The significance of the crystallisation temperature of a glass

A procedure for calculating a continuous-heating-transformation diagram from an isothermal time-temperature-transformation diagram is presented. Application of the procedure to data describing the crystallisation of metallic glasses gives calculated “start” temperatures that are in close agreement with observed crystallisation temperatures. It therefore appears that for most practical purposes the crystallisation temperature of a glass can be interpreted to be the “start” temperature on continuous heating.     

The elastic properties, elastic models and elastic perspectives of metallic glasses

Bulk metallic glass (BMG) provides plentiful precise knowledge of fundamental parameters of elastic moduli, which offer a benchmark reference point for understanding and applications of the glassy materials. This paper comprehensively reviews the current state of the art of the study of elastic properties, the establishments of correlations between elastic moduli and properties/features, and the elastic models and elastic perspectives of metallic glasses. The goal is to show the key roles of elastic moduli in study, formation, and understanding of metallic glasses, and to present a comprehensive elastic perspectives on the major fundamental issues from processing to structure to properties in the rapidly moving field.A plentiful of data and results involving in acoustic velocities, elastic constants and their response to aging, relaxation, applied press, pressure and temperature of the metallic glasses have been compiled. The thermodynamic and kinetic parameters, stability, mechanical and physical properties of various available metallic glasses especially BMGs have also been collected. A survey based on the plentiful experimental data reveals that the linear elastic constants have striking systematic correlations with the microstructural features, glass transition temperature, melting temperature, relaxation behavior, boson peak, strength, hardness, plastic yielding of the glass, and even rheological properties of the glass forming liquids. The elastic constants of BMGs also show a correlation with a weighted average of the elastic constants of the constituent elements. We show that the elastic moduli correlations can assist in selecting alloying components with suitable elastic moduli for controlling the elastic properties and glass-forming ability of the metallic glasses, and thus the results would enable the design, control and tuning of the formation and properties of metallic glasses.We demonstrate that the glass transition, the primary and secondary relaxations, plastic deformation and yield can be attributed to the free volume increase induced flow, and the flow can be modeled as the activated hopping between the inherent states in the potential energy landscape. We then propose an extended elastic model to understand flow in metallic glass and glass-forming supercooled liquid, and the model presents a simple and quantitative mathematic expression for flow activation energy of various glasses. The elastic perspectives, which consider all metallic glasses exhibit universal behavior based on a small number of readily measurable parameters of elastic moduli, are presented for understanding the nature and diverse properties of the metallic glasses.     

Viscous flow recovery in bulk metallic glasses by heat treatment

It is commonly accepted that the ability of metallic glasses to undergo viscous flow sharply and ineversibly drops with increasing duration and temperature of annealing, which is related to an increase in the degree of “irreversible” structural relaxation. The results of isothermal creep measurements show that this ability can be recovered almost completely by means of short-term heating to a temperature above that of the glass transition.     

Metallic glasses from “alchemy” to pure science: Present and future of design,processing and applications of glassy metals

Metallic glasses, first discovered a half century ago, are currently among the most studied metallic materials. Available in sizes up to several centimeters, with many novel, applicable properties, metallic glasses have also been the focus of research advancing the understanding of liquids and of glasses in general.Metallic glasses (MGs), called also bulk metallic glasses (BMGs) (or glassy metals, amorphous metals, liquid metals) are considered to be the materials of the future. Due to their high strength, metallic glasses have a number of interesting applications, for example as coatings. Metallic glasses can also be corrosion resistant. Metallic glasses, and the crystalline materials derived from them, can have very good resistance to sliding and abrasive wear. Combined with their strength – and now, toughness – this makes them ideal candidates for bio-implants or military applications. Prestigious Journals such as “Nature Materials”, “Nature” frequently publish new findings on these unusual glass materials. Moreover Chinese and Asian scientists have also been showing an interest in the study of metallic glasses.This review paper is far from exhaustive, but tries to cover the areas of interest as it follows: a short history, the local structure of BMGs and the glass forming ability (GFA), BMGs’ properties, the manufacturing and some applications of BMGs and finally, about the future of BMGs as valuable materials.     

