Cu-Sn-Ti体系边际二元系界面反应的研究

Cu-Sn-Ti三元系及其相关的3个二元系均具有重要的实用价值.实验制备了Ti/Sn和Cu/Sn固-液扩散偶及Cu/Ti二元固相扩散偶,经电子显微和探针观测发现: Ti/Sn固-液扩散偶在873K下退火30～160min,只生成1个Sn3Ti2中间相; Cu/Sn固-液扩散偶在808K下退火10min时也只生成1个Cu3Sn中间相,但退火时间延长至30min时在Cu与Cu3Sn界面上生成Cu41Sn11,退火60min后在Cu与Cu41Sn11之间又生成了bcc-a2; Cu/Ti二元固相扩散偶在1023K下退火1000h后,在其界面处生成了CuTi2、CuTi、Cu4Ti3、Cu4Ti 4个化合物,而Cu3Ti2相并未在扩散偶中出现.还采用最大驱动力模型对上述3个二元系的界面反应过程进行了计算并成功解释了相应的实验现象.     

纳米Cu-Sn金属间化合物的制备及形成机理

以CuCl2.2H2O和SnCl2.2H2O为原料,NaBH4为还原剂,采用溶剂热法制备Cu10Sn3、Cu3Sn和Cu6Sn5金属间化合物。利用XRD、TEM、SAED对产物的物相、形貌及结构进行表征,考察了溶剂及原料配比对Cu-Sn金属间化合物形成的影响。结果表明,制备的三种产物颗粒尺寸分别为100~150nm、150~200 nm和300 nm;合金化进程是通过原子间相互吸附与扩散实现;反应初始阶段生成Cu10Sn3和Cu3Sn,其中Cu10Sn3是亚稳态,易转变为Cu3Sn。随着反应的继续进行,由于Sn原子不断向Cu3Sn扩散而最终形成Cu6Sn5。     

L12-Ni3 Ga和DO3-Fe3Al非化学计量金属间化合物的活度、热力学因子和互扩散系数

基于Ll2-Ni3Ga和DO3-Fe3Al非化学计量金属间化合物中Ga和Al的活度,利用Φ=xi·(e)lnαi/(e)xi分别计算了不同温度时Ll2-Ni3Ga和DO3-Fe3Al相中扩散的热力学因子Φ.计算表明,在化学计量比处附近Ll2-Ni3Ga和DO3-Fe3 Al相中扩散的热力学因子Φ趋于最大值.根据Darken-Manning公式D=(xBDA* xADB*)·Φ·S,由扩散的热力学因子Φ及自扩散系数分别计算了1123,1223和1261 K下Ll2-Ni3Ga和823 K下DO3-Fe3Al非化学计量金属间化合物的互扩散系数D.     

金锡合金的机械合金化

应用机械合金化的方法合成了AuSn20化合物,X射线衍射及扫描电镜分析表明主要化合物成分为AuSn和Su5Sn.并对合金化的过程进行了阐述.     

我国的金矿物分类及其主要特征（续）

Ⅰ.自然元素、合金及金属互化物(续)(五)金—锡互化物类目前仅知道一种——未定名AuSn.未定名AuSn;原作者名为锡金矿(陈立昌,1984).电子探针分析(%);Au61.23～65.21,Sn29.97～33.27,含少量Ag、Pb.见在砂金片上呈极细小粒状和板片状集合体,或是环带状分布于自然金颗粒的边缘.新鲜面为银白色,氧化后呈灰黑色.金属光泽.易碎.反光镜下反射色为亮淡黄到银白色,均质或弱非均质.见在沅水中更新世阶地冲积层中(陈立昌,1984)和资江下流现     

高能球磨制备铁铝固溶体及其热力学分析

利用新型搅拌式高能球磨机对Fe-Al二元粉末进行了高能球磨,并利用XRD、SEM对Fe-Al二元粉末在球磨反应过程中的物相和形貌变化进行了分析,研究表明:高能球磨促使Al向Fe中逐渐扩散固溶,最终形成了Fe(A1)固溶体,球磨最终产物形貌呈复合片状.热力学计算结果表明:Fe-Al二元系具有形成金属间化合物、固溶体及非晶的热力学驱动力;当Fe-Al二元系因晶粒细化、晶格畸变而储存的能量超过金属间化合物与固溶体形成自用能之差时,反应生成Fe(A1)固溶体.     

