纳米HS型沸石合成及长大机制的研究

通过清夜合成法成功地合成了纳米ＨＳ沸石,通过Ｘ射线粉末衍射法和高分辨率透 射电镜对产物进行了表征,并对其长大机制进行了分析．结果表明,纳米颗粒包含若干个尺寸 大致相同而晶体学位向不同的亚晶,其长大机制为聚集增长机制．     

Green emitting β$\ubeta$-SiAlON:Eu2+ phosphors derived from chemically modified perhydropolysilazanes

We report the first synthesis of β-SiAlON:Eu²⁺ phosphors from single-source precursors, perhydropolysilazane (PHPS), chemically modified with Al(OCH(CH₃)₂)₃, and EuCl₂. The reactions occurring during the precursor synthesis and the subsequent thermal conversion of polymeric precursors into β-SiAlON:Eu²⁺ phosphors have been studied by a complementary set of analytical techniques, including infrared spectroscopy, gas chromatography–mass spectrometry, thermogravimetry–mass spectrometry, X-ray diffraction (XRD), photoluminescence spectroscopy, and scanning electron microscopy. It has been clearly established that Al(OCH(CH₃)₂)₃ immediately reacted with PHPS to afford N–Al bonds at room temperature, whereas N–Eu bond formation was suggested to proceed above 600°C accompanied by the elimination of HCl up to 1000°C in flowing N₂. The subsequent 1800°C-heat treatment for 1 h under an N₂ gas pressure at 980 kPa allowed converting the single-source precursors into fine-grained β-SiAlON:Eu²⁺ phosphors. XRD analysis revealed that the Al/Si of .09 was the critical atomic ratio in the precursor synthesis to afford single-phase β-SiAlON (z = .55). Moreover, Eu²⁺-doping was found to efficiently reduce the carbon impurity in the host β-SiAlON. The polymer-derived β-SiAlON:Eu²⁺ phosphors exhibited green emission under excitation at 460 nm and achieved the highest green emission intensity at the critical dopant Eu²⁺ concentration at 1.48 at%.     

In situ Raman spectroscopy analysis of local structure in dry gel for zeolite beta synthesis

To investigate faster crystallization of zeolite beta by the dry-gel conversion method, the local structure of the dry gel before synthesis was quantitatively evaluated using in situ Raman spectroscopy during the drying process. The dry gel prepared from Si and Al sources, and tetraethylammonium hydroxide solution was crystallized after several hours by the dry-gel conversion method. The conformational change of TEA⁺ cations was observed during the drying process by the deconvolution of the spectrum, and the conformational change was larger than that during the synthesis process. The rate of conformational change was increased with the drying temperature, and the apparent activation energy was estimated to be 68.2 kJ/mol. The generation and transformation of double three-membered silicate rings (D3Rs) and 4-2 type secondary building units (SBUs), which are essential for the crystallization of zeolite beta, were observed during the drying process. The transformation from D3R to 4-2 SBU in the dry gel during drying process could be confirmed quantitatively by the difference of the time variation for the amounts of these silicate building units estimated by in situ observation.     

Gas permeation and thermomechanical properties for macroporous alumina focused on necking size at grain boundaries

The gas permeation and thermomechanical properties of macroporous alumina used as a support substrate for microporous ceramic permselective membranes were investigated. The porosity, pore size, and apparent necking size between grains of macroporous alumina were systematically varied, and the relationships between the porous microstructure and material properties were examined. The grain necking size at alumina grain boundaries was evaluated by microstructural observations. The nitrogen gas permeance of the porous alumina increased with increasing pore size. All the measured thermal and mechanical properties decreased with increasing porosity. The properties of porous alumina samples with extensive grain necking showed higher values even in samples with the largest pore size. The high thermal conductivity of porous alumina with extensive grain necking was due to the low interfacial thermal resistance at grain boundaries. Porous alumina with extensive grain necking had high thermal shock strength due to the higher thermal conductivity. It was demonstrated that a porous structure combining high gas permeability and excellent fracture resistance could be successfully achieved.