Iron oxide (α–Fe2O3) and cobalt oxide (Co3O4) were produced via precipitation reactions carried out in a continuous hydrothermal apparatus. The resulting particles were nanometer-sized because of the high supersaturations generated when metal nitrate solutions are combined with sodium hydroxide or with hot, compressed water. The average particle size increased with the metal nitrate feed concentration and with residence time. A logarithmic relationship was obtained between the particle size and feed concentration and between particle size and residence time in the apparatus. The production of nanoparticles with narrow size distribution was shown to require low metal nitrate feed concentrations and short residence times. In the range of temperatures studied in this work, temperature apparently had no effect on the size except when cobalt nitrate was contacted with supercritical water in the absence of sodium hydroxide. In this case, large cobalt oxide particles were obtained when the temperature was above the critical temperature of water.

In this work, a systematic study of the influence of five deposition parameters, i.e., process pressure, substrate temperature, target power, and substrate bias, as well as gas composition on the residual stress in fully textured polycrystalline aluminum nitride thin films deposited on Si(100) wafers using the reactive sputtering method was performed. Post-growth residual stress measurements were obtained indirectly from radius of curvature measurements of the wafer prior to and after deposition. Two different techniques were used to determine the curvature: an optically levered laser beam and an x-ray diffraction method. Stresses in both cases were then evaluated using the Stoney formulation [G.G. Stoney, Proc. R. Soc. (London) A82, 172 (1909)]. Both methods give similar results, with slight quantitative differences. The existence of a transition region between tensile and compressive stress previously reported in the literature is also confirmed. The transition is shown to be strongly dependent on the process parameters. Optimal films regarding stress were grown at 2 mtorr, 900 W at the target, a 20/45 Ar/N2 gas mixture, and floating potential at the substrate. The substrate temperature did not influence the measured internal stress in the films.

Simulated body fluid (SBF) has been widely used for assessment of bioactivities of different materials. Those kinds of conventional SBF (C-SBF) have a higher Cl− concentration and a lower HCO3− concentration than those of human blood plasma. Therefore, a revised simulated body fluid (R-SBF), with ion concentrations including those of Cl− and HCO3− exactly equal to those of human plasma, was recently developed. Porous glass-ceramic was used as the testing material to evaluate the two kinds of SBF. Results showed that C-SBF is considered more active than R-SBF because the porous glass-ceramic had a higher apatite formation rate on its surface,while R-SBF is considered to simulate the human body fluid more precisely than C-SBF.

Biaxially aligned indium tin oxide (ITO) thin films were prepared by an ion-beamassisted deposition (IBAD) process at room temperature. Films with a transmittance at 550 nm of 90% and an electrical resistivity of 1.1 × 10−3 Ωcm for 300 and 250 nm thickness were obtained. Investigations of the texture evolution during IBAD film growth were carried out and compared to the well-established texture development in yttria-stabilized zirconia. An in-plane texture of 12.6° full width at half-maximum (FWHM) for a 1-μm-thick IBAD-ITO film was achieved. The quality of these films as electrically conductive buffer layers for YBa2Cu3O7-δ (YBCO) high-temperature superconductors was demonstrated by the subsequent deposition of high-currentcarrying YBCO films by thermal co-evaporation using a 3–5-nm-thick Y2O3 interlayer.A Jc of 0.76 MA/cm2 (77K, 0 T) was obtained for a 1 × 1 cm sample with ITO of 20° FWHM.

Self-propagating high-temperature synthesis was used to prepare boride-based functionally graded materials (FGMs) as thermal barriers for space re-entry vehicles. FGMs are characterized by inhomogeneous spatial composition, resulting in different spatial characteristics. In this work, the FGMs were composed of a ceramic [i.e., MB2 (M = Ti, Zr, Hf)] and a metallic (i.e., NiAl) side, joined together by composite layers of graded stoichiometries of the two components. Thus, in the same material, the boride end gives thermal insulation, while the intermetallic end offers an easy junction to the structure of the space aircraft. The prepared FGMs showed good adhesion between the layers and global compactness after preparation and thermal tests. The microhardness along the samples was measured, and their insulating capabilities were evaluated.

