用于氙氪吸附分离的金属-有机骨架材料耐辐照性能的初步研究

由于乏燃料后处理废气中放射性氙（Xenon,Xe）和氪（Krypton,Kr）的去除需求以及高纯度Xe气体的商业价值,Xe和Kr的吸附分离越来越受到重视。目前Xe/Kr的分离主要采用能源和资本密集型的低温精馏法。以金属-有机骨架材料为吸附剂的多孔材料已经展示出在相对较高温度下选择性吸附Xe和Kr的能力,有望替代低温精馏法实现低成本的Xe/Kr分离。实验研究了三种热稳定性良好的金属-有机骨架材料(Co/DOBDC、Ni/DOBDC、Co₃（HCOO）₆)对Xe和Kr的吸附分离性能。从材料在273 K温度下对Xe和Kr的吸附等温线、亨利常数、亨利选择性和理想吸附溶液理论（Ideal Adsorbed Solution Theory,IAST）选择性等测试和计算结果来看,Co/DOBDC和Ni/DOBDC在常压下对Xe具有较大的吸附容量,适用于Xe吸附存储的应用场景;Co₃（HCOO）₆在低压吸附下具有大的Xe亨利常数、Xe/Kr亨利选择性和Xe/Kr IAST选择性,适用于Xe和Kr吸附分离的应用场景。...     

功能化石墨烯吸附模拟反应堆冷却剂中银的研究

设计合成了四氧化三铁/石墨烯/聚乙烯亚胺复合材料（PMRGO）,通过红外光谱、透射电镜、拉曼光谱和XPS等手段表征了PMRGO的化学组成和结构,并研究了该材料在模拟压水堆冷却剂环境下对银离子和银胶体的吸附性能。结果表明,PMRGO在模拟冷却剂条件下对银有良好的吸附性能,对银的吸附在pH=3~8范围内随pH值的升高而增大。随着银初始浓度的增大,PMRGO对银的吸附率逐渐升高。当银初始浓度为5 mg/L时,PMRGO对银离子吸附24 h后基本达到平衡,吸附量可达136 mg/g;对银胶体吸附30 min后基本达到平衡,吸附量可达169 mg/g。吸附等温线符合Langmuir方程,吸附动力学可用准二级动力学方程来描述。     

载银丝光沸石和载银氧化铝对气态碘的吸附研究

针对核设施产生的高湿度、高氮氧化物含碘气体设计一套动态吸附装置，制备了用于吸附气态碘的载银丝光沸石和载银氧化铝，通过改变吸附剂载银量及碘蒸汽的浓度，研究载银丝光沸石和载银氧化铝对气态碘的吸附性能。实验结果表明:实验温度为30℃，相对湿度为100%，NO₂体积含量为0.1%条件下，载银量15.2%的丝光沸石对碘的饱和吸附容量为178.4 mg/g，载银丝光沸石对气态碘的吸附效果优于载银氧化铝；载银丝光沸石和载银氧化铝对气态碘的吸附是一个以化学吸附为主又包括物理吸附的复杂过程。关键词:载银丝光沸石；载银氧化铝；气态碘；动态吸附      

功能化石墨烯吸附模拟反应堆冷却剂中银的研究

设计合成了四氧化三铁/石墨烯/聚乙烯亚胺复合材料(PMRGO),通过红外光谱、透射电镜、拉曼光谱和XPS等手段表征了PMRGO的化学组成和结构,并研究了该材料在模拟压水堆冷却剂环境下对银离子和银胶体的吸附性能。结果表明,PMRGO在模拟冷却剂条件下对银有良好的吸附性能,对银的吸附在pH=3～8范围内随pH值的升高而增大。随着银初始浓度的增大,PMRGO对银的吸附率逐渐升高。当银初始浓度为5 mg/L时,PMRGO对银离子吸附24 h后基本达到平衡,吸附量可达136 mg/g;对银胶体吸附30 min后基本达到平衡,吸附量可达169 mg/g。吸附等温线符合Langmuir方程,吸附动力学可用准二级动力学方程来描述。     

