Application of fission track detection technique for determination of uranium in liquids

A high sensitive (10⁻⁴ ppm) fission track detection technique for determination of uranium in liquids was developed. The technique was applied for the measurement of uranium concentration in extraction phosphoric acid and phosphorus fertilizer, viz., ammophous.     

The discoveries of uranium 237 and symmetric fission - from the archival papers of Nishina and Kimura

Shortly before the Second World War time, Nishina reported on a series of prominent nuclear physical and radiochemical studies in collaboration with Kimura. They artificially produced (231)Th, a member of the natural actinium series of nuclides, by bombarding thorium with fast neutrons. This resulted in the discovery of (237)U, a new isotope of uranium, by bombarding uranium with fast neutrons, and confirmed that (237)U disintegrates into element 93 with a mass number of 237. They also identified the isotopes of several middle-weighted elements produced by the symmetric fission of uranium. In this review article, the highlights of their work are briefly summarized along with some explanatory commentaries.     

Separation of Metal Pairs using Bis (2-Ethylhexyl) Phosphoric Acid (HDEHP); Separation of Cerium from Uranium and from Thorium

A systematic study was performed on the extraction and separation of uranium-cerium and thorium-cerium pairs for HDEHP from pure hydrochloric and sulphuric acid solutions as well as from their binary mixtures. The effect of water miscible alcohols and actone on the separation of these elements was also investigated. The separation of uranium and thorium from macroamounts of cerium can be best achieved from. 2.4 M HCl in presence of 50% isopropyl alcohol. There are other media plausible for the separation of trace cerium from uranium and thorium matrices.     

沉积态铀薄膜表面氧化的X射线光电子能谱

含铀(U)薄膜在激光惯性约束聚变的实验研究中有重要的用途.研究其在不同气氛下的氧化性能可以为微靶制备、储存及物理实验提供关键的实验数据.通过超高真空磁控溅射技术制备了纯U薄膜及金-铀(Au-U)复合平面膜,将其在大气、高纯氩(Ar)气及超高真空度环境中暴露一段时间后,利用X射线光电子能谱仪结合Ar~+束深度剖析技术考察U层中氧(O)元素分布及价态,分析氧化产物及机理.结果显示,初始状态的U薄膜中未检测到O的存在.Au-U复合薄膜中的微观缺陷减弱了Au防护层的屏蔽效果,使其在3周左右时间内严重氧化,产物为U表面致密的氧化膜及缺陷周围的点状腐蚀物,主要成分均为二氧化铀(UO_2).在高纯Ar气中纯U薄膜仅暴露6 h后表面即被严重氧化,生成厚度不均匀的UO_2.在超高真空度环境下保存12 h后,纯U薄膜表面也发生明显氧化,生成厚度不足1 nm的UO_2.Ar~+束对铀氧化物的刻蚀会因择优溅射效应而使UO_2被还原成非化学计量的UO_(2-x),但这种效应受O含量的影响.     

化学光谱法测定U3Si2中17种杂质元素

本文介绍化学光谱法测定Ｕ３Ｓｉ２中１７种杂质元素，用ＴＢＰ作固定相，采用柱上萃取色层法分离铀与杂质元素，铯为外加素体，铟为内标。平均回收率在８８％－１１５％之间，相对标准偏差优于１３％。     

Complexation between variable-valency uranium and organic ligands in solutions,their photostability and spectral identification

We discuss possible directions for searching for prospective materials based on low-valency uranium (III–V) as detection media for hard electromagnetic radiation. We have studied the processes of formation of tetravalent and pentavalent uranium complexes from UO₂(NO₃)₃·6H₂O and UO₂Cl₂·H₂O in DMF and with addition of CCl₄, including when the systems are exposed to radiation in the visible range (400–450 nm). In the first case (UO₂(NO₃)₃·6H₂O solutions in DMF), upon irradiation we observe stable complexes of pentavalent uranium, and when CCl₄ is added to the solution we observe complexes of tetravalent uranium. In the system UO₂Cl₂·3H₂O in DMF, we do not observe the appearance of new forms of uranium; but when CCl₄ is added, then complexes of tetravalent uranium are formed. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 184–187, March–April, 2007.     

