Strength and Fracture Toughness of Isostatically Hot-Pressed Composites of Al2O3 and Y2O3-Partially-Stabilized ZrO2

Composites of Al₂O₃ and Y₂O₃ partially-stabilized ZrO₂ were isostatically hot-pressed using submicrometer powders as the starting material. The addition of Al₂O₃ resulted in a large increase in bending strength. The average bending strength for a composite containing 20 wt% Al₂O₃ was 2400 MPa, and its fracture toughness was 17 MN·w^−3/2     

Sintering Kinetics at Constant Rates of Heating: Effect of Al2O3 on the Initial Sintering Stage of Fine Zirconia Powder

The sinterabilities of fine zirconia powders including 5 mass% Y₂O₃ were investigated, with emphasis on the effect of Al₂O₃ at the initial sintering stage. The shrinkage of powder compact was measured under constant rates of heating (CRH). The powder compact including a small amount of Al₂O₃ increased the densification rate with elevating temperature. The activation energies at the initial stage of sintering were determined by analyzing the densification curves. The activation energy of powder compact including Al₂O₃ was lower than that of a powder compact without Al₂O₃. The diffusion mechanisms at the initial sintering stage were determined using the new analytical equation applied for CRH techniques. This analysis exhibited that Al₂O₃ included in a powder compact changed the diffusion mechanism from grain boundary to volume diffusions (VD). Therefore, it is concluded that the effect of Al₂O₃ enhanced the densification rate because of decrease in the activation energy of VD at the initial sintering stage.     

Coal liquefaction by in-situ hydrogen generation.: 2. Zinc-water model compound reactions

Model compound studies were carried out to elucidate the reaction mechanisms taking place during the liquefaction of coal with the hydrogen produced from the reaction of zinc and water. In compounds of the type Ph-(CH₂)_n-Ph the splitting of the aliphatic bridge was easier with higher n values. Ether type compounds such as diphenylether were unreactive although the C-O bond in dibenzylether was easily cleaved. Condensed ring aromatic compounds gave low conversion with hydrogenation being facilitated by an increase in ring number. Phenolic compounds such as phenol did not react well, but the reactivity increased with increase in aromatic ring size. The cleavage of the aliphatic bridge was accelerated by the OH group, for example, in the case of 4-hydroxydiphenylmethane bond scission was about 15 times higher than that of diphenylmethane. Heterocyclic compounds were unreactive.     

Effects of Annealing on Dielectric Loss and Microstructure of Aluminum Nitride Ceramics

The effect of annealing on tan δ and microstructures of aluminum nitride (AlN) ceramics were explored. Yttria was added as a sintering additive to AlN powders, and the powders were pressureless-sintered at 1900°C for 2 h in a nitrogen flow atmosphere. In succession to sintering, AlN samples were annealed at 720, 970 and 1210°C for 2 and 4 h. Very low tan δ values between 2.6 and 6.0 × 10⁻⁴ at 28 GHz were obtained when the AlN samples were annealed for 4 h at all the annealing temperatures.     

Densification and Thermal Conductivity of AIN Doped with Y2O3, CaO, and Li2O

Small amounts of Li₂O result in sintering in the AIN-Y₂O₃-CaO and AIN-CaO systems at firing temperatures <1600°C. The effect is ascribed to reduction of the liquidus temperature. Furthermore, Li₂O is removed by volatization at temperatures from 1300° to 1600°C, and its content decreases several ppm from the initial 0.3 wt%. Li₂O-doped AIN specimens containing Y₂O₃ and CaO additives are well densified by firing at 1600°C for 6 h, and their thermal conductivity is 135 W^.m^−1.K⁻¹.The effect of Li₂O addition on sintering and thermal conductivity also is discussed through thermo-dynamic considerations.     

Effect of Grain Boundaries on Thermal Conductivity of Silicon Carbide Ceramic at 5 to 1300 K

The thermal conductivity of a SiC ceramic was measured as 270 W·m⁻¹·K⁻¹ at room temperature. At low temperatures ( T < 25 K), the decrease in the conductivity was proportional to T ³ on a logarithmic scale, which indicated that the conductivity was controlled by boundaries. The calculated phonon mean free path in the ceramic increased with decreased temperature, but was limited to ∼4 μm, a length almost equal to the grain size, at temperatures below 30 K. We concluded that the thermal conductivity of the ceramic below 30 K was influenced significantly by grain boundaries and grain junctions.     

