We have fabricated Ni3Al and NiAl thin films on different substrates by the pulsed laser deposition (PLD) technique. A high energy nanosecond laser beam was directed onto Ni–Al (NiAl, Ni3Al) targets, and the evaporated material was deposited onto substrates placed parallel to the target. The substrate temperature was varied between 300 and 400 °C, and the substrate-target distance was maintained at approximately 5 cm. The films were analyzed using scanning electron microscopy, transmission electron microscopy, x-ray diffraction, and Rutherford backscattering spectrometry. At energy densities slightly above the evaporation threshold, a slight enrichment of Al was observed, while at higher energy densities the film stoichiometry was close (<5%) to the target composition. Barring a few particles, the surface of the films exhibited a smooth morphology. X-ray and TEM results corroborated the formation of Ni3Al and NiAl films from similar target compositions. These films were characterized by small randomly oriented grains with grain size varying between 200 and 400 Å.

AlN powders (particle size = 0.44 ± 0.08 μm) containing no deliberate sintering additives were consolidated to near theoretical density in 5 min at 2003 K (1730 °C) using a Plasma Activated Sintering (PAS) process. PAS is a novel consolidation method that combines a very short time at high temperature with pressure application in a plasma environment. The in situ cleaning ability of powder particle during plasma activated densification leads to enhanced particle sinterability. The densities of undoped AlN specimens that were PAS consolidated at 2003 K for 5 min under 50 MPa pressure ranged from 97.5 to 99.3% of theoretical. The initial submicron particle size of AlN powders was retained in the final microstructure that consisted of polycrystalline grains with an average size of ≍0.77 ± 0.1 μm.

The precise structural characteristics of the amorphous solids that are generated during the dehydration of crystalline MgHPO4 · 3H2O (newberyite) are reported. The results show that a dramatic change in the distribution of phosphate anions (i.e., chains of corner-linked PO4 tetrahedra) occurs during the process of dehydration and that anions up to 13 PO4 tetrahedra in length are formed. The distribution of phosphate anions formed at intermediate stages of the dehydration process was found to be in quantitative agreement with the theory of Parks and Van Wazer.

We have compared the quality of Ba2YCu3O7−δ (BYCO) films grown by the BaF2 process on (100) substrates of the perovskites LaAlO3, LaGaO3, NdAlO3, NdGaO3, LiBaF3, and SrTiO3. The films were grown by coevaporation of Y, Cu, and BaF2 followed by a two-stage anneal. The high temperature stage of the anneal, the part of the process during which the BYCO crystal structure and morphology develop, has been varied. LaAlO3 and SrTiO3 support much better films, both electrically and structurally, than the other substrates. Of the oxides, NdGaO3 supports the worst films, while films on LiBaF3 are nonconducting. These results emphasize the overriding importance of chemical compatibility in determining the suitability of a potential substrate material. Unless this criterion is satisfied, the issue of lattice matching is unimportant.

Epitaxial films of Ba2YCu3O7−δ (BYCO), as thin as 250 Å and with Jc's approaching those for the best in situ grown films, can be formed by coevaporating BaF2, Y, and Cu followed by a two-stage anneal. These results extend the work of R. Feenstra et al. [J. Appl. Phys. 69, 6569 (1991)] for film thicknesses >2000 Å. This involves using low oxygen partial pressure [p(O2) = 4.3 Torr] during the high temperature portion of the anneal, which we vary from Ta = 600 to 950 °C. The BYCO melt line is seen to be the upper limit for Ta. The use of lower p(O2) shifts the window for stable BYCO film growth to lower temperature. The lower growth temperature required for the low p(O2) process allows the formation of smooth films with greater microstructural disorder than for films grown in p(O2) = 740 Torr at higher Ta, resulting in higher Jc values by a factor of four. The relationship between the Ta required to grow films with the strongest pinning force and p(O2) is log [p(O2)] ∝ Ta−1, independent of growth method (in situ or ex situ) over a range of five orders of magnitude in p(O2).

Using Bi-based oxide superconductors of the Bi0.96Pb0.24-xSbxSr1.0Ca 1.1 Cu1.6Oy composition which were prepared by the sol-gel method, production of the high-Tc phase and also microstructures of the high-Tc and the low-Tc phases were investigated using the XRD method and the TEM technique. Two superconducting phases showed good linearities of shrinkages of the a, b, and c lattice parameters as the Sb content increased, and so it has been found that Sb can be included in superconducting crystal structures. However, all shrinkages were below 1%. The activation energy of Sb diffusion was estimated from time dependence of changes of the lattice parameters using the Arrhenius plots. Its energy was from 510 to 593 Kj/mol.

