We report the development of a reaction technique which yields ceramic Nd1.85Ce0.15CuO4−y with macroscopically uniform concentrations of Ce and O. Under appropriate argon annealing conditions, samples exhibiting bulk superconductivity as gauged by resistive transition width and diamagnetic shielding are obtained. In addition. metallic behavior, indicated by positive dp/dT above Tc, is obtained for the normal state.

Amorphous lead iron tungstate was prepared from the melt by twin-roller quenching. The rapidly solidified material was characterized in terms of density, x-ray diffraction, differential thermal analysis, and electrical properties. Results are given for the amorphous-crystalline transformation.

A transmission electron microscopy study of a post-annealed YBa2Cu3O7−x thin film shows that extra Cu–O planes within the structure can aggregate as stacking faults to form a defect microstructure rather than forming the well-ordered Y2Ba4Cu8O16 phase. Interaction of the stacking faults with the surrounding matrix results in strain effects and microstructural variations which may hinder ordering as well as influencing superconducting properties if occurring in higher concentration. When viewed normal to the plane of the film, the boundaries of the stacking faults can be imaged as dislocation-like defects, indicating the size and shape of the stacking faults and their relationship to other defects such as twins and second phase precipitates.

The kinetics of the solid-state reaction Y2BaCuO5 + 3BaCuO2 + 2CuO ⇉ 2YBa2Cu3O6.5−x + xO2 was studied by using x-ray diffractometric and thermogravimetric analyses. Both analyses established that the reaction was well described by the kinetic equation: 1 − 3(1 − F)2/3 + 2(1 − F) = k0 exp(− E/RT)t, where F is the fractional conversion of a calcined powder, E is 520 kcal/molc and, for a rcactant mixture with an average particle size of 3 μm, k0 is 2.03 ⊠ 1092 min−1. An unreacted-core shrinking model was proposed to obtain the particle-size dependence of the reaction, and predicted that the pre-exponential constant k0 changed with reactant particle size by k0 = 2.03 ⊠ 1092(3/d)2 exp(4/d − 4/3), where d is the average reactant particle size in μm.

Acoustic emission from sintered ceramic YBa2Cu3O7−x (YBCO) superconductor pellets provides a direct measure of microcracking behavior during processing. By detection and statistical analysis of acoustic events, the effects of cooling rates, processing atmosphere, average grain size, additives, and grain alignment on microcracking in YBCO have been studied. The onset temperature and duration of acoustic emission during cooling correlate well with the oxygen partial pressure in the furnace. Rapid changes in oxygen partial pressure at constant temperature produce acoustic emission that is characteristic of microcracking. A reported critical grain size for microcracking in sintered polycrystalline YBCO of about 1 μm has been confirmed. Two superconducting compounds, YSrBaCu3O7−x and LaBaCaCu3O7−x with the 123 structure but with smaller crystallographic anisotropy were also examined. Recommendations are made for minimizing microcracking during processing of superconducting ceramics.

Comparison of superconducting thin films of Bi–Sr–Ca–Cu–O deposited by laser ablation from a melt-quenched, amorphous, nonsuperconducting target and a polycrystalline sintered superconducting target shows that they have similar superconducting properties, but the melt-quenched target yields a much smoother film. Additionally, the melt-quenched target is much easier to prepare with target preparation time reduced by a factor of twenty-five.

A relationship between continuum mechanical internal stress variables, kinetic back stress, isotropic drag stress, and microscopic local stresses in the dislocation cell interior and cell walls, is developed based upon Mughrabi's composite model of deformation of heterogeneous microstructure during cyclic deformation in cell forming metals. The experimental data on the evolution of kinematic back stress and isotropic drag stress during cyclic deformation of Cu along with TEM measurements of cell diameter and cell width are utilized to determine the evolution of mobile and immobile dislocation densities in the cell interior and cell walls, respectively, as a function of the number of cycles. The range of values obtained is in agreement with the available experimental data.

We report a first observation, of the behavior of clusters of deuterium atoms confined in a lattice vacancy in a Pd crystal, either at equilibrium or under the influence of externally applied lattice strains. Molecular dynamics simulations have been performed on both Pd perfect crystals and Pd crystals with a single vacancy, showing the energetic behavior and the dynamical values of the interatomic distance among deuterium atoms belonging to clusters of different sizes confined within the vacancy. At low temperatures, the smallest interatomic D-D distances are of the order of the D2 molecular bond length and are obtained during the transitory regimes induced by hydrostatic strains applied to the lattice.

