In order to observe the microstructure and morphology of porous titanium -oxide thin film, deposition is performed under a higher Ar gas pressure than is used in the general titanium thin film production method. Black titanium thin film is deposited on stainless steel wire and Cu thin plate at a pressure of about 12 Pa, but lustrous thin film is deposited at lower pressure. The black titanium thin film has a larger apparent thickness than that of the glossy thin film. As a result of scanning electron microscope observation, it is seen that the black thin film has an extremely porous structure and consists of a separated column with periodic step differences on the sides. In this configuration, due to the shadowing effect, the nuclei formed on the substrate periodically grow to form a step. The surface area of the black thin film on the Cu thin plate changes with the bias potential. It has been found that the bias of the small negative is effective in increasing the surface area of the black titanium thin film. These results suggest that porous titanium-oxide thin film can be fabricated by applying the appropriate oxidation process to black titanium thin film composed of separated columns.

In order to develop a process for manufacturing a composite structure of an intermetallic compound foam and a hollow material, the firing and pore form of the Al-Ni precursor in a steel pipe are investigated. When the Al-Ni precursor is foamed in a hollow pipe, if the temperature distribution inside the precursor is uneven, the pore shape distribution becomes uneven. In free foaming, no anisotropy is observed in the foaming direction and the pore shape is isotropic. However, in the hollow pipe, the pipe expands in the pipe axis direction and fills the pipe. The interfacial adhesion between Al3Ni foam and steel pipe is excellent, and interfacial pore and reaction layer are not observed by SEM. In free foaming, the porosity is 90 %, but it decreases to about 80 % in the foam in the pipe. In the pipe foaming, most of the pore shape appears elongated in the pipe direction in the vicinity of the pipe, and this tendency is more remarkable when the inside pipe diameter is small. It can be seen that the pore size of the foam sample in the pipe is larger than that of free foam, because coarse pores remain after solidification of the foam because the shape of the foam is supported by the pipe. The vertical/horizontal length ratio expands along the pipe axis direction by foaming in the pipe, and therefore circularity is reduced.

Structural and mechanical effects of the dynamical precipitation in two copper-base alloys have been investigated over a wide range of deformation temperatures. Basing upon the information gained during the experiment, also some general conclusion may be formulated. A one concerns the nature of dynamic precipitation(DP). Under this term it is commonly understood decomposition of a supersaturated solid solution during plastic straining. The process may, however, proceed in two different ways. It may be a homogeneous one from the point of view of distribution and morphological aspect of particles or it may lead to substantial difference in shape, size and particles distribution. The effect is controlled by the mode of deformation. Hence it seems to be reasonable to distinguish DP during homogeneous deformation from that which takes place in heterogeneously deformed alloy. In the first case the process can be analyzed solely in terms of particle-dislocation-particle interrelation. Much more complex problem we are facing in heterogeneously deforming alloy. Deformation bands and specific arrangement of dislocations in form of pile-ups at grain boundaries generate additional driving force and additional nucleation sites for precipitation. Along with heterogeneous precipitation, there is a homogeneous precipitation in areas between bands of coarse slip which also deform but at much smaller rate. This form of decomposition is responsible for a specially high hardening rate during high temperature straining and for thermally stable product of the decomposition of alloy.

Intermetallic compound matrix composites have been expected to be established as high temperature structural components. Ni3Al is a representative intermetallic alloy, which has excellent ductility even at room temperature by adding certain alloying elements. Ni3Al matrix composites with aluminum oxide particles, which are formed by the in-situ reaction between the alloy and aluminum borate whiskers, are fabricated by a powder metallurgical method. The addition of aluminum borate whiskers disperses the synthetic aluminum oxide particles during sintering and dramatically increases the strength of the composite. The uniform dispersion of reaction synthesized aluminum oxide particles and the uniform solution of boron in the matrix seem to play an important role in the improvement in strength. There is a dramatic increase in strength with the addition of the whisker, and the maximum value is obtained at a 10 vol% addition of whisker. The Ni3Al composite with 10 vol% aluminum oxide particles 0.3 μm in size and with 0.1 wt% boron powder fabricated by the conventional powder metallurgical process does not have such high strength because of inhomogeneous distribution of aluminum oxide particles and of boron. The tensile strength of the Ni3Al with a 10 vol% aluminum borate whisker reaches more than twice the value, 930 MPa, of the parent alloy. No third phase is observed between the aluminum oxide and the matrix.

