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     

块体非晶合金的黏度与玻璃形成能力的关系

基于经典结晶理论讨论了非晶合金的晶化动力学因素和晶化热力学因素对玻璃形成能力（GFA）的影响.分析表明,合金的等温转变（TTT）曲线“鼻尖”温度T_n对应的黏度与晶化阻力因子成正比;重新加热时晶化开始温度T_x对应的黏度与晶化驱动力因子成反比.由此得到了新的GFA参数ω₀=（T_g-T₀）/（T_x-T₀）-（T_g-T₀）/（T_n-T₀）,其中T_g为玻璃转变温度,T₀为理想玻璃转变温度.统计结果显示,ω₀与临界冷却速率具有较高的相关性,R²高达09626.进一步分析表明：新提出的ω₀参数可以合理地解释过冷熔体的黏度、脆性、液相稳定性、热稳定性以及T_rg、ΔT_x、γ、γ_m、ΔT_rg、α、β、δ和φ等参数与GFA的关系. 关键词： 块体非晶合金 黏度 脆性 玻璃形成能力     

Zr-Cu-Ni-Al-Nb大块非晶合金的晶化行为、力学性能及电化学腐蚀行为的研究

利用水冷铜模铸造法成功制备了Zr_65-xCu_17.5Al_7.5Ni ₁₀Nb_x (x=0，2，5)大块非晶合金. X射线衍射、热分析研究结果表 明，Nb的添加显著改变了非晶合金的晶化行为，促进了二十面体准晶相的形成. 各合金的准 静态压缩实验表明，Nb的适量添加有利于提高大块非晶合金的强度和塑性. 其中x=5的大块 非晶合金的抗压强度σ_b和塑性应变量ε_p 关键词： Zr基大块非晶合金 晶化行为 力学性能 耐腐蚀性能     

液态五元Zr57Cu20Al10Ni8Ti5合金的微观结构演变与非晶形成机制

利用电磁悬浮无容器处理技术实现了液态五元Zr₅₇Cu₂₀Al₁₀Ni₈Ti₅合金的深过冷与快速凝固,同时通过分子动力学模拟计算揭示了非晶形成的微观机制.实验发现,凝固组织具有明显的核-壳结构特征,核区为非晶相,壳区主要由ZrCu, Zr₂Cu和Zr₈Cu₅晶体相组成.非晶体积分数随合金过冷度的升高逐渐增大,当达到实验最大过冷度300 K (0.26T_L)时,非晶体积分数增至81.3%.由此导出完全非晶凝固所需临界过冷度为334 K. TEM分析显示,过冷度增大并接近临界过冷度时,合金凝固组织中晶体相主要为Zr₈Cu₅相,而ZrCu和Zr₂Cu相的生长被抑制.在达到临界过冷度后,过冷液相的凝固路径由Zr₈Cu₅结晶生长转变为非晶凝固.此外,合金的晶体壳中存在少量的晶间非晶相,而非晶核中...     

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     

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     

Zr60Al15Ni25大块非晶合金晶化动力学研究

通过等温示差扫描量热法研究了Zr₆₀Al₁₅Ni₂₅大块非 晶合金的晶化动力学.实验结果表明，晶化过程的孕育期很短，即使在743 K这样低的温度下也不过0.52 min，而放热峰宽（反应整个晶化过程进行的时间）却随退火温度的降低明显增大，这说明了结晶过程是一个晶核长大控制的过程.Avrami指数表明在不同的退火温度，该合金的晶化机制发生了变化.晶化机制的变化是由于合金原子在不同温度下的扩散能力相差很大所致. 关键词： 晶化动力学 60Al₁₅Ni₂₅大块非晶合金')" href="#">Zr₆₀Al₁₅Ni₂₅大块非晶合金 示差扫 描量热法（DSC）     

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     

压力对Zr46.75Ti8.25Cu7.5Ni10Be27.5大块非晶合金玻璃转变和晶化动力学的影响

利用X射线衍射和差示扫描量热分析研究了高温高压下Zr_46.75Ti_8.25Cu_7.5Ni₁₀Be_27.5大块非晶合金的玻璃转变和晶化行为，结果发现压力降低了该大块非晶合金中的自由体积、热焓和晶化激活能. 关键词： 大块非晶合金 高压 差示扫描量热分析 玻璃转变     