冷却速率对Sn-3.5Ag焊料中Ag_3Sn金属间化合物的形貌及分布的影响

SnAg焊料合金中Ag3Sn金属间化合物(IMCs)的形态和分布对焊点的可靠性能有着显著的影响。采用X射线衍射(XRD),能量色散谱(EDS)和扫描电镜(SEM)等手段来表征Sn-3.5Ag(Sn-3.5%(质量分数)Ag)共晶焊料的铸态组织显微结构,研究不同冷却速率对Ag3Sn金属间化合物的形貌及分布的影响。实验采用预热石墨模(炉冷)、室温石墨模(空冷)、水冷铜模(水冷)及单辊甩带法(急冷)获得了冷却速率分别为1,10,1×103和1×106K·s-1的Sn-3.5Ag合金样品。研究表明,随着冷却速率增加,晶粒生长时间变短,导致共晶组织细小。Ag3Sn金属间化合物的形貌随着冷却速率增加,表现出了由片状→有片状尾巴的针状→针状→球状的趋势发展。脆性的球状Ag3Sn相在焊料中起到了弥散强化的作用,增强了焊料合金的力学强度,而片状Ag3Sn相则对力学性能有害。本研究得出了Sn-3.5Ag焊料维氏硬度与基体中金属间化合物Ag3Sn晶粒尺寸的关系:HV=9.51+0.11d(1/2),得到该合金的相关常数:Hv,o=9.51和K=0.1。     

SiC纤维增强Ti/Ti_2AlNb叠层复合材料制备及界面行为研究

以SiC纤维、Ti箔、Ti_2AlNb箔为原材料,采用箔-纤维-箔方法,通过真空热压技术制备了SiCf/Ti/Ti_2AlNb叠层复合材料。利用扫描电子显微镜(SEM)、能谱分析仪(EDS)和X射线衍射仪(XRD)对复合材料相组成和微观组织进行了分析。结果表明,当真空热制造参数为920℃/40 MPa/30 min时,SiC纤维与韧性金属Ti实现良好冶金结合,界面反应产物主要为TiC,界面反应层厚度为0.8μm,C涂层厚度为1.3μm;韧性金属Ti层与金属间化合物Ti_2AlNb层通过Ti,Al,Nb 3种元素相互扩散方式形成固相扩散连接,界面平直,复合材料呈现出理想叠层结构。制备态的SiCf/Ti/Ti_2AlNb叠层复合材料主要由α-Ti,β-Ti,SiC,TiC,O相和B2相构成。在Ti与Ti_2AlNb固相扩散连接过程中,由于Al原子的扩散速率大于Nb原子,且Al是α稳定元素,Nb是β稳定元素,从而导致在Ti/Ti_2AlNb界面区域依次形成α+β双相组织和富B2相。在真空热压实验中,韧性金属Ti层与金属间化合物Ti_2AlNb层固相扩散连接过程依次为:物理接触/α+β双相区形成/富B2相区形成/富B2相区增厚。     

扩散连接温度对钼合金与不锈钢连接行为的影响

采用Ni-Cr-B-Si非晶箔作为中间连接层在1 090~1 180℃真空下对钼合金与耐热不锈钢进行液态扩散连接,研究扩散连接温度对钼合金/不锈钢连接样微观结构、成分分布、显微硬度的影响。结果表明:Ni-Cr-B-Si非晶箔熔化后对钼合金及310S不锈钢母材具有较好的润湿性,在真空下可实现较好的冶金结合。中间连接层组织演变为镍基固溶体,并在钼合金一侧发现Mo-Ni-B金属间化合物。随连接温度升高,连接层中的元素向母材的扩散更加充分,生成的金属间化合物层厚度增加,Kirkendall孔洞数量增多。     

