TiNiNb钎焊Cf/SiC与TC4接头组织结构

文中在钎焊温度980℃、钎焊时间15 min的条件下,采用Ti_54.8Ni_34.4Nb_10.8（原子分数,%）共晶合金粉末真空钎焊C_f/SiC复合材料与TC4钛合金.用SEM,EDS及差热分析法（DTA）观察测定了钎料组织、成分及熔点,分析了钎焊接头的微观组织结构.结果表明,Ti_54.8Ni_34.4Nb_10.8共晶钎料由Ti₂Ni及Ti（Nb,Ni）化合物组成,实际熔点为935℃.钎焊过程中,Ti和Nb元素与复合材料反应形成TiC和NbC混合反应层;钎料中的镍与TC4中的镍发生互扩散,在TC4钛合金侧形成扩散层;连接层由弥散分布的Ti（Nb,Ni）化合物和Ti₂Ni相组成.C_f/SiC与连接层界面为接头最薄弱环节,此处易形成裂纹.     

Microstructure studies of Zr65Cu17.5Al7.5Ni10 and Zr65Cu15Al10Ni10 glass forming alloys: Phase morphologies and undercooled melt solidification

Zr₆₅Cu_17.5Al_7.5Ni₁₀ (at.%) and Zr₆₅Cu₁₅Al₁₀Ni₁₀ (at.%) glass forming alloy microstructures have been investigated by means of optical and electron microscopies. They are composed of a fine eutectic matrix with eutectic dendrites (EDs) that have peculiar morphologies. Al and Cu concentrations, in these alloys, favour primary dendrites and determine the ED morphologies and compositions. Their locations within the microstructures suggest a two-step solidification process of the two undercooled melts. The identified crystalline phases indicate the occurrence of solid state phase transformations in agreement with the structural defects observed in the grains. The crystalline phases can be classified into Zr-rich, Cu-rich, Ni-rich and Al-rich compounds resulting from competing diffusion between Cu, Ni, and Al in the melts.     

SiC陶瓷真空钎焊接头界面结构及机理分析

采用Ti-Zr-Ni-Cu钎料对SiC陶瓷进行了真空钎焊,研究了SiC陶瓷真空钎焊接头的界面显微组织和界面形成机理.试验中采用扫描电子显微镜(SEM)对接头组织进行了观察,并进行了局部能谱分析.结果表明,接头界面产物主要有TiC,Ti₅Si₃,Zr₂Si,Zr(s,s),Ti(s,s)+Ti₂(Cu,Ni)和(Ti,Zr)(Ni,Cu)等.接头的界面结构可以表示为:SiC/TiC/Ti₅Si₃+Zr₂Si/Zr(s,s)/Ti(s,s)+Ti₂(Cu,Ni)/(Ti,Zr)(Ni,Cu).钎焊过程分为五个阶段:钎料与母材的物理接触;钎料熔化和陶瓷侧反应层开始形成;钎料液相向母材扩散、陶瓷侧反应层厚度增加,钎缝中液相成分均匀化;陶瓷侧反应层终止及过共晶组织形成;钎缝中心金属间化合物凝固.在钎焊温度960℃,保温时间10 min时,接头抗剪强度可达110 MPa.     

钎焊温度对Ti60合金与Si3N4陶瓷接头界面组织及性能的影响

为研究钎焊温度对Ti60/Si₃N₄接头组织与力学性能的影响,采用Ag-28Cu共晶钎料在870~910℃温度区间,保温10 min条件下进行钎焊连接.利用扫描电子显微镜、能谱仪对钎焊接头界面组织进行分析,得到的典型接头界面组织结构为Ti60/Ti-Cu化合物/Ag（s,s）+Cu（s,s）/Ti-Cu化合物/Ti₅Si₃+TiN/Si₃N₄,并对钎焊接头的组织演变过程进行了分析.结果表明,随着钎焊温度的升高,Ti60侧的Ti-Cu化合物反应层与Si₃N₄陶瓷侧的Ti₅Si₃+TiN反应层厚度逐渐增加,Ag（s,s）与Cu（s,s）含量减少,同时,扩散至Si₃N₄陶瓷侧的Ti元素与液相中Cu元素反应生成Ti-Cu化合物并在Ti₅Si₃+TiN反应层中形核.剪切测试表明,在钎焊温度880℃,保温10 min工艺参数条件下获得的接头最大抗剪强度为61.7 MPa.     

