Amorphous phases generated by pharmaceutical processes lead to cocrystal formation under conditions where there is increased molecular mobility and complementarity. Water, a potent plasticizer, enhances the rate of cocrystallization. This has powerful implications to control process induced transformations.
Low density polyethylene (LDPE)/clay nanocomposites, which can be used in packaging industries, were prepared by melt-mix organoclay with polymer matrix (LDPE) and compatibilizer, polyethylene grafted maleic anhydride (PEMA). The pristine clay was first modified with alkylammonium salt surfactant, before meltmixed in twin screw extruder attached to blown-film set. D-spacing of clay and thermal behavior of nanocomposites were characterized by Wide-Angle X-ray Diffraction (WAXD) and differential scanning calorimetry (DSC), respectively. WAXD pattern confirmed the increase in PEMA contents exhibited better dispersion of clay in nanocomposites. Moreover, DSC was reported the increased PEMA contents caused the decrease in degree of crystallinity. Mechanical properties of blown film specimens were tested in two directions of tensile tests: in transverse tests (TD tests) and in machine direction tests (MD tests). Tensile modulus and tensile strength at yield were improved when clay contents increased because of the reinforcing behavior of clay on both TD and MD tests. Tensile modulus of 7 wt % of clay in nanocomposite was 100% increasing from neat LDPE in TD tests and 17% increasing in MD tests. However, elongation at yield decreased when increased in clay loading. Oxygen permeability tests of LDPE/clay nanocomposites also decreased by 24% as the clay content increased to 7 wt %.
Time-resolved light scattering demonstrates that the early-stage quiescent and flow-induced crystallization kinetics of an intercalated polypropylene clay nanocomposite differs significantly from that of pure polypropylene. The material studied is organophilic montmorillonite clay dispersed at 2.0 wt % by melt mixing in an isotactic polypropylene matrix with maleic anhydride functionalized polypropylene compatibilizer. Characteristic crystallization times are extracted from the time evolution of integral measures of the angularly dependent parallel polarized and cross polarized light scattering intensity. For quiescent isothermal crystallization with undercooling ∆T < 32 °C, measured relative to its melting temperature, the compatibilized, intercalated nanocomposite displays retarded crystallization kinetics compared to that of pure polypropylene. However, the nanocomposite behavior does not differ significantly from that of a polypropylene/maleic anhydride functionalized polypropylene blend within the temperature range for which the characteristic crystallization times of the latter material could be extracted. Debye-Bueche analysis of the polarized light scattering intensity demonstrates significant differences in the time-dependent growth of isotropic morphology in the polymer and the nanocomposite. Marked flow-induced acceleration of crystallization kinetics is observed for the polymer nanocomposite at applied strain rates for which flow has only a modest effect on polypropylene crystallization. By comparing this behavior to that of a blend of polypropylene and compatibilizer, we infer a significant role for the latter species in flow-induced nanocomposite crystallization. We furthermore find that the magnitude of the flow-induced acceleration of crystallization for the polypropylene nanocomposite is a unique function of the applied strain.
Rechargeable zinc–air batteries are deemed as the most feasible alternative to replace lithium–ion batteries in various applications. Among battery components, separators play a crucial role in the commercial realization of rechargeable zinc–air batteries, especially from the viewpoint of preventing zincate (Zn(OH)42−) ion crossover from the zinc anode to the air cathode. In this study, a new hydroxide exchange membrane for zinc–air batteries was synthesized using poly (2,6-dimethyl-1,4-phenylene oxide) (PPO) as the base polymer. PPO was quaternized using three tertiary amines, including trimethylamine (TMA), 1-methylpyrolidine (MPY), and 1-methylimidazole (MIM), and casted into separator films. The successful synthesis process was confirmed by proton nuclear magnetic resonance and Fourier-transform infrared spectroscopy, while their thermal stability was examined using thermogravimetric analysis. Besides, their water/electrolyte absorption capacity and dimensional change, induced by the electrolyte uptake, were studied. Ionic conductivity of PPO–TMA, PPO–MPY, and PPO–MIM was determined using electrochemical impedance spectroscopy to be 0.17, 0.16, and 0.003 mS/cm, respectively. Zincate crossover evaluation tests revealed very low zincate diffusion coefficient of 1.13 × 10−8, and 0.28 × 10−8 cm2/min for PPO–TMA, and PPO–MPY, respectively. Moreover, galvanostatic discharge performance of the primary batteries assembled using PPO–TMA and PPO–MPY as initial battery tests showed a high specific discharge capacity and specific power of ~800 mAh/gZn and 1000 mWh/gZn, respectively. Low zincate crossover and high discharge capacity of these separator membranes makes them potential materials to be used in zinc–air batteries.
The electrical conductivity of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) was enhanced by dipping the thin films prepared by spin coating technique in an aqueous DMSO solution. The low concentration range of DMSO in water between 0-5 vol % was studied in comparison with pure water and pure DMSO. It was found that the electrical conductivity dramatically increased as increasing the concentration of DMSO and reached the constant value of 350 S cm-1 at 2 vol % of aqueous DMSO solution. This could be explained by the conformational change of PEDOT chains from the coil structure to the linear or expanded coil structure as confirmed by Raman spectra. Further, white patches were obviously noticed on the surface of the films dipped in pure DMSO, indicating the phase separation of conductive PEDOT grains and associated PSS. The sulfur element of the dipped film surface was investigated by XPS. The XPS S2p core-level spectra displayed that the unassociated PSS was considerably removed from the surface of PEDOT:PSS films dipped in pure water and 2 vol % of aqueous DMSO solution, indicating that the presence of water in the solvents is important to prominently promote the washing effect. Finally, UV-Vis spectra revealed the improved transparency of the films probably owing to the decreased film thickness
The effect of azodicarbonamide as chemical blowing agent on the morphology, cure kinetics and physical properties of natural rubber foam is investigated. From the morphology, when the amount of chemical blowing agent increases from 3 to 4 phr, the bubble size in the rubber matrix slightly decreases due to the increase of vulcanization reaction rate from the presence of amine fragment species as by-products from the decomposition of azodicarbonamide. The coalescence between bubbles is observed in the specimen with 5 and 6 phr of azodicarbonamide owing to high gas content in the rubber matrix. Moreover, the scorch time slightly reduces and cure rate increases as a function of azodicarbonamide content. The autocatalytic model can be used to explain the curing reaction and mechanism of this natural rubber foam. Furthermore, the activation energy (Ea) directly relates to the bubble size and microvoid structure of natural rubber foam. When compared with the vulcanized natural rubber without adding chemical blowing agent, it is found that the bulk density of natural rubber foam significantly decreases and the volumetric expansion ratio of natural rubber foam increases at high content of chemical blowing agent. Moreover, natural rubber foam at 4 phr of azodicarbonamide exhibits the lowest thermal expansion coefficient due to the smallest bubble size with less coalescence.
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