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Phase transformations and phase stability in the Fe-Cr-Co-20Mn (at.%) alloy system were investigated using optical microscopy, transmission electron microscopy, x-ray diffraction, and vibrating sample magnetometry. Thermal-induced martensitic transformation from the BCC α parent phase to the HCP e martensite phase was observed in the samples with near 36Fe-24Cr-20Co-20Mn compositions. Bainitic transformation from the α phase occurred with aging. Although the α parent phase coexisted with the e martensite phase in the as-quenched specimen and transformation did not proceed with sub-zero treatment, the e martensite was completely induced by cold rolling. Furthermore, the FCC γ phase was obtained by heavy deformation. These results indicate that multiple martensitic transformations from α to e and e to γ occurred. The γ → e martensitic transformation was also observed for 48Fe-16Cr-16Co-20Mn. The phase stabilities of the α, e, and γ phases were similar. The calculated T0 lines successfully predicted the α → e martensitic transformation when the e phase was more stable in the database. Thermodynamic analysis revealed that magnetic ordering in the α phase affected the phase stability, resulting in the novel e loop in addition to the conventional γ loop.

To efficiently construct phase diagrams of alloy systems, a machine learning-based method advanced by thermodynamics on phase equilibria is proposed. With the use of uncertainty sampling in active learning, the next point to be synthesized or measured can be recommended to efficiently draw the phase diagram. For appropriate recommendations, two ingenuities are introduced in the machine learning method: training data preparation when the multiphase coexisting region is detected and search space reduction based on the Gibbs’ phase rule. We demonstrate the construction of ternary phase diagrams using our machine learning method by incorporating these ingenuities. The complicated phase diagram of alloy systems could be effectively plotted even when knowing only the information of single-component systems in the initial step. The recommendation made by our machine learning method can help reduce the number of experiments required to construct a phase diagram to approximately 1/8 compared with random sampling.

A critical determination of a phase diagram of the Zn-Fe binary system was carried out by EPMA analysis for skillfully prepared and equilibrated two-phase alloys for solid phases and by EDS areal analysis for the Fe solubility in the heterogeneously solidified liquid phase instead of the conventional diffusion couple method. It was newly confirmed that equilibrium compositions of intermetallic compounds tend to shift toward the Fe side compared to the previous phase diagram on the whole and that the solubility ranges of the Γ-Fe3Zn10 and Γ1-Fe11Zn40 phases are much narrower than those in the literature. The critical composition of the second-order order-disorder transition between δ1k-FeZn7 and δ1p-FeZn10 at high temperature was estimated by Vickers hardness measurement. Furthermore, the phase separation, i.e., the first-order transition, between the δ1k and δ1p phases in the low temperature region was directly found out and its equilibrium compositions were confirmed by EPMA analysis for the two-phase microstructures. The width of the δ1k + δ1p two-phase region at 500 °C is only 0.5 at.% and the δ1p decomposes into the δ1k and ζ-FeZn13 phases via a eutectoid reaction at a temperature between 455 °C and 445 °C. While being mostly coincident with those in the previous literature at temperatures between 1000 °C and 600 °C, the solubility of Fe in the liquid (L) Zn phase is about twenty times larger than the assessed value in the literature at temperatures below 500 °C. A eutectic reaction, L → ζ + (ηZn), was confirmed to occur by precise EPMA analysis and DSC measurement.

