徐祖耀院士的学术贡献

论述了徐祖耀院士在马氏体相变、贝氏体相变及形状记忆材料方面的学术贡献。其中包括：揭示了无扩散马氏体相变中存在间隙原子（或离子）的扩散;完善了铁合金马氏体相变的热力学;解决了计算Fe-C合金相变开始温度（Ms）的难题;以孤立子理念演算和阐释了相变驱动力与马氏体长大速率之间的关系;以群论研究了形状记忆合金热弹性马氏体相变的对称性并建立了计算热弹性马氏体对称分布的数学模型;创建了铜基合金马氏体相变和贝氏体相变热力学;认证了陶瓷中存在贝氏体相变。     

β—Cu基合金马氏体相变热力学

提出对β-Cu基合金热弹性马氏体相变的热力学处理。计算了Cu-Zn,Cu-Al及Cu-Zn-Al合金马氏体相变驱动力,T_0温度及M_s温度,M_s的计算值与实验值符合很好。母相有序降低Cu-Zn和Cu-Zn-Al的M_s,但升高Cu-Al的M_s(T_0)。并简介了两种估算非化学自由能的方法。     

THERMODYNAMICS OF MARTENSITIC TRANSPORMATION IN β-Cu BASE ALLOYS

提出对β-Cu基合金热弹性马氏体相变的热力学处理。计算了Cu-Zn,Cu-Al及Cu-Zn-Al合金马氏体相变驱动力,T_0温度及M_s温度,M_s的计算值与实验值符合很好。母相有序降低Cu-Zn和Cu-Zn-Al的M_s,但升高Cu-Al的M_s(T_0)。并简介了两种估算非化学自由能的方法。     

热处理原理的进展及其应用

概述热处理原理(主要为相变)的进展对材料生产的重要作用。举例论述了Ehrenfest的相变分类对材料工程的意义,论证马氏体相变特征作为低碳马氏体钢和形状记忆合金开发的理论基础,对M_S温度作了一般讨论。阐述β铜基合金的贝氏体相变及其逆形状记忆效应。     

马氏体相变研究的进展(一)

概述对马氏体相变基本特征认识的进程，以及与马氏体相变密切相关的形状记忆材料的发展。对马氏体相变热力学、动力学、晶体学、形核-长大、非线性物理模型以及形状记忆效应、伪弹性和伪滞弹性研究进展作了总结。对马氏体相变的继续研究和应用作了展望。全文分两期发表。     

贝氏体相变简介

钢、有色合金和一些陶瓷材料中都存在贝氏体相变。贝氏体钢正成为有益的工程材料。总结评述切变学派和扩散学派作者们以形貌、动力学或晶体学对贝氏体相变机制所持的论点。钢中贝氏体相变以过饱和铁素体开始形成之说迄未得到支持。一些实验已发现替代（置换）型合金元素在相界面上的偏聚，并以此所呈现的拖曳效应说明相变的不完全现象，切变学者以切变机制来解释这个现象，但此现象不是钢中贝氏体相变的普遍情况。贝氏体形成时呈现帐篷形浮突，不具不变平面应变特征；有时马氏体相变晶体学表象理论能近似地应用于贝氏体相变晶体学，但不能以此来判定其相变机制为扩散或切变。溶质拖曳效应以及高分辨电镜对相界面结构实验、热力学研究、磁场和应力场对贝氏体相变影响以及一些预相变现象都确证贝氏体相变籍扩散机制进行。本文作者定义贝氏体为：在Ms温度以上，经扩散相变的产物，多呈片状，形成时会在自由表面上呈现帐篷形浮突。提出贝氏体相变机制进一步研究和应用的展望。     

