大.Zr_(50)Cu_(40)Al_(10)块体非晶合金在玻璃转变温度附近,随温度和应变速率的不同而在拉伸实验中显示出均匀的或不均匀的流变行为.非晶合金的高温流变行为不仅可以通过扩展指数函数和自由体积理论来描述,还可以通过基于微剪切畴(shear micro-domains, SMDs)的准点缺陷理论来描述.     

铜基非晶合金热效应和剪切模量变化起源

剪切模量在非晶合金黏性流动、扩散及结构弛豫等行为中起着重要作用. 宏观剪切弹性决定非晶合金热流变化.探索非晶合金在结构弛豫和玻璃转变过程中宏观力学性能与热流的关联有助于理解其力学行为起源. 本研究基于自间隙理论对Cu$_{49}$Hf$_{42}$Al$_{9}$非晶合金热流、剪切模量及黏度进行研究,建立剪切模量与热流之间的关联. 通过测量剪切模量精确测定自间隙缺陷浓度演化规律.从能量角度出发,通过激活能图谱探索自间隙缺陷浓度对非晶合金热力学性能的影响. 借助于动态力学分析仪研究非晶合金从室温到过冷液相区的动态弛豫行为,探索物理时效引起的结构弛豫以及内耗演化规律. 研究结果表明,自间隙理论可准确描述非晶合金的弛豫动力学、剪切软化及结构弛豫诱导的力学行为. 结合热流数据可以很好描述铸态和弛豫态非晶合金剪切模量随温度演化过程,激活能图谱直观表述了单位激活能可激活的自间隙缺陷浓度. 自间隙缺陷在结构弛豫中湮灭,表现为玻璃体系结构向更稳定状态迁移.在玻璃化转变过程中,缺陷浓度显著升高伴随热吸收,表现为原子大规模协同运动和剪切软化. 物理时效诱导非晶合金内耗和原子移动性降低. 过冷液相区内原子移动性高至消除了结构弛豫影响.      

基于微观结构非均匀性的非晶合金力学行为

非晶合金弛豫/晶化、玻璃转变、塑性变形等热力学和动力学行为都与其固有的结构非均匀性密切相关. 但是, 由于淹没在亚稳的长程无序结构中, 探究非晶合金的结构非均匀性十分困难. 尤其, 非晶合金微观结构非均匀性与其力学性能之间的本征关联是一个亟待解决的重要科学问题. 本文基于多尺度时空下的力学激励阐述非晶合金微观结构非均匀性特征与演化规律. 从实验、理论和数值模拟方面出发, 梳理了非晶合金微观结构非均匀性与弛豫机制和力学行为之间的关联. 最后, 针对非晶合金微观结构非均匀性与其物理/力学性能研究的方向提出了建议和展望.      

颗粒介质固-流态转变的理论分析及实验研究

颗粒介质由大量离散的颗粒聚集而成,因而与传统固体和流体不同,运动过程中的颗粒介质中可能同时存在多种流态及其相互间复杂的转换过程. 颗粒介质弹性失稳机理、不可恢复应变量化是研究颗粒介质固态和流态及固-流态转变的关键. 在前期建立的双颗粒温度热力学(two-granular-temperature, TGT) 理论基础上,确定了颗粒介质的弹性稳定性条件,建立了不可恢复应变流动法则,搭建了描述颗粒固态-液态及其相互转化的简单模型. 颗粒堆积体坍塌过程是典型的颗粒介质固态和流态及其转变过程,因此本文首先开展了25 167 个陶颗粒堆积体坍塌过程的实验研究,并使用基于TGT 理论的物质点方法和离散元方法对物理实验进行了模拟. 结果表明,模型数值结果与物理实验在颗粒堆坍塌过程中的形态、速度分布等细节上吻合很好,同时也发现了现阶段所使用的物质点方法和TGT 理论的不足. 初步说明TGT 理论可以实现颗粒介质固态和流态,以及状态转变的描述.      

