Hydrolyzed ZrCl4 and ZrO2 · nH2O have been used as starting compounds in a time-differential perturbed-angular correlation (TDPAC) investigation on the stabilization and thermal evolution of the metastable tetragonal form of ZrO2. This phase, of quadrupole parameters very similar to those reported for the high temperature tetragonal form, emerges at moderate temperatures previous to the monoclinic phase, when starting from hydrolyzed ZrCl4 and from ZrO2 · 2H2O treated previously at 673 K. Though in all cases zirconia appears initially as an amorphous compound characterized by unique hyperfine parameters, two different precursors have been observed to exist immediately previous to the occurrence of either the monoclinic or the metastable tetragonal crystal phases. Each of them exhibits a quadrupole frequency identical with and an asymmetry parameter higher than the ones characterizing the forthcoming corresponding crystal phases. A crystallization enthalpy of (33 ± 5) kJ/mol has been determined for the formation of the metastable tetragonal phase out of its precursor.

The effects of increasing amounts of MnO additions on the microstructures, phase stability, and mechanical properties of ZrO2–12 mol % CeO2 and ZrO2–12 mol% CeO2–10 wt.% Al2O3 were studied. MnO suppressed grain growth in ZrO2–12 mol% CeO2, while enhancing the mechanical properties significantly (strength = 557 MPa, fracture toughness = 9.3 MPa at 0.2 wt.% MnO). The enhanced mechanical properties were achieved despite an increased stability of the tetragonal phase, as evidenced by a lower burst transformation temperature (Mb) and a reduced volume fraction of the monoclinic phase on the fracture surface. In ZrO2–12 mol% CeO2–10 wt.% Al2O3, the addition of MnO suppressed the grain size of ZrO2, while promoting grain growth and changing the morphology of Al2O3. More significantly, the stability of the tetragonal ZrO2 phase decreased (high Mb temperature) with a concurrent increase in fracture toughness (13.2 MPa at 2 wt.% MnO) and transformation plasticity (1.2% in four-point bending). The widths of the transformation zones observed adjacent to the fracture surfaces showed a consistent inverse relation to the transformation yield stress, as would be expected from the mechanics of stress-induced phase transformation at crack tips. The improvements in mechanical properties obtained in the base Ce–TZP and the Ce–TZP–Al2O3 composite ceramics with the addition of MnO are critically examined in the context of transformation toughening and other possible mechanisms.

The pyrolysis process of polytitanocarbosilane, precursor for SiC/TiC ceramics, has been followed step by step using x-ray photoclectron spectroscopy. This study shows that Ti–O bonds, present in the precursor, are stable up to 700 °C. Above this temperature, Ti–C bonds, precursor for TiC network, start to form. From a detailed analysis of Ti(2p) and Si(2p) peaks, the formation of intermediate species such as SiCxOy and TiCxOy has been detected.

The reaction kinetics for the formation of mullite (3Al2O3 · 2SiO2) from sol-gel derived precursors were studied using dynamic x-ray diffraction (DXRD) and differential thermal analysis (DTA). The reaction kinetics of diphasic and single phase gels are compared and different reaction mechanisms are found for each gel. Mullite formation in the diphasic gel exhibits an Avrami type, diffusion-controlled growth mechanism with initial mullite formation temperatures of about 1250 °C and an activation energy on the order 103 kJ/mole. On the other hand, mullite formation from the single phase gel is a nucleation-controlled process with an initial formation temperature of 940 °C and a much lower activation energy of about 300 kJ/mole.

The evolution of atomic composition, atomic depth distribution, and structural states of La(OH)3/Cu bilayers prepared by electron gun evaporation and submitted to ion beam irradiation is described. Chemical reactivity of La with O and H is evidenced in the initially deposited La/Cu bilayer, despite the fact that the pure La layer is coated with a thick Cu layer. Ion beam mixing with energetic Au ions, at 300 K and 700 K, results in breaking down the La–O–H bonds, while Cu atoms are knocked into the layer. There is a depth redistribution of the different atomic species, with formation of nonidentified phases.

Chemical reaction can occur at the fiber/matrix interface of intermetallic matrix composites, leading to a degradation of mechanical properties. Fe–40Al matrix composites were fabricated using SiC, B, W, Mo-base, and Al2O3 fibers. Composite samples were heat treated up to 1500 K to study the reaction kinetics, and reaction rates were determined from reaction zone thickness measurements. The Al2O3 and W fibers were found to be compatible with the Fe–40Al matrix, while the Mo-based fibers reacted moderately and the B and SiC fibers reacted severely. Experimental results are compared to theoretical thermodynamic predictions.

Solid state reactions between SiC and Ni3Al were studied at 1000°C for different times. Multi-reaction-layers were generated in the interdiffusion zone. Cross-sectional views of the reaction zones show the presence of three distinguishable layers. The Ni3Al terminal component is followed by NiAl, Ni5.4Al1Si2, Ni(5.4−x)Al1Si2 + C layers, and the SiC terminal component. The Ni5.4Al1Si2 layer shows carbon precipitation free, while modulated carbon bands were formed in the Ni(5.4−x)Al1Si2 + C layer. The NiAl layer shows dramatic contrast difference with respect to the Ni3Al and Ni5.4Al1Si2 layers, and is bounded by the Ni3Al/NiAl and Ni5.4Al1Si2/NiAl phase boundaries. The kinetics of the NiAl formation is limited by diffusion, and the growth rate constant is measured to be 2 ⊠ 10−10 cm2/s. The thickness of the reaction zone on the SiC side is always thinner than that on the Ni3Al side and no parabolic growth rate is obeyed, suggesting that the decomposition of the SiC may be a rate limiting step for the SiC/Ni3Al reactions. The carbon precipitates were found to exist in either a disordered or partially ordered (graphitic) state, depending upon their locations from the SiC interface. The formation of NiAl phase is discussed based on an Al-rejection model, as a result of a prior formation of Ni–Al–Si ternary phase. A thermodynamic driving force for the SiC/Ni3Al reactions is suggested.

The atomic structures of heterophase interfaces with large misfits (>14% in Ag/Ni and Au/Ni) and with small misfits (∼2% in Ag/NiO and Au/NiO) have been studied by high-resolution electron microscopy (HREM). It is found that all interfaces are strongly faceted on (111) planes. This indicates that (111) interfaces have the lowest interfacial energy in both metal/metal and metal/metal-oxide systems. For the metal interfaces, this also agrees with determinations of interfacial energies by lattice statics calculations. The large misfit of Ag/Ni and Au/Ni interfaces is accommodated by misfit dislocations. Observations of misfit localization by HREM are in good agreement with images derived from computer simulation, based on relaxed structures, obtained in embedded atom calculations. All misfit dislocations at the Ag/Ni and Au/Ni interfaces lie exactly in the plane of the interfaces, while the dislocations at Ag/NiO and Au/NiO interfaces reside at a stand-off distance, 3 to 4 (111)Ag or (111)Au interplanar spacings from the interfaces.

Tungsten wire for incandescent lamp filaments must operate at high temperatures and for long times. To meet these requirements, the grain morphology of the wire must be controlled to reduce the propensity for grain boundary sliding. The morphology is a function of the distribution of very small pockets of potassium in the wire and the mechanical processing from ingot to wire. The behavior of the filament is directly related to the grain morphology. This paper describes the mechanism by which the potassium is incorporated into and distributed in the ingot. The elongation and spheroidization of the bubbles during hot rolling and swaging are also examined and related to the grain morphology of wire. Some indications of the relationship between grain morphology and filament behavior are also given.