Use of poly(methyl methacrylate) in radioactive waste management: I. Radiation stability and degradation

In this study, in order to understand the possible use of PMMA in radioactive waste management as a solidifying agent, radiation stability of the PMMA was studied by gamma irradiations at two different dose rates of 1485 and 82.8 Gy/h. The total dose of irradiation was up to 523 kGy. Degradation nature was tested by studying the changes in mechanical and thermal properties with rate and total dose of irradiation. Ultimate tensile strength and toughness first increased and then decreased with total irradiation dose. Half value dose (HVD) for elongation was 148 kGy and it was 178 kGy for tensile strength at the dose rate of 1485 Gy/h. Half value dose was found from the extrapolation of experimental data as 228 kGy for elongation and 205 kGy for tensile strength at the dose rate of 82.8 Gy/h. The FTIR spectral analysis showed depolymerization degradation of polymer with irradiation. It was concluded from experimental results that PMMA can be used for embedding radioactive wastes.     

氟橡胶F2311辐射降解气体产物研究

氟橡胶F2311在真空、氮气、空气3种气氛条件下经50kGy以上剂量的γ射线辐照发生了降解反应,辐射降解产生的气体用GC－MS分析,气体水溶液用离子选择性电极、原子吸收光谱等方法进行了测试。结果表明,H2（在空气气氛中除外）、HF、HCl、CO2的量随剂量的增加而增大;氮气的存在对F2311的辐射降解反应具有一定的抑制作用;在空气气氛中剂量达到500kGy时产生H2的量为最大,剂量再增加时逐渐减小,测定了3种气氛中辐射降解气体的G值及总分解率。     

Development of function-graded proton exchange membrane for PEFC using heavy ion beam irradiation

The graded energy deposition of heavy ion beam irradiation to polymeric materials was utilized to synthesize a novel proton exchange membrane (PEM) with the graded density of sulfonic acid groups toward the thickness direction. Stacked Poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) films were irradiated by Xe⁵⁴⁺ ion beam with the energy of 6 MeV/u under a vacuum condition. The induced trapped radicals by the irradiation were measured by electron spin resonance (ESR) spectroscopy. Irradiated films were grafted with styrene monomer and then sulfonated. X-ray photo-electron spectroscopy (XPS) spectra showed that the densities of sulfonic acid groups were controlled for injection “Surface” and transmit “Back” sides of the fabricated PEM. The membrane electrode assembly (MEA) fabricated by the function-graded PEM showed improved fuel cell performance in terms of voltage stability. It was expected that the function-graded PEM could control the graded concentration of sulfonic acid groups in PEM.     

Radiation synthesis and characteristics of PTFE-g-PSSA ion exchange membrane applied in vanadium redox battery

Radiation-induced grafting of styrene onto polytetrafluoroethylene （PTFE） membranes was studied by a simultaneous irradiation technique. Grafting was carded out using γ-radiation from a ^60Co source at room temperature. Effects of absorbed dose, atmosphere, dose rate, and the concentration of initial monomer on the degree of grafting （DOG） were investigated and the most appropriate grafting condition was obtained. Subsequently, sulphonation of the grafted PTFE membrane （PTFE-g-PS） was carded out and a series of ion exchange membranes （PTFE-g-PSSA） was prepared. Further characterizations of FTIR, TGA, and SEM testified that grafting and sulphonation of the membranes were successfully processed; moreover, grafting of styrene not only occurred in the surface of PTFE membrane, but also in the micropores of the membrane. Ion exchange capacity （IEC） and conductivity were found increase with the grafting yield. The results suggest that at a low dose, such as 17 kGy, the ion exchange membrane （IEM） which will be suitable for vanadium redox battery （VRB） use can be obtained.     

