ADS/OTAC 혼합 계면활성제 수용액에서 형성된 마이셀과 층막구형체의 크기 및 구조에 대한 작은 각 중성자 산란 연구

김홍운; 이진규; 임경희; Hong-Un Kim; Jin-Kyu Lee; Kyung-Hee Lim

Journal of the Korean Industrial and Engineering Chemistry, Vol.16, No.2, 231-237, April, 2005

A Small-Angle Neutron Scattering Study for Sizes and Structures of Micelles and Vesicles Formed in Aqueous Solutions of Mixed Surfactants ADS/OTAC

김홍운, 이진규¹, 임경희 ^{1, †}

동양공업전문대학 응용화학과
¹중앙대학교 화학공학과

Hong-Un Kim, Jin-Kyu Lee¹, and Kyung-Hee Lim^{1, †}

Department of Applied Chemistry, Dongyang Technology College, Seoul 152-714, Korea
¹Department of Chemical Engineering, Chung-Ang University, Seoul 156-756, Korea

E-mail:

초록

본 연구는 이온성 계면활성제 수용액에 대하여 음이온성 ammonium dodecyl sulfate (ADS)와 양이온성 octadecyltrimethyl ammonium chloride (OTAC)의 단일계 그리고 이들의 혼합 계면활성제 수용액에서 형성되는 혼합 마이셀과 층막구형체(vesicle)의 크기 및 구조에 대하여 작은 각 중성자 산란법을 통하여 해석하였다. 10 mM ADS와 9mM OTAC 수용액에서 형성된 단일 계면활성제 마이셀의 크기는 각각 40과 61 Å이었고, 이들의 구조는 모두 공모양이었다. 농도에 따른 구조 변화는 SANS 스펙트라로는 관찰되지 않았지만, 300 mM까지 농도가 증가할수록 마이셀 사이의 거리가 줄어들었으며 250 mM 이상에서는 거리가 일정하였다. 그러므로 이보다 큰 농도에서 구조전이가 일어날 것으로 기대된다. ADS/OTAC 혼합계의 상도해 상으로 혼합 마이셀과 층막구형체가 공존하는 영역에서 지수 법칙의 지수값이 1.6을 나타내므로 이를 확인하였다. 또한 자발적으로 형성된 층막구형체 영역은 이중막 구조 분석을 통하여 고찰하였으며, 이중막을 이루는 층막구형체의 층 간 두께는 전체 농도가 증가함에 따라 감소하였다. 이는 농도가 증가됨에 따라 같은 전하를 띠고 있는 층막구형체 사이에 반발력이 강하게 작용하여 한층막구형체의 층간 거리는 줄어들고, 이로 인해 농도가 증가할수록 층막구형체의 크기는 감소하는 것으로 해석되었다. ACS가 90 몰%인 혼합용액에서 9 mM은 상도해 상으로 혼합 마이셀과 층막구형체의 경계 영역으로 구분이 되지 않았지만, SANS 분석 결과 층막구형체 영역에 해당하여 보다 정확한 상도해를 완성할 수 있었다.

The sizes and structure of micelles and vesicles formed in ammonium dodecyl sulfate (ADS)/octadecyl trimethyl ammonium chloride (OTAC) mixed aqueous solutions were analyzed by small-angle neutron scattering. In micellar regions of pure ADS and OTAC aqueous solution, the spherical micelles were formed at given concentrations and their sizes were 40 and 61 Å, respectively. The structure transition of pure micelles occurred above 300 mM due to the constancy of the intermicellar distance above 250 mM. The coexisting region of mixed micelles and vesicles in phase diagram of mixed system was also assured. It was investigated that vesicle formed spontaneously took a bilayer structure. The lamellar thickness of vesicles decreased with increasing concentration of vesicle samples. However, the size could not be determined for mixed micelle and vesicle above 100 nm due to limitation of low q ranges. Finally, The 9 mM solution of ADS mole fraction 0.9 (α=0.9) showed bilayer structure compared to phase diagram classified into mixed micelle.

