Simultaneous crystalline-amorphous phase evolution during crystallization of polymer systems

Despite the fact that polymer crystallization has been the object of intense research, this process is far from being fully understood. Traditional polymer crystallization studies using X-ray scattering techniques mainly provide information about the ordered regions. To obtain a more complete information about the time evolution of both the crystalline and the amorphous phase during polymer crystallization, we have developed a technique which allows one to obtain information about both the crystalline and the amorphous phase simultaneously. We report here simultaneous information about three key aspects of the isothermal polymer crystallization process: i) polymer chain ordering, through Wide-Angle X-ray Scattering; ii) lamellar crystals arrangement, through Small-Angle X-ray Scattering; iii) amorphous phase evolution through dielectric spectroscopy. Our results probe that during primary crystallization the average mobility of the amorphous phase is not notably affected. Upon passing through the crossover time, marking the transition from primary to secondary crystallization, the restriction to the mobility of the amorphous phase mainly occurs in the regions between the lamellar stacks regions and not in the amorphous regions within the lamellar stacks. We hypothesize that molecular mobility in the amorphous regions located between consecutive crystals become strongly arrested as soon as the lamellar stack is formed.