The microhardness of monoclinic ZrO2 single-crystals was measured in different environments: air, water, and toluene. An indentation creep process at room temperature was observed for the measurements in moist media pointing for a water-activated plastic relaxation mechanism. This effect is discussed employing the models previously proposed to explain similar behaviors in ZrO2 and other nonmetallic materials. A possible correlation with the conditions for the nucleation in phase transitions is proposed.

Oriented diamond films have been nucleated on single crystal nickel substrates seeded with non-diamond carbon and annealed at high temperatures in atomic hydrogen. The non-diamond carbon seeds included graphite powders, fullerene (60) powders, and gaseous carbon species. It was found that these different non-diamond carbon powders or species were effective in the enhancement of oriented nucleation of diamond. The morphologies of diamond films were similar regardless of the types of carbon used, suggesting a common nucleation mechanism involved. Based on the experimental observations, a revised model was developed for the oriented nucleation of diamond on Ni.

Recently we have found a very effective method for controlling the orientation of YBCO films by metal-organic chemical vapor deposition (MOCVD) using uv laser irradiation during deposition onto a MgO(100) substrate. The irradiated part was strongly a-axis-oriented normal to the surface of the substrate for films prepared at 650-700 °C, whereas the unirradiated parts showed c-axis or (110) orientation. This phenomenon occurs not only on MgO(100) substrates but also on other substrates. We obtained a Tc above 81 K on the a-axis oriented part. The critical current density was over 105 A/cm2 at 4.2 K and O T. The surface morphology depends on the laser power density and the repetition rate. A high degree of the a-axis orientation is obtained only by using uv light during deposition of YBCO film. IR or a visible laser causes only surface melting and the destruction of film orientation. We propose that the nuclei for a-axis orientation are formed by the aggregation of Ba caused by uv laser irradiation near the film surface.

Optical emission spectroscopic studies of dc-94.92 MHz hybrid plasma generated in the newly developed magnetron sputtering system were performed during the growth of YBa2Cu3O7−δ (YBCO) thin films. All the detectable species showed uniform spatial distribution along the radial direction of the target more than 8 mm above the target surface. High cathode current conditions in the hybrid plasma were found to make the plasma with high ion density. The high ionizing efficiency was concluded to be essential in obtaining an excellent crystalline film. This result is explained by the ion acceleration mechanism through the ion sheath formed near the substrate surface. Oxygen gas introduced into the growing chamber during deposition was found to be responsible for the oxidation of the target surface.

As-grown YBa2Cu3Ox films prepared on single crystal (100)MgO substrates by rf thermal plasma evaporation have the advantages of a high deposition rate of 730 nm/min, a large area deposition over 300 cm2, and a high Jc of 6.8 × 105 A/cm2 (77 K, O T), as reported in previous papers.1,2 We report in this paper about the preparation of YBa2Cu3Ox films on yttria-stabilized zirconia (YSZ) polycrystalline substrates for a practical application using this technique to synthesize these films on flexible (metal or flexible polycrystal) substrates. Films prepared on YSZ polycrystalline substrates grew with a c-axis orientation at a relatively high deposition rate and exhibited a zero resistance temperature (TcO) of 88 K and a critical current density Jc of 3500 A/cm2 (77 K, O T). Films prepared on flexible YSZ polycrystalline tapes with a length of 100 mm were also grown with a c-axis orientation and exhibited TcO) over 77 K.

Bi–Sr–Ca–Cu–O (BSCCO) superconducting whiskers (2212 phase) were prepared by heating in air the compacted specimens of the mixtures of melt-quenched Bi2SryCa2Cu4Al1Ox powders and alumina powders. Formation of the whiskers depends on the composition and the applied pressure of the compacts. The optimum composition of the melt-quenched products for preparing the long whiskers is Bi2Sr2Ca2Cu4Al1Ox. Superconducting whiskers <1 mm in length (2212 phase) containing an excess amount of copper were grown numerously from the specimen compacted at 20 MPa; long whiskers (2212 phase) of 1–5 mm in length were obtained from that compacted at 180 MPa. These whiskers showed diamagnetic signals below Tc ≃ 80 K.

We prepared the superconducting Bi-Sr-Ca-Cu-O thin films on Y3Al5O12 (YAG) single crystal substrates by metal-organic chemical vapor deposition (MOCVD). This film of 50 nm thickness on a YAG substrate showed c-axis orientation clearly, and the zero-resistivity (Tc-zero) was achieved at 66 K. The film has the advantageous property of surface smoothness compared with the film fabricated on MgO and SrTiO3 single-crystal substrates. The surface property of the YAG substrate seems to influence the film quality.

