大块玻璃合金射流成形方法的研究

用射流成形方法制备出直径从Φ５ｍｍ到Φ１０ｍｍ的Ｚｒ基大块玻璃离态合金，研究了样品尺寸大小以及保护气氛中含氧量对形成玻璃态合金的影响，结果表明，样品尺寸越上，则合金达到的冷却速率越大，形成的玻璃态合金中析出结晶相越少，消除氧非均匀核的影响，可以减少消除大块玻璃态合金基体中的结晶析出，有利于获得更大尺寸的大块玻璃合金。     

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…     

Crystalline Precipitate in a Bulk Glass Forming Zr-Based Alloy and Its Effect on Mechanical Properties

Cylindrical and sheet samples of bulk metallic glass with a nominal composition of Zr52.sNi14.6AI10Cu17.9Ti5 (at. pct) were prepared by melt injection casting. The crystalline precipitates formed during the casting were studied by metallographic observations and selected-area electron diffractions. The effect of crystalline precipitates on the mechanical properties were investigatedby tensile and compressive tests at room temperature. Oxygen contents and the sample sizes(or cooling rates) strongly affect the formation of the crystalline precipitates. Overheating thealloy melt up to 200 K above its melting temperature can effectively prevent the formation ofthe crystalline precipitates to get fully glass samples with diameters up to 2 mm for cylindersand thickness uo to 1 mm for sheets even the oxv~ren content is as hi~rher as 0.08 wt Dct.     

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。     

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.     

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。     

Effect of Minor Alloying on Crystallization Behavior and Thermal Properties of Zr_(64.5)Ni_(15.5)Al_(11.5)Cu_(8.5) Bulk Amorphous Alloy

Minor alloying plays an important role in the synthesis and improvement of thermal stability of bulk metallic glasses(BMGs).The present study was conducted to investigate the effect of minor additions of Y,Ti and Nb on the crystallization behavior and the thermal properties of Zr64.5Ni15.5Al11.5Cu8.5 alloy.Thermal parameters and the activation energies for crystallization were calculated for four(Zr0.645Ni0.155Al0.115-Cu0.085)100-xMx(M=Y,Ti and Nb,while x=0,2 at.) alloys.The present alloys have wide supercooled liquid region of ≥87 K.Maximum activation energy was found to be greater than 300 kJ/mol for the base alloy.Four crystalline phases were identified in the samples annealed at 823 K for 20 min.Reduced glass transition temperature(Trg) and other thermal parameters such as γ,δ and β were improved by Y and Ti addition.Nb addition resists crystallization below annealing temperature 713 K,however,its effect on thermal properties is not very promising.     

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.     

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.     

TiC颗粒增强非晶钛合金基复合材料的热稳定性

用单辊铜轮旋注法制备了TiC颗粒增强Ti45Zr5Cu25Ni20Sn5非晶合金基复合材料.发现在Ti45Zr5Cu25Ni20Sn5非晶合金中加入TiC颗粒可以提高合金的热稳定性.     

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．     

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。     

Microstructure and bond strength of Ni–Cr steel/Al2O3 joints brazed with Ag–Cu–Zr alloys containing Sn or Al

Abstract

Sintered Al₂O₃ was joined to Ni–Cr steel by the active metal brazing route with Ag–Cu–Zr brazing alloys containing Sn or Al. A single ZrO₂ layer with a monoclinic structure was formed at the Al₂O₃ /brazement interface by the migration of Zr in the molten brazing alloy to the Al₂O₃ surface, followed by a redox reaction between the Al₂O₃ and Zr. The remainder of the brazement formed a Cu–Ag eutectic alloy. Precipitates CuZr₂ and Cu–Zr–Al were formed in the brazements of the Ni–Cr steel/ Al₂O₃ joints brazed with Ag–Cu–Zr alloys and Al containing Ag–Cu–Zr alloys, respectively. On the other hand, no precipitates were formed in the brazement of the Ni–Cr steel/Al₂O₃ joints brazed with Sn containing Ag–Cu–Zr alloys. The Ni–Cr steel/ Al₂O₃ joints brazed with Sn containing Ag–Cu–Zr alloys showed much higher fracture shear strengths than those brazed with Ag–Cu–Zr alloys or Al containing Ag–Cu–Zr alloys.     

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.     

含Be多元合金非晶形成能力的替代效应研究

利用晶胞平移和分子动力学模拟建立了Zr4lTil3.8Be22.5Ni17.5Cu5．2晶态和非晶合金的原子结构模型，利用递归方法研究了Zr4lTi13.8Be22．5Ni17．5Cu5．2晶态及非晶态合金中元素的替代效应．Be与B、Al、Si状态密度形状相似表明Be与B、Al、Si具有相似的性质，可以用Al、B、Si代替Be；非晶态相对于晶态的结构能差表明，用Al、B、Si代替Be后均使合金的非晶形成能力下降，只是Al、B下降的幅度较小；用Al、B替代Be，再用其它过渡金属替代Cu、Ni或zr、Ti可使非晶形成能力达到含Be合金的水平．     

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.     

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。     

Evaluation of glass forming ability in binary and ternary metallic alloy systems – an application of thermodynamic phase diagram calculations

Abstract

The glass forming ability (GFA) of a wide range of binary and ternary alloy systems (Au–Si, Pd–Si, Ti–Be, Zr–Be, Hf–Be, Cu–Ti, Co–Zr, Ni–Zr, Cu–Zr, Ni–P, Pd–P, Ni–Pd–P, Cu–Pd–P, Co–Ti–Zr, Zr–Be–Hf, Ti–Be–Hf, Ti–Be–Zr) was calculated using a combined thermodynamic and kinetic approach. There is good agreement between the predicted glass forming ranges and those experimentally observed. By using this combined approach it has also proved possible to estimate critical cooling rates for phases not observed in the equilibrium phase diagram. A significant advantage of the approach is that, for multicomponent alloys, the melting temperatures and thermodynamic input parameters for the kinetic equations are derived using the constituent binary thermodynamic phase diagram calculations and, therefore, it has the potential to predict GFA in multicomponent systems using information from mainly binary systems.

MST/788     

金属玻璃基复合材料的制备及断裂韧性测试

采用铜模吸铸法制备了(Zr0.55Al0.1Ni0.05Cu0.30)100-xTix(x=0、2、4、6、8)板状哑铃型金属玻璃基复合材料试样。用X射线衍射(XRD)、岛津AG-10TA万能材料力学试验机和JSM-6700F场发射扫描电子显微镜(SEM)对试样的组织结构以及断裂韧性进行了测试。结果表明,当x=0、2、4时,试样为非晶-晶体复合材料,当x=6、8时,试样为晶体材料。表明通过调整Ti的含量可以制备出金属玻璃基复合材料。采用三点弯曲法测定了复合材料的断裂韧性,当x=0、2、4时,试样的断裂韧性KIC值分别为10.529、5.142和3.446MPa.m1/2。