大块非晶合金Zr55Cu30Al10Ni5的电子结构特征及电击穿行为

测定了大块非晶合金Zr55Cu30Al10Ni5晶化前后的费米能级和各元素的电子结合能，研究了非品合金的电子结构特征和电击穿行为．测试并讨论了非晶材料场发射能力和耐电压强度的关系．结果表明，对于Zr基合金，非品态比品态合金具有更大的功函数．比较了Zr55Cu30Al10Ni5合金非晶态与晶态的耐电压强度数值，发现非晶态合金的耐电压强度数值比较分散，品化合金的耐电压强度相对比较集中．耐电压强度平均值表明，Zr基合金非晶态具有更好的耐电压能力．     

Structure Evolution of Bulk Metallic Glass Zr52.5Ni14.6Al10Cu17.9Ti5 during Annealing

To whom correspondence should be addressedE-mail: heguo@bj.col.com.cn1. IDtroductionBulk metallic glasses["2] with size of more than micrometers in three dimensions can be produced evenby conventional technological methods such as metallic mold casting[3] ) high pressure die casting[4], waterquenching('l, melt injection casting[6], unidirectionalzone melting['] etc., because they have very lowercritical cooling rate for glass transformation duringcooling from liquid. Such large glass--forming…     

Zr-Al-Ni-Cu块体非晶合金的制备及其耐蚀性能

块体非晶合金的耐蚀性能与合金元素本身的特性及合金成分密切相关.采用铜模吸铸法制备了Zr_(55)Al_(10)Ni_5Cu_(30)块体非晶合金,用X射线衍射(XRD)、差示扫描量热分析法(DSC)和差热分析法(DTA)考察了合金的非晶特性和热力学属性,通过电化学极化试验和盐雾腐蚀试验测试了合金的耐蚀性.结果表明,制备的Zr_(55)Al_(10)Ni_5Cu_(30)合金为完全的非晶相,且具有较大玻璃形成能力和热稳定性;腐蚀电流密度仅为12.6 nA/cm~2,经144 h盐雾试验无质量变化,表明合金具有优异的耐腐蚀性能.     

Crystallization Behavior of Zr_(55)Al_(10)Cu_(30)Ni_5 Bulk Metallic Glass Rolled at Room Temperature

Zr 55 Al 10 Cu 30 Ni 5 bulk metallic glass was rolled up to 95% in thickness reduction at room temperature, and the dependences of microstructure and thermal stability on the strain were investigated. It is revealed that phase transformations do not occur during the rolling, but the split of the crystallization peaks becomes more and more obvious with increasing thickness reduction. Analyses of the radial distribution functions and the pair correlation functions indicate that the rolling has enhanced the sh...     

弛豫对Zr-Al-Ni-Cu基非晶合金晶化过程的影响

非晶合金的稳定性是制备大块非晶合金的关键，而弛豫后形成的短程有序结构对非晶中的晶体相形核有重要的影响。本文通过差热分析及X射线衍射法研究了预先弛豫处理对Zr60Al8Ni12.5Cu17Si2.5和Zr60Al8Ni10Cu17Si5非晶合金晶化过程的影响。结果表明：预先弛豫处理降低了上述非晶合金的稳定性。Si含量的增加则提高上述非晶合金的稳定性。根据等温转变过程日体相形核孕育期采用Arrhenius公式所确定的晶化激活能更能反映非晶晶化过程及非晶的稳定性。     

Gibbs Free Energy and Activation Energy of ZrTiAlNiCuSn Bulk Glass Forming Alloys

The Gibbs free energy differences between the supercooled liquid and the crystalline mixture for the (Zr_(52.5)Ti_5Al_(10)-Ni_(14.6)Cu_(17.9))_((100-x)/100)Sn_x (x=0, 1, 2, 3, 4 and 5) glass forming alloys are estimated by introducing the equationproposed by Thompson, Spaepen and Turnbull. It can be seen that the Gibbs free energy differences decrease firstas the increases of Sn addition smaller than 3, then followed by a decrease due to the successive addition of Snlarger than 3, indicating that the thermal stabilities of these glass forming alloys increase first and then followed by adecrease owing to the excessive addition of Sn. Furthermore, the activation energy of Zr_(52.5)Ti_5Al_(10)Ni_(14.6)Cu_(17.9) and(Zr_(52.5)Ti_5Al_(10)Ni_(14.6)Cu_(17.9))_(0.97)Sn_3 was evaluated by Kissinger equation. It is noted that the Sn addition increases theactivation energies for glass transition and crystallization, implying that the higher thermal stability can be obtainedby appropriate addition of Sn.     

