Mechanical anisotropy in oriented linear polyethylene of various crystallinities

We have studied the mechanical moduli of oriented linear polyethylene with crystallinities X varying from 0.44 to 0.63 and draw ratios λ = 1–9 by using a dynamic tensile method at 10 Hz and an ultrasonic technique at 10 MHz. Wide-angle X-ray diffraction and birefringence measurements reveal that the chains in the crystalline regions are fully aligned at λ > 4, but the degree of amorphous orientation increases steadily up to the highest draw ratio. From −180°C to the β relaxation region (near 0°C at 10 Hz) the mechanical behavior at all crystallinities is controlled by three factors: molecular orientation, weak c-shear deformation and stiffening effect of taut tie molecules. At low temperature the chain alignment in an oriented sample gives rise to an axial Young's modulus E₀ which is much larger than the transverse Young's modulus E₉₀, with the modulus for the undrawn material lying in-between. However, the results that E₄₅ < E₉₀ and C₄₄ (axial shear modulus) < C₆₆ (transverse shear modulus) imply that a weak c-shear process occurs even at low temperature. At the β relaxation where the amorphous regions are rubbery, the stiffening effect of taut tie molecules becomes prominent and leads to increases in all moduli upon drawing. For the polyethylene with the lowest cyrstallinity a strong c-shear process is activated at the α relaxation (about 50°C at 10 Hz), which gives rise to very low values of C₄₄ and E₄₅. This effect becomes weaker with increasing crystallinity and is hardly observable at X > 0.6.