Investigation of Crystallization and Relaxation Effects in Coarse-Grained Polyethylene Systems after Uniaxial Stretching

In this study, we investigate the thermo-mechanical relaxation and crystallization behavior of polyethylene using mesoscale molecular dynamics simulations. Our models specifically mimic constraints that occur in real-life polymer processing: After strong uniaxial stretching of the melt, we quench and release the polymer chains at different loading conditions. These conditions allow for free or hindered shrinkage, respectively. We present the shrinkage and swelling behavior as well as the crystallization kinetics over up to 600 ns simulation time. We are able to precisely evaluate how the interplay of chain length, temperature, local entanglements and orientation of chain segments influences crystallization and relaxation behavior. From our models, we determine the temperature dependent crystallization rate of polyethylene, including crystallization onset temperature.

Biodegradable Poly(Butylene Adipate-Co-Terephthalate) and Thermoplastic Starch-Blended TiO2 Nanocomposite Blown Films as Functional Active Packaging of Fresh Fruit

Biodegradable polymers can be used for eco-friendly, functional, active packaging to preserve food quality. Incorporation of titanium dioxide (TiO2) nanoparticles into polymer packaging enhances ethylene-scavenging activity and extends the shelf-life of fresh produce. In this study, TiO2 nanoparticles were incorporated into biodegradable poly(butylene adipate-co-terephthalate) (PBAT)- and thermoplastic cassava starch (TPS)-blended films to produce nanocomposite packaging via blown-film extrusion. The effects of TiO2 on morphology, packaging properties, and applications as functional packaging for fresh produce were investigated. Increased TiO2 in the film packaging increased amorphous starch content and hydrogen bonding by interacting with the TPS phase of the polymer blend, with negligible chemical interaction with the PBAT component and identical mechanical relaxation in the PBAT phase. Surface topography indicated void space due to non-homogeneous dispersion causing increased oxygen and carbon dioxide permeability. Homogeneous dispersion of fine TiO2 nanoparticles increased mechanical strength and reduced oxygen, carbon dioxide, and water vapor permeability. Films containing TiO2 also showed efficient oxygen-scavenging activity that removed residual oxygen from the package headspace dependent on the levels and morphology of nanoparticles in the film matrices. Banana fruit packaged in films containing TiO2 recorded slower darkening color change and enhanced shelf-life with increasing TiO2 content.

Effect of relaxation processes during deformation on electrical resistivity of carbon black polypropylene composites

Objectives. To study the relationship between bending deformation and the change in the electrical resistance of carbon black polypropylene composites.Methods. Conductive polypropylene composites filled with carbon black UM-76 were investigated. The samples were deformed and kept under constant bending at temperatures of 20–155 °C.Results. The deformation of the samples led to a reversible increase in their electrical resistance, while subsequent holding of the samples in the deformed state was accompanied by an exponential drop in their electrical resistance. The average times and activation energies of the electrical relaxation of the deformed polypropylene composites were calculated (30–32 kJ/mol) and compared with similar characteristics of polyethylene composites (15–16 kJ/mol).Conclusions. The electrical resistance relaxation of deformed carbon black polypropylene composites at elevated temperatures is similar to their stress relaxation. The average times and activation energies of the electrical relaxation of deformed polypropylene composites are comparable with similar data on their mechanical relaxation. It was found that these electrical and mechanical phenomena are based on the same underlying physical processes.

New Insight into Dynamic Mechanical Relaxation in N-butyl-N-(2-nitroxy-ethyl) Nitramine Plasticized Nitrocellulose through Molecular Dynamic Simulations

We performed dynamic mechanical analysis (DMA) on nitrocellulose (NC) plasticized by an insensitive plasticizer N-butyl-N-(2-nitroxy-ethyl)nitramine (Bu-NENA). NC/Bu-NENA blend shows two mechanical relaxation processes in the temperature ranges of -50~-40oC and 30~40oC, and their variations with deformation frequencies were studied. To explore further the effect of temperature on relaxation, the binary mixture model of NC/Bu-NENA was constructed, and molecular dynamic simulations were conducted. The simulated mean square displacements (MSD) show abrupt increase in the temperature range of -50~-40oC and 30~40oC, which are consistent with those of the two relaxation processes observed in the DMA curves. Moreover, the free volume (Vfree) and torsion energy obtained from molecular dynamic simulations exhibit distinct increase at the temperature above 30oC and -50oC respectively, reflecting the sudden enhancements on the mobility of polymer chain elements and the rotation of molecular bonds. Furthermore, the radial distribution function (RDF) associated with the intermolecular interactions reveals that the intensities of both hydrogen bond and van-der-vaals forces decrease with the increase of temperature, which is responsible for the decrease of storage modulus at high temperature. These computational and experimental studies reveal guidance to strengthening the NC base propellants in broad temperature range.