Effect of thermal crosslinking process on membrane structure and PEM fuel cell applications performed with SPEEK-PVA blend membranes

One of the promising options in the pursuit of clean and sustainable energy is fuel cell technology. PEM fuel cell stands out among fuel cell technologies due to its high efficiency, compactness, and ability to be used in portable applications. SPEEK (with different sulfonation degrees) and PVA blend membranes, which are thought to create a good synergy for PEM fuel cell, were prepared by using the solution casting method. As a result of the weight loss experiments, it was understood that the membranes dissolve in water regardless of the degree of sulfonation. Thermal crosslinking was carried out to prevent the membrane dissolution in water, which is in continuous contact with water in the fuel cell. Dissolution was mostly prevented by means of the thermal crosslinking process. Changes in the physical, chemical, and mechanical structure of the membrane after thermal crosslinking were comparatively determined by fourier transform infrared (FTIR), thermogravimetric analysis – differential thermal analysis (TGA-DTA), differential scanning calorimetry (DSC), water uptake capacity, swelling property, ion exchange capacity (IEC), dynamic mechanical analysis (DMA), electrochemical impedance analysis and oxidative stability. In addition, single-cell performance tests were performed with the membrane that gave the best results in the characterization analyses. Analysis results showed that thermal crosslinking prevented the dissolution of membranes in water ingreat extent. In addition, it was determined that the thermally crosslinked membranes had a more stable structure.     

Research progress on chemical modification of silk fibroin and its applications北大核心CSCD

Mulberry silk is composed of the two major parts of two triangle-like silk fibroin fibers and sericin covering the fibers and a few lipids. After removing the sericin on the raw silk what is left is the silk fibroin fiber. Silk fibroin is the main part of silk accounting for about 75% of the total weight. Silk fibroin contains 18 natural amino acids such as glycine Gly alanine Ala serine Ser serine aspartic acid Asp and tyrosine Tyr . The secondary structure of silk fibroin has three main conformations α-helix β-fold and random coil. Under certain conditions the three conformations can transform into each other and change the mechanical properties of the silk fibroin material. Silk fibroin extracted from silk fiber is a natural polymer with biocompatibility and biodegradability. It can be further processed into different forms of materials nanoparticles films hydrogels sponges etc. It has been applied in many fields such as biomedicine and cosmetics. In order to meet the needs of different fields researchers have conducted further chemical modification treatment based on the original excellent properties of silk fibroin. Meanwhile the active groups on various amino acid residues in silk fibroin also provide chemical reaction sites for the chemical modification of silk fibroin. The chemical modification methods of silk fibroin mainly include amino acid residue modification macromolecular grafting modification and crosslinking reaction modification. Among them amino acid residue modification can modify protein amino acid residues by chemical reagents and some groups can be introduced into the side chains of silk fibroin macromolecules. Grafting modification of silk fibroin macromolecules is one of the main means to bind functional compounds to silk fibroin macromolecular chains. The properties of grafted silk fibroin are affected by the type and grafting rate of the grafts. The chemical crosslinking reaction modification of silk fibroin macromolecules is to make the macromolecular chains connected by covalent bonds and form a network structure by means of crosslinking agents enzymes or ultraviolet irradiation. The cross-linking reaction can not only form covalent bonds within and between the molecular chains of silk fibroin thus changing its structural properties and improving its stability but be used to form covalent bonds with other polymers. At present the chemical modification of silk fibroin is mainly applied in the fields of silk textiles biomedicine and environmental science. In the field of silk textiles graft copolymerization modification of vinyl and other monomers crosslinking agent modification and other methods are used to overcome the shortcomings of silk like being easy to wrinkle. The graft modified monomers mainly include ethylene methacrylate and methylacrylamide. The active groups on crosslinking agents such as polycarboxylic acid / anhydride and epoxide are covalently combined with carboxyl hydroxyl and amino groups on macromolecules of silk fibroin to improve the wrinkle resistance of silk fabrics. In the field of biomedicine silk fibroin materials with appropriate chemical modification have better biological activity drug delivery ability antimicrobial properties and mechanical properties. The optimization of these properties enables silk fibroin materials to show great potential in drug control delivery tissue regeneration and wound repair. The applied research in the field of environmental science mainly focuses on the adsorption separation and catalysis of impurities in water. Therefore the modification of amino acid residues grafting and cross-linking of protein macromolecules can change some important properties of silk fibroin and meet the requirements of various applications and functionalization of silk fibroin. In many fields of chemical modification and application of silk fibroin protein fruitful results have been achieved which has laid a good foundation for the further development of related fields and also shows that the chemical modification of silk fibroin material has great potential and application prospects. However there are still some problems that need to be overcome and further improved in the current chemical modification methods such as mild modification conditions and accurate adjustment of the degree of modification which will be the research direction of related fields in the future. © 2022 Authors. All rights reserved.     