PVA/PEO/Chitosan水凝胶膜的辐照法制备及其性能研究

研究了辐照剂量和壳聚糖含量对水凝胶膜性能的影响。以聚乙烯醇(PVA)、聚氧化乙烯(PEO)和壳聚糖(Chitosan)为原料,采用γ射线辐照法制备了一种新型水凝胶膜。结果表明,随着辐照剂量的增大,凝胶分数会增大,溶胀率会降低;辐照剂量达到21kGy时,凝胶分数可以达到70%,辐照剂量大于21kGy以后,拉伸强度和断裂伸长率会随着辐照剂量的增大而降低;随着壳聚糖含量的增加,水凝胶膜的凝胶分数、拉伸强度和断裂伸长率都会减小,而溶胀率会有一定的提高。辐照后壳聚糖的一些特殊官能团没有改变,将会保持它的抑菌性能,从而获得了一种新型水凝胶膜。     

Gamma-ray irradiation impact of humic substances on apparent formation constants with Cu(II)

Aqueous solution samples of humic acid and fulvic acid were irradiated with gamma-rays in the dose range of 0–500 kGy at two dose rates, 0.1 and 1 kGy/h. The brownish solutions discolored with 500 kGy irradiation indicating degradation by radiolysis, and the index of degree of humification (as the absorbance ratio at 400 nm and 600 nm) was studied using UV-Visible spectroscopy. Apparent formation constants of Cu(II) with humic substances (HSs) in 0.1 M NaClO₄ were determined at 298 K by potentiometric titration using Cu ion selective electrode (ISE), and the effect of gamma irradiation on the constants is herein discussed. To calculate formation constants, the acid dissociation constants of HSs were also measured by potentiometric titration and used as the degree of dissociation. Though the concentration of carboxylic groups decreased drastically with high radiation exposure, no significant change in apparent formation constants was found.     

辐射法制备含氟磺酸型质子交换膜

含氟磺酸型质子交换膜是一类具有高热稳定性、化学稳定性及良好机械性能的离子交换膜，具有极其广阔的应用前景。采用辐射法制备了一种含氟磺酸型质子交换膜，分别测试了该膜的抗拉强度、面电阻、吸碱率等物理化学性能，通过扫描电镜观察了其表面形貌并对其在质子交换膜燃料电池中的应用进行了初步研究。     

Properties of alkali-activated slag-fly ash-metakaolin hydroceramics for immobilizing of simulated sodium-bearing waste

This work is a continuation of previous study of the alkali-activated slag-fly ash-metakaolin hydroceramics (ASFMH) waste form which was designed for solidifying simulated sodium-bearing waste (S-SBW). The thermal stability, resistances to gamma irradiation, freeze–thaw, and water immersion of ASFMH waste form were investigated systematically. The thermal stability results showed that the physical appearance of ASFMH waste forms was intact and without external cracking after calcination at 300, 500, 800 and 1000 °C. Importantly, the main crystalline phase of ASFMH waste form is still analcime after being calcined at 500 °C. The irradiation results indicated that the strong gamma irradiation could not induce the lattice damage of crystalline phases. The durability tests suggested that the compressive strength loss of ASFMH waste forms was 5.07, 19.04 and 10.51% after 500 kGy doses of gamma irradiation, 5 freeze–thaw cycles and 90 days of water immersion, respectively. It is suggested that ASFMH waste form designed for immobilizing S-SBW shows superior basic properties.     

60Co γ射线辐照剂量对明胶特性和结构的影响

本文以0～60 kGy ⁶⁰Co γ射线辐照的明胶为对象,研究了辐照剂量与明胶的黏度、胶凝特性、力学性能、蛋白组分、分子质量的关系。结果表明：明胶的特性黏度、相对黏度、凝胶强度、断裂伸长率、分子质量与剂量呈良好的负相关;明胶的γ、β、α链含量随剂量的增加而减少,大分子链的降解伴随着小分子多肽链混合物的增加,相对分子质量分布逐渐加宽;明胶膜的断裂强度升高而断裂伸长率下降;辐照后明胶表面结构致密而平滑。在有限水和无限氧气存在条件下,辐照明胶以降解为主,同时伴随着少量的交联,剂量越大,反应程度越高。     

全钢载重子午线轮胎过渡层的辐射预硫化及组胎后性能研究

以天然橡胶为基材作为全钢载重子午线轮胎的过渡层,在0 60 kGy吸收剂量范围内,采用电子束辐照技术对其进行辐射预硫化研究,结果表明,过渡层的格林强度随吸收剂量增加,吸收剂量60 kGy时,胶料的格林强度增幅可达300%;低吸收剂量时,胶料的粘度增加较快,之后吸收剂量虽有增加,但粘度变化不大;辐射预硫化与未辐射预硫化的过渡层相比,热硫化后的力学性能相差不大;过渡层减薄1 mm后,单胎质量平均减少1.5 kg而不影响轮胎的主要性能。     

