黏弹性表面活性剂（II）——蠕虫状胶束形成机理及体系构成

doi:10.3969/j.issn.2097-2806.2026.02.001

摘要/Abstract

摘要：

蠕虫状胶束作为一维自组装聚集体，宏观上便显出独特的黏弹性等流变行为。本文系统阐述了该类胶束的形成机理与体系构成：从热力学视角，其生长受疏水效应与头基排斥的协同调控，临界堆积参数主导由球状至柱状的形态演变；动力学上，涉及胶束断裂、重组及分子交换等多时间尺度过程。对阳离子、阴离子、两性离子、非离子蠕虫状胶束体系构建进行了深入总结，简述了超长链表面活性剂在低浓度下形成蠕虫状胶束的新进展。未来研究需进一步揭示组分间微观作用机制，建立结构-性能的定量关联，并拓展其在智能流体、绿色材料及生物医学等领域的应用。

关键词: 黏弹性表面活性剂, 蠕虫状胶束, 热力学, 动力学, 自组装

Abstract:

Wormlike micelles（WLMs）, as versatile one-dimensional nanostructures, impart unique viscoelasticity and shear responsiveness to fluids, making them essential functional materials across numerous industrial and biomedical applications. This review delineates their formation mechanisms and system compositions to provide a theoretical basis for rational surfactant design. WLMs arise from a thermodynamic-kinetic interplay: the hydrophobic effect drives assembly, while headgroup repulsion balances it, with the critical packing parameter guiding the transition to cylindrical morphology. Adjusting molecular structure or milieu such as salt addition or aromatic counterion incorporation modulates curvature to favor elongation. Kinetically, these systems sustain dynamic equilibrium through scission, recombination, and exchange across timescales, governing stress relaxation and rheology. System formulations are categorized into cationic, anionic, zwitterionic, and nonionic types, employing strategies such as high-concentration long-chain surfactants, salt screening, hydrotrope synergism via cation-π interactions, and cosurfactant blending. Notably, ultra-long-chain surfactants（>C₁₈）enable strong viscoelasticity at low concentrations, offering practical and theoretical advantages. Future work should prioritize quantitative insight through advanced characterization and simulation, establish predictive structure-property relationships, and develop stimuli-responsive WLMs for adaptive and sustainable technologies. Such advances will deepen colloidal science and accelerate next-generation soft material innovation.

Key words: viscoelastic surfactant, wormlike micelles, thermodynamics, kinetics, self-assembly

中图分类号:

TQ423

冯玉军. 黏弹性表面活性剂（II）——蠕虫状胶束形成机理及体系构成[J]. 日用化学工业（中英文）, 2026, 56(2): 137-148.

Yujun Feng. Viscoelastic surfactants（II）Formation mechanisms and system formulations of wormlike micelles[J]. China Surfactant Detergent & Cosmetics, 2026, 56(2): 137-148.