The stability of YBa2Cu3O7−x (the 123 compound) in contact with silver (Ag) at temperatures below 900 °C was investigated by conducting SEM and EDX analyses on 123 agglomerates that were enclosed in a dense Ag matrix and subjected to various thermal treatments. The stability of the 123 agglomerates was found to depend heavily on the oxygen content in the Ag matrix. In the case of insufficient oxygen content in Ag, the 123 agglomerates, which were as large as 150 μm thick, decomposed readily at temperatures above 500 °C. The complete decomposition process can be summarized as continuous extraction of Ba from the 123 oxide into the surrounding Ag matrix and is proposed to be driven by high mutual solubilities between Ag and Ba under the oxygen-lean condition. Prolonged preoxygenation of the (123 + Ag) mixture powders at temperatures above 400 °C prevents the occurrence of 123 decomposition in compacted samples during subsequent heat treatment, suggesting that the critical oxygen content in Ag for stabilizing the 123 compound to be no higher than 10−3 at. % (the oxygen saturation solubility at 400 °C). The findings may have implications for the processing of other Ba-containing high-Tc superconducting oxides as well.

We developed an x-ray microdiffractometer using synchrotron radiation with which we analyzed microcrystal structures of heterogeneities in Tl-1223 superconducting wires prepared by different processes, i.e., partial melt and solid/liquid phase reaction. Samples with the nominal composition (Tl0.5Pb0.5)1(Sr0.8Ba0.2)2Ca2Cu3O9 were irradiated by focused SR x-rays of 6 μm × 8 μm size. The diffracted x-rays were two-dimensionally detected with an imaging plate. From crystal structure analysis, we identified the heterogeneities as BaPbO3 and (CaSr)2Cu1O3 which are present in Tl-1223 superconducting wires prepared by both processes. This suggested that these heterogeneous phases coexist with the stable phase in the Tl-1223 phase diagram. Consequently, it is necessary to develop a new processing method such as low temperature annealing or a suitable O2 pressure control method.

The development of passive and active electronics from high-temperature superconducting thin films depends on the development of process technology capable of producing appropriate feature sizes without degrading the key superconducting properties. We present a new class of chelating etches based on di- and tri-carboxylic acids that are compatible with positive photoresists and can produce submicron feature sizes while typically producing increases in the microwave surface resistance at 94 GHz by less than 10%. This simple etching process works well for both the Y-Ba-Cu-O and Tl-Ba-Ca-Cu-O systems. In addition, we demonstrate that the use of chelating etches with an activator such as HF allows the etching of related oxides such as LaAlO3, which is a key substrate material, and Pb(Zr0.53Ti0.47)O3 (PZT) which is a key ferroelectric material for HTS and other applications such as nonvolatile memories.

The creation of a giant magnetoresistance (GMR) effect in a spinodally decomposed and deformed Cu-20% Ni-20% Fe alloy is reported. The alloy is processed to contain a locally multilayered superlattice-like structure with alternating ferromagnetic and nonmagnetic layers with a size scale of 10-20 Å. The microstructural modification produced a dramatic improvement in room-temperature magnetoresistance ratio from ∼0.6 to ∼5%. The observed magnetoresistance is most likely related to the spin-dependent scattering at the two-phase interface and in the ferromagnetic phase, although the exact mechanism involved may be qualitatively different from the usual GMR picture. A rather unusual temperature-dependence of magnetoresistance ratio, i.e., the room-temperature value being greater than that at 4.2 K, was found.

The reaction of n-butyl amine adsorbed on the ternary oxide La2CuO4 has been studied by x-ray photoelectron spectroscopy (XPS), paying special attention to the surface composition. We suggest that n-butyl amine reacting with La2CuO4 reduces CuO to Cu2O. The reaction is confined to the surface because the original composition of the material could be restored after in situ scraping with a stainless steel blade.

The mechanism for plastic deformation of 0.5 μm thick, 0.5 μm grain-size evaporated Al films on oxidized Si wafers has been studied using wafer curvature measurements over a temperature range from room temperature to 500 °C. Extensive evidence for both morphology changes and plastic deformation was obtained. Transmission electron microscopy confirmed the occurrence of grain growth, and stress changes attributed to recrystallization were observed. Deformation under tension could be explained by dislocation glide according to the kinetics observed in bulk Al at the same temperatures, stresses, and grain sizes. The kinetics of deformation under compression were investigated at 400 °C and were completely different from those under tension. This is either due to a difference in the deformation mechanism or to the occurrence of work softening.

The surface area created during tensile deformation and fracture of the reactive metals Ti, Zr, Mg, and Al is probed by real-time measurements of chemisorptive electron emission (CSE) due to oxygen adsorption. CSE is sensitive to the number of fresh metal atoms exposed at the surface as a consequence of plastic deformation. At constant strain rate, Ti, Zr, and Mg all display exponential increases in CSE intensities during loading, reflecting exponential increases in surface area prior to fracture. In Ti and Zr, CSE begins at the onset of unstable necking. In contrast, CSE intensities from Al reflect a nearly constant rate of surface area production during deformation at constant strain rate. Calibration of the Ti CSE intensities per unit surface area allowed determination of the total surface area produced during deformation and fracture. Atomic force microscopy of the necked region in strained Ti samples shows dramatic increases in surface roughness, in near agreement with the CSE results. A model is presented to account for these observations. The utility of CSE measurements as a probe of deformation and ductile fracture is discussed.

