The infrared complex permittivity function of pseudo-cubic, disordered, spinel-type variety of alumina, η–Al2O3, obtained by spray pyrolysis, has been determined from its IR reflectance spectra, measured at near to normal incidence on pressed powder pellets. The optical constants obtained therefrom have been verified by using them in the simulation of the corresponding absorption spectra for KBr-diluted pellets of this material, and these are in excellent agreement with the experimental spectra. All calculations are based on a procedure for the estimation of the effective dielectric function of a mixture incorporating percolation features, which has been recently developed by the authors.

Submicrometer spherical particles of mullite powder were synthesized by ultrasonic spray pyrolysis of emulsion and solutions, using tetra-ethyl-orthosilicate (TEOS) or silicic-acid and Al(NO3)3 · 9H2O as initial compounds. Crystallization of mullite phase was determined by differential thermal (DT), thermogravimetric (TG), infrared (IR), and x-ray analyses. The synthesis of mullite from TEOS emulsion occurs by crystallization of γ–Al2O3 (or Al, Si-spinel) from the amorphous phase and its subsequent reaction with amorphous SiO2, as well as by crystallization of pseudotetragonal mullite below 1000 °C and its subsequent phase transformation into orthorhombic mullite. In the powders produced from silicic acid solutions, synthesis of mullite occurs only by crystallization of γ–Al2O3 between 900 and 1000 °C and its further reaction with amorphous SiO2 between 1100 and 1200 °C. Particle formation mechanism depended directly on the initial emulsion or solution preparation, i.e., on the phase separation in the emulsion and on the silicic-acid crosslinking conditions.

Dislocations produced by 1300 °C indentation of the silicon-terminated (111) face of 3C-SiC were investigated by transmission electron microscopy. They were all found to be either widely separated partial dislocation pairs, or else, arrays of single partial dislocation half-loops on neighboring parallel slip planes and having the same Burgers vector. It was concluded that in the latter case, each array consisted of leading partial dislocations which had nucleated without accompanying trailing partial dislocations. The core nature of both dissociated dislocations and arrays of single partial dislocations has been determined by the technique of large angle convergent beam electron diffraction. The results indicate that the core of all single partial dislocation half-loops constituting an array consists of silicon atoms. It is concluded that, with the present deformation geometry, the Si-core partial dislocations are preferentially nucleated before the C-core partial dislocations. In the case of a dissociated dislocation, when a pair of partials was present, electron microscopy observations revealed that the morphology of the two partial dislocations was very different; while the Si-core partials were smooth, the C-core partial dislocations had a zig-zag morphology.

The roles of metallic droplets, which generated from the cathodic arc spot holes in the technology of Cathodic Arc Plasma Deposition (CAPD), are investigated by SEM, TEM, image analysis apparatus, and electronic probe energy spectrum analysis. The results show that though many papers in recent years are devoted to eliminate them, the metallic droplets, including the macrodroplets, have many important positive roles in the preparation of alloy films: they are the main factor to transfer the original composition of alloy cathodic target to the alloy thick films; they preserve the high deposition rate of CAPD to form the basic characteristics of the microstructure and to affect the pore ratios of the films; they also preserve the high melting point elements in the alloy films, and therefore preserve the corrosion resistance of the alloy in the films. The macrodroplets can be eliminated by raising the substrate temperature properly, which is permitted in some cases, such as depositing alloy films onto middle carbon steel as an anticorrosion system, etc.

A novel mosaic-like structure in SrTiO3 thin films was discovered and characterized by means of transmission electron microscopy (TEM). The films were deposited on a (001) oriented Pt surface. The orientation relationship between SrTiO3 film and Pt substrate was determined, and four types of growth modes were revealed. These four growth modes formed four types of domains, respectively, and these domains and Pt formed peculiarly ordered interfacial structures, i.e., near coincidence site lattices. Antiphase boundaries between two adjacent domains were also observed by high-resolution imaging.

Mixed-conducting yttria-stabilized zirconia-titania (YZTi) has attractive applications in solid oxide fuel cells (SOFC's) and electrocatalysis, particularly when used as a thin film to reduce its electrical resistance. Thin films of yttria (12 mol %) stabilized zirconia-titania (8 mol %) have been prepared using metal-organic deposition (MOD) whereby metal-organic solutions of Zr-, Y-, and Ti-2-ethylhexanoates are spun onto suitable substrates. Variables affecting the film surface-morphology, chemistry, and crystal structure are examined using scanning electron microscopy (SEM), auger electron spectroscopy (AES), and x-ray diffraction (XRD), respectively. Uniform, pore-free films having a low carbon content (<1 at. %) are made by sintering on a hot plate at 530 °C. The effect of thermal cycling on the chemical compatibility and adherence is examined for YZTi films on yttria-stabilized zirconia substrates.

