微量元素Y、Ag对Cu基非晶合金玻璃形成能力的影响

采用单辊旋淬法制备了Cu50Zr42Al8,Cu46 Zr47-xAl7Yx(x=2,5),Cu43Zr42AlsAg7和Cu43Zr42Al8Ag5 Y2非晶合金薄带,利用X射线衍射和差示扫描量热分析研究了合金样品的玻璃形成能力和热稳定性.结果表明,在Cu50Zr42Al8中添加适量的Ag、Y后使得非晶合金的短程有序结构发生改变.合金Cu46Zr47-xAl7Yx(x=2,5)的过冷液相区宽度ΔTx分别比Cu50 Zr42 Al8增加了19K、30K,约化玻璃转变温度Trg从0.565分别增加到0.579和0.566,参数γ从0.402分别增加到0.418和0.420,说明Y的添加提高了非晶合金的热稳定性和玻璃形成能力.合金Cu43Zr42 Al8Ag7和Cu43Zr42Al8Ag5Y2与Cu50Zr42Al8相比,约化玻璃转变温度Trg及参数γ均有了明显的提高,达到了0.619、0.416和0.609、0.411,表明Ag的添加、Ag和Y的同时添加均提高了Cu - Zr -Al系非晶合金的玻璃形成能力,但Ag的效果更加显著.     

锆基大块非晶合金的非等温晶化动力学效应

采用非等温差示扫描量热法(DSC)研究了锆基非晶合金Zr60Al15Ni25、Zr65Al10Ni10Cu15的晶化动力学.结果显示,随着升温速率的加快,这两种非晶合金的特征温度Tg、Tx、Tp均向高温区移动,且过冷液相区逐渐加宽,表明非晶合金的玻璃化转变和晶化均具有动力学效应.分别采用Kissinger法和Ozawa法计算各非晶合金的激活能,两种方法的计算结果相近.从激活能数据得出,两种锆基非晶合金的热稳定性均较强;与非晶合金Zr60Al15Ni25相比,Zr65Al10Ni10Cu15虽较难形成玻璃化转变和开始晶化,但其晶化一旦开始则随后的过程反而更容易进行.     

Al_(86)Ni_5Y_7Er_2非晶合金的晶化动力学研究

采用单辊旋淬法制备了Al86Ni5Y7Er2非晶合金,通过差示扫描量热(DSC)技术研究非晶合金晶化动力学性能,计算得到合金平均晶化激活能,得到平均晶化起始激活能Ex是146.4kJ·mol-1、第一晶化峰值平均激活能Ep1是183.8kJ·mol-1、第二晶化峰值平均激活能Ep2是247.7kJ·mol-1、第三晶化峰值平均激活能激活能Ep3是228.2kJ·mol-1。结果表明Al86Ni5Y7Er2非晶合金具有较好的热稳定性。     

Sm8Fe85Si2C5非晶合金的晶化动力学

用差热分析,结合Ｘ射线衍射研究了Ｓｍ８Ｆｅ８５Ｓｉ２Ｃ５非晶合金的晶化动力学。试验结果表明：在０－９００℃,该合金晶化相和Ｓｍ２（ＦｅＳｉ）１７Ｃｘ在晶化初激活能变化不大,当晶化量Ｘｃ（ａ－Ｆｅ）大于７０％、Ｘｃ「Ｓｍ２（ＦｅＳｉ）１７Ｃｘ」大于５０％时,两相晶激活能开始减小。     

块体Pd77.5Cu6Si16.5非晶合金的晶化动力学研究

应用变温条件下的JMA方程和Kissinger方程研究长体Pd77.5Cu6Si16.5非晶合金的晶化动力学行为。计算了其玻璃转变温度Tg，晶化起始温度Tx，晶化峰值温度Tpl的激活能E，频率因子和Avrami指数等晶化动力学参数。并将这些参数与非晶条带的相应参数做对比，发现一些描述晶化过程的参量发生了变化。实验结果表明，块体非晶合金的原子活动性小于传统非晶条带，而具有更宽的过冷液相区。     

