Synthesis and the thermal decomposition behavior of new molecular precursors, strontium, and calcium zirconyl citrates are presented. The pathway to the metazirconate formation has been found to proceed through a multistep process. The precursors yield SrZrO3 and CaZrO3 fine powders at temperatures as low as 650 °C. Physico-chemical, spectroscopic, thermoanalytical, and microscopic techniques have enabled the identification of the sequence of events leading to the perovskite formation and proposition of a thermolysis scheme. Retention of the molecular level mixing of the metal ions during the course of the precursor decomposition is supported by these techniques. Prior to the formation of MZrO3 (M = Sr and Ca) an ionic oxycarbonate, M2Zr2O5CO3 (M = Sr and Ca), intermediate is produced by the thermal decomposition of the citrate precursors.

Rh nanoparticles supported on ZrO2 powder were prepared by adsorbing Rh4(CO)12 clusters from hexane solution under Ar atmosphere. Four samples with Rh content ranging from 0.25 Rh wt.% up to 4.10 Rh wt.% were studied by x-ray diffraction (XRD), transmission electron microscopy (TEM), x-ray photoelectron spectroscopy (XPS), scanning Auger microscopy (SAM), and time of flight secondary ion mass spectroscopy (ToF-SIMS). TEM measurements show, for all the samples, Rh particles with a size of about 50 Å. The 4.10 Rh wt.% sample also shows some agglomerates of Rh nanoparticles and only for this sample Rh metallic phase was detected by XRD. The profile analysis of the XRD lines indicates an average size of the Rh crystallites of about 60 Å. XPS studies show only a single spectral component for the Zr3d5/2 core line at 182.2 eV. Instead, at least, two components at 307.2 eV and 308.5 eV are detected for the Rh3d5/2 core line. These results suggest that Zr is present only as oxidized state, whereas nonoxidized and oxidized Rh are both observed. A nonoxidized Rh state is also suggested by the XPS valence band electron removal spectrum which exhibits a significant emission within the ZrO2 band gap assigned to Rh 4d bands. A further support to this finding arises from scanning Auger maps of OKVV and RH where nonoxidized Rh is observed. Finally scanning Auger maps using the OKVV and the Zr emissions show surface regions where only the Zr Auger lines are detected, whereas on pure ZrO2 powder this effect is not observed. Since it is possible to rule out from the XPS Zr3d core line spectra, the presence of metallic zirconium hydrogen spillover mechanisms is invoked to explain this result.

Silicon nitride ceramics with ytterbium silicon oxynitride (Yb4Si2O7N2) as secondary phase were fabricated by hot-pressing the powder mixtures, including 50.0 to 97.0 mol% of silicon nitride with a mixture of Yb2O3 and SiO2 (Yb2O3/SiO2 = 4). Sinterability of the materials with Yb2O3 was higher than that with Y2O3 in the same composition of raw powder mixtures. High density materials were obtained under the condition of 50.0 to 89.1 mol% of silicon nitride in raw powder mixtures. Mechanical properties of silicon nitride containing 97.6 mol% of Si3N4 and 2.4 mol% of Yb4Si2O7N2 were measured. Fracture toughness measured by the indentation technique was 5.9 MPam1/2. Bending strength at room temperature and at 1500 °C was 977 MPa and 484 MPa, respectively. The silicon nitride grains consisted of highly elongated rod-like grains and thin needle-like grains. The Yb4Si2O7N2 grains were crystallized at multigrain junctions and bonded close to Si3N4 grains. High strength at high temperature is supposed to be based on the presence of crystalline Yb4Si2O7N2 having a high melting point.

Alumina aerogels were synthesized by low temperature CO2 supercritical drying (SCD) of gels via the Yoldas process. The aerogels have a surface area of ˜425 m2/gr, similar to that obtained under high pressure/temperature SCD. The surface area and the cluster size of the aerogels are strongly influenced by the amount of acid during gelation. Gels and aerogels were studied by small angle x-rays scattering (SAXS), and the data were analyzed using the Fisher–Burford equation. The SAXS results along with TEM observations support the existence of a hierarchical aggregation at the gelation stage, having a mass fractal dimension of Dm = 2.6−2.8. During the SCD the morphology collapses to form a structure with surface fractal dimension Ds = 2.6−2.9.

Polycrystalline Ni50Al50 suitable for high pressure studies was prepared by grinding and subsequent annealing of an inert-gas atomized alloy. The equation of state was determined by energy-dispersive x-ray diffraction in a diamond anvil cell to 25 GPa. The bulk modulus Bo and the pressure derivative of the bulk modulus B′o were found to be Bo = 156 ± 3 GPa and B′o = 4.0 ± 0.5.

