Determination of thorium and uranium at the nanogram per gram level in semiconductor potting plastics by neutron activation analysis

A method was developed to determine thorium and uranium in semiconductor potting plastics. The method is based on neutron activation and subsequent radiochemical separation to isolate and permit measurement of the daughter products²³³Pa and²³⁹Np of the induced²³³Th and²³⁹U. These plastics typically contain macro amounts of silicon, bromine and antimony and nanogram per gram amounts of thorium and uranium. The radiochemical method provides the necessary sensitivity and makes it possible to easily attain adequate decontamination of the tiny amounts of²³³Pa and²³⁹Np from the high levels of radioactive bromine and antimony.Deceased     

Determination of uranium and thorium at the sub-ng/g-level in high-purity aluminium by radiochemical neutron activation analysis

Summary A radiochemical neutron activation analysis technique for the determination of uranium und thorium in highpurity aluminium via the indicator radionuclides ²³⁹Np and ²³³Pa, respectively, has been developed. The separation procedure is based on the removal of ²⁴Na on hydrated antimony pentoxide followed by ion-exchange on Dowex-1X8 from HCl/HF and HCl medium. The eluate fraction being of interest for the determination of uranium and thorium contains > 99% of ²³⁹Np and ²³³Pa and, in addition, 11±2% of hafnium and 29±5% of zirconium, and non-detectable fractions of other radionuclides. For a 3-day irradiation of a 100 mg sample at a thermal neutron flux of 10¹⁴cm^–2s^–1 and a decay time of 5 days, the attainable detection limit for both elements is 0.05 ng/g. The method was applied to the analysis of different high-purity aluminium samples, and the results are compared with those obtained in other laboratories.

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Bestimmung von Uran und Thorium in hochreinem Aluminium im sub-ng/g-Bereich durch radiochemische Neutronenaktivierungsanalyse

     

Non-destructive determination of uranium and thorium in geological materials by resonance-neutron activation analysis

A simple method is described for the determination of uranium and thorium in gological materials. The samples are irradiated in a reactor with resonance and fast neutrons behind a cadmium filter. Compared with an irradiation with the whole reactor neutron spectrum, the matrix activities are reduced to about 1%, those of uranium (²³⁹Np) and thorium (²³³Pa) to about only 50 and 25%, respectively. This relative diminution of matrix activities allows the γ-measurement of²³⁹Np and²³³Pa as early as after two days' cooling time; in samples with high uranium contents the determination of²³³Pa requires one month's cooling time. This non-destructive procedure yields a detection limit of 0.1 ppm for uranium and thorium in samples of 200 mg, with an error of ±5%. Dedicated to ProfessorW. Borchert on the occasion of his 60th birthday.     

Measurement of trace impurities in high purity materials

Neutron activation analysis was used for the determination of 29 trace impurities is high-purity semiconductor grade Ge and Si. In order to determine very low contents of uranium and thorium,²³⁹Np and²³³Pa activation products were separated using anion exchange and LaF₃ coprecipitation methods. The impurity contents were found to be very low, and therefore their adverse effects would be negligible.     

Ultratrace characterization of AlSiCu sputter targets for Th,U and 35 other elements by neutron activation analysis

Instrumental and radiochemical neutron activation analysis has been applied to a comprehensive trace characterization of AlSiCu sputter targets. By instrumental neutron activation analysis via long-lived indicator radionuclides, up to 33 elements were assayed with detection limits between 0.01 and 200 ng·g^–1. The high activity of⁶⁴Cu and²⁴Na produced from the matrix significantly limits the instrumental performance via short- and medium-lived indicator dionuclides. For this reason, a radiochemical separation was developed based on adsorption of²⁴Na on hydrated antimony pentoxide and extraction of⁶⁴Cu by diethylammonium diethyldithiocarbamate from HCl medium. By this radiochemical method, As, Ga, K, La, Mn, Mo, Re, Sb, U and W could be assayed via medium-lived radionuclides and the achievable limits of detection were between 0.1 and 25 ng·g^–1. Further improvement of detection limits for U and Th was achieved by a selective radiochemical separation of²³⁹Np and²³³Pa on a Dowex 1×8 column in HF and HF/NH₄F medium providing limits of detection for U and Th of 0.06 and 0.02 ng·g^–1, respectively. These techniques were applied to the analysis of two AlSiCu sputter target materials. Results are compared with those of glow discharge mass spectrometry.     

