The microstructural evolution of intermetallic alloys, which have dual two-phase microstructure composed of Ni3Al (L12) and Ni3V (D022) phases, was investigated as a function of aging time at 1273K by TEM. At early aging time, the lower microstructure showed structurally decomposed clusters composed of L12 phase and three D022 variant structures. With proceeding aging time, the decomposed L12 and D022 phases coarsened and transformed to lamellar-like microstructures. At longer aging time, the L12 phase disappeared from the lamellar-like microstructure and alternatively the D022 phase composed of two different variant structures prevailed over the lamellar-like microstructures. Corresponding to this microstructural change, the direction of the lamellar and its interfacial plane rotated from <001> to <011> and from {001} to {011}, respectively.

In order to develop non-Pd based high performance hydrogen permeation alloys, microstructure, crystal structure and hydrogen permeability of duplex phase M-ZrNi (M=V and Ta) alloys were investigated using a scanning electron microscope, an X-ray diffractometer and a gas flow meter. These results were compared with those of Nb-ZrNi ones which have been previously published. The hydrogen permeation was impossible in the V-ZrNi alloys, because they were brittle in the as-cast state. On the other hand, duplex phase alloys consisting of the bcc-(Ta, Zr) solid solution and the orthorhombic ZrNi (Cmcm) intermetallic compound were formed and hydrogen permeable in the Ta-ZrNi system. The Ta40Zr30Ni30 alloy shows the highest value of hydrogen permeability of 4.1×10-8 [molH2m-1s-1Pa-0.5] at 673 K, which is three times higher than that of pure Pd.

The compression creep behavior of five Al- Ni-Ru ternary alloys with compositions across the NiAl-RuAl B2 phase field has been investigated within the temperature range of 950 °C to 1050 °C. A continuous increase of the melting temperature and creep resistance with increasing Ru/Ni ratio in these alloys was observed. Post-creep dislocation analyses identified the presence of <100> and <110> edge dislocations in the Al-deficient alloys. Conversely, jogged <100> screw dislocations predominated in the Ru-rich ternary alloys. Dislocation substructures and transient experiments suggest a transition of the creep mechanism from viscous glide controlled to jogged screw motion in these alloys.

Fine grained gamma+beta dual phase microstructures were obtained in aluminum-titanium-vanadium ternary alloys containing 40 at.% aluminum and 60 at.% (titanium and vanadium). Average grain size was about 5, 3, and 2 micrometers in the recrystallized materials containing 20, 30, and 40 at.% vanadium, and the phase constitution was around 50vol.% gamma phase and 50vol.% beta phase. Compression behavior was investigated at temperatures ranging from the room temperature up to 1200K, and compressive creep tests were carried out at 1050-1200K in order to characterize the temperature and chemical composition dependences of strength and deformation. These gamma+beta microduplex materials showed very high strength at room temperature; 0.2% proof stress was around 1200MPa. The compression deformability decreased from about 0.2 to 0.05 true strain with increasing vanadium content. The grain size effect was not clarified yet, but it was rather disappointing that smaller-grained material with Al40Ti20V40 composition did not show effective improvement either in strength or in deformability. 0.2% proof stress showed a considerable weakening at temperatures higher than 900K; the onset temperature of softening became lower as the vanadium content increased. In Al40Ti40V20 material with about 5 micrometer grains, both gamma and beta grains were flattened up to 1000K, however, above 1100K the gamma grain showed no significant shape change even after a heavy deformation. This is probably because the gamma grains were relatively stronger than the beta grains. The gamma grains showed tendency toward agglomeration, which is similar to rafting of precipitate particles. Surface relief was observed after high temperature deformation suggesting activity of boundary sliding on grain boundaries and interfaces. Compressive creep behavior was investigated under a constant true stress in vacuum. Creep curves consisted of a small amount of normal primary transient, the minimum creep rate region, and a steady or slightly accelerating creep region. Stress exponent decreased to about 2 with decreasing vanadium content. It was rather unexpected that smaller grained Al40Ti20V40 material showed larger stress exponent around 3.

Dual multi-phase intermetallic alloys composed of Ni3X (X: Al and V) containing Nb were developed, on the basis of the Ni3Al-Ni3Nb-Ni3V pseudo-ternary alloy system. The dual multi-phase intermetallic alloys were characterized by scanning electron and transmission electron microscopies. High-temperature compression and tension tests, and compression creep test were conducted. It was found that the dual multi-phase intermetallic alloys show high yield and tensile strength with good temperature retention, accompanied with reasonable tensile ductility. The compression creep test conducted at high temperature showed lower creep rate in the dual multi-phase intermetallic alloys than in conventional Ni-base superalloys. The obtained results are superior to the dual multi-phase intermetallic alloys containing Ti.

