分类: 核科学技术 >> 核材料与工艺技术 提交时间: 2023-06-18 合作期刊: 《Nuclear Science and Techniques》
摘要: As a potential matrix of three-dimensional gel dosimeter, agarose hydrogels will be used for measuring radiation doses, hence the importance of studying their radiation resistance and radiolysis mechanism. Physical property and chemical structure of physically cross-linked agarose hydrogel samples irradiated to 0200 kGy by 60Co -rays were analyzed by universal testing machine, gel permeation chromatography, fourier transform infrared spectrometer, ultraviolet visible spectroscopy, nuclear magnetic resonance, and gas chromatography. The results showed that agarose hydrogels had good radiation stability below 25 kGy, and the maximum compression strength of sample was ca. 0.1 MPa at 25 kGy. The irradiated samples degraded obviously and liquefied gradually with increasing doses. Compared with unirradiated sample, carbonyl groups, which generated from the molecular chains of agarose hydrogels, were observed at 25 kGy and increased gradually with dose. The main gas products evolved from irradiated agarose hydrogels were H2, CO2, CO and CH4. Based on the analysis of radiolytic products, the radiolysis mechanism of agarose hydrogels under -radiation was proposed.
分类: 核科学技术 >> 核材料与工艺技术 提交时间: 2023-06-18 合作期刊: 《Nuclear Science and Techniques》
摘要: The trace water-soluble radiolytic products of neat 1-butyl-3-methylimidazolium hexafluorophosphate ([C4mim][PF6]) were identified by analysing water-washed samples of -irradiated ionic liquids. HF and difluorophosphinic acid were confirmed as the main radiolytic products of [C4mim][PF6], and their radiation chemical yields were quantified by 19F NMR (G(F-) = 0.14 mol/J, G(HOP(O)F2) = 0.053 mol/J). Compared to [C4mim][NTf2], [C4mim][PF6] shows better radiation stability.
分类: 核科学技术 >> 核材料与工艺技术 提交时间: 2023-06-18 合作期刊: 《Nuclear Science and Techniques》
摘要: The water-soluble radiolytic products of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ionic liquid ([C2mim][NTf2]) under -radiation, such as CF3SOOH, CF3SO2NH2, HF, and H2SO3, were identified by using 1H NMR, 19F NMR, and ion chromatography. The extraction behavior of Dy3+ using irradiated [C2mim][NTf2] in combination with 2,6-di(5,6-diisobutyl-1,2,4-triazin-3-yl)pyridine (isobutyl-BTP) was studied and the abnormal increase of Dy3+ partitioning after irradiation is mainly attributed to the precipitation formed between Dy3+ and radiolytic products of [C2mim][NTf2] (F- and SO32-). Washing irradiated [C2mim][NTf2] with water provides a simple method for ionic liquid recycling.
分类: 化学 >> 核化学 提交时间: 2023-06-06
摘要: N,N,N,N-Tetraoctyl diglycolamide (TODGA) is one of the most promising extractants tailored for high-level liquid radioactive waste treatment during nuclear fuel reprocessing. The -radiolysis of TODGA (0.2 mol/L) in n-dodecane (nDD) solution with and without pre-equilibrated 3.0 mol/L HNO3 was investigated using HPLC and UPLC-QTOF-MS and compared with the -radiolysis of neat TODGA in this study. With increased absorbed doses, the concentration of TODGA decreased exponentially for the studied systems. Moreover, pre-equilibration with HNO3 (3.0 mol/L) slightly influenced the -radiolysis of TODGA in nDD. Seven radiolytic products generated from the rupture of the C C, C O, and C N bonds in TODGA were identified in the studied extraction system. The influence of -radiation on TODGA/nDD for the extraction of Eu(III) was evaluated using the first combination of extraction experiments and density functional theory (DFT) calculations, in which the complexations of Eu(III) with TODGA and its radiolytic products were systematically compared. Based on the radiolysis kinetic model of TODGA, the slope curve of the distribution ratio of Eu(III) (DEu ) and the absorbed dose, and fluorescence titration analysis, the empirical equation of the absorbed dose and DEu was obtained successfully. Below 300 kGy, the experimental DEu agreed well with the obtained empirical equation for TODGA/nDD. Conversely, at a high absorbed dose, the experimental DEu was higher than the theoretical DEu based on the empirical equation because the radiolytic products of TODGA with similar coordination structures still possessed partial complexation toward Eu(III), which was confirmed by DFT calculations. This work provides a method to predict the extraction distribution ratio of an irradiated extractant system and to understand the complex extraction process.