DD3高温合金与Ti3AlC2陶瓷的真空钎焊

通过对比试验优选出了合适钎料,并进行了后续钎焊试验.在钎焊温度800~900℃,保温时间为10 min的条件下,采用Ag-Cu-Ti钎料实现了DD3镍基高温合金与Ti₃AlC₂陶瓷的真空钎焊连接.利用扫描电镜、能谱仪、XRD等对接头的界面结构进行了分析.结果表明,接头的典型界面结构为DD3/AlNi/Al₃(Ni,Cu)₅+Al(Ni,Cu)+Ag_ss/(Al,Ti)₃(Ni,Cu)₅/Al₄Cu₉+AlNi₂Ti+Ag_ss/TiAg/Ti₃AlC₂.接头的力学性能测试表明,在钎焊温度为850℃,保温时间为10 min的条件下,接头的最高抗剪强度可达135.9 MPa,断裂发生在靠近钎缝的Ti₃AlC₂陶瓷侧.降低和提高钎焊温度对接头界面组织影响不大,但接头强度有一定程度下降.     

钎料中Ti元素含量对Si3N4/Si3N4接头界面结构及性能的影响

在900℃保温10 min的工艺条件下采用Ti含量不同的AgCu+Ti+nano-Si₃N₄复合钎料（AgCu_C）实现了Si₃N₄陶瓷自身的钎焊连接,并对不同Ti元素含量的接头界面组织及性能进行了分析.结果表明,接头典型界面结构为Si₃N₄/TiN+Ti₅Si₃/Ag_（s,s）+Cu_（s,s）+TiN_P+Ti₅Si_3P/TiN+Ti₅Si₃/Si₃N₄.随着复合钎料中Ti元素含量的增加,钎缝中团聚的纳米Si₃N₄颗粒逐渐减少,母材侧的反应层厚度逐渐增加后趋于稳定.当Ti元素含量高于4%时,钎缝中形成了类似于颗粒增强金属基复合材料的界面组织;当Ti元素含量达到10%时,有少量Ti-Cu金属间化合物在钎缝中形成;钎焊接头的抗剪强度随着Ti元素含量的增加而呈现先增加后降低的变化趋势,当Ti元素含量为6%时接头的抗剪强度达到最高值,即75 MPa.     

Infrared brazing of Ti50Ni50 shape memory alloy using two Ag–Cu–Ti active braze alloys

Microstructural evolution, shape memory effect and shear strength of infrared brazed Ti₅₀Ni₅₀ shape memory alloy using Cusil-ABA^® and Ticusil^® active braze alloys are investigated. The Ag–Cu eutectic braze alloy can readily wet Ti₅₀Ni₅₀ substrate by minor titanium additions. The brazed Ti₅₀Ni₅₀/Cusil-ABA^®/Ti₅₀Ni₅₀ joint is mainly comprised of Cu-rich, Ag-rich and CuNiTi phases. On the other hand, the brazed Ti₅₀Ni₅₀/Ticusil^®/Ti₅₀Ni₅₀ joint consists of Ag-rich, Cu-rich and TiCu₂ phases. Because the chemical composition of Ticusil braze alloy is located inside the huge miscibility gap, the molten braze tends to be separated into two liquids during brazing. One is rich in Ag, and the other is rich in both Cu and Ti. The Ag-rich liquid does not react with Ti₅₀Ni₅₀ substrate. In contrast, the copper content is depleted from the matrix of brazed joint due to the formation of interfacial TiCu₂ phase. The TiCu₂ phase is less detrimental to the shape memory effect than CuNiTi phase during the shape recovery bending test. Shear strength of brazed joints exceeds 200 MPa for both braze alloys if the brazing time exceeds 180 s. However, thick interfacial CuNiTi and TiCu₂ layers can deteriorate the shear strength.     