铀矿坑水样中铀电沉积层的表征

描述了硫酸铵溶液中铀矿坑水样品中铀的电沉积层特性。 电沉积液为10 ml 0.8 M的硫酸铵溶液, 电流密度0.6 A/cm2, pH值为2.5, 电镀1 h。 电沉积经化学分离后的水样品和电沉积的纯硝酸铀酰样品进行了比较, 并对二者分别做了红外(IR)光谱、 扫描电镜(SEM)、 元素分析以及α能谱测量。 IR谱上铀酰离子的反对称伸缩振动峰在887 cm-1附近, 使电沉积在不锈钢片上的铀主要以铀酰离子水合物的形式存在, 有一部分NH+4以NH3的形式替代水合物中的水, 使电沉积层中铀的化合物形式为UO2(OH)2·xNH3·yH2O或者UO2(OH)2-x·(ONH4)x·yH2O, 铀酰离子通过链的形式形成聚合结构。 SEM照片显示电沉积层均匀, 没堆积成团现象出现。 α谱表明电沉积层中铀的同位素主要是238U和234U, 相应的α能量峰4198和4773 keV很显著, 没其它峰的干扰。 Characteristics of electrodeposited uranium films of uranium ore water sample in ammonium sulphate was investigated in this work. The optimized electrodeposited conditions were as follows: electrolyte was ammonium sulphate of 0.8 M, and current density at the cathode was 0.6 A/cm2, electrolyte pH value was 2.5, the time of plating on the electrodeposition was 1 h. In this situation, the uniform, thin and adheresive films were produced by electrodeposition method. Two samples were made, one electrodeposition of pure uranyl nitrate, and another electrodeposition of uranium ore water sample after chemical separation. Characteristics of electrodeposited uranium films of uranium ore water sample after chemical separation was studied, making comparisons with electrodeposited films of uranyl nitrate. The analysis of film characteristics was done through infrared (IR) spectrum, scanning electron microscopy(SEM), element analysis and α spectrum measurment. According to Fourier transform infrared spectra, the asymmetric stretching vibration band of uranyl group is around 887 cm-1. In addition, according to IR spectrum, we know that uranium exists mainly as the form of hydrated polymeric compound in the film. Electrodeposited uranium films also included many NH+4. Polymeric structures of variable composition were present in the electrodeposited samples, with the unit monomeric formula UO2(OH)2·xNH3·yH2O or UO2(OH)2-x·(ONH4)x·yH2O. Scanning electron microscopy shows that the two samples have similar surface characteristics and no cluster is observed. The samples were also measured by spectrometer equipped with Passivated Implanted Planar Silicon(PIPS) detector. From the α spectrum, we know that isotopes of uranium in the film are 238U and 234U. 235U is not found in the α spectrum. It also shows that the chemical separation process can isolate uranium from other interfering elements effectively, the result of chemical separation is very satisfactory and electrodeposited process is rather efficient. Source electrodeposited in ammonium sulphate through optimized conditions satisfies the need of high resolution α spectrum.     

Trace determination of uranium in fertilizer samples by total reflection X-ray fluorescence

Uranium is reported to be present in phosphate fertilizers. The recovery of uranium from the fertilizers is important because it can be used as fuel in nuclear reactors and also because of environmental concerns. For both these activities suitable method of uranium determinations at trace levels in these fertilizers are required. Studies have been initiated for such TXRF determination of uranium and the results are reported in the present paper. For TXRF determinations the fertilizer samples were processed with nitric acid and the uranium present in it was removed by solvent extraction using tri-n-butyl phosphate as the extractant. The organic phase containing uranium was equilibrated with 1.5% suprapure nitric acid to bring out uranium in aqueous phase. This aqueous phase was mixed with internal standard Y and the TXRF spectra were measured by depositing samples on float glass supports. The amounts of uranium in four fertilizer samples of Hungarian origin were determined by processing these TXRF spectra. Uranium concentrations in two fertilizer samples were found to be in the range of 4–6 μg/g, whereas two fertilizer samples did not show the presence of uranium. The precision of the TXRF determination of uranium was found to be better than 8% (1σ).     

