Journal of the American Oil Chemists' Society

, Volume 75, Issue 11, pp 1617–1624 | Cite as

Thermal analysis of isothermal crystallization kinetics in blends of cocoa butter with milk fat or milk fat fractions



The kinetics of isothermal crystallization of binary mixtures of cocoa butter with milk fat and milk fat fractions were evaluated by applying the Avrami equation. Application of the Avrami equation to isothermal crystallization of the fats and the binary fat blends revealed different nucleation and growth mechanisms for the fats, based on the Avrami exponent. The suggested mechanism for cocoa butter crystallization was heterogeneous nucleation and spherulitic growth from sporadic nuclei. For milk fat, the mechanism was instantaneous heterogeneous nucleation followed by spherulitic growth. For milk fat fractions, the mechanism was high nucleation rate at the beginning of crystallization, which decreased with time, and plate-like growth. Addition of milk fat fractions did not cause a significant change in the suggested nucleation and growth mechanism of cocoa butter.

Key Words

Avrami equation cocoa butter crystallization kinetics DSC fats fractionation isothermal crystallization milk fat milk fat fractions 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Chaiseri, S., and P.S. Dimick, Cocoa Butter—Its Composition and Properties, Manuf. Confect. 67:115–122 (1987).Google Scholar
  2. 2.
    Ziegleder, V.G., Crystallization of Chocolate Masses. Part 1, Zucker-u-Suss. Wirt. 41:165–168 (1988).Google Scholar
  3. 3.
    Hartel, R.W., Applications of Milk-Fat Fractions in Confectionery Products, J. Am. Oil Chem. Soc. 73:944–953 (1996).CrossRefGoogle Scholar
  4. 4.
    Metin, S., J. Fabian, and R.W. Hartel, Milk Fat Crystallization: An Overview, in Proceeding of Bremer International Workshop on Industrial Crystallization, University of Bremen, Bremen, Germany, 1996, pp. 61–69.Google Scholar
  5. 5.
    Chapman, G.M., E.E. Akehurst, and W.B. Wright, Cocoa Butter and Confectionery Fats. Studies Using Programmed Temperature X-Ray Diffraction and Differential Scanning Calorimetry, J. Am. Oil Chem. Soc. 48:824–830 (1971).CrossRefGoogle Scholar
  6. 6.
    Jewell, G.G., and L. Bradford, Considerations in Chocolate Formulation, Manuf. Conf. 61:26–30 (1981).Google Scholar
  7. 7.
    Edwards, W.P., Uses for Dairy Ingredients in Confectionery, J. Soc. Dairy Technol. 37:122–125 (1984).Google Scholar
  8. 8.
    Kaylegian, K.E., and R.C. Lindsay, Handbook of Milk Fat Fractionation Technology and Application, AOCS Press, Champaign, 1995.Google Scholar
  9. 9.
    Timms, R.E., The Phase Behaviour of Mixtures of Cocoa Butter and Milk Fat, Lebensm. Wiss. Technol. 13:61–65 (1980).Google Scholar
  10. 10.
    Campbell, L. B., A. Anderson, and P.G. Keeney, Hydrogenated Milk Fat as an Inhibitor of the Fat Bloom Defect in Dark Chocolate, J. Dairy Sci. 59:976–979 (1969).CrossRefGoogle Scholar
  11. 11.
    Hendrickx, H., H. DeMoor, A. Huyghebaert, and G. Janssen, Manufacture of Chocolate Containing Hydrogenated Butterfat, Rev. Int. Choc. 26:190–193 (1971).Google Scholar
  12. 12.
    Timms, R.E., and J.V. Parekh, The Possibilities for Using Hydrogenated, Fractionated or Interesterified Milk Fat in Chocolate, Lebensm. Wiss. Technol. 13:177–181 (1980).Google Scholar
  13. 13.
    Barna, C.M., R.W. Hartel, and S. Metin, Incorporation of Milk Fat Fractions into Milk Chocolates, Manuf. Conf. 72:107–116 (1992).Google Scholar
  14. 14.
    Bystrom, C.E., and R.W. Hartel, Evaluation of Milk Fat Fractionation and Modification Techniques for Creating Cocoa Butter Replacers, Lebensm. Wiss. Technol. 27:142–150 (1994).CrossRefGoogle Scholar
  15. 15.
    Lohman, M.H., and R.W. Hartel, Effect of Milk Fat Fractions on Fat Bloom in Dark Chocolate, J. Am. Oil Chem. Soc. 71:267–276 (1994).CrossRefGoogle Scholar
  16. 16.
