金属玻璃原子尺度结构和性能的调控:关于深冷处理的综述

通过调控金属玻璃的原子尺度结构进而提高它们的力学、物理、化学性能极为重要。在过去几十年里,金属玻璃领域研究者投入了大量精力以开发有效调控方法,如深冷处理。本文综述了深冷处理对金属玻璃性能的影响及其对初始结构能量状态的依赖关系,聚焦了金属玻璃中原子结构随深冷处理的演化,这些内容对于深入理解金属玻璃深冷处理效应具有重要作用。     

High-Entropy Metallic Glasses

The high-entropy alloys are defined as solid-solution alloys containing five or more than five principal elements in equal or near-equal atomic percent. The concept of high mixing entropy introduces a new way for developing advanced metallic materials with unique physical and mechanical properties that cannot be achieved by the conventional microalloying approach based on only a single base element. The metallic glass (MG) is the metallic alloy rapidly quenched from the liquid state, and at room temperature it still shows an amorphous liquid-like structure. Bulk MGs represent a particular class of amorphous alloys usually with three or more than three components but based on a single principal element such as Zr, Cu, Ce, and Fe. These materials are very attractive for applications because of their excellent mechanical properties such as ultrahigh (near theoretical) strength, wear resistance, and hardness, and physical properties such as soft magnetic properties. In this article, we review the formation and properties of a series of high-mixing-entropy bulk MGs based on multiple major elements. It is found that the strategy and route for development of the high-entropy alloys can be applied to the development of the MGs with excellent glass-forming ability. The high-mixing-entropy bulk MGs are then loosely defined as metallic glassy alloys containing five or more than five elements in equal or near-equal atomic percent, which have relatively high mixing entropy compared with the conventional MGs based on a single principal element. The formation mechanism, especially the role of the mixing entropy in the formation of the high-entropy MGs, is discussed. The unique physical, mechanical, chemical, and biomedical properties of the high-entropy MGs in comparison with the conventional metallic alloys are introduced. We show that the high-mixing-entropy MGs, along the formation idea and strategy of the high-entropy alloys and based on multiple major elements, might provide a novel approach in search for new MG-forming systems with significances in scientific studies and potential applications.     

Atomic Structure of Cu_(49)Hf_(42)Al_9 Metallic Glass with High Glass-Forming Ability and Plasticity

Electron diffraction was used to study the local atomic structure of Cu_(49)Hf_(42)Al_9 metallic glasses(MGs).The amorphous nature of the MG was fully retained after the compression test.The partial radial distribution functions(PRDFs)of the MG structure obtained from the atomic model using reverse Monte Carlo and density functional theory optimization display that the peaks of the first nearest-neighbour distances for Cu-Cu,Hf-Cu and Hf-Hf atomic pairs were located at 2.56 A,2.78 A and 3.23 A,respectively.The wide distribution of PRDF for Hf-Hf atomic pair explained the high plasticity of the material.     

Hidden order in the fracture surface morphology of metallic glasses

We report the fractal nature of dimple structures on the fracture surface of various metallic glasses (MGs) with significantly different mechanical properties. The analyzed fractal dimension increments of MGs lie in a narrow range of 0.6–0.8. The results indicate that the MGs with marked differences in plasticity and toughness may have a unified local softening mechanism and similar nonlinear plastic behavior in front of the crack tip during fracture. We present a physical picture for the dimple structure formation from the plastic zone in front of the crack tip. The evolution of the plastic zone from the interaction of the shear transformation zones is theoretically modeled as a stochastic process far from thermodynamic equilibrium, and the model can capture the formation and fractal nature of the dimple structures on the fracture surface of metallic glasses.     

Atomistic mechanism of elastic softening in metallic glass under cyclic loading revealed by molecular dynamics simulations

Metallic glasses (MGs) have a great potential for structural applications due to their high strength; however, they soften under cyclic loadings and exhibit low fatigue endurance limits. To understand the softening mechanism, molecular dynamics simulations were carried out to study the Cu₅₀Zr₅₀ MG within the nominal elastic regime, which clearly show that the quasi-static elastic modulus of the MG softens with either the decreasing cyclic frequency or increasing stress amplitude. Through the extensive analysis of the atomic trajectories, we found the complex elastic softening behavior is related to the activation of string-like liquid-like sites and atomic bond breaking in the cyclically deformed amorphous structure. Our current finding provides a quantitative insight into the atomistic mechanism of damage in MGs under cyclic loadings, also shedding light on the important mechanisms for fatigue damage initiation in amorphous solids.     