MA Al alloys are examined to determine the effects of alloying of Mg and Cu and rolling on tensile deformation behavior at 748 K over a wide strain rate range(10−4-103/s). A powder metallurgy aluminum alloy produced from mechanically alloyed pure Al powder exhibits only a small elongation-to-failure(εf < ~50%) in high temperature(748 K) tensile deformation at high strain rates( = 1-102/s). εf in MA Al-0.5~4.0Mg alloys increases slightly with Mg content(εf = ~140% at 4 mass%). Combined addition of Mg and Cu(MA Al-1.5%Mg-4.0%Cu) is very effective for the occurrence of superplasticity(εf > 500%). Warm-rolling(at 393-492 K) tends to raise εf. Lowering the rolling-temperature is effective for increasing the ductility. The effect is rather weak in MA pure Al and MA Al-Mg alloys, but much larger in the MA Al-1.5%Mg-4.0%Cu alloy. Additions of Mg and Cu and warm-rolling of the alloy cause a remarkable reduction in the logarithm of the peak flow stress at low strain rates ( < ~1/s) and sharpening of microstructure and smoothening of grain boundaries. Additions of Mg and Cu make the strain rate sensitivity(the m value) larger at high strain rates, and the warm-rolling may make the grain boundary sliding easier with less cavitation. Grain boundary facets are observed on the fracture surface when εf is large, indicating the operation of grain boundary sliding to a large extent during superplastic deformation.

Binary Ti-Al alloys below 51.0 mass%Al content exhibit a breakaway, transferring from parabolic to linear rate law. The second Al2O3 layer might have some protectiveness before breakaway. Ti-63.1 mass%Al oxidized at 1173 K under parabolic law. Breakaway oxidation is observed in every alloy, except for Ti-63.1 mass%Al. After breakaway, oxidation rates of the binary TiAl alloys below 34.5 mass%Al obey almost linear kinetics. The corrosion rate of Ti-63.1 mass%Al appears to be almost parabolic. As content greater than 63.0 mass% is found to be necessary to form a protective alumina film. Addition of Mo improves the oxidation resistance dramatically. No breakaway is observed at 1123 K, and breakaway is delayed by Mo addition at 1173 K. At 1123 K, no breakaway, but a parabolic increase in mass gain, are observed in the Mo-added TiAl alloys. The binary Ti-34.5 mass%Al exhibits a transfer from parabolic to linear kinetics. At 1173 K, the binary alloys show vary fast linear oxidation and even the Mo-added alloys exhibit breakaway oxidation. The 2.0 mass%Mo-added TiAl exhibits a slope between linear and parabolic. At values of 4.0 and 6.0 mass% added TiAl alloys, slightly larger rates are observed than those for the parabolic rate law, even after breakaway. On those alloys, the second Al2O3 layer appears to be persistently continuous. Oxidation resistance is considerably degraded by the addition of Mn. Mn appears to have the effect of breaking the continuity of the second Al2O3 layer.