    Wood, J.S., Milk-Fat Fraction Incorporation in Dark and Milk Chocolate, Master’s Thesis, University of Wisconsin, Madison, 1994.Google Scholar
  17. 17.
    Metin, S., and R.W. Hartel, Crystallization Behavior of Blends of Cocoa Butter and Milk Fat or Milk-Fat Fractions, J. Thermal Anal. 47:1527–1544 (1996).CrossRefGoogle Scholar
  18. 18.
    Metin, S., Crystallization Behavior and Kinetics of Blends of Cocoa Butter and Milk Fat or Milk Fat Fractions, Ph.D. Thesis, University of Wisconsin, Madison, 1997.Google Scholar
  19. 19.
    Kissinger, H.E., Reaction Kinetics in Differential Thermal Analysis, Anal. Chem. 29:1702–1706 (1957).CrossRefGoogle Scholar
  20. 20.
    Ozawa, T., Kinetics of Non-Isothermal Crystallization, Polymer 12:150–158 (1971).CrossRefGoogle Scholar
  21. 21.
    Duswalt, A.A., The Practice of Obtaining Kinetic Data by Differential Scanning Calorimetry, Thermochim. Acta 8:57–68 (1974).CrossRefGoogle Scholar
  22. 22.
    Augis, J.A., and J.E. Bennett, Calculation of the Avrami Parameters for Heterogeneous Solid State Reactions Using a Modification of the Kissinger Method, J. Thermal Anal. 13:283–292 (1978).CrossRefGoogle Scholar
  23. 23.
    Henderson, D.W., Thermal Analysis of Non-Isothermal Crystallization Kinetics in Glass Forming Liquids, J. Non-Crystalline Solids 30:301–315 (1979).CrossRefGoogle Scholar
  24. 24.
    Weinberg, M.C., On the Analysis of Non-Isothermal Thermoanalytic Crystallization Experiments, J. Non-Crystalline Solids 127:151–158 (1991).CrossRefGoogle Scholar
  25. 25.
    Woldt, E., The Relationship Between Isothermal and Nonisothermal Description of Johnson-Mehl-Avrami-Komogorov Kinetics, J. Phys. Chem. Solids 53:521–527 (1992).CrossRefGoogle Scholar
  26. 26.
    Graydon, J.W., S.J. Thorpe, and D.W. Kirk, Determination of the Avrami Exponent for Solid State Transformations from Non-Isothermal Differential Scanning Calorimetry, J. Non-Crystalline Solids 175:31–43 (1994).CrossRefGoogle Scholar
  27. 27.
    Christian, J.W., The Theory of Transformations in Metals and Alloys, 2nd edn., Pergamon Press, London, 1975.Google Scholar
  28. 28.
    Kawamura, K., The DSC Thermal Analysis of Crystallization Behavior in Palm Oil, J. Am. Oil Chem. Soc. 56:753–758 (1979).Google Scholar
  29. 29.
    Ziegleder, V.G., DSC—Thermal Analysis and Kinetics of Cocoa Butter Crystallization, Fat Sci. Technol. 92:481–485 (1990).Google Scholar
  30. 30.
    Herrera, M.L., and F.J. Marques Rocha, Effects of Sucrose Esters on the Kinetics of Polymorphic Transition in Hydrogenated Sunflower Oil, J. Am. Oil Chem. Soc. 73:321–326 (1996).CrossRefGoogle Scholar
  31. 31.
    Dibildox-Alvarado, E., and J.F. Toro-Vazques, Isothermal Crystallization of Tripalmitin in Sesame Oil, Ibid.:69–76 (1997).CrossRefGoogle Scholar
  32. 32.
    Avrami, M., Kinetics of Phase Change. II. Transformation-Time Relations for Random Distribution of Nuclei, J. Chem. Phys. 8:212–224 (1940).CrossRefGoogle Scholar
  33. 33.
    Doremus, R.H., Rates of Phase Transformations, Academic Press, Orlando, 1985, pp. 24–26.Google Scholar
  34. 34.
    Arvanitoyannis, I., and J.M.V. Blanshard. Rates of Crystallization of Dried Lactose-Sucrose Mixtures, J. Food Sci. 59:197–205 (1994).CrossRefGoogle Scholar
  35. 35.
    Official Methods and Recommended Practices of the American Oil Chemists’ Society, 3rd edn., AOCS, Champaign, 1973, Method Cc 1–25.Google Scholar
  36. 36.
    Sharples, A., Introduction to Polymer Crystallization, Edward Arnold Publishers, Ltd., London, 1966, pp. 4–60.Google Scholar
  37. 37.
    Ahza, A.B., Kinetics of Milk Fat Crystallization in a Continuous Crystallizer, Ph.D. Thesis, University of Wisconsin, Madison, 1995.Google Scholar
  38. 38.
    Chapman, D., The Polymorphism of Glycerides, Chem. Rev. 62:433–456 (1962).CrossRefGoogle Scholar

Copyright information

© AOCS Press 1998

Authors and Affiliations

  1. 1.M&M/Mars, Inc.Hackettstown
  2. 2.University of Wisconsin-MadisonMadison

Personalised recommendations