合金元素对Ti-Ni-Cu系钎料性能的影响

本实验设计一系列不同成分的Ti-Ni-Cu系钎料,研究合金元素B、Si、Zr等对钎料非晶形成能力和性能的影响.结果表明:微量B、Si元素均能显著改善Ti-Ni-Cu系钎料对Si3N4陶瓷的润湿性;在相同试验条件下,添加0.2%B的Ti40Ni15Cu钎料铺展面积最大;不含zr元素的Ti-Ni-Cu系钎料合金的非晶形成能力均很差.本实验设计的Ti40Zr20Ni20CuB0.2、Ti40Zr20Ni25CuB0.2两种钎料既具有良好的润湿性,又具有良好的非晶形成能力;与Ti40Zr25Ni15Cu非晶钎料钎焊Si3N4陶瓷的接头相比,Ti40Zr20Ni20CuB0.2、Ti40Zr20Ni25CuB0.2非晶钎料钎焊Si3N4陶瓷接头的室温强度变化不大,但高温强度有明显提高.     

Ti-Zr-Ni-Cu非晶钎料钎焊Si3N4陶瓷的连接强度

采用Ti40Zr25Ni15Cu20非晶钎料钎焊Si3N4陶瓷,研究钎焊工艺参数对界面反应层和接头连接强度的影响。结果表明:随着钎焊时间的增加和钎焊温度的提高,接头弯曲强度都表现出先上升后下降的趋势;钎焊工艺参数对连接强度的影响主要是由于影响反应层厚度所致;在相同钎焊工艺条件下,采用Ti40Zr25Ni15Cu20非晶态钎料和晶态钎料相比,其接头连接强度提高了84%。     

Ti-Zr-Ni-Cu非晶系的等电子浓度特征

以准晶成分Ti40Zr40Ni20为基准，在Ti—Zr-Ni-Cu系中设计出电子浓度为1.200和原子尺寸为0．1474nm的系列合金，并用铜模吸铸法制备直径为3mm的合金棒试样．结果表明，Ti12Zr55Ni13Cu20成分附近可形成块体非晶合金，而Ti3Zr60Ni12Cu25和Zr60Ni10Cu30成分点上形成了单一的四方Zr2Cu型非晶相关相．准晶、块体非晶合金和Zr2Cu相是具有相同电子浓度的电子化合物，它们在成分图上表现出鲜明的等电子浓度特征，表明块体非晶合金的等电子浓度判据适用于Ti-Zr-Ni-Cu非晶系．二十面体与截角八面体间的结构关联可作为准晶或非晶合金多型性转变成Zr2Cu相的结构模型．     

TiZrFe钎焊料熔点及焊接组织研究

本文在TiZrFe共晶合金的基础上，研究了用Cu、Ni替代Fe对钎料熔点及组织结构的影响。研究结果表明，成分为Ti55Zr20Fe10Ni10Cu5的钎料的熔点最低，为846．1℃。通过快淬工艺将该钎料制成非晶带材，制得的非晶带钎料在真空条件下与母材Ti-6Al-4V进行焊接，用SEM观察钎焊区组织。发现需要在900℃下保温20min可获得较好的焊接组织。     

Sn对Ti-Zr-Cu-Ni系非晶薄带热稳定性及耐蚀性能的影响

通过单辊甩带法制备了Ti40Cu39Zr10Ni11-xSnx(x=0,3,7,11)非晶薄带。运用X射线衍射仪(XRD)、差示扫描量热仪(DSC)、电化学工作站、扫描电镜(SEM)等手段测试了合金的组织与性能特性,研究了Sn替换Ni对合金热稳定性及生物耐蚀性能的影响。结果表明,随着Sn的添加,Ti40Cu39Zr10Ni11-xSnx(x=0,3,7,11)合金试样均表现为完全的非晶结构。与Ti40Cu39Zr10Ni11非晶合金相比,Ti40Cu39Zr10Sn11非晶合金的热稳定性稍有改善,且生物耐蚀性能得到明显提高。因此,不含Be、Ni等对人体有害元素的Ti40Cu39Zr10Sn11非晶合金具有作为生物医用材料的潜力。     