Co对Ti-Ni形状记忆合金相变和形变特性的影响

用热重分析仪、X射线衍射仪、示差扫描量热仪及拉伸试验研究了Co对Ti-49.8Ni(at%,下同)形状记忆合金相变和形变特性的影响。结果表明,中温退火态Ti-49.8Ni合金冷却/加热时的相变类型为A→R→M/M→A(A—母相,R—R相,M—马氏体相);随退火温度升高,该合金的马氏体相变温度升高,R相变温度先升高后降低;该合金室温相组成为马氏体,具有形状记忆效应(SME)。用1%Co置换等量Ti后所得Ti-49.8Ni-1Co合金冷却/加热时的相变类型为A→R→M/M→R→A,相变温度低,室温组成相为母相A,具有超弹性(SE)特性。退火温度低于600℃时,Ti-Ni基合金的SME和SE特性良好,退火温度超过600℃后,合金氧化加剧,SME和SE特性变差,塑性显著提高。     

马氏体相变研究的进展(二)

概述对马氏体相变基本特征认识的进程，以及与马氏体相变密切相关的形状记忆材料的发展。对马氏体相变热力学、动力学、晶体学、形核-长大、非线性物理模型以及形状记忆效应、伪弹性和伪滞弹性研究进展作了总结。对马氏体相变的继续研究和应用作了展望。     

应力作用下的相变

水静压抑制Fe-C和钢中体积膨胀型相变，如铁素体、珠光体、贝氏体和马氏体相变。单向应力促发铁素体和珠光体相变，拉应力的效果尤为显著。0．38C-Cr-Mo钢中，铁素体、珠光体和贝氏体相变在应力下的动力学，可由Johnson-Mehl-Avrami方程中加入应力因子经修正来描述。由于铁素体和珠光体的化学驱动力小，应力所作膨胀功使形核率(J^*)增高和孕育期τ缩短。而贝氏体相变中，可能由于应力下碳自奥氏体贫化，或减少相界面能，从而使τ增高和τ缩短，待试验予以证明。水静压对Ms温度影响的定量描述因不同材料而异。列出Patel-Cohen所建立的dMs／dσ方程，及本文作者提出的应力影响Ms的方程。应力诱发马氏体会改变其晶体学及形态，提出以形核率的数值来判定其形态。奥氏体的力学稳定化在马氏体相变中主要由于奥氏体强化所导致，在贝氏体相变中却主要由于晶体学阻碍长大所造成的。     

母相时效对Cu-17Al-10Mn合金相变温度和形状记忆性能的影响

研究母相时效过程中Cu-17Al-10Mn(摩尔分数,%)形状记忆合金马氏体转变温度Ms和形状记忆性能的变化规律.结果表明:合金淬火态的Ms比室温的低,室温时合金为无序母相结构,低温时可转变为马氏体;随着时效温度的提高,Cu-17Al-10Mn合金的Ms和形状恢复率均逐渐升高,并在150 ℃时效15 min后达到最大值,这主要归因于淬火空位的逸出使其对母相的钉扎作用减弱;随着时效温度的进一步提高,由于母相分解为贝氏体,合金的Ms和形状恢复率都下降,在250 ℃时效15 min后,母相完全分解,合金的形状恢复率降低到零.     

材料热处理的进展和瞻望

概述材料热处理技术和原理的进展。钢中珠光体相变的晚近研究揭示：α和Fe3C与邻近晶粒γ1呈位向关系，但向γ2晶粒生长；α和Fe3C之间存在位向关系，由台阶长大；一个珠光体的领域中α或Fe3C的分枝生长，形成另一领域。贝氏体相变存在切变和扩散两种机制，目前仍有分歧。马氏体相变的有些概念宜应更新，如Magee的动力学公式对低碳钢需加改进；有些成果须待利用，如GCrl5(AISI 52100)钢残余奥氏体经等温马氏体形成，有利于钢件的尺寸稳定性。简述A1—Cu合金时效技术和机制研究的进展以及系列时效合金的发现。介绍回火马氏体致脆的新机制——Fe3C自马氏体析出和自残余奥氏体析出的相关过程，建议短时回火工艺及钢中加Ni以避免回火致脆。基于材料表面状态对疲劳寿命影响的认识，表面处理得以发展，在钢的渗碳中应用动态碳势控制能得到渗碳层碳浓度的理想分布。瞻望绿色热处理的推广材料相变的理论和建模工作值得加以重视。简介以场变数描述显微组织，并根据相场理论作组织变化的模拟。     