Indentation load relaxation (ILR) experiments with indentation depths in the submicron range are described. Under appropriate conditions, the ILR data are found to yield flow curves of the same shape as those based on conventional load relaxation data. Variations in flow properties as a function of depth in submicron metal films deposited on a hard substrate are detected by the experiments described.

The one-electron theory of metals is applied to the calculation of stacking fault energies in face-centered cubic metals. The extreme difficulties in calculating fault energies of the order of 0.01 eV/(interface unit-cell area) are overcome by applying the Force theorem and using the layer–Korringer–Kohn–Rostoker method to determine the charge density of isolated defects. A simple scheme is presented for accommodating deviations from charge neutrality inherent in this approach. The agreement between theoretical and experimental values for the stacking fault energy is generally good, with contributions localized to within three atomic planes of the fault, but suggest the quoted value for Rh is a significant overestimation.

Detailed Fourier line shape analyses considering x-ray diffraction profiles from fault unaffected 10.0, 00.2, 11.0, 20.0, 11.2, and 00.4 reflections and fault affected 10.1, 10.2, 10.3, 20.1, 20.2, 10.4, and 20.3 reflections have been performed on three magnesium base hexagonal alloys used extensively in the aircraft industry. The first of the three alloys (Mg–Al–Mn, Alloy I) had the nominal composition in wt.% of Al-8.3, Mn-0.35, Si-0.2, Cu-0.12, Fe-0.2, and other 0.01; the second alloy (Mg–Zn–Mn, Alloy II) had the nominal composition in wt.% of Zn-4.0, Mn-0.15, Si-0.01, Cu-0.03, Fe-0.01, Zr-0.70, and rare earth elements-1.50; and the last of the alloys (Mg–Zn–Al, Alloy III) had the nominal composition in wt.% of Zn-4.3, Al-0.15, Mn-0.01, Si-0.03, Cu-0.01, Ni-0.005, Zr-0.6, and rare earth-1.4. The microstructural parameters determined in these analyses indicated the average domain size in alloys I, II, and III as 208 Å, 314 Å, and 400 Å, respectively. The deformation fault densities, α, in these alloy systems (∼54 ⊠ 10−3, 35 ⊠ 10−3, and 28 ⊠ 10−3, respectively, in alloys I, II, and III) were found to be appreciably high compared to the earlier work on pure magnesium (0.63 ⊠ 10−3). The deformation twin fault density, β, which was found to be negligible in pure magnesium (∼0.21 ⊠ 10−3), was found to be negative here, also indicating the negligible presence of twin faults in these alloys. These results establish that on cold work the solutes introduce deformation stacking faults in an appreciable quantity in magnesium which is not normally susceptible to faulting when in pure form. Of these three alloys, however, Alloy I (Mg–Al–Mn) was found to be the most prone to deformation faulting.

Samples of CeSi1.86 which exhibit Kondo behavior are shown by neutron powder diffraction and transmission electron microscopy to consist of two closely related tetragonal phases. The primary phase is of the ThSi2 structure type with some vacancies in the silicon sublattice. The second phase presents an ordering of these vacancies. These two phases coexist at low temperature, but the abundance of the second phase increases with decreasing temperature. Neutron diffraction measurements and TEM experiments show that the phase separation occurs reversibly around 260 K, in close relation with an anomaly in the transport properties. The presence of a hysteresis indicates that we are dealing with a first order transition.

The nucleation and growth kinetics of NiSi2 precipitation in amorphous silicon thin films ion implanted with nickel was investigated using scanning transmission electron microscopy. It was found that the nucleation rate could be approximately described by a delta function at time t = 0 when the films were annealed between 325 and 400 °C. The growth kinetics of the precipitates at these temperatures were described by r ∝ tn, where r was the average radius and n was about 1/3. This behavior is consistent with models for growth of three-dimensional particles in a two-dimensional diffusion field. It was also found that the implanted amorphous films displayed an enhanced rate of single crystal silicon formation, apparently catalyzed by migrating silicide precipitates.

Nearly single-phase thin films of three different Pt–Ga intermetallic compounds have been grown on GaAs(001) by co-deposition of Pt and Ga. The resultant films have been annealed at various temperatures and then characterized using x-ray two-theta diffractometry (XRD), Auger electron spectroscopy (AES), and x-ray photoemission spectroscopy (XPS). The XRD results showed that PtGa2 and PtGa thin films are chemically stable on GaAs under one atmosphere of N2 up to 800 °C and 600 °C, respectively, but thin films of Pt2Ga react with GaAs at temperatures as low as 200 °C to form phases with higher Ga concentration PtAs2. The XRD patterns also revealed that the crystallite orientation and texture of the films were dependent on annealing temperature. Segregation of Ga to the surfaces of the films upon annealing was also observed by both AES and XPS. The results demonstrated that the as-deposited films of PtGa2 and PtGa were kinetically stabilized with respect to possible chemical reactions with the GaAs substrates that evolve gaseous As species during open system annealing.