In the present study, the formation and growth behaviors of intermetallic compound (IMC) layers in the interfacial reaction of solid Fe and molten Zn during hot dipping at 450 °C were investigated. In the early stage of the interfacial reaction, Γ-Fe4Zn9, δ1k-FeZn7, and ζ-FeZn13 phases were formed, among which the growth of the ζ layer was dominant. Columns of the δ1p-Fe13Zn126 phase were formed on the δ1k/ζ interface at approximately 90 s, and the four IMC layers grew simultaneously until 600 s. Subsequently, a layer of the Γ1-Fe21.2Zn80.8 phase was formed along the Γ/δ1k interface and started growing, after which all the equilibrium IMC phases of Γ/Γ1/δ1k/δ1p/ζ grew competitively. The total thickness of the five IMC layers, dtotal, increased proportionally with the square root of the reaction time, t, i.e., dtotal = d0 t 0.5, which suggested that the growth of the entire IMC layers was controlled by the volume diffusion. However, the values of the time exponent, n, for the individual IMC layers differed depending on their microstructures and chemical concentrations, under equilibrium or nonequilibrium conditions. The formation of the multilayered columnar ζ phase can be attributed to the heterogeneous supersaturation of Fe in the liquid Zn near the columnar ζ / liquid Zn interface during the early stage of the interfacial reaction. The interdiffusion fluxes, J ϕ , of Fe and Zn in the ϕ phase ( ϕ = Γ, δ1k, and ζ) were estimated from the measured concentration profiles of each phase. This suggested that J ϕ caused the growth of each phase as well as the supersaturation of Fe near the interfacial boundaries, thereby resulting in considerable deviations from the equilibrium concentrations. In the later stage of the interfacial reaction, the interfacial concentrations gradually approached the equilibrium concentrations with decreasing J ϕ .

The atomic arrangement and microsegregation in the vicinity of thermally induced antiphase boundaries in a Ni 50 Mn 20 In 30 Heusler alloy are investigated through multislice simulations, high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray diffraction pattern Rietveld analysis, energy-dispersive X-ray spectroscopy, and modified Bragg–Williams–Gorsky calculations. Intensity analysis of atomic-resolution HAADF-STEM images revealed that a 180° geometrical phase shift occurred across the antiphase boundaries, accompanied by a decay in the degree of atomic order and an enrichment of In. Energy-dispersive (X-ray) spectroscopy analysis revealed an In enrichment as high as 2.7 at.% at the center of the antiphase boundaries, comparable to that (1.0–1.8 at.%) suggested by the parallel tangent law for the Gibbs energy curves of the L 2 1 and B 2 phases using the modified Bragg–Williams–Gorsky calculation. This suggests that microsegregation occurs at the antiphase boundaries and can be understood basically within the framework of the local thermodynamic equilibrium.

A thermal fluctuation-based nucleation model for use in a phase-field model is proposed. In the model, a normally distributed random temperature fluctuation is imposed on a calculation system, and if a given grid temperature is lower than the average, the undercooling is converted to an increase in the crystallized/precipitated phase fraction. The conversion coefficient is derived as a function of a phase-field critical value for nucleation. The idea of a threshold of nucleation for the phase field, i.e., a critical value, is introduced first in the present study. The model is applied to homogeneous nucleation during solidification in a supercooled pure metal, and a reasonable nucleation probability curve is successfully obtained from the numerical calculations. An application to the homogeneous nucleation of an Al-Cu alloy is also demonstrated.

Phase equilibria in multi-phase Zn–Fe–Al alloys were experimentally measured using a field-emission electron probe micro-analyzer for alloy samples, and a precise iso-thermal phase diagram at 450 °C in the entire composition range of the Zn–Fe–Al ternary system, except for the Fe-rich corner, was determined. The ternary solubility ranges of the Γ-Fe4Zn9, Γ1-Fe21.2Zn80.8, δ1k-FeZn7, and ζ-FeZn13 on the Fe–Zn side and of the ζ-FeAl2, η-Fe2Al5, and θ-Fe4Al13 on the Fe–Al side were consistent with the latest corresponding binary data, whereas no δ1p-Fe13Zn126 phase was detected. The single-phase region of the Γ2-Fe8Zn87Al4 ternary intermetallic compound phase is significantly narrower than that reported in the previous studies. The solubility of Fe in the liquid phase increased consistently and continuously from the value in the Zn–Fe binary system (0.6 at.%) up to 1.2 at.% at 31 at.% Al with increasing Al content. In the Al-rich portion of the phase diagram at 450 °C, the Fe(Al, Zn)6 intermetallic compound phase was newly discovered, and confirmed to be an isomorph extended from the FeAl6 phase which is metastable in the Fe–Al binary system.