Radiolytic preparation of poly(styrene sulfonic acid) - grafted poly(tetrafluoroethylene-co-perfluorovinyl vinyl ether) membranes with highly cross-linked networks

In this study, various amounts of a divinylbenzene (DVB) cross-linking agent (5∼30%) were introduced during a simultaneous irradiation grafting of styrene onto a PFA film of a 25 μm thickness in order to prepare a series of poly(styrene sulfonic acid)-grafted poly(tetrafluoroethylene-co-perfluorovinyl vinyl ether) (PFA) membranes with various degrees of cross-linking and grafting (29∼74%). The effects of the DVB cross-linking agent on the properties of the prepared membranes, such as water uptake, proton conductivity, methanol permeability, and chemical stability, were also investigated in this study. The results indicated that the ion exchange capacity (IEC) slightly decreased with increasing DVB content, whereas the water uptake, proton conductivity, and methanol permeability of the membrane greatly decreased. The chemical stability of the prepared membranes was found to be significantly improved with increasing DVB content. The results indicated that the cross-linked network membranes are promising for application in a direct methanol fuel cell.     

PVA/PVP/ws-chitosan水凝胶伤口敷料的辐射制备及性能表征

采用γ射线辐射法制备了聚乙烯醇(PVA)/聚乙烯基吡咯烷酮(PVP)脉溶性壳聚糖(ws-chitosan)共混水凝胶.研究了辐射剂量、ws-chitosan含量及增塑剂(聚乙二醇(PEG)或甘油)对水凝胶性能的影响.实验发现,随着辐射剂量的增大,凝胶分数增大,并在剂量大于27 kGy时达到饱和;ws-chitosan含量增大及加入增塑剂PEG或甘油后,水凝胶的凝胶分数和强度都会减小,而相应的溶胀度会显著增大.通过高级流变仪(ARES)对水凝胶弹性模量的测试显示,随吸收剂量的增加,凝胶强度会相应增大,但在27 kGy以上出现饱和.     

^60Coγ射线辐照降解吡虫啉稀水溶液

采用^60Coγ射线辐照降解吡虫啉稀水溶液,并对辐照前后的水样进行高效液相色谱（HPLC）、离子色谱（IC）和高效液相色谱-质谱联用（HPLC—MS）等检测。实验结果表明,吡虫啉的降解率随吸收剂量的增大而不断增大,当吸收剂量为1．56kGy时,降解率达到100％;吡虫啉的辐照降解产物包括Cl^-1、NO2、NO3-和NH4^＋四种无机产物,2-chloro-5-imidazol-1-ylmethyl-pyridine、1-（6-chloro-pyridin-3-ylmethyl）-1,3-dihydro—imidazol-2-ylideneamine、单羟基化吡虫啉和双羟基化吡虫啉4种有机产物。强氧化性的·OH容易进攻吡虫啉分子中的C=N键、N-N键、C—Cl键以及亚甲基中的C—H键。     

辐射技术制备聚丙烯酸/高岭石吸水凝胶

Superabsorbent polyacrylic acid/montmorillonite composite (SAPC) with high water absorption capacity prepared using 9 MeV electron beam irradiation is presented in this paper, which is different from others in material composition and preparation method.     

辐射技术在淀粉改性中的应用

为实现产业化生产辐射改性淀粉，以玉米淀粉为原料，对采用⁶⁰Co辐照制备辐射改性淀粉的机制和工艺进行了研究和探讨，并检测了改性后淀粉浆料的理化性能。结果表明，采用辐射剂量4～10 kGy对玉米淀粉进行辐照，可使淀粉粘度下降到5～14 mPa·s，同时其浆料性能指标也完全可满足纺织应用要求。相对于化学法制备改性淀粉，辐射法具有工艺简单、操作方便、改性程度稳定、易于控制等优点，在纺织、食品、造纸等行业将有广泛的应用前景。     

