Low-Temperature Sol–Gel Synthesis of NaZr2P3O12

The NZP family of new low-expansion materials has attracted wide interest for its potential in advanced technological applications. NaZr₂P₃O₁₂, which is the parent composition of this family, has been synthesized by the solution sol-gel method using special precursor solutions, which led to its formation (although poorly crystalline) at temperatures as low as 120°C. The lowest temperature of formation of a single phase of NaZr₂P₃O₁₂ with a high degree of crystallinity was found to be 600°C.     

Thermal Expansion Anisotropy and Acoustic Emission of NaZr2P3O12 Family Ceramics

Most members of the NaZr₂P₃O₁₂ (NZP) family possess low, near zero, overall thermal expansion coefficients. However, they also exhibit anisotropy of axial thermal expansion. Some compounds have opposite anisotropy; for example, the a parameter of CaZr₄P₆O₂₄ contracts on heating and that of SrZr₄P₆O₂₄ expands, while the c parameter expands for the Ca compound and contracts for the Sr compound. The anisotropy of the axial thermal expansion of these materials is believed to induce microcracking. The acoustic emission method was employed here to detect microcracking in ceramics due to the axial thermal expansion anisotropy. Acoustic signals were observed during cooling of the Ca and Sr compounds from 500°C, and Na and K compounds from 600°C. On the other hand, no acoustic emission signal is detected in Ca_0.5Sr_0.5Zr₄P₆O₂₄ ceramics, in which the lattice parameters a and c remain nearly unchanged in the temperature range of room temperature to 500°C. Thus, a direct correlation between microcracking of ceramics and their anisotropic axial thermal expansion coefficients was established by employing acoustic emission monitoring techniques.     

Effect of B2O3 and hBN Crystallinity on cBN Synthesis

Four kinds of BN powders—amorphous BN with B₂O₃, partially crystallized BN without B₂O₃, well-crystallized hBN with B₂O₃, and well-crystallized hBN without B₂O₃—were prepared to determine the effect of B₂O₃ on the crystallization of amorphous BN and the effect of BN crystallinity on the formation of cBN under high pressure (4–5 GPa) and at high temperature (1350–1450°C). The amorphous BN with B₂O₃ easily crystallized and transformed to cBN in the presence of A1N catalyst, while the partially crystallized BN without B₂O₃ did not. The well-crystallized hBN transformed very slowly to cBN without B₂O₃, in contrast to fast transformation with B₂O₃. It is thus found that the transformation from hBN to cBN in the presence of AIN catalyst is determined by the degree of BN crystallinity as well as the presence of B₂O₃. Cubic BN can be synthesized only from crystallized hBN under the experimental conditions used. The formation of cBN from amorphous BN is possible through its prior crystallization, which can occur in the presence of B₂O₃.     

PbTiO3-PbO-B2O3 Glass-Ceramics by a Sol-Gel Process

PbTiO₃ (PT)-PbO-B₂O₃ glass-ceramics were produced by a sol-gel process. Achievement of high PT content at levels unattainable by conventional glass-ceramics preparation methods was semiquantitatively shown. PT content was similar to the designed PT volume fraction and seemed rather unaffected by the composition of the glassforming component at a calcination temperature of 700°C. A higher ratio of PbO to B₂O₃ in the glassforming component resulted in a low PT crystallization temperature, <500°C. PT crystals 1-2 μm in size were obtained at calcination temperatures >600°C.     

Improvement in Mechanical Properties of Powder-Processed MoSi2 by the Addition of Sc2O3 and Y2O3

Additions of 1-20 mol% Sc₂O₃ or Y₂O₃ to MoSi₂ eliminate glassy SiO₂, which improves mechanical properties at both ambient and high temperatures. In particular, only 1 mol% ScO₃ additions dramatically enhance three-point bending strength from 521 to 1081 MPa. Vickers hardness, Young's modulus, fracture toughness, and high-temperature strength are also improved by this low level of additive. The improvement of mechanical properties is attributed to the formation of crystalline silicates: Sc₂Si₂O₇, Y₂Si₂O₇, Y₂SiO₅, and Y₄Si₃O₁₂, which are analyzed by XRD, SEM-EDS, and TEM-EDS methods.     

