Thermodynamical properties of Zr-based bulk metallic glasses

The temperature dependence of Gibb's free energy difference (ΔG), entropy difference (ΔS) and enthalpy difference (ΔH) between the undercooled melt and the corresponding equilibrium solid phases of bulk metallic glass (BMG) forming melts has been proved to be very useful in the study of their thermodynamical behavior. The present study is made by calculating ΔG, ΔS and ΔH in the entire temperature range T_m (melting temperature) to T_g (glass transition temperature) for three Zr-based samples of BMGs: Zr₅₇Cu_15.4Ni_12.6Al₁₀Nb₅, Zr_41.2Ti_13.8Ni₁₀Cu_12.5Be_22.5 and Zr_58.5Cu_15.6Ni_12.8Al_10.3Nb_2.8. The study is made on the basis of Taylor's series expansion and a comparative study is also performed between the present result and the result obtained in the framework of expansions proposed by earlier workers, and also with the experimental results. An attempt has also been made to study the glass forming ability for BMGs.     

Minor alloying behavior in bulk metallic glasses and high-entropy alloys

The effect of minor alloying on several bulk metallic glasses and high-entropy alloys was studied. It was found that minor Nb addition can optimize the interface structure between the W fiber and the Zr-based bulk metallic glass in the composites, and improve the mechanical properties. Minor Y addition can destabilize the crystalline phases by inducing lattice distortion as a result to improve the glass-forming ability, and the lattice distortion energy is closely related to the efficiency of space filling of the competing crystalline phases. A long-period ordered structure can precipitate in the Mg-based bulk metallic glass by yttrium alloying. For the high-entropy alloys, solid solution can be formed by alloying, and its mechanical properties can be comparable to most of the bulk metallic glasses.     

Developing aluminum-based bulk metallic glasses

This paper details a systematic investigation of the formation of Al-based bulk metallic glasses, expanding on an earlier brief report [Scripta Mater. 61 (2009) p.423]. We discuss an approach for designing and predicting the best glass-forming composition in the Al–TM–RE systems, based on the atomic cluster packing model for the internal structure of the glass. The effects of additional elements in quaternary and quinary systems on the glass-forming ability and thermal stability of the glasses are also discussed. Three new compositions, Al₈₆Ni₆Y_4.5Co₂La_1.5, Al₈₆Ni₇Y₅Co₁La₁ and Al₈₆Ni₇Y_4.5Co₁La_1.5, are capable of forming fully glassy rods of 1 mm in diameter; their glass transition and other thermal properties are systematically characterized.     

Pd-Si binary bulk metallic glass

Pd_80+x Si_20−x (x = 0, 1, and 2) binary metallic glasses with the diameter ranging from 7 to 8 mm were prepared by a combination of fluxing and water quenching or air cooling. Thermal analysis results show that with increasing Si content, the glass transition temperature T _g, the initial crystallization temperature T _x and the onset crystallization temperature T _p of Pd-Si binary glassy alloys increase. Moreover, the supercooled liquid region reaches 61 K. It indicates that Pd-Si binary alloys possess large glass forming ability, which can be greatly improved by fluxing treatment. Supported by the National Basic Research Program of China (Grant No. 2007CB613905) and the National Natural Science Foundation of China (Grant Nos. 50671050 and 50431030)     

Ni-based Ni-Fe-B-Si-Ta bulk metallic glasses

The glass-forming ability and properties of Ni-based Ni-Fe-B-Si-Ta bulk metallic glasses are explored in this work. The alloy compositions are determined by using a combination of the cluster line approach, the multi-alloying strategy and the substitutions of similar elements. Bulk metallic glasses with diameters of 3 mm take shape at compositions formulated under the clus- ter-plus-glue-atom model [M9B]B~[(Ni1-xFex)7.71(Si0.66Ta0.34)1.29B]B0.94=(Ni1-xFex)70.5B17.7Si7.8Ta4, x=0.35–0.45, where the bracketed part is the cluster and the unbracketed part is the glue atoms. These alloys exhibit good magnetic properties. The maximum Is is found in the (Ni0.55Fe0.45)70.5B17.7Si7.8Ta4 alloy which reaches 0.51 T, with its Hc as low as 8.5 A/m. Interestingly, these alloys display dual glass transitions at (Ni0.65Fe0.35)70.5B17.7Si7.8Ta4, (Ni0.60Fe0.4)70.5B17.7Si7.8Ta4 and (Ni0.55Fe0.45)70.5B17.7- Si7.8Ta4 as unveiled by Temperature-Modulated Differential Scanning Calorimetry.     

