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.     

镁基块体非晶合金的研究进展

Mg基块体非晶合金因其低成本和高比强度而有望成为轻质高强度结构材料,引起人们研究的极大兴趣.通过对Mg基决体非晶合金发展情况的综述研究,尤其是介绍了新成分设计和力学性能改善等方面的研究现况,发现Mg基块体非晶合金的研究主要集中在Mg-Cu基,成分设计以元素替代和合全体系元素优化为主,Mg基非晶合金塑性的改善是当前研究的重点和难点.     

金属玻璃纳米晶化机制研究进展

金属玻璃是一类具有结构和功能应用前景的新型金属材料,是目前物理和材料学科最为活跃的研究领域之一。由于处于热力学亚稳态,金属玻璃在合适的外界条件下会自发地向相应的晶态相发生转变,导致晶化事件的发生。研究金属玻璃的纳米晶化不仅有重要的科学意义,同时也可对金属玻璃的应用提供理论指导。简要介绍了目前几种代表性的金属玻璃纳米晶化微观机制：经典形核理论、基于耦合通量模型的形核机制、基于相分离的纳米晶形核长大机制、有序原子集团沉积机制、非经典形核理论、大过冷度条件下纳米晶化的微观机制等,同时结合作者课题组近年来在这方面的研究进展,对各种机制进行了评述,最后对未来金属玻璃纳米晶化机制研究中需要重视的几个问题进行了简单展望。     

Relating Dynamic Properties to Atomic Structure in Metallic Glasses

Atomic packing in metallic glasses is not completely random but displays various degrees of structural ordering. While it is believed that local structures profoundly affect the properties of glasses, a fundamental understanding of the structure–property relationship has been lacking. In this article, we provide a microscopic picture to uncover the intricate interplay between structural defects and dynamic properties of metallic glasses, from the perspective of computational modeling. Computational methodologies for such realistic modeling are introduced. Exploiting the concept of quasi-equivalent cluster packing, we quantify the structural ordering of a prototype metallic glass during its formation process, with a new focus on geometric measures of subatomic “voids.” Atomic sites connected with the voids are found to be crucial in terms of understanding the dynamic, including vibrational and atomic transport, properties. Normal mode analysis is performed to reveal the structural origin of the anomalous boson peak (BP) in the vibration spectrum of the glass, and its correlation with atomic packing cavities. Through transition-state search on the energy landscape of the system, such structural disorder is found to be a facilitating factor for atomic diffusion, with diffusion energy barriers and diffusion pathways significantly varying with the degree of structural relaxation/ordering. The implications of structural defects for the mechanical properties of metallic glasses are also discussed.     

Evaluation of Cu-Zr-Ti-In Bulk Metallic Glasses via Nanoindentation

In this paper, the mechanical properties of two bulk metallic glasses, Cu₆₀Zr₃₄Ti₅In₁ and Cu₅₈Zr₃₄Ti₅In₃, have been evaluated by nanoindentation tests. The hardness and Young’s modulus of as-cast Cu₆₀Zr₃₄Ti₅In₁ bulk metallic glass increase from the center to the edge of the rod, but Cu₅₈Zr₃₄Ti₅In₃ shows an inverse trend. The Young’s modulus of Cu₅₈Zr₃₄Ti₅In₃ is lower than that of Cu₆₀Zr₃₄Ti₅In₁. For both bulk metallic glasses, serrations on the nanoindentation load-displacement curves depend not only on loading rate but also on the maximum load. Alternatively, the onset position of the appearance of serrations on the curves increases with the loading rate. In addition, the hardness of both samples decreases as the size of the indent increases due to indentation size effects.     

回火Zr-Al-Ni-Cu-Ag块体金属玻璃中的准晶及纳米准晶

通过系统的透射电子显微镜观察,在回火的Zr-Al-Ni-Cu-Ag块体金属玻璃中发现了准晶相和纳米准晶相。具有五次对称性,三次对称性及二次对称性的选区电子衍射谱及微束电子衍射谱证明初始晶化过程中析出的相为二十面体准晶。定量观察表明高的形核率是纳米准晶形成的原因。添加银有助于纳米准晶的形成。二十面体准晶相在初始晶化过程中的析出暗示着块体金属玻璃和二十面体结构之间存在着本征的相关性。     