Titanium thin films have been grown by electron-beam physical vapor deposition on the (0001) surface of sapphire (single crystal α−Al2O3) substrates at growth temperatures ranging from 295 to 1223 K. Single phase α−Ti films grew at all growth temperatures, even at 1223 K which is above the α-β transition temperature of Ti. Crystal quality, as measured by the width of x-ray rocking curves, was found to improve, and the elastic strain to increase, as the growth temperature increased from 295 K to 1023 K. The epitaxial relationship between the Ti and sapphire was (0002)Ti ‖ (0006)Al2O3 and [1120]Ti ‖ [1010]Al2O3. The extent of interdiffusion across the Ti/Al2O3 interface was observed to be small (< 20 nm) at all growth temperatures.

We present the first high temperature x-ray diffraction (HTXRD) studies of in situ quasicrystal-crystal and crystal-crystal transformations in Ti–Zr–Ni alloys. Together with differential scanning calorimetry studies, these x-ray measurements indicate three separate paths for the Ti–Zr–Ni quasicrystal-crystal transformation: single exothermic, single endothermic, or multiple endothermic. The mode of transformation depends on the alloy composition and the level of environmental oxygen. The crystalline products include the Ti2Ni, MgZn2 Laves, α−(Ti, Zr), and β−(Ti, Zr) phases. In the absence of oxygen, the endothermic transformation of the quasicrystal demonstrates that it is the lowest free energy (stable) phase at the Ti53Zr27Ni20 composition. Oxygen stabilizes the Ti2Ni phase, eliminating both the quasicrystal and the MgZn2 Laves phase, at partial pressures as low as a few hundred ppm.

The mechanism of the 1:1 nonstoichiometric short-range ordering in donor-doped Pb(B′1/3B″1/3)O3-type relaxor perovskites was examined using the La2O3-doped Pb(Mg1/3Nb2/3)O3 (PMN) system as a typical example. Based on the dielectric analysis and the transmission electron microscopy (TEM) observation, the observed increase in the degree of diffuse phase transition (DPT) in the presence of La2O3 was interpreted as the enhancement of the 1:1 nonstoichiometric short-range ordering accompanied with the growth of the negatively charged nanodomains. The mechanism of the defect process responsible for the 1:1 nonstoichiometric short-range ordering was elucidated by analyzing the electrical conductivity of the La-doped PMN system as a function of the partial pressure of oxygen. It was shown that the substitution of La3+ ions for Pb2+ ions in the A-site sublattice of perovskite PMN produced the positively charged sites with a concomitant generation of electrons for the electronic compensation. This expedites the growth of the nonstoichiometrically ordered nanodomains in a disordered matrix.

We have investigated mechanical probing of a precracked fine line structure as a new type of thin film fracture mechanics specimen. An idealized mechanics analysis is first presented. Experimentally, two types of precracks are formed. A thin carbon layer to which other layers weakly adhere creates a “processed precrack” by integrated circuit processing techniques. An “indented processed precrack” is formed by precision alignment of a sharp microwedge. The processed precrack is found to reduce the critical tangential load by 50% from a non-precracked line, while the indented processed precrack lowers the load by 200%. From this, a reasonable value of adhesion may be directly calculated. Crack path behavior is observed to depend on strength of the interface. In the case of a weak interface, the crack remains in the interface as it extends. For a strong interface, it kinks into the substrate if the crack is initially short, but remains in the interface if it is initially long. Given the experimental evidence, the mechanics are slightly modified to quantitatively model the experimental data.

In this paper we describe the preparation, microstructure, and x-ray excited luminescence of vapor-deposited CaWO4 films up to about 50 μm thick, comparing them to particulate CaWO4 phosphor screens, used in medical diagnostic imaging. Films that we e-beam evaporated on substrates heated at or above 500 °C were polycrystalline with the scheelite structure, while on unheated substrates, films were initially amorphous but became crystalline after annealing them in air above about 750 °C. Crystalline CaWO4 films irradiated with x-rays produced light emission peaked at 430 nm. The emission intensity depended on film thickness and grain size and was comparable to particulate CaWO4 phosphor screens. Because the vapor-deposited films also exhibited superior resolution, they are promising for diagnostic x-ray imaging.

