It is well known that mechanical properties of commercial stainless steel are improved by alloying with nitrogen. In this study a series of nitrogenated commercial 201 stainless steel alloys with nitrogen levels as high as 2.6 wt. % were obtained by melting in a hot-isostatic-pressure furnace using nitrogen as the pressurizing gas. Nitrogen concentrations in excess of 1.25 wt. % formed a series of different chromium nitride precipitates and morphologies depending upon the nitrogen concentration. Five different nitrogen levels were fabricated using the same processing conditions recommended for 201 stainless steel including hot-and cold-working, and heat-treating at two different temperatures. Tensile strength of the nitrogenated materials at each processing step was related to the interstitial nitrogen concentration and the presence or absence of precipitates. The presence of chromium precipitates did reduce the fracture ductility and changed the fracture features. This U.S. Bureau of Mines study shows that increasing the nitrogen concentration in commercial steels above their current level has positive effects on mechanical properties as long as the nitrogen solubility level is not exceeded and chromium nitride precipitates begin to form.

The saturated vapor pressure and pyrolytic properties of di-n-butyltin(IV) diacetate have been investigated with and without oxygen in order to understand the orientational growth of SnO2 thin films by spray pyrolysis. The dependence of the saturated vapor pressure on temperature was determined: log P(evap.)Torr = −2.827 × 103/T + 7.687. It has been found that the pyrolysis of this compound consisted of two stages: elimination of the n-butyl groups in a temperature range between about 280°and 310 °C, and of the acetoxy groups above 320 °C. Such decompositions were shifted toward lower temperatures under oxygen. It was also found that oxygen in air in addition to intramolecular oxygen contributed to the formation of SnO2 crystal phase. Moreover, it was suggested that pyrolized chemical species preserving the Sn-O bond probably related the orientational growth of the (200) plane of sprayed SnO2 thin films.

Porous copper was produced by electrolytic dealloying of a Cu-Mn alloy (Incramute: Cu, 40-48 wt. % Mn, 1.4-2.3 wt. % Al) conducted in a 0.3 N-NaCl solution at a potential of −0.2 V (SCE). The dealloying time needed for the as-received cold-rolled specimen (50 h) is shorter than that of the annealed specimen (850 °C for 2 h). The pore size, about 1 μm, of the dealloyed cold-rolled specimen is bigger than that, about 0.1 μm, of the dealloyed specimen after annealing. This is probably because annealing reduced the phase inhomogeneity and removed the rolling effects.

The chemical vapor deposition (CVD) of MoS2 by reaction of H2S with molybdenum halides was determined to be thermodynamically favored over a wide range of temperature, pressure, and precursor concentration conditions as long as excess H2S was available. The thermochemical stability of H2S, MoF6, and MoCI5 was also assessed to address their suitability as precursors for the CVD of MoS2. The results from the thermodynamic analysis were used as guidance in the deposition of MoS2 thin films from MoF6 and H2S. The (002) basal planes of MoS2 films deposited above 700 K were preferentially oriented perpendicular to the substrate surface.

The results of a study of point defects in MgS are presented. First we obtain empirical interionic potentials in the framework of a shell model and then calculate defect energies using the HADES and ICECAP simulation procedures. The calculated Schottky formation energy is 10.9 eV in comparison to the cation and anion Frenkel formation energies of 11.9 and 25.1 eV, respectively. The migration energy by the vacancy mechanism of the Mg2+ and S2− ions is predicted to be 2.5 and 3.4 eV, respectively. One-electron ICECAP calculations yield the optical absorption energy of 3.1 eV for the F+ center in MgS.

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.