Synthesis of tetramethyl-p-silphenylenesiloxanedimethylsiloxane triblock copolymer by employing living anionic polymerization

Dimethylsiloxane-tetramethyl-p-silphenylenesiloxane-dimethylsiloxane (DMS-TMPS-DMS) triblock copolymer was synthesized by employing living anionic polymerization of hexamethylcyclotrisiloxane (D₃). Two synthetic methods were carried out for the polymerization. One of those methods was the anionic polymerization of D₃ initiated at the silanolate anion which was prepared from the terminal hydroxyl group of silanol-terminated TMPS prepolymer by reaction with n-butyllithium (method 1). The other was the coupling reaction of vinyl-terminated TMPS prepolymer with hydrosilyl-terminated DMS prepolymer obtained from the anionic polymerization of D₃ by using diphenylmethylsilanolate anion as initiator (method 2). In method 1, DMS contents of the copolymers ranged from 25.8 to 72.5 wt% and the values agreed with the ratio of D₃ to TMPS prepolymer. The weight-average molecular weights ranged from 1.36×10⁴ to 19.4×10⁴ and were close to the predicted values calculated from the $\text{M}\text{?}{}_{\mathrm{v}}$ of the TMPS prepolymer and the amount of D₃ added. In the case of method 2, weight-average molecular weights ranged from 19.5×10⁴ to 24.2×10⁴. The high molecular weight copolymer could thus be obtained by method 2. Intrinsic viscosity values of the triblock copolymers agreed with calculated values obtained by considering the copolymer as a binary mixture of these homopolymers. Differential scanning calorimetry and thermogravimetry were carried out on the triblock copolymers. The equilibrium melting temperatures of each of the copolymers were very close to that of poly-TMPS (160°C). The glass transition temperature and heat of fusion were decreased as the DMS content was increased. The thermogravimetric curves for the copolymers indicated that the thermal stability of the triblock copolymer was intermediate between the DMS and TMPS homopolymers.     

High Thermal Conductivity in Silicon Nitride with Anisotropie Microstructure

Silicon nitride was fabricated by tape casting of α-Si₃N₄ powder with 5 wt% Y₂O₃ and 5 vol% rodlike β-Si₃N₄ seed particles, followed by tape stacking, hot pressing under 40 MPa, and annealing at 1850°C for 2-66 h under a nitrogen pressure of 0.9 MPa. Silicon nitrides fabricated by this procedure exhibited a highly anisotropic microstructure with large elongated grains (developed from seed particles) uniaxially oriented parallel to the casting direction. Thermal conductivities parallel to the grain alignment were much higher than those measured in other directions and exhibited high values of up to 120 W/(m.K). The anisotropic thermal conductivity of the specimen could be explained by the rule of mixture, considering that large elongated grains developed from seeds have higher thermal conductivity than a small-grained matrix.     

Oligomer-Rich Fraction from Polydisperse Sample of Poly(bis(β-phenoxyethoxy)phosphazene)

Poly[bis(-phenoxyethoxy)phosphazene] [PBPEP] had been shown in our previous paper to be a very useful polymer for investigating the crystallization mechanism of polymers, as the crystallization rate of PBPEP is extraordinarily small when isothermally crystallized from the melt. The crystallization of the low molecular weight oligomers of PBPEP was first studied in comparison to the high molecular weight polymers. The oligomer-rich fraction was obtained by fractionation of the as-polymerized sample, which had a broad molecular weight distribution. The fractions thus obtained were characterized by solution viscometry and size exclusion chromatography. The melting temperature and the growth rate of the spherulite from the melt were investigated by differential scanning calorimetry and optical microscopy. The growth rate was one or two orders of magnitude smaller in the oligomer-rich fraction than in the other high molecular weight fractions. A collapsed spherulite appeared in the oligomer-rich fraction at high crystallization temperatures. It is speculated that in the oligomer-rich fraction there is an excess free energy due to defects in the crystal phase. This defect is considerably larger in the oligomer-rich fraction than in the other fractions because a large quantity of short length chains is present.     

The effect of the N-linked glycans on structural features and physicochemical functions of soybean β-conglycinin homotrimers

β-Conglycinin is a trimeric protein consisting of three subunits, α,α′,and β, which are N-glycosylated. The α and α′ subunits contain extension regions in addition to core regions common to all subunits. We purified homogeneous trimers consisting of only α, α′, or β from mutant soybean cultivars containing β-conglycinin lacking one or two subunits: α homotrimers from an α′-lacking mutant, α′ homotrimers from an α-lacking mutant, and β homotrimers from an α-and α′-lacking mutant. Structural features and physicochemical functions of the three homotrimers were examined and compared with those of recombinant homotrimers having no N-linked glycans. The native homotrimers have secondary structures very similar to those of the recombinant ones. In analogy with the recombinant homotrimers, the native ones exhibit different thermal stabilities from one another (β>α′>α), and the native α and α′ homotrimers exhibit better solubility, emulsifying ability, and heat-induced association than the native β homotrimer. Further, the N-linked glycans contribute to solubilities of the three subunits at low ionic strength (μ=0.08) and to the emulsifying ability of the native β homotrimer. N-Linked glycans also prevent heat-induced associations of the native α and α′ homotrimers but do not contribute to the secondary structure and the thermal stability of β-conglycinin.