Easy hydrolysis in alkaline environments limits the use of polyimide fibers in environmental protection. The hydrolysis resistance levels of polyimide fibers can be improved by crosslinking of the macromolecular chain...Easy hydrolysis in alkaline environments limits the use of polyimide fibers in environmental protection. The hydrolysis resistance levels of polyimide fibers can be improved by crosslinking of the macromolecular chains. In this work, crosslinked polyimide fibers(CPI fibers) were produced by intrinsic carboxyl decarboxylation for the first time. The thermal stability of the polyimide fibers containing the intrinsic carboxyl groups(PIC fibers) was studied, and the temperature of the decarboxylation-crosslinking reaction was determined to be 450 ℃. The PIC fibers were hotdrawn to initiate thermal crosslinking of the carboxyl groups and molecular chain orientation at high temperature. The CPI fibers had high tensile strengths(0.72-1.46 GPa) and compressive strengths(401-604 MPa). The oriented macromolecules and chemically crosslinked structure improved the tightness of the molecular chains and endowed the CPI fibers with excellent hydrolytic resistance. The CPI-50 fiber did not dissolve in a 0.5 wt% NaOH solution during heating at 90 ℃ for 10 h, and the tensile strength retention reached 87% when treated in 0.5 wt% NaOH solutions at 90 ℃ for 1 h, providing a guarantee for its application in alkaline corrosive environments.展开更多
Polypropylene(PP) exhibits suboptimal creep resistance due to the presence of methyl groups on its main chain, leading to irregular chain segment distribution, diminished inter-chain interaction, and crystallinity. Th...Polypropylene(PP) exhibits suboptimal creep resistance due to the presence of methyl groups on its main chain, leading to irregular chain segment distribution, diminished inter-chain interaction, and crystallinity. This structural feature causes chain slippage in PP under stress,significantly constraining its service lifetime. In this study, thermally reduced graphene oxide(TrGO) nanosheets were incorporated into the PP matrix, yielding a nanocomposite with exceptional creep resistance performance. Results demonstrated that at a stress of 25 MPa, a 2.0 wt% TrGO content could enhance the creep failure lifetime of PP by 21.5 times compared to neat PP. Rheology, transmission electron microscopy(TEM),and scanning electron microscopy(SEM) characterization techniques were employed to analyze the mechanism of TrGO's influence on PP's creep behavior. It was observed that when TrGO content exceeded 1.0 wt%, an effective particle network structure formed within the PP matrix. This homogeneously dispersed TrGO-formed particle network structure restricted the migration and rearrangement of PP molecular chains, enabling prolonged stress resistance without structural failure. By combining the time-strain superposition method with the critical failure strain as a criterion, generalized creep compliance curves for PP and its composites were established, facilitating the prediction of material creep failure lifetimes, with a strong agreement between experimental and predicted lifetime values. This research proposes a novel strategy aimed at developing polypropylene materials and products with enhanced long-term stability and durability, thus extending service life, reducing failure risk, and broadening their potential across various application domains.展开更多
基金financially supported by the Scientific Research Innovation Plan of Shanghai Education Commission (No. 2019-01-07-00-03-E00001)the National Natural Science Foundation of China (Nos. U21A2087 and 21975040)the Natural Science Foundation of Shanghai (No. 21ZR1400200)。
文摘Easy hydrolysis in alkaline environments limits the use of polyimide fibers in environmental protection. The hydrolysis resistance levels of polyimide fibers can be improved by crosslinking of the macromolecular chains. In this work, crosslinked polyimide fibers(CPI fibers) were produced by intrinsic carboxyl decarboxylation for the first time. The thermal stability of the polyimide fibers containing the intrinsic carboxyl groups(PIC fibers) was studied, and the temperature of the decarboxylation-crosslinking reaction was determined to be 450 ℃. The PIC fibers were hotdrawn to initiate thermal crosslinking of the carboxyl groups and molecular chain orientation at high temperature. The CPI fibers had high tensile strengths(0.72-1.46 GPa) and compressive strengths(401-604 MPa). The oriented macromolecules and chemically crosslinked structure improved the tightness of the molecular chains and endowed the CPI fibers with excellent hydrolytic resistance. The CPI-50 fiber did not dissolve in a 0.5 wt% NaOH solution during heating at 90 ℃ for 10 h, and the tensile strength retention reached 87% when treated in 0.5 wt% NaOH solutions at 90 ℃ for 1 h, providing a guarantee for its application in alkaline corrosive environments.
基金financially supported by Natural Science Foundation of Sichuan Province (No. 2022NSFSC0296)the National Natural Science Foundation of China (Nos. 51903118and U19A2096)State Key Laboratory of Polymer Materials Engineering (No. sklpme2020-1-07, Sichuan University)。
文摘Polypropylene(PP) exhibits suboptimal creep resistance due to the presence of methyl groups on its main chain, leading to irregular chain segment distribution, diminished inter-chain interaction, and crystallinity. This structural feature causes chain slippage in PP under stress,significantly constraining its service lifetime. In this study, thermally reduced graphene oxide(TrGO) nanosheets were incorporated into the PP matrix, yielding a nanocomposite with exceptional creep resistance performance. Results demonstrated that at a stress of 25 MPa, a 2.0 wt% TrGO content could enhance the creep failure lifetime of PP by 21.5 times compared to neat PP. Rheology, transmission electron microscopy(TEM),and scanning electron microscopy(SEM) characterization techniques were employed to analyze the mechanism of TrGO's influence on PP's creep behavior. It was observed that when TrGO content exceeded 1.0 wt%, an effective particle network structure formed within the PP matrix. This homogeneously dispersed TrGO-formed particle network structure restricted the migration and rearrangement of PP molecular chains, enabling prolonged stress resistance without structural failure. By combining the time-strain superposition method with the critical failure strain as a criterion, generalized creep compliance curves for PP and its composites were established, facilitating the prediction of material creep failure lifetimes, with a strong agreement between experimental and predicted lifetime values. This research proposes a novel strategy aimed at developing polypropylene materials and products with enhanced long-term stability and durability, thus extending service life, reducing failure risk, and broadening their potential across various application domains.