The tensile and fatigue fracture behavior of Zr59Cu20Al10Ni8Ti3 bulk metallic glass was investigated. It was found that under tensile load the metallic glass always displays brittle shear fracture and the shear fracture plane makes an angle of θT (=54°) with respect to the stress axis, which obviously deviates from the maximum shear stress plane (45°). Under cyclic tension-tension loading, fatigue cracks first initiate along the localized shear bands on the specimen surface, then propagate along a plane basically perpendicular to the stress axis. Tensile fracture surface observations reveal that fracture first originates from some cores, then propagates in a radiate mode, leading to the formation of a veinlike structure and final failure. The fatigue fracture processes of the specimens undergo a propagation stage of fatigue cracks followed by catastrophic failure. Based on these results, a tensile fracture criterion for bulk metallic glasses is proposed by taking the effect of normal stress into account. It is suggested that both normal and shear stresses affect the fracture process of metallic glasses and cause the deviation of the fracture angle away from 45°

TiO2 ceramic coating films were deposited on silica glass substrates by the sol- gel method using aqueous solutions of Ti(SO4)2 containing polyvinylpyrrolidone (PVP) as the coating solutions. Unless PVP was added to the solution, the wettability of the substrate was poor, leading to failure in gel film formation. When PVP was added to the solution, on the other hand, homogeneous gel films could be deposited on the substrate, which could be converted to crack- free, transparent TiO2 ceramic thin films about 0.1 μm in thickness. The TiO2 films thus obtained had refractive index, porosity, and surface roughness Ra (the arithmetic average deviation of the assessed profile) of 2.68, 2.1%, and 0.94 nm, respectively. For comparison, a TiO2 film was also prepared from an alcoholic solution of Ti(OC3H7i)4, showing refractive index, porosity, and Ra of 2.65, 3.0%, and 0.98 nm, respectively. These values indicate that the TiO2 films prepared from the Ti(SO4)2 aqueous solutions containing PVP are as smooth and dense as those prepared from conventional alkoxide solutions. The solutions were found to be stable in viscosity for more than five months at room temperature in sealed containers. Thermal analysis, infrared absorption spectra measurement, and x- ray diffraction analysis indicated that the gel films are converted to ceramic films on firing via (i) vaporization of H2O; (ii) decomposition of H2SO4 and/or vaporization of H2SO4 · H2O; (iii) decomposition of SO42− coordinating Ti atoms and oxidation and decomposition of PVP, the latter of which leads to formation of residual carbons; (iv) oxidation of the carbonaceous residues; and (v) crystallization of the titania phase. During the gel- to- ceramic film conversion, the thickness decreased by 90%.

Kaolinite mixed with calcite was sintered at low temperature (1100 °C; 5 °C/min). The successive phase transformations are metakaolinite to gehlenite and then anorthite, although the available phase diagram indicates a direct anorthite recrystallization. Transmission electron microscopy and electron diffraction studies of nanocrystallites revealed that the transformation path is favored by the structural similarities of phases. In particular, the pseudolayers of gehlenite have a major orientation relationship with the initial metakaolinite layers. The gehlenite axis, [001]G, is parallel to the metakaolinite axis, [001]A. This direct transition is favored by the existence of Si tetrahedral units and 4–fold–coordinated Al in both structures. Ca atoms, initially in the interlayer spacing of metakaolinite, remain in the interlayers of gehlenite. During the second transformation step, anorthite recrystallizes from gehlenite with axis [020]A parallel to [210]G. It is proposed that this orientation relationship is favored by the orientation and shape of Ca-atom channels through both structures, along [001]G and [100]A axes.