Cu/Al管气体火焰钎焊接头特征及热力学分析

通过计算Cu/Al管氧乙炔气体火焰钎焊条件下形成金属间化合物的各化学反应的熵变,对Cu/Al金属间化合物的形成及向CuAl2转化的趋势进行了化学热力学分析;结合XRD、SEM、EDS研究了Cu/Al管氧乙炔气体火焰钎焊接头组织与元素分布特征.结果表明,Cu/Al管氧乙炔气体火焰钎焊条件下,接头中脆性金属间化合物CuAl2由Cu、Al原子的直接结合和其他Cu/Al金属间化合物与Al原子的继续反应生成,其中CuAl自主转化趋势较强;热力学计算分析与接头XRD分析结果一致.钎焊接头可分为3个特征区域:靠近Al基体侧形成了宽度约30μm的α-Al与α-Al+CuAl2二元共晶区;钎缝中心偏Al基体一侧形成了宽度约150μm组织细密的多元共晶组织区;钎缝中靠近Cu基体宽度约120μm区域,Cu的大量扩散并与Al充分反应,形成了粗大珊瑚状CuAl2.     

Kirkendall Effect and Mechanism of Self-Diffusion in B2 Intermetallic Compounds

Single-phase interdiffusion studies in the B2 intermetallic compounds NiAl and FeAl have demonstrated the incidence of Kirkendall effect in these systems. The implication of this observation on the operating mode of self-diffusion in these systems is discussed. The direct exchange and ring diffusion mechanisms were excluded as the possible mode of substitutional diffusion in metals and alloys on account of the incidence of Kirkendall effect during single-phase interdiffusion studies. It is suggested that on similar phenomenological considerations, the six-jump vacancy cycle mechanism, triple-defect mechanism, and antistructure bridge mechanism are precluded as possible mode of diffusion in B2 intermetallic compounds.     

Diffusion Parameters and Growth Mechanism of Phases in the Cu-Sn System

The tracer diffusion coefficients of the elements as well as the integrated interdiffusion coefficients are determined for the Cu₃Sn and Cu₆Sn₅ intermetallic compounds using incremental diffusion couples and Kirkendall marker shift measurements. The activation energies are determined for the former between 498 K and 623 K (225 °C and 350 °C) and for the latter between 423 K and 473 K (150 °C and 200 °C). Sn is found to be a slightly faster diffuser in Cu₆Sn₅, and Cu is found to be the faster diffuser in Cu₃Sn. The results from the incremental couples are used to predict the behavior of a Cu/Sn couple where simultaneous growth of both intermetallics occurs. The waviness at the Cu₃Sn/Cu₆Sn₅ interface and possible reasons for not finding Kirkendall markers in both intermetallics in the Cu/Sn couple are discussed.     

On the Formation of a Diffusion Bond from Cold-Spray Coatings

To understand the development of diffusion bonding, which can increase the bonding strength, three different cold-sprayed coating/substrate systems were investigated, Ni/Cu, Cu/Cu, and Al/Mg, by annealing at increased temperatures for various times. The formation of intermetallic compounds in the Al/Mg system reduced the bonding strength dramatically. In Cu/Cu and Ni-Cu, diffusion bonds developed at lower temperatures as Ni-Cu forms an isomorphous system, which increased the bonding strength effectively. However, higher temperature annealing reduced bonding strength ultimately because of the Kirkendall pores.     

Regularities of Reactive Diffusion and Phase Formation in Ni ― Bi,Ni ― Zn,and Co ― Zn Binary Systems

Intermetallide layers enriched in bismuth or zinc are the first to grow in the Ni Bi, Ni Zn, and Co Zn reaction pairs. It is not found that high-symmetry phases of equiatomic composition are formed. There is not even a weak correlation between the rate of layer growth and the width of the homogeneity region for these intermetallic compounds. The main factors that determine the formation sequence for the intermetallic layers are the differences in melting point and atomic radius between the components, as well as the crystal structures of the intermetallides. The Kirkendall effect cannot be observed in the growing intermetallic layers. In that case, there is no physical basis for determining integrated diffusion coefficients.     