Internal twin of B19 martensite in equiatomic AuTi binary alloy was examined by conventional transmission electron microscopy observation and the phenomenological theory of martensite crystallography (PTMC). The crystal structure of martensite was B19 (orthorhombic) with the lattice parameters of 0.2944nm, 0.4900nm and 0.4633nm. Most of martensite plates were internally twinned by {111}typeI twin. <211>typeII twin was occasionally observed and {011}compound-twin relationship was observed at boundaries between adjacent martensite plates. However, no martensite plate entirely twinned by the <211>typeII twinning or the {011}compound twinning was observed. PTMC analysis showed that the invariant plane is formed only by the introduction of the internal twin of {111}typeI or <211>typeII twin in the present geometry of the transformation. Geometry of a typical martensite plate with internal twin of {111}typeI twin was in good agreement with that required for the formation of habit plane with the invariant plane character. The observed {111}typeI twin is, therefore, considered to be the lattice invariant shear to minimize the elastic strain energy due to the transformation.

Numerous studies have shown that equiaxed ultra fine grained FePd alloys can be produced by phase transformation of heavily deformed austenitic FePd via the combined reaction mode. As the magnetic properties can be improved by suppression of the polytwinned micro-constituent formed by the conventional ordering mode it appears reasonable to speculate that further grain refinement might lead to further enhancement. In order to reduce the grain size in bulk intermetallic alloys severely plastically deformed austenitic FePd has been phase transformed in this study. Equal channel angular pressing (ECAP) has been used to deform disordered FePd. The microstructure and property evolution during the deformation process and post-deformation annealing have been studied using SEM, TEM and hardness and magnetization curve measurements. The observations are compared to known results from use of other deformation processing routes, such as cold rolling.

The effect of the deformation constraints is examined for the lamellar structure of TiAl where the unconstrained plastic deformation occurs parallel to the lamellae. The constraints generally redistribute the stresses in such a way that the resolved shear stresses are decreased on the most stressed systems and increased on other systems. This behaviour leads to the material strengthening and may enhance the ductility when more deformation modes are activated.

Atomic disorder is investigated for B2- and Heusler-phase CoFe1-xAlx alloys quenched from various temperatures by X-ray diffraction measurements. In the B2-phase region, with increase in quenching temperature, atomic disorder on the Co-site (Co-type disorder) proceeds for x=0.30 but not for x=0.70. In the Heusler-phase region (x=0.45, 0.50 and 0.55), atomic disorder between the Fe- and Al-sites (Fe-Al-type disorder) mainly proceeds. A relation between the magnetic behavior obtained in our previous work and the atomic disorder is examined. As a result, it is found that the Co-type disorder leads to a reduction of the magnetic moment in the B2-phase alloys and that the Fe-Al-type disorder does not significantly affect the magnetic behavior in the Heusler-phase alloys.

We discuss the underlying atomistic mechanism for experimentally observed large tensile ductility in various strongly ordered B2 intermetallic compounds. First-principles calculations demonstrate that all of the compounds exhibit little energy differences between the B2, B27 and B33 phases. These calculations relate observations of ductility in YAg, YCu and ZrCo to shape-memory materials including NiTi. One transformation pathway between the B2 and B33 phases establishes a connection between this phase competition, and stacking faults on the {011}B2 plane. The low energy of such a stacking fault will lead to splitting of the b=<100> dislocations into b/2 partials, observed in ZrCo, TiCo, and in the B19' phase of NiTi. Calculations demonstrate that this pathway is competitive with the traditional pathway for NiTi.

The microstructures and room-temperature tensile properties were examined in the 95% cold-rolled and subsequently heat-treated foils of the boron-free Ni(γ)/Ni3Al(γ') two-phase (Ni-18at.%Al) alloys. The electron backscatter diffraction measurements revealed that the recrystallization started at 873 K/0.5 h and that it completed at 1273 K/0.5 h. While the foils showed no tensile elongation in the cold-rolled state, they became ductile after the heat-treatments at 873 K and above. The tensile elongation increased with the increasing heat-treatment temperature: it reached to 14% at 1273 K/0.5 h. The tensile elongation and the fracture strength were high, compared to those in the γ' single-phase foils. The fracture mode was intergranular, and it changed to a mix of intergranular and transgranular in the foils heat-treated at 1273 K/0.5 h, where the area fraction of crack resistant boundaries such as °1, °3 and °9 was high, 0.63. The high ductility was ascribed to the existence of the ductile γ matrix and to the high fraction of crack-resistant boundaries.