Shape memory materials

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Au-15Cu-10Ni合金时效强化机制研究

常用作电接触材料的Au Cu Ni合金在时效过程中会得到强化,硬度明显增加。采用真空高频熔炼得到Au-15Cu-10Ni合金,对轧制得到的片材进行不同条件下的时效处理,研究其微观组织、晶体结构和力学性能变化。结果表明,150~250℃范围内时效硬化效果显著,并且随温度升高硬度值提高,时效过程中生成的Au CuI有序相是造成硬度提高的主要原因。在200℃的条件下时效2.78 h后,晶粒表面出现了明显的条纹状,组织发生有序转变;时效时间延长至5 d后有序转变完成,晶体结构由fcc转变为fct结构,晶胞发生体积收缩,导致晶界明显宽化。     

Strengthening behavior due to cyclic elastic loading in Pd-based metallic glass

Nanoindentation technique was utilized to unravel the strengthening behavior of Pd-based metallic glass under elastic cyclic loading. This was conducted to ultimately evaluate fatigue behavior which is thought to be a major concern for the structural performance of bulk metallic glasses. The event of shear band formation is considered after subjecting the alloy to loading cycles in the nominal elastic regime, followed by a monotonic deep indent. In all experiments, substantial shift in the load needed to initiate a shear band (indicative of plasticity) was noted. Following prolonged cycling, a fatigue limit was observed evident by the saturation in hardening effect. By varying the amplitude of elastic loading, it appears that a critical loading is needed to initiate strengthening in the bulk metallic glass (BMG); i.e. a specific threshold need to be exceeded for the hardening effect to trigger. This was concluded following successive experiments with increasing number of cycles which proves the effect over multiple cycling. Moreover, the effect of higher loading rates becomes more significant as the successive number of cycles increases. For further assessment, comparative experiments were carried out between holding and cycling in the elastic region. These experiments suggested the necessity of cycling to achieve hardening in the alloy, as no hardening effect was observed following holding experiments. In general, strengthening effect was attributed to the possible development of regions of microplasticity due to the actuating force, without being able to detect these regions in the global load-displacement response. Additional tests were conducted to unravel the irreversibility of these cycling/hardening effects. It was found that slight recovery is possible when no resting time was introduced before the deep indent. This suggests that part of the cycling effects can be reversed which can be linked to the instability of the shear transformation zones (STZs).     

Reverse Transformation in [110]-Oriented Face-Centered-Cubic Single Crystals Studied by Atomic Simulations

Bidirectional transformations, which are achieved by triggering both dynamic forward transformation from the face-centered-cubic (fcc) austenite to the hexagonal-close-packed (hcp) martensite and the reverse transformation from martensite to austenite during cold deformation, have been previously reported in FeMnCoCr-based high-entropy alloys (HEAs). This leads to the permanent refinement of microstructure and hence enhances the work-hardening capacity of alloys. In order to reveal the microscopic mechanism of the reverse transformation in HEAs under deformation, the effect of the sample aspect ratio, i.e., Z/X, on the evolution of deformation systems in the equi-atomic FeMnCoCrNi alloy with [110] orientation during uniaxial tensile loading along the Z direction is investigated by atomic simulations in this study. When the aspect ratio is 0.5, the reverse transformation is more significant compared with other models, while a good plasticity can still be maintained. We then compare the micromechanical behavior of three fcc single crystals, i.e., FeMnCoCrNi, FeCuCoCrNi, and pure Cu. The results show that the stacking fault energy plays a major role in the activation of different deformation mechanisms; however, the lattice distortion in the HEA does not significantly affect the activation of deformation systems. Furthermore, for all materials dislocation slip leads to the softening, while strain hardening is attributed to the initiation of multiple deformation mechanisms. The Shockley partials slip leads to bidirectional phase transition, twinning and detwinning in the three materials. Thus, the reverse transformation can occur in all metallic materials where the fcc to hcp phase transformation is the dominant deformation mechanism. These findings contribute to an in-depth understanding of the deformation mechanism in fcc-structured materials under severe plastic deformation and provide theoretical guidance for the design of alloys with superior strength-plasticity combinations.     