碳分子筛上氪、氙的动态吸附及脱附性能

为筛选快速分离Kr/Xe的材料,研究了不同碳分子筛(CMS)对氙(Xe)和氪(Kr)的动态吸附性能与脱附性能,探讨了压力、气体流量、温度等因素对Kr、Xe的动态吸附系数与脱附率的影响。结果表明,碳分子筛Aladdin TDX-01对Xe的吸附容量最大,其次为光复TDX-01,低温时,Aladdin TDX-01对Kr的动态吸附系数大于光复TDX-01。Aladdin TDX-01碳分子筛对Kr和Xe的吸附能力均随压力升高而增强,随着原料气流量增加而减少,动态吸附系数随着温度升高而降低;采用N₂吹扫对Kr、Xe进行脱附,随着N₂流量增大、温度升高,Kr、Xe的脱附时间缩短。Aladdin TDX-01碳分子筛在25℃、100 kPa条件下对Xe的动态穿透吸附系数为1 283 mL/g,在-50℃、100 kPa条件下对Kr的动态穿透吸附系数为474 mL/g。     

模拟吸附放射性同位素137Cs和90Sr的Cd-MOFs材料合成及评价

为吸附后处理产生的高放废液玻璃固化过程中大量的放射性同位素⁹⁰Sr和¹³⁷Cs,采用溶剂热法合成阴离子型金属有机骨架［DMA］2［Cd₃(FDC)₄］·2H₂O,并评价其对锶、铯离子的吸附能力。采用粉末X-射线衍射、傅里叶红外和热重等方法确认Cd-MOFs的结构。扫描电子显微镜结果显示,在吸附Cs和Sr元素后,Cd-MOFs形貌没有发生明显变化。同时荧光发射光谱证实,Cd-MOFs吸附铕离子后,能够很好敏化铕离子,使材料发射出红色荧光。对锶、铯离子吸附实验结果显示,对锶、铯离子在前50 min即可完成超过50%的吸附,对铯离子的最大吸附量为63.94 mg/g,对锶离子的最大吸附量为53.06 mg/g。通过吸附动力学研究发现,Cd-MOFs对Cs和Sr离子的吸附均符合准二级动力学模型,证明对Cs和Sr离子的速率决策步为化学吸附。推测水合离子半径、有机骨架螺旋链间螺距等因素均对吸附效果有影响。     

UiO-66-(COOH)2的合成及其对锂同位素吸附分离性能研究

为研究金属有机骨架材料对⁷Li的吸附分离性能,本研以水作为溶剂,四氯化锆和均苯四甲酸为起始原料,采用水热法合成金属有机骨架材料UiO-66-(COOH)₂,对合成材料的形貌、孔径、热稳定性等进行表征与分析;通过静态吸附实验探讨吸附时间、反应温度、溶液浓度对UiO-66-(COOH)₂锂离子吸附性能及同位素分离因子的影响;并对Li⁺浓度、⁶Li/⁷Li同位素丰度进行测定。结果表明,UiO-66-(COOH)₂可实现对锂的吸附以及⁷Li的分离,且在293 K Li₂CO₃溶液中,每0.05 g UiO-66-(COOH)₂对10 mL 0.05 mol/L Li₂CO₃进行4 h的静态吸附,最大吸附量Q为9.53 mg/g,分离因子S（⁷Li/⁶Li）为1.019 54。研究结果为⁷Li的分离提供了新途径。     

β-环糊精改性介孔二氧化硅材料对U（Ⅵ）的去除机制

以三乙氧基(3-异氰酸丙基)硅为交联剂,通过后接枝法合成了β-环糊精改性介孔二氧化硅（SBA-15-CD）材料。通过静态吸附试验研究了溶液pH值、SBA-15-CD投加量、吸附时间、温度等因素对SBA-15-CD吸附U(Ⅵ)的影响。通过扫描电镜（SEM）、X射线粉末衍射（XRD）、BET比表面分析、傅里叶红外光谱（FT-IR）和X射线光电子能谱（XPS）对材料进行表征分析,并探讨了SBA-15-CD吸附U(Ⅵ)的机制。结果表明,当U(Ⅵ)初始浓度为5 mg/L、温度为30 ℃时,SBA-15-CD吸附U(Ⅵ)的最佳条件为:pH=5、SBA-15-CD投加量0.20 g/L、吸附平衡时间30 min,在此条件下,平衡吸附量为24.4 mg/g,U(Ⅵ)去除率为98.3%。吸附过程符合准二级动力学模型和Langmuir等温模型,即以化学吸附为主,且主要是通过表面的羟基、酯基和氨基与U(Ⅵ)配位。30 ℃下SBA-15-CD的饱和吸附量达330 mg/g,升高温度有利于吸附的进行。SBA-15-CD具有良好的重复使用性能。     