放射性核素铀在针铁矿中的占位研究

用第一性原理研究放射性同位素铀在针铁矿(α-FeOOH)中的占位情况, 分别考虑铀原子替代针铁矿中的铁的替位缺陷和铀的多种八面体和多种四面体间隙缺陷. 计算发现了三个最稳定的缺陷构型, 它们分别对应于一个铀替位缺陷(S) 及其中的一个铀的八面体(O)和四面体(T)间隙缺陷, 其形成能分别为-13.49, -3.86, -1.60 eV. 也研究了两个相邻的铀原子在针铁矿中的占位情况, 发现双铀原子很容易掺入到相邻的SS或OS位, 它们的形成能分别为-27.392和-16.214 eV, 结合能分别为-0.417和1.131 eV. 表明双原子铀在针铁矿中会以SS形式发生偏聚而较难以OS形式偏聚. 关键词： 铀 针铁矿 占位 第一性原理     

Determination of thorium and uranium contents in soil samples using SSNTD’s passive method

Thorium-to-uranium ratios have been determined in different soil samples using CR-39 and LR-115-II solid-state nuclear track detectors (SSNTDs). A calibration method based on determination of SSNTD registration sensitivity ratio for α-particles of thorium and uranium series has been developed. Thorium and uranium contents of the standard soil samples have been determined and compared with its known values. There is a good agreement between the results of this method and the values of standard samples. The method is simple, inexpensive, non-destructive and has a wide range of applications in environment, building materials and petroleum fields.     

Inverse method for determining radon diffusion coefficient and free radon production rate of fragmented uranium ore

The radon diffusion coefficient and the free radon production rate are important parameters for describing radon migration in the fragmented uranium ore. In order to determine the two parameters, the pure diffusion migration equation for radon was firstly established and its analytic solution with the two parameters to be determined was derived. Then, a self manufactured experimental column was used to simulate the pure diffusion of the radon, the improved scintillation cell method was used to measure the pore radon concentrations at different depths of the column loaded with the fragmented uranium ore, and the nonlinear least square algorithm was used to inversely determine the radon diffusion coefficient and the free radon production rate. Finally, the solution with the two inversely determined parameters was used to predict the pore radon concentrations at some depths of the column, and the predicted results were compared with the measured results. The results show that the predicted results are in good agreement with the measured results and the numerical inverse method is applicable to the determination of the radon diffusion coefficient and the free radon production rate for the fragmented uranium ore.     

锆掺杂二氧化铀中氧缺陷扩散机制的密度泛函计算研究

应用基于量子力学的密度泛函计算和过渡态搜寻的CI-NEB方法,研究了锆掺杂前后二氧化铀晶格中氧空位和氧间隙本征缺陷的扩散机理,计算了扩散路径和扩散能垒。计算结果表明,锆掺杂使得氧空位缺陷<100>方向的扩散能垒降低了0.40 eV,氧间隙交换机制的扩散能垒降低了0.07 eV。锆掺杂后,氧空位远低于氧间隙缺陷的扩散能垒。最后分析了扩散过程中氧原子和金属原子之间的键长,说明锆掺杂导致点缺陷扩散能垒降低与晶格畸变密切相关。Oxygen vacancy and interstitial diffusion mechanisms in uranium dioxide doped with zirconium are investigated by the density functional theory calculations. The migration pathways and barriers are identified using the climbing-image nudge elastic band (CI-NEB) method. It is found that the vacancy migration barrier along the <100> direction decreases by about 0.40 eV, while the indirect interstitial migration barrier decreases by about 0.07 eV in the zirconium doped uranium dioxide. The oxygen vacancy migration barrier is far lower than the oxygen interstitial migration barrier in the uranium dioxide doped with zirconium. Based on the analysis of bond length of local structures during the migration of oxygen atoms, it is concluded that the lattice distortion may be responsible for the reduction of oxygen migration barrier.     

