Processing-microstructure relationships in a silica gel system, based on mixtures of colloidal sol and soluble potassium silicate, have been studied. Quantitative microstructural information regarding colloidal cluster sizes, size distributions, surface areas, and pore-size distribution from the nanopore range to the macropore range was determined via small-angle scattering and transmission electron microscopy. The colloid cluster size distribution varies systematically, with gels fabricated with the least colloidal fraction possessing the most polydisperse microstructure. It is shown that the porosity over the entire range can be tailored by selecting the appropriate starting chemistry; under the same pH conditions, the ratio of the two silicate ingredients controls the average size, the polydispersity of sizes, and the connectivity of the pores. A population of fine (2 nm) uniformly dispersed nanopores, which result from leaching, is responsible for large increases in surface area. The leaching process can be controlled by the surrounding macropore void size, which determines alkali transport. The product material consists of 85% large, open pores, with fine pores within the gel skeleton, making this gel an ideal candidate for controlled-porosity applications such as catalyst supports and magnetic composites.

The effects of reaction temperature (150–300 °C), chemical composition of the starting cerium salt (cerium nitrate and cerium chloride), and doping with trivalent cations (Sc3+ and Y3+) on the coarsening of CeO2 particles in dilute suspensions under hydrothermal conditions were investigated. The particle size was measured by x-ray line broadening and by transmission electron microscopy. The particle coarsening kinetics followed a parabolic law, indicating that the interfacial reaction (dissolution) was the rate-controlling step. Furthermore, the particle size distribution data can be well-described by the Lifshitz–Slyozov–Wagner theory of Ostwald ripening controlled by the interfacial reaction. Doping with 6 at.% Y3+ produced a significant reduction in the coarsening rate but almost no change in the activation energy. At the same concentration, Sc3+ was more effective than Y3+ in reducing the coarsening rate. Particles synthesized from a starting solution of cerium(III) chloride coarsened at a markedly slower rate than that for particles synthesized from cerium(III) nitrate. The mechanisms controlling the coarsening of the particles are discussed.

A series of rare-earth-(RE-)doped α-sialons (RExSi12–4.5xAl4.5xO1.5xN16–1.5x, with x = 0.40 for RE = Nd, Sm, Yb, and x = 0.48 for RE = Y) were prepared and heat-treated in air at 1350 °C for 66–727 h (3–30 days), and the variations in composition and structure with time of the formed oxide scales and matrix materials were investigated. In the oxide scales of the Nd-, Sm-, and Y-containing samples a liquid was formed, apparently in (quasi-)equilibrium with the crystalline phases cristobalite and mullite, while only crystalline Yb2Si2O7, cristobalite, and mullite were observed in the Yb sample. Apparently, the liquid plays an important role in the oxidation process. In the depleted zone, located between the scale and the matrix, the liquid attacks the matrix phases, and a process takes place in which the originally formed phases dissolve and reprecipitate as more oxygen-rich phases. In the Nd- and Sm-doped systems, where the α-sialon phase is inherently metastable at 1350 °C, an extensive α → β-sialon transformation takes place, creating still more liquid. As a consequence, the oxidation resistance of α-sialons containing Nd and Sm is much lower than those containing Y and, in particular, Yb.

The pyramidal indentation-induced surface deformation of brittle ceramics is examined on the basis of extensive test results for indentation load (P)-depth (h) curves during loading/unloading cycle. A mechanically stiff test system is essential for obtaining P-h curves acceptable and reliable for subsequent analyses. Both the loading and unloading P-h curves are expressed by quadratic functions within experimental variations for all the indenters used (Vickers, Berkovich, and Knoop). The loading curve is then related to the Meyer hardness and the unloading curve to Young's modulus by the use of semiempirical equations which enable one to estimate these moduli from the observed loading/unloading parameters. An elastoplastic constitutive equation for indentation surface deformation is theoretically derived. This equation not only predicts well the experimental observations but also gains an important physical insight into the Meyer hardness. The Meyer hardness of brittle materials is not a measure for plasticity, but an elastic/plastic parameter which significantly depends on the geometry of indenter. The concept and experimental determination of “true” hardness as a characteristic material measure for plasticity are proposed.