Extruded NiAl and NiAlZr alloys often show discontinuous yielding on strain aging in compression at room temperature. Two sets of experiments were conducted to understand the reasons for this yield-point behavior. First, strain-aging experiments were carried out on NiAl alloys containing O to 0.1 at. % Zr. The specimens were all deformed in compression at room temperature at a nominal initial strain rate of 1.1 × 10−4S−1, and the effect of annealing at 700 and 1200 K on the stress-strain curves and the yield strength was studied after an initial prestrain. While annealing at 700 and 1200 K consistently reduced the yield strength of both NiAl and NiAlZr, the effects were quite different. In the case of NiAl, annealing at 1200 K did not result in discontinuous yielding, whereas it generally resulted in a sharp yield point for the Zr containing alloys. Second, the PUCOT (piezoelectric ultrasonic composite oscillator technique) was used to measure the dynamic Young modulus, breakaway strain amplitude, and damping for the alloys. Only small differences were observed in the values of Young's modulus, but the breakaway strain was at least a factor of 2 to 3 lower for NiAl than for NiAlZr. The experimentally determined values of damping were used in the Granato-Lücke model to estimate the binding energy for NiAl. While the binding energy values were found to be in agreement with the calculated values of dislocation kink nucleation and migration energies in this material, to within an order of magnitude, other effects, such as dislocation pinning by quenched-in vacancies, cannot be ruled out. The observations made in this study suggest that the yield-point behavior in NiAl may be due to several factors, such as difficulties in double kink nucleation, and single kink migration, as well as dislocation-vacancy interactions; whereas, the yield-point behavior in the Zr-alloyed material is due at least in part to dislocation-solute interaction.

Microtubules are an interesting type of microstructure that resemble miniature drinking straws. Such tubular microstructures are found in nature. In addition, we and others have been investigating strategies for making synthetic analogs. We are especially interested in the idea of making metal microtubules. Four procedures for preparing metal microtubules are described in this paper. The general approach, called template-synthesis, entails using the pores in a microporous membrane as templates for forming the tubules. Microporous anodic aluminum oxide membranes and nuclear track-etch membranes are used as the template membranes. Gold and silver microtubules are made with outer diameters as small as 200 nm. These microstructures are characterized by scanning electron microscopy.

Nickel aluminides exhibit limited ductility and toughness at room temperature. One way to improve these characteristics is by adding ceramic reinforcements to the matrix. In this paper, we have studied the combustion synthesis of Ni3Al and Ni3Al-matrix composites, using the self-propagating high-temperature synthesis (SHS) mode. First, studies of the Ni3Al synthesis were carried out by quenching the reaction during its progress, which revealed the mechanism of the synthesis. The influence of Al2O3 and SiC whiskers or particulates, and B4C particulates added to the reaction mixture prior to combustion synthesis, was investigated next. It was found that, in general, reinforcements are heat sinks and limit the propagation of the reaction. Also, whiskers impede the flow of formed liquid to a larger extent than do particulates. Al2O3 is inert and matrices reinforced with up to 2 wt. % Al2O3 are composed essentially of Ni3Al grains. However, both B4C and SiC react with the Ni-Al matrix and lead to complex phases. In particular, B4C readily forms a Ni-Al-B liquid phase and disrupts dramatically the progress of the Ni3Al matrix synthesis.

A new mask-less electrode patterning method using a thermal transfer printing technique was investigated. Thermal ink ribbons were prepared, which included more than 50 vol. % conductive metal powder. Arbitrary electrode patterns were designed with a computer and printed out on a ceramic green sheet with a serial thermal printer. The ceramic green sheets with printed electrode patterns were stacked up and cofired to obtain a multi-layer ceramic capacitor.

Crack propagation and deformation behavior of a pressureless-sintered Al2O3-24 vol. % ZrO2 composite have been studied by transmission electron microscopy on Vickers-indented specimens from room temperature to 1200 °C. Hardness of the composite gradually decreases with increasing temperature, whereas the ratio of indent to crack lengths, which corresponds to the apparent toughness of materials, decreases up to about 1000 °C and then quickly increases with increasing temperature. In the samples indented at room temperature and 1000 °C, most of the cracks propagate along Al2O3/ZrO2 interfaces and Al2O3 grain boundaries, but a few monoclinic ZrO2 grains are transgranularly fractured. These fractured grains are heavily deformed and produce a marked reduction of the driving force for propagation of cracks at room temperature. In the sample indented at 1200 °C, cracks are hardly observed, but on the other hand, formation of subgrain boundaries, elongation of grains, and grain boundary sliding are observed both in the Al2O3 and ZrO2 grains located around the indentation site.

Microstructure evolution was studied in silicon nitride ceramics by a novel characterization method, and its relevance to the strength was discussed. The characterization method involves an immersion liquid for making green and partially sintered bodies transparent, and a subsequent direct optical microscopic examination. Granules for compaction process were prepared with the spray-drying process and were found to contain pores or deep dimples. Green bodies formed by CIP with these granules contain regularly arrayed pores at the center of granules and also crack-like voids at the boundaries of granules. These pores were preserved in the sintering process and resulted in large pores in the sintered body. They behave as fracture origin in ceramics and reduce the fracture strength. The Weibull modulus was high due to the presence of uniformly distributed pores.