Mehta Rujul, Keawwattana Wirunya, Guenthner Andrew L, Kyu Thein
Department of Polymer Engineering, The University of Akron, Akron, Ohio 44325, USA.
Phys Rev E Stat Nonlin Soft Matter Phys. 2004 Jun;69(6 Pt 1):061802. doi: 10.1103/PhysRevE.69.061802. Epub 2004 Jun 14.
The present article focuses on theoretical elucidation of possible effect of mechanical deformation on spatio-temporal emergence of unusual polymer morphology subjected to quiescent isothermal crystallization conditions. The present theory developed is based on a phase field model consisted of non-conserved time dependent Ginzburg-Landau equation having an asymmetric double well potential in the crystal order parameter signifying metastability for crystallization, coupled with the chain tilt angle involving curvature elasticity and strain recovery potentials. Under quiescent crystallization conditions, the curvature elasticity term is needed to discern the emergence of sectorized single crystals. Upon coupling with the strain recovery potential, the numerical calculation captures ripple formation running across the long lamellar growth front, which may be attributed to lamellar buckling caused by the volume shrinkage. Of particular interest is that these simulated topologies of the single crystals are in good accord with the growth character of syndiotactic polypropylene single crystals observed experimentally by us during isothermal crystallization from the melt.
本文着重从理论上阐明在静态等温结晶条件下,机械变形对异常聚合物形态的时空出现可能产生的影响。所提出的理论基于一个相场模型,该模型由非守恒的含时金兹堡 - 朗道方程组成,在晶体序参量中具有不对称双阱势,这表明结晶具有亚稳性,同时还耦合了涉及曲率弹性和应变恢复势的链倾斜角。在静态结晶条件下,需要曲率弹性项来识别扇形单晶的出现。与应变恢复势耦合后,数值计算捕捉到了横跨长片晶生长前沿的波纹形成,这可能归因于体积收缩引起的片晶屈曲。特别值得关注的是,这些模拟的单晶拓扑结构与我们在熔体等温结晶过程中实验观察到的间规聚丙烯单晶的生长特征高度吻合。