Keywords:mixed micelle;vesicle;lamellar thichness;phase diagram;small angle neutron scattering (SANS)

[References]

Kang KH, Kim HU, Lim KH, Jeong NH, Bull. Korean Chem. Soc., 22(9), 1009 (2001)
Almgren M, Gimel JC, Wang K, Karlsson G, Edwards K, Brown W, Mortensen K, J. Colloid Interface Sci., 202(2), 222 (1998)
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Armarego WLF, Perrin DD, Purification of Laboratory Chemicals, 4th ed., Butterworth-Heinemann, Oxford (1996)
Korea Atomic Energy Research Institute, Computing Guide for HANARO Small-Angle Scattering Data Treatment (2002)
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Pedersen JS, Egelhaaf SU, Schurtenberger P, J. Phys. Chem., 99(4), 1299 (1995)
Kataoka M, Hagihara Y, Mihara K, Goto Y, J. Mol. Biol., 229, 591 (1993)
Ma G, Barlow DJ, Lawrence MJ, Heenan RK, Timmins P, J. Phys. Chem. B, 104(39), 9081 (2000)
Kim HU, Lim KH, Bull. Korean Chem. Soc., 25(3), 382 (2004)
Reiss-Husson F, Luzzati V, J. Phys. Chem., 68, 3504 (1964)
Grabner D, Matsuo T, Hoinkis E, Thunig C, Hoffmann H, J. Colloid Interface Sci., 236(1), 1 (2001)
Kim HU, Ph.D Dissertation, Chung-Aug University (2002)
Iampietro DJ, Kaler EW, Langmuir, 15(25), 8590 (1999)

[Referenced By]

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[1] Kang KH, Kim HU, Lim KH, Jeong NH, Bull. Korean Chem. Soc., 22(9), 1009 (2001)

[2] Almgren M, Gimel JC, Wang K, Karlsson G, Edwards K, Brown W, Mortensen K, J. Colloid Interface Sci., 202(2), 222 (1998)

[3] King SM, www.isis.rl.ac.uk/largescale/loq/documents/sans.htm, Introduction to Small Angle Neutron Scattering (1995)

[4] Ottewill RH, Small Angle Neutron Scattering, in Colloidal Dispersion (J. W. Goodwin ed.), Special Publication No.43, Royal Society of Chemistry (1982)

[5] Hunter RJ, Foundations in Colloid Science, Vol.2, Clarendon Press (1989)

[6] Maconnachie A, Richards RW, Polymer, 19, 739 (1978)

[7] Huggins JS, Benoit HC, Polymers and Neutron Scattering, Oxford Series on Neutron Scattering in Condensed Matter, Vol.8, Clarendon Press (1994)

[8] Perkins SJ, High Flux X-ray and Neutron Solution Scattering, in Methods in Molecular Biology (C. Jones, B. Mulloy, and A. H. Thomas ed.), Vol.22, Humana Press (1994)

[9] Armarego WLF, Perrin DD, Purification of Laboratory Chemicals, 4th ed., Butterworth-Heinemann, Oxford (1996)

[10] Korea Atomic Energy Research Institute, Computing Guide for HANARO Small-Angle Scattering Data Treatment (2002)

[11] Guinier A, Fournet G, Small-Angle Scattering of X-Rays, John Wiley & Sons., New York (1955)

[12] Feigin LA, Svergun DI, Structure Analysis by Small-Angle X-Ray and Neutron Scattering (Ed. by G. W. Taylor), p.68-69, Plenum Press, New York and London (1987)

[13] Roe RJ, Methods of X-ray and Neutron Scattering in Polymer Science, p.155-209, Oxford University Press, New York (2000)

[14] Porod G, Small-Angle X-Ray Scattering (O. Glatter, and O. Kratky ed.), p.17, Academic Press, New York (1982)

[15] Zemb T, Dubois M, Deme B, Gulik-Krzywicki T, Science, 283 (1999)

[16] Holtzer A, J. Polym. Sci., 17, 432 (1955)

[17] Denkinger P, Burchard W, J. Polym. Sci. B: Polym. Phys., 29, 589 (1991)

[18] Pedersen JS, Egelhaaf SU, Schurtenberger P, J. Phys. Chem., 99(4), 1299 (1995)

[19] Kataoka M, Hagihara Y, Mihara K, Goto Y, J. Mol. Biol., 229, 591 (1993)

[20] Ma G, Barlow DJ, Lawrence MJ, Heenan RK, Timmins P, J. Phys. Chem. B, 104(39), 9081 (2000)

[21] Kim HU, Lim KH, Bull. Korean Chem. Soc., 25(3), 382 (2004)

[22] Reiss-Husson F, Luzzati V, J. Phys. Chem., 68, 3504 (1964)

[23] Grabner D, Matsuo T, Hoinkis E, Thunig C, Hoffmann H, J. Colloid Interface Sci., 236(1), 1 (2001)

[24] Kim HU, Ph.D Dissertation, Chung-Aug University (2002)

[25] Iampietro DJ, Kaler EW, Langmuir, 15(25), 8590 (1999)