Crystal structure of the L12 type (Al,X)3Ti alloy (X = Cr,Cu) is analyzed by X-ray diffractometry and the nonuniform strain behavior at high temperature is investigated. The lattice constants for the L12 type (Al,X)3Ti alloys decrease in the order of the atomic number of the substituted atom X, and the hardness tends to increase. In a compressive test at around 473K for Al67.5Ti25Cr7.5, Al65Ti25Cr10 and Al62.5Ti25Cu12.5 alloys, it is found that the stress-strain curves showed serration, and deformation rate dependence appeared. It is assumed that the generation of serration is due to dynamic strain aging caused by the diffusion of solute atoms. As a result, activation energy of 60-95 kJ/mol is obtained. This process does not require direct involvement. In order to investigate the generation of serrations in detail, compression tests are carried out under various conditions. As a result, in the strain rate range of this experiment, serration is found to occur after 470K at a certain critical strain. The critical strain increases as the strain rate increases at constant temperature, and the critical strain tends to decrease as temperature rises under constant strain rate. This tendency is common to all alloys produced. In the case of this alloy system, the serration at around 473K corresponds to the case in which the dislocation velocity is faster than the diffusion rate of interstitial solute atoms at low temperature.

In order to increase the efficiency of the sputtering method widely used in thin film fabrication, a dc sputtering apparatus which supplies both high frequency and magnetic field from the outside was fabricated, and cobalt thin film was fabricated using this apparatus. The apparatus can independently control the applied voltage, the target-substrate distance, and the target current, which are important parameters in the sputtering method, so that a stable glow discharge is obtained even at a low gas pressure of 10−3 Torr. The fabrication conditions using the sputtering method were mainly performed in Ar+O2 mixed gas containing about 0.6% oxygen gas under various Ar gas pressures of 1 to 30 mTorr. The microstructure of Co thin films deposited using this apparatus was examined by electron diffraction pattern and X-ray techniques. The magnetic properties were investigated by measuring the magnetization curves. The microstructure and magnetic properties of Co thin films depend on the discharge gas pressure. The thin film fabricated at high gas pressure showed a columnar structure containing a large amount of the third phase in the boundary region and the thin film formed at low gas pressure showed little or no columnar structure. The coercivity in the plane was slightly larger than that in the latter case.

N-type porous silicon (PS) layers and thermally oxidized PS layers have been characterized by various measuring techniques such as photoluminescence (PL), Raman spectroscopy, IR, HRSEM and transmittance measurements. The top surface of PS layer shows a stronger photoluminescence peak than its bottom part, and this is ascribed to the difference in number of fine silicon particles of 2~3 nm in diameter. Observed characteristics of PL spectra are explained in terms of microstructures in the n-type PS layers. Common features for both p-type and n-type PS layers are as follows: the parts which can emit visible photoluminescence are not amorphous, but crystalline, and such parts are composed of nanocrystallites of several nm’s whose orientations are slightly different from Si substrate, and such fine silicon particles absorb much hydrogen atoms near the surfaces. Light emission is strongly dependent on such fine silicon particles. Photoluminescence is due to charge carrier confinement in such three dimensional structure (sponge-like structure). Characteristics of visible light emission from ntype PS can be explained in terms of modification of band structure accompanied by bandgap widening and localized levels in bandstructure. It is also shown that hydrogen and oxygen atoms existing on residual silicon parts play an important role on emission stability.

In this study, we investigated the overpotential of precipitation related to the catalytic activity of electrodes on the initial process of electrodeposition of Co and Co-Ni alloys on polycrystalline Cu substrates. In the case of Co electrodeposition, the surface morphology and the magnetic property change depending on the film thickness, and the relationship with the electrode potential fluctuation was shown. Initially, the deposition potential(−170 mV) of the Cu electrode as a substrate was shown, the electrode potential(Edep) at the Ton of electrodeposition and the deposition potential(−600 mV) of the surface of the electrodeposited Co film after Toff and when the pulse current was completed were shown. No significant change in the electrode potential value was observed when the pulse current was energized. However, in a range of number of pulses up to 5, there was a small fluctuation in the values of Edep and Eimm. In addition, in the Co-Ni alloy electrodeposition, the deposition potential(−280 mV) of the Cu electrode as the substrate exhibited the deposition potential(−615 mV) of the electrodeposited Co-Ni alloy after pulsed current application, the Edep of electrodeposition at the Ton of each pulse and the Eimm at the Toff varied greatly each time the pulse current was applied. From 20 % to less than 90% of the Co content of the thin film was continuously changed, and the value was constant at a pulse number of 100 or more. In any case, it was found that the shape of the substrate had a great influence.