Elucidating the Catalytic Subunit Composition of Distinct Proteasome Subtypes: A Crosslinking Approach Employing Bifunctional Activity‐Based Probes

In addition to two well‐recognized proteasome subtypes—constitutive proteasomes and immunoproteasomes—mounting evidence also suggests the existence of intermediate proteasome subtypes containing unconventional mixtures of catalytic subunits. Although they appear to play unique biological roles, the lack of practical methods for detecting distinct proteasome subtypes has limited functional investigations. Here, we report the development of activity‐based probes that crosslink two catalytic subunits within intact proteasome complexes. Identification of the crosslinked subunit pairs provides direct evidence of the catalytic subunit composition of proteasomes. Using these probes, we found that U266 multiple myeloma cells contain intermediate proteasomes comprising both β1i and β2, but not β1 and β2i, consistent with previous findings with other cell types. Our bifunctional probes can be utilized in functional investigations of distinct proteasome subtypes in various biological settings.     

Leachability of degradation products from hard chairside reline resins in artificial saliva: Effect of water‐bath post‐polymerization treatment

The effect of a post‐polymerization treatment on the leaching of methacrylic acid (MA) and benzoic acid (BA) from the reline resins [Kooliner (K), New Truliner (N), Ufi Gel hard (U), and Tokuso Rebase Fast (T)] was evaluated. Specimens of each material were divided into two groups: Group C (control) – left untreated; Group WB (water‐bath) – immersion in water at 55 ± 1°C for 10 min. Specimens were placed in artificial saliva at 37 ± 1°C and, after 1‐, 3‐, 5‐, 24‐h and 3‐, 7‐, 14‐, and 30‐day intervals, aliquots were removed and analyzed using high performance liquid chromatography. Data were analyzed by using Wilcoxon, Mann–Whitney or Kruskal–Wallis tests (α = 0.05). At 1 h, the concentration of MA released from U control specimens was higher than those of the other ones, and decreased after 3 h. WB specimens released lower amounts of MA than control specimens only for material U, at the 1‐ and 3‐h periods. For all control specimens, concentrations of leached BA progressively decreased within 5 h and from 24 h to the end. WB specimens released significantly lower amounts of BA than did the control groups. The highest concentration of MA was leached from control specimens of Ufi Gel hard. Water‐bath post‐polymerization treatment caused a significant reduction in elution of BA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Compensation of microwave‐source heating attenuation into epoxy–glass composites: Experimental results

The final goal of this study was to manufacture an epoxy–glass leaf spring by microwave processing. The physical properties of the final part to be manufactured, in particular, the mechanical properties, were directly related at the repartition of microwave‐source heating during the treatment. The major problem in microwave processing, however, is the attenuation of the microwave source. Here, we propose a dielectric effect of attenuation inversion of the electromagnetic waves as a new method for the uniform treatment of epoxy–glass by microwave energy. This solution used the dielectric properties of the mold to control the microwave‐heat‐source attenuation into the composite to be treated. Many experiments were carried out to validate the proposed solution. The results show that the microwave‐source heating attenuation could controlled and inversed. We demonstrated the uniform treatment of epoxy–glass parts about 100 cm long by means of the compensation of microwave‐source attenuation. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39908.     

Influence of a long‐side‐chain‐containing reactive diluent on the structure and mechanical properties of UV‐cured films

The dimethacrylate reactive diluent (HEMA‐DDSA), a long‐side‐chain‐containing reactive diluent, was prepared by reacting 2‐dodecen‐1‐ylsuccinic anhydride with two equivalents of hydroxyethyl methacrylate. Its structure was characterized by IR and ¹H NMR spectroscopy. This new diluent was added into the formulation of UV‐curable epoxy acrylate networks. Results show that the formulation with the addition of HEMA‐DDSA has massively reduced viscosity and shows several attractive properties of epoxy acrylate oligomers. The mechanical resistance of the films is dramatically enhanced with the incorporation of long alkyl groups derived from HEMA‐DDSA, the plastic deformation zone expands, thus decreasing the inner stress of the polymer structure. Moreover, the cured coatings have a higher glass transition temperature as the percentage of HEMA‐DDSA is increased up to 5 wt%. Due to the excellent integrated performance of the polymeric films, HEMA‐DDSA proved to be an effective reactive diluent, which is of potential interest for applications in high performance materials. © 2016 Society of Chemical Industry     