Unidirectional SrO · Al2O3 · 2SiO2 glass-ceramic matrix composites reinforced with uncoated chemical vapor deposited (CVD) SiC (SCS-0) fibers have been fabricated by hot-pressing under appropriate conditions using the glass-ceramic approach. Almost fully dense composites having a fiber volume fraction of 0.24 have been obtained. Monoclinic celsian, SrAl2Si2O8, was the only crystalline phase observed in the matrix by x-ray diffraction. No chemical reaction was observed between the fiber and the matrix after high temperature processing. In three-point flexure, the composite exhibited a first matrix cracking stress of ∼231 ± 20 MPa and an ultimate strength of 265 ± 17 MPa. Examination of fracture surfaces revealed limited short length fiber pull-out. From fiber push-out, the fiber/matrix interfacial debonding and frictional strengths were evaluated to be ∼17.5 ± 2.7 MPa and 11.3 ± 1.6 MPa, respectively. Some fibers were strongly bonded to the matrix and could not be pushed out. The micromechanical models were not useful in predicting values of the first matrix cracking stress as well as the ultimate strength of the composites.

When a ceramic material creeps under a localized stress and then cools under load, a portion of the creep flow stress is retained as a residual compressive stress due to elastic rebound being constrained by the creep zone. Localized contact-creep was used to generate residual compressive surface stress in soda-lime glass and two sintered aluminas. The Vickers indentation technique was used to measure the residual stress within the contact-creep area. Alumina with a higher elastic modulus than glass retained higher residual compressive surface stress. The results were in reasonable agreement with the predicted stress distribution given by finite element analysis.

Carbon nitride thin films have been successfully deposited by ablating a graphite target (99.999%) in nitrogen gas ambient using the second (532 nm) or third (355 nm) harmonic of a Q-switched Nd : YAG laser. Carbon nitride films consisting of approximately 40% nitrogen were obtained at 7.5 × 10−3 Pa of nitrogen gas pressure using the third harmonic laser. The C–N chemical bond in the films was observed by x-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. Ellipsometric studies revealed that the refractive index of the fabricated films decreased with increasing nitrogen concentration.

In this research, two tasks were pursued: (1) determination of the onset temperature of ferroelectric hysteresis properties of SrBi2Ta2O9 thin films by structure development study, and (2) low temperature processing for thin film fabrication. For task (1), a nondestructive optical method using spectroscopic ellipsometry was utilized for characterizing the structure development of SrBi2Ta2O9 thin films. The optical constants and film thickness were measured as a function of annealing temperature by spectroscopic ellipsometry. By observing the changes in refractive indices and film thickness, the temperatures of phase transformation and grain growth were determined. Consistent results were obtained from x-ray diffraction measurements. By comparing the results of the structure development study and ferroelectric hysteresis properties investigation, the onset temperature of the hysteresis curve of SrBi2Ta2O9 with 50% excess Bi was determined to be about 700 °C. The critical factor for the compound to exhibit a well-defined hysteresis curve was found to be the grain size. For task (2), the effects of excess Bi content and Nb/Ta ratio of SrBi2(Ta1−xNbx)2O9 on the ferroelectric hysteresisproperties were studied. It was found that the onset temperature for obtaining well-defined hysteresis properties can be reduced by adding excess Bi or increasing Nb/Ta ratio. By choosing SrBi2Nb2O9 with 50% excess Bi, the onset temperature of the hysteresis curve was reduced to about 650 °C.

The effect of temperature on the fatigue and fracture properties of an in situ reinforced super α alloy Ti–8.5Al–1B–1Si (wt. %) was investigated. At room temperature the as-extruded composite has a strength of 631 MPa with limited ductility. On increasing the temperature to 700 °C only a marginal drop in strength to 610 Mpa was observed along with a significant improvement in ductility to 5.9%. Low-cycle fatigue results indicate a marginal decrease in fatigue life as temperature is increased from room temperature to 700 °C. Fatigue crack growth studies in the as-extruded microstructure indicate a strong influence of R-ratio on both the threshold for fatigue crack growth and crack growth rates in the Paris regimes. At elevated temperatures, the resistance to fatigue crack growth increases with temperature below approximately 500 °C. At 600 °C, however, there is an increase in the near threshold crack growth rate due to embrittlement effects. At higher δK values , the resistance to fatigue crack growth at elevated temperatures is always better than that at room temperature. This improvement is attributed to the increase in the inherent resistance

