Novel branched sulfonated polyimide membrane with remarkable vanadium permeability resistance and proton selectivity for vanadium redox flow battery application

A series of novel branched sulfonated polyimide (bSPI-x) membranes with 8% branched degree are developed for application in vanadium redox flow battery (VRFB). The sulfonation degrees of bSPI-x membranes are precisely regulated for obtaining excellent comprehensive performance. Among all bSPI-x membranes, the bSPI-50 membrane shows strong vanadium permeability resistance, which is as 8 times as that of commercial Nafion 212 membrane. At the same time, the bSPI-50 membrane has remarkable proton selectivity, which is four times as high as that of Nafion 212 membrane. The bSPI-50 membrane possesses slower self-discharge speed than Nafion 212 membrane. Furthermore, the bSPI-50 membrane achieves stable VRFB efficiencies during 200-time charge-discharge cycles at 120–180 mA cm^?2. Simultaneously, the bSPI-50 membrane exhibits excellent capacity retention compared with Nafion 212 membrane. All results imply that the bSPI-50 membrane possesses good application prospect as a promising alternative separator of VRFB.     

Low dielectric constant polyimide mixtures fabricated by polyimide matrix and polyimide microsphere fillers

Polyimide microspheres were prepared via non‐aqueous emulsion polymerization by using pyromellitic dianhydride (PMDA) as anhydride monomer and 2,2‐bis(4‐(4‐aminophenoxy)phenyl)propane as amine monomer. The polyimide microspheres were well characterized by Fourier transform infrared spectroscopy, SEM and laser particle size analyzer. They were spherical in shape and monodisperse and their size was 31–33 μm. Polyimide mixtures formed by polyimide microspheres as fillers and polyimide composed of pyromellitic and dianhydride 4,4′‐oxydianiline (ODA) as matrix were investigated with regard to thermal properties, dielectric properties and mechanical properties. With 10%–50% polyimide microspheres in the polyimide mixtures, the dielectric constants were 2.26–2.48 (1 MHz) and the loss tangents were 0.00663–0.00857 (1 MHz), which were both significantly lower than the values for ODA‐PMDA polyimide. The decomposition temperature and glass transition temperature were above 440 and 290 °C. The polyimide mixtures possessed excellent thermal resistance. When the percentage of polyimide microsphere addition was 30%, the polyimide mixtures had the largest tensile strength (128.50 MPa) and elongation at break (9.01%). These results indicate that the polyimide microspheres were used as both low dielectric fillers and reinforcing fillers. © 2020 Society of Chemical Industry     

GO/PI复合纳米纤维的制备及其过滤性能研究

为制备高过滤效率、低过滤阻力的空气过滤材料,将氧化石墨烯纳米颗粒(GO)掺杂到聚酰亚胺(PI)纺丝溶液中,制备氧化石墨烯/聚酰亚胺(GO/PI)复合纳米纤维过滤材料。通过观察其形貌、过滤性能来确定最优纺丝工艺参数。结果表明:当PI质量分数为30%,GO质量分数为1%,纺丝电压为25 kV,接收距离为20 cm时,复合纳米薄膜的纤维形貌较好,过滤性能优良。与PI纯组分纳米纤维过滤材料相比,GO/PI复合纳米纤维过滤材料的过滤性能更好,制得GO/PI复合纳米纤维膜的平均孔径为1.8μm,过滤效率为99.68%,过滤阻力仅为85.35 Pa。     

High-Tg porous polyimide films with low dielectric constant derived from spiro-(adamantane-2,9′(2′,7′-diamino)-fluorene)

Porous polyimide (PI) films with low dielectric constants and excellent thermal properties have been a pressing demand for the next generation of high-performance, miniature, and ultrathin microelectronic devices. A series of novel porous PI films containing fluorenyl-adamantane groups were prepared successfully via thermolysis of poly(ethylene glycol) (PEG) added in the PI matrix. The cross-sectional morphologies of porous PI films showed closed pores with diameters ranging from 135 to 158 nm, which were uniform and regular in shape without interconnectivity. These porous PI films exhibited excellent thermal properties with a glass-transition temperature at 376 °C whereas the 5% weight loss temperature in air excess of 405 °C due to enhanced rigidity afforded by fluorenyl-adamantane groups. Accompanied by thermolysis content of PEG increasing from 0 to 20 wt %, the density of porous PI films decreased, and the corresponding porosity grew significantly from 0 to 11.48%. Depending on porosity, the dielectric constant and dielectric loss of porous PI films significantly declined from 2.89 to 2.37 and from 0.050 to 0.021, respectively. These excellent properties benefit the as-prepared porous PI films for application as interlayer dielectrics, integrated circuit chips, or multichip modules in microelectronic fields. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47313.     