In the process of crystallization of amorphous melt-spun Nd15Fe77Bx (x = 6–14) alloys, it was found that the crystallization behavior strongly depended upon the boron content even in the same equilibrium three-phase coexistence range. The Nd2Fe14B phase was crystallized directly from the amorphous state in the amorphous Nd-Fe-B materials with relatively lower boron content (Nd15Fe77B6 and Nd15Fe77B8 alloys). In contrast, the metastable body-centered-cubic (bcc) α-iron phase crystallized from the amorphous state prior to the crystallization of the Nd2Fe14B phase in the amorphous Nd-Fe-B materials with relatively higher boron content (Nd15Fe77B10, Nd15Fe77B12, and Nd15Fe77B14 alloys). The existence of the metastable bcc α-iron phase in the amorphous matrix was confirmed by TEM studies, magnetic measurements, and in situ observation by x-ray diffraction. The formation of the metastable phase stabilized the amorphous state, increasing the crystallization temperature of the Nd2Fe14B phase.

Fine KSbOSiO4 (KSS) powders have been prepared by a sol-gel method starting from the system of TEOS, KSb(OH)6, H2O, C2H5OH, or mechanochemical mixing method with a stoichiometric mixture of amorphous silica and KSb(OH)6. The KSS crystallized sluggishly into a tetragonal symmetry in low temperature and transformed into an orthorhombic one in higher temperature, indicating the amorphous-like powder patterns in the intermediate step. This amorphization process could be related to some redistribution of the polysilicate network structures. The mechanochemical activation energy stored in the powder surface, as well as the coexisting matrix (KSbO3), retards the transformation. It was concluded that the KSS powders composed of high molecular weight siloxane polymers, which were formed by hydrolysis in the presence of a small amount of NH3 aqueous solution, showed higher sinterability. The sintering, where the calcining process was omitted, enabled the dense tetragonal-type ceramics stabilized at lower temperature, rather than higher temperature, to fabricate.

Thin films of LiNbO3 were fabricated on sapphire(012), MgO(OOl), and Si(111) substrates by the sol-gel process. Under optimized conditions, films deposited onto sapphire(012) were epitaxially grown. Preferred orientations, however, were not observed in the films on MgO(001) and Si(111) by x-ray diffraction measurements. Morphology of the epitaxial films on sapphire(012) was examined by scanning electron microscopy, which indicated that the films were smooth and had a pore-free surface. Electrical and optical measurements on the epitaxial films revealed that the properties of the films were very similar to those of the single crystalline LiNbO3, while films deposited onto Si(111) did not show any orientational behaviors. The highest quality films with epitaxy were obtained only on sapphire(012). The remaining substrates appeared to be not suitable for growing epitaxial LiNbO3 films by the sol-gel method.

When liquid S is heated above 159 °C, the S8 rings (which are the dominant structural units below this temperature) break open and polymerize into helical chains (S∞). Therefore, samples quenched from liquids at temperatures above or below 159 °C would be different in various properties by the difference in the amount of S∞. The present ultrasonic study of liquid-quenched S in the temperature range from room temperature to 200 °C has revealed this difference. It has been demonstrated that ultrasonics is as powerful as a conventional thermal analysis in dealing with the variation of a material with increasing temperature, even though both techniques were found to be relatively insensitive to the polymerization process.

A theoretical model of the combustion synthesis process has been developed. In particular, a set of nonlinear and interrelated partial differential equations is given that accounts for all of the relevant physical and chemical processes that occur during the combustion synthesis process. The appropriate conservation equations for thermal energy, mass, and momentum densities are correctly described—for each phase at each point in the sample—at all times during the process. In addition, details of the necessary interphase transfer terms are expressed in a number of constitutive relationships, in which the dependence of an independent variable upon its dependent variable(s) is given explicitly. In doing so, microstructural details are accounted for, derived primarily from percolation concepts as applied to disordered porous media. All assumptions that are incorporated into the theoretical model have been tabulated in detail. This theoretical model establishes an approach to the development of a sound, quantitative, and fundamental understanding of the combustion synthesis process, particularly with respect to the processing-microstructure-properties relationship. It also provides a point of departure for conducting detailed, quantitative computer experiments of the combustion synthesis process.

