We have measured enthalpies of formation of YBa2Cu3O7−x, Y2BaCuO5, YBa2Cu4O8, and BaCuO2 using high precision isothermal solution calorimetry. Thermodynamic analysis of the calorimetric data indicates that YBa2Cu3O7−x at the pure-phase composition (1:2:3 cation ratio) is metastable at ≍873 K and 1 atm Po2.

Variations in lattice parameters for materials that form very thin lamellae are analyzed using a thermodynamic model that incorporates surface stress effects. It is predicted that lattice spacing variations should be proportional to the reciprocal of the lamella thickness, in agreement with experimental data for polyethylene, n-paraffins, and a copolymer of tetrafluoroethylene and hexafluoropropylene. The model is then used to calculate the surface stress associated with lamella interfaces in these crystalline materials. The calculated surface stress has the same order of magnitude as a surface tension, but is negative. The model is extended so that surface stresses associated with grain boundaries can be measured in very fine-grained metals and ceramics.

Nitrogen dioxide was used to oxidize nonsuperconducting, powdered YBa2Cu3O6.0 to form a material that exhibits the Meissner effect at liquid nitrogen temperature. Nitrogen dioxide treatment at 200 °C for 70 h results in a mixed-phase material containing superconducting YBa2Cu3O6.9 that exhibits onset of superconductivity at 91.5 K and a midpoint at 88 K. During a 70-h exposure of YBa2Cu3O6 to NO2 at 200 °C, a mixture of oxidation and degradation products is formed, including YBa2Cu3O6.9 (61% by weight) and Ba(NO3)2 (23% by weight). Heating the NO2-treated product to 900 °C results in the evolution of NO, NO2, and O2; cooling the sample and annealing at 400 °C in an O2 stream generates the superconducting oxide.

Working principles are developed as guidelines for the selection and/or design of organometallic polymers for processing fiber precursors to metal oxide fibers. These principles form the basis for the selection of metal carboxylate preceramics as an optimal approach to processing yttrium barium cuprate (123) ceramic superconducting fibers. A variety of candidate yttrium, barium, calcium, strontium, bismuth, and copper metal carboxylates were synthesized. Solubility and empirical rheology tests were conducted to screen these compounds to choose spinnable precursor systems. Simple extrusion studies confirmed that THF solutions of mixtures of yttrium, barium, and copper isobutyrates with some quantity of barium 2-ethyl-hexanoates can be used to successfully form 60–70 μm diameter 123 precursor fibers.

Fifty-two faceted grain boundary segments ([001] tilt boundaries) in clusters of bulk-scale YBa2Cu3O7−x crystals having coincident c-axes were characterized by optical microscopy techniques. Grain boundary orientations were widely distributed. All grain boundaries, except those far from the symmetric condition and those with {110} facets, exhibited well-developed matching of the twin domains across the boundary. It is suggested that this newly reported phenomenon of twin pattern matching occurs due to a local coordination of the tetragonal → orthorhombic transformation strain across grain boundaries and may be beneficial with regard to electrical transport in highly textured polycrystalline material.

An alternative synthetic approach was attempted for the fabrication of the Bi–Ca–Sr–Cu oxide superconductor. In this approach a mixed Sr–Ca–Cu oxide powder was first formed, and the resulting powder was subsequently reacted with Bi2O3. With this reaction scheme, problems associated with the low reactivity of CuO and SrCO3 can be partially removed by converting the mixed oxide/carbonate precursors to the reactive Sr–Ca–Cu compound. An enhanced rate of formation of the high-Tc (110 K) phase was observed in the two-step reaction, and this was explained in terms of the low activation free energy path for the formation of the high-Tc phase, which increased the decomposition rate of the remnant CuO. Under the condition of rapid heating, the formation of the high-Tc phase in the one-step reaction was expedited by the Cu-rich liquid phase. However, the liquid phase caused the formation of an insulating layer between the superconducting grains in spite of its catalytic activity in the high-Tc phase formation.