Temperature memory effect of Ti50Ni30Cu20 (at.%) alloy

After the reverse thermal induced martensitic transformation process of shape memory alloy is arrested at a temperature between the reverse transformation start and finish temperatures (A_s and A_f), and then cooled to a temperature below M_f, a kinetic stop will occur in the next heat flow curve during the heating process. The kinetic stop is closely related to the arrested temperature. This phenomenon is called temperature memory effect (TME). TME of Ti₅₀Ni₃₀Cu₂₀ (at.%) shape memory alloy with phase transformation between B2 austenite and B19 martensite has been investigated by differential scanning calorimeter in this paper. The results indicate that TME of Ti₅₀Ni₃₀Cu₂₀ alloy only exists in the heating process.     

A comparative study on the hydriding kinetics of Zr-based AB2 hydrogen storage alloys

Two kinetic models (Jander model and Chou model) are used to investigate the hydrogen absorption kinetic mechanism of Zr-based AB₂ type Laves phase alloys (Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.5Co_0.5, Ti_0.1Zr_0.9(Mn_0.9V_0.1)_1.1Fe_0.5Ni_0.5 and Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.55Ni_0.55). The analysis shows that the rate-controlling step is the diffusion process at high temperatures in the range from 673 K to 923 K with a low hydrogen concentration (solid solution phase). Both models can well describe the experimental data but Chou model is preferred. Chou model is simpler and easier to use for analyzing the experimental results. The activation energies calculated using Chou model with the least square method are 29.3 kJ/mol H₂ for Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.5Co_0.5, 43.8 kJ/mol H₂ for Ti_0.1Zr_0.9(Mn_0.9V_0.1)_1.1Fe_0.5Ni_0.5 and 48.5 kJ/mol H₂ for Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.55Ni_0.55, which are close to the values reported in the literature (28.3 kJ/mol H₂ for Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.5Co_0.5 and 40.3 ± 1.5 kJ/mol H₂ for both Ti_0.1Zr_0.9(Mn_0.9V_0.1)_1.1Fe_0.5Ni_0.5 and Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.55Ni_0.55).     

Effect of immersion Ag surface finish on interfacial reaction and mechanical reliability of Sn–3.5Ag–0.7Cu solder joint

A comparative study on the preparation of specific titanium silicides (including Ti₃Si, Ti₅Si₃, Ti₅Si₄, TiSi, and TiSi₂) in the Ti–Si system was experimentally conducted by self-propagating high-temperature synthesis (SHS) from elemental powder compacts of their corresponding stoichiometries. The effect of initial sample stoichiometry was investigated on combustion characteristics and product composition. Experimental evidence shows a distinct combustion front traversing the entire reactant compact in a self-sustaining manner for all of the samples adopted in this study. However, as a result of the eutectic reaction, test samples composed of Ti:Si = 3:1 and 1:1 experienced excessive melting during the propagation of the reaction front. Moreover, the flame-front propagation rate and combustion temperature were found to vary significantly with starting stoichiometry of the powder compact. The flame-front velocity up to 50 mm/s was observed in the samples of Ti:Si = 5:4 and 5:3, in contrast to the values in the range of 2.6–3.5 mm/s for the compact of Ti:Si = 1:2. Reaction front temperatures between 1380 and 1460 °C were achieved by the powder compacts with Ti:Si = 5:4 and 5:3. For the samples of Ti:Si = 3:1 and 1:1, their flame-front temperatures were comparable and about 1330 °C. Consistent with its slow reaction front, the Ti + 2Si sample had the lowest combustion temperature close to 1150 °C. The XRD analysis confirms complete conversion from the reactant with Ti:Si = 5:3 to a single-phase silicide Ti₅Si₃. Powder compacts of Ti:Si = 5:4 and 1:1 yielded two silicide phases, Ti₅Si₄ and TiSi, in their end products. In spite of formation of a minor amount of TiSi, the disilicide TiSi₂ was identified as the dominant composition in the product obtained from the Ti + 2Si sample. Combustion products containing Ti₅Si₃ and a large amount of unreacted Ti were synthesized from the powder compacts of Ti:Si = 3:1, implying a poor degree of phase conversion.     