超声波筛选激光增材制造非晶合金

目的 快速优化出无缺陷非晶合金激光增材制造工艺。方法 以Zr51Ti5Cu25Ni10Al9非晶合金为模型材料,利用超声波对金属内部缺陷的衰减,来快速筛选激光增材制造非晶合金的最佳工艺组合(激光功率和扫描速度)。结果 超声波检测可以准确有效地检测出非晶合金试件的晶化比例,并且当激光功率为1 300 W、扫描速度为600 mm/min时超声波衰减系数降至最低。进一步对该工艺下获得的样品分析发现,该工艺成型的Zr51Ti5Cu25Ni10Al9非晶合金缺陷最少、晶化程度最低、性能最佳。结论 超声波技术是快速筛选激光增材制造非晶合金等高性能金属最佳工艺参数的有效技术手段。     

Zr基大块非晶合金成分的等电子浓度和等原子尺寸判据

制备了6种合金Zr65.5Al5.6Ni6.5Cu22.4,Zr65.3Al6.5Ni8.2Cu20,Zr65Al7.5Ni10Cu7.5,Zr64.8Al8.3Ni11.4Cu5.5,Zr64.5Al9.2Ni13.2Cu13.1和Zr63.8Al11.4Ni17.2Cu7.6,共晶成分位于合金Zr64.5Al9.2Ni13.2Cu13.1和合金Zr63.8Al11.4Ni17.2Cu7.6的成分之间，这6种合金均显示了非晶相的形成和较宽的过冷液相区范围△Tx值，以及较大的约化玻璃转变温度Trg值，除合金Zr63.8Al11.4Ni17.2Cu7.6的△Tx值为87K外，其余5种成分合金的△Tx值均在97K以上，最宽的达105K，表明这6种合金是一个具有大玻璃形成能力和高热稳定性的非晶合金系列，合金Zr63.8Al11.4Ni17.2Cu7.6是6种合金中玻璃表成能力和热稳定性最高的，其Tg，Tx和Trg值最高，Inoue非晶合金Zr65Al7.5Ni10Cu17.5并不是最佳非晶成分，提出以等电子浓度和等原子尺寸规律作为设计大块非晶合金成分的判据。     

Friction Stir Welding of Zr_(55)Al_(10)Ni_5Cu_(30) Bulk Metallic Glass to Crystalline Aluminum

The Zr55Al10Ni5Cu30 bulk metallic glass plate were successfully welded to crystalline aluminum plates by using a friction stir welding (FSW) method. The welded zone was examined. No defects, cracks or pores were observed and no other crystalline phases except for aluminum were found in the welded joint. The strength of the joint is higher than that of aluminum. The glassy phase in the stir zone keeps the amorphous state, showing a successful welding. The storage modulus softens over the glass transition. An...     

新型Zr-Nb基大块非晶合金的形成及性能

本文用水淬法制备 Zr-Nb基大块非晶合金 ;并采用 DSC热分析法测定了该种合金的玻璃转变温度和热稳定性 ;采用超声检测方法精确测定了材料的声学性能 ,由此计算得到一组大块非晶合金的弹性性能参数。     

锆基大块非晶合金及其晶化合金在0.5mol/L H2SO4中的腐蚀行为研究

根据合金的DSC曲线制定了Zr60Al15Ni25、Zr52.5Al10Ni10Cu15Be12.5和Zr65Al10Ni10Cu15等锆基大块非晶合金的等温退火工艺,获得了与非晶态合金具有相同成分的晶化合金。通过研究非晶态合金和晶化合金在0.5mol/L H2SO4中的极化曲线,结合扫描电镜(SEM)和能量散射X射线谱(EDS)分析,发现,在0.5mol/LH2SO4中非晶态合金和晶化合金都具有非常优异的耐腐蚀性能,但非晶合金的耐腐蚀性能要比晶化合金稍好。这主要是因为晶态合金的结构中不存在晶界、位错等缺陷,同时非晶态合金中的组元具有很高的活性,使合金更快地进入钝态。     