Characterization of Freeze-Dried Al2O3 and Fe2O3

Oxide crystallite formation and growth from freeze-dried sulfates were studied for the representative materials Al₂O₃ and Fe₂O₃. Transmission and scanning electron micrographs showed the formation and growth of chainlike aggregates of crystallites. Aggregation occurred as part of the nucleation and growth of the oxide, and discrete oxide particles were never present. Orientation of the chain aggregates was related to the ice structure formed during freezing. X-ray line broadening data showed that crystallite size is a function of the 1/5 to 1/7 power of time for isothermal treatments. A qualitative analysis of material transport favored the surface diffusion mechanism.     

Effects of Sm2O3 and Gd2O3+ Nd2O3 on Electromechanical Properties of PbTiO3 Ceramics

The electromechanical properties of PbTiO₃ ceramics, modified by substitution of Sm or Gd + Nd (same average atomic radius as Sm) for Pb, were studied in the range of 6% to 14% substitution. The modified PbTiO₃ ceramics were stable, and the Curie temperature decreased linearly over this composition range. The 10% Sm composition had a large anisotropy in the coupling factor ratio, k _t / k _p , and a similar, but weaker, effect developed for 12% (1/2 Gd + 1/2 Nd). This indicates that other than average ion size may influence the electromechanical coupling factor ratio.     

Depolymerization of GeO2 and B2O3-GeO2 Network Glasses by Sb2O3

Binary Sb₂O₃-GeO₂ glasses containing 45 mol% Sb₂O₃ and ternary Sb₂O₃-B₂O₃-GeO₂ glasses containing 50 mol% GeO₂ were prepared. Their densities (volumes), refractive indices, and infrared spectra were determined, and their colors and high-temperature viscosities were estimated visually. Small amounts of Sb₂O₃ (∼10 mol%) appear to perturb neither the Ge-O-Ge network nor those B-O-Ge networks with small B/Ge ratios (∼0.2). The B-O-Ge networks with larger B/Ge ratios (∼1.0) depolymerize in the presence of even less Sb₂O₃. Amounts of Sb₂O₃ >10 mol% appear to depolymerize the Ge-O-Ge and Ge-O-B networks progressively, possibly with the formation of chains. A structurally sensitive ir isofrequency contour technique developed for ternary glass systems was applied successfully to these Sb₂O₃-B₂O₃-GeO₂ glasses. These contours can thus readily detect significant network depolymerization in the absence of the usual network modifiers.     

Stabilization of β-Bi2O3 by Sb2O3 Doping

The metastable β form of bismuth sesquioxide was obtained by doping antimony oxide. The solubility of antimony was 4 to 10 at. %in β specimens, where more than 75% of the antimony atoms were valenced at 5+.     

Syntheses and Unit-Cell Determination of Ba3V4O13 and Low-and High-Temperature Ba3P4O13

The syntheses and the results of unit-cell determinations ofBa₃V₄O₁₃ and the two forms (low- and high-temperature) of Ba₃P₄O₁₃ are presented. Ba₃V₄O₁₃ crystallizes in the monoclinic system, space group Cc or C2/c with unit-cell dimensions a=16.087, b=8.948, c=10.159 (x10nm), β=114.52° Low-Ba₃P₄O₁₃ crystallizes in the triclinic system, space group P1 or P1 with unit-cell dimensions a=5.757, b=7.243, c=8.104 (x10 nm) α=82.75°, β=73.94°, γ=70.71°. Low-Ba₃P₄O₁₃ transforms at 870°C into high-Ba₃P₄O₁₃ which crystallizes in the orthorhombic system, space group Pbcm (No. 57) (or Pbc2, No. 29) with unit-cell dimensions a =7.107, b=13.883, c=19.219 (x10 nm). No relations have been found between the structures of the tribarium tetravanadate and the tribarium tetraphosphate.     

