Environmental Stress Cracking of High-Density Polyethylene Applying Linear Elastic Fracture Mechanics.

The crack propagation rate of environmental stress cracking was studied on high-density polyethylene compact tension specimens under static loading. Selected environmental liquids are distilled water, 2 wt% aqueous Arkopal N100 solution, and two model liquid mixtures, one based on solvents and one on detergents, representing stress cracking test liquids for commercial crop protection products. The different surface tensions and solubilities, which affect the energetic facilitation of void nucleation and craze development, are studied. Crack growth in surface-active media is strongly accelerated as the solvents induce plasticization, followed by strong blunting significantly retarding both crack initiation and crack propagation. The crack propagation rate for static load as a function of the stress intensity factor within all environments is found to follow the Paris-Erdogan law. Scanning electron micrographs of the fracture surface highlight more pronounced structures with both extensive degrees of plasticization and reduced crack propagation rate, addressing the distinct creep behavior of fibrils. Additionally, the limitations of linear elastic fracture mechanisms for visco-elastic polymers exposed to environmental liquids are discussed.

Modelling of Pore Collapse during Polymer Sintering: Viscoelastic Model with Enclosed Gas.

Frenkel's model for the late stage of coalescence of viscous particles has been extended to describe pore collapse in a viscoelastic melt during polymer sintering. The shrinkage of a pore in a polymer melt driven by surface tension is extended by taking into account the effects of trapped gas and gas transport out of the pore. Viscoelasticity has been shown to have a considerable impact on the time scale of the coalescence process. In addition, gas diffusion modifies the coalescence dynamics. Based on a parameter study, different regimes for the pore collapse have been identified. At the beginning of pore collapse, surface tension is considerably stronger than gas pressure within the pore. In this time interval (surface-tension-driven regime), the pore shrinks even in the absence of gas diffusion through the matrix. In the absence of gas transport, the shrinkage dynamic slows down and stops when the surface tension balances the gas pressure in the pore. If gas transport out of the pore is possible, surface tension and gas pressure are balanced while the gas pressure slowly decreases (diffusion-controlled regime). The final phase of pore collapse, which occurs when the gas pressure within the pore decreases sufficiently, is controlled again by surface tension. The limitations of the model are discussed. To analyze the interplay between different mechanisms and process steps during selective laser sintering, the respective time scales are compared using experimental data.

Effect of Graphite Nanoplate Morphology on the Dispersion and Physical Properties of Polycarbonate Based Composites.

The influence of the morphology of industrial graphite nanoplate (GNP) materials on their dispersion in polycarbonate (PC) is studied. Three GNP morphology types were identified, namely lamellar, fragmented or compact structure. The dispersion evolution of all GNP types in PC is similar with varying melt temperature, screw speed, or mixing time during melt mixing. Increased shear stress reduces the size of GNP primary structures, whereby the GNP aspect ratio decreases. A significant GNP exfoliation to individual or few graphene layers could not be achieved under the selected melt mixing conditions. The resulting GNP macrodispersion depends on the individual GNP morphology, particle sizes and bulk density and is clearly reflected in the composite's electrical, thermal, mechanical, and gas barrier properties. Based on a comparison with carbon nanotubes (CNT) and carbon black (CB), CNT are recommended in regard to electrical conductivity, whereas, for thermal conductive or gas barrier application, GNP is preferred.

Note: Piezoelectric polymers as transducers for the ultrasonic-reflection method and the application in mechanical property-screening of coatings.

In the last years, non-destructive ultrasonic testing methods are more and more frequently employed in order to investigate the drying and curing processes of different coatings. Among them an ultrasonic reflection method was developed allowing the simultaneous measurement with longitudinal and transversal waves. In order to generate the ultrasonic pulse, piezoelectric ceramics or oxides are usually used as transducer materials which are connected to a delay line. Here, we demonstrate a similar approach for the ultrasonic reflection method installing piezoelectric polymers as ultrasonic transducer materials. In detail, poly(vinylidene fluoride and trifluoroethylene) [P(VDF-TrFE)] copolymers were prepared as piezoelectric transducer layers directly onto the metallization of glass delay lines avoiding additional bonding processes. The film preparation was carried out by solvent casting the polymer onto an area with a diameter of 12 mm and is optimized so that relatively homogeneous polymer layers with thicknesses between 14 and 35 µm are adjusted by the deposited amount of the polymer. Electrical poling renders the polymer piezoelectric. The ultrasonic properties of the P(VDF-TrFE) transducer and their usability for the ultrasonic reflection method are described also in comparison to previous measurements using LiNbO(3) transducer.

Scaling behavior of nonisothermal phase separation.

The phase separation process in a critical mixture of polydimethylsiloxane and polyethylmethylsiloxane (PDMS/PEMS, a system with an upper critical solution temperature) was investigated by time-resolved light scattering during continuous quenches from the one-phase into the two-phase region. Continuous quenches were realized by cooling ramps with different cooling rates kappa. Phase separation kinetics is studied by means of the temporal evolution of the scattering vector qm and the intensity Im at the scattering peak. The curves qm(t) for different cooling rates can be shifted onto a single mastercurve. The curves Im(t) show similar behavior. As shift factors, a characteristic length Lc and a characteristic time tc are introduced. Both characteristic quantities depend on the cooling rate through power laws: Lc approximately kappa(-delta) and tc approximately kappa(-rho). Scaling behavior in isothermal critical demixing is well known. There the temporal evolutions of qm and Im for different quench depths DeltaT can be scaled with the correlation length xi and the interdiffusion coefficient D, both depending on DeltaT through critical power laws. We show in this paper that the cooling rate scaling in nonisothermal demixing is a consequence of the quench depth scaling in the isothermal case. The exponents delta and rho are related to the critical exponents nu and nu* of xi and D, respectively. The structure growth during nonisothermal demixing can be described with a semiempirical model based on the hydrodynamic coarsening mechanism well known in the isothermal case. In very late stages of nonisothermal phase separation a secondary scattering maximum appears. This is due to secondary demixing. We explain the onset of secondary demixing by a competition between interdiffusion and coarsening.