Effects of Intergranular Phase Chemistry on the Microstructure and Mechanical Properties of Silicon Carbide Ceramics Densified with Rare-Earth Oxide and Alumina Additions

Based on the processing strategy of improving the mechanical properties of liquid-phase-sintered materials by modifying the secondary phase chemistry, four rare-earth oxides (RE₂O₃, RE = La, Nd, Y, and Yb), in combination with alumina, were used as sintering aids for a submicrometer-size β-SiC powder. Doped with 5 vol% RE₂O₃+ Al₂O₃ additives, all specimens were hot-pressed to near full-densities at 1800°C, and they exhibited similar microstructures and grain size distributions. The SiC grains in all specimens revealed a core-rim structure after being plasma-etched, indicating that they were densified via the same solution-reprecipitation mechanism. It was found that a decrease in the cationic radius of the rare-earth oxides was accompanied by an increase in Young's modulus, hardness, and flexural strength of the SiC ceramics, whereas the fracture toughness was improved by incorporating rare-earth oxides of larger cationic radius. The changes in the mechanical properties were attributed to the difference in the chemistry of the intergranular phases in the four ceramics.     

High‐pressure synthesis of a 12CaO·7Al2O3–12SrO·7Al2O3 solid solution

Solid solutions of 12CaO·7Al₂O₃ (C12A7) and 12SrO·7Al₂O₃ (S12A7) crystals were synthesized under high pressure. X‐ray diffraction patterns revealed that the lattice constants of the synthesized samples depend linearly on the compositional ratio of C12A7 and S12A7. Electron‐probe X‐ray microanalyses show that the chemical compositions of the crystals are represented by xC12A7·(1?x)S12A7 (0<x<1). These results indicate that the variation in the lattice constants is originated from a difference in the ionic radii of Ca²⁺ and Sr²⁺ ions. From impedance measurements, it was found that S12A7 has the highest conductivity (~1 × 10^?3 Scm^?1 at 550°C) among the solid solutions in the C12A7–S12A7 system.     

Enzyme-resistant fractions of beans lowered serum cholesterol and increased sterol excretions and hepatic mRNA levels in rats

Feeding rats beans with resistant starch reduces their serum cholesterol concentration; however, the mechanism by which this occurs is not fully understood. We examined the effects of enzyme-resistant fractions of adzuki (Vigna angularis) and tebou (Phaseolus vulgaris, var.) beans on serum cholesterol and hepatic mRNA in rats. Rats were fed a cholesterol-free diet with 50 g of cellulose powder (CP)/kg, 50 g of an enzyme-resistant fraction of adzuki starch (AS)/kg, or 50 g of an enzyme-resistant fraction of tebou starch (TS)/kg diet for 4 wk. There were no significant differences in body weight, liver weight, and cecum contents among the groups, nor was there a significant difference in food intake among the groups. The levels of serum total cholesterol, VLDL + intermediate density lipoprotein + LDL-cholesterol, and HDL cholesterol in the AS and TS groups were significantly (P<0.05) lower than in the CP group throughout the feeding period. Total hepatic cholesterol in the CP group was significantly (P<0.05) lower than in the AS and TS groups, fecal cholesterol excretion in the TS group was significantly (P<0.05) greater than in the CP and AS groups, and the fecal total bile acid concentrations in the AS and TS groups were significantly (P<0.05) higher than in the CP group. Cecal acetate, propionate, and n-butyrate concentrations in the AS and TS groups were significantly (P<0.05) higher than in the CP group. The level of hepatic scavenger receptor class B1 (SR-B1) mRNA in the TS group was significantly (P<0.05) higher than in the CP group, and the levels of hepatic cholesterol 7α-hydroxylase mRNA in the AS and TS groups were significantly (P<0.05) higher than in the CP group. These results suggest that AS and TS have a serum cholesterol-lowering function due to the enhanced levels of hepatic SR-B1 and cholesterol 7α-hydroxylase mRNA.     

