NMR signature of evolution of ductile-to-brittle transition in bulk metallic glasses

The mechanical properties of monolithic metallic glasses depend on the structures at atomic or subnanometer scales, while a clear correlation between mechanical behavior and structures has not been well established in such amorphous materials. In this work, we find a clear correlation of (27)Al NMR isotropic shifts with a microalloying induced ductile-to-brittle transition at ambient temperature in bulk metallic glasses, which indicates that the (27)Al NMR isotropic shift can be regarded as a structural signature to characterize plasticity for this metallic glass system. The study provides a compelling approach for investigating and understanding the mechanical properties of metallic glasses from the point of view of electronic structure.     

不均匀性:非晶合金的灵魂

非晶合金,即金属玻璃,是一类特殊的由基本化学元素组成的非晶态物质,由于其独特的微观组织结构,展现出了不同于传统晶态合金材料的特殊物性,而成为高性能材料应用领域的重要一员.由于非晶合金的结构无序性,且当前精确表征其微观结构的实验手段缺乏,相应的理论模型也不完善,人们对非晶合金中一些基础物理问题的认识尚且不足,无法形成基本的理论框架来精确地描述其物性产生的微观机理.因而,当前非晶合金研究的核心问题可以概括为:如何建立以微观特征或结构为基础的基本理论框架,准确地概括非晶合金物性的微观机理.在过去几十年里,针对非晶合金的大量研究表明,在非晶合金长程无序的特征中,隐藏着本征的不均匀性和有序,且这些不均匀性的特征与材料物性有着密切的关联,使得建立以不均匀性特征为基础的理论框架成为可能.本文从非晶合金微观特征的不均匀性包括静态不均匀性和动态不均匀性的视角出发,概括性地总结了非晶合金材料与物理研究中取得的丰硕成果,及当前需要关注的重要科学问题,并针对未来可能的研究模式进行了展望.     

Effect of icosahedral clusters on β-relaxations in metallic glasses

The most pronounced β-relaxation was found in the Y-based binary metallic glasses(MGs). The correlation betweenβ-relaxation and local atomic structure was studied. The dynamic mechanical measurements were performed for three chosen binary systems: Zr-, Ti-, and Y-based MGs. The experimental results show that, in each system,the larger negative enthalpy of mixing(?Hm) between the component elements makes β-relaxation become more pronounced. The less negative value of ?Hm facilitates the formation of icosahedral clusters, which have a pinning effect on the excitation of β-relaxations and correspondingly make the β-relaxation become less pronounced. These chemical effects on β-relaxations can only be compared in the same MG system, and it is not suitable for the comparison between different systems due to the different features of the major metallic elements.     

基于分数阶微分流变模型的非晶合金黏弹性行为及流变本构参数研究

近年来, 基于非晶合金名义弹性区的流变力学行为探索其结构及形变机理是非晶合金领域研究的热点之一. 本文根据非晶合金结构不均匀性的特征, 提出能够比拟树状分形网络结构的分数阶微分流变模型研究非晶合金的黏弹性行为. 通过室温纳米压痕实验, 对三种不同泊松比和玻璃化转变温度的非晶合金的黏弹性变形行为进行了研究. 实验结果表明: 在表观弹性区, 非晶合金的变形表现出与加载速率相关的线性黏弹性性质. 根据Riemann-Liouville分数阶微积分定义, 分别由分数阶微分及整数阶Kelvin模型对实验结果进行了分析. 分析结果表明, 相对于整数阶流变模型, 分数阶微分流变模型能更精细地表征材料的黏弹性变形特征; 在流变模型参数中, 黏性系数η_A和分数阶次α反映出材料的流变特性和流动趋势, 流变参数与玻璃转变温度、泊松比之间具有较好的相关性, 上述相关性有助于从微观结构角度理解材料塑性与泊松比的关联.     

