微量Al添加对铜基大块非晶合金性能的影响

为了进一步提高铜基大块非晶合金的玻璃形成能力及力学性能,采用添加微量Al元素的方法对块体非晶合金Cu52.5Ti30Zr11.5Ni6进行了成分优化.热分析与X射线衍射结果显示,随着微量Al的添加,液相线温度从非晶合金Cu52.5Ti30Zr11.5Ni6的1150 K逐步降低到Cu50.5Ti30Zr11.5Ni6Al2的1134 K,临界直径相应的从5 mm提高到6 mm.大块非晶Cu50.5Ti30Zr11.5Ni6Al2的压缩断裂强度达到2286 MPa,比经典的铜基非晶合金Cu47Ti34Zr11Ni8提高约100 MPa,表明微量Al的添加在有效提高玻璃形成能力的同时,强度也略有提高.     

大块非晶合金的性能、制备及应用

综述了大块非晶合金的性能、制备方法及应用，对比了吸铸法制备的棒状Zr41.2Ti13.8Cu12.5Ni10Be22.5,Zr57Cu20Al10Ni8Ti5,Zr52.5Ti5Cu17.9Ni14.6Al10(原子分数)大块非晶样品的过冷温度区间宽度(△Tx)，给出了3种大块非晶合金系列的热稳定性参数Tg、Tx及△Tx，提出了大块非晶合金领域存在的问题及发展方向．     

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.     

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。     

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.     

锆基大块非晶在HCl溶液中的耐腐蚀性研究

利用CHI660B型电化学工作站研究了4种不同成分（Zr55Al10Ni5Cu30，Zr60Al15Ni25，Zr65Al10Ni10Cu15，Xr52．5Al0Ni10Cu15Be12．5）的锆基非晶态合金以及其中两种成分（Zr65Al10Ni10Cu15，Zr52．5Al10Ni10Cu15Be12．5）的晶态合金在2．5mol／L的HCl溶液中的腐蚀行为。通过Tafel曲线的测试结果表明，非晶合金的耐腐蚀性能与其成分有很大的关系，这4种非晶合金试样的耐腐蚀性由强到弱的顺序依次为Zr60Al15Ni25〉Zr65Al10Ni10CU15〉Zr52．5Al10Ni10Cu15Be12．5〉Zr55Al10Ni5Cu30。两种成分的非晶态合金与其对应成分的晶态试样相比，非晶态合金具有较低的腐蚀电流，显示出较好的耐腐蚀性。最后，根据电化学腐蚀原理，从合金的微观结构、化学成分以及腐蚀介质的性质3个方面探讨了影响合金耐腐蚀性的因素。     

微合金化对Ti基非晶复合材料的组织和力学性能的影响

采用悬浮熔炼-水冷铜模吸铸法制备了(Ti0.5Ni0.5-xZrx)80Cu20(x=0,0.02,0.04,0.06和0.08)。通过对Zr的添加量的控制制备具有组织连续梯度的非晶复合材料,研究其组织和力学行为及微量Zr的添加对此非晶复合材料的组织和力学性能的影响。结果表明,凝固过程的温度梯度决定了复合材料的组织梯度,由表及里,主要为非晶相、马氏体相和奥氏体树枝晶相。铸态非晶基体上析出了B2-Ti(Ni,Cu)过冷奥氏体相和B19’-Ti(Ni,Cu)热诱发马氏体相,加载断裂后应力诱发马氏体相变,马氏体衍射峰比铸态增强且马氏体择优取向。随着Zr的不断添加,此系列非晶合金非晶形成能力先提高后降低,奥氏体含量不断下降,相变诱发塑性减弱,从而塑性逐级递减,强度先升高后降低。     

低压铸造-轧制法快速制备Al-Cu复合材料

采用低压铸造-轧制法实现了快速制备650mm×30mm×7mm×R3.5mm的Al/Cu复合材料,并通过SEM、EDS、XRD和电子万能试验机(AG-X)表征其结构和界面剪切强度。结果表明:在Cu管预热温度200℃,轧制压下率30%,冷却水通量400L/h,Al液温度680~740℃条件下均可实现Al-Cu之间的冶金结合,界面合金层随着Al液温度的升高而变宽;复合材料的导电性能和界面结合剪切强度受界面金属间化合物层宽度的影响,其宽度越宽,剪切强度降低。低压铸造法制备Al-Cu复合材料工艺流程短,一次成形快,并能对界面物相进行有效调控。     

大块非晶合金Zr55Cu30Al10Ni5及其晶态合金的氧化行为研究

采用DSC、TGA、XRD等实验手段研究了大块非晶合金Zr55Cu30Al10Ni5各种状态的氧化行为。结果表明非晶态样品的氧化速率最快,稳定晶化态样品的氧化速率最慢,这说明晶态相Zr2Cu具有良好的抗氧化性。非晶态和晶态样品的氧化动力学均遵循线性规律。     

晶化分数对钛基非晶复合材料热塑性成形能力的影响

目的 研究晶化分数对原位晶化钛基非晶复合材料热塑性成形能力的影响,优化Ti基非晶复合材料的制备和设计。方法 首先采用电弧熔炼和铜模铸造制备出成分为Ti45Zr20Be29Fe6和Ti45Zr20Be29Cu6的非晶合金,通过连续加热DSC及等温DSC研究其晶化动力学,然后根据得到的等温晶化规律制备不同晶化体积分数的非晶复合材料,并通过静态热机械分析(TMA)表征其热塑性成形能力。结果 Ti45Zr20Be29Fe6在406 ℃与411 ℃时,等温晶化过程为形核率随时间增大的形核长大过程;Ti45Zr20Be29Cu6在370,375,380,385 ℃时,等温晶化过程为形核率随时间减小的形核长大过程;XRD物相分析表明,等温处理后Ti45Zr20Be29Fe6和Ti45Zr20Be29Cu6的析出相分别为β-Ti和α-Ti2Zr;两种内生复合材料的热塑性成形能力均随晶化相体积分数的增大而降低,且Ti45Zr20Be29Fe6基体复合材料的热塑性成形能力比以Ti45Zr20Be29Cu6为基底的复合材料更好。结论 晶化分数增加会降低钛基非晶复合材料的热塑性成形性能,且其影响程度与复合材料的基体和晶体第二相的特性有关。     