Effect of thermal crosslinking on the properties of sulfonated poly(phenylene sulfone)s as proton conductive membranes

The synthesis and characterization of crosslinked aromatic polymer membranes with high ion exchange capacity (IEC) values are reported. Through aromatic nucleophilic substitution polycondensation and the subsequent sulfonation reaction, the highly sulfonated polymers SPPSU‐2S and SPPSU‐4S with high molecular weight (M_n = 138–145 kDa, M_w = 200–279 kDa) and well‐defined structures were synthesized. By solution casting and thermal annealing treatment, flexible crosslinked membranes with high solvent insolubility were obtained. The membranes exhibited mechanical and chemical stability as confirmed by dynamic mechanical analysis (DMA) and conductivity measurement. The crosslinked SPPSU‐4S membrane with IEC = 3.20 meq/g showed the highest proton conductivity of 0.163 S/cm at 120 °C, 90% RH, and improved thermal stability compared with its precursor (uncrosslinked) membrane. The results show that simple annealing method could improve significantly membranes properties of highly sulfonated aromatic polymers. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44218.     

Crosslinking of polybenzimidazole membranes by divinylsulfone post‐treatment for high‐temperature proton exchange membrane fuel cell applications

Phosphoric acid‐doped polybenzimidazole (PBI) has been suggested as a promising electrolyte for proton exchange membrane fuel cells operating at temperatures up to 200 °C. This paper describes the development of a crosslinking procedure for PBI membranes by post‐treatment with divinylsulfone. The crosslinking chemistry was studied and optimized on a low‐molecular‐weight model system and the results were used to optimize the crosslinking conditions of PBI membranes. The crosslinked membranes were characterized with respect to chemical and physiochemical properties, showing improved mechanical strength and oxidative stability compared with their linear analogues. Fuel cell tests were further conducted in order to demonstrate the feasibility of the crosslinked membranes. Copyright © 2011 Society of Chemical Industry     

Photocrosslinking of functionalized rubbers. X. Butadiene–acrylonitrile copolymers

The photocrosslinking of polyacrylonitrile‐block‐polybutadiene‐block‐polyacrylonitrile (ABA) was shown to proceed within seconds at ambient temperature upon UV exposure in the presence of an acylphosphine oxide photoinitiator. The curing process was followed by infrared spectroscopy, insolubilization, and hardness measurements. Complete insolubilization could not be achieved with the neat ABA rubber because of the poor reactivity of the 2‐butene double bond and the low vinyl content of the polybutadiene chain. The addition of multifunctional acrylate monomers (20 wt %) causes a substantial increase of both the reaction rate and the crosslink density of the polymer, which becomes completely insoluble in toluene in less than 1 s upon UV irradiation. An even greater effect was observed by using small amounts (1 wt %) of a trifunctional thiol crosslinker. Both the thiol and the photoinitiator concentrations were shown to affect the kinetics of the thiol–ene polymerization and the polymer network crosslink density. A direct relationship was found to exist between the swelling degree of the UV‐cured rubber and the interchain molecular weight of the network. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2204–2216, 2001     

Effect of various efficient vulcanization cure systems on the compression set of a nitrile rubber filled with different fillers

Effect of various efficient vulcanization (EV) sulfur cure systems on the compression set of a nitrile rubber filled with carbon black and silica/silane fillers was examined. The cure systems had different amounts of thiuram and sulfenamide accelerators and elemental sulfur, whilst the loading of zinc oxide and stearic acid activators was kept constant. The fillers had surface areas from 35 to 175 m²/g. In this study, the lowest compression set was measured for the rubber filled with carbon black with 78 m²/g surface area, which was cured with an EV cure system made of a small amount of elemental sulfur and large amounts of the two accelerators. Interestingly, a small change in the amount of elemental sulfur had a bigger effect on the compression set than did large changes in the loading of the accelerators in the cure system. Among the fillers, carbon black caused less compression set of the rubber vulcanizate than the silica/silane system did. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41512.