图/表 5

图1

图2

图3

图4

图5

参考文献 59

[1]	冯玉军. 黏弹性表面活性剂(I)——百年胶束发展史及蠕虫状胶束的发现[J]. 日用化学工业(中英文), 2026, 56(1): 8-16.
[2]	Nagarajan R. Molecular thermodynamics of giant micelles. In: Zana R, Kaler E, eds. Giant micelles: properties and applications[M]. CRC Press, Boca Raton, 2007: 1-40.
[3]	de Souza R N, Jora M Z, Alves D L G T, et al. A new interpretation of the mechanism of wormlike micelle formation involving a cationic surfactant and salicylate[J]. J. Colloid Interface Sci., 2019, 552: 794-800. doi: 10.1016/j.jcis.2019.05.025
[4]	Sabadini E, Clinckspoor K J. New insights into the formation of wormlike micelles: kinetics and thermodynamics. In: Dreiss C A, Feng Y, eds. Wormlike micelles: advances in systems, characterisation and applications. Soft Matter Series No.6[M]. The Royal Society of Chemistry, London, 2017: 298-329.
[5]	Israelachvili J N. Intermolecular and surface forces (3^rd ed.)[M]. Academic Press, San Diego, 2011.
[6]	Danov K D, Kralchevsky P A, Stoyanov S D, et al. Analytical modeling of micelle growth. 2. Molecular thermodynamics of mixed aggregates and scission energy in wormlike micelles[J]. J. Colloid Interface Sci., 2019, 551, 227-241. doi: 10.1016/j.jcis.2019.05.017
[7]	May S, Ben-Shaul A. Molecular theory of the sphere-to-rod transition and the second CMC in aqueous micellar solutions[J]. J. Phys. Chem. B, 2001, 105(3): 630-640. doi: 10.1021/jp003021o
[8]	Cates M E, Candau S J. Statics and dynamics of worm-like surfactant micelles[J]. J. Phys.: Condens. Matter, 1990, 2: 6869-6892. doi: 10.1088/0953-8984/2/33/001
[9]	Spenley N A, Cates M E, McLeish T C B. Nonlinear rheology of wormlike micelles[J]. Phys. Rev. Lett., 1993, 71: 939-942. pmid: 10055406
[10]	Jensen G V, Lund R, Gummel J, et al. Monitoring the transition from spherical to polymer-like surfactant micelles using small-angle X-ray scattering[J]. Angew. Chem. Int. Ed., 2014, 53(43): 11524-11528. doi: 10.1002/anie.201406489 pmid: 25197008
[11]	Löf D, Niemiec A, Schillén K, et al. A calorimetry and light scattering study of the formation and shape transition of mixed micelles of EO₂₀PO₆₈EO₂₀ triblock copolymer (P123) and nonionic surfactant (C₁₂EO₆)[J]. J. Phys. Chem. B, 2007, 111(21): 5911-5920. doi: 10.1021/jp071101n
[12]	Ito T H, Clinckspoor K J, de Souza R N, et al. The thermal signature of wormlike micelles[J]. J. Chem. Thermodynamics, 2016, 94: 61-66. doi: 10.1016/j.jct.2015.10.021
[13]	Zilman A, Safran S A, Stottmann T, et al. Temperature dependence of the thermodynamics and kinetics of micellar solutions[J]. Langmuir, 2004, 20(6): 2199-2207. pmid: 15835671
[14]	Reiss-Husson F, Luzzati V. The structure of micellar solutions of some amphiphilic compounds in pure water as determined by absolute small-angle X-ray scattering experiments[J]. J. Phys. Chem., 1964, 68: 3504-3511. doi: 10.1021/j100794a011
[15]	Ekwall P, Mandell L, Solyom P. The aqueous cetyl trimethylammonium bromide solutions[J]. J. Colloid Interface Sci., 1971, 35: 519-527. doi: 10.1016/0021-9797(71)90210-4
[16]	Fontell K, Khan A, Lindström B, et al. Phase equilibria and structures in ternary systems of a cationic surfactant (C₁₆TABr or (C₁₆TA)₂SO₄), alcohol and water[J]. Colloid Polym. Sci., 1991, 269: 727-742. doi: 10.1007/BF00657411
[17]	Porte G, Poggi Y, Appell J, et al. Large micelles in concentrated solutions. The second critical micellar concentration[J]. J. Phys. Chem., 1984, 88: 5713-5720. doi: 10.1021/j150667a051
[18]	Gravsholt S. Viscoelasticity in highly dilute aqueous solutions of pure cationic detergents[J]. J. Colloid Interface Sci., 1976, 57(3): 575-577. doi: 10.1016/0021-9797(76)90236-8
[19]	Debye P, Anacker E W. Micelle shape from dissymmetry measurements[J]. J. Phys. Colloid Chem., 1951, 55: 644-655. pmid: 14832754
[20]	Candau S J, Hirsch E, Zana R, et al. Network properties of semidilute aqueous KBr solutions of cetyltrimethylammonium bromide[J] J. Colloid Interface Sci., 1988, 122(2): 430-440. doi: 10.1016/0021-9797(88)90377-3
