Thermodynamische Stabilität makromolekularer Kristalle

Abstract

The density of free energy of a chain crystal contains two terms of opposed sign dependent on the numberN of chain elements in the straight section of the macromolecules between the surfaces of the crystal perpendicular to thec-axis. The surface energy contributes a positive term decreasing withN. The amplitude Φ of the periodic lattice field opposing the chain translation in thec-axis yields the negative term. Due to the incoherent longitudinal thermal vibration of the four first-order neighbours of any chain the fieldΦ is smeared out. Its amplitude decreases the more the higherN and hence yields an increase in free energy density with increasingN. As a consequence of the opposite sign of surface energy and lattice field changes withN the free energy density shows a minimum at finiteN corresponding to the thermodynamically stable crystal thickness. With increasing temperature and lower interaction between adjacent chainsN increases in perfect qualitative agreement with experimental data.