• 한국세라믹학회지
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• 제30권7호
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• pp.535-542
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• 1993

It was investigated in this study that a preparation method, activation energy, surface area, pore volume, pore size distribution and DTA analysis of the dry gel in process of producing monolithic porous gel in Li2O-Al2O3-TiO2-SiO2 system by the sol-gel technique using metal alkoxides. Activation energy for gellation according to the variation of water concentration and the kind of catalysts ranged from 10 to 20kcal/mole. Monolithic dry gels were prepared after drying at 9$0^{\circ}C$ when the amount of water for gellation was 4~8 times more than the stoichiometric amount, that was necessary for the full hydrolysis of the mixed metal alkoxide. The specific surface area, the pore volume, the average pore radius of the dried gel at 18$0^{\circ}C$ according to the various kinds of catalyst were about 348~734$m^2$/g, 0.35~0.70ml/g and 10~35$\AA$, respectively. It showed that the dry gels were porous body. As a result ofthe analysis of DTA, it was confirmed that the exothermaic peaks at 715$^{\circ}C$ and 77$0^{\circ}C$ was clue to the crystallization of dried gel.

• 한국세라믹학회지
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• 제32권4호
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• pp.507-515
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• 1995

The monolithic dry gels of the Li2O-Al2O3-TiO2-SiO2 system were prepared by the sol-gel technique using metal alkoxides as starting materials to obtain monolithic glass-ceramics at low temperature without melting. Activation energy for the crystal growth of the gel with 6.05% TiO2, nucleating ageng, for the preparation of Li2O-Al2O3-TiO2-SiO2 system glass-ceramic was 101.14kcal/mol. As a result of the analysis of DTA & XRD, it was confirmed that the crytallization of Li2O-Al2O3-TiO2-SiO2 system glass-ceramic was the most efficient when 6.05% TiO2, nucleating agent, was added. $\beta$-eucryptite solid solution crystals and $\beta$-spodumene solid solution crystals were detected in the sample heat treated above 85$0^{\circ}C$. The sintered gel heat treated at 85$0^{\circ}C$ had the specific surface area of 185$m^2$/g, the pore volume of 0.19cc/g and the average pore radius of 20.8$\AA$. This shows that the sintered gel is also comparatively porous material. In temperature range of 25~85$0^{\circ}C$ thermal expansion coefficient of the specimen which was crystallized for 10hrs at 85$0^{\circ}C$ was 6.7$\times$10-7/$^{\circ}C$, which indicated that the crystallized specimen was turned out to be the glass-ceramic with low thermal expansion.

• 공업화학
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• 제18권6호
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• pp.568-574
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• 2007

투명결정화 유리의 전구체로서 균열이 없는 $Li_2O1{\cdot}7Al_2O_3{\cdot}8.6SiO_2$ 조성인 다공성 괴상 겔을 formamide를 첨가한 알콕시드 용액으로부터 sol-gel방법으로 합성하였다. 겔 합성에서 겔화 활성화 에너지, 비표면적, 습윤겔의 완전 탈수에 필요한 온도, 기공의 부피 및 기공크기와 분포를 측정하였고, 겔의 결정화온도를 검토하고자 시차열분석을 실시하였다. 겔화의 활성화에너지는 가수분해에 필요한 물의 첨가량에 따라 13~14 kcal/mol 범위를 나타내고, 물의 첨가량이 가수분해시 필요한 이론량의 3배 이상일 경우, $70{\sim}75^{\circ}C$, 건조속도 0.1~0.3 %/h에서는 겔의 균열을 방지할 수 있어 안정한 괴상 겔을 제조할 수 있었다. $180^{\circ}C$에서 건조한 겔체는 비표면적, 기공부피 및 기공크기분포는 $239.40m^2/g$, 0.001~0.03 mL/g 그리고 1~122 nm 반지름의 미세구조로 된 투명 겔체로서 다공질 물질임이 확인되었고, 건조겔의 시차열분석 결과 $800^{\circ}C$ 부근에서 1차 발열피크, $980^{\circ}C$ 부근에서가 2차 발열피크가 확인되어 결정화가 일어남을 알 수 있었다.

• 한국세라믹학회지
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• 제32권12호
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• pp.1357-1368
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• 1995

Nasigels of composition Na0.75Zr2PSi2O12 and Na3Zr2PSi2O12 have been synthesized by the sol-gel technique using metal alkoxide precursors. The monolithic dry gels of Na0.75Zr2PSi2O12 with no crack have been prepared by the control of the shrinkage rte, but gels of Na3Zr2PSi2O12 were impossible to prepare without cracking. The gels treated up to 80$0^{\circ}C$ led to the formtion of glass but the glasses were converted to the crystalline phases at above this temperature. Crystaline phases precipitated from the Na0.75Zr2PSi2O12 glass were NASICON-like phase, Na2Si2O5, and free Zirconia. Phase that precipitated from the Na3Zr2PSi2O12 was only rhombohedral NASICON. For Na0.75Zr2PSi2O12 gels, framework of PO4 tetrahedra and SiO4(PO4) tetrahedra formed at low temperature but changed to that of SiO4 and SiO4(PO4) tetrahedras as it were crystallized. In the case of Na3Zr2PSi2O12 gel, framework of isolated PO4 and SiO4 tetrahedras formed at low temperature but changed to SiO4(PO4) tetrahedra framework which usually formed in the NASICON crystal after crystallization at high temperature. The gels treated up to 80$0^{\circ}C$ contained the residual water. The ionic conduction was attributed to the motion of proton and Na+ ion at low (up to 150~20$0^{\circ}C$) and high temperatures, respectively. As the temperature of heat treatment increased, ionic conductivity gradaully increased with the extent of precipitation of crystalline phase.