Effect of microstructures on dielectric breakdown strength of sintered reaction-bonded silicon nitride ceramics

Silicon nitride (Si₃N₄) was prepared from silicon by a sintered reaction-bonded silicon nitride method using yttria and magnesia as sintering additives. Post-sintering (PS) of nitrided compacts was carried out at 1850°C under a nitrogen pressure of 1 MPa. Effect of PS time on microstructure and dielectric breakdown strength (DBS) of the prepared Si₃N₄ ceramics was evaluated. The DBS was measured using specimens with four different thicknesses (0.30, 0.20, 0.10, and 0.05 mm) in order to examine the thickness dependence. The porosity of the sintered Si₃N₄ decreased by prolonging the PS time, and the full density could be achieved at the PS time of over 6 h. After full densification, rod-like β-Si₃N₄ grains grew up, and their maximum grain size increased from 45.1 to 154.7 μm by prolonging the PS time from 6 to 48 h. The DBS of the thick Si₃N₄ substrates (0.30 mm) showed little variation from 35.4 to 47.0 kV/mm, regardless of the PS time. On the other hand, that of the thin ones (0.05 mm) dramatically decreased from 99.5 to 9.8 kV/mm with increased the PS time from 6 to 48 h. Because the DBS sharply decreased at the thin substrate sintered for longer time in which some large-elongated grains might span the substrate thickness-wise throughout, it was inferred that the interface between β-Si₃N₄ grains and grain boundary phase/intergranular glassy films might be a path of the dielectric breakdown.     

Polymer-derived β-SiAlON:Eu2+ phosphors

A series of β-SiAlON:Eu²⁺ phosphors were synthesized from single-source precursors, perhydropolysilazane chemically modified with Al(OCH(CH₃)₂)₃, AlCl₃, and EuCl₂. The single-source precursors were converted to β-SiAlON:Eu²⁺ phosphors by pyrolysis under flowing N₂ or NH₃ at 1000°C, followed by heat treatment at 1800°C under an N₂ gas pressure at 980 kPa. By varying the molar ratio of the chemical modifiers, β-SiAlON:Eu²⁺ with the compositions close to the theoretical ones expressed as Si_6−zAl_zO_z−2yN_8−z+2y:yEu²⁺ were synthesized, where the z values and Eu²⁺ contents were controlled in the ranges of .44–.78 and .35–1.48 mol%, respectively. The polymer-derived β-SiAlON:Eu²⁺ phosphors exhibited green emission under excitation at 460 nm attributed to the 4f⁷–4f⁶(7f³)5d¹ transition of dopant Eu²⁺. High-angle annular dark-field-scanning transmission microscopy analysis confirmed that the doped-Eu²⁺ existed interstitially within the channels along the c axis of host β-SiAlON. Compared with the conventional powder metallurgy route, the polymer-derived ceramic route in this study offers some advantages in the grain growth of host β-SiAlON and photoluminescence properties in terms of green emission intensity under excitation at 460 nm, and the highest intensity was achieved for the polymer-derived β-SiAlON:Eu²⁺ with z = .64 and .37 mol% Eu²⁺.     

Pulsed Electric Current Sintering of Silicon Nitride

Pulsed electric current sintering (PECS) has been used to densify α-Si₃N₄ powder doped with oxide additives of Y₂O₃ and Al₂O₃. A full density (>99%) was achieved with virtually no transformation to β-phase, resulting in a microstructure with fine equiaxed grains. With further holding at the sintering temperature, the α-to-β phase transformation took place, concurrent with an exaggerated grain growth of a limited number of elongated β-grains in a fine-grained matrix, leading to a distinct bimodal grain size distribution. The average grain size was found to obey a cubic growth law, indicating that the growth is diffusion-controlled. In contrast, the densification by hot pressing was accompanied by a significant degree of the phase transformation, and the subsequent grain growth gave a broad normal size distribution. The apparent activation energy for the phase transformation was as high as 1000 kJ/mol for PECS, almost twice the value for hot pressing (∼500 kJ/mol), thereby causing the retention of α-phase during the densification by PECS.     