Double Dianhydride Backbone Polyimide Aerogels with Enhanced Thermal Insulation for High‐Temperature Applications

Aerogels owe their high thermal insulation and other unique properties to their nanostructure configuration. However, controlling the aerogels' morphology is always a scientific challenge. In this study, double dianhydride backbone (double backbone) polyimide aerogels with tailored nanostructure assembly are created for the first time. This is achieved by controlled polymerization reaction of oligomers with distinct dianhydride monomers. Combining the two oligomers through a controlled polymerization reaction is a successful strategy for tailoring the aerogels nanostructure assembly as well as other properties. The fabricated double backbone aerogel presents 40% reduced thermal conductivity of 19.7 mW mK^?1 over previously studied polyimide aerogels along with the compression modulus of 1.64 MPa at a relatively low density of 0.068 g cm^?3. Such low thermal conductivity is comparable with the inorganic counterparts. Light in weight and high thermally insulated polyimide aerogels with suitable mechanical properties and high service temperature are an appropriate replacement for current fireproof insulation materials.     

Fabrication and Thermal Dissipation Properties of Carbon Nanofibers Derived from Electrospun Poly(Amic Acid) Carboxylate Salt Nanofibers

Polyimides (PIs) possess excellent mechanical properties, thermal stability, and chemical resistance and can be converted to carbon materials by thermal carbonization. The preparation of carbon nanomaterials by carbonizing PI‐based nanomaterials, however, has been less studied. In this work, the fabrication of PI nanofibers is investigated using electrospinning and their transformation to carbon nanofibers. Poly(amic acid) carboxylate salts (PAASs) solutions are first electrospun to form PAAS nanofibers. After the imidization and carbonization processes, PI and carbon nanofibers can then be obtained, respectively. The Raman spectra reveal that the carbon nanofibers are partially graphitized by the carbonization process. The diameters of the PI nanofibers are observed to be smaller than those of the PAAS nanofibers because of the formation of the more densely packed structures after the imidization processes; the diameters of the carbon nanofibers remain similar to those of the PI nanofibers after the carbonization process. The thermal dissipation behaviors of the PI and carbon nanofibers are also examined. The infrared images indicate that the transfer rates of thermal energy for the carbon nanofibers are higher than those for the PI nanofibers, due to the better thermal conductivity of carbon caused by the covalent sp² bonding between carbon atoms.     

Synthesis of highly transparent and thermally stable copolyimide with fluorine-containing dianhydride and alicyclic dianhydride

The development of optical films is highly desirable for applications in flexible displayers. In this work, a copolyimide (co-PI) film with high thermal stability and high transparency was prepared by the copolymerization of 2,2′-bis(trifluoromethyl)-4,4′-diaminodiphenyl ether, cyclobutanetetracarboxylic dianhydride, and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA). The effects of aliphatic dianhydride and fluorine dianhydride monomers on the optical, thermal, and mechanical properties of the co-PIs were discussed in detail based on the experimental results and theoretical simulations. We found that the preparation of polyimide (PI) based on the combination of two dianhydrides could obtain the PI film with excellent comprehensive performance due to nonconjugated structure and strong electron-withdrawing effect. Through the structure and composition optimization, a PI film of PI-6FDA-70 with T_g of 300 °C, T_d10% more than 500 °C, the average transparency of 90% and the elongation at the breakage more than 8% was prepared. Such molecular design provides a practical approach to develop high-performance colorless PI films. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48603.     

人造金刚石填充聚酰亚胺树脂基复合材料防刺性能

为研究树脂材料的防刺性能及防刺机制,利用手糊成型与热压法成型制备了手糊分层结构和均布结构层2种结构的人造金刚石填充聚酰亚胺树脂基复合树脂片,并探讨了人造金刚石粒径、填充体积分数对树脂片防刺性能的影响。研究结果表明:经过人造金刚石填充的聚酰亚胺树脂片的防刺性能得到提高,并且均布结构层分层复合结构的树脂片的防刺性能更好;随着人造金刚石粒径的减小,树脂片防刺性能出现先减小后增加的趋势,故防刺机制基本在于碰撞概率与树脂基的防挡;比较防刺力和消耗功发现,不同填充体积分数的单层防刺树脂片的防刺性能随人造金刚石填充体积分数的增加而逐渐降低,该趋势的成因在于复合树脂片的脆化与破坏;在颗粒等效粒径为300 μm、体积分数为10%时,其防刺性能最好。     

Enhancing the electrical and thermal stability of organic thin-film transistors by utilizing fluorinated polyimide and silicon dioxide bilayer gate dielectric

The grand vision of next generation electronics is expected to realize via the wholescale industrialization of organic devices. However, one serious obstacle hindering the practical application for organic devices is their instability regardless of it induced by high temperatures or sustained gate bias stress. Herein, pentacene-based thin-film transistors (TFTs) with both good heat resistance and high electrical stability were realized. The TFTs, where fluorinated polyimide (ODA–6FDA PI) and a silicon dioxide (SiO₂) bilayer are used as gate dielectric, exhibit superior electrical stability under protracted gate bias stress for 150 min (ΔV_th ~1 V with voltage range of 30 to −60 V) and are extremely less susceptible to annealing treatment for temperatures up to 150 °C (Δμ/μ₀ ~2.9%), as compared to counterparts with a single dielectric layer. We demonstrated that the excellent bias-stress stability arises from the higher activation energy of defects of fluorinated PI surface based on exponential barrier distribution model and the suppression of charge injection and back-channel effect via bilayer. Also, the superior thermal stability is ascribed to the restraint of film cracks and phase transformation of pentacene at high temperatures induced by the better match between the thermal expansion coefficients of semiconductor and dielectric. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47013.