引入源-样品距离影响的主动中子多重性质量反演公式北大核心CSCD

主动中子多重性计数测量方法是常用的核材料质量无损测量方法,已广泛应用于核材料衡算、核安保测量与军控核查等领域。我们通过对JMCT中子-光子输运程序的二次开发,实现了对经典点模型铀样品质量估算实验的数值模拟,并提出了改进的铀样品质量计算公式。该算法可以显著降低本实验中源-样品耦合与源中子反照等作用对铀样品质量估算精度的影响。建立了主动中子多重性计数测量探测系统模型和32个铀样品半球壳模型,模拟得到了与铀样品距离不同的DT源和AmLi源主动中子多重性计数,利用数值模拟手段检验了质量估算算法的有效性。数值模拟结果表明,改进的铀质量估算算法可以使质量估算的平均偏差率降低到10%以下。     

Study of Raman spectrum of uranium using a surface‐enhanced Raman scattering technique

Raman spectroscopic investigation on weak scatterers such as metals is a challenging scientific problem. Technologically important actinide metals such as uranium and plutonium have not been investigated using Raman spectroscopy possibly due to poor signal intensities. We report the first Raman spectrum of uranium metal using a surface‐enhanced Raman scattering‐like geometry where a thin gold overlayer is deposited on uranium. Raman spectra are detected from the pits and scratches on the sample and not from the smooth polished surface. The 514.5‐ and 785‐nm laser excitations resulted in the Raman spectra of uranium metal whereas 325‐nm excitation did not give rise to such spectra. Temperature dependence of the B_3g mode at 126 cm⁻¹ is also investigated. Copyright © 2011 John Wiley & Sons, Ltd.     

流动注射分光光度法测定煤灰中的微量铀

在稀硝酸介质中,以2-(3-羧基苯偶氮)-7-(4-氯-2-膦酸基苯偶氮)-1,8-二羟基-3,6-萘二磺酸(CPA-mK)作为显色剂,建立了一种测定微量铀的流动注射分光光度法,在最佳实验条件下,该方法的线性范围为0-35mg/L,检出限为0.026mg/L,应用该方法测定煤灰样品中的铀,其相对标准偏差为1.8%-3....     

空气中痕量铀的现场光度法测定

作为一种天然放射性金属元素,铀及其化合物可以地气为分散系,以气溶胶形式稳定存在并随空气迁移。气相中铀可经多种途径对人体造成放射性危害,而其浓度变化与该区域核能开发与利用有关。因此,对空气中铀的快速现场检测具有现实意义。采用普通气泵对低品位铀矿石上方的空气进行采样,并以2.0 mol·L-1硝酸溶液对气体进行吸收,向溶液中添加固体试剂包,对溶液中微量铀进行显色后以手持式光度计进行现场光度分析。结果表明：对于普通低品位铀矿石样品,空气中铀含量可用本方法检出,该方法多次测定的RSD为1.72%,其结果与ICP-MS分析结果一致。将该方法用于区分铀矿石和其他矿石,具有成本低廉,操作方便,结果准确可靠等优点。     

Determination of residual metal concentration in metallurgical slag after acid extraction using total reflection X‐ray fluorescence spectrometry