Fine powders of intermetallic NiAl and Ni3Al were synthesized through organometallic precursors, which were coprecipitated from aqueous solutions of NiCl2 and AlCl3 by the addition of ammonium benzoate and hydradinium monochloride as precipitants. Ni3Al and NiAl were synthesized by a two-step heat treatment of the precursors. The initial step was the thermal decomposition of organic groups to form homogeneous mixtures of Ni3C, amorphous Al2O3, and free C below 1000 °C. The other step was the reaction above 1300 °C to form the intermetallics. Single phase powders of NiAl and Ni3Al with the particle size less than 3 μm were obtained above 1300 and 1400 °C, respectively.

Glancing angle x-ray reflectivity and EXAFS measurements have been made on a series of UHV prepared Al/Ni bilayers with varying amounts of oxygen impurities. These samples show an intrinsic reacted region prior to annealing, and for clean samples further reaction occurs at 250 °C. Oxygen is found to influence strongly the course of the reaction with an effect which depends on its location. A few percent O impurity within the Al film strongly suppresses the grain boundary diffusion path, which allows the growth of a smooth NiAl3 layer. Interfacial O exposures of 60 and 600 Langmuir both inhibit the initial reaction and raise the temperature at which further reaction occurs to as much as 300 °C with an effect which depends on exposure. The thickness of the intrinsic reaction zone is about 60 Å for clean samples, and is nearly eliminated for contaminated interfaces. The results indicate that surface/interface, grain boundary, and bulk diffusion all play important roles in the formation of these interfaces, and that each of these is influenced by O impurities.

Ternary sublattice site occupancy in two L12-structured intermetallic compounds were evaluated by a transmission electron microscope technique called ALCHEMI, or atom site location by channeling enhanced microanalysis, and by x-ray diffractometry, through measuring the relative integrated intensity of fundamental and superlattice x-ray diffraction peaks. The x-ray diffractometry showed that in nickel-rich Ni3Al + Hf hafnium was found to occupy preferentially the aluminum sublattice, and in a multiphase alloy an L12-structured phase with the composition Al74.2Ti19Ni6.8 nickel atoms showed a strong preference for the titanium sublattice. The ALCHEMI data broadly agreed with the x-ray results for Ni3Al but gave completely the opposite result, i.e., a preference of nickel for the titanium sublattice, for Al3Ti. The methods of ALCHEMI and x-ray diffractometry are compared, and it is concluded that ALCHEMI data may be easily convoluted by peak overlap and delocalization effects.

The yield strength and interfacial bonding are properties of interest for understanding void formation in thin film interconnect and subsequent failure of VLSI devices. A method is presented to examine the mechanical properties of thin polycrystalline films attached to substrates by measuring the change in thermal residual stress, due to the difference in coefficient of expansion between the film and substrate, as a function of decreasing temperature of the sample. The yield strengths of passivated 0.5, 1.0, and 2.0 μm thin films of Al–2% Cu on oxidized Si wafer substrates have been determined with this method to be 325, 170, and 120 MPa, respectively. Unpassivated films of the same thicknesses were also examined, but yielding did not occur for these films even though the residual stress reached a value of over 400 MPa. The lack of yielding in the unpassivated samples and the thickness dependence of the passivated samples is attributed to the grain size of these materials, which is less than the film thickness for the unpassivated case and greater than the film thickness after passivation. Debonding occurred in the 2 μm unpassivated sample but in none of the others, indicating a thickness dependence of the energy for delamination.

The microstructure of the ordered intermetallic alloy with a nominal composition of Al66Fe9Ti24 is nearly single-phase L12 structure, with a few second phase agglomerates at some grain corners. Room temperature compression tests showed that this material exhibits a plastic strain of about 11% at fracture. Final fracture of the compression specimens occurred by a shear-off process along a surface oriented about 45 degrees to the compression axis. Fractographic analysis revealed that the fracture is transcrystalline and the fracture mode is mainly quasicleavage plus tearing. Transmission electron microscopy (TEM) was used to explore its deformation mechanisms. The dislocation density was low after homogenization, but is greatly increased during deformation. The deformation mode was found to be 〈110〉 {111} slip instead of twinning as in Al3Ti. The a〈110〉 superdislocations dissociated into two partials of a/3〈211〉-type, bounding a superlattice intrinsic stacking fault (SISF) on the {111} slip plane.