Unidirectionally solidified TiAl alloys were prepared by optically-heated floating zone method at growth rates of 10 to 70 mm/h in flowing argon. The microstructures and tensile properties of these crystal bars were found to depend strongly on the growth rate and alloy composition. TiAl alloys with composition of 47 and 50 at.%Al grown under the condition of 10 mm/h showed Ti3Al(α2)/TiAl(γ) layer structures similar to single crystals. As the growth rate increased, the alloys with 47 and 50 at.%Al compositions showed columnar-grain structures. However, the alloys fabricated under the condition of 10 mm/ h had a layered structure, but the alloy with increased growth rate consisted of γ single phase grains. The alloy with a 53 at.%Al composition showed a γ single phase regardless of the growth rate. Room-temperature tensile tests of these alloys revealed that the columnar-grained material consisting of the layered structure showed a tensile ductility of larger than 4 % and relatively high strength. The high strength is caused by stress concentration at the grain boundaries; this enhances the secondary slip or deformation twinning across the layered structure in the vicinity of the grain boundaries, resulting in the appreciable ductility.

Binary Ti-Al alloys containing 50 to 60 atomic percent aluminum are rapidly solidified by hammer anvil method under an argon atmosphere. Constituent phases in each alloy are identified by X-ray diffractometry and microstructures of the alloys are investigated using a transmission electron microscope. In alloys with aluminum content between 50 and 54 percent, a second phase exists besides TiAl(γ); this second phase is identified as Ti3Al(α2). The α2 phase is observed in two types of morphology. One is as fine lamellar alternating with γ and the other is as a particle. It is concluded that the existence of a metastable phase with the morphologies stated above should arise from a higher quenching rate attained by the hammer anvil method as compared to the conventional roll or splat-quench method. Implications of the above observation are discussed with respect to the phase relations in the Ti-Al binary system; these implications are still controversial in many respects.

Grain morphology, phase stability and mechanical properties in binary Ti-Al alloys containing 43-52 mo1% Al have been investigated. Isothermal forging was used to control the grain sizes of these alloys in the range of 5 to 350 μm. Grain morphology and volume fraction of α2 phase were observed by optical metallography and scanning electron microscopy. Compressive properties were evaluated at room temperature, 1070 K, and 1270 K in an argon atmosphere. Work hardening is significant at room temperature, but it hardly took place at 1070 K and 1270 K because of dynamical recrystallization. The grain morphologies were determined as functions of aluminum content and processing conditions. The transus curve of α and α+γ shifted more to the aluminum-rich side than was the case in McCullough’s phase diagram. Flow stress at room temperature depends strongly on the volume fraction of the α2 phase and the grain size, whereas flow stress at 1070 K is insensitive to the alloy composition or the grain size, and flow stress at 1270 K depends mainly on the grain size. The α2 phase in the alloys does not increase the proof stress at high temperatures. These observations indicate that improvement of both the proof stress at high temperature and the room temperature ductility should be achieved to obtain slightly Ti-rich TiAl base alloys.

Tensile tests and creep tests were carried out at high temperatures on an Al-Al4C3 alloy prepared by mechanical alloying technique. The material contains about 2.0 % carbon and 0.9 % oxygen in mass percent, and the volume fractions of Al4C3 and Al2O3 particles are estimated at 7.4 and 1.4 %, respectively, from the chemical composition. Minimum creep rate decreased steeply near two critical stresses, σcl (the lower critical stress) and σcu (the upper critical stress), with decreasing applied stress at temperatures below 723 K. Instantaneous plastic strain was observed in creep tests above a critical stress, σci, at each test temperature. σcu and σci were fairly close to the 0.2% proof stress obtained by tensile tests at each test temperature. It is thought that σcl and σcu correspond to the microscopic yield stress and the macroscopic yield stress, respectively. The lower critical stress corresponds to the local yield stress needed for dislocations to move in the soft region within subgrains. The creep strain in the low stress range below 723 K arises mainly from the local deformation of the soft region. The upper critical stress is equivalent to the macroscopic yield stress necessary for dislocations within subgrains or in subboundaries; this stress can extensively move beyond subboundaries under a stress above the critical point to yield a macroscopic deformation. At higher temperatures above 773 K, the influence of the diffusional creep increases and the stress exponent of the creep rate decreases.