Superconducting YBa2Cu3Ox films were prepared by rf plasma flash evaporation on MgO(100) single crystals. 4 MHz rf Ar–O2 plasma was used and Y–Ba–Cu–O (YBCO) powder as raw material was fed into the plasma. The growth rate of 730 nm/min was achieved. Texture of the grown films varied from a-axis orientation to c-axis with increasing growth temperature and decreasing growth rate. The films without heat treatment exhibited zero resistance temperature (Tc0) more than 77 K. The deposited films using the stoichiometric powder were slightly poor in Y. The sample using Y-rich powder revealed nearly stoichiometric composition and exhibited a Tc0 of 90.6 K and a critical current density (Jc) of 6.8 × 105 A/cm2 at 77 K in zero applied field.

Textured superconducting films of YbBa2Cu3O7−δ were grown on single crystals of MgO (100) and SrTiO3 (100) by oxidation of a liquid alloy precursor. The substrates were coated by dipping them in molten YbBa2Cu3 (m.p. ~870 °C). After removal from the melt, the liquid layers on the substrates were oxidized in pure oxygen to form the tetragonal oxide phase, i.e., YbBa2Cu3O7−δ, then annealed at 500 °C to obtain the superconducting orthorhombic phase of the same compound. The microstructure of the films obtained in this way was found to be related to the nature of the substrate as well as to processing variables that included oxidation temperature and oxidation time. Films grown on MgO (100) showed c-axis texture as well as a random growth structure. Films prepared on SrTiO3 (100) showed either a c-axis texture or a mixture of c-axis and a-axis texture. The superconducting properties of the as-prepared films and the effects of key process parameters on film quality and microstructure are presented and discussed.

Stoichiometric iron nitride layers have been synthesized by high dose, high energy nitrogen implantation into Fe using a two-step implantation process. First, a nitrogen preimplantation at ~100 °C is used to form nitride precipitates. A low temperature is necessary to restrict the nitrogen mobility. Second, 1 MeV implantation at ~300 °C leads to the formation of a stoichiometric γ′–Fe4N layer at the position of the preimplanted N atoms. Growth of this nitride layer proceeds by diffusion of the implanted N through either the α–Fe matrix (for 200 or 500 keV preimplantations) or the nitride layer itself (for 1 MeV preimplantation). During annealing above 350 °C the γ′ layers dissolve in a planar fashion, characterized by an activation energy of 2.3 eV. Phase formation during preimplantation and phase transformations during subsequent annealing or hot implantation can be understood from the thermodynamics for the Fe–N system, while the kinetics of layer growth is influenced by the beam-induced defects. The experiment and model suggest that γ′ is not a thermodynamically stable phase below 310 ± 10 °C and should decompose into α (ferrite) and ∊ nitride.

The solidification behavior of Al62Cu20Co15Si3 and Al61Cu19.5Co14.5Si5 alloys was studied by means of optical metallography, scanning and transmission electron microscopy, energy-dispersive x-ray analysis, powder x-ray diffraction, and differential thermal analysis. Slowly as well as rapidly cooled ingots of both alloys contained a decagonal quasicrystalline phase as the dominant phase with, additionally, several minor crystalline phases. The structure of the rapidly solidified Si-containing alloys was similar to that of the ternary Al65Cu20Co15 alloy. In the slowly solidified alloys the substitution of 3 at. % Al by Si did not change the basic phase constitution. Si was only partially incorporated in the decagonal phase and a significant quantity of Si was found in elemental form. The increase of Si concentration to 5 at. % resulted in the appearance of new minor phases.

Previous studies of a single lot of NiAl powder which had been ground under high intensity conditions in liquid nitrogen (cryomilling) indicated that this processing leads to a high strength, elevated temperature NiAl–AlN composite. Because this was the first known example of the use of the reaction milling process to produce a high temperature composite, the reproducibility of this technique was unknown. Two additional lots of NiAl powder and a lot of a Zr-doped NiAl powder have been cryomilled, and analyses indicate that AlN was formed within a NiAl matrix in all three cases. Compression testing between 1200 K and 1400 K has shown that the deformation resistance of these heats is similar to that of the first lot of NiAl–AlN; thus cryomilling can improve the creep resistance of NiAl by a factor of six. Based on this work, it is concluded that cryomilling of NiAl powder to form high temperature, high strength NiAl–AlN composites is a reproducible process.