稀有气体原子与Pu（100）表面相互作用的第一性原理研究

采用第一性原理研究了稀有气体原子在Pu（100）表面上的吸附。计算结果表明：除He原子外,其他稀有气体原子在桥位处的吸附能均为最大;稀有气体原子在Pu（100）表面吸附后,稀有气体原子失去电荷,而Pu原子得到电荷,稀有气体原子中Xe原子的电荷转移数最大。差分电荷密度的计算结果表明,对位于Pu（100）表面穴位和桥位处的Xe原子,可观察到较明显的电荷再分布现象,这表明Xe原子具有一定极化效应,能与Pu（100）表面发生相互作用,从He到Xe,原子的极化效应越来越明显。     

壳聚糖-生物炭复合材料对U(Ⅵ)的吸附性能试验研究

以壳聚糖（CTS）和生物炭（AC）为原料,采用原位沉淀法制备了壳聚糖-生物炭（CTS-AC）复合材料,研究了吸附时间、铀初始浓度、初始pH值、温度和干扰离子等因素对CTS-AC吸附U(Ⅵ)的影响,探讨了CTS-AC对U(Ⅵ)的吸附动力学、等温线,采用傅里叶红外光谱（FT-IR）、X射线衍射（XRD）、扫描电镜（SEM-EDS）及比表面积分析（BET）等手段进行了相关机理分析。实验结果表明,CTS-AC吸附U(Ⅵ)的最佳条件为：pH=4、CTS-AC投加量0.8～1 g/L、吸附时间240 min,在此条件下,最大吸附率可达94.85%。CTS-AC对U(Ⅵ)的吸附等温线模型符合Langmuir模型,U(Ⅵ)的吸附动力学符合准二级模型;高浓度Cu²⁺对CTS-AC吸附U(Ⅵ)的抑制作用明显;FT-IR、XRD和EDS结果表明,CTS的负载未改变AC的原结构,仅增大了其孔径、增加了结合位点。CTS-AC对U(Ⅵ)的吸附机制为配位作用以及离子交换。     

Transport properties of U0.7Ce0.3O2 − x

We have determined a number of transport properties of $\text{U}{}_{0.7}\text{Ce}{}_{0.3}\text{O}{}_{\mathrm{2-x}}$ at 1273 K for various deviations from stoichiometry and compared them with available results on $\text{(UPu)O}{}_{\mathrm{2\; ?\; x}}$. They are: the electrical conductivity, Seebeck coefficient, effective charge number and chemical diffusion coefficient.A very characteristic behaviour is observed for the electronic properties of $\text{(UCe)O}{}_{\mathrm{2\; ?\; x}}$. A p-type conduction for all the studied deviations from stoichiometry (up to $\text{x = 3 × 10}{}^{\mathrm{?2}}$) is interpreted in terms of a high electronic disorder in the stoichiometric compound. Electronic disorder at stoichiometry is probably less important in $\text{(UPu)O}{}_{\mathrm{2\; ?\; x}}$, which presents a sharp p-n transition at $\text{x = 5 × 10}{}^{\mathrm{?3}}$.Ionic transport properties obtained on $\text{(UCe)O}{}_{\mathrm{2\; ?\; x}}$ indicate an approximate proportionality between the ionic conductivity resulting from oxygen ions transport and the deviation from stoichiometry. Results available on $\text{(UPu)O}{}_{\mathrm{2\; ?\; x}}$ do not appear to be compatible with ours and some arguments are presented which cast doubt on their validity.     

Equi-chemical-potential curves in ternary uranium oxides MyU1−yO2+x

Using Schuhmann's method the chemical potentials of three components in nonstoichiometric ternary uranium oxides $\text{M}{}_{\mathrm{y}}\text{U}{}_{\mathrm{1?y}}\text{O}{}_{\mathrm{2+x}}$(M = Mg and Pu) have been calculated. The obtained results are shown in the form of equi-chemical-potential curves (surface of partial molar free energy) in the composition triangle. In the hypostoichiometric region the contour lines of the surface are dense and run parallel with each other. Taking account of this fact the difficulty in attainment of homogeneity in the fabrication of mixed oxide fuel is discussed.     