Preparation and characterization of Fe-based bulk metallic glasses in plate form

Amorphous alloys with composition (at%) Fe₄₈Cr₁₅Mo₁₄C₁₅B₆Gd₂ (alloy A) and Fe₄₈Cr₁₅Mo₁₄C₁₅B₆Y₂ (alloy B) were prepared either using pure elements (A and B1) and a commercial AISI430 steel as a base material (B2). When prepared from pure elements both alloys (A and B1) could be cast in plate form with a fixed thickness of 2 mm and variable lengths between 10 and 20 mm by means of copper-mold injection in air atmosphere. In the case of alloy B2, prepared using commercial grade raw materials, rods of 2 mm diameter were obtained.     

具有优良玻璃形成能力添加Al的CuZr基大块金属玻璃

在CuZr二元大块金属玻璃的基础上，利用铜模吸铸方法制备出了添加Al组元的CuZr 基大块 金属玻璃.CuZr基大块金属玻璃在很宽的成分范围内有很强的玻璃形成能力，在Al含量从4％ 到8％之间，CuZr基大块金属玻璃都可以做出直径至少5 mm的非晶样品.通过实验分析，解释 了CuZr基大块金属玻璃具有良好玻璃形成能力的物理机理.CuZr基金属玻璃组分简单、成本 低廉，有潜在的应用价值；同时，制备CuZr基金属玻璃的方法为开发新的大块金属玻璃体系 提供了一条切实有效的途经. 关键词： 大块金属玻璃 玻璃形成能力 CuZr基金属玻璃     

Fe-B-Y-Nb bulk metallic glasses in relation to clusters

Bulk metallic glass formations in the Fe-B-Y-Nb quaternary alloy system were investigated by using the cluster line rule in combination with the minor alloying principle. The Fe-B-Y ternary system was selected as the basic system and the intersections of cluster lines were taken as the basic ternary compositions. The basic compositions were further alloyed with minor amounts of Nb. After 3–5 at.% Nb was added, the basic composition Fe_68.6B_25.7Y_5.7, which was developed from the most densely packed cluster Fe₈B₃, formed 3 mm bulk metallic glasses. These quaternary bulk metallic glasses (Fe_68.6B_25.7Y_5.7)_100−x Nb _x (x = 3–5 at.%) are expressed approximately with a unified simple composition formula: (Fe₈B₃)₁(Y, Nb)₁. The (Fe_68.6B_25.7Y_5.7)₉₇Nb₃ bulk metallic glass has the largest glass forming ability with the following characteristic parameters T _g = 907 K, T _x = 1006 K, T _g/T _l = 0.644, γ = 0.434, and longness t = 22 mm. The combination of the cluster line rule and the minor-alloying principle is a promising new route towards the quantitative composition design of multi-component metallic glasses. Supported by the National Natural Science Foundation of China (Grant Nos. 50671018, 50631010 and 50401020) and the National Basic Research Program of China (Grant No. 2007CB613902)     

金属玻璃的热塑性成型

金属玻璃在其过冷液相区内表现出随着温度升高黏度逐渐降低的特性,因此可以对其进行热塑性加工.该性质颠覆了传统金属的加工成型方式,使得其在远低于传统金属材料加工的温度和应力作用下可以按照人们的要求进行成型.因此,一些具有低玻璃转变温度的金属玻璃又被称作金属塑料.另外,由于金属玻璃是一种无序结构材料,不存在位错、晶界等晶体缺陷,且热膨胀系数小,在热塑性成型中具有优异的尺寸精度,因此被认为是理想的微成型材料,有广阔的应用前景.本文系统介绍了金属玻璃的热塑性成型性质及其应用,从热塑性成型的基本概念出发,阐述了金属玻璃热塑性成型能力的评估指标、热塑性成型技术、热塑性微成型及其理论、热塑性微成型的应用等,对认识金属玻璃的热塑性及扩展其应用有重要的意义.     