温度对高应变率下三元乙丙橡胶力学性能影响的实验研究

利用加装了自行研制的半导体高低温调控装置的特别加长的分离式Hopkinson杆,对三元乙丙橡胶在变温度(233K～323K)、变应变率(1.8×103/s～3×103/s)条件下进行力学性能实验.为贴近军事装备相关的自然环境要求,分别测定和拟合了三元乙丙橡胶在各个相同温度条件下不同应变率以及各个相同应变率条件下不同温度的应力-应变曲线.结果表明:三元乙丙橡胶的力学性能受温度和应变率影响明显,其刚度随着应变率的增加而增加,其柔性随着温度的增加而增强.温度和应变率对其力学性能的影响有一定的等效性.文中给出了三元乙丙橡胶材料高应变率条件下由橡胶态向玻璃态转变的温度值.     

活性粉末混凝土力学性能及基本构件设计理论研究进展

对活性粉末混凝土(RPC)的基本力学性能的研究发展与基本构件设计理论的研究成果做了较为全面地评述.在分析研究活性粉末混凝土的工程与理论意义的基础上,先后介绍了RPC试件的基本力学性能、各组成原材料含量对试件力学性能的影响、动态载荷作用下的力学性能、RPC基本构件的设计理论等.对研究中的不足与亟待解决的问题做了综合分析,RPC基本构件设计理论与框架结构的破坏特性研究是未来一段时期内较为有意义的研究方向.      

An empirical constitutive model for complex glass-forming liquids using bitumen as a model material

While extensive research efforts have been devoted to understand the dynamics of chemically and structurally simple glass-forming liquids (SGFLs), the viscoelasticity of chemically and structurally complex glass-forming liquids (CGFLs) has received only little attention. This study explores the rheological properties of CGFLs in the vicinity of the glass transition. Bitumen is selected as the model material for CGFLs due to its extremely complex chemical composition and microstructure, fast physical aging and thermorheological simplicity, and abundant availability. A comprehensive rheological analysis reveals a significant broadening of the glass transition dynamics in bitumen as compared to SGFLs. In particular, the relaxation time spectrum of bitumen is characterized by a broad distribution of long relaxation modes. This observation leads to the development of a new constitutive equation, named the broadened power-law spectrum model. In this model, the wide distribution of long relaxation times is described by a power-law with positive exponent and a stretched exponential cut-off, with parameter β serving as a measure of the broadness of the distribution. This characteristic shape of the bitumen spectrum is attributed to the heterogeneous freezing of different molecular components of bitumen, i.e., to the coexistence of liquid and glassy micro-phases. Furthermore, as this type of heterogeneous glass transition behavior can be considered as a general feature of complex glass-forming systems, the broadened power-law spectrum model is expected to be valid for all types of CGFLs. Examples of the applicability of this model in various complex glass-forming systems are given.     

含膦酸酯官能团离子液体对钢/铝摩擦副的润滑作用研究

合成了3种新型1-(O,O-二乙基膦酰丙基)-3-烷基咪唑六氟磷酸盐离子液体,采用SRV型摩擦磨损试验机评价了所制备的离子液体作为润滑剂对钢／铝摩擦副摩擦学性能的影响,并探讨了其润滑机理．结果表明,所合成的离子液体作为润滑剂对钢／铝摩擦副具有优良的润滑作用,摩擦系数低,抗磨性能优良．表面分析结果表明含膦酸酯官能团的离子液体在摩擦副接触表面形成化学吸附边界润滑膜,从而有效地起到抗磨和提高承载能力的作用．     

Normal droplet impact on horizontal moving films: an investigation of impact behaviour and regimes

Investigations of the impact regimes for a liquid droplet impacting onto horizontal moving liquid films are presented here for the first time. The aim of this study is to show the main impact outcomes and to highlight the effect the movement of films has upon these outcomes. The droplet diameters used in this experiment were 2.47 and 3.86 mm with impact Weber number of between 0.6 and 460. The Reynolds number of the moving film was between 351 and 1,818 depending on the flow rate (1–5.5 L/min) with changes in the film height of between 4.3 and 9.4 mm. The results showed that the impact outcomes exhibit the same regimes established for the impact on static liquids but with different transition boundaries. Moreover, the shape of the impact outcomes is unsymmetrical similar to the inclined impact on static liquids. The impact outcomes are shown to undergo a transition as the Reynolds number of the film increases, this occurs at a threshold value close to the expected transition between laminar and turbulent flow.     