A diffusion-kinetic model for predicting solder/conductor interactions in high density interconnections

A combined thermodynamic and diffusion-kinetic approach is very viable for developing microjoining and interconnection materials and processes, in particular, whenever thinner metallizations, coated overlayers, or smaller solder-joint volumes are encountered in very high density electronics. A diffusion-kinetic model based on the utilization of integrated diffusion coefficients and mobilities is introduced and discussed for calculating the layer growth of intermetallic compounds between metal conductors and tin-based solders and is exemplified with a relatively simple ternary Cu/SnBi system. The model has also been used for calculating the local nominal composition of the effective joint or contact region. Moreover, the mobilities of Sn and Cu in Cu₆Sn₅ and Cu₃Sn intermetallic compounds are determined, and the role of both stable and metastable phase diagrams is discussed in predicting the appearance of possible reaction products as well as the driving forces for the dissolution, diffusion, and precipitation processes.     

Mechanism of Diffusion in Intermetallic Compounds

In a previous paper appearing in this journal (Tiwari and Mehrotra, Metall. Mater. Trans. A, vol. 43A, 2012, pp. 3654–62), the present authors advanced the hypothesis that the six-jump vacancy cycle, triple-defect mechanism, and antistructure bridge mechanism cannot explain the incidence of Kirkendall effect in B2 intermetallic compounds and hence their suitability as the operative mode of diffusion in these systems rests on dubious foundation. In the preceding contribution, Belova and Murch (BM) contested our hypothesis. This article is a reply to the BM’s critique of our paper.     

Interfacial reactions in molten Sn/Cu and molten In/Cu couples

The interfacial reactions of molten Sn and molten In with solid Cu substrate were determined by studying their reaction couples. The annealing temperature was 300 °C. The phases formed at the interface were examined by optical microscopy, scanning electron microscopy, and electron probe microscopy analysis (EPMA). The thickness of the reaction layers was measured using an image analyzer. For Cu/Sn couples, two phases, ε and η, were found. Only the Cu₁₁In₉ phase was observed at the interface of the Cu/In couples. In comparison with the results of couples of solid Sn and solid In with solid Cu substrate, their phase formation sequences were similar; however, the interfacial morphology and the reaction rates were different. For the liquid/solid couples, the reaction rate was much faster and the interface was nonplanar. A mathematic model was also proposed to describe the dissolution of the Cu substrate and the growth of the intermetallic compounds. Fast dissolution of the substrate was observed in the beginning of the reaction and was followed by a relatively slow growth of the intermetallic compounds at the interface.     

Effect of Substrate Composition on Sn Whisker Growth in Pure Sn Films

Pure Sn films deposited on Cu and Cu alloys are prone to spontaneous whisker formation. One way of preventing whisker formation is to alloy Pb into Sn coatings. However, restriction on the use of Pb demands the development of alternative methods for preventing whisker growth. The present work reports the effect of substrate composition on whisker formation and morphology. Despite employing identical plating conditions, long filament-like whiskers grew only on Sn-plated Cu samples and not on brass. The presence or lack of Sn whiskers has been explained via the thermodynamic stability of various intermetallic compounds at the Sn/substrate interface.     

Analysis of low-temperature intermetallic growth in copper-tin diffusion couples

A multiphase diffusion model was constructed and used to analyze the growth of the ε- and η-phase intermetallic layers at a plane Cu-Sn interface in a semi-infinite diffusion couple. Experimental measurements of intermetallic layer growth were used to compute the interdiffusivities in theε andη phases and the positions of the interfaces as a function of time. The results suggest that interdiffusion in the ε phase(≈D _ε) is well fit by an Arrhenius expression with D₀ = 5.48 × 10⁻⁹ m²/s andQ = 61.9 kJ/mole, while that in the η phase (≈D_η) has D₀ = 1.84 × 10⁻⁹ m²/s andQ = 53.9 kJ/mole. These values are in reasonable numerical agreement with previous results. The higher interdiffusivity in theη phase has the consequence that theη phase predominates in the intermetallic bilayer. However, the lower activation energy for interdiffusion in theη phase has the result that theε phase fills an increasing fraction of the intermetallic layer at higher temperature: at 20 °C, the predicted ε-phase thickness is ≈10 pct of that ofη, while at 200 °C, its thickness is 66 pct of that ofη. In the absence of a strong Kirkendall effect, the original Cu-Sn interface is located within theη-phase layer after diffusion. It lies near the midpoint of theη-phase layer at higher temperature (220 °C) and, hence, appears to shift toward the Sn side of the couple. The results are compared to experimental observations on intermetallic growth at solder-Cu interfaces.