The effects of 1 Me V electron irradiation in air at a fixed accumulated dose and dose rates of 393.8,196.9,78.8,and 39.4 Gy s^(-1)on a shape memory epoxy(SMEP)resin were studied.Under low-dose-rate irradiation,accele...The effects of 1 Me V electron irradiation in air at a fixed accumulated dose and dose rates of 393.8,196.9,78.8,and 39.4 Gy s^(-1)on a shape memory epoxy(SMEP)resin were studied.Under low-dose-rate irradiation,accelerated degradation of the shape memory performance was observed;specifically,the shape recovery ratio decreased exponentially with increasing irradiation time(that is,with decreasing dose rate).In addition,the glass transition temperature of the SMEP,as measured by dynamic mechanical analysis,decreased overall with decreasing dose rate.The dose rate effects of 1 Me V electron irradiation on the SMEP were confirmed by structural analysis using electron paramagnetic resonance(EPR)spectroscopy and Fourier transform infrared(FTIR)spectroscopy.The EPR spectra showed that the concentration of free radicals increased exponentially with increasing irradiation time.Moreover,the FTIR spectra showed higher intensities of the peaks at 1660 and 1720 cm^(-1),which are attributed to stretching vibrations of amide C=O and ketone/acid C=O,at lower dose rates.The intensities of the IR peaks at 1660 and 1720 cm^(-1) increased exponentially with increasing irradiation time,and the relative intensity of the IR peak at 2926 cm^(-1)decreased exponentially with increasing irradiation time.The solid-state13 C nuclear magnetic resonance(NMR)spectra of the SMEP before and after 1 Me V electron irradiation at a dose of 1970 k Gy and a dose rate of 78.8 Gy s^(-1) indicated damage to the CH_(2)–N groups and aliphatic isopropanol segment.This result is consistent with the detection of nitrogenous free radicals,a phenoxy-type free radical,and several types of pyrolytic carbon radicals by EPR.During the subsequent propagation process,the free radicals produced at lower dose rates were more likely to react with oxygen,which was present at higher concentrations,and form the more destructive peroxy free radicals and oxidation products such as acids,amides,and ketones.The increase in peroxy free radicals at lower dose rates was thought to accelerate the degradation of the macroscopic performance of the SMEP.展开更多
The epoxy shape memory polymer(SMP)with adjustable phase transition temperature is a kind of high-performance shape mem-ory polymer,which can change its phase transition temperature and improve its mechanical properti...The epoxy shape memory polymer(SMP)with adjustable phase transition temperature is a kind of high-performance shape mem-ory polymer,which can change its phase transition temperature and improve its mechanical properties through the process of photo curing.An epoxy SMP constitutive model combining phase transition and viscoelasticity is established by discretizing the epoxy SMP into several glass phase units and rubbery phase units in this paper.The model includes the viscoelastic constitutive equa-tions of glass phase units and rubber phase units,the parameter expression during shape memory process,and material parameter equation during photocuring process.And the stress relaxation behavior of epoxy SMP at different temperatures and the change of material parameters during the photo-curing process are simu-lated numerically,and the simulation results perform consistency with the experimental data.The model can not only relate shape memory effect and phase transformation in physics but also better characterize the viscoelastic properties of SMP and predict the shape memory response of SMP.展开更多
基金support of the 111 Project(No.B18017)the National Equipment Pre-Research Project of the 13th Five-Year Plan(No.30508040601)。
文摘The effects of 1 Me V electron irradiation in air at a fixed accumulated dose and dose rates of 393.8,196.9,78.8,and 39.4 Gy s^(-1)on a shape memory epoxy(SMEP)resin were studied.Under low-dose-rate irradiation,accelerated degradation of the shape memory performance was observed;specifically,the shape recovery ratio decreased exponentially with increasing irradiation time(that is,with decreasing dose rate).In addition,the glass transition temperature of the SMEP,as measured by dynamic mechanical analysis,decreased overall with decreasing dose rate.The dose rate effects of 1 Me V electron irradiation on the SMEP were confirmed by structural analysis using electron paramagnetic resonance(EPR)spectroscopy and Fourier transform infrared(FTIR)spectroscopy.The EPR spectra showed that the concentration of free radicals increased exponentially with increasing irradiation time.Moreover,the FTIR spectra showed higher intensities of the peaks at 1660 and 1720 cm^(-1),which are attributed to stretching vibrations of amide C=O and ketone/acid C=O,at lower dose rates.The intensities of the IR peaks at 1660 and 1720 cm^(-1) increased exponentially with increasing irradiation time,and the relative intensity of the IR peak at 2926 cm^(-1)decreased exponentially with increasing irradiation time.The solid-state13 C nuclear magnetic resonance(NMR)spectra of the SMEP before and after 1 Me V electron irradiation at a dose of 1970 k Gy and a dose rate of 78.8 Gy s^(-1) indicated damage to the CH_(2)–N groups and aliphatic isopropanol segment.This result is consistent with the detection of nitrogenous free radicals,a phenoxy-type free radical,and several types of pyrolytic carbon radicals by EPR.During the subsequent propagation process,the free radicals produced at lower dose rates were more likely to react with oxygen,which was present at higher concentrations,and form the more destructive peroxy free radicals and oxidation products such as acids,amides,and ketones.The increase in peroxy free radicals at lower dose rates was thought to accelerate the degradation of the macroscopic performance of the SMEP.
基金This work was supported by the National Key Research and Development Program of China[2017YFC0307604].
文摘The epoxy shape memory polymer(SMP)with adjustable phase transition temperature is a kind of high-performance shape mem-ory polymer,which can change its phase transition temperature and improve its mechanical properties through the process of photo curing.An epoxy SMP constitutive model combining phase transition and viscoelasticity is established by discretizing the epoxy SMP into several glass phase units and rubbery phase units in this paper.The model includes the viscoelastic constitutive equa-tions of glass phase units and rubber phase units,the parameter expression during shape memory process,and material parameter equation during photocuring process.And the stress relaxation behavior of epoxy SMP at different temperatures and the change of material parameters during the photo-curing process are simu-lated numerically,and the simulation results perform consistency with the experimental data.The model can not only relate shape memory effect and phase transformation in physics but also better characterize the viscoelastic properties of SMP and predict the shape memory response of SMP.