Ni-Ti-Zr-Al-Cu-Si块体非晶合金的形成及压缩性能

利用DSC，DTA，XRD研究了NiTiZrAlCuSi块体非晶合金的形成。采用铜模铸造工艺使块体金属玻璃最大直径从Ni42Ti25Zr25Al8合金的小于0．5mm增加到Ni42Ti20Zr25Al8Cu5的1mm，然后增加到Ni42Ti20Zr21.5Al8Cu5Si3.5合金的4mm。在Ni42Ti20Zr21.5Al8Cu5Si3.5和Ni42Ti20Zr20.5Al8Cu5Si4.5合金中获得最大的约化玻璃转变温度Trg（=Tg／T1）及最大的过冷液相区△Tx（=Tx-Tg），分别为0．570和93K。Si显著增加玻璃形成能力主要是抑制引起异质形核的Ni（TiZr）相和（TiZr）（CuAl）2相的形成。室温压缩实验表明：Ni42Ti20Zr21.5Al8Cu5Si3.5合金抗压断裂强度为2724MPa。     

Ti-Zr-Ni-Cu非晶钎料在Si3N4陶瓷上的润湿性研究

针对Si3N4陶瓷的高温活性钎焊要求,设计了高温Ti-Zr-Ni-Cu非晶钎料成分,并采用单辊急冷法成功制备了Ti-Zr-Ni-Cu非晶钎料.对比分析了相同成分的Ti-Zr-Ni-Cu非晶和晶态钎料在Si3N4陶瓷表面的润湿情况.结果表明:在低真空条件下,晶态钎料能够润湿Si3N4陶瓷,非晶钎料却因完全氧化而失效.在5×10-3Pa高真空条件下,非晶钎料的润湿性优于晶态钎料,在研究的Ti-Zr-Ni-Cu非晶钎料中,Ti40Zr25Ni15Cu20非晶钎料对Si3N4陶瓷的润湿性最佳.     

Ti40Zr25Ni15Cu20非晶钎料钎焊Si3N4陶瓷的界面结构及强度

采用Ti40Zr25Ni15Cu20非晶钎料进行了Si3N4陶瓷真空钎焊连接,利用SEM、EDX等微观分析手段,研究了钎焊界面的微观结构,得出界面反应层有两部分组成,接头界面微观结构为Si3N4/TiN/Ti-Si,Zr-Si化合物/钎缝中心;在相同钎焊工艺条件下,研究对比了晶态和非晶态钎料钎焊接头的强度,发现非晶态钎料钎焊的接头强度大大超过用晶态钎料钎焊的接头.     

初生纳米晶对Ti40Zr25Ni8Cu9Be18非晶合金结构稳定性的影响

通过感应熔炼喷铸法制备具有非晶/纳米晶复合结构的块体Ti40Zr25Ni8Cu9Be18合金。在与全非晶结构的Ti40Zr25Ni8Cu9Be18合金进行比较的基础上,研究Ti40Zr25Ni8Cu9Be18非晶/纳米晶合金在均匀流变过程中的晶化程度,分析其在连续升温过程中的晶化动力学。结果表明:初始纳米晶的存在不会明显降低非晶/纳米晶合金在过冷液相区流变过程中的结构稳定性;非晶/纳米晶合金的晶化激活能约为233.21 kJ/mol,与非晶合金的晶化激活能大致相同;随着转变分数的增加非晶/纳米晶合金的局部Avrami指数从2变化到0.5,明显低于非晶合金的局部Avrami指数;这表明初始纳米晶并没有明显加速非晶的晶化过程。     

Al对Ti-Zr-Cu-Ni-Be非晶合金热稳定性和力学性能的影响

利用X射线衍射(XRD)、透射电镜(TEM)、差示扫描量热(DSC)和室温压缩试验等分析手段,通过替代(Ti40Zr20Cu8Ni9Be18Al5)和掺杂[(Ti40Zr25Cu8Ni9Be18)0.95Al0.05)]两种元素添加方法,研究了5%(摩尔分数)Al元素对Ti40Zr25Cu8Ni9Be18非晶合金铸态组织、热稳定性和力学性能的影响。替代和掺杂的Al元素使直径为3mm的非晶合金棒状试样中分别析出了纳米晶和准晶。Al替代Zr使非晶合金薄带试样的过冷液相区从46K升高到50K,而以掺杂方式添加时却使其降低为31K。替代方式添加的Al元素使非晶合金的压缩断裂强度从1924MPa提高到2121MPa,但塑性应变从3.9%降低到了0.2%;而掺杂方式添加的Al元素使非晶合金强度降低为1475MPa,并呈现零塑性。     