Al-Co-Y合金系非晶的形成及其晶化过程

利用熔体快淬法制备出了Al92-xCo8Yx（x=4,6,8,9,10）薄带,采用X射线衍射（XRD）和扫描电镜（SEM）进行结构分析,示差扫描量热仪（DSC）进行热稳定性分析。研究了Y的加入对合金的非晶形成能力的影响以及Al84Co8Y8合金薄带等温退火的晶化过程。结果表明：当Y的原子分数为8%时,合金系的非晶形成能力最好;非晶态Al84Co8Y8合金的晶化过程分为3个阶段进行,退火过程中的组织结构转变为：非晶合金→非晶基体＋初晶α-Al＋少量未知亚稳相→α-Al相＋未知亚稳相＋Al9Co2→α-Al相＋Al9Co2相＋Al3Y相。     

非晶合金Cu77Ni8Sn8P7的玻璃转变和晶化激活能

通过对非晶合金Cu_(17)Ni_8Sn_8P_7的初淬和退火态进行DSC分析(差动扫描量热分析),得到多种加热速度下的玻璃化温度及晶化温度,用Henderson提出的变温动力学方法计算了非晶合金在晶化开始温度和蜂值温度下的转变激活能,并确定了非晶合金玻璃转变激活能的方法。最后讨论了转变激活能和温度的关系,并估算了晶化过程中成核和生长的激活能。     

非晶Pr8Fe86B6合金的晶化动力学

用差热分析（DTA），结合X射线衍射（XRD）研究了非晶Pr8Fe86B6合金的晶化动力学。结果表明：该非晶Pr8Fe86B6合金的晶化相为α－Fe固溶体和Pr2Fe14B金属间化合物，通过对两相晶化激活能的分析得出：α－Fe相的激活能在晶化初期变化不大，当其体积分散大于8％时，其晶化激活能开始减小，而Pr2Fe14B相的激活能随其体体积分数的增加而减小，且α－Fe相较Pr2Fe14B相容易易化析出。     

Cu,Co置换Ni对Al-Ni-La非晶合金晶化行为的影响

通过单辊快淬制备了Al85Ni9-xMxLa6和Al86Ni9-xMxLa5(M=Cu或Co,x=0～9)合金的薄带,利用X射线衍射仪(XRD)研究了薄带快淬态和退火态的结构,利用差示扫描量热仪(DSC)研究了上述合金薄带的晶化过程。结果表明,过量Cu,Co置换Ni降低合金的非晶形成能力,形成非晶相和晶态相的混合结构;Cu,Co置换Ni分别促进fcc-Al和亚稳相作为初生相析出:Al85Ni9-xCuxLa6合金的初生相由单独亚稳相MP1逐渐向单独fcc-Al转变,而Al86Ni9-xCoxLa5合金的初生相由单独fcc-Al逐渐向fcc-Al、亚稳bcc-(AlNi)11La3-like相和MP1转变,并趋于析出单独MP1;Cu,Co置换Ni分别降低和提高热稳定性:Al85Ni9-xCuxLa6和Al86Ni9-xCuxLa5合金的晶化开始温度Tx1分别从x=0时的545.5和520.3 K逐渐减至x=8时的415.0 K和x=7时的390.1 K,而Al85Ni9-xCoxLa6和Al86Ni9-xCoxLa5合金的Tx1分别逐渐增至x=6时的592.2 K和x=9时的576.8 K;Cu,Co置换Ni分别减弱和增强玻璃转变:Al85Ni9-xCuxLa6合金的玻璃转变迅速减弱,过冷液相区宽度ΔTx从x=0时的16.5 K逐渐减至x=2时的14.6 K,并于x2时完全消失,Al86Ni9-xCuxLa5合金即使当x=1时玻璃转变也随之消失,而Al85Ni9-xCoxLa6和Al86Ni9-xCoxLa5合金的ΔTx分别从x=0时的16.5和15.4 K逐渐增至x=6时的26.0 K和x=5时的19.9 K。     