Kinetics of isothermal creep in metallic glasses including the statistical distribution of activation parameters

A generalized theoretical model is proposed for the structural relaxation of metallic glasses under load. Structural relaxation is treated as a set of irreversible, uncorrelated, two-stage atomic displacements in some regions of the structure, the “relaxation centers.” In loaded samples structural relaxation acquires a directional character, leading to the buildup of plastic deformation in accordance with the magnitude and orientation of the applied mechanical stress. General equations are obtained for creep kinetics including a continuous statistical distribution of the principal activation parameters. These equations are compared with the results of a special experiment. The model is found to provide an adequate interpretation of the observed creep kinetics, except for the first 10¹–10² seconds after loading. It is argued that the initial stage of creep is determined by reversible atomic realignments in relaxation centers having symmetric two-well potential. Fiz. Tverd. Tela (St. Petersburg) 39, 2008–2015 (November 1997)     

块体非晶合金的韧塑化

块体非晶合金因其独特的原子结构而具有许多优异的力学性能,成为近年来材料领域的研究热点之一,但是由于其在变形过程中的室温脆性和应变软化等关键问题一直制约着其实际工程应用.为解决此问题,块体非晶合金领域的研究者们提出了多种方案,包括通过在非晶合金中调控其内禀特性如弹性常数、结构不均匀性,通过外加手段改变其应力及缺陷状态,通过外加和内生的方法在非晶基体中引入晶态增强相等方式,获得了一系列力学性能优异的块体非晶合金及其复合材料.特别是利用"相变诱导塑性"(transformation-induced plasticity,TRIP)概念研制出的块体非晶合金复合材料,同时具有大的拉伸塑性和加工硬化能力.本文围绕块体非晶合金的韧塑化这个关键科学问题,对单相非晶及非晶复合材料的韧塑化方案及机理进行了综述,着重介绍了TRIP韧塑化块体非晶合金复合材料的制备、性能、组织调控及韧塑化机理等,并对此领域的未来发展进行了展望.     

非晶合金及合金液体的局域五次对称性

简要回顾了从20世纪30年代至今,有关非晶合金及合金液体的局域结构五次对称性的实验、理论和模拟研究.在简单液体的早期研究中,人们已经意识到五次对称性在简单液体的无序结构、过冷和晶化等起着重要作用,二十面体短程序作为五次对称性的典型代表受到了广泛关注.自从Frank提出简单液体中二十面体短程序的结构单元,大量的理论和实验研究已经明确在简单液体、合金液体和金属玻璃中存在局域五次对称性,并且建立了局域五次对称性与合金液体复杂动力学行为、玻璃转变、液体-液体相变以及非晶合金的形变等统一的定量描述和物理图像,表明了局域五次对称性作为结构参量的简单、普遍和有效性.     

Multiscale structures and phase transitions in metallic glasses:A scattering perspective

Amorphous materials are ubiquitous and widely used in human society, yet their structures are far from being fully understood. Metallic glasses, a new class of amorphous materials, have attracted a great deal of interests due to their exceptional properties. In recent years, our understanding of metallic glasses increases dramatically, thanks to the development of advanced instrumentation, such as in situ x-ray and neutron scattering. In this article, we provide a brief review of recent progress in study of the structure of metallic glasses. In particular, we will emphasize, from the scattering perspective, the multiscale structures of metallic glasses, i.e., short-to-medium range atomic packing, and phase transitions in the supercooled liquid region, e.g., crystallization and liquid-to-liquid phase transition. We will also discuss, based on the understanding of their structures and phase stability, the mechanical and magnetic properties of metallic glasses.     

Metallic liquids and glasses: atomic order and global packing

In this Letter, we have revealed the common structural behavior of metallic glasses through scrutinizing the evolution of pair distribution functions from metallic liquids to glasses and statistically analyzing pair distribution functions of 64 metallic glasses. It is found that the complex atomic configuration in metallic glasses can be interpreted globally as a combination of the spherical-periodic order and local translational symmetry. The implications of our study suggest that the glass transition could be visualized mainly as a process involving in local translational symmetry increased from the liquid to glassy states.     