Various rate controlled sintering (RCS) schedules were used on isostatically pressed particulate compacts of ZnO with Bi2O3 and Sb2O3 additives. For low additive content, smaller average grain sizes with more rapid RCS schedules were attributable to thermal schedules which minimized the time at elevated temperatures where grain growth could occur. β–Bi2O3, Zn7Sb2O12, and Zn2Sb3Bi3O14 phases formed during/after sintering. Elevated heat-treatment temperatures favored the formation of Zn7Sb2O12 and additional β–Bi2O3, while Zn2Sb3Bi3O14 was dominant in sintered samples where the RCS schedule did not result in temperatures in excess of 1100 °C. Zn2Sb3Bi3O14 precipitated during sintering, functioning as grain boundary pinning sites which impeded ZnO grain growth. Bismuth and antimony oxide-based liquid facilitated sintering at lower temperatures, which in turn resulted in decreased average grain size. Rapid RCS schedules for samples with low dopant content resulted in lower sintering temperatures, since time was not allowed for Zn2Sb3Bi3O14 precipitation to deplete the liquid phase. For higher dopant contents, liquid phase was adequately plentiful, wherein longer RCS schedules resulted in lower sintering temperatures. Increasing concentration of second phase generally fostered decreased grain size and attenuated the effect of thermal schedule on the microstructure. Electrical resistance and breakdown voltage increased consistent with decreasing ZnO average grain size.

The new procedure for the hardness measurements of superhard materials including diamond using the scanning force microscope with the ultrahard fullerite C60 tip was developed. It is shown that diamond is plastically deformed under the indentation by the ultrahard fullerite indenter at room temperature. Now the correct measurements of diamond hardness have become possible. The hardness values measured are 137 ± 6 and 167 ± 5 GPa for the diamond faces (100) and (111), respectively.

The diffusion of magnesium into lithium niobate single crystal under different diffusion conditions has been studied by x-ray diffraction, glancing-incidence x-ray diffraction, differential thermal analysis, and scanning electron microscopy in an attempt to determine the diffusion mechanism and evaluate the crystallinity of the diffused layer. It is found that the magnesium diffused layer exhibits the crystal structure of an unknown compound from the Mg–Li–Nb–O ternary system and MgNb2O6. The MgNb2O6 is in the surface layer of the magnesium diffused layer, while the unknown compound is in the subsurface layer beneath the MgNb2O6. It is proposed that this unknown compound and MgNb2O6 which form during a solid state reaction between a thin layer of MgO and a lithium niobate crystal in a Li2O-rich atmosphere are the real sources for Mg ion indiffusion into lithium niobate crystal. The changes in Curie temperature with diffusion parameters are noted. Reasons of lattice distortion and mechanisms of Mg ion indiffusion are discussed and analyzed.

The influence of total pressure in the chamber and carrier gases on the chemical vapor deposition of aluminum using tri-isobutyl aluminum was studied. The superior penetrability of chemical vapor deposition is expected to make it effective for aluminum deposition onto complex-shaped materials such as turbo-charger rotors, fibrous preform, and multifilament. It may also be a suitable method for the development of fiber-reinforced composite materials. The apparatus was composed of a raw material gas supply system, a three-zone electric furnace, a reaction chamber, an auto pressure controller, and an exhaust system. Aluminum was deposited onto a graphite fiber in the quartz reactor. The results show that, in the diffusion rate-determining stage of aluminum thermal decomposition, the rate of deposition for aluminum shows a marked increase as the pressure increases; in contrast, in the reaction rate-determining stage, this tendency is limited. This can be explained by the fact that, as the total pressure decreases, the gas diffusion coefficient becomes larger, and there is an increase in the uniformity of film formation. On the other hand, as the carrier gas flow rate increases, the amount of raw material supplied increases; consequently, a higher rate of deposition is obtained. Moreover, in the diffusion rate-determining stage, there is a tendency for an increase in flow rate to elevate the probability of arrival of the raw material, and, in combination with high temperatures, for nucleus generation to be accelerated and the average diameter of aluminum granules to become smaller. In the reaction rate-determining stage, there appears to be hardly any dependency of granule diameter on the flow rate. When Ar or He is used as the carrier gas, under the same conditions argon, rather than helium, is seen to increase the rate of deposition.

A solution precursor method based on metal alkoxides was used to produce epitaxial LiNbO3 thin films, ≈200 nm thick, on (0001) sapphire substrates. Transmission electron. microscopy revealed that the major cause of surface roughness in these films was grain boundary grooves between mosaic grains with misorientations ≤5°. It is postulated that these low angle boundaries directly result in surface grooving and roughness. The epitaxial films also contained two distinguishable variants in the film/substrate interfacial plane, namely, an aligned variant, and a 60° rotated variant, . A seeded grain growth method was used to minimize the presence of the 60° rotated variant. An epitaxial buffer layer of Fe2O3 was used to lower the mismatch strain, eliminate the 60° rotated variant, and reduce the mosaic nature of the LiNbO3 film. X-ray rocking curve full-width-at-half-maximum (FWHM) values measured on the film peak indicate that the mosaic character can be reduced from 1.5° to 0.76° by using a buffer layer.