Neutralization of static electricity charged on running vinyl chloride sheet by the use of soft beta-ray sources (author's transl)

The feasibility of 147Pm and 3H beta-ray sources as static eliminator was experimentally investigated. A sheet of vinyl chloride of 0.1 mm in thickness was used as an example of electrified materials. Its surface charge densities before and after beta-ray neutralization were measured as the function of electrostatic charge changing the speed of the sheet and the distance between the beta-ray source and the sheet. With a 147Pm beta-ray source of 200mCi in effective activity, almost complete neutralization was found for the sheet with the charge density less than 6 X 10(-6) C/m2 running at the speed of 0.18 m/s. In the case of the running speed of 0.5 m/s frequently used in industry, the electrostatic charge below 3 X 10(6) C/m2, where corona discharger is not so effective, was also perfectly eliminated. It was found that the optimal distance between the beta-ray source and the sheet was 10 cm in the case of 147Pm. The use of 3H beta-ray source of 1 Ci was not satisfactory. These results demonstrate that 147 Pm beta-ray source operates most efficiently as static eliminator when the charge density of material and/or its moving speed is not high.     

A new approach to determine Pm in irradiated fuel solutions

Developments carried out in the Laboratory of Isotopic, Nuclear and Elementary Analyses in order to quantify ¹⁴⁷Pm in spent nuclear fuels analyzed at the CEA within the framework of the Burn Up Credit research program for neutronic code validation are presented here. This determination is essential for safety-criticality studies.The quantity and the nature of the radionuclides in irradiated fuel solutions force us to separate the elements of interest before measuring their isotopic content by mass spectrometry. The main objective of this study is to modify the separation protocol used in our laboratory in order to recover and to measure the ¹⁴⁷Pm at the same time as the other lanthanides and actinides determined by mass spectrometry.A very complete study on synthetic solution (containing or not ¹⁴⁷Pm) was undertaken in order to determine the yield of the various stages of separation carried out before obtaining the isolated Pm fraction from the whole of the elements present in the spent fuel solutions. With the lack of natural tracer to carry out the measurement with the isotope dilution technique, the great number of isotopes in fuel, the originality of this work rests on the use of another present lanthanide in fuel to define the output of separation. The yields were measured at the conclusion of each stage of separation with two others lanthanides in order to show that one of them could be used as a tracer to correct the measurement of the ¹⁴⁷Pm with the separation yield. The total yield (at the conclusion of the two stages of separation) was measured at the same time by ICP-MS and liquid scintillation. This last determination made it possible to validate the use of the ¹⁴⁷Sm (natural) to measure the ¹⁴⁷Pm in ICP-MS since the outputs determined in liquid scintillation and ICP-MS (starting from the radioactive decrease of the source having been used to make the synthetic solution) were equivalent. It is the first time that such measurement is performed in ICP-MS.The measurement of the ¹⁴⁷Pm was finally taken on fuels UOx and MOx by using the ¹⁵³Eu like a tracer of the separation yield. The results obtained are in very good agreement with those obtained from neutronic calculation code.     

A simple procedure for the fabrication of high activity beta-radiation sources of147Pm for use in beta-ray thickness gauges

A simple procedure is described for the fabrication of mCi level strong sources of¹⁴⁷Pm radioisotope on a noble metal substrate like Palladium as a source for β⁻-ray thickness gauge. The procedure is based on the principle of internal electro-deposition of¹⁴⁷Pm from aqueous solutions containing¹⁴⁷Pm³⁺ ions, using metallic magnesium for the purpose. Investigations conducted towards ascertaining the adherence of the¹⁴⁷Pm radioactivity onto the palladium substrate. Leaching studies conducted on these source indicated that the radioactive film is satisfactorily adherent to the palladium substrate, suggesting that the method can be used for fabricating satisfactorily safe high β⁻-activity sources of¹⁴⁷Pm contained in small active dimensions. Results of leaching studies keeping the sources fully immersed in boiling water for 15 minutes are also presented.     

