계면활성제 수용액에서 미셀형성(제2보) -계면활성제/탄화수소/물의 상 변화에 따른 자기확산-

최성옥; 이진희; 김상춘; 남기대

Journal of the Korean Industrial and Engineering Chemistry, Vol.10, No.1, 112-117, February, 1999

Studies on the Micelle Formation of Surfactant Solution(2) -Self-Diffusion by Phase Transition in Ternary System of Surfactant/Hydrocarbon/Water-

최성옥, 이진희, 김상춘, 남기대

초록

Pulsed Field Gradient NMR(FT-PFGE)을 이용하여 N-alkyl-N, N-dimethylamine oxide/hydrocarbon/D₂O[C_nDMAO/C_n'H_2n'+2/D₂O] 3성분계에서 자기확산 계수를 측정하였다. 여기서 n=12, 14, 16인 계면활성제를 사용하였으며, n'=6, 8, 10, 12, 14인 탄화수소를 사용하였다. 미셀 상에서 주로 확산은 미셀의 유체역학적 이동에 지배되며, 미셀들의 충돌로 가용화된 탄화수소의 교환에 의해서도 일부 이루어진다. 이 연구는 계면활성제의 알킬 사슬 길이와 탄화수소 분자크기의 변화에 따라서 검토되었다. 그 결과 큐빅 상에서 용매는 물의 연속상에서 거동에 대한 전형적인 자기확산 계수 값을 나타내고, 이때 장애물로서 마이크로에멀젼 액적이 작용한다. 겔 상태에서 계면활성제의 유동성은 낮고, 알킬 사슬 길이가 가장 짧은 계면활성제에 대해서만 결정되었다. 겔 내에서 미셀들 간의 탄화수소 교환은 호핑 과정에 의해서 일어나는 것을 알았고, 회합율은 계면활성제의 알킬 사슬 길이에 따라 감소하였다.

The pulsed field gradient NMR method has been used to determine self-diffusion coefficients in ternary N-alkyl-N, N-dimethylamine oxide/hydrocarbon/D₂O system. For n=12, 14, 16 and n'=8, 10, 12, 14, 16, in the micellar phase, diffusion is chiefly governed by the hydrodynamic transport of micelles, supplemented by an exchange of solubilized hydrocarbon upon micellar collisions. This investgation is performed by variations in both the surfactant alkyl chain length and in the size of the hydrocarbon molecules. In cubic phases, the solvent still exhibits values of the diffusion coefficients which are typical for motion in a continuous water phase, with the microemulsion droplets acting as obstacle. Mobilities of the surfactant in the gel state were low and have been determined only for the surfactant(C₁₂DMAO) with the shortest alkyl chain length. Exchange of hydrocarbon between micellar entities in the gel was found to be occured by a hopping process, the associated rate decreased with alkyl chain length of the surfactant.

Keywords:¹HNMR;Self-diffusion;FT-PGSE Method

[References]

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[1] Fontell K, Colloid Polym. Sci., 268, 264 (1990)

[2] Fontell K, Adv. Colloid Interface Sci., 41, 127 (1992)

[3] Fontell K, Mandell L, Ekwall P, Acta Chem. Scand., 22, 3209 (1968)

[4] Mesa CL, Khan A, Fontelland K, Lindman BJ, J. Colloid Interface Sci., 103, 373 (1985)

[5] Anderson DA, Wennerstrom H, J. Phys. Chem., 94, 8683 (1990)

[6] Lindman B, Shinoda K, Olsson U, Anderson D, Colloids Surf., 38, 205 (1989)

[7] Russo PS, ACS Symp. Ser., 1, 350 (1987)

[8] Oetter G, Hoffmann H, Colloid Sur., 38, 225 (1989)

[9] Gradzielski M, Hoffmann H, Oetter G, Colloid Polym. Sci., 268, 167 (1990)

[10] Walther KL, Gradzielski M, Hoffmann H, Wokaun A, J. Colloid Interface Sci., 153, 272 (1992)

[11] Stejskal EO, Tanner JE, J. Chem. Phys., 42, 288 (1964)

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

[13] Tiddy GJT, J. Colloid Interface Sci., 53, 461 (1975)

[14] Stilbs P, J. Colloid Interface Sci., 89, 547 (1982)

[15] Nilsson PG, Lindman B, J. Phys. Chem., 88, 4764 (1984)

[16] Haggerty JF, Roberts JE, J. Appl. Polym. Sci., 58(2), 271 (1995)

[17] Stilbs P, Prog. NMR Spectrosc., 19, 1 (1987)

[18] Eriksson PO, Lindman G, Burnell EE, Tiddy GJT, J. Chem. Soc.-Faraday Trans., 84, 3219 (1988)

[19] Aniansson EAG, Wall SN, Almgreen M, Hoffmann H, J. Hem., 80, 905 (1976)

[20] Oradd G, Lindman G, Johansson L, Wikander G, J. Phys. Chem., 96, 5176 (1992)

[21] Crank J, The Mathematics of Diffusion. Claredon., Oxford (1075)