We report x-ray diffraction experiments investigating the lattice expansion due to hydrogen in Nb/Ta superlattices and thin Nb films. For low hydrogen concentrations (cH < 0.09 H/metal), the lattice expands only normal to the plane of the film due to the epitaxial constraints imposed by the substrate. At higher concentrations, corresponding to strains on the order of the critical strains expected for the formation of misfit dislocations, we find a structural instability which leads to the formation of two metal-H phases, one of which has a lattice expansion in the plane of the film. These results differ significantly from the expected phase diagram and properties of the bulk metal-H systems.

We have analyzed the phase relationships in two titanium aluminides containing 3.4 at. % Mo with different aluminum compositions. The alloys were first homogenized in the β field, then cooled continuously at different cooling rates from 80 °C/s to 0.1 °C/s. The continuous cooling transformation diagrams (CCT) show that phase transformations and resulting microstructures are highly dependent on cooling rate. The microstructure consists of ordered α2 (DO19), ordered β0 (B2), and athermal ω (hexagonal) phases. The “tweed microstructure” is observed. The evolution of microhardness was determined as well as the relative partitioning of Al and Mo in (α2', α2) and β0 phases as a function of cooling rate.

In (α + β) titanium alloys, the interface between the α and β phases has been widely studied, and many conflicting results have been published concerning the formation of an interface phase having an hcp or fcc crystalline structure. Several authors consider that this phase is an artifact and consists of a titanium hydride formed during thin foil preparation for TEM examination. This paper reports examinations by TEM and STEM of heat-treated Ti–6Al–4V alloy and two titanium molybdenum aluminides. The formation of an α/β interface phase is discussed as a function of composition heat-treatment and thin foil preparations. Particularly, for Ti–6Al–4V in a nonequilibrium state, a strong concentration gradient was revealed in the α/β interface, and a metastable interface phase enriched in beta-stabilizers with an fcc structure has been clearly characterized.

We have employed the Local Harmonic (LH) model and the Embedded Atom Method (EAM) to examine the structural and thermodynamic properties of a series of twelve [001] twist boundaries in gold for temperatures between 0 K and 700 K. For the majority of the grain boundary misorientations, metastable structures were observed with grain boundary energies that were typically less than 0.1% larger than the stable structures. Four of the twelve grain boundaries underwent first order structural phase transitions as seen by the crossing of the free energy versus temperature curves for the competing structures. Relatively small cusps or inflections in the grain boundary free energy versus misorientation curves were observed at Σ5 (36.87°) and Σ13 (22.62°) at low temperatures, at Σ13 (22.62°) and Σ17 (28.07°) at intermediate temperatures, and at Σ5 (36.87°) and Σ17 (28.07°) at elevated temperatures. A maximum in the grain boundary entropy versus misorientation was observed at Σ17 (28.07°) for all temperatures, and local minima were observed at Σ5 (36.87°) at low temperature and in Σ13 (22.62°) at high temperature. The excess volume associated with the grain boundary shows a roughly linear dependence on grain boundary free energy at each temperature examined. The room-temperature mean-square vibrational amplitude is approximately 25% larger than that for the bulk at the (002) plane adjacent to the boundary and decays to within 2% of the bulk value by the second (002) plane from the boundary. The room-temperature mean-square vibrational amplitude is dominated by the in-plane (parallel to the grain boundary) vibrations at the (002) plane nearest the grain boundary.

This report gives results of a study of the bulk mechanical properties of samples of nanocrystalline Cu and Pd consolidated from powders prepared by inert gas condensation. Fourier analysis x-ray diffraction techniques, used to determine average grain size and mean lattice strains of the as-consolidated samples, show grain sizes in the range of 3–50 nm and lattice strains ranging from 0.02–3%. Sample densities range from 97–72% of the density of a coarse-grained standard. Microhardness of the nanocrystalline samples exceeds that of annealed, coarse-grained samples by a factor of 2–5, despite indications that sample porosity reduces hardness values below the ultimate value. Uniaxial tensile strength of the nanocrystalline samples is similarly elevated above the value of the coarse-grained standard samples. Restrictions on dislocation generation and mobility imposed by ultrafine grain size are believed to be the dominant factor in raising strength. Residual stress may also play a role. Room temperature diffusional creep, predicted to be appreciable in nanocrystalline samples, was not found. Instead, samples appear to show logarithmic creep that is much smaller than the predicted Coble creep.