Critical Factors Affecting the Wettability of α-Alumina by Molten Aluminum

The wetting behaviors of α-Al₂O₃ single crystals with three different faces—R(01 1 2), A(011 2 0), and C(0001)—and polycrystals (PC) by molten aluminum were studied over a wide temperature range using both a conventional and an improved sessile-drop method. The critical factors affecting the wettability, such as temperature, atmosphere, substrate surface roughness, and crystallographic orientation, and the influence from the experimental technique, were thoroughly investigated. The results show that the aluminum surface oxidation and the thickness of the oxide film have a pronounced effect on the wettability, especially at low temperatures. To eliminate this effect, the experimental temperature must be over a critical value. Vacuum favors lowering this value compared with atmosphere, and the improved sessile-drop method, particularly using an impingement-dropping mode (I-mode), helps to weaken this effect by mechanical disruption and removal of the oxide film. However, the dropping distance and the dropping force must be controlled to prevent an overspreading of the drop. The effects of the substrate surface roughness and temperature are not significant in the case of a clean aluminum surface and a fine-prepared alumina surface. On the other hand, the effect of the alumina surface crystallographic orientation is noticeable and the wettability is in the order of R > A > PC > C. The intrinsic contact angles of the Al/α-Al₂O₃ system in the temperature range of 1000°–1500°C were estimated to be 76°–85° for the R and A faces, 88°–100° for the C face, and 77°–90° for the polycrystal, depending on the temperature.     

Critical Factors Affecting the Wettability of α-Alumina by Molten Aluminum

The wetting behaviors of α-Al₂O₃ single crystals with three different faces—R(01[Onemacr]2), A(01[Twomacr]0), and C(0001)—and polycrystals (PC) by molten aluminum were studied over a wide temperature range using both a conventional and an improved sessile-drop method. The critical factors affecting the wettability, such as temperature, atmosphere, substrate surface roughness, and crystallographic orientation, and the influence from the experimental technique, were thoroughly investigated. The results show that the aluminum surface oxidation and the thickness of the oxide film have a pronounced effect on the wettability, especially at low temperatures. To eliminate this effect, the experimental temperature must be over a critical value. Vacuum favors lowering this value compared with atmosphere, and the improved sessile-drop method, particularly using an impingement-dropping mode (I-mode), helps to weaken this effect by mechanical disruption and removal of the oxide film. However, the dropping distance and the dropping force must be controlled to prevent a receding contact angle. The effects of the substrate surface roughness and temperature are not significant in the case of a clean and a fine-prepared aluminum surface. On the other hand, the effect of the aluminum crystallographic orientation is noticeable and the wettability is in the order of R > A > PC > C. The intrinsic contact angles of the Al/α-Al₂O₃ system in the temperature range 1000°–1500°C were estimated to be 76°–85° for the R and A faces, 88°–100° for the C face, and 77°–90° for the polycrystal, depending on the temperature.     

Formation of microcapsules of medicines by the rapid expansion of a supercritical solution with a nonsolvent

The rapid expansion from a supercritical solution with a nonsolvent (RESS‐N) was applied to the formation of polymeric microcapsules containing medicines such as p‐acetamidophenol, acetylsalicylic acid, 1,3‐dimethylxanthine, flavone, and 3‐hydroxyflavone. A suspension of medicine in carbon dioxide (CO₂) containing a cosolvent and dissolved polymer was sprayed through a nozzle to atmospheric pressure. The pre‐expansion pressure was 10–25 MPa, and the temperature was 308–333 K. The polymers were poly(L ‐lactic acid) (molecular weight = 5000), poly(ethylene glycol) (PEG; PEG4000, molecular weight = 3000; PEG6000, molecular weight = 7500; and PEG20000, molecular weight = 20,000), poly(methyl methacrylate) (molecular weight = 15,000), ethyl cellulose (molecular weight = 5000), and PEG–poly(propylene glycol)–PEG triblock copolymer (molecular weight = 13,000). The solubilities of the polymers as coating materials and these medicines as core substance were very low in CO₂. However, the solubilities of these polymers in CO₂ significantly increased with the addition of low molecular weight alcohols as cosolvents. After RESS‐N, polymeric microcapsules were formed according to the precipitation of the polymer caused by a decrease in the solvent power of CO₂. This method offered three advantages: (1) enough of the coating polymers, which were insoluble in pure CO₂, dissolved; (2) the microparticles of the medicine were encapsulated without adhesion between the particles because a nonsolvent was used as a cosolvent and the cosolvent remaining in the mixture was removed by the gasification of CO₂; and (3) the polymer‐coating thickness was controlled with changes in the feed composition of the polymer for drug delivery. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 742–752, 2003     