The influence of nitrogen on amorphous silicon carbide films deposited at room temperature using pulsed laser ablation has been investigated. Depositions were carried out either in ultrahigh vacuum or in a nitrogen ambient ranging from 10 to 100 mT. The mechanical and optical properties, as well as composition and structure of the resulting films, were evaluated using a variety of analytical techniques. Vacuum-deposited films exhibited high hardness but suffered from high compressive stresses (>1 GPa). At low nitrogen background pressures (<30 mT), films with an optimum balance among hardness (∼16 GPa), adhesion, and intrinsic stress (<220 MPa) were found, making them ideal candidates for protective coating applications. As nitrogen pressure was increased, mechanical performance degraded due to the increasing amount of SiO2 found in the films as evidenced by spectroscopic ellipsometry, infrared spectroscopy, and Auger electron spectroscopy measurements. The source of oxygen is attributed to residual water vapor present in our vacuum system. Optical emission spectroscopy was used to confirm the presence of Si–O species in the laser-induced plasma plume.

Mechanical behavior of hot-pressed SiC platelet reinforced alumina composites has been analyzed as a function of SiC platelet content for two different alumina matrix powders. Fracture toughness and flexural strength at temperatures ranging from 25 to 1200 °C, R-curve behavior, and thermal shock resistance have been determined. Small differences in the impurity content of the starting Al2O3 powders strongly determine the microstructure and the mechanical behavior of Al2O3/SiC-platelet composites. Low alkali content alumina led to composites with large matrix grain size which presented spontaneous microcracking. At high temperature, a high viscosity liquid phase is formed that shields cracks enhancing mechanical properties and R-curve behavior. A small amount of impurities reduced Al2O3 matrix grain size and avoided spontaneous microcracking. Enhanced fracture toughness (up to 30%) at room temperature, R-curve behavior, and thermal shock resistance were achieved for these materials.

Multilayers of TiC and a series of metals have been fabricated by ion beam sputtering deposition to simulate nacre. The individual layer thickness varies from 1 to 10 nm, and the total thickness of the multilayers is about 1 μm. Transmission electron microscopy (TEM), low-angle x-ray diffraction (LXRD), and high-resolution electron microscopy (HREM) show their periodicity and lattice images. A particular method is devised to evaluate the relative toughness of this artificial pearlite. It is shown that the toughness of these nanocomposite materials can be tremendously improved. A maximum of toughness appears at a certain modulation. Metals with high plasticity such as Al and Cu can produce a particularly spectacular effect on increasing the toughness of these multilayers.

Variations of residual stresses in layers on substrates can occur in directions parallel and perpendicular to the surface as a result of compositional inhomogeneity and/or porosity or cracks. Diffraction methods to evaluate such stress variations are presented. Comparison of the experimental value for the stress with a calculated value of the “diffraction-averaged stress,” on the basis of a model for the local stresses, proved to be a useful method of stress analysis. It is shown that a direct evaluation of occurring stress-depth profiles is less practical. The method of stress analysis proposed, is applied to chemically vapor deposited TiN coatings on Mo substrates. In these coatings a large tensile stress parallel to the surface develops during cooling from the deposition temperature, due to difference in thermal shrink between coating and substrate. As a result of the cooling-induced stress, cracking of the coating occurs. The mesh width of the crack pattern allows determination of the fracture-surface energy and the fracture toughness of the coating material. Conceiving the cracked coatings as assemblies of freestanding columns, and assuming full elastic accommodation of the thermal mismatch at the column/substrate interface, the stress variations in the coating are calculated. On this basis the diffraction-averaged stress and the depth profile of the laterally averaged stress can be predicted accurately for the cracked TiN layers.

