Hostname: page-component-586b7cd67f-tf8b9 Total loading time: 0 Render date: 2024-11-25T15:38:14.762Z Has data issue: false hasContentIssue false

Impurity Induced Slowing oF Nucleation in Emulsified Liquids

Published online by Cambridge University Press:  10 February 2011

Amy Herhold
Affiliation:
Exxon Research and Engineering Company, Clinton Township, Route 22 East, Annandale, New Jersey 08801
Deniz Ertaş
Affiliation:
Exxon Research and Engineering Company, Clinton Township, Route 22 East, Annandale, New Jersey 08801
Alex J. Levine
Affiliation:
Exxon Research and Engineering Company, Clinton Township, Route 22 East, Annandale, New Jersey 08801
H. E. King Jr
Affiliation:
Exxon Research and Engineering Company, Clinton Township, Route 22 East, Annandale, New Jersey 08801
Get access

Abstract

We report detailed nucleation studies on the liquid -to -solid transition of hexadecane using nearly monodisperse hexadecane -in -water emulsions. A careful consideration of the kinetics of isothermal and nonisothermal freezing show deviations from predictions of classical nucleation theory, if one assumes that the emulsion droplet population is homogeneous. Similar deviations have been observed previously [3]. As an explanation, we propose a novel argument based on the dynamic generation of droplet heterogeneity mediated by mobile impurities. This proposal is in excellent agreement with existing data.

Type
Research Article
Copyright
Copyright © Materials Research Society 1999

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

[1] Vonnegut, B., J. Colloid Sci. 3, p. 563 (1948).Google Scholar
[2] Turnbull, D., J. Chem. Phys. 20, p. 411 (1952).Google Scholar
[3] Turnbull, D. and Cormia, R. L., J. Chem. Phys. 34, p. 820 (1961).Google Scholar
[4] Kelton, K. F., Solid State Physics 45, p. 75 (1991).Google Scholar
[5] Perepezko, J. H., Materials Science and Engineering A 226–228, p. 374 (1997).Google Scholar
[6] Perepezko, J. H., Materials Science and Engineering 65, p. 125 (1984).Google Scholar
[7] Bibette, J., J. Colloid Interface Sci. 147, p. 474 (1991).Google Scholar
[8] Kandori, K., Kishi, K. and Ishikawa, T., Colloids and Surfaces 55, p. 73 (1991).Google Scholar
[9] Kandori, K., Kishi, K. and Ishikawa, T., Colloids and Surfaces 61, p. 269 (1991).Google Scholar
[10] Uhlmann, D. R., Kritchevsky, G., Straff, R. and Scherer, G., J. Chem. Phys. 62, p. 4,896 (1975).Google Scholar
[11] Oliver, M. J. and Calvert, P. D., J. Crystal Growth 30, p. 343 (1975).Google Scholar
[12] McClements, D. J.; Dickinson, E. and Povey, M. J. W., Chem. Phys. Lett. 172, p. 449 (1990).Google Scholar
[13] Dickinson, E., Kruizenga, F.-J., Povey, M. J. W. and Molen, M. v. d., Col. and Surf. A 81, p. 273 (1993).Google Scholar
[14] Dickinson, E., Goller, M. I., McClements, D. J., Peasgood, S. and Povey, M. J. W., J. Chem. Soc. Faraday Trans. 86, p. 1,147 (1990).Google Scholar
[15] Dickinson, E., McClements, D. J. and Povey, M. J. W., J. Colloid Interface Sci. 142, p. 103 (1991).Google Scholar
[16] Turnbull, D. and Spaepen, F., J. Polym. Sci., Polym. Symp. 63, p. 237 (1978).Google Scholar
[17] Small, D. M., The Physical Chemistry of Lipids: From Alkanes to Phospholipids,\Plenum Press, New York, 1986.Google Scholar
[18] Nakayama, H., Shinoda, K. and Hutchinson, E., J. Phys. Chem. 70, p. 3,502 (1966).Google Scholar
[19] Hato, M. and Shinoda, K., J. Phys. Chem. 77, p. 378 (1973).Google Scholar
[20] Shao, H., Ph.D Thesis, X-ray Scattering Study of Structures and Phase Transitions of Normal Alkanes, The Ohio State University, 1995.Google Scholar
[21] Turnbull, D. and Fisher, J. C., J. Chem. Phys. 17, p. 71 (1949).Google Scholar
[22] Wu, D., Solid State Physics 50, p. 37 (1996).Google Scholar
[23] We neglect the difference in specific heats Cp between the liquid and solid phases in this case.Google Scholar
[24] Turnbull, D., Contemp. Phys. 10, p. 473 (1969).Google Scholar
[25] At typical crystal growth velocities of meters per second, the time lag between nucleation and completion of growth in a single emulsion droplet is on the order of a microsecond. Even though these materials form plate-like structures during freezing which suggests slower growth along certain crystallographic directions, the ratio of the slow rate to the fast one would have to be less than 10–6 to have an effect on the experiments.Google Scholar
[26] Sirota, E. B., Langmuir 14, p. 3,133 (1998).Google Scholar
[27] Sirota, E. B. and Herhold, A. B., Science (to be published.)Google Scholar
[28] Siano, D. B., J. Chem. Educ. 49, p. 755 (1972).Google Scholar
[29] The standard deviation for the emulsion droplet volume distribution is about 0.3.Google Scholar
[30] Lifshitz, E. M. and Pitaevskii, L. P., Statistical Physics, 3rd Edition, Part 1, Pergamon Press, New York, 1980, Chap. 9.Google Scholar
[31] Ertaş, D., Herhold, A., Levine, A. J., and King, H. E. Jr., in preparation.Google Scholar
[32] Kurz, J. L., J. Phys. Chem. 66, p. 2,239 (1962); M. Muramatsu and M. Inove, J. Colloid Interface Sci. 55, p. 80 (1976).Google Scholar