Abstract
Processing-relevant relationships between the microstructure and flow behavior of concentrated surfactant solutions were determined by a combination of basic rheological experiments, rheo-flow velocimetry tests, and flow birefringence measurements. The most common surfactant microstructures found in liquid soaps and other consumer care products—spherical, worm-like, and hexagonally packed micelles and lamellar structures—were recreated by varying the concentration of sodium laureth sulfate in water from 20 to 70 wt% and adding salt in some cases. It was found that common features of flow curves, such as power-law shear thinning behavior, resulted from a wide variety of material responses including shear-induced wall slip in micellar samples and plug flow in lamellar samples. Knowledge of key processing-structure-property relationships for concentrated solutions will allow engineers to develop more efficient industrial workflows for the scalable manufacturing of materials and feedstocks with reduced economic and environmental costs.
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References
Ahir SV, Petrov PG, Terentjev EM (2002) Rheology at the phase transition boundary: 2. Hexagonal phase of Triton X100 surfactant solution. Langmuir 18:9140–9148. https://doi.org/10.1021/la025793c
Ahmed Siddig M, Radiman S, Jan L, Muniandy S (2006) Rheological behaviours of the hexagonal and lamellar phases of glucopone (APG) surfactant. Colloids and Surfaces A: Physicochem Enig Aspects 276:15–21. https://doi.org/10.1016/j.colsurfa.2005.10.004
Anderson R. (2016). Companies get serious about water use—BBC News. Retrieved October 29, 2018, from BBC News website: https://www.bbc.com/news/business-35613148
Aoudia M, Al-Haddabi B, Al-Harthi Z, Al-Rubkhi A (2010) Sodium lauryl ether sulfate micellization and water solubility enhancement towards naphthalene and pyrene: effect of the degree of ethoxylation. J Surfactant Deterg 13(1):103–111. https://doi.org/10.1007/s11743-009-1131-9
Archer LA, Ternet D, Larson RG (1997) “Fracture” phenomena in shearing flow of viscous liquids. Rheol Acta 36:579–584. https://doi.org/10.1007/BF00368135
Basappa G, Kumaran V, Nott P, Ramaswamy S, Naik V, Rout D (1999) Structure and rheology of the defect-gel states of pure and particle-dispersed lyotropic lamellar phases. Eur Phys J B 12:269–276. https://doi.org/10.1007/s100510051004
Berni MG, Lawrence CJ, Machin D (2002) A review of the rheology of the lamellar phase in surfactant systems. Adv Colloid Interf Sci 98(2):217–243. https://doi.org/10.1016/S0001-8686(01)00094-X
Berret, J-F (2006) Rheology of wormlike micelles: equilibrium properties and shear banding transition. In Molecular gels P Terech & RG Weiss (Eds.). Springer, Germany pp 667–720
Berret J-F, Séréro Y (2001) Evidence of shear-induced fluid fracture in telechelic polymer networks. Phys Rev Lett 87(4):048303. https://doi.org/10.1103/PhysRevLett.87.048303
Berret J-F, Séréro Y, Winkelman B, Calvet D, Collet A, Viguier M (2001) Nonlinear rheology of telechelic polymer networks. J Rheol 45(2):477–492. https://doi.org/10.1122/1.1339245
Bice, J. E. (2017). Using ultrasonic spceckle velocimetry to detect fluid instabilities in a surfactant solution (Master thesis Purdue University). Retrieved from https://search.proquest.com/docview/2016113604?accountid=13360. Accessed December 2018
Bird, R. B., Stewart, W. E., & Lightfoot, E. N. (2007). Transport phenomena (2nd ed.; W. Anderson, Ed.). New York: John Wiley & Sons, Inc.