Structural characterization of Nd-doped Hf-zirconolite Ca1−xNdxHfTi2−xAlxO7 ceramics

Because of its high incorporation capacity and of the high thermal neutron capture cross-section of hafnium, Hf-zirconolite (CaHfTi₂O₇) ceramic can be envisaged as a potential waste form for minor actinides (Np, Am, Cm) and plutonium immobilization. In this work, Nd-doped Hf-zirconolite Ca_1−xNd_xHfTi_2−xAl_xO₇ (x = 0; 0.01 and 0.2) ceramics have been prepared by solid state reaction. Neodymium has been used as trivalent actinide surrogate. The ceramic samples structure has been studied by X-ray diffraction and refined by the Rietveld method. This revealed that Nd³⁺ ions only enter the Ca site, whereas part of Hf⁴⁺ ions substitute titanium into Ti(1) sites and Al³⁺ ions mainly occupy the Ti(2) split sites and Ti(3) sites of the zirconolite structure. Using various spectroscopic techniques (electron spin resonance, optical absorption and fluorescence), the environment of Nd³⁺ cations in Hf-zirconolite has been studied and compared with that of Nd³⁺ cations in Zr-zirconolite (CaZrTi₂O₇). Different local environments of Nd³⁺ cations have been detected in Hf-zirconolite that can be attributed to the existence of an important disorder around Nd in the Ca site probably due to the statistical occupancy of the next nearest cationic site of neodymium (a split Ti site) by Ti⁴⁺, Al³⁺ cations and vacancies. No significant differences were observed concerning Nd³⁺ cations environment and distribution in Hf- and Zr-zirconolite ceramics.     

Phase relation and defect structures of nonstoichiometric U4O9±y and UO2+x at high temperatures

Phase relations in the composition range from $\text{UO}{}_{\mathrm{2+x}}$ to $\text{U}{}_3\text{O}{}_{\mathrm{8?z}}$ were studied by electrical-conductivity measurements and X-ray diffraction in the ranges $\text{1025°C ? T ? 1140°C}$ and . The plot of log σ versus log showed straight lines with distinct slopes, which corresponded to four regions ($\text{UO}{}_{\mathrm{2+x}}$, $\text{U}{}_4\text{O}{}_{\mathrm{9?y}}$, $\text{U}{}_4\text{O}{}_{\mathrm{9+y}}$ and $\text{U}{}_3\text{O}{}_{\mathrm{8?z}}$). The existence of the hyperstoichiometric $\text{U}{}_4\text{O}{}_{\mathrm{9+y}}$ phase was suggested in the temperature range from 1025 to 1126°C. The peritectoid temperature ($\text{U}{}_4\text{O}{}_{\mathrm{9\pm y}}\text{= UO}{}_{\mathrm{2+x}}\text{+ U}{}_3\text{O}{}_{\mathrm{8?z}}$) was estimated to be present between 1126 and 1131°C. The partial free enthalpies and entropies for the two-phase equilibrium ($\text{U}{}_4\text{O}{}_{\mathrm{9+y}}\text{+ U}{}_3\text{O}{}_{\mathrm{8?z}}$, and $\text{U}{}_4\text{O}{}_{\mathrm{9?y}}\text{+ UO}{}_{\mathrm{2+x}}$) were calculated and compared with previous results. From the dependence of the electrical conductivity on the oxygen partial pressure the nonstoichiometric defect structures of $\text{UO}{}_{\mathrm{2+x}}$ and $\text{U}{}_4\text{O}{}_{\mathrm{9\pm y}}$ were interpreted as consisting of doubly charged oxygen interstitials (O_i'') and doubly charged oxygen vacancies (V_O''). At room temperature, the homogeneity range of the U₄O₉ phase was investigated with a Debye-Scherrer camera.     