Co77.5Si13.5B9非晶合金的制备与非等温晶化动力学效应

采用旋铸急冷工艺在大气环境中制备出了Co77.5Si13.5B9非晶合金带材。X射线衍射（XRD）和透射电镜（TEM）分析表明样品为完全非晶。用差热分析仪测量了非晶薄带的热稳定性参数Tg,Txi,Tpi,加热速度分别为5,10,15,35,55,75,95 K.min^-1。分析了合金的非等温晶化动力学行为,计算了两个析晶峰的晶化表观激活能。研究发现：不同升温速率的DTA曲线表明非晶合金的晶化过程为两步晶化,在连续加热条件下,随升温速率的加快,Co77.5Si13.5B9非晶合金的特征温度Tg,Txi,Tpi均向高温区移动,说明其玻璃转变和晶化行为均有动力学效应。当分别采用晶化开始温度和两个峰值温度时,所得非晶合金的激活能并不是一稳定值。Ozawa方法计算出的激活能值与Kissinger法计算出的结果是一致的。非晶态Co77.5Si13.5B9合金的晶化百分比与退火温度和退火时间的关系曲线均呈S型曲线,随加热速度的增加,非晶合金的晶化百分比与温度的关系曲线向高温处移动,晶化百分比与时间的关系曲线则向时间缩短的方向移动。     

Crystallization kinetics of amorphous magnesium-rich magnesium-copper and magnesium-nickel alloys

Amorphous magnesium-rich alloys Mg _y X_1-y (X=Ni or Cu and 0.82<y<0.89) have been produced by melt spinning. The crystallization kinetics of these alloys have been determined by in situ X-ray diffraction (XRD) and isothermal and isochronal differential scanning calorimetry (DSC) combined with ex situ XRD. Microstructure analysis has been performed by means of transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS). Crystallization of the Mg-Cu alloys at high temperature takes place in two steps: primary crystallization of Mg, followed by simultaneous crystallization of the remaining amorphous phase to Mg and Mg₂Cu. Crystallization of the Mg-Cu alloys at low temperatures takes place in one step: eutectic crystallization of Mg and Mg₂Cu. Crystallization of the Mg-Ni alloys for a Mg content, y>0.85, takes place in two steps: primary crystallization of Mg and of a metastable phase (Mg_∼5.5Ni, with Mg content y=0.85), followed by the decomposition of Mg_∼5.5Ni. Crystallization of the Mg-Ni alloys for a Mg content y<0.85 predominantly takes place in one step: eutectic crystallization of Mg and Mg₂Ni. Within the experimental window applied (i.e., 356 K<T<520 K and 0.82<y<0.89), composition dependence of the crystallization sequence in the Mg-Cu alloys and temperature dependence of the crystallization sequence in the Mg-Ni alloys has not been observed.     

Ball-milling-induced crystallization and ball-milling effect on thermal crystallization kinetics in an amorphous FeMoSiB alloy

Microstructure evolution in a melt-spun amorphous Fe_77.2Mo_0.8Si₉B₁₃ alloy subjected to high-energy ball milling was investigated by means of X-ray diffraction (XRD), a transmission electron microscope (TEM), and a differential scanning calorimeter (DSC). It was found that during ball milling, crystallization occurs in the amorphous ribbon sample with precipitation of an α-Fe solid solution, and the amorphous sample crystallizes completely into a single α-Fe nanostructure (rather than α-Fe and borides as in the usual thermal crystallization products) when the milling time exceeds 135 hours. The volume fraction of material crystallized was found to be approximately proportional to the milling time. The fully crystallized sample with a single α-Fe nanophase exhibits an intrinsic thermal stability against phase separation upon annealing at high temperatures. The ball-milling effect on the subsequent thermal crystallization of the amorphous phase in an as-milled sample was studied by comparison of the crystallization products and kinetic parameters between the as-quenched amorphous sample and the as-milled partially crystallized samples. The crystallization temperatures and activation energies for the crystallization processes of the residual amorphous phase were considerably decreased due to ball milling, indicating that ball milling has a significant effect on the depression of thermal stability of the residual amorphous phase.     

Effect of the structure of amorphous electrodeposited Ni-W and Ni-Co-W alloys on their crystallization

The microstructure and phase composition of amorphous electrodeposited Ni-W and Ni-Co-W films are studied using transmission electron microscopy, X-ray diffraction, and differential thermal analysis. The thermal stability of the amorphous films is shown to depend on their chemical composition and network microstructure. The temperatures of the onset of crystallization and the sequence of phase transformations during transition to an equilibrium crystalline state are determined.     