Bonn D, Denn MM (2009) Yield stress fluids slowly yield to analysis. Science 324(5933):1401–1402. https://doi.org/10.1126/science.1174217
Briceño-Aumada Z, Soltero A, Maldonado A, Perez J, Langevin D, Impéror-Clerc M (2016) On the use of shear rheology to formulate stable foams. Example of a lyotropic lamellar phase. Colloids Surf A Physicochem Eng Asp 507:110–117. https://doi.org/10.1016/j.colsurfa.2016.07.077
Caicedo-Casso E, Sargent J, Dorin RM, Wiesner UB, Phillip WA, Boudouris BW, Erk KA (2018) A rheometry method to assess the evaporation-induced mechanical strength development of polymer solutions used for membrane applications. J Appl Polym Sci 136:47038. https://doi.org/10.1002/app.47038
Carreau PJ (2006) Rheometry of pastes, Suspensions and granular materials. Applications in industry and environment. Rheol Acta 46:317–318. https://doi.org/10.1007/s00397-006-0118-y
Cassagnau P (2013) Linear viscoelasticity and dynamics of suspensions and molten polymers filled with nanoparticles of different aspect ratios. Polymer 54(18):4762–4775. https://doi.org/10.1016/j.polymer.2013.06.012
Christel M, Yahya R, Albert M, Abboud Antoine B (2012) Stick-slip control of the Carbopol microgels on polymethyl methacrylate transparent smooth walls. Soft Matter 8:7365–7367. https://doi.org/10.1039/c2sm26244d
Diat O, Roux D, Nallet F (1995) “Layering” effect in sheared lyotropic lamellar phase. Phys Rev E Stat Nonlinear Soft Matter Phys 51(4):3296–3300
Dimitriou CJ, Casanellas L, Ober TJ, McKinley GH (2012) Rheo-PIV of a shear-banding wormlike micellar solution under large amplitude oscillatory shear. Rheol Acta 51(5):395–411. https://doi.org/10.1007/s00397-012-0619-9
Divoux T, Barentin C, Manneville S (2011a) From stress-induced fluidization processes to Herschel-Bulkley behaviour in simple yield stress fluids. Soft Matter 7(18):8409. https://doi.org/10.1039/c1sm05607g
Divoux T, Barentin C, Manneville S (2011b) Stress overshoot in a simple yield stress fluid: an extensive study combining rheology and velocimetry. Soft Matter 7(19):9335–9349. https://doi.org/10.1039/c1sm05740e
Divoux T, Fardin MA, Manneville S, Lerouge S (2016) Shear banding of complex fluids. Annu Rev Fluid Mech 48:81–103. https://doi.org/10.1146/annurev-fluid-122414-034416
Erk KA, Martin JD, Hu YT, Shull KR (2012) Extreme strain localization and sliding friction in physically associating polymer gels. Langmuir 28(9):4472–4478. https://doi.org/10.1021/la204592r
Ezrahi S, Tuval E, Aserin A (2006) Properties, main applications and perspectives of worm micelles. Adv Colloid Interf Sci 128–130:77–102. https://doi.org/10.1016/j.cis.2006.11.017
Fardin MA, Divoux T, Guedeau-Boudeville MA, Buchet-Maulien I, Browaeys J, McKinley GH, Manneville S, Lerouge S (2012a) Shear-banding in surfactant wormlike micelles: elastic instabilities and wall slip. Soft Matter 8(8):2535. https://doi.org/10.1039/c2sm06992j
Fardin MA, Ober TJ, Grenard V, Divoux T, Manneville S, Mckinley GH, Lerouge S (2012b) Interplay between elastic instabilities and shear-banding: three categories of Taylor-Couette flows and beyond. Soft Matter 8:10072. https://doi.org/10.1039/c2sm26313k
Feigin LA, & Svergun DI (1987) Structure analysis by small-angle X-ray and neutron scattering (George W. Taylor, Ed.). Springer, New York
Fritz G, Wagner NJ, Kaler EW (2003) Formation of multilamellar vesicles by oscillatory shear. Langmuir 19:8709–8714. https://doi.org/10.1021/la0349370
