Hostname: page-component-cd9895bd7-lnqnp Total loading time: 0 Render date: 2024-12-27T02:01:26.969Z Has data issue: false hasContentIssue false
  • English
  • Français

Anomalous Surface Conformation for Polymeric Gas-Hydrate-Crystal Inhibitors

Published online by Cambridge University Press:  21 March 2011

H.E. King ,
Jeffrey L. Hutter ,
Min Y. Lin  and
Thomas Sun
H.E. King
Affiliation:
ExxonMobil Research and Engineering Company Annandale, NJ 08801
Jeffrey L. Hutter
Affiliation:
ExxonMobil Research and Engineering Company Annandale, NJ 08801
Min Y. Lin
Affiliation:
ExxonMobil Research and Engineering Company Annandale, NJ 08801 Also at the National Institute of Standards and Technology, Gaithersburg, MD 20899
Thomas Sun
Affiliation:
ExxonMobil Research and Engineering Company Annandale, NJ 08801
Get access

Abstract

We have used both conventional small-angle neutron scattering and contrast variation techniques to characterize the polymer conformations of two non-ionic water soluble polymers: poly(ethylene oxide) and poly(N-vinyl-2-pyrollidone). The second of these is able to kinetically suppress hydrate crystallization, and an objective of these studies is to obtain a understanding of this inhibition mechanism. The dilute-solution polymer conformation in a hydrate-forming tetrahydrofuran/water fluid shows only a small difference between the polymers. The single- chain characteristics are unperturbed, but the hydrate inhibitor polymer seems to show an enhanced tendency to form aggregates in solution. This is evidenced by excess low-q scattering following a q-2.5 power law. Much more evident is the strong perturbation in the conformation of the inhibitor polymer upon crystallization of the hydrate. We utilize contrast variation methods to resolve the scattering of the polymer on the hydrate surface. Unlike expectations from polymer scaling laws, the resulting layer is considerably thicker (550) than the single- chain radius of gyration, 80. Also surprising, only 2 percent of the available crystal surface is covered. Within the covered areas, the polymer concentration is significantly enhanced over that in the surrounding solution, about 2.5c* (where c* is the overlap concentration). This suggests a coverage of clumps of polymer widely separated from one another. Consideration of the concentration and implied spacing of such clumps on the hydrate surface suggests that they can effectively inhibit crystal growth.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 651: Symposium T – Dynamics in Small Confining Systems V , 2000 , T8.4.1
Copyright
Copyright © Materials Research Society 2001

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]Davidson, D. W. In: Franks, F. (Ed.), Water: A Comprehensive Treatise NY, London: (Plenum Press, 1973); Vol. 2; pp. 115.Google Scholar
[2]Kvenvolden, K. A.; Ginsburg, G. D. and Soloviev, V. A., Geo-Marine Letters 13, 32 (1993).Google Scholar
[3]Sloan, E. D. Jr, Clathrate Hydrates of Natural Gases, New York: (Marcel Dekker, Inc., 1990), pp. 276.Google Scholar
[4]Sloan, E. D. Jr, Journal of Petroleum Technology 43, 1414 (1991).Google Scholar
[5]Lederhos, J. P.; Long, J. P; Sum, A.; Christiansen, R. L. and Sloan, E. D. Jr, Chemical Engineering Science 51, 1221 (1996).Google Scholar
[6]Makogon, T. Y.; Larsen, R.; Knight, C. A. and Sloan, E. D. Jr, Journal of Crystal Growth 179, 258 (1997).Google Scholar
[7]Larsen, R.; Knight, C. A. and Sloan, E. D. Jr, Fluid Phase Equilibria 150–151, 353 (1998).Google Scholar
[8]Sloan, E. D. Jr; Subramanian, S.; Matthews, P. N.; Lederhos, J. P. and Kokhar, A. A., Industrial and Engineering Chemistry Research 37, 3124 (1998).Google Scholar
[9]Hanley, H. J. M.; Meyers, G. J.; White, J. W. and Sloan, E. D. Jr, International Journal of Thermophysics 10, 903 (1989).Google Scholar
[10]Hutter, J.; King, H. E. Jr, and Min, L. Y., Macromolecules 33, 2670 (2000).Google Scholar
[11]Devanand, K. and Selser, J. C., Macromolecules 24, 5943 (1991).Google Scholar
[12]Sun, T. and King, H. E. Jr, Macromolecules 29, 3175 (1995).Google Scholar
[13]King, H. E. Jr; Hutter, J.; Lin, M. Y. and Sun, T., Journal of Chemical Physics 112, 2523 (1999).Google Scholar
[14]Beaucage, G., Journal of Applied Crystallography 29, 134 (1996).Google Scholar
[15]Beaucage, G., Journal of Applied Crystallography 28, 717 (1995).Google Scholar
[16]de Gennes, P. G., Comptes Rendus de L'Académie des Sciences (Paris), Serie II 313, 1117 (1991).Google Scholar