Thermorheological properties near the glass transition of oligomeric poly(methyl methacrylate) blended with acrylic polyhedral oligomeric silsesquioxane nanocages

Two distinct oligomeric species of similar mass and chemical functionality (M _w≈2,000 g/mol), one a linear methyl methacrylate oligomer (radius of gyration R _g≈1.1 nm) and the other a hybrid organic–inorganic polyhedral silsesquioxane nanocage (methacryl-POSS, r≈1.0 nm), were subjected to thermal and rheological tests to compare the behaviors of these geometrically dissimilar molecules over the entire composition range. The glass transition temperatures of the blends varied monotonically between the glass transition temperatures of the pure oligomer (T _g=−47.3°C) and the pure POSS (T _g=−61.0°C). Blends containing high POSS contents (with volume fraction φ _POSS≥0.90) exhibited enhanced enthalpy relaxation in differential scanning calorimetry (DSC) measurements, and the degree of enthalpy relaxation was used to calculate the kinetic fragility indices m of the oligomeric MMA (m=59) and the POSS (m=74). The temperature dependences of the viscosities were fitted by the free-volume based Williams–Landel–Ferry (WLF) and Vogel–Fulcher–Tammann (VFT) framework and a dynamic scaling relation. The calculated values of the fragility from the WLF–VFT fits were similar for the POSS (m=82) and for the oligomer (m=76), and the dynamic scaling exponent was similar for the oligomeric MMA and the POSS. Within the range of known fragilities for glass-forming liquids, the temperature dependence of the viscosity was found to be similarly fragile for the two species. The difference in shape of the nanocages and oligomer chains is unimportant in controlling the glass-forming properties of the blends at low volume fractions (φ _POSS<0.20). However, at higher volume fractions, adjacent POSS cages begin to crowd each other, leading to an increase in the fractional free volume at the glass transition temperature and the observed enhanced enthalpy relaxation in DSC.     

Rheology of critical LCST polymer blends: poly(styrene-co-maleic anhydrite)/poly(methyl methacrylate)

The shear rheology of a binary polymer blend exhibiting a lower critical solution temperature (LCST) phase diagram and a small dynamic asymmetry (difference of glass transition temperatures between its constituents) has been investigated in the vicinity of phase separation; it is a mixture of a random copolymer of styrene and maleic anhydrite and poly(methyl methacrylate). In the linear viscoelastic regime, the material functions are sensitive to phase separation, and the effects of critical concentration fluctuations, which dominate the mechanical response, are quantified, yielding both the binodal and spinodal curves. The weak dynamic asymmetry is apparently responsible for the reduced magnitude of the observed effects, compared to blends exhibiting much larger contrast in glass transition; therefore, this property affects to some degree the accuracy of the rheologically determined phase diagram. The steady shear properties are weakly sensitive to phase separation, and suggest that shear-induced demixing may be possible. They also indicate the importance of the amount of strain energy introduced to the blend in controlling the effects of flow on phase behavior.This investigation demonstrates that the universal effects of concentration fluctuations can be detected in LCST binary polymer blends, provided that some dynamic asymmetry exists, and further they can be quantified in order to characterize the interplay between rheology and thermodynamics of these systems.Dedicated to the memory of Professor Tasos C. Papanastasiou     

Transition from laminar to turbulent flow in liquid filled microtubes

The transition to turbulent flow is studied for liquids of different polarities in glass microtubes having diameters between 50 and 247 µm. The onset of transition occurs at Reynolds numbers of ~1,800–2,000, as indicated by greater-than-laminar pressure drop and micro-PIV measurements of mean velocity and rms velocity fluctuations at the centerline. Transition at anomalously low values of Reynolds number was never observed. Additionally, the results of more than 1,500 measurements of pressure drop versus flow rate confirm the macroscopic Poiseuille flow result for laminar flow resistance to within –1% systematic and ±2.5% rms random error for Reynolds numbers less than 1,800.An erratum to this article can be found at     

Some thermal and rheological properties of homogeneous interpenetrating polymer networks