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．     

Fabrication of Cu rich bulk metallic glass composites via solidification method

Abstract

Cu based bulk metallic glasses and composites with tiny crystalline phases embedded in metallic glass matrix have been successfully fabricated by solidification technique in the present work. The formation of crystalline phases and structure inhomogeneity in bulk metallic glasses was characterised. Al is used as the minor alloying element to partly substitute Cu element in 61Cu–34Zr–5Ti. The results show that quarternary 60Cu–34Zr–5Ti–1Al alloy exhibits monoamorphous feature, and 56Cu–34Zr–5Ti–5Al alloy has a few crystalline peaks superimposed on a broad diffraction peak, suggesting that a composite structure forms in certain solidification conditions. To further identify the microstructure of the as cast rod, all samples were characterised by scanning electron microscopy (SEM). Small size phases are found in 2 mm diameter 56Cu–34Zr–5Ti–5Al rod, which has larger plastic deformation. The composition of those crystalline phases is also investigated. All results indicate that the presence of certain phases in metallic matrix benefits the mechanical properties of the as cast bulk metallic glasses.     

Pressure Effect on Crystallization of Zr55Cu30Al10Ni5 Bulk Metallic Glass

The effect of pressure on the variation of the crystallization phases of the Zr55u30Al10Ni5 bulk glass and its thermal stability under high pressure annealing was investigated by X-ray diffraction (XRD)and differential scanning calorimeter(DSC).The mode of crystallization and products of crystallization of the Zr55Cu30Al10Ni5 bulk glass were quite different pressure.At ambient pressure,the crystallization products consisted of NiZr2 and CuZr2,while at pressure of 1 Gpa and 3 Gpa,the alloys crystallized into NiZr2 and Cu10Zr7,respectively.The alloy was nearly not crystallized and only a small amount of Cu10Zr7 was precipitated under 5 Gpa.DSC proved that the mode of the crystallization under high pressure was different from that at ambient pressure.     

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.     

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。     

Effects of Cr,Mn, Si,Cu and Zr on microstructure and mechanical properties of high carbon Fe–16Al alloy

Abstract

Effects of alloying elements Cr, Mn, Si, Cu and Zr on the microstructure and mechanical properties of Fe₃Al (Fe–16Al) based alloy containing ～0·5 wt-%C have been investigated. Six alloys were prepared by a combination of air induction melting with flux cover and electroslag refining (ESR). ESR ingots were hot forged and hot rolled at 1373 K and were further characterised with respect to microstructure and mechanical properties. The base alloy and the alloys containing Cr, Mn, Si and Cu exhibit a two phase microstructure of Fe₃AlC_0·5 precipitates in Fe₃Al matrix whereas the alloy containing Zr exhibits a three phase microstructure, the additional phase being Zr rich carbide precipitates. Cr and Mn have high solubility in Fe₃AlC_0·5 precipitates as compared to Fe₃Al matrix whereas Cu and Si have very high solubility in Fe₃Al matrix compared to Fe₃AlC_0·5 precipitate and Zr has very low solubility in both Fe₃Al matrix and Fe₃AlC_0·5 precipitate. No significant improvement in room and high temperature (at 873 K) strengths was observed by addition of these alloying elements. Furthermore, it was observed that addition of these alloying elements has resulted in poor room and high temperature ductility. Addition of Cr, Mn, Si and Cu has resulted in marginal improvement in creep life, whereas Zr improved the creep life significantly from 22·3 to 117 h.     

Precipitation characteristics of Cu–15Cr–0·15Zr in situ composite

Abstract

The precipitation characteristics of Cu–15Cr–0·15Zr in situ composite made by cold drawing have been studied using analytical TEM and hardness measurement. It has been observed that the in situcomposite reaches peak hardness at a lower aging temperature than the corresponding alloy which is not subjected to cold working prior to aging treatment. The Cr rich precipitates in the peak aged composite are much smaller than those in the peak aged alloy. Under peak aging conditions, precipitation free zones adjacent to the grain boundaries of the Cu matrix are also observed in both the alloy and the composite. The addition of Zr enhances the precipitation hardening effect in the alloy and the composite. The major mechanism of this enhancement may be through increasing the Cr rich precipitate nucleation rate and precipitate/matrix interfacial energy.     

熔渗温度对Si/Al复合材料组织及性能的影响

采用无压熔渗法制备Si/Al复合材料,研究了熔渗温度对所制备Si/Al复合材料Si相形貌的影响,对Si相间基体合金的凝固组织进行了分析,测试了Si/Al复合材料热膨胀系数、热导率及抗弯强度。结果表明,在相同熔渗时间下,随着熔渗温度升高,所制备Si/Al复合材料中Si相从颗粒状到形成网络状。Si相间的Al-Si基体合金中不再是典型的初生相和共晶组织,而是出现了类似离异共晶的结晶现象,即初晶Si和共晶Si是在原存的Si相上结晶长大。XRD分析显示在所制备复合材料中只有Si相和Al相。随着熔渗温度升高复合材料热膨胀系数、热导率以及抗弯强度均出现下降。     

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…