Thermodynamic modeling and composition design for the formation of Zr–Ti–Cu–Ni–Al high entropy bulk metallic glasses

This work explores the idea of predicting metallic glass forming composition in a multi component alloy for which an equilibrium phase diagram is yet to be deciphered. Deep eutectic regions in a quaternary alloy (Zr–Ti–Cu–Ni) have been extrapolated to the quinary Zr–Ti–Cu–Ni–Al system for designing a potential bulk glass forming composition. P_HSS parameter which is the product of mixing enthalpy, mismatch entropy and configurational entropy of an alloy, has been utilized for thermodynamic modeling. P_HSS values are computed through substitution of Al into the each of the fifteen quaternary eutectics that have been reported in the literature in the Zr–Ti–Cu–Ni system. A good correlation of P_HSS range between modeled alloys and established glass formers indicates the subtle efficacy of this method for high entropy amorphous alloy design through a rationale thermodynamic approach.     

Brazing of TiBw/TC4 composite and Ti60 alloy using TiZrNiCu amorphous filler alloy

TiB_w/TC4 composite was brazed to Ti60 alloy successfully using TiZrNiCu amorphous filler alloy, and the interfacial microstructures and mechanical properties were characterized by SEM, EDX, XRD and universal tensile testing machine. The typical interfacial microstructure was TiB_w/TC4 composite/β-Ti + TiB whiskers/(Ti, Zr)₂(Ni, Cu) intermetallic layer/β-Ti/Ti60 alloy when being brazed at 940 °C for 10 min. The interfacial microstructure evolution was influenced strongly by the diffusion and reaction between molten fillers and the substrates. Increasing brazing temperature decreased the thickness of brittle (Ti, Zr)₂(Ni, Cu) intermetallic layer, which disappeared finally when the brazing temperature exceeded 1020 °C. Fracture analyses indicated that cracks were initialized in the brittle intermetallic layer when (Ti, Zr)₂(Ni, Cu) phase existed in the brazing seam. The maximum average shear strength of joints reached 368.6 MPa when brazing was conducted at 1020 °C. Further increasing brazing temperature to 1060 °C, the shear strength was decreased due to the formation of coarse lamellar (α+β)-Ti structure.     

Effect of brazing temperature and brazing time on the microstructure and tensile strength of TiAl-based alloy joints with Ti-Zr-Cu-Ni amorphous alloy as filler metal

An amorphous Ti-37.5Zr-15Cu-15Ni (wt.%) ribbon fabricated by vacuum arc remelting and rapid solidification was used as filler metal to vacuum braze TiAl alloy (Ti-45Al-2Mn-2Nb-1B (at.%)). The effects of brazing temperature and time on the microstructure and strength of the joints were investigated in details. The typical brazed joint major consisted of three zones and the brazed joints mainly consisted of α_2-Ti₃Al phase, α-Ti phase and (Ti, Zr)₂(Cu, Ni) phase. When the brazing temperature varied from 910 °C to 1010 °C for 30 min, the tensile strength of the joint first increased and then decreased. With increasing the brazing time, the tensile strength of the joint increased. The maximum room temperature tensile strength was 468 MPa when the specimen was brazed at 930 °C for 60 min. All the fracture surfaces assumed typical brittle cleavage fracture characteristic. The fracture path varied with the brazing parameter and cracks preferred to initiate at (Ti, Zr)₂(Cu, Ni) phase and propagation path were mainly determined by the content and distribution of α-Ti phase and (Ti, Zr)₂(Cu, Ni) phase.     

Structure and properties of composites prepared from partially amorphous ZrCuNiTi and nanocrystalline silver

Alloys of composition Zr40Cu40Ni10Ti10 and Zr48,5Cu32.5Ni9Ti10 (in at.%) were ball milled for 40 h starting from elemental powders or melt spun from cast ingots. In both cases amorphous structure was obtained, however in the case of ribbons, larger crystals of Cu₁₀Zr₇ or Ni₇Zr₂ phases of size of a few hundred nm were observed. In the case of milled alloys much finer intermetallic phases such as Zr₂Cu or Cu₁₀Zr₇ were identified within the amorphous matrix using X-ray diffraction or HRTEM. In both alloys DSC studies have shown higher crystallization temperature for the powder, than for the ribbon. It was explained by a different structure of preexisting intermetallic nuclei crystallizing in milled powders. The milled amorphous powder was also used as a matrix for composites containing 20% or 50% of nanocrystalline silver powder, prepared from silver powder by ball milling. The composites hot pressed at the same temperature as the amorphous samples show in some places very narrow transition phase enriched in silver containing also other elements of the amorphous phase. Composites containing more silver show lower hardness and strength, but exhibit a few percent of plastic deformation in the compression test. Scanning electron studies of deformed composite samples show crack initiation within the amorphous phase, not at the components interfaces.     