Ti600和Ni-25%Si合金钎焊接头性能及失效机理分析

采用Ti-Zr-Ni-Cu非晶钎料对高温钛合金Ti600和Ni-25%Si (原子分数,%)合金进行钎焊试验,重点研究了钎焊温度对镍硅与钛合金接头组织及性能的影响,结合接头组织特征及断口结构分析阐明了Ti600和Ni-25%Si合金钎焊接头的失效机理. 结果表明,钎缝内部包含多个区域,随着连接温度从900 ℃上升至980 ℃,包含(Ti,Zr)₂Si和Ti₂Ni相的区域逐渐消失,包含Ti₅Si₃和Ti₂Ni相的区域逐渐变厚,最终占据全部钎缝. 力学性能分析表明,随着钎焊温度的升高,接头抗剪强度先增大后降低. 当钎焊温度为960 ℃时,接头的抗剪强度能够达到峰值177 MPa. 在脆性Ti₂Ni相基体上弥散分布的Ti₅Si₃相颗粒破坏了Ti₂Ni相的连续性,阻碍了裂纹在钎缝内部的扩展是钎焊接头抗剪强度提升的根本原因.     

碳化硅复合材料与碳钢钎焊接头的抗剪强度及微观结构

采用磁控溅射镀膜技术对碳/碳化硅复合材料(C/SiC)表面进行镀Ti金属化,以AgCu₂₈为钎料,无氧铜为中间层与碳钢进行钎焊连接. 研究无氧铜中间层、Ti膜厚度和钎焊温度对接头组织形貌和力学性能的影响. 结果表明,采用无氧铜中间层可有效降低接头的残余应力,提高接头强度,并阻挡C/SiC复合材料中的Si元素在钎焊过程中扩散至碳钢侧,防止了碳钢界面FeSi_x恶性反应层的形成. 在试验范围内,钛膜厚度和钎焊温度与接头抗剪强度之间均存在峰值关系. 860 ℃,3 μm Ti膜接头平均抗剪强度最高,达到25.5 MPa. 由剪切试样碳钢侧断口,可观察到大量平行断口方向的碳纤维和碳纤维脱粘坑. 断裂发生在C/SiC复合材料内部距界面约300 μm处. C/SiC界面反应产物以Ti₅Si₃为主,含少量TiC. 钎缝中有TiCuSi相生成.     

采用Cu-Ti钎料高温连接Si3N4陶瓷

采用Cu80Ti20钎料在1413~1493 K的温度,保温时间5~15 min的工艺条件下分别进行了Si₃N₄陶瓷的高温活性钎焊,在所选工艺条件下均成功得到了无明显缺陷和裂纹的钎焊接头,通过对接头组织和成分的分析,接头的组成为Si₃N₄陶瓷/TiN界面反应层/Cu-Ti化合物+Ti5Si3/TiN界面反应层/Si₃N₄陶瓷.在1413 K保温10min条件下,固溶体中的Ti元素扩散至钎缝与母材的界面并发生反应,形成了致密连续的厚度约为1 μm的反应层.获得了钎焊温度、保温时间、钎缝宽度及界面层厚度等对接头强度的影响规律,在试验中所采用的工艺参数条件下,接头抗剪强度达到了105 MPa.     

The ternary system Al–Ni–Ti Part I: Isothermal section at 900°C; Experimental investigation and thermodynamic calculation

