Skip to main content
SpringerLink
Log in

Influence of Surfactants on the Rheology and Stability of Crystallizing Fatty Acid Pastes

  • Original Paper
  • Published:
Journal of the American Oil Chemists' Society

Abstract

Complex fluids containing crystallizing fatty acids are important for consumer care products. The key features of these materials are their ability to support their weight under gravity due to the formation of a fatty acid crystal network, and to yield or flow beyond a critical applied strain. In model formulations comprised of two synthetic surfactants and a fatty acid in water, we have shown that the fatty acid crystal network consists of crystal aggregates linked by a non-crystallized mixed fatty acid—surfactant mesophase. We hypothesize that this mixed surfactant—fatty acid mesophase is critical for the macroscopic stability of the formulations. Rheological measurements combined with differential scanning calorimetry (DSC), X-ray scattering, and polarized light microscopy (PLM) measurements show the importance of surfactant loading on the overall stability of the formulations by linking morphology to rheology. Macroscopically homogeneous formulations are realized with 7–10 wt% of fatty acid. Increasing the fatty acid content without adding surfactant leads to inhomogeneous, phase separating formulations. Although both stable and unstable formulations show the presence of a surfactant—fatty acid mixed phase, a critical loading of surfactants is found to be necessary to create macroscopically homogenous formulations. We demonstrate how the rheology, microstructure and the macroscopic stability can be tuned by varying the relative amounts of surfactants and fatty acid.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Coussot P (2005) Rheometry of pastes, suspensions, and granular materials: applications in industry and environment. Wiley-Interscience, Hoboken

    Book  Google Scholar 

  2. Coussot P (2007) Rheophysics of pastes: a review of microscopic modelling approaches. Soft Matter 3:528–540

    Article  CAS  Google Scholar 

  3. Stokes JR, Frith WJ (2008) Rheology of gelling and yielding soft matter systems. Soft Matter 4:1133–1140

    Article  CAS  Google Scholar 

  4. Stokes JR, Telford JH (2004) Measuring the yield behaviour of structured fluids. J Nonnewton Fluid Mech 124:137–146

    Article  CAS  Google Scholar 

  5. Mewis J, Wagner NJ (2009) Thixotropy. Adv Colloid Interface Sci 147–48:214–227

    Article  Google Scholar 

  6. Heertje I, Lewis DF (1993) Structure and function of food-products—a review. Food Structure 12:343–364

    Google Scholar 

  7. Marangoni AG (2005) Fat crystal networks. Marcel Dekker, New York

    Google Scholar 

  8. Wiking L, De Graef V, Rasmussen M, Dewettinck K (2009) Relations between crystallisation mechanisms and microstructure of milk fat. Int Dairy J 19:424–430

    Article  CAS  Google Scholar 

  9. Wright AJ, Scanlon MG, Hartel RW, Marangoni AG (2001) Rheological properties of milkfat and butter. J Food Sci 66:1056–1071

    Article  CAS  Google Scholar 

  10. Cebula DJ, Smith KW (1991) Differential scanning calorimetry of confectionery fats—pure triglycerides—effects of cooling and heating variation. J Am Oil Chem Soc 68:591–595

    Article  CAS  Google Scholar 

  11. Marangoni AG, McGauley SE (2003) Relationship between crystallization behavior and structure in cocoa butter. Cryst Growth Des 3:95–108

    Article  CAS  Google Scholar 

  12. Litwinenko JW, Rojas AM, Gerschenson LN, Marangoni AG (2002) Relationship between crystallization behavior, microstructure, and mechanical properties in a palm oil-based shortening. J Am Oil Chem Soc 79:647–654

    Article  CAS  Google Scholar 

  13. MacMillan SD, Roberts KJ, Rossi A, Wells MA, Polgreen MC, Smith IH (2002) In situ small angle X-ray scattering (SAXS) studies of polymorphism with the associated crystallization of cocoa butter fat using shearing conditions. Cryst Growth Des 2:221–226

    Article  CAS  Google Scholar 

  14. Mazzanti G, Guthrie SE, Sirota EB, Marangoni AG, Idziak SHJ (2004) Novel shear-induced phases in cocoa butter. Cryst Growth Des 4:409–411

    Article  CAS  Google Scholar 

  15. De Graef V, Dewettinck K, Verbeken D, Foubert I (2006) Rheological behavior of crystallizing palm oil. Eur J Lipid Sci Technol 108:864–870