Thin film metallic glasses: Preparations,properties, and applications

With unique properties such as high strength, amorphous alloys in the bulk form have been a focus for many studies in recent years. Yet, the amorphous alloys (metallic glass) in the thin film form have not received much attention. In this paper, we will review and report some important and interesting results obtained from these thin film metallic glasses in which unique physical and mechanical properties can be enhanced by changing their compositions and by the precipitation of nanoscale particles.     

Corrosion behavior of Zr-based metallic glass coating on type 304L stainless steel by pulsed laser deposition method

The surface morphology and corrosion behavior of Zr-based amorphous metallic glass (MG) of Zr₅₉Ti₃Cu₂₀Al₁₀Ni₈ alloy and MG coated type 304L stainless steel in different nitric acid media of 1 M, 6 M and 11.5 M HNO₃ is reported. Zirconium based MG of Zr₅₉Ti₃Cu₂₀Al₁₀Ni₈ alloy was successfully deposited on type 304L stainless steel using pulsed laser deposition technique. The SEM morphology revealed a scattered particles of “Donut” shaped features distributed in the amorphous matrix. The atomic force microscope measurement indicated the formation of dense metallic deposited layer of agglomerate of granular clusters with negligible pores or micro-crack in metallic glass coated sample. The results of the potentiodynamic polarization shows that the amorphous MG coated type 304L stainless steel exhibited marginally lower corrosion resistance than MG alloy which is attributed to the presence of corrosion-induced defects in the coated layer. This work reports suitability of using pulsed laser deposition for the preparation of thin film amorphous metallic coating to achieve improved corrosion resistance in nitric acid medium.     

Correlation between the elastic modulus and the intrinsic plastic behavior of metallic glasses: The roles of atomic configuration and alloy composition

Recent reports suggest that Poisson’s ratio (ν), or the related ratio of shear modulus G to bulk modulus B, indicates the potential of metallic glasses (MGs) to sustain plastic strain. Using molecular dynamics simulations of the Cu₆₄Zr₃₆ MG as a representative, we demonstrate why and how these elastic and plastic properties are correlated, in terms of the common structural origin underlying these mechanical behaviors in MGs. The full icosahedral ordering has been identified as the key structural feature in the Cu–Zr MGs that controls not only the G and the G/B (or ν), but also the initiation of shear localization and the intrinsic plasticity. Additional analysis of the Cu–Zr MGs of different compositions and MGs in different alloy systems reveals a general correlation of the plasticity with the G/B ratio, as the latter is able to represent and couple the effects of both the atomic configuration and the alloy composition.     

Correlation between elastic structural behavior and yield strength of metallic glasses

Tremendous research effort has been put into the study of plastic deformation mechanisms of metallic glasses (MGs) in an attempt to elucidate the origin of their high fracture strength. Little attention has, however, been paid to the elastic deformation of MGs. In this paper, a series of MGs with different yield strengths are studied, with a focus on the fine structural evolution (at the atomic level) during elastic deformation. Our results reveal that an atomic reorientation happens in the first nearest-neighbor shell due to elastic deformation. This reorientation subsequently leads to a drop in the local stress, which further results in a cooperative shift of surrounding atoms to counterbalance this change in local stress level. A concordant region is formed as a result. The relation between this concordant region and the yield strength is thoroughly discussed in terms of its size and the stress level in this region. It is proposed that this concordant region could be the missing part that bridges the macroscopic yield strength and the microscopic atomic structure.     

Local order influences initiation of plastic flow in metallic glass: Effects of alloy composition and sample cooling history

Bulk metallic glasses (MGs) with tunable plasticity and strength have been reported recently. Using Cu–Zr and Cu–Zr–Al MG models, here we illustrate how and why alloy composition and cooling history influence the initial flow behavior in the early stage of plasticity. Starting from Cu₄₆Zr₅₄, either increasing the Cu concentration, or substituting Al for a few percent of Zr, increases the resistance to the initiation of plastic flow, the softening after the local yielding, and the propensity for strain localization. These effects are shown to be intrinsic to the uniform, fully amorphous MGs and rooted in their internal structure. Our quantitative monitoring of the local environment, especially the role of full-icosahedral clusters in shear transformations, identifies the fertile and resistant structural entities controlling deformation. The structural mechanisms have implications for macroscopic plasticity, and the alloy dependence of the MG structure reveals a microscopic origin underlying the varying mechanical properties.     

