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Pressure-Induced Amorphization and Disordering on Cooling in Semi-Crystalline Polymers; calorimetrie evidence for inverse melting in one component system

Published online by Cambridge University Press:  10 February 2011

S. Rastogi
Affiliation:
Dutch Polymer Institute/Eindhoven Polymer Laboratories, Eindhoven University of Technology, Eindhoven, The Netherlands
G. Höhne
Affiliation:
Department of Physics, University of Ulm, Ulm, Germany
A. Keller
Affiliation:
H.H. Wills Physics Lab., University of Bristol, Bristol, U.K.
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Abstract

We report some unusual phase behaviour, of general implication for condensed matter, on the polymer poly-4-methyl pentene-1 (P4MP1) induced by changes in pressure (P) and temperature (T), as observed by in-situ X-ray diffraction and high pressure DSC. Upon increasing pressure beyond a threshold value, the polymer, crystalline at ambient conditions, looses its crystalline order isothermally. The process is reversible. This behaviour is observed in two widely separated temperature regions, one below the glass transition temperature (< 50°C) and one close to the melting temperature (250°C), thus showing solid state amorphization and inversion in the melting temperature with increasing pressure. This further suggests inverse melting, i.e. re-entrant of the two widely separated liquid and amorphous phases along the T-axis at fixed P. This is confirmed experimentally as disordering in the crystalline structure on cooling. The inverse melting in P4MP1 raises the possibility of exothermic melting and endothermic crystallization as anticipated by Tammann (1903). The anticipated exothermic melting and endothermic crystallization is confirmed experimentally in the one component system P4MP1. We are observing similar features in a range of polymers.

Type
Research Article
Copyright
Copyright © Materials Research Society 1998

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References

REFERENCES

1. Tammann, G., Kristallisieren und Schmelzen, Verlag Johann Ambrosius Barth, Leipzig (1903)Google Scholar
2. Rastogi, S., Newman, M., Keller, A., Nature 353, 55 (1991); J. Polym. Sci. (Phy) B31, 125 (1993)Google Scholar
3. Rastogi, S., Höhne, G., Keller, A., manuscript in preparation.Google Scholar