    Article  Google Scholar 

  16. De Graef V, Foubert I, Smith KW, Cain FW, Dewettinck K (2007) Crystallization behavior and texture of trans-containing and trans-free palm oil based confectionery fats. J Agric Food Chem 55:10258–10265

    Article  Google Scholar 

  17. De Graef V, Goderis B, Van Puyvelde P, Foubert I, Dewettinck K (2008) Development of a rheological method to characterize palm oil crystallizing under shear. Eur J Lipid Sci Technol 110:521–529

    Article  Google Scholar 

  18. Thareja P, Street CB, Wagner NJ, Vethamuthu MS, Hermanson KD, Ananthapadmanabhan KP (2011) Development of an in situ rheological method to characterize fatty acid crystallization in complex fluids. Colloids Surf A: Physiochem Eng Aspects 388:12–20

    Article  CAS  Google Scholar 

  19. Street CB, Yarovoy Y, Wagner NJ, Vethamuthu MS, Hermanson KD, Ananthapadmanabhan KP (2012) TDNMR study of a model crystallizing surfactant system. Colloids Surf A: Physicochem Eng Aspects 406:13–23

    Article  CAS  Google Scholar 

  20. de Graef V, van Puyvelde P, Goderis B, Dewettinck K (2009) Influence of shear flow on polymorphic behavior and microstructural development during palm oil crystallization. Eur J Lipid Sci Technol 111:290–302

    Article  Google Scholar 

  21. Verma AR (1955) Interferometric and X-ray investigation of the growth of long-chain fatty acid crystals 1. Polymorphism and polytypism in palmitic acid crystals. In: Proceedings of the Royal Society of London Series a-Mathematical and Physical Sciences 228:34–50

  22. Krog N, Borup AP (1973) Swelling behavior of lamellar phases of saturated monoglycerides in aqueous systems. J Sci Food Agric 24:691–701

    Article  CAS  Google Scholar 

  23. Eccleston GM (1986) The microstructure of semi soild creams. Pharm Int 7:63–70

    CAS  Google Scholar 

  24. Eccleston GM (1997) Functions of mixed emulsifiers and emulsifying waxes in dermatological lotions and creams. Colloids Surf A: Physicochem Eng Aspects 123:169–182

    Article  Google Scholar 

  25. Hallett J, Mason BJ (1958) The influence of temperature and supersaturation on the habit of ice crystals grown from the vapour. In: Proceedings of the Royal Society of London Series a-Mathematical and Physical Sciences 247:440–443

  26. Sarig S, Eidelman N, Glasner A, Epstein JA (1978) Effect of supersaturation on the crystal characteristics of potassium-chloride. J Appl Chem Biotech 28:663–667

    CAS  Google Scholar 

  27. Tzocheva SS, Kralchevsky PA, Danov KD, Georgieva GS, Post AJ, Ananthapadmanabhan KP (2012) Solubility limits and phase diagrams for fatty acids in anionic (SLES) and zwitterionic (CAPB) micellar surfactant solutions, J Colloid Interface Sci 369:274–286

    Article  CAS  Google Scholar 

Download references

Acknowledgments

Financial support for this work was provided by Unilever, Inc. The authors would like to thank Dr. Steve Sauerbrunn of Mettler Teledo for providing assistance with the calorimetric measurements.

Author information

Author notes

  1. Prachi Thareja

    Present address: Indian Institute of Technology, Gandhinagar, Gujarat, India

  2. Anne Golematis

    Present address: DuPont Analytical Sciences, Wilmington, DE, USA

Authors and Affiliations

  1. Center for Molecular Engineering and Thermodynamics, Department of Chemical and Biomolecular Engineering, University of Delaware Newark, 150 Academy St, Newark, DE, 19716, USA

    Prachi Thareja, Anne Golematis, Carrie B. Street & Norman J. Wagner

  2. Unilever Research and Development, Trumbull, CT, USA

    Martin S. Vethamuthu, Kevin D. Hermanson & K. P. Ananthapadmanabhan

Authors
  1. Prachi Thareja
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Anne Golematis
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Carrie B. Street
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Norman J. Wagner
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Martin S. Vethamuthu
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Kevin D. Hermanson
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. K. P. Ananthapadmanabhan
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Norman J. Wagner.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 1622 kb)

About this article

Cite this article

Thareja, P., Golematis, A., Street, C.B. et al. Influence of Surfactants on the Rheology and Stability of Crystallizing Fatty Acid Pastes. J Am Oil Chem Soc 90, 273–283 (2013). https://doi.org/10.1007/s11746-012-2161-4

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11746-012-2161-4

Keywords

Search

Navigation