Pressure-Volume-Temperature of molten and glassy polymers

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Journal titleJournal of Polymer Science Part B: Polymer Physics
Pages270285; # of pages: 16
Subjectequation-of-state; free volume; glass transition; phase behavior; statistical thermodynamics; thermodynamics; vitreous state behavior
AbstractThe pressure–volume–temperature (PVT) dependencies of several amorphous polymers (PS, PC, PPE, and PPE/PS 1:1 blend) in the glassy and molten state were studied. The Simha–Somcynsky (S–S) lattice-hole equation of state (EOS) was used. Fitting the PVT data in the molten state to the EOS yielded the free volume quantity, h = h(T, P), and the characteristic reducing parameters, P*, V*, and T*. The data within the glassy region were interpreted assuming that the latter parameters are valid in the molten and vitreous state, than calculating h = h(T, P) from the experimental values of V = V(T, P). Next, the frozen free volume fraction in the glass was computed as FF = FF(P). The FF values of polystyrene (PS) resins at ambient pressure showed little scattering (FFP=₁ = 0.691 ± 0.008), while their P-dependencies varied, reflecting the thermodynamic history of the glass formation as well as the PVT measurements protocol. The pressure gradient of Tg was compared with the Ehrenfest relation for the second-order transition; here also agreement depended on the method of vitrification. The experimental values of FF at ambient pressure decreased with increasing values of the characteristic temperature reducing parameter, T*.
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AffiliationNational Research Council Canada (NRC-CNRC); NRC Industrial Materials Institute
Peer reviewedYes
NRC number48950
NPARC number15774993
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Record identifier14600a6a-9cc3-4019-aa14-19d207218bf3
Record created2010-07-05
Record modified2016-05-09
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