油水相界面张力对乳化炸药性能的影响

采用白金环法测定了乳化炸药复合油相与硝酸铵水溶液的界面张力,并研究了乳化剂质量分数、温度、分子结构和热值对油水相界面张力的影响以及界面张力对乳胶基质微观结构和储存稳定性的影响。结果表明,随着乳化剂质量分数的升高,界面张力先下降后保持恒定;随着温度升高,界面张力呈线性下降趋势;复合蜡组分的异构化烷烃含量越高,环状化合物越少,热值越低,油水相界面张力越低。随着界面张力和临界质量分数的降低,乳胶基质的粒径减小。乳胶基质的储存稳定性随着油相材料界面张力的降低而增强。     

Free volume theories of the glass transition and the special case of metallic glasses

Theories based on the concepts of free volume and the existence of holes in liquids are briefly reviewed. Available experimental data on the changes in specific heat and thermal expansion at the glass transition temperature and the temperature dependence of viscosity near transition have been utilized to evaluate the hole formation energy and critical hole size in palladium-, platinum- and gold-based metallic glasses. It has been found that in conformity with theoretical predictions, transport in metallic glasses occurs by the movement of highly ionized atoms. A linear relationship exists between the hole formation energy and glass transition temperature of metallic glasses. It is suggested that a high energy of hole formation is a necessary criterion for easy vitrification of metallic melts. The behaviour of vacancies in crystalline metals is compared with the behaviour of holes in metallic glasses.On leave from the Department of Metallurgical Engineering, Banaras Hindu University, Varanasi-5, India     

Wetting and spreading of liquid metals on ZrB2-based ceramics

The possibility to exploit commercially the peculiar characteristics of refractory metallic and ceramic materials and in particular of Zirconium diboride ceramics—a class of promising materials for high temperature applications—often depends to a great extent on the ability to join different ceramics one to the other or to special metallic alloys. As the behaviour of a metal-ceramic joint is ruled by the chemical and the physical properties of the interface, the knowledge of wettability, interfacial tensions and interfacial reactions is mandatory to understand what happens at the liquid metal-ceramic interface during joining processes. In the framework of an extensive study aimed at evaluating the wettability and the interfacial characteristics of different metal-ceramic systems, the behaviour of ZrB₂ in contact with liquid Ag and its alloys (Cu, Ti, Zr, Hf) has been studied. ZrB₂ pure, with different sintering aids or “alloyed” with other ceramic materials (SiC, Si₃N₄), have been used. The wetting and spreading experiments have been performed by the sessile drop technique under controlled atmospheres. The wetting and spreading characteristics and the interfacial reactions are discussed as a function of time, compositions of the ceramic and of the alloy involved. The interfacial morphologies, analysed by SEM and EDS, show the presence of regular interfaces and adsorption layers and of different bulk phases which are interpreted in terms of the relevant phase-diagrams.     

金属玻璃切削加载的形变屈服准则与实验验证

以金属玻璃切削过程中的屈服形变为研究对象,引入源于岩土领域的M-C屈服准则来解决传统Treaca准则及Mises准则不能反映金属玻璃的应力敏感性问题。另外鉴于金属玻璃的温度敏感特性以及切削加工时较高的切削温升,将经过温度修正的改进型M-C屈服准则应用于金属玻璃的切削模型之中。切削力实验表明,基于传统屈服准则、不含温度项的M-C屈服准则以及经过温度修正的M-C屈服准则所建立的切削力模型中,后者的解析解与切削力实测值相比误差最小(平均误差8.92%),说明经过温度修正的M-C屈服准则可以较好地反映金属玻璃切削加载的切削力及材料形变过程,为后续金属玻璃切削机理的深入研究奠定了理论基础。     

高熵非晶合金耐腐蚀性能研究进展

高熵非晶合金是近年来发展起来的一种新型合金材料,因其兼具高熵合金和非晶合金优异的力学性能、耐腐蚀性能、磁性能等功能特性,引发了众多学者的广泛关注。本文简述了高熵非晶合金的含义与特点,介绍了高熵非晶材料的制备方法及组织与性能;归纳了该类材料的耐蚀机理与耐腐蚀性能的最新研究成果;展望了采用机器学习助力设计高熵非晶合金的新范式,并指出探究工况环境下的腐蚀失效机制、完善高熵非晶合金微观耐蚀机理与优化相关制备工艺是该材料广泛应用的前提条件。针对高熵非晶合金的开发及其耐腐蚀性开展的应用基础研究,将为我国海洋事业的“远洋化、深海化”提供先进的技术支撑和材料保障。     

Inverse ductile–brittle transition in metallic glasses?

There is evidence that metallic glasses can show increased plasticity as the temperature is lowered. This behaviour is the opposite to what would be expected from phenomena such as the ductile–brittle transition in conventional alloys. Data collected for the plasticity of different metallic–glass compositions tested at room temperature and below, and at strain rates from rate 10^?5 to 10³ s^?1, are reviewed. The analogous effects of low temperature and high strain rate, as observed in conventional alloys, are examined for metallic glasses. The relevant plastic flow in metallic glasses is inhomogeneous, sharply localised in thin shear bands. The enhanced plasticity at lower temperature is attributed principally to a transition from shear on a single dominant band to shear on multiple bands. The origins of this transition and its links to shear bands operating ‘hot’ or ‘cold’ are explored. The stress drop on a shear band after initial yielding is found to be a useful parameter for analysing mechanical behaviour. Schematic failure mode maps are proposed for metallic glasses under compression and tension. Outstanding issues are identified, and design rules are considered for metallic glasses of improved plasticity.     