非晶材料与物理近期研究进展

由于结合了金属和玻璃的特性,非晶合金表现出许多新奇和优异的力学和物理性质,在很多领域具有广泛的应用前景.非晶合金具有连续可调的成分、简单无序的原子结构、丰富多变的材料性质,为研究非晶态物理中的许多共性科学问题提供了理想的模型材料.块体非晶合金的发展更是将玻璃和液体及其相关科学问题的研究推进到凝聚态物理和材料科学的研究前沿.中国科学院物理研究所极端条件物理重点实验室亚稳材料合成、结构及性能研究组(EX4组)近二十年来一直致力于非晶材料和物理的研究,在新型非晶合金的制备、物性以及相关机理的研究上取得了许多重要成果.本文介绍团队最近在非晶材料和物理机理方面取得的研究成果,包括非晶合金的动力学行为和调控、非晶合金的表面动力学、功能应用以及材料探索新方法等.     

非晶中结构遗传性及描述

非晶态物质广泛存在于人们的日常生活和工业生产活动中,但人们对其原子结构及其结构与性能关系的认识还远不如对晶体材料那样充分.非晶态物质的原子结构不具备空间平移对称性,这使得传统针对晶体材料的实验技术和手段无法直接有效地应用到非晶态物质的结构分析中.用常规的衍射实验数据分析方法并不能直接地观察到非晶态物质的本征结构特征,但这些实验衍射数据往往隐含有极其重要的微观结构信息.本文简要综述了这些衍射数据背后所隐含的与金属玻璃中程序相关的结构信息.研究发现,非晶态物质中的一类隐含序与晶体结构中的球周期序紧密相关,意味着非晶态物质与晶体材料之间在原子结构上存在着非凡的同源性.进一步的研究结果还表明,不同隐含拓扑序之间纠缠的强弱与体系本身的玻璃形成能力存在明显的对应关系,这为衡量金属合金玻璃形成能力强弱的经验规律——混乱原理提供了微观结构上的理解,同时为进一步深入认识和理解非晶态材料衍射数据所隐含的微观结构信息提供了新的分析思路和方法.     

非晶合金中的流变单元

非晶合金是一类具有诸多优异性能的先进金属材料,同时也是研究非晶态物质的模型体系.最近,大量的实验和模拟证据显示,在非晶合金中可能存在类似晶体中缺陷的"流变单元",这些动力学单元和非晶合金的的流变、物理、力学性能密切关联.本文主要综述了流变单元提出的背景、实验证据、流变单元的特征、激活与演化过程、相互作用以及相关的理论.文中提供了大量实验证据证明流变单元模型不仅可以帮助理解非晶态物质中如形变、玻璃转变、弛豫动力学以及非晶结构和性能的关系等重要的基本物理问题,而且可以指导非晶合金性能的调控和设计,获得性能优异的非晶合金材料.     

Creep kinetics of linearly heated metallic glasses

A quantitative theory of creep in linearly heated metallic glasses is developed in terms of new ideas on the kinetics of irreversible structural relaxation under external mechanical stress. The validity of the resulting flow equation has been confirmed by a specially devised experiment. It is shown that the temperature dependence of Newtonian viscosity is determined by the rate of heating and the energy spectrum of irreversible structural relaxation. Fiz. Tverd. Tela (St. Petersburg) 39, 2186–2190 (December 1997)     

Mechanisms of inelastic deformation in metallic glasses

The phenomenology of inelastic deformation in metallic glasses is briefly reviewed. This is followed by a short review of methods used to characterize the glassy structure. Considerable emphasis is put on the amorphous soap bubble raft as a two-dimensional analog medium that can give quantitatively accurate simulations of both the structural properties ofmetallic glasses and the mechanisms of their inelastic deformation. Analysis of such sheared bubble rafts has established that the basic ingredient of inelastic deformation in these materials is shear transformations occurring in small, atomic size volume elements that are only weakly interacting. Through the use of an inter-bubble potential, the changes in energy of these shear transformations can be analyzed in great detail. This has disclosed a remarkable capability in the model to parallel and predict complex relaxation phenomena in metallic glasses down to the detail of simulating the distributed nature of the structure and the free energies for transformation. This has led further to a very satisfactory model for the kinetics of anelastic and viscoplastic response of the structure for processes on shear localization, and nas led even to a semi-quantitative model for embrittlement resulting from physical ageing.     

