Pulsed deuteron NMR spectroscopy is described, which has recently been developed to become a powerful tool for studying molecular dynamics in solid polymers. It is shown that by analyzing the line shapes of2H absorption spectra and spectra obtained via solid echo and spin alignment, respectively, both type and timescale of rotational motions can be determined over an extraordinary wide range of characteristic frequencies, approximately 10 MHz to 1 Hz. By applying these techniques to selectively deuterated polymers, motional mechanisms involving different segments of the monomer unit can be monitored. In addition, motional heterogeneities in glassy polymers can be detected. The information about polymer dynamics available now is illustrated by a number of experimental examples. The chain motion in the amorphous regions of linearpolyethylene is discussed in detail and it is shown that it can clearly be distinguished from the chain motion of an amorphous polymer above the glass transition, wherepolystyrene is used as an example. Localized motions in the glassy state are illustrated through the jump motion phenyl groups exhibit both in the main chain (polycarbonate) and as a side group (polystyrene). The latter polymers also serve as examples for detecting motional heterogeneity. Finally, the mobility in novel classes of systems,liquid crystalline polymers andpolymer model membranes as revealed by2H NMR are described.

Molecular dynamics of solid polymers as revealed by deuteron NMR

Pulsed deuteron NMR is described, which has recently been developed to become a powerful tool for studying molecular order and dynamics in solid polymers. In drawn fibres the complete orientational distribution function for the polymer chains can be determined from the analysis of deuteron NMR line shapes. By analyzing the line shapes of 2H absorption spectra and spectra obtained via solid echo and spin alignment, respectively, both type and timescale of rotational motions can be determined over an extraordinary wide range of characteristic frequencies, approximately 10 MHz to 1 Hz. In addition, motional heterogeneities can be detected and the resulting distribution of correlation times can directly be determined.

Deuteron NMR — a new tool for studying chain mobility and orientation in polymers

The compression yield behaviour of PMMA has been investigated, here, over a wide range of experimental conditions which cannot be reached in tensile tests owing to the brittle nature of the material. The plot of the ratio of the compression yield stress to absolute temperature, as a function of the logarithm of the strain-rate, gives a set of parallel curves which can be accurately superimposed by shifting along a slanting straight line. A master curve is built from which the yield behaviour may be predicted for any state of stress, or value of temperature and strain-rate in the glassy range, using Bauwens' yield criterion.

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The compression yield behaviour of polymethyl methacrylate over a wide range of temperatures and strain-rates

The tensile yield stress is compared with the uniaxial compression yield stress for specimens of polycarbonate tested at constant strain rate from −120 to + 120°C. The strain rate dependence of the tensile yield stress is also studied from − 140 to + 20°C.

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The Temperature Dependence of Yield of Polycarbonate in Uniaxial Compression and Tensile Tests

The compression yield behaviour of polycarbonate, at constant strain-rate, over a wide range of temperatures, is described by the Ree-Eyring theory of non-Newtonian viscosity linked with a treatment which takes into account a distribution function of activation energies. The proposed yield mechanism relies on the assumption that theβ process considered in the Ree-Eyring theory and the loss peak revealed by oscillatory measurements are related to the same molecular movements. A relation is given between theβ transition conditions in yield measurements and in damping tests; its validity is checked. The broadness and the shape of theβ loss peak are correlated with a spectrum of activation energies. The compression yield-stress curve, giving the yield stress versus temperature at constant strain-rate, is computed from the measurements of the loss tangent, as a function of temperature, at the frequency corresponding to the strain-rate and is found to fit the data fairly well.

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Giancarlo Locati

Papers

Studies of the toughness of polycarbonate of bisphenol a in light of its secondary transition