用渗流铸造法制备Zr55Al10Ni5Cu30非晶复合材料

用渗流铸造法制备出以Zr55Al10Ni5Cu30合金为基体，以W丝束为增强相的大块非晶复合材料，采用X-射线衍射分析了基体的相组成，在扫描电镜（SEM）下观察了反应界面的形貌，利用电子探针研究了元素的迁移情况，通过改变渗流温度和时间。研究了W丝和基体间界面的作用过程，选择适当的渗流温度和时间，可以制备出长65mm直径4.3mm的大块W丝束增强Zr55Al10Ni5Cu30非晶复合材料，在一定范围内提高渗流温度降低渗流时间或降低渗流温度延长渗流时间能得到同样的结果，在渗流铸造前，液态金属的过热有利于提高基体的非晶形成能力，降低渗流铸造时产生的缺陷。     

Impurity-driven nanocrystallization of Zr-based bulk amorphous alloys

The effect of oxygen content and Ti addition on the glass forming ability (GFA) and crystallization kinetic of Zr-based bulk glass forming alloys have been studied by means of thermal analysis and X-ray diffraction techniques. Presence of oxygen triggers the formation of a nanocrystalline metastable f.c.c. Zr2 Ni-type phase which can act as heterogenous nucleation sites for the formation of dendrites during solidification. An increase in oxygen content changes the crystallization behaviour from a single- to a double-step process and triggers the crystallization of stable Zr2(Cu,Al) besides metastable Zr2 Ni-type phase. Oxygen-triggered nucleation of a nanocrystalline metastable Zr2 Ni-type phase is found to be the initial step of crystallization. The important parameters of GFA such as glass transition temperatures, Tg, the crystallization temperatures, Tx, and crystallization enthalpies, deltaH, were determined by using DSC. It was observed that the presence of oxygen, even in a very small amount, and Ti addition cause a drastic reduction of the supercooled liquid region, deltaTx, accompanied by a change of the crystallization kinetic. This leads to the decrease in stability of the supercooled liquid, consequently results in a deterioration of the glass forming ability of the alloy.     

Microstructure Evolution of Zr50Cu18Ni17Al10Ti5 Bulk Metallic Glass during Cold-rolling

Zr50Cu18Ni17Al10Ti5 bulk metallic glass has been rolled at room temperature up to 95% in thickness reduction, and the dependence of microstructure on the strain was investigated. With increasing thickness reduction, the full width at half maximum (FWHM) and crystallization enthalpy decrease gradually till 80%, and then increase evidently at 95%. It is revealed that the reversible transition between the ordered and disordered atomic configurations was found in the metallic glass as the deformation proceeds, which is further verified by the high-resolution transmission electron microscopy images. The final microstructure in metallic glass during cold-rolling is the net result of two competing processes between shear-induced disordering and diffusion controlled reordering.     

添加AlN对机械合金化Zr65Al7.5CU17.5Ni10非晶态合金热稳定性的影响

以成分为Zr65Al7.5Cu17.5Ni10的元素的粉末混合物及AIN颗粒为起始材料,经机械合金化形成非晶态合金为基体的复合材料,AIN添加量为5％－30％（体积分数,下同）,利用X射线衍射（XRD）,透射电子 显微镜（TEM）和差示扫描量热计（DSC）分析了含AIN复合材料的结构特性,玻璃转变与晶化行为,TEM观察表明,AIN第二相粒子弥散分布在晶Zr基合金基体上,粒子尺寸为20－200nm,仍为初始的晶体结构,与未添加AIN的Zr基非晶态合金相比,含5％－10％AIN的复合材料仍表现出较宽的过冷液态温度区域,玻璃转变温度（Tg)和晶化激活能（Ex)没有显著变化,但晶化起始温度（Tx)向高温移动大约10K,导致过冷液态温度区域的扩宽,AIN含量增至30％,明显的玻璃转变消失,Tx升高的20K。     

新型Zr57Nb5Cu15.4Ni12.6Al10大块非晶态合金的制备及其室温单轴压缩断裂行为

应用铜模真空吸铸法制备直径达5mm的棒状新型Zr57Nb5Cu154Ni12.6Al10大块非晶样品.X射线衍射检测证明样品完全为非晶态.通过等温示差扫描量热法(DSC)测试了Zr57Nb5Cu15.4Ni12.6Al10大块非晶的晶化动力学效应,同时研究了大块非晶合金的室温单轴压缩变形和断裂行为.结果表明:Zr57Nb5Cu15.4Ni12.6Al10块体非晶晶化过程具有动力学效应;其室温压缩变形过程主要表现为弹性变形;断裂面与压缩方向约呈45°,断口呈现典型的脉状花样.     