Phase relations in the ternary system Al–Ni–Ti have been experimentally established for the isothermal section at 900°C for concentrations 0.1x_Al0.7. The investigation is based on X-ray powder diffraction, metallography, SEM and EMPA-techniques on about 40 ternary alloys, prepared by argon-arc or vacuum-electron beam melting of proper elemental powder blends. The existence of four ternary compounds, τ₁ to τ₄, is confirmed, however, in contrast to earlier investigations at significantly different compositions and with different shape of the homogeneity regions. This is particularly true for the phase regions of τ₃-Al₃NiTi₂ with the MgZn₂-type structure ranging from Al₃₀Ni₂₈Ti₄₂ (composition lowest in Al) to Al₅₀Ni₁₆Ti₃₄ (composition richest in Al) and for τ₂-Al₂NiTi. The complex atom site substitution mechanism in τ₃ changing from Ti/Al exchange at Al-poor compositions towards Ni/Al replacement for the Al-rich part was monitored in detail by quantitative X-ray powder diffraction techniques (Rietveld analyses). In contrast to earlier reports, claiming a two-phase region Ni{Al_xTi_1-x}₂+τ₃, we observed two closely adjoining three-phase equilibria: ₂-AlTi₃+Ni{Al_xTi_1-x}₂+ τ₄-AlNi₂Ti and ₂-AlTi₃+τ₃-Al₂NiTi₂+τ₄-AlNi₂Ti. The earlier reported “homogeneous phase at Al₂₃Ni₂₆Ti₅₁′” was shown by high resolution microprobe and X-ray diffraction measurements to be an extremely fine-grained eutectic. The experimental results are in fine agreement with the thermodynamic calculation.     

Cu-25Sn-10Ti活性钎焊SiO2f/SiO2复合材料与Invar合金

采用Cu-25Sn-10Ti钎料钎焊SiO_2f/SiO₂复合材料与Invar合金,研究了界面组织结构及其形成机理,分析了不同钎焊保温时间下界面组织对接头性能的影响.结果表明,在钎焊温度880℃,保温时间15 min的工艺参数下,接头在SiO_2f/SiO₂复合材料侧与Invar合金侧均形成了连续的界面反应层,界面整体结构为Invar合金/Fe₂Ti+Cu(s,s)+(Ni,Fe,Cu)₂TiSn/Cu(s,s)+Cu₄₁Sn₁₁+CuTi/TiSi+Ti₂O₃/SiO_2f/SiO₂复合材料.在钎焊温度一定时,随着保温时间的延长,复合材料侧TiSi+Ti₂O₃反应层厚度逐步增加,Fe₂Ti颗粒逐步呈大块状连续依附其上,接头强度先增大后减小.当钎焊温度880℃,保温时间15 min时,接头室温抗剪强度达到11.86 MPa.     

Sn改性Ti-Zr-Cu-Ni钎料的微观组织和力学性能

采用自制Ti-Zr-Cu-Ni-Sn钎料钎焊TA2钛合金,研究了不同Sn元素含量改性Ti-Zr-Cu-Ni钎料的熔化特性、微观组织及物相、润湿及熔蚀性、接头拉伸强度。研究表明,Sn含量增加,Ti-Zr-Cu-Ni-Sn钎料固、液相线温度基本升高,但温度差值基本变窄,可更好地抑制钎焊界面脆性化合物形成。Ti-Zr-Cu-Ni-5Sn钎料组织由Ti、Zr基体和晶体相构成,Sn倾向与Ti、Zr结合形成Ti₂Sn₃、Ti₆Sn₅、Zr₅Sn₃等低熔点共晶相。Sn≤1.5%时,随Sn含量增加,钎料对TA2钛合金的润湿性逐渐变差;继续增加Sn,钎料润湿性改善,添加5%Sn的钎料对基体润湿最佳。添加5%Sn并降低Cu、Ni总量的改性钎料对TA2钛合金熔蚀减弱。相同钎焊工艺下,添加5%Sn接头的强度和塑性均有提升。钎焊温度升高,Ti-Zr-Cu-Ni钎料产生更多强化物相,致接头强度大幅提升,而Ti-Zr-Cu-Ni-5Sn钎料产生的含Sn物相强化作用对接头强度提升有限;相...     

