Bulk-alloy microstructural analogues for transient liquid-phase bonds in the NiAl/Cu/Ni system

Transient liquid-phase (TLP) bonds between dissimilar materials can have complex microstructures that evolve both during holding at the bonding temperature and on cooling. In this article, an examination is made of the feasibility of producing bulk-alloy microstructural analogues for individual microstructural features of dissimilar material TLP bonds. The ultimate intent of this work is to enable the contribution of individual microstructural features to the overall properties of TLP bonds to be determined. Specifically, the article focuses on the production, characterization, and applications of microstructural analogues for TLP bonds in an NiAl/Cu/Ni model system. The article examines the use of five different cast Ni-Al-Cu alloys, together with heat treatment of selected materials, as bulk analogues for six distinct microstructural regions of the NiAl/Cu/Ni bonds. Each of these analogues is characterized in detail by transmission electron microscopy (TEM) and compared to the relevant target region of the bond. An initial examination is also made of the use of bulk alloys in aiding an understanding of phase transformations and structure-property relationships in these bonds.     

Transient liquid-phase bonding in the Ni-Al-B system

Transient liquid-phase (TLP) bonding experiments were performed using a Ni-10.3 at. pct Al alloy and a Ni-10 at. pct B filler material, and the results were compared to simulations performed using the finite-difference diffusion code, DICTRA. For the simulations, a thermodynamic assessment of the Ni-Al-B system was used to define the phase diagram and the thermodynamic factors of the diffusion coefficients. Composition-dependent diffusion mobilities were assessed for the ternary system. Predicted liquid widths as functions of time were in good agreement with the experiments. The calculated and experimental Al composition profiles agree in the matrix but not in the liquid. The simulations qualitatively predicted the observed precipitation and later dissolution of the intermetallic τ phase (Ni₂₀Al₃B₆) in the base material. This research demonstrated the potential for modeling the formation of spurious phases during TLP bonding of practical superalloy systems.     

Transient liquid-phase bonding in two-phase ternary systems

The process of isothermal solidification during transient liquid-phase (TLP) bonding in a ternary system is analyzed. In the most usual situation, and in contrast to the binary case, the composition of the liquid is required to change continuously as solidification proceeds. If the solubilities and/or diffusion coefficients of the two solutes are very different, the solidification stage is clearly divided into two parabolic regimes, the first dominated by the “faster” solute and the second by the slower of the two. In extreme cases, full solidification may not be realized in experimentally accessible times.     

Microstructural development in transient liquid-phase bonding

The applicability of conventional models of the transient liquid-phase (TLP) bonding process to the joining of nickel using ternary Ni-Si-B insert metals is considered in this article. It is suggested that diffusion of boron out of the liquid and into the solid substrate before the equilibration of the liquid and solid phases can result in the development of significant boron concentrations in the substrate. This, in turn, leads to the precipitation of boride phases in the substrate during holding at bonding temperatures below the binary nickel-boron eutectic temperature. The formation of boride phases during holding at the bonding temperature is of importance, because first, it is not predicted by the standard models of the TLP process, and second, the borides are not removed by prolonged holding at the bonding temperature and therefore may influence the in-service properties of the joint. In contrast, when bonding above the binary nickel-boron eutectic temperature, localized liquation of the substrate takes place. This liquid region resolidifies following prolonged holding and does not result in the formation of persistent boride phases. Experimental support is presented for the formation of borides during bonding, and characterization of the boride phases formed in the substrate is described.     

Microstructural development in NiAl/Ni-Si-B/Ni transient liquid phase bonds

A transmission electron microscopy (TEM) based investigation of microstructural development during transient liquid phase bonding of near-stoichiometric NiAl to commercial purity nickel is presented in this article. The work described employed Ni-4.5 wt pct Si-3.2 wt pct B (BNi-3) melt-spun interlayers. The precipitation of both Ni-Al based phases and borides within the joint and adjacent substrate regions is discussed. The article considers martensite formation (within the NiAl substrate) and the precipitation of Ll₂ type phases (both within the joint and at the interface with the NiAl substrate). The relative roles of the two substrate materials (NiAl and Ni) in the isothermal resolidification process are identified. The preferential formation of Ni₃B boride phases in the Ni substrate near the original location of the Ni substrate-joint interface is discussed and contrasted with the absence of similar events in the NiAl substrate.     