[21]	Quirion F, Magid L J. Growth and counterion binding of cetyltrimethylammonium bromide aggregates at 25 ℃: A neutron and light scattering study[J]. J. Phys. Chem., 1986, 90(21): 5435-5441. doi: 10.1021/j100412a108
[22]	Raghavan S R, Kaler E W. Highly viscoelastic wormlike micellar solutions formed by cationic surfactants with long unsaturated tails[J]. Langmuir, 2001, 17(2): 300-306. doi: 10.1021/la0007933
[23]	Croce V, Cosgrove T, Maitland G, et al. Rheology, cryogenic transmission electron spectroscopy, and small-angle neutron scattering of highly viscoelastic wormlike micellar solutions[J]. Langmuir, 2003, 19(20): 8536-8541. doi: 10.1021/la0345800
[24]	Siriwatwechakul W, Lafleur T, Prud’homme R K, et al. Effects of organic solvents on the scission energy of rodlike micelles[J]. Langmuir, 2004, 20(21): 8970-8974. pmid: 15461475
[25]	Schubert B A, Wagner N J, Kaler E W, et al. Shear-induced phase separation in solutions of wormlike micelles[J]. Langmuir, 2004, 20(9): 3564-3573. pmid: 15875385
[26]	Imai S, Shikata T. Viscoelastic Behavior of Surfactant Threadlike Micellar Solutions: Effect of Additives 3[J]. J. Colloid Interface Sci., 2001, 244(2): 399-404. doi: 10.1006/jcis.2001.7992
[27]	Rehage H, Hoffmann H. Rheological properties of viscoelastic surfactant systems[J]. J. Phys. Chem., 1988, 92(16): 4712-4719. doi: 10.1021/j100327a031
[28]	Oelschlaeger C, Waton G, Candau S J. Rheological behavior of locally cylindrical micelles in relation to their overall morphology[J]. Langmuir, 2003, 19(25): 10495-10500. doi: 10.1021/la035082u
[29]	Dreiss C A. Wormlike micelles: where do we stand? Recent developments, linear rheology and scattering techniques[J]. Soft Matter, 2007, 3: 956-970. doi: 10.1039/b705775j pmid: 32900044
[30]	Bijma K, Engberts J B F N. Effect of counterions on properties of micelles formed by alkylpyridinium surfactants. 1. conductometry and ¹H NMR chemical shifts[J]. Langmuir, 1997, 13(18): 4843-4849. doi: 10.1021/la970171q
[31]	Bijma K, Blandamer K J, Engberts J B F N. Effect of counterions and headgroup hydrophobicity on properties of micelles formed by alkylpyridinium surfactants. 2. Microcalorimetry[J]. Langmuir, 1998, 14(1): 79-83. doi: 10.1021/la970216n
[32]	Bachofer S J, Turbitt R M. The orientational binding of substituted benzoate anions at the cetyltrimethyl ammonium bromide interface[J]. J. Colloid Interface Sci., 1990, 135(2): 325-334. doi: 10.1016/0021-9797(90)90003-7
[33]	Brown W, Johansson K, Almgren M. Threadlike micelles from cetyltrimethylammonium bromide in aqueous sodium naphthalene sulfonate solutions studied by static and dynamic light scattering[J]. J. Phys. Chem., 1989, 93(15): 5888-5894. doi: 10.1021/j100352a047
[34]	Singh M, Ford C, Agarwal V, et al. Structural evolution in cationic micelles upon incorporation of a polar organic dopant[J]. Langmuir, 2004, 20(23): 9931-9937. pmid: 15518477
[35]	Couillet I, Hughes T, Maitland G, et al. Growth and scission energy of wormlike micelles formed by a cationic surfactant with long unsaturated tails[J]. Langmuir, 2004, 20(22): 9541-9550. pmid: 15491184
[36]	Porte G, Gomati R, El H O, et al. Morphological transformations of the primary surfactant structures in brine-rich mixtures of ternary systems (surfactant/alcohol/brine)[J]. J. Phys. Chem., 1986, 90(22): 5746-5751. doi: 10.1021/j100280a055
[37]	Magid L J, Li Z, Butler P D. Flexibility of elongated sodium dodecyl sulfate micelles in aqueous sodium chloride: A small-angle neutron scattering study[J]. Langmuir, 2000, 16(26): 10028-10036. doi: 10.1021/la0006216
[38]	Arleth L, Bergström M, Pedersen J S. Small-angle neutron scattering study of the growth behavior, flexibility, and intermicellar interactions of wormlike SDS micelles in NaBr aqueous solutions[J]. Langmuir, 2002, 18(14): 5343-5353. doi: 10.1021/la015693r
[39]	Mu J H, Li G Z, Jia X L, et al. Rheological properties and microstructures of anionic micellar solutions in the presence of different inorganic salts[J]. J. Phys. Chem. B, 2002, 106(44): 11685-11693. doi: 10.1021/jp014096a