Cu-Zr-Ti三元非晶合金形成范围的热力学预测

用基于热力学观点的定量预测三元合金形成非晶成分范围的方法,对Cu-Zr-Ti三元合金系形成非晶的成分范围进行了计算。该方法通过比较晶态固溶体的自由能和相应的非晶态的自由能来确定非晶形成的成份范围,在自由能的计算中,三元系的热力学数据用相应的3个二元系的热力学数据由Toop模型外推得到,二元合金系的形成焓则通过Miedema理论的计算得出。结果表明,理论预测的形成非晶的成分范围与已有的实验结果符合得比较好。     

Research on Zr50Al15−xNi10Cu25Yx amorphous alloys prepared by mechanical alloying with commercial pure element powders

Amorphous Zr₅₀Al_15−xNi₁₀Cu₂₅Y_x alloy powders were fabricated by mechanical alloying at low vacuum with commercial pure element powders. The effects on glass forming ability of Al partial substituted by Y in Zr₅₀Al₁₅Ni₁₀Cu₂₅ and thermal stability of Si₃N₄ powders addition were investigated. The as-milled powders were characterized by X-ray diffraction, scanning electron microscopy and differential scanning calorimeter. The results show that partial substitution of Al can improve the glass forming ability of Zr₅₀Al₁₅Ni₁₀Cu₂₅ alloy. Minor Si₃N₄ additions raise the crystallization activation energy of the amorphous phase and thus improve its thermal stability.     

Investigation of short‐range structural order in Zr69.5Cu12Ni11Al7.5 and Zr41.5Ti41.5Ni17 glasses,using X‐ray absorption spectroscopy and ab initio molecular dynamics simulations

Short‐range order has been investigated in Zr_69.5Cu₁₂Ni₁₁Al_7.5 and Zr_41.5Ti_41.5Ni₁₇ metallic glasses using X‐ray absorption spectroscopy and ab initio molecular dynamics simulations. While both of these alloys are good glass formers, there is a difference in their glass‐forming abilities (Zr_41.5Ti_41.5Ni₁₇ > Zr_69.5Cu₁₂Ni₁₁Al_7.5). This difference is explained by inciting the relative importance of strong chemical order, icosahedral content, cluster symmetry and configuration diversity.     

1at％ Ag替代Zr57Cu20Al10Ni8Ti5金属玻璃中各组元对玻璃形成能力及热稳定性的作用分析

以1at％ Ag元素分别等量替代Zr57Cu20Al10Ni8Ti5金属玻璃的各个组元,利用差示扫描量热升温分析获得不同试样的热力学参数,并结合不同尺寸(Φ8,Φ10,Φ12)吸铸试样的X-射线衍射分析结果,考察、验证元素替代后合金的实际玻璃形成能力及热稳定性的变化规律.经比较发现,Ag替代Ti元素,其玻璃形成能力显著提高(直径实际增大4 mm),同时热稳定性也明显改善,且临界冷却速率也明显降低,而Ag替代其他组元却无明显规律.针对玻璃形成能力的相关数据比较分析表明,本文结果未显示符合其Inoue的尺寸准则,混合焓判据也未显示出明显符合的现象.通过对堆垛密度的计算发现,1 at％ Ag替代Ti元素后使金属玻璃体系内部的堆垛密度增加.通过动力学分析,从晶化激活能、晶化反应速率常数两方面探讨了元素替代对玻璃形成能力和热稳定性的作用机理.     

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.     

