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Tf
We can understand the Tf of real polymers by considering the free energy of fusion: G f = H f Tf Sf = 0 Tf is determined by the relative changes in enthalpy and entropy in going from the crystalline state to the amorphous state. Tf = H f Sf
GCH 6101- Polymer states of matter: crystalline state PM Wood-Adams 1
1 1 R 0 = XB Tf Tf H f
XB = 2M 0 MN
XB =
Vu 1 V1
where Vu = molar volume of mer units and V1= molar volume of solvent, 1 = volume fraction solvent. Molar volumes are calculated from molar mass and density.
GCH 6101- Polymer states of matter: crystalline state PM Wood-Adams 2
PM Wood-Adams
Effect of flexibility
Consider polyesters with the general formula shown below where the group R has a large effect on Tf.
PM Wood-Adams
increasing polarity
PM Wood-Adams
PM Wood-Adams