Structural mechanisms as revealed by real time mechano optical behavior of polylactic acid films in uni and biaxial deformation and heat setting processes.

摘要

In this study, structural development during PLA film processing was investigated with a new instrumented biaxial stretcher capable of real time monitoring of true stress, true strain and in-plane as well as out-of-plane birefringence under fast deformation rates. The effects of stretching rate and mode on mechano-optical behaviors and correspondent morphology development were investigated. At low deformation levels, a linear regime I associated with orientation of amorphous chains was observed in all modes of deformation. Following regime I, a steeper regime II associated with stress induced crystallization was observed during uniaxial constrained width (UCW) stretching under low rates before birefringence begins to level off in regime III due to finite extensibility of chains. During UCW stretching under high rate, regime I transformed directly into regime III, and this is associated with the formation of a very stable nematic mesophase. Direct transformation from regime I to regime III is observed during simultaneous biaxial (SIM) stretching under all rates.; The kinetics of structural changes during heat setting from a pre-oriented state was investigated by rapid tracking of in and out-of-plane birefringence of pre-oriented films with a new instrumented annealing chamber capable of fast sample insertion and removal. Development of birefringence, which reflects overall chain orientation, and associated structural evolution during constrained annealing of extended PLA films were clarified. Structural evolution is determined by the competition between chain relaxation and registration of segments into well oriented nuclei that grow during annealing, leading to formation of a long range network of chains that arrests the chains in their oriented state. At low deformation the temporal evolution of birefringence first involves relaxation followed by a rapid increase associated with crystallization. The initial relaxation disappears with increase in deformation in the precursor films exhibiting distinct oriented crystalline structure. At all levels of deformation in those films extended at fast rates, the relaxation stage always was observed. The extent of relaxation was found to decrease with deformation but could not be entirely eliminated in the deformation range investigated. This was directly attributed to the absence of a well established long range connected physical network in this "looser" structure.