In this paper we report a novel process for the production of ultralight cellular ceramics. The foams are generated by the heat treatment of crystals of the aluminum chloride isopropyl ether complex [AlCl3(Pri2O)]. The crystals, which are the only foam precursor, are obtained from concentrated solutions of AlCl3, Pri2O, and CH2Cl2. The foams consist of an arrangement of closed cells, 50–300 μm in diameter, having cell walls approximately 1–2 μm thick. An exceptionally high porosity is obtained ranging from 94 to 99%, and the cellular structure is retained during heating at 1500 °C. The foaming mechanism involves two consecutive nonhydrolytic sol-gel chemical reactions and physical processes including crystal dissociation, solvation, phase separation, and foaming. While other foaming mechanisms cited in the literature utilize one or more of the processes above, no analog mechanism exists in the organic, ceramic, or metal foam production processes. The effectiveness of the process originates from an initial precursor which contains all the necessary foaming components in such a way that the application of mild heating accelerates its transformation to a solid, dry, ultralight foamed material.

Crack-free and transparent Sr2KNb5O15 (SKN) thin films have been synthesized by the chemical solution deposition method. A homogeneous and stable precursor solution was prepared via controlling the reaction of metal alkoxides. SKN precursor was found to be the complex alkoxide between Sr[Nb(OEt)6]2 and KNb(OEt)6 with high structural symmetry. SKN powders and thin films on fused silica substrates directly crystallized to the polycrystalline tetragonal tungsten bronze phase at 600 °C. Highly oriented SKN thin films with the tetragonal tungsten bronze phase were fabricated on MgO(100) and Pt(100)/MgO(100) substrates. Two crystal lattice planes of SKN were intergrown at an orientation of 18.5° on MgO(100). The dielectric constant of SKN thin films on Pt(100)/MgO(100) was about 590 at 20 °C at 1 kHz.

Lead zirconate titanate (PZT) has been successfully fabricated via a unique one-step sintering processing route, which is simpler than the traditional precursor-calcinationmilling- pelleting-sintering route and is able to deliver an enhanced sintered density at a much reduced sintering temperature. The hydroxide precursor was prepared by coprecipitation from a mixed nitrate solution containing Pb2+, Zr4+, and Ti4+ ions, and it was then compacted into pellets without being calcined at a low temperature. The precursor pellets were dehydrated at 400, 500, and 600 °C for 4 h, respectively, followed by an isostatic pressing at 350 MPa, prior to being sintered at a high temperature. Dehydration temperature has a large impact on the sintering behavior of these hydroxide-derived PZT ceramics. The PZT dehydrated at 400 °C was seriously cracked when sintered at temperatures ranging from 950 to 1150 °C, due to the incomplete dehydration. A sintered density of 99.2% theoretical density was obtained at 1050 °C for 2 h for the powder pellet dehydrated at 500 °C for 4 h. It exhibits a dielectric constant of 1024 and a dielectric loss of 2.1% at a frequency of 1 kHz at room temperature. A calcination at a too-high temperature, e.g., 600 °C, results in a reduction in the sinterability of the precipitate-derived PZT ceramic.

In this paper we present sol-gel synthesis and thermal and structural characterization of some lithium borophosphates. The as-prepared samples are mostly partially crystalline, and densification heat treatments at 500 °C cause samples to crystallize. In the phosphorus-rich part of the composition triangle we have lithium excess with respect to the nominal composition, which is likely due to the low reactivity of the phosphorus precursor. On the boron-rich side, in contrast, lithium losses are found which probably occur during syneresis.

Titanium carbide foams are synthesized by a self-propagation high-temperature synthesis technique using carbon black, which generates gases during the synthesis. The synthesis is performed under terrestrial and microgravity conditions. The effects of gravity on the synthesis are evaluated in this study. The foaming is mainly caused by H2O and CO gases from the carbon black. The elongation of the products increases with decreasing environmental pressure and increasing amount of generated gases. Since the gas flows out along the direction of the combustion wave propagation, the products expand only along this direction. The propagation velocity of the combustion wave increases with increasing amount of generated gases and environmental pressure, which is due to the amount of molten Ti transporting into the reaction/preheat zone. Under higher environmental pressures, thermal convection of the environmental gases mainly affects the propagation velocity. However, at lower pressures, the behavior of the molten Ti has a great effect compared with the gases surrounding the specimens.