Simultaneous determination of trace uranium and thorium by radiochemical neutron activation analysis

A method for the simultaneous, radiochemical neutron activation analysis of uranium and thorium at trace levels in biological materials is described, based on a technique known as LICSIR, in which a double neutron irradiation is employed. In the first, long irradiation²³³Pa (27.0 d) is induced by neutron capture on²³²Th and then the sample is cooled for several weeks. A second short irradiation to induce²³⁹U (23.5 m) is followed by a rapid sequential radiochemical separation by solvent extraction of²³⁹U with TBP and²³³Pa with TOPO. Chemical yields of²³⁹U and²³³Pa were measured for each sample aliquot using added²³⁵U and²³¹Pa tracers from the -spectra of the separated fractions. The technique was validated by quality control analyses.     

Radiochemical neutron activation analysis of trace impurities in high purity aluminum

Rapid radiochemical neutron activation analysis (RNAA) procedures were developed and employed for the determination of 32 trace impurities in high purity aluminum thin foils. Anion exchange column chromatography was developed for the sequential group chemical separation of various elements which helped in reducing the spectral interferences and improving the sensitivity of the method. The procedure is simple and requires a very short time to separate the elements in three groups for radiometric assay. To determine very low contents of uranium and thorium,²³⁹Np and²³³Pa as activation products were separated using anion exchange and coprecipitation methods. The impurity contents were found to be low, therefore, their adverse effects on microelectronic devices would be negligible. Our data could partially be compared with the data reported in literature.     

Neutron activation determination of the uranium content of the primary coolant of water-water nuclear reactors

A neutron activation method for determination of uranium dissolved in the coolant of the first cycle of nuclear power stations is proposed. The method is based on preliminary concentration on activated carbon, irradiation with epithermal neutrons and gamma-spectrometry of²³⁹Np. The detection limit amounts to 1,3·10^–8 U/l. The method was sucessfully applied for the determination of uranium in the coolant of a nuclear power station.     

High precision elemental abundances for tektites and crater glasses-thorium,uranium and potassium

Thorium, uranium and potassium mean abundances for 15 Ivory Coast tektites, 23 Australites, 10 Philippinites, 25 Thailandites, 16 Bediasites and 12 Moldavites are reported. Abundances are also reported for Muong Nong type tektites, Nordlinger Ries crater glass, Bosumtwi crater glass and Darwin crater glass. Previous measurements are reviewed. The value of the present work lies in the fact that high precision instrumental neutron activation analysis was employed to measure a large number of tektites encompassing the major strewn fields. Four independent measurements of thorium were made for each specimen with two Ge(Li) gamma spectrometers. Two of the measurements were based on the 312 keV gamma of²³³Pa, while the other two measurements were based on the uranium and X-rays which accompany the decay of²³³Pa. Internal consistency among the four thorium measurements is high. The uranium measurements were based on the 106 keV gamma of²³⁹Np, while potassium was measured from the 1524 keV gamma of⁴²K.     

The leachability of some natural and man-made radionuclides from soil and sediments on acid attack

A radiotracer study was made of the leachability of some natural and man-made radionuclides from soils and sediments subjected to attack by various acid mixtures. Particular attention was paid to the nuclides²³⁸U,²³²Th, Pa (as²³³Pa) and Np (as²³⁹Np), since for these neutron activation can be used to study recoveries and/or to induce in situ radionuclides in samples. Thus conventional NAA allowed determination of total²³⁸U and²³²Th instrumentally, and also enabled analysis of leachates and residues by radiochemical or instrumental NAA. Activation of these nuclides produced samples endogenously labelled with²³³Pa and²³⁹Np whose behaviour on acid dissolution/leaching could be examined. Furthermore, comparison of neutron irradiated and non-irradiated samples allowed us to investigate the possibility of increased leachability induced by nuclear recoil reactions; however, this effect was negligible. We also investigated the acid leaching of americium adsorbed on the surface of sediment. In general, unsatisfactory leaching recoveries were found for²³³Pa,²³⁹Np and²³²Th for most materials, indicating the need for total dissolution procedures.     