New noncovalent bonding polymer/clay hybrids were prepared, including the polymer poly(tetramethyl-p-phenylenediamine) (poly-TMPD). Polymerization occurred in the interlayer space of clay mineral successively after intercalation of monomers. Two types of clay minerals with different surface properties—a hydrophilic lithium fluorotaeniolite (TN) and four kinds of organophilic fluorotaeniolites (org-TNs)—were used as the hosts. Powder x-ray diffraction results showed an increase of 0.7–1.0 nm in the basal spacings, indicating the formation of poly–TMPD in the interlayer space of the hosts. Intercalative polymerization was also supported by Fourier transform infrared spectroscopy. The orientation of the poly-TMPD and thermal behavior were also discussed.

In this paper, we report the preparation by the sol-gel technique of organic–inorganic hybrid composites containing the biopolymer chitosan incorporated in a siloxane-based inorganic network. The hybrid xerogels were transformed into porous silica particles by elimination of the organic phase. Surface characteristics of the silica samples can be easily tailored. In this way Brunauer–Emmett–Teller areas, pore volume, and pore diameter of the prepared silica can be predetermined within a wide range. Morphology of the particles at longer length scales can be designed to obtain either irregularly shaped particles with layered morphology or spherical particles. The results are explained on the basis of the cationic polyelectrolytic properties of chitosan, which allows easy association with siloxane oligomers, the precursors of silica in forming hybrid nanocomposites.

The evolution of agglomerate structure during drying of particles from suspension has been studied for a nanocrystalline Y2O3 (8% mol fraction)-stabilized ZrO2 powder. Agglomerates in drying and dried suspensions were examined at the smallest size scales (1 nm to 1 μm) using ultra-small angle x-ray scattering (USAXS) and at the largest size scales (100 nm to 10 μm) using scanning electron microscopy. The results were correlated with the degree of particle dissolution in each suspension (measured by flame absorption spectroscopy of the suspension filtrate) and the zeta potential of the particles in suspension prior to drying. Results show that large agglomerates readily form across a pH range from 2 to 9. The fact that Y+3 ion dissolution varies by over four orders of magnitude in this range leads to the conclusion that there is little direct correlation between the degree of Y dissolution and agglomeration in this system (Zr ion dissolution was below the detection limit at all pH values studied). The observation of large agglomerates well before the introduction of air-water interfaces into the drying mass likewise leads to the conclusion that capillary forces are not essential to agglomerate formation. Instead, agglomerates appear to form as a direct consequence of increasing suspension concentration. Zeta potential also plays a role. Specifically, there was a notable change in agglomerate morphology as the isoelectric point was approached, at approximately pH 8. Here USAXS shows the particles in suspension to have a layered interior structure, with small primary particles aggregated in sheets to form each blocky particle. This is in contrast to the more rounded agglomerates formed away from the isoelectric point, which appear to be composed of the same primary particles arranged in chainlike structures. USAXS of powders from the dried suspensions confirms that the structures seen after drying are the same as those present in suspension. The two structural morphologies are attributed to diffusion-limited (sheets) versus reaction-limited (chains) aggregation, respectively.

Subsurface cracking after nano- and Vickers indentation on transparent silica–(meth)acrylate hybrid coatings deposited on a polycarbonate substrate was observed for the first time. It appeared that after initiation at the interface, these cracks propagated toward the surface and in radial directions as the indentation load increased. It was found that, for chemically identical coatings, the thicker the coating, the higher load necessary to initiate these cracks. Subsurface cracks formed during nanoindentation occur at lower loads than the normally observed surface cracks and are accompanied by a very small change in the slope of the loading curve.

Quantified wavelength dispersive spectroscopy (WDS) x-ray element maps were used to characterize active (Pb,La)(Ti,Zr)O3 (PLZT) layers on Pt/PLZT/Al2O3 substrates, one fired at 1050 °C and the other at 1150 °C. In the layer fired at 1050 °C, randomly distributed micrometer-sized compositional irregularities were observed as La-rich regions that were in most cases enriched also with Ti and deficient in Pb and Zr compared to the matrix. Such compositional imperfections were not observed in the PLZT layer fired for the same duration at 1150 °C. The level of microheterogeneity for all elements in the specimen fired at 1150 °C and for Pb, Ti, and Zr in the specimen fired at 1050 °C was below 1% relative at confidence level of 99% while for La it was as much as 2.5% relative. In point-beam line profiles across the active layer starting from the Pt electrode toward the outer surface of the cross-section of the PLZT film, the Pb concentration decreased continuously in both samples, confirming the importance of providing a properly equilibrated partial pressure of Pb around the sample during the entire firing process. Better dielectric and ferroelectric characteristics of the specimen fired at 1150 °C compared to the sample fired at 1050 °C were attributed to the differences in compositional heterogeneity between these samples. The study of the micro-compositional characteristics of these ceramic materials with quantitative WDS mapping has contributed to the optimization of processing parameters and hence to the understanding of the properties of ferroelectric PLZT materials.