相变研究的展望与发展《材料形态学》雏议

提出相变研究的展望,如无能垒形核的理论与实验。由于材料形态和性质紧密相关,初步建议重视发展《材料形态学》。对共析钢中珠光体相变的过冷度或相变温度和珠光体片间距之间的关系以及珠光体形态（片间距）影响珠光体强度的文献作了总结。本文提出了一个过冷度和珠光体强度间关系的定量表达式。     

凝固过程晶粒生长动力学及拓扑转变机制的相场研究

基于连续相场动力学模型,研究了凝固过程形核、长大及粗化阶段的组织形貌演化,动力学转变,以及粗化过程拓扑转变,分析了形核与长大过程的关系。研究结果表明,形核长大过程中,晶粒体积分数逐渐增大至平衡值,总表面积先增大后减小,体积自由能是形核的驱动力,表面能是形核的阻力。形核伴随着长大,两者是相互重叠相互竞争的两个过程。晶粒生长过程中,边数大于六的晶粒持续长大,而边数少于六的晶粒不断缩小。小晶粒消失机制有:临近切换机制;三边﹑四边及五边晶粒直接消失机制;四边交叉点分离并最终导致小晶粒消失机制;晶界直接消失机制。模拟结果与实验结果符合较好。     

In situ analysis of the strain evolution during welding using low transformation temperature filler materials

ABSTRACT

Compared to conventional welding consumables using low transformation temperature (LTT) filler materials is an innovative method to mitigate tensile residual stresses due to delayed martensite transformation of the weld. For the effective usage of LTT filler materials, a deeper understanding of the complex processes that lead to the final residual stress state during multi-pass welding is necessary. Transformation kinetics and the strain evolution of multi-pass welds during welding were investigated in situ at the beamline HEMS@PETRAIII, Germany. Compared to conventional welds, the total strain was reduced and compression strain was achieved when using LTT filler materials. For an optimal use of the LTT effect in the root of multi-pass welds, the alloying concept must be adapted taking care of dilution.     

Structural changes of Co70Fe5Si10B15 amorphous alloy induced during heating

In this study we present the results on complex structural changes of the Co₇₀Fe₅Si₁₀B₁₅ amorphous alloy induced during heating in the temperature range between 20 and 1000 °C. The structural and phase transformation changes were correlated with DTA, XRD and SEM properties. It is shown that initial Co₇₀Fe₅Si₁₀B₁₅ alloy during heating undergoes complex crystallochemical changes. In the range between ambient temperature and near 400 °C, investigated alloy retains the solid-state amorphous properties. Prolonged heating induces complete transformation to crystalline solid state. The solid–solid amorphous to crystalline state transformation process is completed at 500 °C, when two nanocrystalline phase alloy systems are formed. Prolonged thermal treatment between 600 and 1000 °C, influenced further elemental segregation and phase transition. At 1000 °C, the composite material consisting of two FCC cobalt-rich alloys and a hexagonal unidentified alloy are formed.     

Al-Si-Cu-Mg-Zn合金的高温相变储热性能研究

制备了20种基于Al-Si-Cu-Mg-Zn合金的高温相变储热材料,采用综合热分析技术研究其储热性能。结果表明,20种储热材料的相变温度处于440℃~650℃之间,均具有较大的相变潜热,大部分储热材料的相变潜热在200 J.g-1以上。Al-Si合金储热材料具有较高的单位质量储热量;Al-Cu-Zn合金储热材料具有较大的单位体积储热量;Mg、Zn能显著降低相变温度,具有较好的扩大储热温度范围作用。