Ductility enhancement in NiAl (B2)-base alloys by microstructural control

An attempt to improve ductility of NiAl (B2)-base alloys has been made by the addition of alloying elements and the control of microstructure. It has been found that a small amount of fccγ phase formed by the addition of Fe, Co, and Cr has a drastic effect not only on the hot workability but also on the tensile ductility at room temperature. The enhancement in ductility is mainly due to the modification of Β-phase grains by the coexistence ofγ phase. The effect of alloying elements on the hot forming ability is strongly related to the phase equilibria and partition behavior amongγ,γ′ (L1₂ structure), and Β phases in the Ni-Al-X alloy systems. The ductility-enhancement method shows promise for expanding the practical application of nickel aluminide.     

高界面结合强度铜/钼/铜叠层复合材料的制备研究

采用非平衡态的高能铜离子注入技术,对钼芯材表面进行改性并一次覆铜形成过渡铜层,将原本不固溶的的钼/铜界面转化为铜/铜界面,制得高界面结合强度的铜/钼/铜叠层复合材料;采用近终形的热等静压复合技术进行二次覆铜,结合小变形量冷轧工艺进行复合板材精整,降低各层协同变形量,保证了叠层复合材料的板形、芯层质量、表面粗糙度及平行度。本方法所制备的铜/钼/铜叠层复合材料具有界面结合强度高、板形良好、芯层质量好且平行度好的优点,可作为一种电子封装材料或热沉材料应用于电子、信息技术领域。     

石墨-铜扩散连接的界面行为

以Ag Cu Ti合金粉末为过渡层,采用扩散连接法对石墨与铜进行扩散连接实验。利用X射线衍射仪、扫描电镜、金相显微镜及万能材料实验机对连接界面的性能及微观形貌进行研究。研究结果表明:在工艺参数为870℃/200 k Pa/10 min的条件下可实现石墨-Cu连接,其接头界面组织结构为石墨/Ti C/铜基固溶体+富银区/铜;接头剪切强度为17 MPa,断裂在石墨母材;并分析了石墨/Ag-Cu-Ti/铜真空加压烧结接头的形成机理。     

Triclinic Ni2AI phase in 63.1 atomic percent NiAl

Transmission electron microscopy (TEM) studies on the 63.1 at pct NiAl specimens aged in the Ll₀ phase indicate the presence of localized regions consisting of very high-density twins along with precipitates of Ni₂Al stoichiometry. In regions representative of the 7R phase, it is observed that the ordered Ni₂Al phase exists in lattice correspondence with the 7R phase. Based on the electron-diffraction results, the crystal structure of this Ni₂Al phase is determined to be triclinic, belonging to the space group . This new Ni₂Al phase alternatively may be viewed as a periodically microtwinned monoclinic Ni₂Al phase, existing in coherence with the matrix Ll₀ phase that is also periodically microtwinned.     

Tensile strength of Ni/Cu/(001)Ni triple layer films

Tensile properties of Ni/Cu/(001)Ni triple layer films and single crystal films of (00l)Cu and (00l)Ni were studied. The specimen films having the thickness of 50 to 500 nm were prepared by the epitaxial evaporations on (001)NaCl substrates. The stress-strain curves of tensile tests in the direction of [100] of Ni/Cu/(001)Ni triple layer films were almost linear until fracture and showed extremely small plastic deformation. The yield stresses of these specimens were 600 to 700 MPa independently of the layer thicknesses, which were 2.5 to 5 times higher than those of Ni or Cu single crystal films, and were also higher than the values given by the mixture rule for Ni and Cu single crystal films. The increase of yield stress was evaluated from the repulsive force acting on the mobile dislocations originating from the stress fields of misfit dislocation arrays at the Ni-Cu interface. Formerly Graduate Student, Faculty of Engineering, Osaka University     

Atomistic modeling of quaternary alloys: Ti and Cu in NiAl

The change in site preference in NiAl(Ti,Cu) alloys with concentration is examined experimentally via ALCHEMI and theoretically using the Bozzolo-Ferrante-Smith (BFS) method for alloys. Results for the site occupancy of Ti and Cu additions as a function of concentration are determined experimentally for five alloys. These results are reproduced with large-scale BFS-based Monte Carlo atomistic simulations. The original set of five alloys is extended to 25 concentrations, which are modeled by means of the BFS method for alloys, showing in more detail the compositional range over which major changes in behavior occur. A simple but powerful approach based on the definition of atomic local environments also is introduced to describe energetically the interactions between the various elements and therefore to explain the observed behavior.     