Zr基块体非晶合金玻璃形成能力与压铸成型性能研究

本文分析了熔体温度、铸造压力和化学成分对非晶合金玻璃形成能力(GFA)与压铸成型性能的影响,并探究两种性能的工艺关联。研究发现:随熔体温度升高,Zr基非晶合金GFA先提高后减小,且合金成分不同,熔体化学成分,局域原子团簇特征和合金实际冷却速率就不同,非晶合金GFA与玻璃稳定性也就存在差异。非晶合金的压铸成型能力随熔体温度和铸造压力升高不断提高,但与GFA存在相互限制的作用:当合金GFA较强时,熔体内原子堆垛密实,粘滞系数较高严重阻碍过冷液流动成形,且玻璃稳定性越好压铸成型性能越差;而当熔体温度过高,非晶合金GFA减弱,过冷液粘度降低时,才能快速提高非晶合金的压铸成型性能。因此,选择最佳的合金成分、优化工艺参数有利于非晶精密结构件成型。     

Atomistic basis for the plastic yield criterion of metallic glass

Because of their disordered atomic structure, amorphous metals (termed metallic glasses) have fundamentally different deformation mechanisms compared with polycrystalline metals. These different mechanisms give metallic glasses high strength, but the extent to which they affect other macroscopic deformation properties is uncertain. For example, the nature of the plastic-yield criterion is a point of contention, with some studies reporting yield behaviour roughly in line with that of polycrystalline metals, and others indicating strong fundamental differences. In particular, it is unclear whether pressure- or normal stress-dependence needs to be included in the plastic-yield criterion of metallic glasses, and how such a dependence could arise from their disordered structure. In this work we provide an atomic-level explanation for pressure-dependent yield in amorphous metals, based on an elementary unit of deformation. This simple model compares favourably with new atomistic simulations of metallic glasses, as well as existing experimental data.     

Strength statistics of single crystals and metallic glasses under small stressed volumes

It has been well documented that plastic deformation of crystalline and amorphous metals/alloys shows a general trend of “smaller is stronger”. The majority of the experimental and modeling studies along this line have been focused on finding and reasoning the scaling slope or exponent in the logarithmic plot of strength versus size. In contrast to this view, here we show that the universal picture should be the thermally activated nucleation mechanisms in small stressed volume, the stochastic behavior as to find the weakest links in intermediate sizes of the stressed volume, and the convolution of these two mechanisms with respect to variables such as indenter radius in nanoindentation pop-in, crystallographic orientation, pre-strain level, sample length as in uniaxial tests, and others. Experiments that cover the entire spectrum of length scales and a unified model that treats both thermal activation and spatial stochasticity have discovered new perspectives in understanding and correlating the strength statistics in a vast of observations in nanoindentation, micro-pillar compression, and fiber/whisker tension tests of single crystals and metallic glasses.     

Nitrogen as an alloying element in some metallic glasses

Glassy alloy ribbons containing nitrogen as an alloying element have been produced by chill block melt-spinning master alloys which were specially pre-melted for enhanced nitrogen content. Alloying substantial amounts of Cr, a potent nitride former, has been found to greatly increase the amount of nitrogen in solution. In turn, thermal stability of the Cr-bearing metallic glasses has been found to increase as much as 31 K with only a 0.5 at% nitrogen addition. No analogous changes in glassy alloy embrittlement or Curie temperature have been observed. However, although weak, the response of Curie temperature to annealing in the Cr-bearing metallic glasses was found to be affected by the presence of nitrogen. Thus, nitrogen appears to be a viable alloying element in some metallic glasses and may have a potent effect on some properties.     

Comparison of compressive deformation and fracture behaviors of Zr- and Ti-based metallic glasses with notches

Compressive tests on the Zr- and Ti-based metallic glasses with different notches were investigated to compare their shear fracture mechanism and plastic deformation abilities. It is found that the plasticity of the two metallic glasses can be improved by installing two semicircular symmetrical notches even for the Ti-based metallic glass which has nearly zero compressive plasticity. The enhanced plasticity may be ascribed to the easy initiation of shear bands (SBs) around the notches, and the consequent blocking effect of notches on the propagation of shear bands according to the large-scale stress gradient. Additionally, based on a theoretical model originated from the concept of critical steady shear displacement (CSSD), compared with the sizes of smooth regions on the fracture surface, the plasticity difference of the two different metallic glasses was analyzed quantitatively. The current findings might provide an approach to understand and estimate the difference in the plastic deformation abilities on diverse metallic glasses, as well as the ones with large-scale stress gradient.     