The mechanical behavior at high temperatures of three hot gunning refractory mixtures used for coke oven repair was studied. The materials were characterized by chemical, mineralogical, granulometric, and microscopic analyses, exhibiting differences in composition and particle size distributions of both aggregates and bonding phases. The hot adhesion of the mixtures to silica bricks was determined using torsional forces, and the interphase between them was analyzed by scanning electron microscopy. Thermal expansion up to 1200 °C and creep under compressive load (172 kPa at 1200 °C, 3 h) were carried out on prisms prepared by ramming and sintering (1200 °C, 1 h). The creep strain–time data are well fitted using constitutive equations. The mixtures showed differences in both hot adhesion and thermal expansion–creep tests: the material based on calcium aluminates exhibited poorer properties than those based on calcium silicate. The results are explainded taking into consideration the characteristics of both aggregates and bonding phases.

A solid solution of lead magnesium niobate (PMN), a relaxor ferroelectric, with lead zirconate (PZ), an antiferroelectric, gives rise to a system that behaves like a relaxor ferroelectric for lower concentrations of PZ, and like a normal ferroelectric above 50% substitution by PZ. This paper reports the heat-capacity behavior of (1 – x)PMN–xPZ for the composition range x = 0.30 to 0.95 and temperature range 300–600 K. It was observed that, although the atomic structure of the material is basically crystalline throughout, with sharp x-ray diffraction peaks, the crossover from normal–ferroelectric behavior to relaxor–ferroelectric behavior (on decreasing x) is accompanied by a matching crossover from crystalline behavior to glassy behavior, as exhibited in the heat-capacity plots. In other words, the heat-capacity curves for the relaxor compositions bear resemblance to those observed for canonical or conventional glasses, with the glass-transition temperature and the continuous step in specific heat changing gradually as a function of the composition parameter x. However, not all properties match those for canonical glasses. For example, soaking for 24 h at a temperature or 10 to 20 K below the mean glass-transition temperature does not raise the specific heat to a value nearly equal to the value in the unfrozen state. Similarly, the glass-transition temperature (for 0.7PMN–0.3PZ) increases, though only marginally (from 337 K to 343 K), when the rate of heating across the transition is increased by a factor of 50 (from 0.1 K per minute to 5 K per min.). Further, the temperature interval ΔT over which most of the glass transition occurs in the relaxor ferroelectric is typically as large as 30–40 K, compared to only about 10 K for canonical glasses.

Piezoelectric properties k33 and d33 of 0.67 Pb(Mg1/3Nb2/3)O3–0.33 PbTiO3 single crystals grown by a modified Bridgman method were measured in the temperature range of 20–150 °C. Recoverability of the properties after the samples were heated to 110 °C, above the ferroelectric–ferroelectric (F–F) phase transition temperature of the composition, was found. From 20 to approximately 80 °C, k33 increases slightly, while d33 is almost doubled. Between approximately 90 and 100 °C, k33 decreases sharply to roughly a level of PZT-5 ceramics and d33 decreases to about 700 pC/N. They increase again with further increase of temperature; at 140 °C they attain 0.74 and approximately 1300 pC/N, respectively, and then decrease quickly and approach zero at about 150 °C. When heating to 110 °C followed by cooling to room temperature, the property decay is small. After more than one dozen heating–cooling cycles, k33 and d33 tend to be stable at 0.89 and approximately 1220 pC/N, respectively. The results might be helpful for device design and applications of PMN–PT single crystals.