계면활성제 수용액에서 미셀형성(제3보) -비이온성과 이온성계면활성제의 혼합 미셀에 있어 자기확산 및 프로톤 이완-

최성옥; 곽광수; 박흥조; 남기대

Journal of the Korean Industrial and Engineering Chemistry, Vol.10, No.6, 876-880, October, 1999

Micelle Formation of Surfactant Solution(3) -Self-Diffusion and ¹H Relaxation for Mixed Micelle of Nonionic and Ionic Surfactants-

최성옥, 곽광수, 박흥조, 남기대

초록

이온성과 비이온성계면활성제의 혼합 미셀 용액의 자기확산계수는 NMR FT-PGSE법으로 측정하였다. 또한 프로톤 NMR 피크의 폭을 관찰하였다. 연구된 계는 C_{12EO₅/SDS/D₂O, C₁₂EO₅/DTAC/D₂O 및 C₁₂EO₈/SDS/D₂O의 혼합계이다. 모든 시료에서 솔벤트와 계면활성제의 몰비는 일정하고 계면활성제의 혼합비는 다양하게 실험을 하였다. C₁₂EO₅ 계에서 계면활성제의 자기확산계수는 이온성계면활성제의 혼합비가 약 25%일 때 최소치를 나타내었다. 비이온성게면활성제가 이온성계면활성제로 치환됨에 따라서 자기확산계수가 감소하는 것은 미셀간의 반발력이 증가하기 때문이다. 이온성계면활성제의 높은 분율에서 자기확산계수가 증가하는 것은 미셀의 크기가 감소하기 때문이다. C₁₂EO₈ 계에서 계면활성제의 혼합비의 효과는 분자의 기하학적 구조와 큰 관능기의 면적 때문에 거의 없다. 프로톤 NMR 피크와 자기확산계수는 상호 밀접한 관계를 나타내고 알킬 사슬의 메틸렌 시그날의 넓혀짐 현상은 자기확산계수가 작을 때 나타난다.}

The surfactant self-diffusion coefficients of mixed micellar solutions of ionic and nonionic surfactants have been measured by the NMR pulsed field gradient spin echo(FT-PGSE) method. In addition, the line widths of ¹H NMR signal have been monitored. The system investgated are C₁₂EO₅/SDS/D₂O, C₁₂EO₅/DTAC/D₂O, and C₁₂EO₈/SDS/D₂O. In the sample series, the molar ratios of D₂O to surfactant(ionic + nonionic) were kept constant while the surfactant mixing ratio was varied. For the C₁₂EO₅ system, the surfactant self-diffusion coefficient indicates minimum when the surfactant mixing ratio is about 20% ionic surfactant. The observed decrease in self-diffusion coefficients as nonionic surfactant was replaced by ionic surfactant is interpreted to mainly be due to an increased micelle-micelle repulsion. The increase in self-diffusion coefficients occurring at higher fraction of ionic surfactant is shown to be due to a decrease in micelle size. For the C₁₂EO₈ system, the effect of the surfactant mixing ratio is much weaker which can be understood by considering the molecular geometry and large headgroup area. The proton NMR line widths correlate well with the self-diffusion coefficients and broadening of the alkyl chain methylene signals is found when the self-diffusion coefficients is low.

Keywords:¹H self-diffusion;¹H-relaxation;FT-PGSE method

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[6] Scamehorg JF, Schechter RS, Wade WH, J. Dispersion Sci. Technol., 3, 261 (1982)

[7] Hoffman H, Ber. Bunsenes. Phys. Chem., 58, 1078 (1984)

[8] Oetter G, Hoffman H, J. Disp. Sci. Technol., 9, 49

[9] Rehage H, Hoffman H, Fard. Disc. Chem. Sci., 76, 363 (1983)

[10] Thurn H, Lobl M, Hoffman H, J. Phys. Chem., 89, 517 (1985)

[11] Stejskal EO, Tanner JE, J. Chem. Phys., 42, 20 (1965)

[12] Charvolin J, J. Chem. Phys., 58, 3999 (1973)

[13] London RE, Avitable J, J. Am. Chem. Soc., 23, 7765 (1977)

[14] Ulmius J, Lindman B, Lindblom G, Drakenberg T, J. Colloid Interface Sci., 65(1), 88 (1977)

[15] Otejskal EO, Tanner JE, J. Chem. Phys., 42, 288 (1965)

[16] Choi SO, Jeong HK, Lee JH, Nam KD, J. Korean Ind. Eng. Chem., 9(6), 822 (1998)

[17] Wennerstroma H, Linblom G, Q. Rev. Biophys., 10, 67 (1977)

[18] Wennerstroma H, Ulmius J, J. Mater. Reson., 23, 431 (1976)

[19] Bech P, J. Colloid Sci., 17, 325 (1962)

[20] Wennerstrom H, Lindman B, Phys. Rep., 52, 1 (1979)

[21] Abrahmsenalami S, Stilbs P, J. Phys. Chem., 98(25), 6359 (1994)

[22] Elseoud OA, Blasko A, Bunton CA, Langmuir, 10(3), 653 (1994)

[23] Balmbra RR, Clunie JS, Goodman JF, Nature, 222, 1159 (1969)

[24] Bull T, Lindman B, Mol. Cryst. Liq. Cryst., 28, 155 (1973)

[25] Fontell K, Mol. Cryst. Liq. Cryst., 63, 59 (1981)

[26] Leaver M, Furo I, Olsson U, Langmuir, 11(5), 1524 (1995)