Process influences on the structure,piezoelectric, and gas‐barrier properties of PVDF‐TrFE copolymer

The influence of annealing between the Curie transition and the melting point of solvent cast polyvinylidene fluoride trifluoroethylene copolymer films on the crystalline structure, mechanical and electrical properties, and oxygen permeability is investigated. Annealing leads to remarkable changes in the structure and properties of the copolymer, within the first four hours of treatment, and with kinetics depending on the temperature. The crystallinity increases by 19% (relative), resulting in a 10 K increase in the Curie transition, a 4 K increase of the melting temperature and a 2 K decrease in the glass transition temperature. A crystalline phase transition from the paraelectric α‐phase to the ferroelectric β‐phase is also evidenced using in‐situ X‐ray diffraction. The elastic modulus is found to increase by more than three‐fold at room temperature and the loss peak at the glass transition is considerably reduced. The piezoelectric coefficient is found to increase by 40% and the dielectric properties are significantly changed. The most remarkable influence is the ten‐fold reduction of the oxygen permeability, with a drastic reduction of the activation energy for oxygen transport. The improvement in oxygen barrier properties of the annealed copolymer is attributed to the restricted mobility of oxygen molecules in the semicrystalline polymer with nanometer sized crystallites. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 496–506     

An Interface-Bridged Organic–Inorganic Layer that Suppresses Dendrite Formation and Side Reactions for Ultra-Long-Life Aqueous Zinc Metal Anodes

Aqueous zinc (Zn) batteries (AZBs) are widely considered as a promising candidate for next-generation energy storage owing to their excellent safety features. However, the application of a Zn anode is hindered by severe dendrite formation and side reactions. Herein, an interfacial bridged organic–inorganic hybrid protection layer (Nafion-Zn-X) is developed by complexing inorganic Zn-X zeolite nanoparticles with Nafion, which shifts ion transport from channel transport in Nafion to a hopping mechanism in the organic–inorganic interface. This unique organic–inorganic structure is found to effectively suppress dendrite growth and side reactions of the Zn anode. Consequently, the Zn@Nafion-Zn-X composite anode delivers high coulombic efficiency (ca. 97 %), deep Zn plating/stripping (10 mAh cm⁻²), and long cycle life (over 10 000 cycles). By tackling the intrinsic chemical/electrochemical issues, the proposed strategy provides a versatile remedy for the limited cycle life of the Zn anode.     

Recent Updates on the Barrier Properties of Ethylene Vinyl Alcohol Copolymer (EVOH): A Review

The gas barrier properties of ethylene vinyl alcohol copolymer (EVOH) against oxygen, carbon dioxide and water vapor have been widely investigated in relation to different material characteristics, environmental conditions and new processing technologies. Recently, EVOH is gaining more attention as a barrier material against other gases and organic substances such as aromas, flavors, fuels, chemicals (e.g., BTEX), and as a functional barrier, e.g., to avoid mineral oil migration. This review contains an update on permeability data of EVOH emphasizing its potential as a barrier material for new and versatile applications in food and pharmaceutical packaging, agriculture, construction, automotive, etc.     

Correlation between Performances of Hollow Fibers and Flat Membranes for Gas Separation

This work presents an attempt at correlating the available permeability/selectivity literature data for hollow fibers and flat membranes. Therefore, this paper gathers the information pertaining to membrane materials for which membrane properties of flat membranes and hollow fibers have both been reported. An overview of the relations between selectivity and permeance of hollow fiber membranes for various gas pairs (O₂/N₂, CO₂/CH₄, CO₂/N₂, H₂/N₂, H₂/CO₂, H₂/CH₄ and He/N₂) is presented first. The upper bound lines are the ones proposed by Robeson, which were calculated by assuming a one-micron-thick skin layer as proposed by Robeson in 2008. From the results obtained, a relation between the selectivity ratio in both kinds of membranes (α_H/α_f) and skin layer thickness (l) calculated from flat membranes and hollow fibers gas permeation data for these pairs of gases is also presented. The skin layer thicknesses measured using seven different experimental techniques for six commercial membranes are compared. The influences of spinning parameters on the morphology and performance of hollow fiber membrane gas separation are discussed. Finally, an analysis is made of the reasons why the dense skin layer thicknesses of a hollow fiber calculated using permeance and permeability data vary for different gases and also differ from direct experimental measurements.     

Ferric metal-organic framework for microwave absorption

In this study, we have shown for the first time that ferric metal-organic framework (Fe-MOF) has the ability to attenuate gigahertz-range electromagnetic radiation through means of a novel interference mechanism. A large reflection loss value of ?54.2 dB can be obtained, equivalent to over 99.999% absorption efficiency. The microwave absorption performance is largely dependent on the dielectric permittivity and magnetic permeability properties. The electrical loss ratio tgδ_ε increases with the frequency from 0.13 at 1.0 GHz to 0.69 at 18.0 GHz, while the magnetic loss ratio tgδ_μ is only between 0.05 and 0.14. The conductivity σ increases with the frequency from 0.08 S/m at 1.0 GHz to 5.24 S/m at 18.0 GHz, while the skin-depth δ decreases with the frequency. The thickness (d) of the absorber is inversely proportional to the reflection loss peak value (RL_peak), the reflection loss peak frequency (f_peak), and the critical reflection loss peak width (Δf₁₀). The non-zero magnetic susceptibility (χ) accelerates the shift of f_peak to lower values as d grows bigger; however, it improves the RL_peak value and larger microwave absorption efficiency and reduces the quick narrowing of the critical frequency range. The microwave performance of Fe-MOF is likely related to its microwave conductivity, which may originate from the polar rotations in the interface or defects. A new mechanism is proposed for the large reflection loss based on the interference of the reflected microwave from the front and back surface of the microwave absorber, especially when the thickness matches with the odd integer values of the wavelength.     