Chemical study on the separation and purification of promethium-147

A chemical process for the separation of¹⁴⁷Nd/¹⁴⁷Pm from fission products of synthetic radioactive waste solution has been developed. The process includes: (1) denitration, (2) removal of high concentration of uranium by 30% TBP/kerosene extraction, (3) removal of⁹⁵Nb,¹⁰³Ru,¹³⁷Cs and part of⁹⁰Sr by 50% TBP/dodecane extraction, (4) separation of¹⁴⁷Nd/¹⁴⁷Pm from part of⁹⁰Sr and⁹⁵Zr by oxalic acid precipitation, and (5) removal of¹⁴⁴Ce by mixture of 0.4M D2EHPA and 0.2M TBP extraction. Experimental results indicate that the recovery of¹⁴⁷Nd/¹⁴⁷Pm in the final separated solution is about 90%. The purification of¹⁴⁷Nd and¹⁴⁷Pm from some other rare earth elements, viz.¹⁵³Sm,¹⁵⁴Eu and¹⁴⁴Ce was further investigated by using a Dowex 50W×8 ion-exchanger. Parameters of flow rate, eluent concentration and pH were examined. The results show that the recovery and radionuclide purity of¹⁴⁷Nd plus¹⁴⁷Pm under the present separation conditions are 77.8% and 98.6% for diethylenetriaminepentaacetic acid (DTPA) and 87.3% and 99.5% for nitrilotriacetic acid (NTA), respectively.     

Colloidal forms of radionuclides and their separation from water solution

Colloidal properties of¹⁴⁴Ce(III),¹⁴⁷Pm(III),⁹¹Y(III), and other, radionuclides were determined from the course of their self-diffusion. A reduced self-diffusion indicated the formation of colloidal radionuclides. The decrease in the self-diffusion coefficient began from a certain value of pH, and a pH region of slowest self-diffusion existed for each of the radionuclides studies. The maximum formation of colloidal radionuclides may be assumed to lie in the range of these pH values. An increase in the rate of self-diffusion was observed with radionuclides in colloidal forms under the effect of gamma-radiation. The possibility of mutual interaction between radionuclides was also inferred from the course their self-diffusion. High effective sorption of¹⁴⁷Pm(III) was attained on hydrated ferric oxide in the pH range were hydrolytic products and colloidal forms of¹⁴⁷Pm(III) were formad to a large extent.     

Salient Features in the Preparation of Promethium-147 Activated Zinc Sulphide Phosphor Light Sources

Activation of zinc sulphide phosphor with beta radiation of ¹⁴⁷Pm will provide self-sustaining light sources and are widely used as nocturnal illumination devices. Use of ¹⁴⁷Pm as energy source is most promising since it forms non-volatile salts. By virtue of this property, it has been precipitated as hydroxide from its aqueous solution for in situ deposition on zinc sulphide phosphor. In this paper, the details of various reaction parameters such as the rate of deposition of ¹⁴⁷Pm(OH)₃ on ZnS, duration of shaking, specific activity of phosphor and effect of fatty acid (additive) concentration versus luminosity are illustrated with experimental evidence so as to obtain, under optimum conditions, an overall luminosity of 1000 micro lamberts (lm).     

Anodically oxidised aluminium layer as a useful substrate for the fabrication of147Pm sources for beta-ray thickness gauges

An anodically oxidised layer of aluminium was found to be a satisfactory substrate for holding millicurie amounts of carrier-free¹⁴⁷Pm activity, which is used as a source of -radiation in -ray thickness gauges. The sources fabricated by this method showed satisfactory performance regarding leaching and adherence of the radioactivity held up in the oxide layer. Details regarding the anodic oxidation conditions used for making these source substrates are given. Leaching studies conducted on these sources indicated influence of the acid concentration at which¹⁴⁷Pm activity was deposited in the oxide layer. Better performance characteristics of these sources could be achieved whenever¹⁴⁷Pm activity was absorbed in the oxide layer under near neutral conditions of acidity.     

