Nonideal Mixed Micelles of Fluorinated and Hydrogenous Surfactants in Aqueous Solution. NMR and SANS Studies of Anionic and Nonionic Systems

被引:28
作者
Almgren, Mats [1 ]
Garamus, Vasil M. [2 ]
Nordstierna, Lars [3 ]
Luc-Blin, Jean [4 ]
Stebe, Marie-Jose [4 ]
机构
[1] Uppsala Univ, Dept Phys & Analyt Chem, SE-75123 Uppsala, Sweden
[2] GKSS Forschungszentrum Geesthacht GmbH, D-21502 Geesthacht, Germany
[3] Chalmers Univ, Dept Chem & Biol Engn, Div Appl Surface Chem, SE-41296 Gothenburg, Sweden
[4] Nancy Univ, CNRS, UMR 7565, Equipe Physicochim Colloides,SRSMC, F-54506 Vandoeuvre Les Nancy, France
关键词
SMALL-ANGLE SCATTERING; HYDROCARBON SURFACTANTS; NEUTRON-SCATTERING; SODIUM PERFLUOROOCTANOATE; CONTRAST VARIATION; LIQUID-MIXTURES; FLUOROCARBON; MISCIBILITY; SULFATE; DEMICELLIZATION;
D O I
10.1021/la903764u
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Contrast variation SANS and F-19 chemical shifts were measured for three mixed equimolar micelle systems: sodium perfluorooctanoate (SPED) and sodiumdecylsulfate (SDeS) in 200 mM NaCl, lithium perlluorononanate LiPFN) and lithium dodecylsulfate (Li DS) in 200 mM LiCl, and a nonionic system C8F17C2H4(OC2H4)(9) and C12H25(OC2H4)(8) in water, all at 25 C. The chemical shift measurements allow the calculation of the average fraction of nearest neighbors of each kind around the reporter group (the trifluoromethyl group). A preference for like neighbors were found in all systems, smallest in the SDeS/SPFO system and largest in the nonionic system, but in all cases substantially smaller than expected at critical conditions. From the SANS measurements the width of the micelle composition distribution was obtained. For the ionic systems similar values were obtained, showing a broadening compared to ideal mixtures, but not broad enough for demixing or clearly bimodal distributions. In the nonionic system the width was estimated as sigma = 0.18 and 0.22 using two different evaluation methods. These values suggest that the system is close to critical conditions. The lower value refers to a direct modeling of the system, assuming an ellipsoidal shape and a Gaussian composition distribution. The modeling showed the nonionic mixed micelles to be prolate ellipsoids with axial ratio 2.2 and an aggregation number larger than 100. whereas the two ionic systems fitted best to oblate shapes (axial ratios 0.8 and 0.65 for SDeS/SPFO and LiDS/LiPFN. respectively) and aggregation numbers of 60 for both.
引用
收藏
页码:5355 / 5363
页数:9
相关论文
共 58 条