Al-rich portion of the Al–Fe binary phase diagram was determined by conventional heat-treatment for equilibration, the diffusion couple method and thermal analysis. Equilibrium compositions are mostly coincident with the generally accepted phase diagram in the literature up to 1000 °C, except the solubility range of θ-Fe 4 Al 13 phase. The solubility ranges of the η-Fe 2 Al 5 and the θ-Fe 4 Al 13 phases were confirmed to increase and incline to the Fe-rich side with increasing temperature. Phase boundaries and the eutectoid composition of the e-Fe 5 Al 8 phase were determined from the diffusion couple method and heating curves of DSC measurement, which were slightly shifted to a higher Fe concentration. Transformation temperatures of liquidus, solidus and invariant reactions determined from heating curves of DSC measurement were mostly lower than those in the phase diagram evaluated by Kattner and Burton. An invariant reaction related to the formation of the θ-Fe 4 Al 13 phase was confirmed as the peritectic reaction of Liquid + η-Fe 2 Al 5 = θ-Fe 4 Al 13 in this study taking equilibrium compositions of the η-Fe 2 Al 5 + θ-Fe 4 Al 13 phases and solidus temperatures of the θ-Fe 4 Al 13 phase into consideration.

The thermodynamic properties for Nd2Fe14B, the main constituent of rare-earth magnets, were investigated from absolute zero to high temperature. Standard entropies Δ 0 T S m ○ were determined by measuring the molar heat capacity C p , m ° from 2 K via the Debye-Einstein-spin wave functions. The temperature dependence of the standard Gibbs energy of formation Δ f G m ° (T) from absolute zero to high temperature was determined by combining Δ 0 T S m ○ with reference formation energies from first principles calculations. We found that the Δ f G m ° (T) based on the open core approach, in which the Nd 4f components of the projected density of states are localized in the core, agrees well with that estimated from phase equilibria. Our measurements of the Sommerfeld parameter provided further support for the open-core concept. The magnetic moment, calculated as a function of C p , m ° , agrees with the result of direct magnetization measurement, suggesting that separating the spin and lattice vibration terms is necessary from very low to high temperature via the Curie temperature at 585.3 K. This work is expected to contribute significantly to magnetic materials design.

Phase equilibria in the Ir–W, Ir–Al and Ir–W–Al systems at temperatures between 1100 °C and 1600 °C were experimentally investigated using diffusion couples and two- or three-phase alloys, and the mechanical properties of γ′ (L12) strengthened Ir–W–Al alloys were examined by hardness and compression tests at room and elevated temperatures. The phase boundaries between the γ(A1)/e′(D019), e′/e(A3) and e/e″(B19) in the Ir–W system at 1400 °C–1600 °C and those between the γ/β(B2) and β/Al2.7Ir in the Ir–Al system at 1100 °C–1400 °C were determined. The phase diagrams in the Ir-rich corner of the Ir–W–Al ternary system at 1300 °C and 1400 °C were also determined. The existence of the γ′ phase of the Ir3(W,Al) ternary compound was confirmed, and this system was found to consist of the γ, γ′, e, e′ and β phases in the Ir-rich portion. It was also found from hardness and compression tests up to 1200 °C that Ir–Al–W alloys having the γ + γ′ structure with a small lattice misfit show high hardness and strength at room and high temperatures.

