Cherayil, Binny J (1993) Critical phenomena in polymer solutions: Scaling of the free energy. In: Journal of Chemical Physics, 98 (11). pp. 9126-9133.
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The thermodynamics of monodisperse solutions of polymers in the neighborhood of the phase separation temperature is studied by means of Wilson’s recursion relation approach, starting from an effective ϕ4 Hamiltonian derived from a continuum model of a many‐chain system in poor solvents. Details of the chain statistics are contained in the coefficients of the field variables ϕ, so that the parameter space of the Hamiltonian includes the temperature, coupling constant, molecular weight, and excluded volume interaction. The recursion relations are solved under a series of simplifying assumptions, providing the scaling forms of the relevant parameters, which are then used to determine the scaling form of the free energy. The free energy, in turn, is used to calculate the other singular thermodynamic properties of the solution. These are characteristically power laws in the reduced temperature and molecular weight, with the temperature exponents being the same as those of the 3d Ising model. The molecular weight exponents are unique to polymer solutions, and the calculated values compare well with the available experimental data.
|Item Type:||Journal Article|
|Additional Information:||Copyright of this article belongs to American Institute of Physics.|
|Department/Centre:||Division of Chemical Sciences > Inorganic & Physical Chemistry|
|Date Deposited:||03 Feb 2011 08:11|
|Last Modified:||03 Feb 2011 08:11|
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