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Crystallization of PDMS: The effect of physical and chemical crosslinks

T. Dollase1,2,3, H. W. Spiess1,2, M. Gottlieb1,3 and R. Yerushalmi-Rozen1,3

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Calorimetric studies of the crystallization behavior of physically and chemically crosslinked semicrystalline polymer, polydimethylsiloxane (PDMS) are presented. Physical crosslinks are introduced either via entanglements in high-molecular-weight PDMS, or by anchoring chain ends to rigid polyethylene oxide (PEO) endblocks in a PEO-b-PDMS-b-PEO triblock copolymer. Chemical end-linking of di-vinyl PDMS chains results in the formation of a crosslinked network. Comparison of the thermograms obtained for each of these systems at constant cooling/heating rates with their noncrosslinked analogues indicates that, contrary to conventional wisdom, the different types of crosslinks result in an increased crystallization tendency. We suggest that this effect is a manifestation of the enhancement of local ordering together with reduced dynamics as compared to the non-crosslinked melt.


PACS

61.25.H- Macromolecular and polymers solutions; polymer melts

68.35.Md Surface thermodynamics, surface energies

Subjects

Soft matter, liquids and polymers

Surfaces, interfaces and thin films

Dates

Issue 3 (November 2002)

Received 22 April 2002, accepted for publication 19 August 2002



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