Gentile L, Rossi CO, Olsson U (2012) Rheological and rheo-SALS investigation of the multi-lamellar vesicle formation in the C12E3/D2O system. J Colloid Interface Sci 367:537–539. https://doi.org/10.1016/j.jcis.2011.10.057
Gentile L, Silva BFB, Lages S, Mortensen K, Kohlbrecher J, Olsson U (2013) Rheochaos and flow instability phenomena in a nonionic lamellar phase. Soft Matter 9(4):1133–1140. https://doi.org/10.1039/c2sm27101j
Giagnorio M, Amelio A, Grüttner H, Tiraferri A (2017) Environmental impacts of detergents and benefits of their recovery in the laundering industry. J Clean Prod 154:593–601. https://doi.org/10.1016/j.jclepro.2017.04.012
Graham AL, Mammoli AA, Busch MB (1998) Effects of demixing on suspension rheometry. Rheol Acta 37(2):139–150. https://doi.org/10.1007/s003970050100
Hanlon AD, Gibbs SJ, Hall LD, Haycock DE, Frith WJ, Ablett S (1998) Rapid MRI and velocimetry of cylindrical couette flow. Magn Reson Imaging 16(8):953–961. https://doi.org/10.1016/S0730-725X(98)00089-7
Herle V, Manneville S, Fischer P (2008) Ultrasound velocimetry in a shear-thickening wormlike micellar solution: evidence for the coexistence of radial and vorticity shear bands. Eur Phys J E 26(1–2):3–12. https://doi.org/10.1140/epje/i2007-10304-3
Husband DM, Mondy LA, Ganani E, Graham AL (1994) Direct measurements of shear-induced particle migration in suspensions of bimodal spheres. Rheol Acta 33:185–192. https://doi.org/10.1007/BF00437303
Hutton JF (1963) Fracture of liquids in shear. Nature 200(4907):646–648. https://doi.org/10.1038/203177a0
Hutton JF (1969) Fracture and secondary flow of elastic liquids. Rheol Acta 8:54–59. https://doi.org/10.1007/BF02321355
Israelachvili JN (2011) Intermolecular and surface forces, 3rd edn. Academic Press, Waltham
Kiewiet S, Janssens V, Miltner HE, Van Assche G, Van Puyvelde P, Van Mele B (2008) RheoDSC: a hyphenated technique for the simultaneous measurement of calorimetric and rheological evolutions. Rev Sci Instrum 79(2):234904. https://doi.org/10.1063/1.2838585
Koehler A, Wildbolz C (2009) Comparing the environmental footprints of home-care and personal-hygiene products: the relevance of different life-cycle phases. Environ Sci Technol 43(22):8643–8651. https://doi.org/10.1021/es901236f
Kotula AP, Meyer MW, De Vito F, Plog J, Hight Walker AR, Migler KB (2016) The rheo-Raman microscope: simultaneous chemical, conformational, mechanical, and microstructural measures of soft materials. Rev Sci Instrum 87(10):105105. https://doi.org/10.1063/1.4963746
Kresta SM, Paul EL, & Atiemo-Obeng, VA (2004) Handbook of industrial mixing: science and practice. John Wiley & Sons, Inc., Germany
Larson RG (1992) Instabilities in viscoelastic flows. Rheol Acta 31(3):213–263. https://doi.org/10.1007/BF00366504
Larson RG (1999) The structure and rheology of complex fluids. Oxford University Press, New York
Laughlin RG (1994). The aqueous phase behavior of surfactants. Academic Press, London
Lerouge S, Berret J-F (2009) Shear-induced transitions and instabilities in surfactant wormlike micelles. In Polymer characterization. K Dusek & J Joanny (Eds.). Springer, Germany p 71 https://doi.org/10.1007/12_2009_13
Lettinga P, Manneville S (2009) Competition between shear banding and wall slip in wormlike micelles. Phys Rev Lett 103(24):1–4. https://doi.org/10.1103/PhysRevLett.103.248302