Mechanical Strength and Surface Roughness of Magnesium-Based Metallic Glasses

This work evaluated the mechanical strength and surface roughness of MgZn₃₀Ca₅ ribbon manufactured via a melt spinning technique for applications in the biomedical field. Annealing was performed at 280°C. The inner side (in contact with the wheel) and the outer side (not in contact with the wheel) of the ribbons were mechanically evaluated using nanoindentation, and its surfaces were analyzed by an optical profilometer. Differential scanning calorimeter (DSC) and X-ray diffraction (XRD) analyses were also performed to identify the structure and devitrification of the magnesium metallic glass (MgMG). The nanohardness and elastic modulus increased after annealing (p < 0.0001). No differences were seen in the strength between the two sides of the ribbons (p > 0.05). Although both sides of the ribbons showed different surface profiles (p < 0.0001), no statistical difference was detected in roughness parameters on either ribbon side before (p = 0.3094) and after (p = 0.8742) annealing. DSC curves showed disturbances in enthalpy attributed to a relaxation in the MgMG structure and free volume annihilation. The DRX diffractogram showed sharp peaks after annealing, with MgZn and Ca₂Mg₅Zn₁₃ phases being identified. Although the use of MgMG in biomedical applications is promising, the ribbons displayed limited ductility, toughness, and a relevant embrittlement after the annealing procedure. There were significant changes in the surface profile of both sides of the ribbons. Nevertheless, neither annealing nor the ribbon side had influenced surface roughness parameters.     

新型块体铁基非晶合金的形成与性能

利用铜模铸造法制备了(Fe100-xCox)74Mo6P10C7.5B2.5(x=0-15)新型块体铁基非晶合金。Fe-Co-Mo-P-C-B系块体非晶合金具有临界直径为4mm的高非晶形成能力,以及维氏硬度为10.6～10.85GPa的高硬度和饱和磁感应强度为0.98～1.07T的优异性能。研究结果表明,非晶合金硬度及饱和磁感应强度都随着Co含量的提高逐渐增加。合金的非晶形成能力则与Co的含量密切相关。适量Co的添加扩大非晶合金的过冷液体区间(ΔTx)及增加γ值,从而提高非晶合金的热稳定性及其非晶形成能力。     

Serrated Flow Model for Metallic Glasses under Compressive Loading

A rheological model is proposed that incorporates the serrated flow nature of metallic glasses. It involves the process of the nucleation, propagation and the arrest of a shear bands in the samples subjected to compressive deformation at room temperature. Numerical resolution of the constitutive equations resulting from the model is compared with the stress-strain curve obtained from in-situ nano-compression test in SEM of Zrbased metallic glass. Parametric identification method was applied and enabled us to release the physical parameters of the model. The obtained results showed that the model is adequately valid to describe the experimental data and the almost adjustable model parameters are physically meaningful and comparable to literature.     

Nanoindentation Mechanical Properties of Indium-Alloyed Cu-Based Bulk Metallic Glasses

In this paper, two Indium-alloyed Cu-based bulk metallic glasses, Cu₅₄Zr₃₇Ti₈In₁ and Cu₅₀Zr₃₇Ti₈In₅, have been evaluated with nanoindentation testing. Both bulk metallic glasses have homogenous nature in structure. Both hardness and Young’s modulus of bulk metallic glasses do not show a loading rate-dependent. Addition of In decreases hardness and Young’s modulus, but increases creep-resistance of bulk metallic glasses. Indentation creep of two bulk metallic glasses has also been investigated. The displacement-time curves of creep processes were described with generalized Kelvin model. The creep displacement, compliance spectrum, and retardation spectrum for each bulk metallic glass were discussed comparatively. The results showed that Cu₅₀Zr₃₇Ti₈In₅ has better creep-resistance at room temperature and a more relaxed state.     

Impact Conditions for Cold Spraying of Hard Metallic Glasses

As compared to thermal spray techniques, cold spraying allows to retain metastable phases of the feedstock material like amorphous structures, due to lower process gas temperatures. Compared to crystalline metals, metallic glasses are brittle at ambient temperature but viscous at higher temperatures. Therefore, cold spray parameters must be optimized for conditions that allow softening of the amorphous spray material for successfully producing coatings. For this study, a FeCoCrMoBC metallic glass was used that in comparison to others offers advantages with respect to higher hardness, less costly feedstock powder, and minimum reactivity with the environment. Necessary impact conditions were investigated to meet the window of deposition in cold gas spraying. According to calculations and cold spray experiments, neither the glass transition temperature T _g nor the melting temperature T _m can describe required conditions for bonding. Thus, a so called softening temperature between the glass temperature and the melting temperature had to be defined to calculate the critical velocity of metallic glasses. With respect to the bonding mechanism, impact morphologies could prove that a transition to viscous flow gets more prominent for harsher spray conditions. By sufficiently exceeding the critical condition for bonding, coatings with rather dense microstructures can be processed at deposition efficiencies of about 70%. The coatings have a hardness of 1100?HV 0.3, but the results also demonstrate that further work is still needed to explore the full potential for bulk metallic glasses.     

