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
The aging of natural rubber(NR)at high temperatures will seriously affect its service lifetime in many key applications.In the present work,the changes in microstructure and mechanical properties of semi-efficient vul...The aging of natural rubber(NR)at high temperatures will seriously affect its service lifetime in many key applications.In the present work,the changes in microstructure and mechanical properties of semi-efficient vulcanized NR/carbon black(CB)vulcanizates during thermooxidative aging at high temperatures(150-200℃)and a moderate temperature(95℃)were compared.At high temperatures,a two-stage aging behavior,which was characteristic of a first rapid decline and then a continuous rise in the crosslinking density(ve),was identified and was found to be closely related to the depletion behavior of antioxidants.The surface cracking behavior observed in the second stage of high-temperature aging was discussed in terms of the grafting reaction of macromolecular radicals on CB particles and thermal expansion.In contrast,the aging of NR at moderate temperatures was much mild,which featured a continuous increase in ve and an oxidation mechanism dominated by peroxy radicals attacking double bonds.In general,the mechanical properties of NR vulcanizates during high-temperature aging depended on the competition effects of structural evolution in the crosslinked network and oxidation-induced chain scission.展开更多
The influence of polystyrene particles with different nanoscale roughnesses on the morphology of polyisobutylene/poly-dimethylsiloxane blends was studied under shear flow by using confocal laser scanning microscopy.It...The influence of polystyrene particles with different nanoscale roughnesses on the morphology of polyisobutylene/poly-dimethylsiloxane blends was studied under shear flow by using confocal laser scanning microscopy.It was found that the surface roughness of particles strongly affected their diffusion and distribution behaviors,thereby determining the size and spatial arrangement of droplets in the blends.The roughness effect of particles was found to possess a strong dependence on both the blend ratio and the shear rate.The result suggested that the particle roughness can serve as a new parameter to control the structure-property correlation in particle-filled polymer blends,especially under slow flow.展开更多
Silica rods with homogeneous(hydrophilic or hydrophobic)and amphiphilic surface properties were synthesized and their efficiencies in suppressing the flow-induced droplet coalescence of immiscible polyisobutylene(PIB)...Silica rods with homogeneous(hydrophilic or hydrophobic)and amphiphilic surface properties were synthesized and their efficiencies in suppressing the flow-induced droplet coalescence of immiscible polyisobutylene(PIB)/polydimethylsiloxane(PDMS)blends were evaluated via in situ visualization technique.The flow-induced coalescence behavior of blends was found to strongly depend on the surface nature and concentration of silica rods added as well as the blend ratio.While a trace amount of rods promoted coalescence,all kinds of rods demonstrated a morphology refinement effect at high rod concentrations.Good compatibilization effects were obtained at high rod concentrations,especially for hydrophilic and amphiphilic rods.Based on confocal laser scanning microscopy results,these phenomena observed were interpreted reasonably in terms of the selective distribution and aggregation of silica rods,which were suggested to be decisive for the stabilization mechanism and efficiency of these rods.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.
基金financially supported by the National Natural Science Foundation of China(Nos.51790504 and U19A2096)the Programme of Introducing Talents of Discipline to Universities(No.B13040)State Key Laboratory of Polymer Materials Engineering(No.sklpme2019-2-07)。
文摘The aging of natural rubber(NR)at high temperatures will seriously affect its service lifetime in many key applications.In the present work,the changes in microstructure and mechanical properties of semi-efficient vulcanized NR/carbon black(CB)vulcanizates during thermooxidative aging at high temperatures(150-200℃)and a moderate temperature(95℃)were compared.At high temperatures,a two-stage aging behavior,which was characteristic of a first rapid decline and then a continuous rise in the crosslinking density(ve),was identified and was found to be closely related to the depletion behavior of antioxidants.The surface cracking behavior observed in the second stage of high-temperature aging was discussed in terms of the grafting reaction of macromolecular radicals on CB particles and thermal expansion.In contrast,the aging of NR at moderate temperatures was much mild,which featured a continuous increase in ve and an oxidation mechanism dominated by peroxy radicals attacking double bonds.In general,the mechanical properties of NR vulcanizates during high-temperature aging depended on the competition effects of structural evolution in the crosslinked network and oxidation-induced chain scission.
基金the National Natural Science Foundation of China(Nos.51873111 and 51721091)the Programme of Introducing Talents of Discipline to Universities(No.B13040)the Graduate Innovation Foundation of Sichuan University(No.2018YJSY088).
文摘The influence of polystyrene particles with different nanoscale roughnesses on the morphology of polyisobutylene/poly-dimethylsiloxane blends was studied under shear flow by using confocal laser scanning microscopy.It was found that the surface roughness of particles strongly affected their diffusion and distribution behaviors,thereby determining the size and spatial arrangement of droplets in the blends.The roughness effect of particles was found to possess a strong dependence on both the blend ratio and the shear rate.The result suggested that the particle roughness can serve as a new parameter to control the structure-property correlation in particle-filled polymer blends,especially under slow flow.
基金supported by the National Natural Science Foundation of China(Nos.51873111,51721091)the Scientific Research Foundation of Sichuan Province(No.2018HH0001)+1 种基金the Programme of Introducing Talents of Discipline to Universities(No.B13040)the Graduate Innovation Foundation of Sichuan University(No.2018YJSY088).
文摘Silica rods with homogeneous(hydrophilic or hydrophobic)and amphiphilic surface properties were synthesized and their efficiencies in suppressing the flow-induced droplet coalescence of immiscible polyisobutylene(PIB)/polydimethylsiloxane(PDMS)blends were evaluated via in situ visualization technique.The flow-induced coalescence behavior of blends was found to strongly depend on the surface nature and concentration of silica rods added as well as the blend ratio.While a trace amount of rods promoted coalescence,all kinds of rods demonstrated a morphology refinement effect at high rod concentrations.Good compatibilization effects were obtained at high rod concentrations,especially for hydrophilic and amphiphilic rods.Based on confocal laser scanning microscopy results,these phenomena observed were interpreted reasonably in terms of the selective distribution and aggregation of silica rods,which were suggested to be decisive for the stabilization mechanism and efficiency of these rods.