Combustion synthesis of elemental powder compacts has been used to produce alloys with compositions corresponding to Al3Ti, Al73Ti24Cr3, and Al67Ti25Cr8. The binary composition exhibits a strong exothermic reaction at ∼665 °C, resulting in formation of single phase Al3Ti with the tetragonal DO22 structure. The heat of formation of the compound at 298 K, δHf(298), was estimated from peak reaction temperature measurements to be −35.0 kJ mol−1. Additions of Cr lowered the reaction initiation temperature and resulted in the formation of intermediate products attributed to Al–Cr reactions. The DO22 structure remained the primary reaction product in Cr-containing alloys. The Cr particles did not completely dissolve during initial reaction; an additional heat treatment at 1200 °C or above was required to homogenize the material, resulting in partial or complete transformation of the DO22 structure to the cubic L12 structure, depending upon Cr content. Homogenization at 1250 °C for 4 h produced material consisting approximately of a 50-50% mixture of the DO22 and L12 structures for Al73Ti24Cr3, and 100% L12 for Al67Ti25Cr8. In all cases, reaction at ambient pressure was accompanied by swelling, resulting in final densities less than 60% of theoretical. Application of external pressure, either during or subsequent to combustion synthesis, produced near theoretical density materials exhibiting a homogeneous and equiaxed microstructure.

The environmental embrittlement for the nearly stoichiometric TiAl compound, the microstructure of which consists of monophase γ with equiaxed grains, was evaluated by tensile tests, to determine the effects of the atmospheres used (vacuum, O2 gas, air, and H2 gas) and the testing temperatures (R.T. to 1173 K). At room temperature, the highest elongation and UTS values were observed in the samples tested in vacuum, while the worst values were observed in the samples tested in H2 gas. Transgranular cleavage fracture was dominant and primarily independent of the environmental media. At intermediate temperatures, the samples tested in vacuum exhibited higher elongation and UTS values than those tested in air. Intergranular fracture became more dominant as temperature increased but was insensitive to the environmental media. Based on these results, the mechanism responsible for the observed environmental embrittlement and the implications were discussed.

MoSi2 is a promising high-temperature material with low density (6.3 g/cm3), high melting point (2020 °C), and good oxidation resistance at temperatures to about 1900 °C. However, in the intermediate temperature range between 400 and 600 °C, it is susceptible to a “pest” reaction which causes catastrophic disintegration by a combination of oxidation and fracture. In this study, we have used polycrystalline MoSi2, produced by arc-casting of the pure elements and by cold and hot pressing of alloy powders, to characterize the pest reaction and to determine the roles of composition, grain or phase boundaries, and physical defects on the oxidation and fracture of specimens exposed to air at 500 °C. It was found that pest disintegration occurs through transport of oxygen into the interior of the specimen along pre-existing cracks and/or pores, where it reacts to form MoO3 and SiO2. The internal stress produced during the formation of MoO3 results in disintegration to powder. Near the stoichiometric ratio, the susceptibility to pest disintegration increases with increasing molybdenum content and with decreasing density. Silicon-rich alloys were able to form protective SiO2 and showed no indication of disintegration, even at densities as low as 60%.

Thermodynamic properties of the melts of several Al–Y and Al–Fe–Y alloys are studied by means of calibrated differential thermal analysis. The results can be used to optimize process parameters of rapid solidification which are important for glass formation in the Al-based alloys. Close examinations of the melt-spun alloys show that the process parameters, particularly the temperature of the melts, will influence not only the amorphicity and the chemical short-range order but also the crystallization process of the glasses. A key point of glass formation in the Al-based alloys is found to be related to the content in the melts of a certain amount of the intermetallic compounds which are gradually dissolved in the premelted α Al matrix.

Artificial multilayers, or microlaminates, composed of alternating layers of Nb and MoSi2 of equal thickness were synthesized by d.c., magnetron sputtering. Four different modulation wavelengths, λ, were studied: 7, 11, 20, and 100 nm. The compositions, periodicities, and microstructures of the microlaminates were characterized by Auger electron spectroscopy and transmission electron microscopy. Structural characterization revealed that the as-deposited Nb layers are polycrystalline, while the MoSi2 layers are amorphous. The hardnesses and elastic moduli of the films were measured using nanoindentation techniques. Neither a supermodulus nor a superhardness effect could be identified in the range of wavelengths investigated; for each of the microlaminates, both the hardness and modulus were found to fall between the bounds set by the properties of the monolithic Nb and MoSi2 films. Nevertheless, a modest but a measurable increase in both hardness and modulus with decreasing wavelength was observed, thus indicating that behavior cannot be entirely described by a simple rule-of-mixtures. The hardness was found to vary linearly with Δ−1/2 in a manner similar to the Hall–Petch relationship. Annealing the microlaminates at 800 °C for 90 min produces significant increases in hardness and modulus due to chemical interaction of the layers.

