Raman spectroscopy has been used to measure the molecular stress distribution in high-modulus, high-strength polyethylene fibres (Allied Spectra 1000 and Spectra 900) at low temperature and as a function of time during creep at room temperature. Increase in band width or change of band shape is interpreted as due to a distribution of stress or strain in molecules in the all-trans configuration. Fibres loaded at 77 K show two peaks in the stress distribution, as was found by van Eijk et al. at 240 K. About one-sixth of the all-trans molecules in a Spectra 1000 fibre as produced carry little load. The rest carry from half to twice the mean load. Spectra 1000 fibres loaded at over 1 GPa for a few minutes at room temperature show two well defined peaks in each of the C-C stretching Raman bands at 1064 and 1130 cm- 1 and thus a sharp bimodal distribution of stress. At long creep times, the higher stress peak increases in width while keeping the same area. Eventually, the stress distribution has a single peak with a broad tail on the high-stress side. This result unifies the previous two observations, one of which found only a single asymmetric peak and the other only two peaks in the stress distribution. As the tail broadens, the number of very highly strained molecules increases, and a significant number reach strains of 10%. It is not surprising that this leads to fracture of the fibre. After loading for less than a minute at room temperature or for a few minutes at 273 K, there is only a single peak in the stress distribution. The fibre structure is thus undergoing complex changes during creep, and the stress distribution seen at room temperature is not simply related to the original structure.
Посилання на статтю:
Molecular stress distribution and creep of high-modulus polyethylene fibres* / David T. Grubbt and Zong-Fu Li // Polymer. – 1992. – Vol 33. – P. 2587-2597.