A spinodal alloy, Fe30Ni20Mn25Al25, was produced by casting followed by hot extrusion. The microstructure consisted of coherent, 20-30 nm wide rods of alternating body-centered cubic (b.c.c.) and ordered B2 phases aligned along <100>. The room temperature mechanical properties were determined under compression over a range of strain rates. The as-extruded yield strength, which was strain-rate dependent, was ~1400 MPa. Annealing at 550°C led to the precipitation of large unit cell cubic phase and to an increase in hardness. Post-mortem TEM analysis of the compressed specimens identified dislocations having <111> Burgers vectors.

B2 (CsCl) CoZr intermetallic alloys with different chemical compositions were hot-rolled and subsequently recrystallized to evaluate tensile properties and rolling workability. Co-49.0Zr, -49.5Zr and -50.0Zr alloys showed the B2-matrixed microstructure containing C15 Co2Zr dispersions, while Co-50.5Zr and -51.0Zr alloys showed the B2-matrixed microstructure containing C16 CoZr2 dispersions. These homogenized ingots were successfully hot-rolled without edge cracks, except for the Co-51.0Zr alloy. The tensile tests revealed that the Co-49.5Zr, -50.0Zr and -50.5Zr alloys exhibited a notable tensile ductility at room temperature as well as at elevated temperatures. Moreover, the recrystallized CoZr alloys were cold-rolled up to 70% reduction without intermediate annealing. It was also found that tensile ductility was most prominent in the Co-50.0Zr alloy with the least volume fraction of second phase dispersions in the investigated alloys, suggesting that the B2 phase of CoZr was inherently ductile. Deformation microstructures were characterized by means of XRD and TEM observations. Mechanisms responsible for the observed large tensile ductility of the CoZr alloys were discussed, on the basis of the observed deformation microstructures.

The influence of experimental condition on morphology of FePt and Sm-Co nanoparticles synthesized by sputtering in a relatively high gas pressure has been studied. The sputtering apparatus is equipped with an annealing furnace that enables pre-deposition annealing of the nanoparticles. The effect of the annealing temperature on the ordering to the L10 FePt nanoparticles was also investigated. The morphology of the particles depends on a gas pressure and gas flow rate, but the sensitivity to experimental condition differs between FePt and Sm-Co. The morphology and domain structure of FePt nanoparticle are relatively the same in a wide range of experimental condition, whereas those of Sm-Co nanoparticle are significantly changed by variation of a gas pressure. FePt nanoparticles annealed in the annealing furnace prior to their deposition onto the substrate have the ordered L10 phase, which has an advantage for producing a magnetic recording media.

To obtain deeper understanding of the Ð structure, the formation of the Ð structure in the (bcc¨bcc+Ð) reaction at 873K and 1173K have been investigated by transmission electron microscopy. As for the orientation relationship between the bcc and Ð structures, as a results, both the common first relation of [110]bcc//[110]Ð and three second relations given by α=0°, 33°, and 64° were found in the 1173K annealing, where α is an angle between the [_110]bcc and [001]Ð directions. In the 873K annealing, on the other hand, there was only one second relation with α=0°. Based on the α=0° relation found in both annealing temperatures, the features of atomic shifts in the Ð-structure formation were also discussed.

Based on our analysis of a lot of creep rate-strain curves of PST crystals with the different angles between the lamellar plate and the stress axis, designated as ø, it was confirmed that the creep rate and the creep deformation manner strongly depend on the ø. It was supposed that the predominant creep deformation using γ plate during the transient stage is derived by the fully suppression of the operation of another slip systems not parallel to γ plate through α2 plate. It was also confirmed that the initial stress axes of the PST crystals within the standard stereographic triangle move for the [001]-[111] line, and then turn their directions for [111] pole during the transient stage. This moving manner of the stress axis indicated that the first slip system of [101](111) continues to the area near the [001]-[111] line in the standard stereographic triangle, and then, the second slip system of [110](111) operates. By comparing this moving manner to the creep rate-strain curve, it is suggested that the first slip system of [101](111) operates during the Stage I where the light decrease in the creep rate remains, after that, the second slip system of [110](111) appears and leads to steep decrease in the creep rate. This stage was designated as the Stage II. According to this conception, it is supposed that the strain at the end of the Stage I is directly correlated with the angle from the initial stress axis to the [001]-[111] line in the standard stereographic triangle. In this study, this supposition was confirmed by conducting the creep tests at 1148 K/68.6 MPa using two PST crystals with ø of 31° and 34°. The initial stress axis of the PST crystal with ø of 31° locates nearer to the [001]-[-111] line than that of the PST crystal with ø of 34°. The strain at the end of the Stage I of the PST crystal with ø of 31° is half that of the PST crystal with ø of 34°. By analyzing the inverse pole figures of the creep interrupted PST crystals, it was confirmed that the angle from the initial stress axis to the [001]-[111] line is correlated with the strain of the transient stage.

