TEM Observation of Natural Rubber Thin Films Crystallized under Molecular Orientation

Abstract

Abstract Morphology of natural rubber (NR) thin films crystallized under molecular orientation was examined by transmission electron microscopy (TEM). A thin film of NR (RSS#1) was made by casting its n-hexane (or benzene) solution onto the water surface, and prestretched up to a desired amount of strain (%). Each of the specimens thus prepared was introduced into a TEM column and isothermally crystallized at −25 °C with a cryo-transfer specimen-holder. Morphological observations in bright- and dark-field imaging modes revealed directly that the length of the lamellae, which were oriented perpendicular to the stretching direction, decreased with increasing strain. The result seems to be related to the population density of “γ-filaments” (named by Andrews) generated only by prestretching. Time-resolved bright-field observations by in situ TEM of the thin film prestretched up to a strain of 200% revealed the following. Though the film gave crystalline reflections in its selected-area electron diffraction even before isothermal crystallization, no well-defined lamellae were recognized. Subsequent isothermal crystallization for 2 h, however, formed well-defined lamellae oriented perpendicular to the stretching direction. This observation, conceivably, suggests that “γ-filaments” were formed immediately by prestretching and then the lamellae were nucleated on the γ-filaments at −25 °C.