New experimental measurements of the phase diagram and the mixing enthalpy of liquid phase along with the previous experimental data were used in a reassessment of the Ni–Ga system. A set of self-consistent thermodynamic parameters of the Ni–Ga system is obtained using the calculation of phase diagram (CALPHAD) technique, and the available phase diagram and thermodynamic data are reproduced well within experimental error limits. Some noticeable improvements are obtained in the present work compared with the previous assessment: (1) the calculated Ga-rich liquidus is more reasonable; (2) Ni3Ga7 is adopted as the most Ga-rich compound rather than NiGa4; (3) the Ni5Ga3 phase is treated as the nonstoichiometric compound with consideration of its narrow homogeneity range; (4) the phase transformation between B81.5_Ni3Ga2 and Ni13Ga9 is considered instead of treating them as Ni3Ga2 phase simply; (5) the latest experimental data of mixing enthalpy for the liquid phase are adopted. The present study can be used as a basis for the development of a thermodynamic database of the Ni-based semiconductor alloy systems.

Experimental investigation and thermodynamic evaluation of the Co–Ta binary phase diagram was carried out. Equilibrium compositions obtained in two-phase alloys and diffusion couples were measured by electron probe microanalyzer (EPMA). A very narrow λ3(C36) + λ2(C15) two-phase region is confirmed to be present around 26.5 at.% Ta at temperatures between 950 °C and 1448 °C. Equilibrium relationships above 1500 °C among the liquid, Laves (λ1(C14), λ2 and λ3, whose stoichiometry is described by Co2Ta), μ(D8b) and CoTa2(C16) phases were investigated by microstructural examination in as-cast Co-(24–60 at.%)Ta alloys. The solvus temperature of the γ′ Co3Ta (L12) phase precipitated in the 5.8 at.%Ta γ(Co) and the peritectoid temperature of the Co7Ta2 phase in an 8.5 at.%Ta alloy were determined to be 1013 °C and 1033 °C, respectively, by differential scanning calorimeter (DSC). Fine precipitates of the γ′ phase precipitated in the γ (A1) matrix were observed by transmission electron microscope (TEM). Analyzing the present experimental results synthetically, the γ′ Co3Ta phase was identified to be a metastable phase, of which the γ/γ′ transition temperature of the stoichiometric Co3Ta alloy was estimated to be 2000 °C. Thermodynamic assessment of the Co–Ta binary system was carried out based on the present results as well as on experimental data in the literature. Calculated results of not only stable but also metastable equilibria were found to be in good agreement with the revised phase diagram. The evaluated stability of the metastable γ′ Co3Ta coincides with the enthalpy of formation (ΔH(γ'Co3Ta) = −23.44 kJ/mol) calculated by the ab initio method.

Phase equilibria between αFe and γ(Fe,Ni) in the Fe–Ni binary system at low temperatures above 400 °C were determined experimentally, and thermodynamic descriptions to calculate the Gibbs energy of involved phases were revised with taking into account the interaction effect between the chemical and magnetic orderings. Heat-treatment for equilibration of gas-atomized powder of Fe–Ni alloys without deformation resulted in the formation of a microstructure consisting of directional γ precipitates in α' martensite matrix. Converge-milling processing, a kind of mechanical alloying technique, in advance of heat-treatment, was applied to introduce a large number of lattice defects into powder particles, which enhanced α + γ recrystallization to form an equiaxed dual-phase polycrystalline microstructure. Equilibrium compositions of the equiaxed grains of the α and γ phases were measured by an FE-EPMA, the spatial resolution of quantitative analysis of which is 0.5 μm in diameter with accelerating voltage of 6 kV. Equilibrium compositions of the γ phase coincided with the phase diagram assessed in accordance with experimental results in the literature. On the other hand, the solubility of Ni in the α phase exhibited considerable deviation from “retrograde solubility” determined according to previous data. Thermodynamic analysis with revised parameters suggests that the underestimated solubility of Ni in the αFe phase is caused by the additional Gibbs energy due to lattice defects in the α’ martensitic structure.