Li Y, McKenna GB (2015) Startup shear of a highly entangled polystyrene solution deep into the nonlinear viscoelastic regime. Rheol Acta 54(9–10):771–777. https://doi.org/10.1007/s00397-015-0876-5
Ligoure C, Mora S (2013) Fractures in complex fluids: the case of transient networks. Rheol Acta 52(2):91–114. https://doi.org/10.1007/s00397-012-0668-0
Macosko CW (1994) Rheology—principles, measurements, and applications. Wiley-VCH, Germany https://doi.org/10.1002/aic.690411025
Makhloufi R, Decruppe JP, Aït-Ali A, Cressely R (1995) Rheo-optical study of worm-like micelles undergoing a shear banding flow. (EPL) 32(3):253–258. https://doi.org/10.1209/0295-5075/32/3/011
Malkin AY, Patlazhan SA (2018) Historical perspective wall slip for complex liquids—phenomenon and its causes. Adv Colloid Interf Sci 257:42–57. https://doi.org/10.1016/j.cis.2018.05.008
Manaia EB, Abuçafy MP, Chiari-Andréo BG, Silva BL, Oshiro Junior JA, Chiavacci LA (2017) Physicochemical characterization of drug nanocarriers. Int J Nanomedicine 12:4991–5011. https://doi.org/10.2147/IJN.S133832
Manneville S, Becu L, Colin A (2004) High-frequency ultrasonic speckle velocimetry in sheared complex fluids. The European Physical Journal-Applied Physics 28(3):361–373. https://doi.org/10.1051/epjap:2004165
Manneville S, Colin A, Waton G, Schosseler F (2007) Wall slip, shear banding, and instability in the flow of a triblock copolymer micellar solution. Phys Rev E Stat Nonlinear Soft Matter Phys 75(6):1–11. https://doi.org/10.1103/PhysRevE.75.061502
Markus R, Wilert C, Wereley S, & Kompenhans J (2007). Particle image velocimetry: a practical guide, 2 edn. Springer, Germany
Mishra BK, Samant SD, Pradhan P, Mishra SB, & Manohar C (1993) A new strongly flow birefringent surfactant system. Langmuir 9:894-898. https://pubs.acs.org/doi/abs/10.1021/la00028a004
Mohammadigoushki H, Muller SJ (2016) A flow visualization and superposition rheology study of shear-banding wormlike micelle solutions. Soft Matter 12(4):1051–1061. https://doi.org/10.1039/c5sm02266e
Montalvo G, Valiente M, Rodenas E (1996) Rheological properties of the L phase and the hexagonal, lamellar, and cubic liquid crystals of the CTAB/benzyl alcohol/water system. Langmuir 12(21):5202–5208. https://doi.org/10.1021/la9515682
Murray LR, Bice JE, Soltys EG, Perge C, Manneville S, Erk KA (2018) Influence of adsorbed and nonadsorbed polymer additives on the viscosity of magnesium oxide suspensions. J Appl Polym Sci 135(3):45696. https://doi.org/10.1002/app.45696
Panizza P, Colin A, Coulon C, Roux D (1998) A dynamic study of onion phases under shear flow: size changes. Eur Phys J B 4(1):65–74. https://doi.org/10.1007/s100510050352
Panton RL (2013) Imcompresible flow, 4th edn. John Wiley & Sons, Inc., Hoboken
Poelma C (2017) Ultrasound imaging velocimetry: a review. Exp Fluids 58(1):3. https://doi.org/10.1007/s00348-016-2283-9
Rehage H, Hoffmann H (1982) Shear induced phase transitions in highly dilute aqueous detergents solutions. Rheol Acta 21:561–563. https://doi.org/10.1007/BF01534347
Richtering W (2001) Rheology and shear induced structures in surfactant solutions. Curr Opin Colloid Interface Sci 6(5–6):446–450. https://doi.org/10.1016/S1359-0294(01)00118-2
Rogers SA, Calabrese MA, Wagner NJ (2014) Rheology of branched wormlike micelles. Curr Opin Colloid Interface Sci 19:530–535. https://doi.org/10.1016/j.cocis.2014.10.006