Cu-Zr-Ti系Cu基块体非晶合金的形成和成分优化

利用与团簇相关的变电子浓度判据研究了过渡金属Cu-Zr-Ti系中Cu基块体非晶合金的形成区域和成分特征.据此判据在Cu-Zr-Ti系相图中确定出三条特殊的成分线，(Cu_9／13Zr_4／13)_100-xTi_x，(Cu_0.618Zr_0.382)_100-xTi_x和(Cu_0.56Zr_0.44)关键词： 块体非晶合金 Cu-Zr-Ti合金 原子团簇 电子浓度     

超高强块体非晶合金的研究进展

研制具有极限力学性能的金属材料一直是材料研究人员的梦想.超高强块体非晶合金是一类具有极高断裂强度(4 GPa)、高热稳定性(玻璃化转变温度通常高于800 K)和高硬度(通常高于12 GPa)的新型先进金属材料,其代表合金材料Co-Ta-B的断裂强度可达6 GPa,为目前公开报道的块体金属材料的强度记录值.本文系统地综述了该类超高强度块体非晶合金的组分、热学性能、弹性模量及力学性能,阐述了该类材料的研发历程;以弹性模量为联系桥梁,阐明了该类超高强块体非晶合金材料各物理性能的关联性,并揭示了其高强度、高硬度的价键本质.相关内容对于材料工作者了解该类超高强度金属材料的性能和特点,并推进该类材料在航空航天先进制造、超持久部件、机械加工等领域的实际应用有着重要意义.     

新型Pr基大块非晶及其特性研究

用铜模吸铸法获得了直径为5mm的一种新的Pr基大块非晶.与以往其他稀土-过渡金属(RE-TM)大块非晶不同的是，这种新的Pr基大块非晶具有明显的玻璃转变和稳定的过冷液相区，且其玻璃转变温度在目前已知的大块非晶中是最低的，T_g=409K.研究了该大块非晶的玻璃转变动力学，并给出了Kauzmann温度T_k、Vogel-Fulcher温度T⁰_g及脆性参数m等重要参数. 关键词： 大块非晶 玻璃转变 脆性参数m     

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.     

Corrosion behavior of bulk metallic glasses in different aqueous solutions

The corrosion behavior of as-cast fully amorphous, structural relaxed amorphous and crystallized Fe65.5Cr4Mo4Ga4P12C5B5.5 bulk metallic glasses (BMGs) in NaCl, HCl and NaOH solutions was investigated by electrochemical polarization and immersion methods. X-ray photoelectron spectroscopy measurements was used to analyze the changes of the elements on the alloy surface before and after immersion in various solutions. The corrosion resistance of the Fe65.5Cr4Mo4Ga4P12C5B5.5 BMG was better than its structural r...     

大块非晶临界冷却速率的非等温转变计算模型

在非等温转变理论以及非稳态形核理论基础上提出了计算大块非晶合金连续冷却转变曲线和 临界冷却速率的新模型,以用于评估合金的非晶形成能力. 依据此模型对Zr基和Pd基8种合金 进行了计算，计算结果与实验值符合较好. 计算结果表明，影响临界冷却速率的主要因素为 黏度、临界形核功和临界结晶分数. 随着黏度增大，临界冷却速率降低；随临界形核功增大 ，临界冷却速率急剧降低；随临界结晶分数增大，临界冷却速率起初降低较快，达到一定程 度后下降速率趋于缓慢. 关键词： 临界冷却速率 非晶形成能力 大块非晶 连续冷却转变曲线     

Glass formation and magnetic properties of Fe-C-Si-B-P-(Cr-Al-Co) bulk metallic glasses fabricated using industrial raw materials

Formation of Fe-C-Si-B-P-(Cr-Al-Co) bulk metallic glasses with enhanced glass-forming ability (GFA) and magnetic properties fabricated using industrial pig-iron and Fe-P alloys as raw materials has been studied. It was found that GFA of the pig-iron (Fe_79.5C_18.0Si_2.3P_0.2, at%) could be improved by proper additions of only metalloids C, Si, P and B, and fully glassy structure was obtained in the Fe_75.5C_7.0Si_3.3B_5.5P_8.7 alloy with a critical diameter of 1 mm. With suitable additions of metallic elements Cr, Co and Al, the GFA is further increased and fully amorphous rods in 4 mm diameter can be prepared for the Fe_68.2C_7.0Si_3.3B_5.5P_8.7Cr_2.3Al_2.0Co_3.0 alloy that shows a unique combination of good soft-magnetic properties (M_s=1.03 T, H_c=9.39 A/m), high GFA and high fracture strength. These low-cost Fe-based bulk metallic glasses fabricated using industrial raw materials have a potential to be utilized as engineering materials.     