Ni-C composite films were prepared by co-deposition using a combined technique of plasma CVD and ion beam sputtering deposition. Depending on the deposition conditions, Ni-C thin films manifested three kinds of microstructure: (1) nanocrystallites of non-equilibrium carbide of nickel, (2) amorphous Ni-C film, and (3) granular Ni-C film. The electrical resistivity was also found to vary from about 102 μΩcm for the carbide films to about 104 μΩcm for the amorphous Ni-C films. The Ni-C films deposited at ambient temperatures showed very low TCR values compared with that of metallic nickel film, and all the films showed ohmic characterization, even those in the amorphous state with very high resistivity. The TCR value decreased slightly with increasing of the flow rate of CH4. For the films deposited at 200 oC, TCR decreased with increasing CH4 flow rate; especially, it changed sign from positive to negative at a CH4 flow rate of 0.35 sccm. By increasing the CH4 flow rate, the amorphous component in the film increased; thus, the portion of Ni3C grains separated from each other became larger, and the contribution to electrical conductivity due to thermally activated tunneling became dominant. This also accounts for the sign change of TCR when the filme was deposited at higher flow rate of CH4. The microstructures of the Ni-C films deposited in these ways range from amorphous Ni-C alloy to granular structures with Ni3C nanocrystallites. These films are characterized by high resistivity and low TCR values; the electrical properties can be adjusted over a wide range by controlling the microstructures and compositions of the films.

Ti films were deposited on glass substrates under various preparation conditions in a chamber of two-facing-target type dc sputtering; after deposition, the electric resistivity values were measured using a conventional four-probe method. Crystallographic orientations and microstructures, including the texture and columnar structure, were also investigated for the Ti films. The morphological features, including the columnar structures and surface roughness, are well explained on the basis of Thornton’s zone model. The electric resistivity and the thermal coefficient of the resistivity vary with the sputtering gas pressure. The minimum value of resistivity was around 0.4 Pa for both the 0.5 μm and 3.0 μm thick films; the apparent tendencies are almost the same for the two films, with a small difference in resistivity because of the different film thicknesses. The films deposited at high gas pressures show higher resistivities. The maximum of TCR is also around 0.4 Pa, which is the same as that obtained from the relationship between the resistivity and the gas pressure. The lattice spacing also decreases with increasing sputtering gas pressure for both the 0.5 μm and 3.0 μm thick films. Because they are strongly related to the sputtering gas pressures for Ti films that have a crystallographic anisotropy that is different from cubic symmetry, these changes are well explained on the basis of the film microstructures. It is shown that resistivity measurement can serve as a promising monitor for microstructures in sputtered Ti films.

The high temperature deformation behavior of Ni3Al and Ni3(Al,Mo) single crystals that were oriented near <112> was investigated at low strain rates in the temperature range above the flow stress peak temperature. Three types of behavior were found under the present experimental conditions. In the relatively high strain rate region, the strain rate dependence of the flow stress is small, and the deformation may be controlled by the dislocation glide mainly on the {001} slip plane in both crystals. At low strain rates, the octahedral glide is still active in Ni3Al above the peak temperature, but the active slip system in Ni3(Al,Mo) changes from octahedral glide to cube glide at the peak temperature. These results suggest that the deformation rate controlling mechanism of Ni3Al is viscous glide of dislocations by the <110>{111} slip, whereas that of Ni3(Al,Mo) is a recovery process of dislocation climb in the substructures formed by the <110>{001} slip. The results of TEM observation show that the characteristics of dislocation structures are uniform distribution in Ni3Al and subboundary formation in Ni3(Al,Mo). Activation energies for deformation in Ni3Al and Ni3(Al,Mo) were obtained in the low strain rate region. The values of the activation energy are 360 kJ/mol for Ni3Al and 300 kJ/mol for Ni3(Al,Mo).