Tribological Properties of Silicon Carbide and Silicon Carbide–Graphite Composite Ceramics in Sliding Contact

A monolithic SiC ceramic and two SiC–C composite ceramics containing 10 and 20 vol% graphite were fully densified with Al₄C₃ and B₄C as additives. The tribological properties of these materials were evaluated by sliding against sintered silicon carbide under dry conditions using two tribometers, block-on-ring and pin-on-disk, where wear occurred under low and high contact stresses, respectively. For all three materials, under low stress, worn surfaces were smooth and wear processes were dominated by tribochemical reaction; under high stress, worn surfaces were rough and wear processes were dominated by fracture and three-body abrasion. A lubricating effect of the graphite particles in the SiC–C composites was observed in all sliding tests. However, while the addition of graphite could concurrently result in a reduction in friction and an increase in wear resistance in the block-on-ring tests, the addition of graphite led to sharply enhanced wear rates despite the lowered coefficients of friction in the pin-on-disk tests. The cause for that difference was attributed to the effect of both the hardness of the materials and the contact stresses.     

Thermoelectric properties of oxide ceramics

Thermoelectric properties of several oxides were investigated. Al₂O₃-, TiO₂- or ZrO₂-doped ZnO showed large power factor over the wide temperature range. Fe₂O₃. showed large power factor by doping of TiO₂. BaO-doped RuO₂, BaRuOi₃ and CaRuO₃ showed large power factor at high temperature. Improvement of electrical conductivity by doping was effective to increase power factor in these oxide materials.     

Round-robin exercise on the three- and four-point flexural strength of thin ceramic plates for power modules

Round-robin exercises on three- and four-point flexural tests were successfully conducted to evaluate the fracture strength of Si₃N₄, Al₂O₃, and AlN thin plates for power modules. A 0.64 mm × 12 mm × 40 mm test specimen was loaded in three-point flexure with a major span of 30 mm or was loaded in four-point flexure with a major/minor span of 30/10 mm. For a 0.32 mm × 12 mm × 20 mm test specimen, both major and minor spans were halved. All test specimens were loaded in a fully articulated fixture provided by the test organizer. Reasonable consistencies in the resultant flexural strength were obtained between laboratories, indicating our new test condition for three- and four-point bending of thin ceramic plates is satisfactory for reliable measurement of the flexural strength.     

IR Practical Extinction Coefficients of Water in Alkali Lime Silicate Glasses Determined by Nuclear Reaction Analysis

Infrared spectroscopy (IR) is widely used to determine the water concentration in glasses, whereas determination of the IR practical extinction coefficient is necessary to deduce the absolute water concentration of glasses on the basis of Beer–Lambert law. From the nuclear reaction analysis data, the IR practical extinction coefficients of water were successfully determined for the alkali lime silicate glasses with different levels of sodium/potassium cation (Na/K) ratio. The two‐band method is well‐known to be useful for the determination of the water concentration in some alkali lime silicate glasses. It is proved here that the two‐band method is not applicable to the variety of composition for alkali lime silicate and soda lime aluminosilicate glasses, whereas it is valid for the similar composition of soda lime silicate glasses [SLS: Composition (in mol%) 16Na₂O·10CaO·74SiO₂]. The single‐band procedure with the IR practical extinction coefficient is crucial for the determination of the precise water concentration in the wide variety of glass composition although the determination of the IR practical extinction coefficient is troublesome. It also appears that the ion radius of alkali affects the IR practical extinction coefficient and the chemical state of OH group in glasses.