Stable and Metastable Equilibria in the Systems Y2O2-Al2O3, and Gd2O3-Fe2O3

The phase equilibrium relations in the systems Y₂O₃-Al₂O₃ and Gd₂O₃-Fe₂O₃ were examined. Each system has two stable binary compounds. A 3:s molar ratio garnet-type compound exists in both systems. The 1:1 distorted perovskite structure is stable in the system Gd₂O₃-Fe₂O₃ but only metastable in the system Y₂O₃-AI₂O₃. This interesting example of metastable formation and persistence of a compound with ions of high Z/r values explains the discrepancies in the literature on the structure of the composition YA1O₃. A new 2:1 molar ratio cubic phase has been found in the system Y₂O₃-A1₂O₃. Since silicon can be completely substituted for aluminum in this compound, the aluminum ions are presumably in fourfold coordination.     

R-Curve Behavior of In-Situ-Toughened Al2O3:CaAl12O19 Ceramic Composites

The mechanical behavior of reaction-sintered alumina: 30 vol% calcium hexaluminate (Al₂O₃:CaAl₁₂O_19,or A1₂O₃: CA₆) composites was evaluated using the indentation strength in bending technique. A composite in which the hexaluminate (CA₆) phase possessed a platelike morphology showed more-pronounced R -curve behavior than a composite in which the CA₆ phase consisted of equiaxed grains. Toughness curves derived from the indentation-strength data exhibited a "crossover," such that the platelet composite exhibited the lower toughness at small flaw sizes, but the higher toughness at large flaw sizes. Incorporation of the platelet CA₆ resulted in enhanced toughening, compared to single-phase alumina of comparable grain size, thus demonstrating the viability of the in-situ -toughening approach. A simple grain-pullout model was used to estimate the toughening increment due to bridging by the platelet grains; the value obtained was in good agreement with toughness curves derived from indentation-strength measurements. Finally, fabrication of trilayer specimens, whereby outer layers of equiaxed A1₂O₃:CA₆ composite were strongly bonded to the platelet A1₂O₃:CA₆ composite, demonstrated high strength over the range of tested flaw sizes.     

Film Synthesis of Y3Al5O12 and Y3Fe5O12 by the Spray–Inductively Coupled Plasma Technique

Thin films of yttrium aluminum garnet (YAG, Y₃Al₅O₁₂) and yttrium iron garnet (YIG, Y₃Fe₅O₁₂) were synthesized on single-crystal Al₂O₃ substrates by a modification of spray pyrolysis using a high-temperature inductively coupled plasma at atmospheric pressure (spray–ICP technique). Using this technique, films could be grown at faster rates (0.12 μm/min for YAG and 0.10 μm/min for YIG) than using chemical vapor deposition (0.005–0.008 μm/min for YAG) or sputtering (0.003–0.005 μm/min for YIG). The films were dense and revealed a preferred orientation of (211). The growth of YIG was accompanied by coprecipitation of α-Fe₂O₃. The coprecipitation, however, could be largely suppressed by preliminary formation of a Y₂O₃ layer on the substrate.     

Interreaction Between Al2O3 and a CaO-Al2O3 Melt

Poly crystalline and single-crystalline α-alumina were reacted with a eutectic CaO-Al₂O₃ melt at 1530°C. A reaction zone develops in which a strongly textured CA₆ layer, as well as a CA₂ layer, forms, with a remaining layer of unreacted CaO-AI₂O₃ melt. Silica, an impurity in the α-alumina, is rejected by the advancing CA₆ phase and accumulates as calcium alumino-silicates in channels that assist in the reaction as fast transport paths. Reaction mechanisms and welding are briefly discussed.