Linking high- and low-temperature plasticity in bulk metallic glasses: thermal activation,extreme value statistics and kinetic freezing

Abstract

At temperatures well below their glass transition, the deformation properties of bulk metallic glasses are characterized by a sharp transition from elasticity to plasticity, a reproducible yield stress and an approximately linear decrease of this stress with increasing temperature. In the present work, it is shown that when the well-known properties of the undercooled liquid regime, in terms of the underlying potential energy landscape, are assumed to be also valid at low temperature, a thermal activation model is able to reproduce the observed onset of macroscopic yield. At these temperatures, the thermal accessibility of the complex potential energy landscape is drastically reduced, and the statistics of extreme value and the phenomenon of kinetic freezing become important, affecting the spatial heterogeneity of the irreversible structural transitions mediating the elastic-to-plastic transition. As the temperature increases and approaches the glass transition temperature, the theory is able to smoothly transit to the high-temperature deformation regime where plasticity is known to be well described by thermally activated viscoplastic models.     

金属玻璃形成液体的热力学特性

通过分析规则熔体的热力学模型，计算了典型金属玻璃的熔体混合焓ΔH^mix和混合熵ΔS^mix.结合临界冷却速率，归纳出典型金属玻璃形成液体的热力学特性,并提出基于原子尺寸、元素组成以及元素之间混合焓等参数的形成大块金属玻璃的成分判定方法.结果表明，当ΔH^mix<-15 kJ·mol^-1且ΔS^mix>0.6 J·K^-1mol^-1时，合金易于形成大块金属玻璃.金属玻璃的临界冷却速率R_c具有明显的尺寸效应，其值与熔体的ΔS^mix值呈指数关系，可以用R_c＝42.24×10⁴exp(-13.91ΔS^mix)+19.66粗略判断.运用该方法成功设计并制备出远离原有Zr基大块金属玻璃形成区域(55at%—65at%Zr)的Zr₄₀Al₁₀Ni₁₅Cu₃₅和四元Fe-B基Fe₅₃Co₅Nd₁₂B₃₀大块金属玻璃. 关键词： 混合焓 混合熵 大块金属玻璃 玻璃形成能力     

Interactions between high-temperature deformation and crystallization in zirconium-based bulk metallic glasses

High-temperature deformation of a ZrTiCuNiBe bulk metallic glass (BMG) is investigated by compression tests in the supercooled liquid region. When the temperature is decreased or strain rate increased, the amorphous alloy exhibits the usual Newtonian/non-Newtonian transition behaviour. Using specific heat treatments, partially crystallized alloys are produced, the associated microstructures characterized and the volume fractions of the crystal measured. The interaction between high-temperature deformation and crystallization is investigated by appropriate mechanical testing. According to these measurements, partial crystallization is responsible for a significant increase in flow stress and the promotion of non-Newtonian behaviour. Deformation does not significantly change the volume fraction, composition or size of the crystal. The flow-stress increase with crystallization is analyzed under different hypotheses. We conclude that the flow-stress increase cannot be interpreted through a compositional change in the residual amorphous matrix, either by reinforcement due to hard crystallites or by connections between crystals. It appears that the effect is due to the nanometric size of the crystals alone.     

聚变堆第一镜材料块体金属玻璃表面特性

研究了块体金属玻璃（块体非晶合金）Zr65Al7.5Ni10Cu17.5, Co61.2B26.2Si7.8Ta4.8和金属多晶钼3种第一镜材料经低温等离子体H和Ar辐照后的表面特性变化。结果表明,两种块体金属玻璃的抗H等离子体溅射能力与其成分有关。随着等离子体辐照时间的增加,金属多晶钼和块体金属玻璃Zr65Al7.5Ni10Cu17.5的表面粗糙度增大,镜面反射率降低;而块体金属玻璃Co61.2B26.2Si7.8Ta4.8的表面粗糙度减小,镜面反射率升高。X射线衍射仪（XRD）分析表明,块体金属玻璃在离子体溅射过程中,表面微结构具有自修复性。