Structural chemistry and phase relations in intermetallic systems Ti–{Pd,Pt}–Al

Phase relations in the ternary systems Ti–{Pd,Pt}–Al have been experimentally established for the partial isothermal sections at 950°C in the Pd/Pt-poor region (<25 at.% Pd/Pt). The investigation is based on X-ray powder diffraction, metallography, SEM and EMPA techniques on about 45 alloys, which were prepared by various methods employing arc melting, levitation melting under argon or by powder reaction sintering in closed crucibles. Three ternary compounds were observed at 950°C in the Ti–Pd–Al system: τ₃-(Ti,Pd)(Ti,Pd,Al)₂ with Laves-MgZn₂-type, τ₂-(Ti,Al)₆(Ti,Pd,Al)₂₃₊₁ with a filled Th₆Mn₂₃₊₁-type and τ₁-(Ti,Pd,Al)(Ti,Pd,Al)₃ with AuCu₃-type. Due to the wide extension of the Laves phase field, there is no compatibility among γTiAl and τ₂-(Ti,Al)₆(Ti,Pd,Al)₂₃₊₁. The Ti–Pt–Al system at 950°C contains three ternary compounds: τ₃-(Ti,Al)(Ti,Pt,Al)₂ with Laves-MgZn₂-type, τ₂-(Ti,Al)₆(Ti,Pt,Al)₂₃₊₁ with the filled Th₆Mn₂₃₊₁-type and τ₁-(Ti,Pt,Al) with Cu-type. Compatibility exists for Al-rich γTiAl and τ₂-(Ti,Al)₆(Ti,Pt,Al)₂₃₊₁. The typical feature for both alloy systems studied is the three-phase equilibrium: ₂Ti₃Al+γTiAl+τ₃-(Ti,Pd/Al)(Ti,Pd/Pt,Al)₂. The solid solubility of palladium and platinum in the binary titanium aluminides, as observed from EMPA and X-ray data, is rather small and at 950°C accounts to about 2.5 at.% Pd and 2.0 at.% Pt. Two new oxide compounds Ti₃PdAl₂O_x and Ti₃PtAl₂O_x with a filled Ti₂Ni-type are observed in both quaternary systems.     

Effect of amorphous–crystalline interfaces on the martensitic transformation in Ti50Ni25Cu25

A partially crystallized amorphous Ti₅₀Ni₂₅Cu₂₅ melt-spun ribbon showing spherical particles in martensite has been investigated. Microstructural observations support the hindering of the martensitic transformation as well as the production of additional autoaccommodated structures nearby the interface compared with the ones used inwards.     

Hydrogen-caused phase transformations, relaxation and hysteretic phenomena in fcc alloys Fe55Cr25Ni20 and Fe50Ni50

Hydrogen-induced phases, relaxation and hysteretic phenomena in Fe₅₅Cr₂₅Ni₂₀ and Fe₅₀Ni₅₀ alloys were studied using neutron scattering and internal friction. Substitution of chromium by nickel prevents the hydrogen-induced γ→ transformation, which was used for interpretation of the IF peaks. A new relaxation peak is observed in the hydrogen-charged Fe₅₀Ni₅₀ alloy.     

Effects of TiC addition on formation of Ti3SiC2 by self-propagating high-temperature synthesis

Formation of Ti₃SiC₂ was conducted by self-propagating high-temperature synthesis (SHS) from both the elemental powder compacts of Ti:Si:C = 3:1:2 and the TiC-containing samples compressed from powder mixtures of Ti/Si/C/TiC with TiC content ranging from 4.3 to 33.3 mol%. The effect of TiC addition was studied on combustion characteristics and the degree of phase conversion. For the elemental powder compacts, with the progress of combustion wave the sample experiences substantial deformation, including axial elongation and radial contraction. The extent of sample deformation and flame-front propagation velocity were considerably reduced for the samples with TiC addition, because the dilution effect of TiC lowered the reaction temperature. Two reaction mechanisms were adopted to explain the formation of Ti₃SiC₂, one involving the reaction of a Ti–Si liquid phase with solid reactants for the elemental powder compact and the other dominated by the interaction of solid-phase species for the TiC-containing sample. For all products synthesized in this study, the XRD analysis identifies formation of Ti₃SiC₂ along with a major impurity TiC and a small amount of Ti₅Si₃. The resulting Ti₃SiC₂ is typically elongated grains. Based upon the XRD profile, the Ti₃SiC₂ content at a level of 71.5 vol.% was obtained in the product from the elemental powder compact. With the addition of TiC, an improvement in the yield of Ti₃SiC₂ was observed and an optimal conversion reaching 85 vol.% was achieved by the sample with 20 mol% of TiC. However, further increase of the TiC amount led to a decrease in the Ti₃SiC₂ content, because of the low reaction temperature around 1150 °C.