This paper provides a comprehensive overview of state-of-the-art computational techniques to thermodynamically model magnetic and chemical order–disorder transitions. Recent advances as well as limitations of various approaches to these so-called lambda transitions are examined in detail, focussing on calphad models and first-principles methods based on density functional theory (DFT). On the one hand empirical implementations –based on the Inden–Hillert–Jarl formalism –are investigated, including a detailed interpretation of the relevant parameters, physical limiting cases and potential extensions. In addition, Bragg–Williams-based approaches as well as cluster-variation methods of chemical order–disorder transitions are discussed. On the other hand, it is shown how magnetic contributions can be introduced based on various microscopic model Hamiltonians (Hubbard model, Heisenberg model and beyond) in combination with DFT-computed parameters. As a result of the investigation we were able to indicate similarities between the treatment of chemical and magnetic degrees of freedom as well as the treatment within the calphad and DFT approaches. Potential synergy effects resulting from this overlap have been derived and alternative approaches have been suggested, in order to improve future thermodynamic modelling of lambda transitions.

The phase equilibria among γ (A1), γ′ (L12), χ (D019), β (B2) and μ (D85) phases and the γ′ solvus and γ solidus temperatures were investigated in the Co–Al–W-based quaternary systems with alloying elements of Ti, V, Nb, Ta, Cr, Mo, Mn, Fe, Ni, Si, Zr, Hf, Ru and Ir by electron probe microanalysis (EPMA) using multiphase alloys and by differential scanning calorimetry (DSC). It was found that Ta, Nb, Ti, V, Mo and W are partitioned to the γ′ or χ phase rather than to the γ phase, while Cr, Mn and Fe tend to be distributed to the γ phase. The correlation between the partition coefficient of alloying elements between γ/γ′, γ/χ and γ/β phases and ab initio formation energy of Co3X (L12), Co3X (D019) and CoX (B2) was respectively obtained. It was also found that the γ′ solvus temperature increases by the addition of the γ′ former elements such as Ta, Nb and Ti, which decreases the γ solidus temperature.

The normal grain growth behaviors at 750, 800 and 900°C in block and sheet samples of Cu­Al­Mn shape memory alloy with the bcc single-phase structure were investigated. The grain growth exponents, n, evaluated in the two- and three-dimensional grain growths were found to be larger than those in most other metals and were located between 10 and 18. Furthermore, the two-dimensional growth in thin sheet samples was much slower than the three-dimensional growth in block samples due to the grooves formed along grain boundaries on the specimen surface, these grooves constituting a hindrance to the movement. [doi:10.2320/matertrans.M2013167]

Phase equilibria in the Fe–Si binary system were investigated experimentally and thermodynamic assessment was carried out. The αFe (A2) + α"Fe3Si (D03) two-phase microstructures at 600°C and 650°C were obtained, whose grain sizes were sufficiently coarsened to be analyzed by FE-EPMA with a spatial resolution below 0.5 μm under the condition of 6 kV accelerating voltage. α'FeSi (B2) + α"Fe3Si (D03) two-phase equilibria above 700°C were detected for the first time and equilibrium compositions were determined by the diffusion couple method. The horn-shaped two-phase miscibility gap extends from the low temperature αFe + α"Fe3Si equilibrium along the B2/D03 second-order transition boundary and closes below 1000°C. Four-sublattice split compound energy formalism was applied to calculate the Gibbs energy of the bcc phases, A2(αFe), B2(α'FeSi) and D03(α"Fe3Si), and the thermodynamic parameters in the Fe–Si binary system were evaluated. Equilibrium relations in the binary system were well reproduced, especially the effect of the B2 and D03 ordering on the liquidus and solidus curves and the miscibility gap between bcc phases. Optimized thermodynamic parameters as well as the experimental results are expected to be helpful for developing higher multi-component systems for practical steels.