反应磁控溅射MgO薄膜溅射模式的分形维表征

用反应磁控溅射的方法制备了MgO薄膜，基于原子力显微镜观测，并借助Fourier变换，计算了薄膜表面形貌的分形维数。发现分形维数变化对应于薄膜溅射模式的变化，二者之间有相关性，氧分压30％的分形维数是一个临界点，分形维数若发生明显跌落，意味着溅射模式发生变化，界于临界值两侧的分形维数，分别对应两种截然不同的溅射模式，与临界值对应的溅射状态则处于金属模式和氧化物模式的混和状态。     

A combinatorial thin film sputtering approach for synthesizing and characterizing ternary ZrCuAl metallic glasses

We report a combinatorial sputtering approach for synthesizing ternary metallic glass alloys on both silicon and sapphire substrates. ZrCuAl metallic-glass thin films were co-deposited using a multi-source radio-frequency magnetron-sputtering process. The combinatorial synthesis process yields a wide range of compositions via a single co-sputter deposition process. The compositions of the films were characterized by the energy-dispersive X-ray spectroscopy (EDS), and the structure of the ZrCuAl alloy thin films was investigated by the X-ray diffraction (XRD). Thorough phase analyses indicated the phases present in the films at different compositions were in good agreement with the binary Zr–Cu phase diagram. Nanoindentation results showed that mechanical properties of the bulk-metallic glasses (BMGs) thin film, such as elastic modulus and hardness, are functions of the Zr (or Cu) concentration. The composition with a moderate Zr content (45 atomic percent (at.%)) resulted in a high film modulus and hardness. The post anneal treatment increased the film elastic modulus and hardness. Small additions of aluminum slightly enhanced the film mechanical properties. Using this combinatorial technique could facilitate the development of the new multi-element metallic-glass alloy, particularly for systems with many elements. The first attempt of casting the optimum resultant ternary BMGs rod was successful.     

Manipulation of thermal and mechanical stability by addition of multiple equiatomic rare-earth elements in Al-TM-RE metallic glasses

In the present study, we demonstrate that the addition of multiple equiatomic rare-earth elements (REs) in the order of electronegativity in Al₈₄Ni₁₀RE₆ (RE = La, Ce, Nd, Gd, Y) metallic glasses (MGs) can result in stabilizing supercooled liquid region and destabilizing shear avalanches via controllably induced compositional complexity. In detail, the addition of multiple equiatomic REs leads to a relatively fragile glass, but interrupts easy crystallization behavior in Al₈₄Ni₁₀(LaCeNdGdY)₆MG, which causes a larger supercooled liquid region and higher thermoplastic formability. Furthermore, the increased structural instability reduces cut-off size of self-organized shear avalanches and increases the number of chaotic shear avalanches, which can distribute the applied strain more homogeneously, resulting in enhanced intrinsic ductility. These results provide a guideline on how to design promising Al-based MGs with high thermal stability and improved mechanical stability, which is a key step to developing ductile Al-based bulk metallic glasses through thermoplastic forming process.     

The role of magnetic element Fe in pronounced slow β-relaxation in metallic glasses

Most metallic glasses (MGs) exhibit weak evidence of slow β-relaxation in their dynamic mechanical spectroscopy. In contrast to other MGs, we find a series of Fe-based MGs with unusual distinct β-relaxation peaks in their relaxation spectra. The investigation on the β-relaxation behavior of Fe-based MGs suggest that the magnetic element Fe plays the critical role in the pronounced β-relaxation behaviors in the Fe-based metallic glasses, which could provide deep insight into the mechanism of β-relaxation dynamic mode in metallic glasses.     