Neutron activation determination of uranium by coprecipitation of neptunium-239 on zirconium phosphate

A method is proposed for neutron activation determination of U via²³⁹Np. This is separated by coprecipitation of ZrO(H₂PO₄)₂ and its 106 keV γ-peak measured. The sensitivity of the determination is 10⁻⁹ g. The method is based on the well-known ability of Np(IV) to coprecipitate with zirconium phosphate, while Np(VI) does not form insoluble phosphates or fluorides. This permits elimination of elements interfering, with the determination of²³⁹Np via the 106 keV γ-peak: Sm, Nd, Yb, Lu, Pa (from Th) and Ta. The rare earths are eliminated by coprecipitation on LaF₃, and Pa and Ta as insoluble phosphates in an oxidizing medium. The method is suitable for phosphorus-containing samples: phosphorites, apatites and their industrial treatment products. The results obtained for the uranium content with the proposed method are in good agreement with the results of other methods and authors.     

Determination of sub-PPB contents of uranium and thorium in high-purity aluminium by RNAA

Aluminium samples, irradiated in a reactor, are dissolved in nitric acid²³³Pa and²³⁹Np are adsorbed on an anion exchange column and then separately eluted. The neptunium fraction is very pure and can be counted in a liquid scintillation counter with 100% efficiency. From the other fraction protactinium is extracted by trioctylphosphine oxide and measured by -ray spectrometry. With samples of 3 g, a thermal flux of 3·10¹³ n cm^–2s^–1 and an irradiation time of 24 hours detection limits are 0.0005 ng/g for U and 0.01 ng/g for Th.     

Low level measurements of thorium and neptunium in environmental samples using the (γ, f) reaction

A new highly sensitive track method for the determination of thorium (²³²Th) and neptunium (²³⁷Np) has been developed. The technique includes the radiochemical separation procedure of the isotopes followed by the irradiation of the resultant samples on the MT-25 microtron. The detection limit is équivalent up to 3·10^–13 g of²³²Th and 7·10^–14 of²³⁷Np. The method was used to determine²³²Th and²³⁷Np isotopes in water samples.     

Instrumental neutron activation determination of rare earth,noble and other elements in mineral raw materials of The Socialist Republic of Vietnam

The possibilities of multielement neutron activation analysis of the mineral raw materials of the Socialist Republic of Vietnam, have been studied. Samples were activated by a²⁵²Cf neutron source (yield 4·10⁹ n·s^–1). The induced activity was measured by coaxial Ge(Li) and planar Ge detectors. The content of gold, thorium, uranium, rare earths and other elements, was determined and evaluated in ores and concentrates by an absolute method.     

Determination of thorium in human urine by neutron activation

A routine procedure for the determination of thorium in urine of workers has been developed by the neutron activation method. The technique suggested by Dang, et. al. has been modified in order to reduce the costs involved and the sample processing time. The samples were irradiated in the MIT (Massachusetts Institute of Technology-Boston) reactor, in a thermal neutron flux of 8×10¹²n.cm^–2.s^–1 for 31/2 hours. Thorium-232 was determined by counting²³³Pa.     

Neutron activation determination of2 3 7Np in irradiated experimental fuels and in waste solutions and distribution studies in sea-water and submarine fauna and flora of disposal areas

The determination of^{2 3 7}Np by activation analysis^{2 3 7}Np(n,)^{2 3 8}Np (2. 2. d). Main gamma ray 984.4 keV is disturbed either by highly activable elements or by uranium giving interference. Therefore, a pre-irradiation chemical separation step is used.^{2 3 7}Np determination has been performed in irradiated experimental fuels, waste solutions, nuclear fuel zircaloy sheats and in studies of distribution in sea-water and submarine fauna and flora from disposal sites. The detection limit is 5·10^–13 g of^{2 3 7}Np corresponding to 2.5·10^–9 mg/kg for 200 ml sea-water sample.     

