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March 28, 2017 | Polymers Textiles | By admin | 0 Comments

By Ingo Pinnau and Benny D. Freeman (Eds.)

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ACS Symposium Series; American Chemical Society: Washington, DC, 2004. ch002 30 A value of one indicates a totally rigid structure over the time frame of the simulation while a value of zero indicates totally free bond rotation. , the i+3 Si-atom). , the ith Si-atom) with the O-atom of the adjacent repeating unit. For P D M S M , it was defined as Si(/)-C(/)~Si(i+l)--C(/+l), a vector connecting one Si-atom with the C-atom of the adjacent repeating unit. Vectors were also assigned to the five different substituent groups — methyl, «-propyl, trifluoropropyl, phenyl, and cyclohexyl.

I will emphasize the solvation Gibbs energy, which directly relates to the solubility coefficient. In the second part, solvation enthalpies and entropies are discussed. In particular, I will pay attention to the physical interpretation of the polymerpenetrant interaction and cavity formation terms in die enthalpy and entropy expressions. In the section entitled "Thermodynamics of small permanent gases in liquid poly(ethylene)," some results from M D simulations of gas sorption in a poly(ethylene) melt will be discussed to illustrate the feasibility of calculating all thermodynamic quantities from molecular simulations.

G. reference (/#)), they remain difficult to understand, perhaps even conflicting with intuitive reasoning that tells us that formation of a cavity is the first thing must happen before a penetrant can dissolve. A hand-waving argument to explain this abstract thermodynamic fact is provided by realizing that the energy invested to create a cavity in the polymer fluid is distributed amongst a vast number of polymer degrees of freedom causing the fluid entropy to increase (the entropy of a molecular system increases with its energy content).

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