Internal friction peaks in metallic glasses

Low-temperature, thermally-activated internal friction peaks have been observed in three binary metallic glasses containing only metallic components: Cu₅₀Zr₅₀, Co₃₅Y₆₅ and Co₃₅Dy₆₅. The magnitudes of the activation energies and the characteristic relaxation times obtained for these materials as well as the sharpness of the peaks point to process involving either atomic jumps of a specific nature or similar localized reordering. Possible local structural configurations with built-in, non-uniform stress distributions that could lead to such relaxation effects are discussed.     

Evidence of distributed interstitialcy-like relaxation of the shear modulus due to structural relaxation of metallic glasses

The interstitialcy theory is used to calculate the kinetics of shear modulus relaxation induced by structural relaxation of metallic glasses. A continuous distribution of activation energies is shown to be a salient feature of the relaxation. High precision in situ contactless electromagnetic acoustic-transformation shear modulus (600- kHz) measurements performed on a Zr-based bulk metallic glass are found to strongly support the approach under consideration. It is revealed that the activation energy spectra derived from isothermal and isochronal shear modulus measurements are in good agreement with each other. It is concluded that the increase of the shear modulus during structural relaxation can be understood as a decrease of the concentration of structural defects similar to dumbbell interstitials in simple crystalline metals.     

Structural evolution in deformation-induced rejuvenation in metallic glasses: A cavity perspective

Classical molecular dynamics simulations have been performed to investigate the structural evolution in deformationinduced rejuvenation in Cu_(80)Zr_(20) metallic glass. Metallic glasses obtained by different cooling rates can be rejuvenated into the glassy state with almost the same potential energy by compressive deformation. The aging effect in different metallic glasses in cooling process can be completely erased by the deformation-induced rejuvenation. The evolution of cavities has been analyzed to understand the structural evolution in rejuvenation. It is found that as metallic glasses are rejuvenated by mechanical deformation, a lot of cavities are created. The lower the potential energy is, the more the cavities are created. The cavities are mainly created in the regions without cavities or with small cavities populated, indicating that the irreversible rearrangements induced by deformation are accompanied by the creation of cavity. This finding elucidates the underlying structural basis for rejuvenation and aging in metallic glasses from the cavity perspective.     

Quantitative structure-plasticity relationship in metallic glass:A machine learning study

The lack of the long-range order in the atomic structure challenges the identification of the structural defects, akin to dislocations in crystals, which are responsible for predicting plastic events and mechanical failure in metallic glasses(MGs). Although vast structural indicators have been proposed to identify the structural defects, quantitatively gauging the correlations between these proposed indicators based on the undeformed configuration and the plasticity of MGs upon external loads is still lacking. Here, we systematically analyze the ability of these indicators to predict plastic events in a representative MG model using machine learning method. Moreover, we evaluate the influences of coarse graining method and medium-range order on the predictive power. We demonstrate that indicators relevant to the low-frequency vibrational modes reveal the intrinsic structural characteristics of plastic rearrangements. Our work makes an important step towards quantitative assessments of given indicators, and thereby an effective identification of the structural defects in MGs.     

The influence of efficient atomic packing on the constitution of metallic glasses

Efficient atomic packing is shown to be a fundamental consideration in the formation of metallic glasses. A simple concept of packing efficiency, based on atom packing in the first coordination shell of solute-centred clusters, is proposed and developed. This model leads to the prediction that specific radius ratios, defined as the radius of the solute atom divided by the radius of the solvent atom, are preferred in the constitution of metallic glasses. Analysis of a large number of binary and complex metallic glasses shows that these specific critical radius ratios R* are indeed preferred in known metallic glasses. The predictions of this model extend previous proposals to describe the influence of topology on the formation of metallic glasses. Although this model represents a simple idealization, the strong agreement with published metallic glasses suggests that efficient atomic packing, enabled by solute-centred clusters, forms a fundamental consideration in the constitution of metallic glasses.