Recent progress in the development of thermodynamic and kinetic databases of micro-soldering alloys, which were constructed within the framework of the Thermo-Calc and DICTRA software, was presented. Especially, a thermodynamic tool, ADAMIS (alloy database for micro-solders) was developed by combining the thermodynamic databases of micro-solders with Pandat, a multi-component phase diagram calculation software program. ADAMIS contains 11 elements, namely, Ag, Al, Au, Bi, Cu, In, Ni, Sb, Sn, Zn and Pb, and can handle all combinations of these elements in the whole composition range. The obtained thermodynamic and kinetic databases can not only provide much valuable thermodynamic information such as phase equilibria and phase fraction, but also shows the kinetics and the evolution of microstructures when they are combined with some appropriate software programs and models, such as the phase field method and ADSTEFAN software. From the viewpoints of computational thermodynamics and kinetics, some technical examples were given to demonstrate the great utility of these databases for the applications in the development of micro-soldering materials. These databases are expected to be powerful tools for the development of micro-solders and Cu substrate materials, as well as for promoting the understanding of interfacial phenomena and microstructure evolution between solders and substrates in electronic packaging technology.

A materials design tool for developing Pb-free soldering alloys in electronic package was developed based on comprehensive experimental data of phase equilibria and thermodynamic properties data accumulated with the CALPHAD (calculation of phase diagrams) method and contains 10 elements, namely, Ag, Au, Bi, Cu, In, Ni, Sb, Sn, Zn and Pb. It can handle the calculation of phase diagrams in all combinations of these elements and all composition ranges. In addition, based on this tool, the liquidus, solidus, phase fractions and constitutions, equilibrium and non-equilibrium solidification behavior, surface tension and viscosity of liquid, diffusion reactions and microstructural evolution, etc. can be predicted. Typical examples of the calculation and application of this tool are presented. The design tool is expected to be a powerful tool for the development of Pb-free solders, as well as for promoting the understanding of the interfacial phenomena between Cu substrate and Pb-free solders in electronic packaging technology.

The phase equilibria at 200 °C, 250 °C, 300 °C, and 400 °C and the phase transformation of the Sn-Au-Bi system were investigated by using the electron probe micro-analyzer (EPMA) and differential scanning calorimeter (DSC), respectively. It is found that there is a new ternary intermetallic compound with a possible AuSn structure (called the ϕ phase in the present work), which has a limited solubility of Au in the Au-rich portion, and the ϕ phase decomposes peritectically at about 313 °C. Based on the experimental data reported in the previous papers and new experimental data determined by the present work, thermodynamic assessments of the Sn-Au-Bi system were carried out by the calculation of phase diagrams (CALPHAD) method. The thermodynamic parameters for describing the Gibbs free energy of each phase were optimized, and reasonable agreement between the calculated results and experimental data was obtained in the Sn-Au-Bi ternary system.

Mechanical properties of Fe-20Mn-(10-14)Al-(0-1.8)C (mass%) quaternary and Fe-20Mn-(10-14)Al-(0.75-1.8)C-5Cr (mass%) quinary alloys were investigated by hardness, cold-workability and tensile tests at room temperature. The γ(fcc) alloys in both quaternary and quinary systems with a low density of less than 7.0 g/cm 3 showed an excellent ductility and their hardness and tensile strength increased with increasing Al and C contents. The γ+α(bcc) duplex alloys also exhibited a high tensile strength by controlling the α volume fraction. TEM observation confirmed that high hardness and tensile strength of the alloys with high Al and C contents are caused by the precipitation of nano-size κ-carbide with perovskite structure during cooling from the annealing temperature. Fe-20Mn-11Al-1.8C-5Cr alloy with a density of 6.51 g/cm 3 showed a high specific strength of more than 180 MPa · cm 3 /g with a good tensile elongation of 40 %. The present Fe-20Mn-Al-C(-5Cr) alloys showed a higher specific strength than conventional steels.

Phase equilibria and stabilities of intermetallic phases appearing in the Co-rich portion of the Co-W-Ga ternary alloys were investigated and isothermal section diagrams at 1200, 1100, 1000, and 900 °C were determined. A fine cuboidal phase with an L12 structure was observed at 900 and 800 °C, where the composition of the new ternary compound obtained by aging at 900 °C for the Co-7.4W-12.0Ga alloy was Co-11.2W-11.4Ga (at.%). It was confirmed that this compound is metastable at 900 °C but is more stable at 800 °C. These results mean that the thermodynamic stability of the metastable Co3W L12 phase, especially in the low temperature region, increases by the addition of Ga.

