Isobaric thermal expansivities of polyethylenes with various crystallinities over the pressure range from 0.1 to 300 MPa and over the temperature range from 303 to 393 K

A pressure-controlled scanning calorimeter (PCSC) has been applied for measuring the isobaric volume thermal expansivities (α_p) of crystalline polymers as a function of pressure up to 300 MPa at various temperatures. The measurements have been performed for several well-defined polyethylenes with various degrees of crystallinity at 302.6, 333.0, 362.6, and 393.0 K. The results are reported as values of coefficients in a correlation equation, which facilitates the use of reported data over large ranges of temperature and pressure. The general pressure-temperature behavior of α_p for all polyethylenes under study is such that α_p increases with temperature and decreases with pressure. The increase with temperature is smaller at high pressures and the isotherms of α_p have a tendency to converge at high pressures; α_p decreases linearly with the crystallinity of the polyethylene over the whole range of pressure and temperature under investigation. From the linear approximation of experimental data for polyethylenes with various crystallinities the estimated α_p for both crystal and amorphous phases of polyethylenes have been determined as a function of pressure up to 300 MPa at 302.6, 333.0, and 362.5 K. The obtained results have been compared with available literature crystallographic data and with the values derived from the Pastine theoretical equation of state for both crystalline and amorphous phases. © 1996 John Wiley & Sons, Inc.