Comb-shaped sulfonated poly(aryl ether sulfone) proton exchange membrane for fuel cell applications

Structure design is the primary strategy to acquire suitable ionomers for preparing proton exchange membranes (PEMs) with excellent performance. A series of comb-shaped sulfonated fluorinated poly(aryl ether sulfone) (SPFAES) membranes are prepared from sulfonated fluorinated poly(aryl ether sulfone) polymer (SPFAE) and sulfonated poly(aryl ether sulfone) oligomer (SPAES-Oligomer). Chemical structures of the comb-shaped membranes are verified by ¹H nuclear magnetic resonance (NMR) and Fourier transform infrared (FT-IR) spectra. The comb-shaped SPFAES membranes display more continuous hydrophilic domains for ion transfer, because the abundant cations and flexible side-chains structure possess higher mobility and hydrophilicity, which show significantly improved proton conductivity, physicochemical stability, mechanical property compared to the linear SPFAE membranes. In a H₂/O₂ single-cell test, the SPFAES-1.77 membrane achieves a higher power density of 699.3 mW/cm² in comparison with Nafion® 112 (618.0 mW/cm²) at 80 °C and 100% relative humidity. This work offers a promising example for the synthesis of highly branched polymers with flexible comb-shaped side chains for high-performance PEMs.     

Synthesis and characterization of a long side-chain double-cation crosslinked anion-exchange membrane based on poly(styrene-b-(ethylene-co-butylene)-b-styrene)

By choosing a triple block polymer, poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS), as the backbone and adopting a long side-chain double-cation crosslinking strategy, a series of SEBS-based anion-exchange membranes (AEMs) was successively synthesized by chloromethylation, quaternization, crosslinking, solution casting, and alkalization. The 70C16-SEBS-TMHDA membrane showed high OH⁻ conductivity (72.13 mS/cm at 80 °C) and excellent alkali stability (only 10.86% degradation in OH⁻ conductivity after soaking in 4-M NaOH for 1700 h at 80 °C). Furthermore, the SR was only 9.3% at 80 °C and the peak power density of the H₂/O₂ single cell was up to 189 mW/cm² at a current density of 350 mA/cm² at 80 °C. By introducing long flexible side chains into a polymer SEBS backbone, the structure of the hydrophilic–hydrophobic microphase separation in the membrane was constructed to improve the ionic conductivity. Additionally, network crosslinked structure improved dimensional stability and mechanical properties.     

减水剂类型对赤泥—矿渣基地聚物注浆材料性能的影响及机理研究

针对赤泥等固体废弃物对环境危害性大且利用率低等问题,以碱激发赤泥-矿渣基地聚物注浆材料为 研究对象,研究了不同掺量的聚羧酸(PA)减水剂、醛酮缩合物(AKC)减水剂和萘系(N)减水剂对材料凝结时间、流动 性及强度等的影响,并通过 XRD、傅里叶红外光谱及 SEM 等设备对减水剂的作用机理进行研究。 结果表明:减水剂增 强了材料的流动性但降低了材料的剪切应力;N 和 PA 减水剂能缩短材料的凝结时间,但 AKC 减水剂会延长材料的凝 结时间;N 和 AKC 减水剂能提高材料的强度,但 PA 减水剂会降低材料的强度;N 减水剂对材料的综合性能提升效果 更加明显,其最优掺量为 0. 7%;减水剂对赤泥-矿渣基地聚物性能提升的作用机理主要是促进地聚合物凝胶的形成。 研究成果为拓展赤泥在工程上的使用途径和效率提供了理论指导。     

The surface carboxyl group of carbonaceous microspheres effects on the synthesis and structure of SiOC ceramics

In this study, C/SiOC and C/SiO₂ composites were prepared by using carbonaceous microspheres with different surface functional groups. Carbonaceous microspheres based on hydrothermal reaction of glucose contains hydroxyl group, while the surface carboxyl group increases after NaOH etching. The hydroxyl group increases the oxygen-enriched structural units of SiOC ceramics, and the C spheres are closely enwrapped in SiOC matrix after pyrolysis at 900 °C. However, the interfacial reaction of surface carboxyl with Si–OH results in the formation of cristobalite SiO₂, and C spheres are not only encased inside the SiOC matrix, but also dispersed outside of SiOC ceramics. After removal of C via calcination at 500 °C for 5 h, C/SiOC and C/SiO₂ composites are transformed into amorphous SiO₂ and cristobalite SiO₂, respectively. The thermogravimetric analysis indicates the oxidation resistance of SiOC is superior to that of C and SiO₂.     