Dynamic mechanical relaxation behavior of Zr35Hf17.5Ti5.5Al12.5Co7.5Ni12Cu10 high entropy bulk metallic glass

Non-equiatomic high entropy bulk metallic glasses were reported recently and show unique mechanical and physical properties.Dynamic mechanical relaxation behavior of Zr35Hf17.5Ti5.5Al12.5C07.5Ni12Cu10 high entropy bulk metallic glass was investigated by dynamic mechanical analysis(DMA)and the mechanical spectra could be well described by the quasi-point defects(QPD)theory.Compared to typical metallic glasses,the intensity of the β relaxation of Zr35Hf17.5Ti5.5Al12.5Co7.5Ni12Cu10 high entropy bulk metallic glass is lower due to the sluggish diffusion.At the same time,the correlation factor χ is higher than that of conventional metallic glasses and this is ascribed to the high configuration entropy.In paral-lel,physical aging below the glass transition temperature leads to a decrease of atomic mobility,caused by a decrease of the concentration of defects.     

具有大过冷液相温度区间的Cu基大块非晶合金的制备和机械性能

利用铜模铸造方法制备了具有大过冷液相温度区间的Cu-Zr-Ti-Ni系高强度Cu基大块非晶合金,对于Cu55Zr55Ti15Ni5合金,最大直径达5mm.过冷液相区温度范围ΔTx达45.48～70.98 K.Cu基玻璃合金棒表现出非常高的机械性能和明显的塑性,对于Cu50Zr25Ti15Ni10、Cu55Zr25Ti15Ni5和Cu54Zr22Ti18Ni6合金,压缩断裂强度分别达2155MPa、2026MPa和1904MPa,维氏硬度分别达674、678和685.加入Co元素扩大了CuZr-Ti-Ni系合金的ΔTx,Cu50Zr22Ti18Ni6Co4合金的ΔTx高达74.5K.     

Oxygen Behavior in Bulk Amorphous Zr—base Alloy

Bulk Zr55Al10Ni5Cu30 metallic glass plates with a dimension of 85 mm×35mm×4 mm and a complicated plate were fabricated by injecting casting method using spongy zirconium and industrial purity aluminum, nickel and copper as raw materials. It was shown that the holding time of liquid metals at elevated temperatures had a great influence on the oxygen content of the plates due to the contamination resulting from the atmosphere. Increasing holding time resulted in the increase of oxygen content in the injected alloy. The glass transition temperatures of the bulk metallic glass plates are higher than that reported in the literature and crystallization temperature is lower for the one with higher oxygen content at the same heating rate. The extension of the undercooled liquid region △Tx reaching about 87 K is 3 K higher than that previously reported and 26 K higher than that with oxygen content of 0.076 wt pct for the one with oxygen content as high as 0.065 wt pct. Therefore the oxygen content of the alloy has     

Effects of Pressure on the Solidification Microstructure of Mg_(65)Cu_(25)Y_(10) Alloy

The Mg65Cu25Y10 melts were quenched at a temperature of 973 K under various pressures in the range of 2-5 GPa and ambient pressure. The microstructure of the solidified specimens has been investigated by X-ray diffraction, transmission electron microscope and electron probe microanalysis. Experimental results show that the pressure has a great influence on the solidification microstructure of the Mg65Cu25Y10. At ambient pressure, the solidification products are Mg2(Cu,Y) and a very small amount of Y2O3 inclusion. As the pressure is above 2 GPa, a new Cu2(Y,Mg) phase appears, while Y2O3 is not observed at the pressure of 3, 4 and 5 GPa. When the pressure increases from 2 GPa to 5 GPa, the grain sizes of Mg2(Cu,Y) and Cu2(Y,Mg) decrease from 125, 96 nm to 80, 7 nm, respectively. The mechanisms for the effects of the pressure on the phase evolution and microstructure during solidification process of Mg65Cu25Y10 alloy have been discussed.