Neutron production cross sections and energies for the reactions 7Li(p,n)7Be and 7Li(p,n)7Be1

Center-of-mass best values for the normalized Legendre coefficients and the 0° differential cross sections as functions of input energy have been derived from various experimental results for the reactions ⁷Li(p,n)⁷Be and ${}^7\text{Li}\text{(p,n)}{}^7\text{Be}{}^1$ (431 keV). This information has been used to calculate laboratory differential cross sections as functions of the laboratory proton energy and neutron emission angle which are given in tabular form together with the corresponding neutron energies.     

Effects of ion irradiation on the mechanical properties of SiNawOxCyHz sol-gel derived thin films

A study of the effects of ion irradiation of hybrid organic/inorganic modified silicate thin films on their mechanical properties is presented. NaOH catalyzed SiNa_wO_xC_yH_z thin films were synthesized by sol-gel processing from tetraethylorthosilicate (TEOS) and methyltriethoxysilane (MTES) precursors and spin-coated onto Si substrates. After drying at 300 °C, the films were irradiated with 125 keV H⁺ or 250 keV N²⁺ at fluences ranging from 1 × 10¹⁴ to 2.5 × 10¹⁶ ions/cm². Nanoindentation was used to characterize the films. Changes in hardness and reduced elastic modulus were examined as a function of ion fluence and irradiating species. The resulting increases in hardness and reduced elastic modulus are compared to similarly processed acid catalyzed silicate thin films.     

Damage creation in ion irradiated Si1−xGex/Si structures

Strained SiGe/Si structures have been proposed as substrates for fabrication of high speed metal oxide semiconductor transistors. However, influence of strain and/or presence of Ge atoms on damage creation during ion irradiation have not been explored to a significant extent. In this study, Rutherford backscattering spectrometry (RBS) was used to characterize Si_1−xGe_x/Si structures irradiated by 140 keV He⁺ ions at room temperature. When compared with pure Si, strained samples show enhanced damage accumulation as a function of He fluence. Channeling angular scans did not reveal any specific configuration of displacements. Possible mechanisms for enhanced damage in strained Si are discussed.     

Investigations on UAlx-Al dispersion fuels for high-flux reactors

The paper outlines the preparation of $\text{UAl}{}_{\mathrm{x}}\text{-Al}$ dispersion fuel plates for thermal high-flux reactors. The work described includes the preparation of UAl₂, UAl₃ and UAl₄ compounds by induction melting and their processing to Al-clad fuel plates using the picture-frame technique. Induction melting in alumina crucibles and subsequent homogenisation can be used to produce relatively homogeneous $\text{UAl}{}_{\mathrm{x}}$ compounds. After comminution to a predetermined size range and blending with Al, the pressed compacts can be rolled into Al-clad fuel plates. UAl₃ and UAl₂ compounds react with Al forming UAl₄. The reactions begin at about 673 K, and have an activation energy of 52.6 and 42.6 kcal/mol, respectively. The measured properties of the dispersions and UAl-phases such as thermal expansion, thermal and electrical conductivity, tensile strength, microhardness and hot hardness are affected by the concentration of the dispersed phase and can be explained in the light of existing theoretical models. Due to its potential as a high-flux reactor fuel with higher uranium content the preparation and properties of UAl₂-Al dispersions as well as the preliminary data about their stability under irradiation may be of particular interest.     

Statistical thermodynamic study of the ternary compounds ThXyHx (X = C,N;y < 1;x < 2)

The stability and the nature of bonding in hypostoichiometric ThH₂, hcp ThC_0.46H_x and fcc ThN_yH_x (y = 0.486 and 0.692) are studied on the basis of statistical thermodynamics. The discussions are made in terms of the atomic partition function of H in these condensed phases and of the interaction energy terms. It is concluded that the nature of bonding in ThN_yH_x is approximately the same as that in ThH₂. On the other hand, the nature of bonding in ThC_yH_x is found to be significantly different from that in ThH₂.     

Wavelengths and classifications of emission lines due to 2s22pn−2s2pn + 1 and 2s2pn−2pn + 1 transitions, Z ≤ 28

Tables of wavelengths and classifications of observed emission lines due to 2s²2pⁿ?2s2p^{n + 1} and 2s2pⁿ?2p^{n + 1} transitions are presented. The accuracy of data derived from different experimental methods is discussed. Revised and predicted wavelengths are added. Energy levels are derived from the wavelength data.