졸-겔법에 의한 TiO2 미분말 합성과 반응메카니즘(I):Titanium isopropoxide의 가수분해

명중재; 정용선; 경진범; 김호건

Journal of the Korean Industrial and Engineering Chemistry, Vol.7, No.4, 794-801, August, 1996

Export Citation

졸-겔법에 의한 TiO2 미분말 합성과 반응메카니즘(I):Titanium isopropoxide의 가수분해

Synthesis of TiO₂ Fine Powder by Sol-Gel Process and Reaction Mechanism(Ⅰ) : Hydrolysis of Titanium Isopropoxide

명중재, 정용선, 경진범, 김호건

초록

Isopropanol 용매 내에서 titanium isopropoxide(Ti(O-ⁱPr)₄)의 가수분해반응에 의하여 TiO₂ 미분말을 합성하였고 가수분해 반응 속도를 자외선분광법에 의하여 측정하였다. 반응은 Ti(O-ⁱPr)₄)의 농도에 비하여 물 농도를 크게 하여 유사일차반응으로 진행시켰고, 물 농도 및 온도의 변화에 따른 반응속도상수를 Guggenheim method로 계산하였다. 또한 물의 동위원소 효과를 측정하여 반응에 참여하는 물분자의 촉매성을 확인하였다. 입도분석과 미세구조 관찰 결과, 얻어진 TiO₂ 미분말은 0.3㎛정도의 입자크기를 갖는 구형의 입자로 확인되었다. 또한 반응속도로부터 전이상태에 참여하는 n value와 열역학적 파라메타를 계산한 결과, Ti(O-ⁱPr)₄)의 가수분해반응은 이분자 반응인 S_N 2 mechanism으로 진행하는 것으로 추정되었다.

TiO₂ fine powders were synthesized via hydrolysis reaction of titanium isopropoxide in isopropanol solvent and the reaction rates were studied by use of UV spectroscopic method. The reactions were controlled to proceed to pseudo-first-order reaction in the presence of excess water in isopropanol solvent. The rate constants which varied with temperature and concentration of water were calculated by Guggenheim method. Reactions using D₂O were also carried out to determine the catalytic character of water. n value of water molecules in transition state and the thermodynamic parameters showed that the reaction proceeded by S_N2 mechanism. TiO₂ powders synthesized in this reaction were almost spheric forms and had average particle sloe of 0.3㎛ diameter.

[References]

Ikeda M, Lee SK, Shinozaki K, Mizutani N, J. Ceram. Soc. Jpn., 100, 680 (1992)
Stober W, Fink A, Bohn E, J. Colloid Interface Sci., 26, C199 (1982)
Huynh TC, Bleier A, Bowen HK, Bull. Am. Ceram. Soc., 61, 336 (1982)
Fegley B, Bowen HK, Rigione LJ, Todd D, Bull. Am. Ceram. Soc., 62, 374 (1983)
Hartel RW, Berglund KA, Mater. Res. Soc., 73, 633 (1986)
Babonneau F, Leaustic A, Livage J, Mater. Res. Soc., 121, 317 (1988)
Doeuff S, Henry M, Sanchez C, Livage J, J. Non-Cryst. Solids, 89, 206 (1987)
Assink RA, Kay BD, Mater. Res. Soc., 121, 25 (1988)
Pouxviel JC, Boilot JP, Beloeil JC, Lallemand JP, J. Non-Cryst. Solids, 89, 345 (1987)
Guggenheim EA, Phil. Mag., 2, 538 (1926)
Kingery WD, Bowen HK, Uhlmann DR, "Introduction to Ceramics," 2/e, 95, John Wiley & Sons, New York (1960)
Williams CE, May RP, Guinier A, "Materials Science and Technology," eds. R.W. Cahn, P. Haasen and E.J. Kramer, 2B, 611, VCH, New York (1993)
Barringer EA, Bowen HK, Commun. Am. Ceram. Soc., C199 (1982)
Bunton CA, Shiner VJ, J. Am. Chem. Soc., 83, 3207 (1961)
Fedor LR, Bruice TC, J. Am. Chem. Soc., 87, 4138 (1965)
Gopalakrishnan G, hogg JL, J. Org. Chem., 46, 4959 (1981)
Hudson RF, Ber. Bunsenges Physic. Chem., 68, 215 (1964)
Brown DA, Hudson RF, J. Chem. Soc., 883 (1953)
Kivinen A, Acta. Chem. Scand., 19, 845 (1965)
Livage J, "Chemical Processing of Ceramics," eds. B.I. Lee and E.J.A. Pope, 3, Marcel Dekker Inc., New York (1994)

[Referenced By]

[1] Ikeda M, Lee SK, Shinozaki K, Mizutani N, J. Ceram. Soc. Jpn., 100, 680 (1992)

[2] Stober W, Fink A, Bohn E, J. Colloid Interface Sci., 26, C199 (1982)

[3] Huynh TC, Bleier A, Bowen HK, Bull. Am. Ceram. Soc., 61, 336 (1982)

[4] Fegley B, Bowen HK, Rigione LJ, Todd D, Bull. Am. Ceram. Soc., 62, 374 (1983)

[5] Hartel RW, Berglund KA, Mater. Res. Soc., 73, 633 (1986)

[6] Babonneau F, Leaustic A, Livage J, Mater. Res. Soc., 121, 317 (1988)

[7] Doeuff S, Henry M, Sanchez C, Livage J, J. Non-Cryst. Solids, 89, 206 (1987)

[8] Assink RA, Kay BD, Mater. Res. Soc., 121, 25 (1988)

[9] Pouxviel JC, Boilot JP, Beloeil JC, Lallemand JP, J. Non-Cryst. Solids, 89, 345 (1987)

[10] Guggenheim EA, Phil. Mag., 2, 538 (1926)

[11] Kingery WD, Bowen HK, Uhlmann DR, "Introduction to Ceramics," 2/e, 95, John Wiley & Sons, New York (1960)

[12] Williams CE, May RP, Guinier A, "Materials Science and Technology," eds. R.W. Cahn, P. Haasen and E.J. Kramer, 2B, 611, VCH, New York (1993)

[13] Barringer EA, Bowen HK, Commun. Am. Ceram. Soc., C199 (1982)

[14] Bunton CA, Shiner VJ, J. Am. Chem. Soc., 83, 3207 (1961)

[15] Fedor LR, Bruice TC, J. Am. Chem. Soc., 87, 4138 (1965)

[16] Gopalakrishnan G, hogg JL, J. Org. Chem., 46, 4959 (1981)

[17] Hudson RF, Ber. Bunsenges Physic. Chem., 68, 215 (1964)

[18] Brown DA, Hudson RF, J. Chem. Soc., 883 (1953)

[19] Kivinen A, Acta. Chem. Scand., 19, 845 (1965)

[20] Livage J, "Chemical Processing of Ceramics," eds. B.I. Lee and E.J.A. Pope, 3, Marcel Dekker Inc., New York (1994)