Development of High Strength Ni–Cu–Zr–Ti–Si–Sn In-Situ Bulk Metallic Glass Composites Reinforced by Hard B2 Phase

In the present study, the influence of atomic ratio of Zr to Ti on the microstructure and mechanical properties of Ni–Cu–Zr–Ti–Si–Sn alloys is investigated. The alloys were designed by fine replacement of Ti for Zr from Ni₃₉Cu₂₀Zr_36?xTi_xSi₂Sn₃. The increase of Ti content enhances glass forming ability of the alloy by suppression of formation of (Ni, Cu)₁₀(Zr, Ti)₇ phase during solidification. With further increasing Ti content up to 24 at.%, the B2 phase is introduced in the amorphous matrix with a small amount of B19′ phase from alloy melt. The bulk metallic glass composite containing B2 phase with a volume fraction of ~ 10 vol% exhibits higher fracture strength (~ 2.5 GPa) than that of monolithic bulk metallic glass (~ 2.3 GPa). This improvement is associated to the individual mechanical characteristics of the B2 phase and amorphous matrix. The B2 phase exhibits higher hardness and modulus than those of amorphous matrix as well as effective stress accommodation up to the higher stress level than the yield strength of amorphous matrix. The large stress accommodation capacity of the hard B2 phase plays an important factor to improve the mechanical properties of in situ Ni-based bulk metallic glass composites.     

Crystallographic and electrochemical characteristics of melt-spun Ti-Zr-Ni-Cu alloys

Ti44Zr32Ni22Cu2 and Ti41Zr29Ni28Cu2 alloys were prepared by the melt-spinning method. The phase structure was analyzed by X-ray diffraction,and the electrochemical performances of the melt-spun alloys were investigated. The results indicated that the Ti44Zr32Ni22Cu2 alloy was composed of the icosahedral quasicrystals and amorphous phases,and the Ti41Zr29Ni28Cu2 alloy comprised icosahedral quasicrystals,amorphous,and Laves phases. The maximum discharge capacity was 141 mAh/g for the Ti44Zr32Ni22Cu2 alloy and 181 mAh/g for the Ti41Zr29Ni28Cu2 alloy,respectively. The Ti41Zr29Ni28Cu2 alloy also showed a better high-rate dischargeability and cycling stability. The better electrochemical properties should be ascribed to the high content of Ni,which was beneficial to the electrochemical kinetic properties and made the alloy more resistant to oxidation,as well as to the Laves phase in the Ti41Zr29Ni28Cu2 alloy,which could work as the electro-catalyst and the micro-current collector.     

Effect of La on the crystalline and electrochemical properties of Ti-Zr-Ni melt-spun alloys

Ti45Zr30Ni25 and Ti45Zr30Ni25La alloys were prepared by melt-spinning, and the phase structure and electrochemical performances of the melt-spun alloys were investigated. The results showed that the Ti45Zr30Ni25 alloy was composed of the quasicrystalline phase, amorphous phase and Laves phase. The Ti445Zr30Ni25La alloy contained quasicrystalline and amorphous phases. The maximum discharge capacity was 111 mAh/g for the Ti45Zr30Ni25 alloy electrode, and 124 mAh/g for the Ti45Zr30Ni25La alloy electrode. The Ti45Zr30Ni25La alloy electrode ex-hibited a better high-rate dischargeability and cycling stability than the Ti45Zr30Ni25 alloy electrode. The improvement of electrochemical properties was mainly ascribed to the increase in the amorphous phase due to the addition of La.     

一种铜基电阻焊电极合金

报道了一种新的无Ｃｏ，低Ｂｅ电阻焊电极合金Ｃｕ－Ｎｉ－Ｚｒ－Ｂｅ－Ｔｉ（Ｂ合金）。将其组织性能同常用的Ｃｕ－Ｃｏ－Ｂｅ（Ａ合金）电极合金作了对比分析。结果表明，Ｂ俣金硬度，软化度同Ａ合金相近，但导电、导热性明显高于Ａ合金 。