Rosevear FB (1954) The microscopy of the liquid crystalline neat and middle phases of soaps and sythetic detergents. J Am Oil Chem Soc 31:628–639. https://doi.org/10.1007/BF02545595
Rosevear FB (1968) Liquid crystals: the mesomorphic phases of surfactant compositions. J Soc Cosmet Chem 19(1):581–594
Roux D, Nallet F, Diat O (1993) Rheology of lyotropic lamellar phases. (EPL) 24(1):53–58. https://doi.org/10.1209/0295-5075/24/1/009
Saouter E, Van Hoof G, Pittinger CA, Feijtel TCJ (2001) The effect of compact formulations on the environmental profile of northern European granular laundry detergents. Int J Life Cycle Assess 6(6):363–372. https://doi.org/10.1007/BF02978867
Shapley NC, Armstrong RC, Brown RA (2002) Laser Doppler velocimetry measurements of particle velocity fluctuations in a concentrated suspension. J Rheol 46(1):241–272. https://doi.org/10.1122/1.1427908
Sprakel J, Spruijt E, Stuart MAC, Besseling NAM, Lettinga MP, Van Der Gucht J (2008) Shear banding and rheochaos in associative polymer networks. Soft Matter 4:1696–1705. https://doi.org/10.1039/b803085e
Sui C, McKenna GB (2007) Instability of entangled polymers in cone and plate rheometry. Rheol Acta 46:877–888. https://doi.org/10.1007/s00397-007-0169-8
Sushko ML, Seddon JM, Templer RH (2002) History-dependent rheology of a surfactant hexagonal phase. Phys Rev E 65(031501):1–10. https://doi.org/10.1103/PhysRevE.65.031501
Takeda M, Kusano T, Matsunaga T, Endo H, Shibayama M, Shikata T (2011) Rheo-SANS studies on shear-thickening/thinning in aqueous rodlike micellar solutions. Langmuir 27(5):1731–1738. https://doi.org/10.1021/la104647u
Thornell TL, Subramaniam K, Erk KA (2016) The impact of damage accumulation on the kinetics of network strength recovery for a physical polymer gel subjected to shear deformation. J Polym Sci B Polym Phys 54(17):1693–1701. https://doi.org/10.1002/polb.24071
Veerman C, Sagis LMC, Venema P, Van Der Linden E, Veerman C, Sagis ALMC et al (2005) Shear-induced aggregation and break up of fibril clusters close to the percolation concentration. Rheol Acta 44:244–249. https://doi.org/10.1007/s00397-004-0403-6
Walker LM (2001) Rheology and structure of worm-like micelles. Curr Opin Colloid Interface Sci 6:451–456. https://doi.org/10.1016/S1359-0294(01)00116-9
Wunderlich I, Hoffmann H, Rehage H (1987) Flow birefringence and rheological measurements on shear induced micellar structures. Rheol Acta 26(6):532–542. https://doi.org/10.1007/BF01333737
Acknowledgements
The authors are greatly indebted to Prof. Sébastien Manneville (Laboratoire de Physique, Ecole Normale Supérieure de Lyon, France) for his thoughtful advice and guidance during the construction of the USV system at Purdue. Fruitful discussions with a number of P&G scientists are also acknowledged, including Marco Caggioni, Emilio Tozzi, and Will Hartt.
Funding
Funding for this system was generously provided by The Procter & Gamble Company as well as support for E.A.C.C.
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Caicedo-Casso, E.A., Bice, J.E., Nielsen, L.R. et al. Rheo-physical characterization of microstructure and flow behavior of concentrated surfactant solutions. Rheol Acta 58, 467–482 (2019). https://doi.org/10.1007/s00397-019-01147-x
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DOI: https://doi.org/10.1007/s00397-019-01147-x