The sheets of uranyl ions (U6+O2)2+ in the structures of all uranyl oxide hydrates (UOH) (and the structurally related α- and β-forms of U3O8) are based on only four structural unit chains. Each sheet type may be reduced to its underlying sheet anion topology to determine the chains present within each topology and to describe the structural relationships among these phases. Each sheet type is described by a chain stacking sequence. The four chain types required to construct the UOH sheet anion topologies are the H-chain, the R-chain, the P-chain, and the directional “arrowhead” chains denoted by U and D. The H-chain is found only in the sheet anion topology of α-UO2(OH)2 and consists of hexagonal sites sharing opposing edges. In α–UO2(OH)2, all hexagons are populated with uranyl ions. The “arrowhead” chain is composed of pentagonal sites populated with uranyl ions and sharing edges and alternating with vacant triangular sites. Arrowhead chains are present in the sheet anion topologies of all other UOH sheets. Arrowhead chains are directional and can occur in both U and D “senses” within a single anion topology. The P-chain consists of edge-sharing pentagonal sites populated with uranyl ions forming a zigzag chain. The P-chain is flanked on both sides by arrowhead chains of the same “sense”. The remaining structural unit is a discontinuous “chain” of rhombic sites. This “R-chain” is produced when nested; adjacent U and D “arrowhead” chains are translated diagonally. The R-chain occurs in the sheet anion topologies of sheets which contain only 4-coordinate uranyl ions and those containing both 4- and 5-coordinate uranyl ions. The rhombic sites may be populated with a uranyl ion, a U4+ or other cation and two apical oxygens, or they may be vacant.

Rate-controlled sintering (RCS) of isostatically pressed particulate compacts of ZnO showed lower average grain sizes and intragranular pore densities than constant heating rate temperature controlled sintering. Valid comparisons of this form could only be made after corrections to hardware and software which reduced specimen creep under dilatometer pushrod load, nonuniform pushrod expansion, reproducible specimen temperature determination, thermal expansion during sintering, and instantaneous termination of sintering at the specified end of RCS. The improved microstructures from RCS were attributed to maximized efficiency of densification, optimizing the time and temperatures permitted for grain growth.

Monolithic gels of phosphate ceramics were synthesized using PO(OH)3−x(OR)x and alkoxides of silicon and titanium. The PO(OH)3−x(OR)x species were synthesized from the reaction of P2O5 and ethanol or n-butanol, and the products consisted of approximately equal molar amounts of mono- and dialkyl phosphate. The phosphate gels containing titanium lost less phosphorus than from the gels of silicon/phosphorus upon firing of gels in air. At phosphorus contents above 60 mole %, the gels were completely crystallized upon firing at temperatures above 700 °C, while the gels containing zinc and alkali metals remained amorphous after firing at 850 °C. Solid state nuclear magnetic resonance spectroscopy showed that all of the silicon is hexacoordinated in the phosphate gels containing silicon and titanium upon firing at temperatures above 520 °C

Transparent, conductive indium-tin oxide (ITO) and tin oxide thin films were deposited on soda-lime-silicate (SLS) float glass and silica glass substrates by an RF aerosol plasma technique in an atmospheric environment. The ITO films were deposited from solutions with various In: Sn ratios. The dependence of the film properties on the substrate temperature, deposition time, and tin concentration has been studied. The films were characterized by several techniques including XRD, EDS, electrical resistivity, SEM, optical (IR-UV-Vis transmission), Mössbauer, and infrared spectroscopy. The results showed that film phase, morphology, thickness, crystallite size, and conductivity depend on the solution composition and deposition parameters. XRD revealed that In2O3 was present in the film when a In: Sn ratio of 5: 5 or higher was used; otherwise only SnO2 shown. SEM analysis showed that dense and uniform films were formed with particle sizes ranging from approximately 50 nm to 150 nm. The resistivity of the ITO films ranged from 0.12 to 5.0 ohm-cm at room temperature. Optical transmission of the ITO-coated glasses was not different from the uncoated samples. Infrared results indicated that the structure of the near surface of the glasses was significantly modified with a higher indium concentration. The advantages of the atmospheric, RF aerosol plasma deposition process over other techniques are discussed.

Surface grinding was performed on two silicon nitrides with different microstructures. The ground surfaces of both materials were observed with scanning electron microscopy (SEM) to consist of areas of microfracture, smeared areas, and areas covered with fine debris particles. It was determined that microfracture is the primary mechanism for material removal. Subsurface grinding damage was revealed by a bonded-interface technique to take the form of median-type cracks extending from the plastic zones. Distributed intergranular microcracks and intragrain twin/slip bands were observed within the plastic zones. The strengths of transverse-ground specimens were measured in four-point flexure. For the silicon nitride with a fine grain size and a mildly rising toughness-curve, grinding damage resulted in a drastic strength degradation compared to polished specimens. In contrast, the silicon nitride with large and elongated grains and a steeply rising toughness curve showed relatively little strength loss. The relationship between the ceramic microstructure and the damage tolerance in abrasive machining is discussed in light of these results.

