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Volumn 137, Issue , 2008, Pages 125-222

Generalized entropy theory of polymer glass formation

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EID: 39649109065     PISSN: 00652385     EISSN: None     Source Type: Book Series    
DOI: 10.1002/9780470238080.ch3     Document Type: Article
Times cited : (211)

References (349)
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    • The theory formally can be extrapolated to the limit of monomers and thus can be applied to describe nonpolymeric glass-forming liquids.
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    • Considering the permutational collective motion in a fluid, Feynman (Phys. Rev. 91, 1291 (1953)) argues that the probability of an nth particle collective displacement is on the order of the nth power of the probability of an elementary binary displacement event. This argument is equivalent to the first AG hypothesis if the CRRs of cooled classical fluids are identified with the string-like particle permutational motions that Feynman discusses for liquid He near its superfluid transition. Feynman treates the superfluid transition in He as a kind of equilibrium polymerization transition, and in a separate paper [246], we analyze glass-forming liquids from a similar phenomenological perspective.
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    • The configurational entropy obtained from the simulations is calculated by sampling the number of basins in the potential energy landscape and by identifying the minima of these basins with distinguishable fluid configurations that are used in defining the thermodynamic entropy (see Refs. 64-68).
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    • T) is often modeled by an alternative VFTH equation.
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    • I) can be larger for polymer fluids than indicated by Eq. (42).
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    • g is evident in specific heat data at equilibrium, but a peak is observed under nonequilibrium conditions and is often taken as the definition of the glass transition. Unfortunately, this nonequilibrium peak cannot be addressed within the LCT of glass formation. We strictly avoid a discussion of the specific heat, given the complications of interpreting these data for polymer materials and the omission of the important vibrational component in the LCT treatment.
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    • B for high molar mass F-S polymer fluids at pressures of P = 1 atm and P = 240 atm equals 0.1933 and 0.2147, respectively, and can be regarded, to a first approximation, as pressure independent.
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    • This approximation is not explicitly stated in Ref. 39.
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    • The expression (59) reasonably describes data for the isothermal compressibility of many polymers over a wide temperature range if A and B are treated [39,40] as adjustable parameters.
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