The National Natural Science Foundation of China [50425101, 50571084]; The Ministry of Science and Technology of China [2004CCA04200]; The Ministry of Education of China [20050384003, 105100, 707037]; Grant-Aid Core Research for Evolution Science and Tech

The phase equilibria at 300, 400, 500, and 600 °C in the Ag–Bi–Ni system and 300, 400, and 500 °C in the Cu–Bi–Ni system were experimentally determined by metallography and electron probe microanalysis on equilibrated alloys and diffusion couples. Differential scanning calorimetry was used to measure the temperatures of phase transformations. All the experimental results show that the solubilities of the ternary elements of the binary intermetallic compounds in the Ag–Bi–Ni system are limited. However, the binary intermetallic compounds have some solubilities of the ternary elements in the Cu–Bi–Ni system. No ternary intermetallic compound was found in the Ag–Bi–Ni and Cu–Bi–Ni systems. On the basis of the determined results, the phase equilibria in the Ag–Bi–Ni and Cu–Bi–Ni systems were thermodynamically assessed, and reasonable agreement between the calculated results and experimental data was obtained.

Three types of inexpensive Pb-free solder joints, namely Zn-based and Bi-based solders, and a CuSn alloy were studied for application to the high-temperature operation of wide band-gap power semiconductor devices using GaN or SiC. Zn–Al solder sheets, whose melting point is 380°C were prepared, and then surface oxides were removed by RF plasma etching. Subsequently, Cu thin films were deposited by the DC sputtering method on the solder sheet. After that, joint samples were fabricated using a conventional electrical furnace with H2/N2 gas flow. That the joints were sufficiently dense was confirmed by scanning acoustic microscope. The wettability of the solder was improved due to contact between the pure Zn–Al solder without oxide and the Ni surface of the substrate, and the chemical reaction between the Zn–Al solder and the deposited Cu thin film. Bi with CuAlMn particle solders, whose melting point is 270°C, were fabricated and it was found that the solder has almost double the tensile strength of pure Bi. Excellent wettability was observed with the Ni or Pd thin film deposited on the Cu substrate. It was found that deposited Ni or Pd was not observed in the interface between the substrates after the joint samples were fabricated. CuSn alloy joints were fabricated using Sn thin films deposited and annealed on Cu substrates. The temperature during the annealing was kept at approximately 350°C; therefore, only the Sn film was melted and some chemical reaction occurred between the liquid Sn and solid Cu. Then, Cu3Sn alloy, whose melting point is 640°C, appeared in the joint and the composition was confirmed by X-ray diffraction analysis. Furthermore, it was found that the CuSn alloy is harder than Cu as measured by nano indentation analysis. In addition, the joints showed excellent thermal cycle reliability.Finally, the properties of these joints are summarized.

Phase equilibria between the α (A2), α' (B2) and γ (A1 ) phases in the Fe-Rh binary system were investigated using electron probe micro-analysis (EPMA) and differential scanning calorimetry (DSC) techniques. The A2/B2 order-disorder transformation temperature was also examined by a transmission electron microscope (TEM) observations and high-temperature X-ray diffraction (HTXRD). It was confirmed that while the transition temperature from the α (A2) phase to the γ (A1 ) phase decreases with increasing Rh content up to about 20 at% Rh, the b.c.c. region is stabilized by further Rh addition in the composition range between about 20 and 50 at% Rh, and then again the stability of b.c.c. phase decreases in the composition region over 50 at% Rh. It was also shown by TEM observation and HTXRD examination that the compositions of the phase boundary of the A2/B2 ordering at 500°C and 600°C were determined to be 16.5 and 19.1 at% Rh, respectively. On the basis of those experimental results, a thermodynamic analysis was carried out. The results of the thermodynamic calculation suggest that the anomalous behavior of the stability of the b.c.c. phase is caused by the A2/B2 ordering.