Nanostructured yttria powders were prepared by a gel combustion technique. The technique involves exothermic decomposition of an aqueous citrate-nitrate gel. The decomposition is based on a thermally induced anionic redox reaction. A variety of yttria powders with different agglomerate structures can be made by altering the citrate-nitrate ratio γ. The gel with γ = 0.098 in situ yields nanostructured yttria powder at 258 °C that is porous and agglomerated with an average of 25 nm primary particles. Its specific surface area is 55 m2/g. The decomposition of the gels was investigated by simultaneous thermogravimetry analysis (TGA) and differential thermal analysis (DTA) experiments. The produced ashes and calcined powders are characterized by x-ray diffraction (XRD), ir spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Brunauer, Emmett, and Teller (BET) analysis.

In this paper, a new hydrothermal method—discharging-gas method—is introduced. ZnO acicular particles with the ratio of length and diameter 16: 1 are synthesized by the hydrothermal discharging-gas method using a mixed solution of Zn(CH3COO)2 with NaNO2 as precursor at 190 °C for 1 h. The effects of reaction temperature and precursor concentration on formation of acicular particles are investigated. The results show that the main factor for formation of acicular particles prepared by the hydrothermal discharging-gas method is the extent of crystallinity of ZnO powders before releasing gas.

Highly anisotropic Si3N4 ceramics were successfully fabricated by tape-casting of raw α–Si3N4 powders with β–Si3N4 single-crystal particles as seed particles and Y2O3 as an effective sintering aid, followed by hot isostatic pressing at a temperature of 2773 K for 2 h under a nitrogen gas pressure of 200 MPa. The microstructure consists of very large elongated grains (diameter ~10 μm; length of ~200 μm), highly oriented in the tape-casting direction. The thermal conductivity along this direction reaches 155 W m-1K-1 at room temperature, but varies significantly between room temperature and 1273 K. This thermal conductivity is closely related to (1) formation of extremely large elongated β–Si3N4 grains with a reduced amount of crystal defects due to the high-temperature firing and to (2) orientation of β–Si3N4 grains due to addition of seed particles and to tape-casting.

Control of Co particle size was archived by a germ-growth method during inverse micelle synthesis. Magnetic coercivity and blocking were both a function of the particle size, which ranged from 38 to 88 Å. Interparticle dipolar interaction was proven to be important in order to interpret the magnetic properties for large-size particles.

Protective residual stresses may be developed in the near surface layers of tribological contacts which enable loads sufficiently large to cause initial plastic deformation to be accommodated purely elastically in the longer term. This is the process of shakedown and, although the underlying principles can be demonstrated by reference to relatively simple stress systems, the situation is complex under a moving Hertzian pressure distribution. Bounding theorems can be used to generate appropriate load or shakedown limits not only for uniform half-spaces but also those with plastic and/or elastic properties which vary with depth. In this way, shakedown maps, which delineate the boundaries between potentially safe and unsafe operating conditions, can be generated for both hardened and coated surfaces.

We have sputter deposited NiMnSb/PtMnSb Heusler alloy superlattices with bilayer periods from 9–160 Å. X-ray diffraction and cross-sectional transmission electron microscopy (TEM) measurements indicate that even for short bilayer periods, the superlattices are compositionally modulated, epitaxial, and maintain the Heusler alloy C1b structure. Low- and high-angle diffraction profiles are in agreement with simulations of the superlattice peaks. TEM images reveal defects, including stacking faults, which help relieve lattice mismatch strain. Energy minimization calculations of the stacking fault density are within a factor of 3 of the density observed by TEM. The saturation magnetization of the superlattices is close to bulk PtMnSb and NiMnSb, with a tendency for perpendicular magnetization at short bilayer periods.