Summary Homogeneous interpenetrating polymer networks, (IPNs), consisting of methacrylic and epoxy networks, were obtained at various compositions from a simultaneous polymerization of DGEBAMA and DGEBA. For each composition, the glass transition occurs at a well-defined temperature which is lower than the weighted average of the glass transition temperatures of each component. Tensile experiments showed a change of mechanical behaviour above some critical strain value. This phenomenon was corroborated by stress relaxation tests which allowed the determination of a complete relaxation below a critical strain. This strain is increasing with the temperature and decreasing with the crosslink density. Such a property disappeared after the addition of grafting molecules which prevented both networks from any relative sliding. In this way this behaviour appears to be a specific property of interpenetrating networks.With 10 figures     

Thermodynamic aspects of the glass-rubber transition

Summary In 1933 Ehren/est defined transitions in which not only the thermodynamical potential but also the specific volume and entropy of the two states are equal. For these transitions he derived three relations, between the differences of the coefficients of dilatation and of compressibility and the specific heat on one hand and the slope of the transition curve in /)-T-space on the other hand.Although it is beyond any doubt that the glass-rubber transition in polymers is not a second order transition as defined by Ehren]est, yet the term second order transition is often applied to it.The confusion arising from this abuse of a physically well defined eonce]?t is enhanced by the fact that some of Ehren/est's relations are under certain circumstances valid for the glass rubber transition, although in those cases the physical background of these relations is quite different from that of a second order transition in Ehren/est's sense. In fact, the essence of the glass transition has been formulated clearly and correctly by Simon in 1931 and consists in the assumption that in a glass one or more internal parameters are not in equilibrium but are frozen in.The conditions required for the validity of each of EhrenJest's relations are inspected. The equality of two functions of the dilatation and the compressibility coefficients and the specific heats of the two states depends on the condition that there is only one frozen parameter in the glass state. I f there is more than one fl'ozen parameter, then the equality turns into an inequality and the physical meaning of the difference between the two sides is derived.Similar relations as those derived between the quantities mentioned, can be derived between the specific heat, the modulus of elasticity and the temperature coefficient of that modulus. These new relations are more interesting for practical purposes and less subject to experimental errors than the older ones.Finally the expressions for the slope of the transition curve are investigated. The validity of any one of the expressions depends on the physical condition required for a material to become a glass. Reversely from the validity of any of the possible expressions insight in the glass transformation can be derived. The scarce available data give the impression that a material turns into a glass whenever its excess entropy decreases below a critical value.     

非匹配结点的有限单元等参插值方法及其应用研究

针对两零件的异构网格单元结点在接触界面不能相互匹配导致结点属性不能连续过渡和传递的问题,提出非匹配结点的有限单元等参插值方法,通过构建非匹配结点的形函数和修正原结点的形函数,将结点属性值的影响范围限制在可控的局部区域,从而实现两异构网格结点属性在接触界面的连续过渡和传递。通过两个异构的四边形单元网格的结点属性在接触界面的过渡实例和啮合齿轮的接触分析应用,验证了该方法的正确性和有效性。     

Electrically-excited (electroosmotic) flows in microchannels for mixing applications

We propose an asymptotic model for quite general liquid microchannel flows in the presence of electrical double layers (EDLs). The model provides an “inner” solution for the wall layer, which reflects the dominant balance between electrical forces and viscous forces (tangentially), respectively between electrical forces and pressure and viscous forces (normally). The electrically-neutral core of the flow is governed by the standard Navier–Stokes equations, providing the “outer” solution. The asymptotic matching of both solutions provides a method for the simplified numerical treatment of such EDLs. The superposition of the solutions in both regions then allows to infer an approximate solution, valid within the entire domain.Based on this model, we apply external oscillatory electrical fields to excite secondary flows (i) in microchannels with an internal obstacle or (ii) in folded (meander) microchannels. These secondary flows are demonstrated to greatly enhance the mixing of two liquids flowing in a layered fashion through these microchannels. Thus, electrical excitation has considerable potential if micromixers for ionic liquids are designed within electrically-insulating (e.g. plastics, glass) substrates.