Samples of γ-Fe2O3 have been prepared from uniform α-Fe2O3 particles obtained by homogeneous hydrolysis in solution and directly by spray pyrolysis methods. The crystalline structure of these samples was analyzed by using x-ray and electron diffraction. It was concluded that, depending on the preparation method and parameters, different degrees of order in the distribution of vacancies were present. The study of the magnetic properties of these samples included the measurement of both intrinsic (saturation magnetization) and extrinsic properties (coercive force and magnetization behavior in the approach to saturation region). It was found that all the above-mentioned quantities depended on the degree of order in the distribution of vacancies.

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.

In this study, nanoindentation is used to determine Young's modulus of chemically vapor deposited films consisting of silicon carbide, silicon nitride, boron carbide, boron nitride, and silicon dioxide. Diethylsilane and ditertiarybutylsilane were used as precursors in the synthesis of the silicon-based material, while triethylamine borane complex was used for the boron-based material. The modulus of these films was observed to be dependent on the processing conditions and resulting composition of the deposits. For the silicon carbide, silicon nitride, boron carbide, and boron nitride films, the carbon content in the films was observed to increase significantly with higher deposition temperatures, resulting in a corresponding decrease in values of Young's modulus. The composition of the silicon dioxide films was near stoichiometry over the investigated deposition temperature range (375–475 °C) with correspondingly small variations in the micromechanical properties. Subsequent annealing of these oxide films resulted in a significant increase in the values of Young's modulus due to hydrogen and moisture removal.

The chemical composition of amorphous SiOx has been analyzed by oxidation studies and is found to be SiO1.7. SiO1.7 appears to be a monophasic amorphous material on the basis of 29Si nuclear magnetic resonance, high resolution electron microscopy, and comparative behavior of a physical mixture of Si and SiO2. Carbothermal reduction and nitridation reactions have been carried out on amorphous SiO1.7 and on amorphous SiO2 obtained from oxidation of SiO1.7. At 1623 K reactions of SiO1.7 lead exclusively to the formation of Si2N2O, while those of SiO2 lead exclusively to the formation of Si3N4. Formation of copious fibers of α-Si3N4 was observed in the latter reaction. It is suggested that the partial pressure of SiO in equilibrium with reduced SiO1.7 and SiO2 during the reaction is the crucial factor that determines the chemistry of the products. The differences in the structures of SiO2 and SiO1.7 have been considered to be the origin of the differences in the SiO partial pressures of the reduction products formed prior to nitridation. The effect of the ratios, C:SiO1.7 and C:SiO2, in the reaction mixture as well as the effect of the temperature on the course of the reactions have also been investigated.

ZnO/PrCoOx and ZnO/PrCoOx/ZnO junctions have been fabricated by sputtering as a model of a single grain boundary in a ceramic ZnO varistor. The relations between barrier parameters and varistor characteristics were investigated using voltage-current (V-I) capacitance-voltage (C-V), and deep-level transient spectroscopy (DLTS) measurements. The varistor voltage of the junctions increases as the donor density (ND) of the ZnO film decreases. The interface states vary according to the method of ZnO sputtering. A clear correlation has been established between the α value and the interface states. The highest α value is obtained when ND is ≃ 1018 cm−3, the interface level is 0.70 eV, and the breakdown voltage is 3–4 V. Oxygen is effective on control of ND in ZnO and the interface states. Al added as a dopant is also effective in terms of its ability to increase ND in ZnO. However, Al doping was found to degrade the interface states and increase the leakage current.