Short surface cracks were generated by Vickers indentation on the polished surface of alumina and different zirconia toughened alumina (ZTA) specimens, and their morphology was studied by serial sectioning. These cracks were grown in three-point bend tests under stepwise loading, and variation of toughness with crack extension was plotted to graphically separate the contributions from residual stress intensity and applied stress intensity factors. The plateau toughness determined from the intercept height of the crack extension plots exhibited an upward trend with zirconia content up to 15 vol % ZrO2 addition in the composition, which was proportional to the fraction of transformable tetragonal grains contributing to transformation toughening.

In this work the normal reflectance, R, at a planar silica aerogel interface and the normal transmittance, T, of a silica aerogel slab were measured using a Fourier Transform Infrared Spectrometer. Two procedures were used to obtain the effective optical constants, i.e., the refractive index n and the absorption index κ, of silica aerogel. One procedure determined κ from the measured transmittance T and then determined n from the results for κ and from the measured reflectance R using the Kramers–Kronig relation; the other procedure determined n and κ of silica aerogel from n and κ of fully dense silica glass by using the Clausius–Mossotti equation, Maxwell Garnett formula, and Bruggeman formula. The first procedure has a relatively large error due to the inaccuracy of the transmission and reflection measurements. The second procedure, especially the Clausius–Mossotti equation, yields values of n that are consistent with experiments and may be used for the calculation of the effective optical constants and the extinction coefficient of silica aerogel.

Copper-incorporated carbon films have been prepared on Si(100) and Corning (7059) glass substrates by the pulsed excimer laser deposition technique using KrF radiation (λ = 248 nm). Cold-pressed composite pellets, having compositions from 2 at. % to 11 at. % copper in carbon, were used as targets for ablation. Good quality, scratch-proof films were obtained at a laser energy density of 2−3 J/cm2 and a substrate temperature of 50 °C. The films were characterized by x-ray diffraction (XRD), Raman spectroscopy, x-ray photoelectron spectroscopy (XPS), UV-visible spectrometry, ellipsometry, and four-point probe resistivity measurements. Under similar deposition conditions, films obtained from composite targets of lower copper concentration are seen to have better diamond-like character as compared to those obtained from a pure graphite target. At such low concentrations, copper is seen to cluster in the form of nanoparticles. As the copper concentration increases in the films, they tend to acquire disordered graphitic network with degraded DLC characteristics, and the size of copper agglomerates increases from about 5 nm (for the 2 at. % case) to 85 nm (for the 11 at. % case). It is seen that an increase in the copper content leads to modifications in the carbon network, additional interband transitions, and reduction of the band gap.

Quantitative and qualitative investigations on the size distribution of ultrafine particles in KDP solutions were performed by a laser light scanning particle counter and by comparing with scattering polystyrene particles of standard size. The ultrafine particles are of a size distribution from <70 nm to 2000 nm, and the density of the particles sharply decreased with increasing particle size. Most of them were smaller than 100 nm, and almost no particles were >1000 nm. The size of the visual particles, which are distinguished individually by a laser light-scattering technique,3 was estimated in the size range from 200 nm to 1000 nm. The reliability of the results was evaluated.

Nanoindentation load-displacement curves provide a “mechanical fingerprint” of a materials response to contact deformation. Over the last few years, much attention has been focused on understanding the factors controlling the detailed shape of unloading curves so that parameters such as true contact area, Young's modulus, and an indentation hardness number can be derived. When the unloading curve is well behaved (by which we mean approximating to linear behavior, or alternatively, fitting a power-law relationship), then this approach can be very successful. However, when the test volume displays considerable elastic recovery as the load is removed [e.g., for many stiff hard materials and many inhomogeneous systems (e.g., those employing thin hard coatings)], then the unloading curve fits no existing model particularly well. This results in considerable difficulty in obtaining valid mechanical property data for these types of materials. An alternative approach, described here, is to attempt to understand the shapes of nanoindentation loading curve and thus quantitatively model the relationship between Young's modulus, indentation hardness, indenter geometry, and the resultant maximum displacement for a given load. This paper describes the development and refinement of a previous approach by Loubet et al1 originally suggested for a Vickers indenter, but applied here to understand the factors that control the shape of the loading curve during nanoindentation experiments with a pointed, trigonal (Berkovich) indenter. For a range of materials, the relationship P = Kmδ2 was found to describe the indenter displacement, δ, in terms of the applied load P. For each material, Km can be predicted from the Young's modulus (E) and the hardness (H). The result is that if either E or H is known, then the other may be calculated from the experimental loading curve. This approach provides an attractive alternative to finite element modeling and is a tractable approach for those cases where analysis of unloading curves is infeasible.