Relaxation processes in polymer surface layers

A recently built and patented device Nanoluminograph is used for the investigation of the relaxation processes in the surface layers of HDPE films, produced at various conditions. The work of the device is based on the phenomenon of radiothermoluminescence. The use of high-frequency low-power, low-temperature plasma as an ionizing source, and a reduction of the consumed energy down to several orders of magnitude (as compared to that used in similar devices) provides excitation of a surface layer as thin as 100-200 nm. The high sensitivity of the device enables one to reduce the excitation time to 1-2 seconds for obtaining a sufficient intensity of glow curves even from ultrathin layers 20-30 nm thick. All of that minimizes the modifying plasma action on the samples under investigation and provides well reproducible and reliable data. it is found that the intensity, number and positions of peaks on the glow curves are strongly influenced by the preparation conditions of polymer films. The complicated profile of glow curve peaks allows one to assume the overlapping of multiple relaxation processes. Decomposing and fitting peak profiles with the help of a PEAKFIT computer program result in revealing at least 4 relaxation transitions in the temperature region from 109 to 213 K. The temperatures and activation energies of relaxation transitions in surface layers appeared to be lower than those inferred from the DSC data for the bulk polymer. The activation energies of trap depletion upon heating are calculated. The nature of traps is discussed in terms of molecular conformations, morphology and structural defects, as well as the attribution of the observed relaxation transitions to defreezing mobility of different kinetic units.