The dependence of shear modulus on dynamic relaxation and evolution of local structural heterogeneity in a metallic glass

Starting from the nanoscale structural heterogeneities intrinsic to metallic glasses (MGs), here we show that there are two concurrent contributions to their microscale quasi-static shear modulus G_I: one (μ) is related to the atomic bonding strength of solid-like regions and the other (G_II) to the change in the possible configurations of liquid-like regions (dynamic relaxation). Through carefully designed high-rate nanoscale indentation tests, a simple constitutive relation (μ = G_I + G_II) is experimentally verified. On a fundamental level, our current work provides a structure–property correlation that may be applicable to a wide range of glassy materials.     

Cooling rate effect on Young's modulus and hardness of a Zr-based metallic glass

It is known that cooling rate can affect the atomic structure and thus may possibly affect the mechanical properties of metallic glasses (MGs). In spite of the considerable efforts on the cooling rate, its effect on the mechanical properties is controversial at the present time. In this study, we present a micromechanical study of the cooling-rate effect on Young's moduli and hardness of the cast bulks and melt-spun ribbons for a Zr₅₅Pd₁₀Cu₂₀Ni₅Al₁₀ metallic glass. Using the classic nanoindentation method, the Young's moduli of the ribbon samples obtained at higher cooling rates were measured which appeared to be much lower than those of the bulk samples. However, through further experiments on slice samples cut from the as-cast bulks and finite-element (FE) analyses, we have clearly demonstrated that the measured difference in elastic moduli was mainly caused by the sample thickness effect in nanoindentation tests. To overcome such a confounding effect, microcompression experiments were performed on the as-cast and as-spun MG samples, respectively. Being consistent with the findings from nanoindentation, the microcompression results showed that the cooling rate, as ranging from ∼10² to ∼10⁶ K/s, essentially has no influence on the Young's modulus and hardness of the metallic glasses.     

Alloy compositions of metallic glasses and eutectics from an idealized structural model

Using an idealized atomic packing model for metallic glasses (MGs), we predict the binary alloy compositions structurally favorable for the stability of MGs. Such compositions are proposed to be the likely candidates to obtain MGs. The predicted compositions coincide very well with the experimental glass-forming range for a large number of systems. The relationship between these compositions and the eutectic compositions in the equilibrium phase diagrams is established. Direct correlations are found for symmetric eutectic systems, especially for deep eutectics, whereas off-eutectic MGs are suggested for asymmetric eutectic systems. Rationales from the structural standpoint are also presented to explain the increased frequency of appearance of eutectics at certain composition ratios (the Stockdale/Hume-Rothery puzzle).     

Flow units perspective on sensitivity and reliability of metallic glass properties

The metastability of metallic glasses (MGs) can be well described by the Weibull distribution function. We study the relationship between flow units and mechanical properties and find that the concentration of flow units also follows the Weibull distribution function as do other properties of MG. The results suggest that the properties' sensitivity and metastability of MGs described by the Weibull distribution function can be explained by the structural heterogeneity (or flow unit) perspective and attributed to the variation of the flow units.     

Nanogrinding of multi-layered thin film amorphous Si solar panels

Nanogrinding was performed on the cross-sections of amorphous Si thin film solar panels, which are nanoscale multi-layer structures consisting of hard and brittle materials. The deformed structures of the panel cross-sectional surfaces after grinding were investigated using electron and atomic force microscopy. The nanogrinding results were compared with those obtained from polishing and nanoscratching, demonstrating that the three processes had produced consistent surface characteristics. Though nanogrinding produced nanometric surface roughness with ductile material removal, but could cause cracking, edge chipping and delamination at thin film interfaces. The results of this work are of value for developing the efficient machining process for thin film solar panels and other brittle multi-layer materials.     

TaN薄膜局部腐蚀早期过程的ECAFM原位研究

电化学原子力显微镜(ECAFM)可以在液体环境下工作，能原位观察电极反应过程中的腐蚀界面形貌。文章介绍利用ECAFM从纳米空间分辨度上原位研究离子束增强沉积TaN膜在0.4mol／L HCl溶液中的局部腐蚀早期过程，结果发现，表面形貌为颗粒状结构的TaN膜在0.4mol／L HCl中进行阳极极化时，颗粒结构的微观顶峰优先溶解，导致颗粒高度降低，边界扩大蔓延，使膜层表面趋于平整化。