Strain Rate and Temperature Influence on Micromechanisms of Plastic Deformation of Polyethylenes Investigated by Positron Annihilation Lifetime Spectroscopy.

Plastic deformation of low/high density polyethylene (LDPE/HDPE) was analyzed in this work using positron annihilation lifetime spectroscopy (PALS). It was shown that in undeformed LDPE, both the mean ortho-positronium lifetime (τ3) and its dispersion (σ3), corresponding to the average size and size distribution of the free-volume pores of the amorphous component, respectively, were clearly higher than in HDPE. This effect was induced by a lower and less uniform molecular packing of the amorphous regions in LDPE. During the deformation of LDPE, an increase in the τ3 value was observed within the local strains of 0-0.25. This effect was mainly stimulated by a positive relative increase in interlamellar distances due to the deformation of lamellar crystals oriented perpendicular (increased by 31.8%) and parallel (decreased by 10.1%) to the deformation directions. At the same time, the dimension of free-volume pores became more uniform, which was manifested by a decrease in the σ3 value. No significant effect of temperature or strain rate on the τ3 and σ3 values was observed during LDPE deformation. In turn, in the case of HDPE, with an increase in the strain rate/or a decrease in temperature, an intensification of the cavitation phenomenon could be observed with a simultaneous decrease in the τ3 value. This effect was caused by the lack of annihilation of ortho-positonium (o-Ps) along the longer axis of the highly anisotropic/ellipsoidal cavities. Therefore, this dimension was not detectable by the PALS technique. At the same time, the increase in the dimension of the shorter axis of the cavities was effectively limited by the thickness of amorphous layers. As the strain rate increased or the temperature decreased, the σ3 value during HDPE deformation increased. This change was correlated with the initiation and intensification of the cavitation phenomenon. Based on the mechanical response of samples with a similar yield stress, it was also proven that the susceptibility of the amorphous regions of LDPE to the formation of cavities is lower than in the case of amorphous component of HDPE.

Density Scaling Based Detection of Thermodynamic Regions of Complex Intermolecular Interactions Characterizing Supramolecular Structures.

In this paper, applying the density scaling idea to an associated liquid 4-methyl-2-pentanol used as an example, we identify different pressure-volume-temperature ranges within which molecular dynamics is dominated by either complex H-bonded networks most probably leading to supramolecular structures or non-specific intermolecular interactions like van der Waals forces. In this way, we show that the density scaling law for molecular dynamics near the glass transition provides a sensitive tool to detect thermodynamic regions characterized by intermolecular interactions of different type and complexity for a given material in the wide pressure-volume-temperature domain even if its typical form with constant scaling exponent is not obeyed. Moreover, we quantify the observed decoupling between dielectric and mechanical relaxations of the material in the density scaling regime. The suggested methods of analyses and their interpretations open new prospects for formulating models based on proper effective intermolecular potentials describing physicochemical phenomena near the glass transition.

Inflection point in the Debye relaxation time of 2-butyl-1-octanol.

We report a striking anomaly in the pressure dependent Debye-relaxation time of the branched monohydroxy alcohol 2-butyl-1-octanol. Evidence of a crossover from slower to faster than exponential pressure dependency was obtained at different temperatures via high pressure broadband dielectric spectroscopy. At the same time, viscosity measurements reveal similar behavior in the viscosity, respectively, the structural relaxation time, indicating a similar origin of the phenomena.