[40]	von Berlepsh H, Dautzenberg H, Rother G, et al. An investigation of the micellar phase of sodium sulfopropyl octadecyl maleate in aqueous sodium chloride solutions by light scattering techniques. evidence of nearly rodlike micelles[J]. Langmuir, 1996, 12(15): 3613-3625. doi: 10.1021/la960036y
[41]	Bergström M, Pedersen J S. Formation of tablet-shaped and ribbonlike micelles in mixtures of an anionic and a cationic surfactant[J]. Langmuir, 1999, 15(7): 2250-2253. doi: 10.1021/la981495x
[42]	Raghavan S R, Fritz G, Kaler E W. Wormlike micelles formed by synergistic self-assembly in mixtures of anionic and cationic surfactants[J]. Langmuir, 2002, 18(10): 3797-3803. doi: 10.1021/la0115583
[43]	Ziserman L, Abezgauz L, Ramon O, et al. Origins of the viscosity peak in wormlike micellar solutions. 1. mixed catanionic surfactants. A cryo-transmission electron microscopy study[J]. Langmuir, 2009, 25(18): 10483-10489. doi: 10.1021/la901189k pmid: 19572608
[44]	Hassan P A, Raghavan S R, Kaler E W. Microstructural changes in SDS micelles induced by hydrotropic salt[J]. Langmuir, 2002, 18(7): 2543-2548. doi: 10.1021/la011435i
[45]	Nakamura K, Shikata T. Threadlike micelle formation of anionic surfactants in aqueous solution[J]. Langmuir, 2006, 22(24): 9853-9859. pmid: 17106973
[46]	Thiele T, Berret J F, Muller S, et al. Rheology and nuclear magnetic resonance measurements under shear of sodium dodecyl sulfate/decanol/water nematics[J]. J. Rheol., 2001, 45(1): 29-48. doi: 10.1122/1.1332387
[47]	Douliez J P, Navailles L, Nallet F. Self-assembly of fatty acid-alkylboladiamine salts[J]. Langmuir, 2006, 22(2): 622-627. doi: 10.1021/la052377u
[48]	Hoffmann H, Rauschera A, Gradzielski M, et al. Influence of ionic surfactants on the viscoelastic properties of zwitterionic surfactant solutions[J]. Langmuir, 1992, 8(9): 2140-2146. doi: 10.1021/la00045a013
[49]	Fischer P, Rehage H, Grüning B. Linear flow properties of dimer acid betaine solutions with and without changed ionic strength[J]. J. Phys. Chem. B, 2002, 106(42): 11041-11046. doi: 10.1021/jp0127263
[50]	Jerke G, Pedersen J S, Egelhaaf S U, et al. Flexibility of charged and uncharged polymer-like micelles[J]. Langmuir, 1998, 14(21): 6013-6024. doi: 10.1021/la980390r
[51]	Bernheim-Groswasser A, Wachtel E, Talmon Y. Micellar growth, network formation, and criticality in aqueous solutions of the nonionic surfactant C₁₂E₅[J]. Langmuir, 2000, 16(9), 4131-4140. doi: 10.1021/la991231q
[52]	Imanishi K, Einaga Y. Wormlike micelles of polyoxyethylene alkyl ether mixtures C₁₀E₅+ C₁₄E₅ and C₁₄E₅ + C₁₄E₇: hydrophobic and hydrophilic chain length dependence of the micellar characteristics[J]. J. Phys. Chem. B, 2007, 111(1): 62-73. doi: 10.1021/jp065317l
[53]	Miyake M, Einaga Y. Characteristics of wormlike pentaoxyethylene decyl ether C₁₀E₅ micelles containing n-dodecanol[J]. J. Phys. Chem. B, 2007, 111(3): 535-542. doi: 10.1021/jp0664465
[54]	Kumar R, Kalur G C, Ziserman L, et al. Wormlike micelles of a C₂₂-tailed zwitterionic betaine surfactant: from viscoelastic solutions to elastic gels[J]. Langmuir, 2007, 23(26): 12849-12856. pmid: 18004899
[55]	Han Y, Feng Y, Sun H, et al. Wormlike micelles formed by sodium erucate in the presence of a tetraalkylammonium hydrotrope[J]. J. Phys. Chem. B, 2011, 115(21): 6893-6902. doi: 10.1021/jp2004634
[56]	Han Y, Chu Z, Sun H, et al. “Green” anionic wormlike micelles induced by choline[J]. RSC Adv., 2012, 2(8): 3396-3402. doi: 10.1039/c2ra20136d
[57]	Chu Z, Feng Y, Su X, et al. Wormlike micelles and solution properties of a C₂₂-tailed amidosulfobetaine surfactant[J]. Langmuir, 2010, 26(11): 7783-7791. doi: 10.1021/la904582w pmid: 20429541
[58]	Zhang Y, Luo Y, Wang Y, et al. Single-component wormlike micellar system formed by a carboxylbetaine surfactant with C₂₂ saturated tail[J]. Colloid Surf. A-Physicochem. Eng. Asp., 2013, 436: 71-79. doi: 10.1016/j.colsurfa.2013.06.016
[59]	Feng Yujun, Wang Ying, Yan Wei, et al. Wormlike micelles formed by ultra-long-chain nonionic surfactant[J]. Colloid Polym. Sci., 2021, 299: 1295-1304. doi: 10.1007/s00396-021-04848-z