Temperature dependence of the elastic modulus of crystalline regions of polyethylene with different microstructures—explanation with the kinked-chain model
Nishino, T.; Ohkubo, H.; Nakamae, K.; Nishino, T.; Department of Industrial Chemistry Faculty of Engineering, Kobe University; Ohkubo, H.; Department of Industrial Chemistry Faculty of Engineering, Kobe University; Nakamae, K.; Department of Industrial Chemistry Faculty of Engineering, Kobe University
Журнал:
Journal of Macromolecular Science, Part B
Дата:
1992
Аннотация:
AbstractTemperature dependence of the elastic modulus E <sub>1</sub> of crystalline regions in the direction parallel to the chain axis has been measured by x-ray diffraction for various kinds of polyethylene (PE) with different microstructures. The E <sub>1</sub> value is 235 GPa for all kinds of PE at room temperature. However, in some cases, E <sub>1</sub> began to decrease at a certain temperature, in one case at 50°C and in one at 65°C. The lattice spacing for the (002) plane also decreased with increasing temperature. The thermal expansion coefficient αc changed discontinuously around the temperature range where E <sub>1</sub> began to decrease. This indicates that axial thermal molecular motion (i.e., incoherent thermal motion) is enhanced at high temperature. These phenomena could well be explained with the kinked-chain model where two gauche conformations are incorporated in the all-trans, fully extended conformation. The kinked chain deforms very easily through the change of internal rotation around the C—C bond, which has a small force constant. So it is considered that the decrement of E <sub>1</sub> at high temperature is due to the incorporation of a small amount of contracted portions in the chain molecules. On the other hand, in some cases, the E <sub>1</sub> value was constant at 235 GPa up to 110°C In these cases, αc did not change with increasing temperature. Consequently, whether the molecular motion which brings the decrement of E <sub>1</sub> occurs or not is the origin of the difference of the temperature dependence of E <sub>1</sub> of PE. The E <sub>1</sub> value of PE obtained at -155°C is as high as 254 GPa.
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