While the high-energy radiation effects on polypropylene, which are crucial for the cable industry for nuclear power plants, have been thoroughly studied, the property changes of PP at low-dose-rate electron-beam irra...While the high-energy radiation effects on polypropylene, which are crucial for the cable industry for nuclear power plants, have been thoroughly studied, the property changes of PP at low-dose-rate electron-beam irradiation are far from elucidated. Herein, the influence of electron-beam irradiation on the structure and properties of PP was examined. The static EB irradiation conditions were 1.2 MeV at a low dose rate of 20 kGy/h to achieve absorbed doses ranging from 45, to 60, 100, and 200 kGy.The molecular structure was first evaluated by measuring the carboxyl index and the relative radical concentrations via Fourier transform infrared spectroscopy and electron spin resonance, respectively. Mechanical, differential scanning colorimetric, and rheological tests were carried out to further investigate the changes in the properties(tensile, crystalizing, and viscoelastic properties) of irradiated PP, which showed good agreement with the structural analysis results. We found that radio-oxidative degradation(chain scission) was predominant, which can be due to the low dose rate facilitating oxygen diffusion into the PP matrix during electron-beam irradiation.展开更多
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
As an innovative manufacture technology,there has been a considerable development about the electron beam (EB) curing advanced composites in recent years.Epoxy resin,which has a lot of excellent properties and differe...As an innovative manufacture technology,there has been a considerable development about the electron beam (EB) curing advanced composites in recent years.Epoxy resin,which has a lot of excellent properties and different molecular structure,is widely used as polymer matrix in composites.Most variety of epoxy resin has been confirmed to possess radiation reactivity and have already become a chief resin matrix used in EB curable composites.The radiation curing feature of bisphenol A epoxy resin was studied in this paper.Firstly,the technique of chemical extraction was used to test the curing degree of epoxy resin and the relationship between radiation dosage and curing degree was analyzed.The experimental data indicate the resin curing degree is increased with the rising of radiation dosage.But after the radiation dosage reached 100?kGy,the increasing extent became very small.The penetration process of electron beam in radiated resin and the structure of cured resin were studied.By analyzing radiation curing area of epoxy resin,it can be seen that EB exhibits intensively scattering in resin system.Around the radiation direction,the curing reaction can be initiated,and the penetration depth of EB will get to a fixed value on account of the gradual attenuation of electron energy.The results of observing the cured areas indicate that EB curing reaction spreads outwards layer upon layer around an active center when EB radiates the epoxy resin.The whole cured area is consisting of many lamellar structures.展开更多
基金supported by the "Strategic Priority Research Program" of the Chinese Academy of Science(No.XDA02040300)the National Natural Science Foundation of China(No.11575277)
文摘While the high-energy radiation effects on polypropylene, which are crucial for the cable industry for nuclear power plants, have been thoroughly studied, the property changes of PP at low-dose-rate electron-beam irradiation are far from elucidated. Herein, the influence of electron-beam irradiation on the structure and properties of PP was examined. The static EB irradiation conditions were 1.2 MeV at a low dose rate of 20 kGy/h to achieve absorbed doses ranging from 45, to 60, 100, and 200 kGy.The molecular structure was first evaluated by measuring the carboxyl index and the relative radical concentrations via Fourier transform infrared spectroscopy and electron spin resonance, respectively. Mechanical, differential scanning colorimetric, and rheological tests were carried out to further investigate the changes in the properties(tensile, crystalizing, and viscoelastic properties) of irradiated PP, which showed good agreement with the structural analysis results. We found that radio-oxidative degradation(chain scission) was predominant, which can be due to the low dose rate facilitating oxygen diffusion into the PP matrix during electron-beam irradiation.
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.
文摘As an innovative manufacture technology,there has been a considerable development about the electron beam (EB) curing advanced composites in recent years.Epoxy resin,which has a lot of excellent properties and different molecular structure,is widely used as polymer matrix in composites.Most variety of epoxy resin has been confirmed to possess radiation reactivity and have already become a chief resin matrix used in EB curable composites.The radiation curing feature of bisphenol A epoxy resin was studied in this paper.Firstly,the technique of chemical extraction was used to test the curing degree of epoxy resin and the relationship between radiation dosage and curing degree was analyzed.The experimental data indicate the resin curing degree is increased with the rising of radiation dosage.But after the radiation dosage reached 100?kGy,the increasing extent became very small.The penetration process of electron beam in radiated resin and the structure of cured resin were studied.By analyzing radiation curing area of epoxy resin,it can be seen that EB exhibits intensively scattering in resin system.Around the radiation direction,the curing reaction can be initiated,and the penetration depth of EB will get to a fixed value on account of the gradual attenuation of electron energy.The results of observing the cured areas indicate that EB curing reaction spreads outwards layer upon layer around an active center when EB radiates the epoxy resin.The whole cured area is consisting of many lamellar structures.