The effect of metallic elements on the crystallization behavior of amorphous Fe-Si-B alloys

The crystallization behavior of amorphous Fe_84-X Si₆B₁₀M_X (M=Nb, Zr, V, or Cu) alloys was examined using differential scanning calorimetry (DSC) and transmission electron microscopy (TEM) with the aim of clarifying the effect of additional M elements. The compositional dependence of the first crystallization temperatureT _x1 increased in the order of Zr > Nb > V; however, the addition of 1 at. pct Cu caused a decrease inT _x1. Such an effect of the M elements on the thermal stability of an amorphous phase was interpreted in terms of the difference in the atomic size. These alloys were composed of a mixed structure ofα-Fe and amorphous phases after aging for 3.6 ks in the first exothermic temperature range. The addition of more than 3 at. pct Nb or Zr significantly affected the morphology and grain size of theα-Fe phase. However, their particles possessed dendritic morphology with a grain size of 0.1 to 0.3 μm, when the Nb or Zr content was less than 2 at. pct. Further addition of these elements brought about the formation of sphericalα-Fe particles. The average grain size, for instance, was as small as 20 nm in the aged alloy containing 6 at. pct Nb, which shows that a remarkable grain refinement occurs with increasing Nb content.     

An investigation of hydrogen storage kinetics of melt-spun nanocrystalline and amorphous MgeNi-type alloys

The nanocrystalline and amorphous Mg2Ni-type Mg2–xLaxNi (x=0,0.2) hydrogen storage alloys were synthesized by melt-spinning technique.The as-spun alloy ribbons were obtained.The microstructures of the as-spun ribbons were characterized by X-ray diffraction (XRD),high resolution transmission electronic microscopy (HRTEM) and electron diffraction (ED).The hydrogen absorption and desorption kinetics of the alloys were measured using an automatically controlled Sieverts apparatus,and their electrochemical kinetics were tested by an automatic galvanostatic system.The electrochemical impedance spectrums (EIS) were plotted by an electrochemical workstation (PARSTAT 2273).The hydrogen diffusion coefficients in the alloys were calculated by virtue of potential-step method.The obtained results showed that no amorphous phase was detected in the as-spun La-free alloy,but the as-spun alloys substituted by La held a major amorphous phase,con-firming that the substitution of La for Mg markedly intensified the glass forming ability of the Mg2Ni-type alloy.The substitution of La for Mg notably improved the electrochemical hydrogen storage kinetics of the Mg2Ni-type alloy.Furthermore,the hydrogen storage kinetics of the experimental alloys was evidently ameliorated with the spinning rate growing.     

铜模吸铸与高能球磨制备Zr46Cu46Al8非晶合金的组织结构及晶化动力学研究

采用铜模吸铸法制备出直径3 mm的Zr₄₆Cu₄₆Al₈块体非晶合金, 利用高能球磨法获得了不同粒径的合金粉体, 通过X射线衍射仪、示差扫描量热仪、扫描电镜等测试手段及热力学计算方法, 研究了制备方法对非晶合金组织结构及晶化动力学的影响。结果表明, 块体合金和粉体合金均可获得完全非晶结构; 块体非晶合金玻璃转变和晶化过程具有明显的动力学效应; 单因素变量法制备非晶粉体的最佳参数为: 转速300 r·min-1, 球料比30:1, 球磨时间15 h; 相同条件下, 除过冷液相区外, 块体非晶合金热力学参数普遍高于非晶粉体, 且晶化放热更剧烈; 随着加热速率增大, 二者热力学参数均向高温区移动, 过冷液相区的宽度也逐渐增加; 块体非晶合金和非晶粉体的特征温度表观激活能数值相近, 块体非晶态合金的表观激活能较非晶粉体高, 热稳定性更优。     

Composition dependency of crystallization in Fe80 (B1-xPx)20 amorphous alloys

The annealing behavior of amorphous materials particularly the ribbon alloys involving iron group transition metals with the metalloids have been investigated extensively in the past.1-6 Two distinct annealing stages often occur in transforming the amorphous structure into the equilibrium two phase state where the first annealing stage is usually associated with a transition to an intermediate metastable structure while the second stage transforms this intermediate structure to the equilibrium state^1-3