The Zn-Al(-Cu) eutectic alloys (melting point 381°C) are candidates for use as Pb-free high-temperature solders as a substitute for Pb-based solders, which are suitable for severe working environments such as the engine room of hybrid vehicles equipped with an inverter system as well as a heat engine. In this study, the interfacial reaction between Zn-Al(-Cu) alloys and the Ni substrate during soldering, aging, and thermal cycling was investigated. Semiconductor chips and Ni substrates were soldered with Zn-Al(-Cu) alloys at various temperatures under a nitrogen atmosphere. The soldered assemblies were then heat-treated at 200°C and 300°C to examine the microstructural evolution at the soldered interface. The effect of severe thermal cycles between −40°C and 250°C in air on the microstructure and fracture behavior at the solder joint was investigated. Even after a 1000-cycle test, the thickness of the Al3Ni2 layer formed at the interface between the Zn-Al-based solder and the Ni substrate, which is responsible for the damage of the soldered assemblies, was quite small.

On the basis of the CALPHAD (Calculation of Phase Diagrams) method, the compositional range of stable miscibility gap and volume fractions of the two liquid phases in the Cu–Fe–Cr–Ni system were predicted, which can provide the guidance for design of self-formed composite materials. Based on such information, the self-formed pencil-like bulk composite materials consisting of copper alloy and two kinds of stainless steels were prepared by controlling the compositions of Cu-rich and Fe-rich phases in immiscible liquid system by the conventional casting process. The experimental results are in good agreement with the ones predicted by calculation. This study indicates that it is possible to develop the pencil-like bulk composite materials consisting of copper alloy and stainless steels by the conventional casting process.

A novel Bi-base solder for mounting semiconductor power devices on inverters used in hybrid and fuel-cell vehicles was studied. The solder consists of Bi-base matrix (m.p. (melting point) =270°C), which facilitates high-temperature soldering, and dispersion particles of a Cu-Al-Mn alloy, whose thermoelastic martensitic microstructure is expected to relax the thermal stress. The tensile strength of the developed solders was found to be remarkably improved compared with that of pure Bi. Results of tensile tests at elevated temperatures showed greater elongation and lower strength than those at room temperature. However, sufficient tensile strength was still remained at 195°C. Effects of the CTE (coefficient of thermal expansion) and the surface substance of chips and substrates on the IMC (intermetallic compound) formation and thermal cycling properties were investigated. Even after 1983 thermal cycles between -40°C and 200°C, neither intermetallic compounds nor cracks were observed at the Cu/Bi-base solder interfaces in the CTE matched samples.

Phase equilibria between the y and y' phases at 900°C in the Co-(10-70)Ni-Al-W system were determined by electron probe microanalysis (EPMA) and X-ray diffractometry (XRD). It was found that the "/ phase with L1 2 structure continuously exists from the Co side to the Ni side in Co-Ni-Al-W system and that it widens to the low W region with increasing Ni content. The partition of Al into the y' phase increased with Ni content, while the W changed from a y' former to a y former by increase of Ni content. Differential scanning calorimetry (DSC) measurements also revealed that the y' solvus temperature increases with Ni content, while the solidus temperature is hardly affected by such content. The lattice parameter of the y and y' phases and the mismatch decreased with increasing Ni content, which caused the morphologic change of the γ' precipitates from cubes to spheres.

The recrystallization and grain growth characteristics of pre-deformed Fe–1.9vol%Bi alloy specimens in the two-phase region of αFe and liquid Bi were investigated by microstructural observation. Precipitate-free zones (PFZs) were mainly formed in the vicinity outside of the curved grain boundaries. Furthermore, large Bi particles were also observed on the grain boundaries of the matrix along the PFZs. These results suggest that the intragranular liquid Bi particles were trapped and dragged by grain boundaries. The grain growth of the matrix phase was extremely retarded by the effect of this dragging.