This study deals with the tensile drawing behavior of a polylactide material containing 4% of d-stereoisomer units, in the amorphous state. The draw temperature domain spanned from the glass ...transition to the onset of thermal crystallization, namely 70−100 °C. The stress−strain curves exhibit a strain-hardening strongly sensitive to the draw temperature regarding both the onset and the slope of the phenomenon. A detailed structural investigation reveals that various strain-induced phase changes take place depending on the draw temperature. For T d = 70 °C, a mesomorphic form develops from the strain-oriented amorphous chains, starting at a strain level ε ≈ 130%. In the case T d = 90 °C, a well-defined crystalline phase grows beyond the strain ε ≈ 250%. In the midtemperature range, i.e. T d = 80 °C, both the mesomorphic and the crystalline phases are generated in parallel. In all cases, the final weight content of ordered phases at rupture was roughly 30%, irrespective of their form. The observed evolution with increasing draw temperature of the strain-induced structure from mesomorphic to crystalline is quite surprising with regard to the concomitant drop of the strain-hardening. Indeed, if the latter finding is consistent with the thermal activation of plasticity, it also means that the mesomorphic form is almost as much cohesive as the crystalline form in spite of its imperfect ordering. The occurrence of the mesomorphic form is specifically discussed in terms of both chain mobility and thermodynamic metastability.
Different types of polyethylene blown films (HDPE, LDPE, LLDPE) differ significantly in the ratio between machine and transverse direction tear resistance. In this paper, low density polyethylene ...(LDPE), linear low density polyethylene (LLDPE) and high density polyethylene (HDPE) blown films at different draw-down ratios are studied, and the relation between crystalline structure and anisotropy of blown film properties is investigated. The crystalline morphology and orientation of HDPE, LDPE, LLDPE blown films were probed using microscopy and infrared trichroism. Significant differences in crystalline morphology were found: at medium DDR HDPE developed a row-nucleated type morphology without lamellar twisting, LDPE showed rod-like crystalline morphology and turned out to the row-nucleated structure with twisted lamellae at high draw-down ratio (DDR), while a spherulite-like superstructure was observed for LLDPEs at all processing conditions. They also showed quite different orientation characteristics corresponding to different morphologies. The morphologies and orientation structure for LDPE, LLDPE and HDPE are related to the stress applied (DDR) and their relaxations in the flow-induced crystallization process, which determine the amount of fibrillar nuclei available at the time of crystallization and therefore, the final crystalline morphology. These structure differences are shown to translate into different ratios of machine and transverse direction tear and tensile strengths.
The crystallization behavior and the crystalline structure of nylon6-clay nanocomposites are investigated with regard to the processing conditions and thermal treatment. Microextruded bulk samples as ...well as blown films are under concern. The often reported nucleating effect of the clay particles is shown to strongly depend on the processing parameters prior to the solidification step, namely, the shear intensity which promotes self-nucleation and the temperature of the melt which regulates the density of these unstable nuclei. The MMT content influences the crystallization kinetics and the crystalline structure via the shear amplification phenomenon which increases the densities of both the shear-induced and the MMT-induced nuclei. The MMT platelets also turned out to hinder the crystal growth. The cooling rate plays a major role on the final crystalline structure by shifting the crystallization temperature in the specific growth range of either the α- or the γ-crystal forms of the nylon6 matrix. Blown films corroborate the findings from microextruded samples regarding the competition between nucleation and growth in the resulting crystalline form of the nylon6 matrix. Besides, the strong texturing of the nanocomposite films provides information on the local arrangement of the chains and crystal unit cell on the MMT platelets.
In this study, high-density polyethylene films (HDPE) were produced using different processes (film blowing and biaxial orientation) and processing conditions. The orientation of the films was ...characterized in terms of their biaxial crystalline, amorphous and global orientation factors using birefringence, Fourier transform infrared spectroscopy (FTIR) using a tilted incidence technique and X-ray pole figures. Evaluation of a simplified FTIR procedure without using the tilted method for the determination of crystalline orientation factors proposed in the literature is also evaluated and assessed. The results indicate that FTIR overestimate the crystalline orientation factors, particularly for the crystalline a-axis. Significant discrepancies are also observed for the b-axis orientation, which may be due to an overlap of the amorphous contribution and/or saturation of FTIR bands. Those differences are larger for films with low orientation, such as blown films. Amorphous phase orientation from FTIR depends on the band used and is not necessarily in agreement with that determined from combination of X-ray and birefringence.
The aim of this work was to develop and characterise electrically conductive materials for proton exchange membrane fuel cells and bipolar plates (BPPs). These BPPs were made from highly conductive ...blends of polyethylene terephthalate (PET) and polyvinylidene fluoride (PVDF), as matrix phase. The conductive materials were developed from carefully formulated blends composed of conductive carbon black (CB) powder and, in some cases, graphite synthetic flakes mixed with pure PET, PVDF or with PVDF/PET systems. They were first developed by twin‐screw extrusion process then compression‐molded to give BPP final shape. As the developed blends have to meet properties suitable for BPP applications, they were characterised for their rheological properties, electrical through‐plane resistivity (the inverse of conductivity), oxygen permeability, flexural and impact properties. Results showed that lower resistivity was obtained with PVDF/CB blends due to the higher interfacial energy between the PVDF matrix and CB and also the higher density and crystallinity of PVDF, compared to those of PET. It was also observed that the lowest resistivity values were obtained with mixing PVDF and PET at controlled compositions to ensure PVDF/PET co‐continuous morphology. Also, slow cooling rates helped to attain the lowest values of through‐plane resistivity for all studied blends. This behaviour was related to the higher crystallinity obtained with low cooling rates leading to smaller amorphous regions in which carbon particles are much more concentrated.
This work deals with the structural evolution under biaxial drawing of PA6/tie/PE multilayer films as a function of composition. The occurrence of plastic instabilities in the PA6 layer in the ...multilayers is strongly reduced with respect to the PA6 monolayer film and the maximum biaxial drawability of PA6 is considerably improved with increasing PE layer thickness. Quantitative evaluation by trichroic infrared analysis of the various crystal forms of the PA6 component shows that the strain-induced β–α crystalline phase transition is delayed in the multilayers, i.e. equivalent level of phase transformation is reached at higher strains. Similar phenomenon is observed regarding the orientation within the film plane of the PA6 chains in the strain-induced α-crystals, i.e. equivalent chain orientation is reached at higher strains in the multilayers. The deformation synergism between the PA6 and PE layers is discussed in terms of benefiting effect from the PE layer that prevents plastic instabilities and promotes homogeneous deformation accompanied with orthotropic extension of the chains in the PA6 layer. This is the driving force to the delay of the detrimental β–α phase transition of PA6, the mechanically anisotropic α-crystals being highly crack-prone in contrast to the ductile isotropic β-crystals. Film rupture is shown to occur when the PA6 strain-induced α-crystals reach a constant content of about 10%, irrespective of film composition and draw temperature in the range 80–110°C. This kind of critical phenomenon is assigned to a percolation process of the crack-prone α-crystals.
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