Fe–Ni–Si–B metallic glasses have been annealed and crystallized using short electrical current pulses. Two types of electrical heat treatment have been used. The first one is an isothermal annealing treatment using a very high initial heating rate while the second one is a thermal spike applied on an amorphous sample held at various initial temperatures. The microstructure of the alloys after heat treatment has been characterized by x-ray diffraction, transmission electron microscopy, and Mössbauer spectroscopy. The thermal and magnetic properties of the samples measured by DSC and hysteresis loop tracer have been studied after the various heat treatments and correlated with the microstructure of the alloys. The crystallization at high temperatures produces the gamma phase only, while at low temperatures, a mixture of the gamma and alpha phases (the alpha phase being predominant) is usually observed. The samples initially held at liquid nitrogen temperature and heat treated with a thermal spike remain amorphous and show improved magnetic properties (lower coercive field and higher induction at saturation) without loss of ductility.

The influence of implanted impurities (B, O, P, Ar, Xe, Pb, and Bi) on the rate of low-temperature (138 °C), solid-phase epitaxial growth (SPEG) of amorphized CoSi2 has been studied. SPEG rates of impurity-implanted CoSi2, as determined from time-resolved reflectivity measurements, were retarded for all impurities compared to that of Si-implanted CoSi2. The extent of retardation varied from a factor of 1.5 for P to 9.4 for Xe. Channeling measurements of impurity-implanted CoSi2 indicated that Xe and Bi atoms were located on nonsubstitutional lattice sites while ∼40% of Pb atoms occupied either substitutional sites or vacant interstitial cation sites following annealing. The presence of impurities did not affect the CoSi2 post-anneal crystalline quality, and no significant impurity diffusion was apparent at 138 °C from secondary-ion mass spectrometry measurements.

The conductivity and photoconductivity are measured on a high-surface-area disordered carbon material, i.e., activated carbon fibers, to investigate their electronic properties. This material is a highly disordered carbon derived from a phenolic precursor, having a huge specific surface area of 1000–2000 m2/g. Our preliminary thermopower measurements show that the dominant carriers are holes at room temperature. The x-ray diffraction pattern reveals that the microstructure is amorphous-like with Lc ≃ 10 Å. The intrinsic electrical conductivity, on the order of 20 S/cm at room temperature, increases by a factor of several with increasing temperature in the range 30–290 K. In contrast, the photoconductivity in vacuum decreases with increasing temperature. The magnitude of the photoconductive signal was reduced by a factor of ten when the sample was exposed to air. The recombination kinetics changes from a monomolecular process at room temperature to a bimolecular process at low temperatures, indicative of an increase in the photocarrier density at low temperatures. The high density of localized states, which limits the motion of carriers and results in a slow recombination process, is responsible for the observed photoconductivity.

Cross-sectional TEM studies of ion implantation induced amorphization in a large number of semiconductors have been performed. Samples of Si, AlAs, GaAs, GaP, GaSb, InP, InAs, and ZnSe were simultaneously implanted at 77 K with 20 keV Si+ at doses between 1 × 1014/cm2 and 1 × 1016/cm2. A dose of 1 × 1015/cm2 minimized the ion beam induced epitaxial crystallization and sputtering effects. The depth of the amorphous layer at this dose was compared with Monte Carlo damage density distribution calculations (TRIM'90). The threshold damage density (TDD) necessary for amorphization was determined for each compound. The values of the threshold damage density vary from as low as 2.4 × 1019 keV/cm3 for InAs up to 7.3 × 1020 keV/cm3 for AlAs. ZnSe never became amorphous and GaSb exhibited an unusual disordering after the highest dose. The values of the threshold damage density for the various compositions were compared with known thermochemical data and several bond energy estimates. No single calculation explained all of the trends observed.