Measurements on the thermal expansivity α∥ and α⟂ (along and normal to the draw direction, respectively) have been carried out for a series of oriented polymers with widely different crystallinities (0.36–0.81) and draw ratios (1–20) and over large temperature ranges covering the major amorphous transitions in each case. While α⟂ increases with temperature, α∥ tends to decrease sharply above the transition temperature. For highly crystalline polymers, α∥ decreases to values typical of polymer crystals (−1 × 10−5 K−1) and this can be attributed to the constraining effect of the crystalline bridges connecting the crystalline blocks. However, for polymers of lower crystallinity, α∥ may become an order of magnitude more negative and this remarkable phenomenon is attributed to the rubber–elastic contraction of taut tie‐moleucles. Since taut tie‐molecules and bridges have drastically different effects on α∥ at high temperatures, this allows a rough determination of their relative fractions.
Thermal conductivities of six oriented semicrystalline polymers which range from 0.37 to 0.63 in crystallinity and 1 to 5 in draw ratio λ (up to about 15 for two polymers) have been measured between 100 and 340 K. It was found that for increasing λ the conductivity K∥ (along the draw direction n̂) increases rapidly while K⊥ (normal to n̂) decreases slightly; K∥ also increases with temperature, but K⊥ shows no simple pattern in temperature dependence. These general features can be reproduced reasonably well at low draw ratio (λ < 5) by the modified Maxwell model, and the discrepancy in details may be attributed to the fact that the model does not take into account the possible anisotropy of the amorphous phase of the oriented polymers. At high draw ratio the intercrystalline bridge effect becomes important, and one must resort to the Takayanagi model, but the lack of corroborating x‐ray data has rendered a detailed comparison impossible.
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