Synthetic multilayers consisting of periodic layers of the refractory metal Mo and the oxide ceramic Al2O3 have been produced by alternating d.c. and r.f. reactive sputter deposition. Microlaminates with four different modulation wavelength—5, 20, 30, and 100 nm—were investigated in this study. The compositions, periodicities, and microstructures of the microlaminates were characterized by Auger electron spectroscopy, low-angle x-ray diffraction, and transmission electron microscopy, including high resolution lattice imaging and microdiffraction. Transmission electron microscopy from the microlaminates indicated that the as-deposited Mo layers are polycrystalline, while the as-deposited Al2O3 layers are primarily amorphous. The Mo and Al2O3 layers are thermally compatible at 800 °C for 6 h, showing no evidence of atomic interdiffusion between the layers. The mechanical properties of the microlaminates, as well as those of monolithic films of Mo and Al2O3 (i.e., the baseline materials), were investigated using nanoindentation methods. A higher than expected modulus and hardness were observed for the microlaminate with the longest wavelength (100 nm); otherwise the mechanical properties are explainable by a rule-of-mixtures. The enhanced mechanical properties of the 100 nm microlaminate may be attributed to crystallization of the amorphous Al2O3 layers and the evolution of a structural texture within this phase.

We have developed a two-step hot filament chemical vapor deposition method to form polycrystalline films of diamond on Hastelloy substrates. The first step at a lower temperature results in the deposition of a composite layer of carbon, diamond-like carbon, and diamond, which provide nucleation sites for diamond growth in the second step at a higher temperature. To obtain a cleaner amorphous carbon-free diamond film, we introduced an intermediate hydrogen etching step. Using this procedure, we have obtained high quality polycrystalline diamond film on Hastelloy substrates, as characterized by scanning electron microscopy and Raman measurements.

13C cross-polarization (CP) and direct-polarization (DP) spectra of an 83 mg sample of a chemical vapor deposited (CVD) diamond film (combined from 12 separate depositions) have been obtained via dynamic nuclear polarization (DNP) combined with magic-angle spinning (MAS). With DNP, the presence of unpaired electron spins in the sample, measured to be 2 × 1018 spins/g, provides a way to enhance the 13C or the “residual” 1H signal by irradiating the sample with microwaves at or near the electron spin resonance (ESR) Larmor frequency; the interactions between the unpaired electrons and protons or 13C spins lead to a transfer of polarization from the electron spin system to the 1H and/or 13C spin systems. No signal for sp2 hybridized carbons could be observed. The DNP-CP-MAS spectrum, obtained in an experiment in which the DNP-enhanced proton polarization is in turn transferred via CP to the 13C spin system, differs significantly from the DNP-DP-MAS spectrum, in which the 13C spins are directly enhanced.

It now appears generally accepted that the process of stress-induced orientation and graphitization of a thermoset-resin-derived matrix in a carbon-fiber/carbon-matrix (C/C) composite is principally a result of molecular orientation induced during the pyrolysis process as a consequence of the restraint of pyrolysis shrinkage at the fiber/matrix interface by attractive or frictional forces between fiber and matrix. We hypothesize that the critical factor for the formation of lamellar graphite (by subsequent high-temperature heat treatment), instead of fibrillar or isotropic glassy carbon, is a state of multiaxial deformation in the pyrolysis step. Finite-element stress analyses of the relative stresses in the regions of interfilament matrix, as the matrix pyrolyzes from polymer to carbon, reveal patterns of biaxial and triaxial stress consistent with experimental observations of lamellar graphite formation in the matrix by the techniques of optical microscopy, scanning electron microscopy, and transmission electron microscopy. The implications of localized matrix orientation and graphitization for C/C composite properties are discussed in terms of a “duplex” system of composite reinforcement. An example is presented showing crack deflection and blunting at the matrix/matrix-sheath interface produced as a result of such orientation and graphitization.