Total reflection X‐ray fluorescence spectrometry (TXRF) was used to determine residual metal content in metallurgical slag after sulfuric acid extraction. A slag sample provided by a copper smelter industry and submitted to a recycling process with the aim of extracting valuable metals was analyzed. Slurry sampling was evaluated as a simple sample preparation procedure for the determination of major (Si, Fe, K, Ca) and trace elements (Ti, Ni, Cu, Zn, As, Pb, Sr, Rb, Mn) in two certified reference materials (lake and river sediments) to evaluate the accuracy of the procedure. Precision was evaluated as relative standard deviation (%) of three replicates, being usually lower than 10%. Detection limits were in the range of 1.1–1079 µg g^?1. Additionally, it was evaluated to use Si – a major component of the slag – as intrinsic reference to determine residual elements in the slag residues. A two‐element internal standard (Ga + P) was employed to determine all the elements. Ga was used as internal standard for the determination of elements from K to Pb, and P was required for the quantification of Si. The optimal procedure of slurry sampling was applied for the analysis of the original metallurgical slag and the solid residues. It was found that As and Pb are accumulated in the slag, whereas Cu, Zn, and Fe are extracted to a percentage >90% from the slag. This was confirmed by analysis of the sulfuric acid extracts of the metallurgical slag. Copyright © 2014 John Wiley & Sons, Ltd.     

基于X射线透射谱的铀浓度测量方法

在核燃料后处理流程中,需对工艺中的铀浓度进行准确测量。利用X射线管照射铀溶液,通过测量铀的L边界X射线透射谱确定铀浓度。文章设计了铀的L边界X射线透射谱测量系统。通过配制1~200 g·L-1铀标准溶液,建立铀浓度测量工作曲线,并对系统的精密度、准确度和稳定性进行测试。结果表明,铀浓度测量工作曲线线性拟合参数R2=0.999 9;系统对57.004 g·L-1铀溶液测量精密度为0.21%,对38.255 g·L-1铀溶液测量相对误差为0.32%;对2.236 g·L-1铀溶液进行连续测量,99.67%数据落在μ±3 s。     

贫铀药型罩材料中微量杂质对聚能射流性能的影响

 通过对贫铀药型罩的静破甲实验，研究了材料中微量元素对射流性能的影响。实验结果表明，贫铀中的碳含量对射流性能起着非常重要的作用，随着碳含量的增加，静破甲威力下降十分显著。最后讨论了有害微量杂质对射流造成影响的原因，指出有害杂质可以以点缺陷形式或向晶界偏聚的形式存在于材料中，它们对材料的滑移变形均起到阻碍作用，其结果造成材料延展性能下降。     

Total reflection X-ray fluorescence and energy-dispersive X-ray fluorescence characterizations of nuclear materials

Nuclear energy is one of the clean options of electricity generation for the betterment of human life. India has an ambitious program for such electricity generation using different types of nuclear reactors. The safe and efficient generation of electricity from these reactors requires quality control of different nuclear materials, e.g. nuclear fuel, structural materials, coolant, moderators etc. These nuclear materials have to undergo strict quality control and should have different specified parameters for their use in nuclear reactors. The concentration of major and trace elements present in these materials should be within specified limits. For such chemical quality control of these materials, major and trace elemental analytical techniques are required. Since some of these materials are radioactive, the ideal chemical characterization techniques should have multielement analytical capability, should require very less sample (micrograms level) for analysis so that the radioactive waste generated, and radiation exposure to the detector and operator are minimum. Total reflection X-ray fluorescence (TXRF) and energy dispersive X-ray fluorescence (EDXRF) with improved features, e.g. application of filters, secondary target and instrumental geometry require very small amount of sample and thus can be suitably used for the characterization of nuclear materials mainly for the determination of elements at trace and major concentration levels. In Fuel Chemistry Division, TXRF analytical methods have been developed for trace element determinations in uranium and thorium oxides, chlorine determination in nuclear fuel and cladding materials, sulphur in uranium, uranium in sea water etc. Similarly, EDXRF analytical methods with radiation filters (to reduce background) and improved sample preapartion techniques, e.g. fusion bead and taking samples in the form of solution on filter papers have been used for developing analytical methods for the determination of U and Th in their mixed matrices, Cd in uranium etc. Some of these studies have been reported in this paper.