Morphology and formation processes of lamellar grain boundaries in titanium rich binary TiAl intermetallics were studied. TiAl alloys containing aluminum content of 44 to 48 at.% were induction-heated to 1723 K followed by helium-gasquenching at various temperatures. For the Ti-44%Al, few lamellae were observed in samples quenched from higher than 1473 K. Although small peaks of beta phase were detected using X-ray diffraction, only the ordered hexagonal phase (α2) with clear APB contrast was observed in TEM observation. For the Ti-48 at.%Al alloy, almost no lamellar structure, and straight grain boundaries were observed in samples quenched from higher than 1623 K. The formation of lamellae along grain boundaries was observed in the sample quenched from 1573 K. The fully lamellar microstructures with serrated boundaries were observed in samples quenched from lower than 1473 K. It was found that the formation of γ platelets took place at higher temperatures in Ti-48 at.%Al than in Ti-44 at.%Al. Although the size of the serration is different, serrated lamellar grain boundaries could be obtained for all alloy compositions employed. The serration appeared to be due to the grain boundary migration induced by precipitation and growth of γ. Differences in transformation characteristics with aluminum content are discussed.

The fatigue strength of a nickel-base superalloy was studied. Stress-controlled fatigue tests were carried out at 700 oC and 5 Hz using triangular wave forms. In this study, two kinds of testing procedures were adopted. One is the conventional tension-zero fatigue test(R = 0). The other was a procedure in which the maximum stress was held at 1000 MPa and the minimum stress was diverse from zero to 1000 MPa at 24 and 700 oC. The results of the fatigue tests at 700 oC indicate that the fracture mechanism changed according to both the mean stress and the stress range. At a higher stress range, γ ' precipitates are sheared by a/2<110> dislocation pairs coupled by APB. Therefore, in a large stress range, the deformation occurred by shearing of γ ' by a/2<110> dislocations, which brought about crystallographic shear fracture. As the stress range was decreased, the fracture mode gradually changed from crystallographic shear fracture to gradual growth of fatigue cracks. At an intermediate stress range, as it became more difficult for a/2<110> dislocation pairs to shear γ ' particles, cracks started to propagate in the matrix, avoiding the harder γ ' particles. High mean stress induced creep deformation, that is, γ ' particles were sheared by {111}<112> slip systems, which led to the formation of stacking faults in the precipitates. Thus, the change in fracture mechanism brought about the inversion of the S-N curves.

Fundamental studies of microstructural changes and high temperature deformation of titanium aluminide (TiAl) were conducted from the view point of the effect of Al content in order to develop the manufacturing process of TiAl. Microstructures in an as cast state consisted mainly of lamellar structure irrespective of Al content. By homogenization at 1473 K, the microstructures of Ti-49Al and Ti-51Al were transformed into an equiaxial structure which was composed of γ-TiAl, while the lamellar structure that was observed in Ti-46Al and Ti-47Al was much more stable. We found that the reduction of Al content suppressed the formation of equiaxial grains and resulted in a microstructure of only a lamellar structure. On Ti-49Al and Ti-51Al, dynamic recrystallization occurred during high temperature deformation, and the microstructure was transformed into a fine equiaxial one, while the microstructures of Ti-46Al and Ti-47Al contained few recrystallized grains and consisted mainly of a deformed lamellar structure. We observed that on the low-Al alloys the lamellar structure under hard mode deformation conditions deformed as kink observed B2-NiAl. High temperature deformation characteristics of TiAl were strongly affected by Al content. An increase of Al content resulted in a decrease of peak stress and activation energy for plastic deformation and an increase of the recrystallization ratio in TiAl.