Phase transformation behaviour in continuously cooled Zr65Al7.5Ni10Cu17.5− x Pd x (x = 0 − 17.5) glass-forming alloys and consequences for structure and property control

Continuous cooling transformation (CCT) diagrams were successfully constructed for Zr₆₅Al_7.5Ni₁₀Cu_{17.5? x} Pd _x (x?=?0???17.5) glass-forming alloys, comparing phase-transformation features in the alloy system to composition. While a low-Pd alloy (x?=?5) showed a single transformation curve, corresponding to the formation of a crystalline phase on the high-temperature side of the undercooled-liquid region, for a given time-scale, a high-Pd alloy (x?=?17.5) revealed an additional curve, corresponding to quasicrystalline phase formation on the lower temperature side. The result provides a clue to the structural and property control on the alloy system. Glassy specimens of the same size but with different intrinsic structure, evaluated by structural relaxation during continuous heating, could be fabricated for the low-Pd alloy (x?=?5). Plasticity was found to increase proportionally with the relaxation enthalpy. On the other hand, the critical size for glass formation could be improved considerably from 5 to 7 mm in diameter for the high-Pd alloy (x?=?17.5).     

Prediction of spinodal wavelength in continuously cooled metallic liquid

The spinodal decomposition of a deeply undercooled metallic liquid Zr_41.2 Ti_13.8Cu_12.5Ni₁₀Be_22.5 between 800 and 700 K is analysed in the framework of the theory of Cahn and Hilliard for continuous cooling, and the wavelength with maximum amplification is predicted, using as input parameters thermodynamic values gained in experiments. Electron microscopical studies show the microstructure of glass forming alloys Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5. The as‐cast material exhibits a two phase mixture of amorphous regions with different compositions. Evidence for spinodal decomposition is given, and the computed maximum‐amplitude wavelength corresponds well with the one found in the experiments.     

注入Mo 在Zr57Nb5Cu15.4Ni12.6Al10非晶合金中的扩散

通过二次离子质谱仪（SIMS）研究了Mo在Zr₅₇Nb₅Cu_15.4Ni_12.6Al₁₀非晶合金中的扩散，并计算出其扩散激活能Q和前置系数D₀分别为1.95 eV和1.13×10^-5m²s^-1.根据Stokes-Einstern关系式研究了玻璃转变温度以下593—673 K之间Zr₅₇Nb 关键词： 扩散 离子注入 二次离子质谱（SIMS） 黏滞特性     

Specific heat of around the glass transition

Dynamic calorimetric measurements are performed for the quaternary metallic glass Zr₆₅Al_7.5Cu_17.5Ni₁₀ in order to analyse the dependence on different heating rates for the glass transition temperature T_g. We compare two different temperature programs used for sample relaxation, to estimate the influence of the thermal history on T_g. A lower limit for the glass transition temperature T_g was calculated according to two different models based on the fact, that width and temperature of the glass transition depend on the experimental time scale set by the heating rate: One model assumes a Vogel-Fulcher-Tammann type behaviour, as used to describe more or less “fragile” glass formers and the other assumes an Arrhenius-like behaviour, which is related to “strong” glass formers. The values obtained from both models differ by about 80K. From additional absolute specific heat capacity measurements we calculate the Kauzmann temperature T_K, as a lower limit for the temperature of the glass transition from thermodynamic aspects. Comparing T_K with the temperature values obtained from the two evaluation models we can classify the quaternary metallic glass Zr₆₅Al_7.5Cu_17.5Ni₁₀, to behave more like a “strong” glass former. Received: 23 January 1998 / Received in final form and Accepted: 31 August 1998     

Formation,thermal stability and mechanical properties of Ti<Subscript>42.5</Subscript>Zr<Subscript>7.5</Subscript>Cu<Subscript>40</Subscript>Ni<Subscript>5</Subscript>Sn<Subscript>5</Subscript> bulk metallic glass

Ti_42.5Zr_7.5Cu₄₀Ni₅Sn₅ bulk metallic glass with a critical diameter of 4 mm was fabricated by the conventional copper mould casting method. The supercooled liquid region ΔT _x, reduced glass transition temperature T _rg, γ parameter, and δ parameter of the alloy were measured to be 63.9 K, 0.561, 0.393, and 1.400, respectively, implying that the alloy has an excellent glass-forming ability. The bulk metallic glass exhibits high compressive fracture strength of 2162 MPa with distinct plastic strain of 0.9%. The fracture surface consists mainly of vein-like patterns, typical of bulk glassy alloys. Supported by the Program for New Century Excellent Talents in University of China and the National Natural Science Foundation of China (NSFC)(Grant No. 50771040)