Homogeneous maghemite (γ–Fe2O3) nanoparticles with an average crystal size around 5 nm were synthesized by successive hydrolysis, oxidation, and dehydration of tetrapyridino-ferrous chloride. Morphological, thermal, and structural properties were investigated by transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and x-ray diffraction (XRD) techniques. Rietveld refinement indicated a cubic cell. The superstructure reflections, related to the ordering of cation lattice vacancies, were not detected in the diffraction pattern. Kinetics of the solid-state phase transition of nanocrystalline maghemite to hematite (α–Fe2O3), investigated by energy dispersive x-ray diffraction (EDXRD), indicates that direct transformation from nanocrystalline maghemite to microcrystalline hematite takes place during isothermal treatment at 385 °C. This temperature is lower than that observed both for microcrystalline maghemite and for nanocrystalline maghemite supported on silica.

Ba6–3xNd8+2xTi18O54 (BNT) is a useful dielectric resonator at microwave frequencies. Recent work has shown that the major secondary phase in this system can be indexed as Nd4Ti9O24 (JCPDS 33–943). The present study has evealed that when half of the stoichiometric Ba+2 is replaced with Ca+2 or Sr+2, a third, tilted perovskite-structured phase, NdTiO3, is also present. It forms as coherent intragranular regions within BNT grains and always contains some of the divalent dopant species. The orientational relationship between NdTiO3 and BNT has been established.

Aluminum-tantalum bilayers have been investigated for their potential to serve as conductive barriers to oxygen diffusion when annealed at conditions corresponding to crystallization of perovskite dielectrics such as lead lanthanum titanate (PLT). Ta (50 nm)/Al (15 nm) structures have been deposited on Si substrates and annealed in oxygen at 650 and 700 °C for various amounts of time. The as-deposited and annealed structures have been characterized by x-ray diffraction (XRD), Rutherford backscattering spectroscopy (RBS), and Auger electron spectroscopy (AES) analysis and by four-point probe electrical measurements. It has been found that the Al–Ta structures can withstand complete oxidation when exposed to oxygen at 650 °C for 30 min or 700 °C for 1 min and the oxide layer formed at the surface of the structure acts as a barrier to further oxygen diffusion. When a PLT film was deposited directly on the Al–Ta structures intermixing took place. It was therefore necessary to insert a Pt layer between the Al–Ta barrier and PLT layer. In such a case the PLT showed electrical properties similar to those obtained when deposited on SiO2/Pt; however, the Al–Ta structure did interact with Pt during the perovskite formation anneal. It has been found that this interaction can be prevented by preannealing the Al–Ta, in oxygen, prior to the deposition of Pt.

Epitaxial films of TiC1-x (0.15 < x < 0.50) were deposited on MgO(001) and 6H–SiC(0001) at 250 and 400 °C by coevaporation of C60 and Ti. Films deposited on MgO(001) were single-crystalline down to deposition temperatures of at least 250 °C as determined by x-`ray diffraction (XRD), low energy electron diffraction (LEED), and transmission electron microscopy (TEM). Films deposited on 6H–SiC(0001) were also epitaxial at 250 °C, but TEM showed a columnar microstructure due to the occurrence of twinned domains in the [111] growth direction normal to the substrate.

TaSiN films deposited as layered TaN–SiN structures of various compositions have been examined for their oxidation resistant properties during annealing in oxygen at annealing conditions commonly used to prepare perovskite dielectrics. The films have been characterized by Rutherford backscattering analysis (RBS), x-ray diffraction (XRD), and electrical resistivity measurements. Films with less than 15 at.% Si showed some resistance to oxidation after annealing for 1 min at 650 °C but became fully oxidized after longer anneals. Increasing the Si content up to 28 at.% increasingly improved the oxidation resistance of the alloys to the point where the films resisted complete oxidation for up to 5 min at 700 °C. For alloys with greater than 28 at.% Si, no oxidation could be detected by RBS or electrical measurements for anneals up to 5 min at 700 °C. Furthermore, these high Si content alloys were still conductive with resistivities of near 1000 μΩ cm. It was also found that TaSiN and lead lanthanum titanate (PLT) interact strongly during annealing, and another nonoxidizing barrier metal, such as Pt, is required between the two materials if TaSiN is to be used as an electrode/barrier with lead-based perovskites.