Modern interpretation on the high-stretching of natural rubber attained by the classic ‘racking’ method

To investigate the mechanism of high elongation of natural rubber attained by the ‘racking method’, a strip of smoked-sheet was elongated up to 150 times in length, by stretching rapidly at room temperature and forcing to shrink at 75-80 °C repeatedly. On X-ray diffraction, a typical fibre pattern with an amorphous ring appeared already at ×10 (stretch ratio=10). The degree of crystallinity increased to the level of 17-18% at ×20 and turned to decrease after ×60, but the degree of crystallite orientation reached at a high level already at ×10 and did not change significantly and the half-height width of reflection profiles stayed almost at a constant level, while the Young's modulus increased up to ca. 300 MPa at ×100 and then fell rather discontinuously. It was assumed that some fractions of chain segments between entanglements were gradually broken in each step of stretching operation, rather than disentangled and slipped.     

Crystallographic Texture Development in Bismuth Sodium Titanate Prepared by Reactive-Templated Grain Growth Method

Bi_0.5Na_0.5TiO₃ (BNT) and 0.94Bi_0.5Na_0.5TiO₃·0.06BaTiO₃ (BNT–BT) bulk ceramics with extensive 〈100〉 texture were prepared by the reactive-templated grain growth method, using platelike Bi₄Ti₃O₁₂ (BIT) particles as templates for BNT. Calcined compacts were composed of matrix grains with random orientation and 〈100〉-oriented grains transformed from aligned BIT particles, and the texture developed by the growth of oriented grains during sintering. Ceramics with extensive texture were obtained by using the starting mixture containing the maximum concentration of platelike BIT to form the maximum volume fraction of oriented grains.     

Rapid evaluation of oxidation catalysis by gas sensor system: total oxidation, oxidative dehydrogenation, and selective oxidation over metal oxide catalysts

The rapid evaluation of catalysis is an indispensable technology for the success of combinatorial chemistry. A small-sized, less expensive, easily operating screening is desirable for parallel settings which dramatically shortens the evaluation time. Recent advances in gas sensors have enabled us to use them for the rapid evaluation of oxidation catalysis. Three typical catalytic oxidations over metal oxide catalysts were evaluated by gas sensor systems optimized for each catalytic system. The first one is the total oxidation of carbon monoxide in air. Five catalytic combustion-type gas sensors were used in a parallel reactor system to shorten the evaluation time. The second one is the oxidative dehydrogenation (ODH) of ethane over the mixed oxide of nickel and iron. The evaluation of the ODH catalysis was performed by a selective olefin sensor which determines the concentration of C₂H₄ in C₂H₆. The third one is the selective oxidation catalysis of propane over alkali modified Fe/SiO₂. The effluents including CO, CO₂, aldehydes and ketones in propane were analyzed by the CO, CO₂ and semiconductor-type gas sensors selective toward aldehydes and ketones. These evaluation results indicated that gas sensors have a good potential for the rapid evaluation of oxidation catalysts.     

Preparation of sharp-melting hard palm midfraction and its use as hard butter in chocolate

Preparation of hard palm midfractions (PMF) and its use as a cocoa butter equivalent ingredient were studied. Hard PMF is obtained by multistep fractionation of palm oil involving dry fractionation (DF) and/or solvent fractionation (SF), usually using hexane or acetone. From our experience, in acetone, a polar solvent, symmetrical 1,3-disaturated triacylglycerols tend to selectively crystallize more than nonsymmetrical 1,2- or 2,3-disaturated triacylglycerols, making it suitable for obtaining the solid midfraction. Unfortunately, triacylglycerols are very soluble in hexane, and temperatures at least 15 degrees lower than those required for acetone must be used for equivalent crystal yields. On the other hand, DF is a less expensive and safer process. Thus, multistep fractionation combining DF and SF using acetone was developed to achieve sufficient removal of high-melting components, and further enrichment of 1,3-dipalmitoyl-2-oleoylglycerol and the hard PMF was obtained by triple-step fractionation of palm olein or double-step fractionation of soft PMF. Compared to conventional hard PMF, this hard PMF had a steeper melting curve and better snapping and sharp-melting qualities when used in chocolate. Heat resistance of the hard PMF chocolate was similar to the conventional hard PMF chocolate, and its bloom resistance could be improved by adding polyglycerol fatty acid esters.     