Dislocations in continuous filament reinforced W/NiAl and Al2O3/NiAl composites

Continuous filament reinforced W/NiAl and Al₂O₃/NiAl composites (as-processed, annealed, and thermally cycled) have much higher dislocation densities than that of monolithic NiAl. These higher dislocation densities resulted from the relaxation of thermal residual stress, which developed during the cooling of the sample from elevated temperatures and was caused by the difference in the coefficients of thermal expansion between the matrix and the reinforcement. The dislocation density in the region adjacent to the matrix-filament interface was high and decreased only slightly with distance from the interface in the 30 vol pct composites. The as-processed and annealed composites exhibited a rather homogeneous dislocation density in the matrix. After thermal cycling, these composites showed no large difference in the dislocation density and morphology. However, there were local regions of lower dislocation densities. This difference was examined in relationship to filament fracture, surface matrix cracking, and degree of bonding.     

The influence of solid-state and liquid-phase bonding on fatigue at Al/Al2O3 interfaces

Fracture and fatigue experiments have been conducted on liquid phase bonded (LPB) and solid-state bonded (SSB) aluminum-alumina interfaces. The LPB interfaces contain voids and dendritic FeAl₃ precipitates, whereas SSB interfaces are relatively defect-free. These precipitates result in local embrittlement, yet both interfaces are strong and tough. Upon cyclic loading, mode 1 cracks in both systems grow alternately along the interface and within the Al. The development of a tortuous crack path elevates the apparent fatigue threshold through crack closure. Under mixed mode loading, fatigue cracks approaching SSB interfaces propagate through the Al rather than along the interface. Conversely, for LPB interfaces, mixed mode cyclic crack growth along the interface occurs in preference to propagation in the Al. Correlation between the striation spacing and the crack tip opening displacement suggests a growth mechanism based on crack tip blunting. A.G. EVANS, Professor, formerly with the Division of Engineering and Applied Sciences, Harvard University, Cambridge, MA 02138     

Factors affecting the leachability of Ni/Co/Cu slags at high temperature

An oxidative pressure acid leaching process was investigated for the extraction of Ni/Co/Cu/Zn metal values from base metal smelter slags. The process is applicable to smelting furnace dump slags, as well as to mid-stream converter slags. In addition to the economical advantages, extracting the base metal values from the dump slags produces an environmentally benign residue. To produce high level of extraction for the metal values, it is necessary to have the slag in crystalline structure. This, in turn, requires cooling the molten smelter slags sufficiently slowly during solidification. It was shown that if the same slags are quenched in water thereby producing an amorphous structure, the resulting metal extractions are substantially lower. The role of oxygen in the leaching reactions was also tested. The presence of oxygen is necessary for successful leaching of the metal values. After fine grinding, the slags were subjected to pressure acid leaching at 250 °C with an oxygen overpressure of 520 kPa. Sulfuric acid at a typical 0.3 acid to slag ratio was employed. Extractions higher than 90% of each of the nickel, cobalt, copper and zinc were achieved. Operating at 250 °C ensures that the concentration of Fe and Al impurity metals in leached solution remains very low. It was finally found that for high concentrations of divalent metals (Ni + Co + Cu + Mg) in the slag, a much higher quantity of sulfuric acid than the stoichiometric value is required. The latter is due to the drop of hydrogen ion concentration due to bisulphate formation.     

The influence of solid-state and liquid-phase bonding on fatigue at Al/Al2O3 interfaces

Fracture and fatigue experiments have been conducted on liquid phase bonded (LPB) and solid-state bonded (SSB) aluminum-alumina interfaces. The LPB interfaces contain voids and dendritic FeAl₃ precipitates, whereas SSB interfaces are relatively defect-free. These precipitates result in local embrittlement, yet both interfaces are strong and tough. Upon cyclic loading, mode 1 cracks in both systems grow alternately along the interface and within the A1. The development of a tortuous crack path elevates the apparent fatigue threshold through crack closure. Under mixed mode loading, fatigue cracks approaching SSB interfaces propagate through the A1 rather than along the interface. Conversely, for LPB interfaces, mixed mode cyclic crack growth along the interface occurs in preference to propagation in the A1. Correlation between the striation spacing and the crack tip opening displacement suggests a growth mechanism based on crack tip blunting.