Stages 4-6 FeCl3-graphite intercalation compounds (GIC's) have been prepared by an ordinary two-bulb method, and FeCl3-IBr-graphite bi-intercalation compounds (GBC's) are synthesized by holding the FeCl3-GIC's in the saturated vapor of IBr. The x-ray diffraction patterns of the FeCl3-IBr-GBC's obtained from stages 4, 5, and 6 FeCl3-GIC's give the stacking sequences as G(FeCl3)GG(IBr)GG(FeCl3)G, G(FeCl3)GG(IBr)GGG(FeCl3)G, and G(FeCl3)GG(IBr)GG(IBr)GG(FeCl3)G, respectively, where G, (FeCl3), and (IBr) refer to the graphite, FeCl3, and IBr layers, respectively. The multi-intercalation of H2SO4 into the FeCl3-IBr-GBC's synthesized from stages 4 and 6 FeCl3-GIC's occurs at all the vacant galleries of the GBC's at the same time. In contrast, the multi-intercalation of H2SO4 into the FeCl3-IBr-GBC obtained from the stage 5 FeCl3-GIC takes place in two processes. The first multi-intercalation occurs at the gallery adjacent to the bi-intercalated IBr layer, and the stacking sequence of the resulting graphite multi-intercalation compound is determined to be G(FeCl3)GG(IBr)G(H2SO4)GG(FeCl3)G, where (H2SO4) refers to the H2SO4 layer. The second multi-intercalation occurs at all the rest of the vacant galleries.

Site preference and the effects of ternary additions (Mn, V, etc.) on the twin energy in γ-TiAl were studied by means of all-electron total energy self-consistent calculations based on the local density approximation. The results show that when Mn, Ti, or V substitute on the Al-sites in γ-TiAl, the twin energy is about 20–25% lower than that of stoichiometric γ-TiAl; this may explain observations of increased twinning activity in 48% Al TiAl. By contrast, when ternary additions of V (or Al) occupy Ti-sites, the twin energy has nearly the same value as that of pure γ-TiAl, which is consistent with the observation of only a few twins for Al-rich compositions. By comparing the total energy of Ti6(XAl5) and (Ti5X)Al6 supercells, it is found that the relative stability of Ti6(XAl5) over (Ti5X)Al6 (i.e., the preference for occupying Al-sites) is increased in going from Nb, V, Cr, and Ti to Mn, in agreement with observation that excess Ti occupies Al-sites, and Nb preferentially substitutes on the Ti-sites. The results indicate that Mn preferentially substitutes on the Al-sites, and V (or Cr) may occupy both Ti- and Al-sites.

Room-temperature current-voltage dependence of ultrafine-grained ferroelectric Pb(Zr, Ti)O3 thin films has been investigated. Both strong varistor type behavior and space charge limited conduction (SCLC) were observed. Differences in the current-voltage characteristics are attributed to differences in the nature of the grain boundaries resulting from variations in processing conditions. The strong varistor type behavior is believed to be due to the presence of highly resistive grain boundaries and thus may be termed grain boundary limited conduction (GBLC). A double-depletion-layer barrier model is used to describe the origin of high resistivity of the grain boundaries. It is suggested that the barrier height varies significantly with the applied field due to the nonlinear ferroelectric polarization, and that the barrier is overcome by tunneling at sufficiently high fields. In some other cases, the resistivity of the grain boundaries is comparable to that of the grains, and therefore the intrinsically heterogeneous films degenerate into quasi-homogeneous media, to which the SCLC theory is applicable. As such, a unified grain boundary modeling reconciles different types of conduction mechanisms in the ultrafine-grained ferroelectric thin films. This grain boundary modeling also well accounts for some other dc-related phenomena observed, including abnormal current-voltage dependencies, remanent polarization effect, electrode interface effect, and unusual charging and discharging transients. In addition, many other electrical properties of the ferroelectric films may be better understood by taking the effect of grain boundaries into account.

Incramute Cu-Mn alloys were dealloyed to remove Mn by selective electrolytic separation. The porous dealloyed specimens were compressed at 0.17-14 GPa, resulting in densities of 55-88% of the density of pure copper. Some porous copper specimens before compression were soaked in a mixture of monomer (MMA) and the initiator (AIBN), compressed, and then polymerized by heating. Young's moduli of both the dealloyed porous copper and its PMMA composite were found to decrease exponentially with porosity and volume fraction of PMMA, respectively. The apparent activation energy for damping of Cu-PMMA composite near the glass transition temperature of PMMA was found to increase with decreasing volume fraction of PMMA.