金属玻璃的功能性应用及相关基础研究

金属玻璃是一类具有热力学非平衡特征和亚稳特性、以金属元素为主要组分、原子排列处于无序结构的固体材料。近年来,随着金属玻璃研究领域的蓬勃发展,涌现出很多新的研究方向和热点。简要综述了近期金属玻璃在化学反应中表现出的优异催化性能和高反应速率等相关的功能性应用和基础研究进展,主要介绍了金属玻璃在降解污水中的偶氮染料方面的功能性应用和基础研究。实验结果表明,镁基和铁基金属玻璃粉降解偶氮染料的效率分别达到商业晶态铁粉的1000倍和200倍以上。而且,相对于液体雾化法制备的金属玻璃粉,用球磨粉碎法制备的金属玻璃粉反应活性更高,这可能与球磨金属玻璃粉比表面积增加、残余应力导致的反应激活能降低有关。最后对金属玻璃的功能性应用和相关基础研究的未来研究前景进行了展望。     

On Temperature Rise Within the Shear Bands in Bulk Metallic Glasses

Room temperature deformation process in a bulk metallic glassy sample was studied by using a hydraulic thermomechanical simulator. The temperature rise during each separate shear band propagation event was measured with a high data acquisition frequency by a thermocouple welded to the sample. Calculation showed that when propagation of the well developed shear bands takes place along the entire sample the temperature inside the shear band should be close to the glass-transition temperature. It was also possible to resolve the temporal stress distribution and a double-stage character of stress drops was also observed. The obtained results are compared with the literature data obtained by infrared camera measurements and the results of finite elements modeling.     

放电等离子烧结制备FeSiB块体非晶合金

采用DSC测定FeSiB非晶粉末的玻璃态转变点(Tg)、初始晶化点(Tx)和过冷液相区(ΔTx),以此为基础,利用放电等离子烧结技术制备出了φ10mm×7mm、致密度为92.3%的块体非晶合金。采用XRD、SEM、VSM、万能试验机分析了烧结块体样品的相组成、微观形貌、磁性能和抗压强度。研究表明,当烧结条件为压力500MPa、温度360℃时,得到的块体非晶合金致密度最高,其饱和磁化强度为1.44T,抗压强度为1200MPa。400℃晶化后块体样品的饱和磁化强度为1.54T,抗压强度为2039MPa。     

Ti-Cu-Ni三元大块非晶合金的制备与力学性能

采用铜模喷铸法成功制备出成本较低、直径为2 mm的Ti基Ti50Cu42Ni8大块非晶合金.利用XRD、DSC及SEM等手段研究了Ti50Cu50-xNix(x=5, 8, 11)合金的非晶形成能力、力学性能与变形行为.结果表明:Ti50Cu42Ni8大块非晶合金具有明显且较高的玻璃转变温度Tg(659 K)、晶化初始温度Tx(716 K)、宽的过冷液相区ΔTx=Tx－Tg(57 K)、高的约化玻璃转变温度Trg=Tg/Tm(0.565)和压缩断裂强度(2008 MPa).     

FeMoCrPC非晶态合金的制备及其性能研究

通过Fluxing提纯技术和J-quenching快速凝固技术相结合的方法制备Fe_(80-x-y)Mo_xCr_yP_(13)C_7(x=3,y=0;x=5,y=0;x=7,y=0;x=5,y=5;x=5,y=10;x=0,y=5,a(%))块体非晶态合金,研究Mo和Cr部分置换Fe对合金性能的影响。结果表明,用Mo和Cr适量置换Fe可以有效提高合金的玻璃化形成能力,但过量置换将导致玻璃化形成能力下降;随着Mo和Cr含量的增加,合金的玻璃转变温度(T_g)和起始晶化温度(T_x)均增加,合金热稳定性提高;随着Mo含量的增加,合金抗腐蚀性能先增加后减小,当Mo含量a(%)为5%时合金抗腐蚀性能最好,随着Cr含量的增加,合金抗腐蚀性能提高。