Spatiotemporal Magnetocaloric Microenvironment for Guiding the Fate of Biodegradable Polymer Implants

The degradation behavior of implants is significantly important for bone repair. However, it is still unprocurable to spatiotemporally regulate the degradation of the implants to match bone ingrowth. In this paper, a magneto-controlled biodegradation model is established to explore the degradation behavior of magnetic scaffolds in a magnetothermal microenvironment generated by an alternating magnetic field (AMF). The results demonstrate that the scaffolds can be heated by magnetic nanoparticles (NPs) under AMF, which dramatically accelerated scaffold degradation. Especially, magnetic NPs modified by oleic acid with a better interface compatibility exhibit a greater heating efficiency to further facilitate the degradation. Furthermore, the molecular dynamics simulations reveal that the enhanced motion correlation between magnetic NPs and polymer matrix can accelerate the energy transfer. As a proof-of-concept, the feasibility of magneto-controlled degradation for implants is demonstrated, and an optimizing strategy for better heating efficiency of nanomaterials is provided, which may have great instructive significance for clinical medicine.     

Mechanical Properties of Single-Layer Diamond Reinforced Poly(vinyl alcohol) Nanocomposites through Atomistic Simulation

Low-dimensional carbon nanostructures are ideal nanofillers to reinforce the mechanical performance of polymer nanocomposites due to their excellent mechanical properties. Through molecular dynamics simulations, the mechanical performance of poly(vinyl alchohol) (PVA) nanocomposites reinforced with a single-layer diamond – diamane is investigated. It is found the PVA/diamane exhibits similar interfacial strengths and pull-out characteristics with the PVA/bilayer-graphene counterpart. Specifically, when the nanofiller is fully embedded in the nanocomposite, it is unable to deform simultaneously with the PVA matrix due to the weak interfacial load transfer efficiency, thus the enhancement effect is not significant. In comparison, diamane can effectively promote the tensile properties of the nanocomposite when it has a laminated structure as it deforms simultaneously with the matrix. With this configuration, the interlayer sp³ bonds endows diamane with a much higher resistance under compression and shear tests, thus the nanocomposite can reach very high compressive and shear stress. Overall, enhancement on the mechanical interlocking at the interface as triggered by surface functionalization is only effective for the fully embedded nanofiller. This work provides a fundamental understanding of the mechanical properties of PVA nanocomposites reinforced by diamane, which can shed lights on the design and preparation of next generation high-performance nanocomposites.     

中低温煤焦油基炭微球的制备

通过馏分切割、温和加氢相结合对中低温煤焦油进行精制处理，精制后的原料采用分级热聚制备中间相炭微球。考察了精制处理条件对原料性质、中间相炭微球宏观外貌及微晶结构的影响。采用FTIR、GC-MS、族组成、元素分析对原料进行表征，采用SEM、XRD对中间相炭微球进行表征。结果表明：中低温煤焦油中300～430℃馏分油是制备中间相炭微球的较佳馏分。300～430℃馏分油中正庚烷可溶物（HS）质量分数高达84.76%，吡啶不溶物（PI）质量分数低至0.23%，杂原子含量低，芳烃化合物的环数为2～4环。300～430℃馏分油在T_H=350℃、p=8MPa、t=1.5h、剂油比1∶40（质量比）的条件下温和加氢得到的精制原料，经420℃热聚6h得制备的中间相炭微球宏观外貌、微晶结构较好。中低温煤焦油基炭微球的粒径范围为5～15μm，小球表面光滑，微观结构为地球仪型，经1450℃高温煅烧后，石墨化度达到12.33%。     

Blocked crystallization in capped ultrathin polymer films studied by molecular simulations

The crystallization of capped ultrathin polymer films is closely dependent on film thickness and interfacial interaction. Using dynamic Monte Carlo simulations, the crystallization behaviors of polymer films confined between two substrates were investigated. The crystallization rate of confined polymers is reduced with high interfacial interactions. Above a critical strength of interfacial interaction, polymer crystallization in the thin film is inhibited within the simulation time scales. An increase in film thickness leads to a rise in critical interfacial interaction. In thicker films, the chains have more space to change conformation to form crystal stems. In addition, there are fewer absorbed segments in confined chains for the thicker films, and thus the chains have stronger ability to adjust their conformation. Therefore an increase in film thickness can cause a reduction in the entropic barrier required for the formation of crystals and thus an increase in the critical interfacial interaction. © 2018 Society of Chemical Industry     

Synthesis and Characterization of Co Nanocomposite Based on Poly(benzimidazole-amide) Matrix and Their Behavior as Catalyst in Oxidation Reaction

2,6-Bis(5-amino-1H-benzimidazol-2-yl)pyridine was prepared and characterized by Fourier transform infrared spectroscopy, elemental analysis, ¹H-NMR, and ¹³C-NMR spectroscopic methods. Then a new poly(benzimidazole-amide) was synthesized by polymerization of the corresponding diamine and isophthalic acid. The obtained poly(benzimidazole-amide) exhibited good yield and high thermal stability. Due to the existence of benzimidazole moieties in polymer’s structure, it has the tendency to form complexes with metal ions. So, a new poly(benzimidazole-amide)/Co nanocomposite was prepared. Morphological studies revealed that metal nanoparticles were dispersed in the polymer matrix without any aggregation. poly(benzimidazole-amide)/Co nanocomposite was used as a catalyst in the oxidation of ethyl benzene to acetophenone with tert-butyl hydroperoxide.