Phase equilibria in the ternary systems M–Si–N and M–B–N (M = Cu, Ag, Au, Zn, Cd, Al, In, Tl, Sn, Pb, Sb, and Bi) at temperatures 50–100 °C below the melting point of the metal components were investigated by means of x-ray powder analysis and are represented in the form of isothermal sections. No ternary compound formation was observed in any of the combinations M–Si–N and M–B–N. Silicon nitride and boron nitride, respectively, coexist with all metals investigated and with all binary compounds stable at the chosen temperatures. From unit cell dimensions negligible mutual solid solubilities are indicated between Si3N4 or BN and the metal components.

A variety of materials of the general type A2BB′O6 that have an ordered perovskite structure have been prepared and examined as possible substrate candidates for high Tc superconducting films. Materials containing either Ca or Sr as the A cation and either Ga or Al in combination with Nb or Ta as the B and B′ cations have been shown to be congruent melting compounds. These compounds have melting points easily accessible using conventional rf heating techniques and are therefore materials that could possibly be grown in bulk form using the Czochralski growth technique.

High temperature forming of a fine-grain ceramic is demonstrated by a series of extrusion experiments with fine-grain ZrO2, 3 mole% Y2O3. Piston velocities, ranging up to 5 mm/min (for a die with an initial diameter of 30 mm and a final diameter of 10 mm), can be achieved at 1500 °C with piston stresses of 70 MPa and graphite paper lubrication. These piston velocities are consistent with a calculation based on the creep behavior of this ceramic. The calculation is based on a model of material flow through the die, consistent with experiments involving internal markers of graphite foil.

Aluminum nitride (AlN) is currently under investigation as a potential candidate for replacing aluminum oxide (Al2O3) as a substrate material for electronic circuit packaging. The requirements for such a material are that it can be metallized and joined to produce hermetic enclosures for semiconductor devices. A technique for brazing AlN using a nonactive metal braze has been investigated. The process involves the in situ decomposition of an active metal hydride. This process improves the wetting of the AlN and led to the development of strong bonding between braze and ceramic. The ceramic-braze interface was studied using scanning electron microscopy (SEM). The nature of the interfacial reactions and the reaction products have been identified using x-ray diffraction (XRD). The progress of the reaction has been followed using differential thermal analysis (DTA). The experimental results have been correlated with thermodynamic predictions of the reaction processes. In addition to joining ceramic to ceramic, braze joints of AlN to copper and to a low expansion iron-nickel lead frame alloy were made. Residual stress resulting from a mismatch of thermal expansion coefficients between AlN and copper caused cracking in the ceramic upon cooldown from the brazing temperature. No cracking occurred in the ceramic when joined to the iron-nickel alloy. The results obtained are important for the realization of AlN as a ceramic packaging material for semiconductor devices.

The mechanism of formation of titanium nitride by the self-propagating high-temperature synthesis was investigated. Samples were quenched in liquid argon at different stages of the reaction and analyzed by x-ray diffraction and electron microprobe methods. A mechanism is proposed in which the propagation of the reaction wave results in the formation of a thin surface layer of TiN and an unsaturated solid solution. The layer then dissolves to form a solid solution of nitrogen in titanium and then re-forms with continued reaction. On the basis of phase equilibria and diffusion information, an analysis is made in which the feasibility of the proposal mechanism is demonstrated.

We describe an algorithm for computing the motion of a solid-liquid interface in 2D, which is applicable to geological pressure solution or to pressure sintering. The backward motion (toward the solid) of the interface is due to dissolution of the solid, and the forward motion (away from the solid) is due to the inverse process of reprecipitation. The interface velocity is assumed proportional to the difference between the solubility of the solid and the concentration of the solution. The former is dependent upon stress (the phenomenon of “pressure solution”), so our algorithm must also keep track of the stress. We use a Lagrangian grid, with constant-stress periodic boundary conditions. The method has been applied to porosity reduction in sandstone. It is applicable to other interface-following problems, such as freezing, if the motion is slow enough that heat transport is not rate-limiting.