Stereoselective partitioning of organic substrates by thermoresponsive polymers in aqueous phases

Partitioning of organic substrates by thermoresponsive polymer having N‐acryloylaminoalcohol moieties in aqueous phase has been studied. Thermoresponsive polymers, such as poly(N‐isopropylacrylamide) (PNIPAAm) and poly(NIPAAm‐co‐N‐acryloyl‐(±)‐alaninol) (poly(NIPAAm‐co‐HIPAAm)), were found to concentrate several organic substrates into the hydrophobic field generated during their phase transition. The amount of the substrates recoverd from the polymer phase mainly depended on the hydrophobicity of the substrates. Aqueous solutions of PNIPAAm (lower critical solution temperature, LCST = 33°C) and poly(NIPAAm‐co‐HIPAAm) (LSCT = 41°C) containing 1‐phenylethanol showed LCSTs at 22°C and 33°C, respectively. The changes of LCSTs indicate that specific interactions such as hydrogen bonding between the side chain functionalities of the polymers and the substrates influence the phase transition behavior. Moreover, new optically active polymers having chiral aminoalcohol moieties have been synthesized by copolymerizations of NIPAAm with N‐acryloylaminoalcohols such as N‐acryloyl‐(S)‐alaninol and N‐acryloyl‐(S)‐prolinol. The (R)/(S) ratio of 1‐phenylethanol recovered from poly(NIPAAm‐co‐N‐acryloyl‐(S)‐alaninol) and poly(NIPAAm‐co‐N‐acryloyl‐(S)‐prolinol) were determined to be 75/25 and 68/32, respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3458–3464, 2013     

Raman spectra of high‐density,low‐density,and linear low‐density polyethylene pellets and prediction of their physical properties by multivariate data analysis

Raman spectra have been measured for pellets of five samples of high‐density polyethylene (HDPE), seven samples of low‐density polyethylene (LDPE), and six samples of linear low‐density polyethylene (LLDPE). The obtained Raman spectra have been compared to find out characteristic Raman bands of HDPE, LDPE, and LLDPE. Principal component analysis (PCA) was applied to the Raman spectra in the 1600–650 cm^?1 region after multiplicative scatter correction (MSC) to discriminate the Raman spectra of the three different PE species. They are classified into three groups by a score plot of PCA factor 1 vs. 2. HDPE with high density and high crystallinity gives high scores on the factor 1 axis, while LDPE with low density and low crystallinity yields negative scores on the same axis. It seems that factor 1 reflects the density or crystallinity. A PC weight loadings plot for factor 1 shows six upward peaks corresponding to the bands arising from the crystalline parts or all‐trans ? (CH₂)_n? groups and seven downward peaks ascribed to the bands of the amorphous or anisotropic regions and those arising from the short branches. Partial least‐squares (PLS‐1) regression was applied to the Raman spectra after MSC to propose calibration models that predict the density, crystallinity, and melting points of the polyethylenes. The correlation coefficient was calculated to be 0.9941, 0.9800, and 0.9709 for the density, crystallinity, and melting point, respectively, and their root‐mean‐square error of cross validation (RMSECV) was found to be 0.0015, 3.3707, and 2.3745, respectively. The loadings plot of factor 2 for the prediction of melting point is largely different from those for the prediction of density and crystallinity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 443–448, 2002     

Synthesis of 4‐Aryl‐2‐Quinolones via Copper‐Catalyzed Hydroarylation of (o‐Aminophenyl)propiolates with Arylboronates

4‐Aryl‐2(1H)‐quinolones were efficiently synthesized via copper‐catalyzed hydroarylation of (o‐aminophenyl)propiolates with arylboronic acid neopentyl glycol esters. The substrate propiolates were prepared from the corresponding silylalkynes with carbon dioxide by Kondo’s carboxylation method using N,N‐dimethylformamide as a solvent. Hydroarylation was performed in the presence of 3 mol% copper(II) acetate in methanol at 28 °C for 12 h and subsequent deprotection using trifluoromethanesulfonic acid (3.0 equiv.) at 65 °C for 2 h in the same pot to afford the desired 4‐aryl‐2(1H)‐quinolones in 39–89% yields.