금속 알콕시드를 이용한 투명 결정화유리의 저온 합성 (1) Li2Oㆍ1.7Al2O3ㆍ8.6SiO2 다공성 겔체의 합성

전경수; 탁중재; Kyung-Soo Chun; Joong-Jae Tak

Journal of the Korean Industrial and Engineering Chemistry, Vol.18, No.6, 568-574, December, 2007

Low Temperature Preparation of Transparent Glass-Ceramic Using Metal-Alkoxides (1) Synthesis and Properties of Porous Monolithic Gel in Li2Oㆍ1.7Al2O3ㆍ8.6SiO2

전경수^†, 탁중재¹

경원대학교 화학과
¹여주대학 인테리어 세라믹 디자인학과

Kyung-Soo Chun^†, and Joong-Jae Tak¹

Department of Chemistry, Kyungwon University, Songnam-Si 461-701, Korea
¹Department of Interior Ceramic Design, Yeo Joo Institute of Technology, Yeojoo-gun 469-705, Korea

E-mail:

초록

투명결정화 유리의 전구체로서 균열이 없는 Li2Oㆍ1.7Al2O3ㆍ8.6SiO2 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∼75 ℃, 건조속도 0.1∼0.3 %/h에서는 겔의 균열을 방지할 수 있어 안정한 괴상 겔을 제조할 수 있었다. 180 ℃에서 건조한 겔체는 비표면적, 기공부피 및 기공크기분포는 239.40 m2/g, 0.001∼0.03 mL/g 그리고 1∼122 nm 반지름의 미세구조로 된 투명 겔체로서 다공질 물질임이 확인되었고, 건조겔의 시차열분석 결과 800 ℃ 부근에서 1차 발열피크, 980 ℃ 부근에서가 2차 발열피크가 확인되어 결정화가 일어남을 알 수 있었다.

Crack-free dried gel monoliths of the composition Li2Oㆍ1.7Al2O3ㆍ8.6SiO2 have been prepared as a precursor of transparent glass-ceramic by the hydrolysis and polycondensation of mixed metal alkoxides in solutions containing N,N-dimethylformamide as the drying control chemical additive, alcohols, and water. It was investigated that activation energy for gelation according to the variation of water concentration ranged from 13 to 14 kcal/mol. Only when the amount of water for gelation was 3 times higher than the stoichiometric amount, monolithic dry gels were successfully prepared after drying at 70∼75℃ and at a rate of 0.1∼0.3%/h. The specific surface area, the pore volume, the average pore diameters of dried gel at 180℃ were about 239.40 m2/g, 0.001∼0.03 mL/g, and 145.62 Å, respectively. It showed that the dried monolithic gel had a porous body. The DTA curve had the first exothermic peak around 800 ℃ and the 2nd peak around 980 ℃, which may correspond to crystallization of the gel.

Keywords:hydrolysis;monolithic dry gel;specific surface;exothermic peak;pore volume

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[1] Beall GH, Duke DA, J. Mater. Sci., 4, 340 (1969)

[2] Buch A, Ish-shalom M, Reisfeld R, Kisilev A, Mat. Sci. ＆ Eng., 71, 383 (1985)

[3] Park YW, Kim HJ, J. Kor. Cer. Soc., 28, 406 (1991)

[4] Kim HG, Komatsu T, Shioya K, Matusita K, Tanaka K, Hirao K, Forum on Glass Science and Technology, Korea, 8 (1997)

[5] Sakka S, Kozuka H, Zhao G, Sol-Gel Optics, 108, 111 (1994)

[6] Glass Handbook, 作花濟夫, 境野照雄, 高橋克明, 213 (1975)

[7] Innocenzi P, Kozuka H, Sakka S, J. Sol-Gel Sci. Technol., 1305 (1994)

[8] Sakka S, Kozuka H, Zhao G, Forum on Glass Science and Technology, Korea,, 94 (1997)

[9] Spanhel L, Mennig M, Schubert H, Mat. Res.Soc. Symp. Proc., 272, 133 (1992)

[10] Fernander Navarro JM, Villegas MA, Glastech. Ber., 65, 32 (1992)

[11] Stooky SD, British patent 752243 (1954)

[12] 和田正道, 結晶化 glassの建材への應用, 第15回 New Ceramics Seminar (New Ceramics 技術開發の新たな指針の探る), 53 (1988)

[13] 機能性 Glasses, 堂山昌男, 山本良一, 164, 東京大學出版會 (1985)

[14] Yang JS, Sakka S, J. Kor. Cer. Soc., 25, 541 (1988)

[15] Yang JS, Sakka S, Mater. Sci., 25, 1773 (1990)

[16] Yang JS, Sakka S, Mater. Sci., 26, 1827 (1991)

[17] Yang JS, Kim BG, Kor. J. Mat. Res., 3, 207 (1993)

[18] Yang JS, Cho HS, J. Kor. Cer. Soc., 30, 535 (1993)

[19] Yang JS, Cho HS, J. Kor. Cer. Soc., 32, 507 (1995)

[20] Kweon CH, Ph.D. dissertation, Kyunghee Univ., Seoul, Korea (1992)

[21] Yang JS, J. Mater. Sci. Tech., 11, 145 (1998)

[22] Yoldas BE, Partlow DP, J. Mater. Sci., 23, 1895 (1988)

[23] Yang JS, Lee YT, Choi YW, J. Kor. Cer. Soc., 34, 611 (1997)

[24] Colby MW, Osaka A, Mackenzie JD, J. Non-Cryst. Solids, 99, 129 (1988)

[25] Brunauer S, Emmett PH, Teller E, J. Am. Chem. Soc., 60, 309 (1938)

[26] Powder Surface Area and Porosity, S. Lowell, and J. E. Shields, 2nd ed., 54, Chapma and Hall, London (1984)

[27] 作花濟夫, 162, 承風社, 東京 (1988)

[28] Bechtold MW, Vest RD, Plambec L, J. Am. Chem. Soc., 90, 4590 (1968)

[29] Brunauer S, Deming LS, Deming WE, Teller E, J. Am. Chem. Soc., 62, 1723 (1940)

[30] Brinker CJ, Scherer GW, Sol-Gel Science, 521, Academic Press, New York (1990)

[31] Gregg SJ, Sing KSW, Adsorption Surface Area and Porosity, 2nd ed., 111, Academic Press, London (1982)

[32] Kawaguchi T, Hishikura H, Iura J, Kokubo Y, J. Non-Cryst. Solids, 63, 61 (1984)

[33] Krol DM, Vanlierop JG, J. Non-Cryst. Solids, 63, 131 (1984)

[34] Prassas M, Phalippou J, Hench LL, J. Non-Cryst. Solids, 63, 375 (1984)