Intermetallic growth study on SnAgCu/Cu solder joint interface during thermal aging

The intermetallic compound (IMC) growth behavior at SnAgCu/Cu solder joint interface under different thermal aging conditions was investigated, in order to develop a framework for correlating IMC layer growth behavior between isothermal and thermomechanical cycling (TMC) effects. Based upon an analysis of displacements for actual flip-chip solder joint during temperature cycling, a special bimetallic loading frame with single joint-shear sample as well as TMC tests were designed and used to research the interfacial IMC growth behavior in SnAgCu/Cu solder joint, with a focus on the influence of stress–strain cycling on the growth kinetics. An equivalent model for IMC growth was derived to describe the interfacial Cu-Sn IMC growth behavior subjected to TMC aging as well as isothermal aging based on the proposed “equivalent aging time” and “effective aging time”. Isothermal aging, thermal cycling (TC) and TMC tests were conducted for parameter determination of the IMC growth model as well as the growth kinetic analysis. The SnAgCu/Cu solder joints were isothermally aged at 125, 150 and 175 °C, while the TC and TMC tests were performed within the temperature range from ?40 to 125 °C. The statistical results of IMC layer thickness showed that the IMC growth for TMC was accelerated compared to that of isothermal aging based on the same “effective aging time”. The IMC growth model proposed here is fit for predicting the IMC layer thickness for SnAgCu/Cu solder joint after any isothermal aging time or thermomechanical cycles. In addition, the results of microstructure evolution observation of SnAgCu/Cu solder joint subjected to TMC revealed that the interfacial zone was the weak link of the solder joint, and the interfacial IMC growth had important influence on the thermomechanical fatigue fracture of the solder joint.     

A theoretical description of grain boundary electron scattering by an effective mean free path

A mathematical analysis based on the Mayadas-Shatzkes model indicates that we may define an “effective mean free path” in order to describe electronic conduction in both thin polycrystalline and monocrystalline metallic films. Under this condition a Fuchs-Sondheimer function can be introduced to evaluate the total film resistivity and its temperature coefficient in the presence of external surfaces. A possible extension to other theories derived from the Fuchs theory is mentioned.     

Spherulitic growth and recrystallization in barium silicate glasses

The growth and recrystallization of spherulites formed in barium disilicate glasses between 700 and 900° C has been studied by electron microscopy and electron diffraction. Spherulites formed at 700° C consist of fibrillar (～ 100 Å diameter) monoclinic crystals in confocal arrangement with preferred crystallographic growth axes. High temperature (900° C) spherulites are composites of radially oriented plate-shaped orthorhombic crystals with lateral growth of epitaxially nucleated fibrillar monoclinic crystals. At intermediate temperatures “axialites”, consisting of a single orthorhombic “midrib” crystal with monoclinic fibrillar side-growths, grow in competition with the low temperature spherulite morphology. The monoclinic fibrillar phase is believed to be an intermediate metastable structure which is able to grow more rapidly than the orthorhombic phase via cellular transformation in the presence of impurities. Brief comparison is made between the observed morphologies and theories for interface instability and cellular crystallization. Recrystallization, induced mainly by the large interfacial area of spherulite fibrils, produces faulted and twinned monoclinic grains which transform slowly to the orthorhombic stable crystal phase. A glassy intercrystalline residue becomes more prominant with grain growth.     

Bulk Metallic Glasses with Functional Physical Properties

In this review, we report on the formation of a variety of novel, metallic, glassy materials that might well have applications as functional materials. The metallic glasses, with excellent glass‐forming ability, display many fascinating properties and features such as excellent wave‐absorption ability, exceptionally low glass‐transition temperatures (～35–60 °C) approaching room temperature, ultralow elastic moduli comparable to that of human bone, high elasticity and high strength, superplasticity and polymer‐like thermoplastic formability near room temperature, an excellent magnetocaloric effect, hard magnetism and tunable magnetic properties, heavy‐fermion behavior, superhydrophobicity and superoleophobicity, and polyamorphism, all of which are of interest not only for basic research but also for technological applications. A strategy based on elastic‐moduli correlations for fabrication of bulk metallic glasses (BMGs) with controllable properties is presented. The work has implications in the search for novel metallic glasses with unique functional properties, for advancing our understanding of the nature and formation of glasses, and for extending the applications of the materials.