Characterization of an epithermal irradiation facility

An epithermal energy neutron irradiation facility has been used to perform instrumental activation analysis for iodine, silicon, nickel, zirconium, uranium and thorium. The facility, which is adjacent to the fuel of the University of Virginia 2.0 MW pool reactor, consists of a dry sample region surrounded by a fixed cadmium shield. A boron nitride capsule can be used to hold the sample in the cadmium facility to further enhance the reduction of thermal neutron activation. The neutron fluence rate is 2.2×10¹⁶ n·m^–2·s^–1 for fission spectrum energy neutrons (measured with Ni(n,p)Co) and 8.2·10¹⁵ n·m^–2·s^–1 for resonance energy neutrons (measured with gold).Iodine has been measured at concentrations as low as 0.1 mg/kg with 3% counting statistics in powdered infant formula and 0.15 mg/kg with 5% statistics in liquid infant formula. Silicon has been measured at concentrations of 0.2% in biological samples with counting statistics between 5 and 10% and in coal and soil at concentrations greater than 4% with better than 1% statistics. Nickel has been measured in coal and soil at the 20 mg/kg level and higher with 6% statistics. Zirconium has been determined at 600 mg/kg and greater in ceramics with counting errors less than 3%. Uranium and thorium have been measured at the 10 mg/kg level with 3% counting statistics.     

Feasibility study of <Superscript>233</Superscript>Pa and <Superscript>233</Superscript>U determination in neutron irradiated thorium for future applications in thorium–uranium nuclear fuel cycle

With regard to the use of thorium fuel for future nuclear energy production, two methods of ²³³U assay were studied in neutron irradiated thorium and in a mixture of thorium and uranium. The former was based on gamma-spectrometry determination of the ²³³Pa radionuclide, a precursor of ²³³U. The latter was direct determination of ²³³U by neutron activation analysis with counting of delayed neutrons. The mass of ²³³U determined by both methods is compared with that calculated using Maple9.5 software package.     

Multielement radiochemical neutron activation analysis of high purity aluminium

Summary A radiochemical neutron activation analysis technique for the determination of 51 elements in high purity aluminium via medium- and long-lived indicator radionuclides has been developed. It is based on a separation procedure involving the removal of ²⁴Na, produced via the reaction ²⁷Al(n,), on a hydrated antimony pentoxide column and further separation of the radionuclide mixture into 11 groups on two Dowex 1X8 columns and one Dowex 50X8 column from HCl/HF and HCl media as well as the extraction of copper with APDTC in chloroform. The indicator radionuclides for the significant impurities thorium and uranium, ²³³Pa and ²³⁹Np, were separated with satisfactory selectivity in one fraction. For 43 elements, the limits of detection are <10 ng/g, for thorium and uranium, they are 50 pg/g. The method was applied to the analysis of different high purity aluminium samples. For a number of elements, the results of this technique are compared with those of other techniques.

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Radiochemische Multielement-Neutronenaktivierungsanalyse von hochreinem Aluminium

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Dedicated to Prof. Dr. W. Fresenius on the occasion of his 75th birthday     

Diffusion of actinides in glasses containing simulated radioactive wastes

Diffusion coefficients of radionuclides²³⁷Np,²³⁹Pu and²⁴¹Am in simulated alumina phosphate and alumina borosilicate glasses at temperatures lower than their transformation temperature were determined. Actinides are known to be the least mobile elements. In particular, the diffusion coefficients of actinides in alumina phosphate glasses at 673 K are about 10^–18 m²·s^–1, and in alumina borosilicate at 773 K about 10^–19 m²·s^–1. It is shown that crystallization of glasses leads to increasing²³⁷Np diffusion mobility. It is also shown that a rather small quantity of water absorbed by a crystallized alumina phosphate glass in tensifies low-temperature migration of²³⁷Np.