Structure and permeability of gels

The textures of silica gels made by two-step acid/base and acid/acid catalysis of TEOS have been examined by thermoporometry (TPM) and NMR, and their permeabilities (D) have been measured by a thermal expansion technique. Using the pore size distribution given by TPM, which includes a large proportion of macropores (30 nm), calculated values of D are seriously overestimated. We conclude that, consistent with a theoretical prediction, compliant materials such as gels undergo contraction during freezing in the calorimeter, so that most of the macropore volume reported by TPM is actually extracted from mesopores. The mesopore radius reported by TPM is underestimated by only 20%, even if 50% of the pore liquid is drained during crystallization, assuming that the change in pore radius is related to the cube root of the volume change. NMR does not distinguish macropores, because of diffusional averaging, but provides an apparent distribution that permits an accurate estimate of the permeability.     

Detailed study of ultra-soft magnetic properties of Fe74Cu0.8Nb2.7Si15.5B7

The magnetic properties of nanocrystalline Fe₇₄Cu_0.8Nb_2.7Si_15.5B₇ alloy, which were rapidly solidified and then annealed at various temperatures between 475 and 650°C for different holding time, have been studied. Grain size, silicon content and the lattice parameter of α-Fe(Si) nanograins at the annealing temperatures were determined. Curie temperature of the amorphous phase was determined from the temperature dependence of permeability. For higher annealing temperatures and times, some Si diffused out of the α-Fe(Si) phase and formed an ordered DO₃ phase of Fe₃Si. This changed the overall magnetostriction and average anisotropy of the matrix, which deteriorated the magnetic softness of the material at higher annealing temperatures. Ultra-soft magnetic properties were achieved by averaging the random anisotropy via exchange interaction. Hysteresis loops for samples in as-cast and annealed conditions have also been studied.     

Nanoformulation Development to Improve the Biopharmaceutical Properties of Fisetin Using Design of Experiment Approach

This study aimed to design an effective nanoparticle-based carrier for the oral delivery of fisetin (FST) with improved biopharmaceutical properties. FST-loaded nanoparticles were prepared with polyvinyl alcohol (PVA) and poly(lactic-co-glycolic acid) (PLGA) by the interfacial deposition method. A central composite design of two independent variables, the concentration of PVA and the amount of PLGA, was applied for the optimization of the preparative parameter. The responses, including average particle size, polydispersity index, encapsulation efficiency, and zeta potential, were assessed. The optimized formulation possessed a mean particle size of 187.9 nm, the polydispersity index of 0.121, encapsulation efficiency of 79.3%, and zeta potential of −29.2 mV. The morphological observation demonstrated a globular shape for particles. Differential scanning calorimetry and powder X-ray diffraction studies confirmed that the encapsulated FST was presented as the amorphous state. The dissolution test indicated a 3.06-fold increase for the accumulating concentrations, and the everted gut sac test showed a 4.9-fold gain for permeability at the duodenum region. In conclusion, the optimized FST-loaded nanoparticle formulation in this work can be developed as an efficient oral delivery system of FST to improve its biopharmaceutic properties.     

直接甲醇燃料电池用阻醇质子导电聚乙烯醇-聚苯乙烯磺酸共混膜

制备了聚乙烯醇 (PVA)与聚苯乙烯磺酸 (PSSA)的共混膜 ,并研究了膜的组成、热处理温度、甲醇水溶液浓度等对膜电导率和甲醇透过率的影响。与目前普遍使用的NafionTM膜相比 ,这种由阻醇材料PVA与离子交换材料PSSA共混后形成的聚合物膜既能提高阻醇性能 ,又具有一定的电导率。一种以聚苯乙烯磺酸含量为 17%的膜 ,其电导率可达 3× 10 -3 S·cm-1,但甲醇透过率P仅为 2× 10 -8cm2 ·s-1。如果以σ/P为综合指标 ,则此膜的综合性能比NafionTM膜高约 4 0倍     

Synthesis of sulfonated poly(imidoaryl ether sulfone) membranes for polymer electrolyte membrane fuel cells

New sulfonated poly(imidoaryl ether sulfone) copolymers derived from sulfonated 4,4′‐dichlorodiphenyl sulfone, 4,4′‐dichlorodiphenyl sulfone, and imidoaryl biphenol were evaluated as polymer electrolyte membranes for direct methanol fuel cells. The sulfonated membranes were characterized with Fourier transform infrared spectroscopy, thermogravimetric analysis, and proton nuclear magnetic resonance spectra. The state of water in the membranes was measured with differential scanning calorimetry, and the existence of free water and bound water was discussed in terms of the sulfonation level. The 10 wt % weight loss temperatures of these copolymers were above 470 °C, indicating excellent thermooxidative stability to meet the severe criteria of harsh fuel‐cell conditions. The proton conductivities of the membranes ranged from 3.8 × 10^?2 to 5 × 10^?2 S/cm at 90 °C, depending on the degree of sulfonation. The sulfonated membranes maintained the original proton conductivity even after a boiling water test, and this indicated the excellent hydrolytic stability of the membranes. The methanol permeabilities ranged from 1.65 × 10^?8 to 5.14 × 10^?8 cm²/s and were lower than those of other conventional sulfonated ionomer membranes, particularly commercial perfluorinated sulfonated ionomer (Nafion). The properties of proton and methanol transport were discussed with respect to the state of water in the membranes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5620–5631, 2005