Stability of raft structure in nickel base superalloys has been examined by using elastic energy calculations based on a microelasticity theory. The numerical calculation method for a structurally heterogeneous system is applied. The results indicate that the raft structure is significantly stabilized by introductions of creep deformations till the critical creep deformation at which the lattice misfit between gamma and gamma-prime phases is completely compensated by creep dislocations. When the magnitude of creep deformations exceed the critical value, the (001) lamellar interfaces become elastically unstable and a tilted lamellar interface become the most stable one. This instability of the 001 raft structure leads a tilted or wavy lamellar interfaces for reducing the internal strain energy, that is a precursor to collapse the raft structure.

We have successfully developed thin foils of boron-free Ni3Al (below 100 μm in thickness) by cold rolling, and recently found that the foils exhibit high catalytic activity for methanol decomposition. A little has been known about catalytic activity in Ni3Al. Even more interestingly, the high catalytic activity appears on flat foils whose surface area is very low. This paper provides a review of the characteristic features of the catalytic properties investigated in my group. Methanol was effectively decomposed into H2 and CO over the foils above 713 K. The production rates of H2 and CO increased with an increase of time during the initial period of reaction, indicating that the Ni3Al foils were spontaneously activated under the reaction conditions. Surface analyses revealed that fine Ni particles dispersed on carbon nanofibers formed on the foils during the reaction. The high catalytic performance of the foils can be attributed to the spontaneous formation of this nanostructure during the reaction.

A series of binary V-B alloys, with compositions spanning the eutectic, were produced by arc melting and drop casting. Microstructural examination revealed that the fully eutectic structure occurs at V-11B rather than V-15B as reported in the V-B phase diagram (all compositions in at.%). The V-11B eutectic was directionally solidified in an optical floating zone furnace, resulting in a composite microstructure consisting of a V matrix and flake or trigonal shaped V3B2 phase. The boride flake spacing (ë) decreases with increasing growth rate (R), following the relation ë2.56R=C, where C is a constant. TEM observations showed that the orientation relationship between the V and V3B2 phases is given by: [001]V // [001]V3B2 and (100)V // (100)V3B2. The growth direction and the V/V3B2 interface are parallel to the [001] direction and (100) planes in the two phases, respectively. Tensile tests were used to investigate the temperature dependence of the strength and ductility of the composite. At temperatures to 600°C, the yield strength of the eutectic is about 140 MPa higher than that of a commonly used vanadium solid-solution alloy, V-4Cr-4Ti. Surprisingly, the eutectic shows 5% tensile ductility at room temperature which increases to 10% as the test temperature is raised to 800°C.

Mechanical properties and phase constitution of an E21-type Ti3AlC-base alloy were investigated by compression tests in a temperature range from room temperature (RT) to 1273K, scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD). The unit cell of E21 Ti3AlC is constructed by ¡§L12 Ti3Al¡¨ and a carbon atom occupying the body-center octahedral-interstitial-site surrounded by the Ti atoms. The nominal composition of the alloy was chosen to be the stoichiometric composition of 60mol%Ti-20mol%Al-20mol%C. The alloy was synthesized by mechanical alloying using high purity elemental powders followed by hot pressing at 1473K for 3hrs. It was found by XRD and SEM that the alloy was mainly composed of E21 Ti3AlC in addition to Cr2AlC-type Ti2AlC precipitates as a second phase. The density of Ti3AlC is calculated to be 4.29g/cm3 based on the lattice parameter of 0.4134nm of E21. The average grain size was 2μm by SEM. By the compression tests, the 0.2% flow stress at the temperature range from RT to 1073K exceeded 1GPa. The yield stress is comparably higher than those of other E21 intermetallic carbides: at 1073K, 1084MPa for Ti3AlC, 50MPa for Mn3AlC and 135MPa for Fe3AlC. Besides, a weak positive temperature dependence of strength was observed where the peak temperature was around 900K. This suggests that a Kear-Wilsdorf type dislocation pinning mechanism may be activated. It is concluded that E21 Ti3AlC-base alloy shows promise for a new high-temperature light-weight structural material.