Development of sulfonated FEP-Nafion hybrid proton exchange membranes for PEFC

The performance of polymer electrolyte fuel cell (PEFC) is affected by an interfacial property between a proton exchange membrane (PEM) and electrodes. Thus, to develop a well-laminated membrane electrode assembly (MEA), a hybrid PEM (FN) was fabricated by mixing a radiation grafted membrane (sulfonated FEP) with ionomer (Nafion^® dispersion) which is applied to coat the interface of the PEM and electrodes.The obtained FN, sulfonated FEP and Nafion^®112 were characterized in terms of water uptake, ion exchange capacity (IEC), polarization performance and electrochemical impedance. FN showed high IEC and water uptake, which would induce the highest ionic conductivity (IC) among tested PEMs. In terms of FN, the interface between the PEM and electrodes should have been improved because FN showed the lowest charge transfer resistance than other tested PEMs. The high IC and improved interface between the PEM and electrodes resulted in the best cell performance of FN in tested PEMs.     

过氟化聚合物的苯乙烯接枝研究--辐照条件与反应条件的影响

Fuel cell is in focus as a very low exhaust new dynamo system. Especially polymer electrolyte fuel cells (PEFC) using proton exchange membranes (PEM) have attracted much attention for the electrical vehicle and other mobile applications such as cellar phone and personal computer. Conventional perfluoro-sulfonic acid membranes such as Nation() (DuPont de Nemours LTD.) have been the popular PEM used in PFEC. However, there are still several problems such as insufficient gas barrier properties, low thermal resistance, and their high costs.In this study, hawse have studied the partially fluorinated PEM for PEFC by radiation grafting onto per-fluorinated polymers such as PFA, FEP and ETFE with reactive styrene monomers using pre-irradiation grafting method in gas and in liquid phase, respectively, and successive sulfonation. Characteristic properties of the grafted and sulfonated materials have been discussed and optimized fabricating conditions were determined.Characteristic properties of the obtained materials have been measured by differential scanning calorimetry,thermogravimetric analysis and FT-IR spectroscopy, etc.In the case of irradiation in air, glass transition temperatures (Tg) of the grafted materials depend on the yields of styrene grafting onto the materials. That is higher yields of grafting give lower thermal stability. On the other hand, when the peroxy radicals were converted trapped radicals by exposure in air after irradiation under oxygen-free atmosphere, Tg of the grafted materials hardly depends on the grafting yields.Moreover, the yields of grafting in gas phase were higher than that of liquid phase. However, the sample form of grafting in gas phase has been greatly changed, whereas the sample form of grafting in liquid phase has kept its original feature.Therefore, it is suggested that the fabricating conditions for PEFC membranes were preferred to irradiation under oxygen-free atmosphere and grafting in liquid phase.Ion exchange capacities of the sulfonated-materials could be 3.0meq/g. Other properties of the obtained membranes such as chemical structure were also discussed.     

Studies on mechanical, thermal and morphological properties of irradiated recycled polyamide and waste rubber powder blends

The aim of this article was to show the effect of gamma irradiation on mechanical and thermal properties of recycled polyamide (rPA) copolymer blended with different content of waste rubber powder (WRP). In order to study the structural modifications of prepared blends have been subjected to irradiation doses up to 200 kGy were applied to all samples. Non-irradiated blends were used as control samples. Mechanical properties, namely, tensile strength (TS), elastic modulus, elongation at break and hardness have been followed up as a function of irradiation dose and degree of loading with rubber content. Furthermore, the influence of radiation dose in the thermal parameters, melting temperature, heat of fusion, ΔH_f of the recycled PA and its blend with waste rubber powder (WRP) was also investigated.     

Effect of absorbed dose and storage length on electron paramagnetic resonance （EPR） signal strength in irradiated alfalfa seeds

1 Introduction Human salmonellosis associated with the con- sumption of alfalfa seed sprouts has been documented in several countries and people have applied several techniques to kill microorganisms in the alfalfa seeds[1]. Gamma irradiation can effectively kill the microorganisms in the seeds over a certain range of absorbed dose[2]. As a prerequisite, a suitable detection method for distinguishing whether or not a kind of food has been irradiated lies not only in whether some differences be…     

Electron-beam radiation effects on the structure and properties of polypropylene at low dose rates

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.