Determination of <Superscript>151</Superscript>Sm and <Superscript>147</Superscript>Pm using liquid scintillation tracer methods

The long-lived rare earth isotopes ¹⁵¹Sm (90 years, β _max = 76.3 keV) and ¹⁴⁷Pm (2.62 years, β _max = 224.6 keV) are low-yield fission products that generally require lengthy separation procedures to isolate and count by their beta emissions. We will describe novel liquid scintillation counting techniques using radioactive tracers to determine radiochemical yields from an environmental matrix. The recovery of ¹⁵¹Sm is determined from the alpha decay (2.25 MeV) of ¹⁴⁷Sm in the natural Sm carrier and is in excellent agreement with the gravimetric recovery. The ¹⁴⁷Pm recovery is determined by the use of ¹⁴⁵Pm (17.7 years, EC) tracer, custom-produced at LANL using an isotopically enriched target of ¹⁴⁴Sm. We have determined the ¹⁴⁵Pm recovery both from the 37.4 keV k_α1 X-ray, and the electron-capture emissions by LSC. A comparison of these recovery methods is presented.     

Sorption of144Ce(III) and147Pm(III) on hydrated iron sesquioxide

The sorption of¹⁴⁴Ce(III) and of¹⁴⁷Pm(III) on hydrated iron sesquioxide suspension and the sorption of¹⁴⁴Ce(III) on hydrated iron sesquioxide in a laboratory column were studied. The dependence of the sorption on pH and time, the sorption isotherm, the temperature-dependence of sorption, and the effects of ionic strength on sorption and desorption were determined under static conditions. The maximum sorptions of¹⁴⁴Ce(III) and¹⁴⁷Pm(III) were reached at pH=7.4 (K_d=8.9·10⁵) and pH=9.1 (K_d=6.2·10⁵), respectively.     

Bioligand-mediated partitioning of radionuclides to the aqueous phase

The aqueous-phase partitioning of ⁵⁹Fe, ¹⁴⁷Pm, ²³⁴Th and ²⁴¹Am by complexing compounds from subsurface bacteria has previously been studied in the presence of quartz sand. In this study the aqueous-phase partitioning of pico-to submicromolar amounts of ⁵⁹Fe, ¹⁴⁷Pm, ²³⁴Th and ²⁴¹Am was analyzed in the presence of TiO₂ and exudates from three species of subsurface bacteria: Pseudomonas fluorescens, Pseudomonas stutzeri, and Shewanella putrefaciens. All were grown under aerobic conditions and P. stutzeri and S. putrefaciens were grown under anaerobic conditions as well. The supernatants of the aerobic and anaerobic cultures were collected and radionuclide was added. TiO₂, with BET surface area of 49.9 m²·g⁻¹, was added to the supernatant radionuclide mix, and the pH was adjusted to approximately 8. After incubation, the amount of radionuclide in the liquid phase of the samples and controls was analyzed using scintillation method. Two types of values were calculated: solution% = the activity maintained in solution relative to the total activity, and Q-values = the quotient between the activity in samples and the activity in controls. Aerobic supernatants had solution% values between 89% and 100% for ⁵⁹Fe and between 18 and 43% for ²³⁴Th. The solution% values for ²⁴¹Am and ¹⁴⁷Pm were less than 2% overall, but the Q-values were between 34 and 115 times more ²⁴¹Am in bacterial supernatants than in controls. The corresponding values for ¹⁴⁷Pm ranged from 6 to 20 times more than in the control. The solution% values for all elements in the presence of anaerobic supernatants were below 2%, but the Q-values clustered around 7 for ⁵⁹Fe and ranging from 2 to 29 for ^234Th, indicated that anaerobic supernatants partitioned these elements to the aqueous phase. Both aerobic and anaerobic supernatants tested positive for complexing compounds when analyzed, using the Chrome Azurol S assay. Complexation with excreted organic ligands is most likely the reason for the higher amounts of metals in samples than in the controls. Hence, aerobically and anaerobically excreted organic ligands seem able to influence the mobility of radionuclides in aerobic and anaerobic environments contaminated with these compounds.     

Simultaneous determination of lanthanides by radioisotope x-ray fluorescence spectrometry based on characteristic K-radiation

The use of radiosiotope-induced x-ray fluorescence is examined for the determination of lanthanides via their characteristic K x-ray lines. Various synthetic mixtures of barium and 14 rare-earth elements were prepared and their homogeneity was checked. The intensity from each mixture was measured for 10 min with excitation by the 88-keV γ-ray from a 3.5-mCi cadmium-109 source or by direct β-particles from a 100-μCi promethium-147 source. Typical spectra and their corrected peak intensities are presented. The spectral backgrounds produced by ¹⁴⁷Pm and ¹⁰⁹Cd are considered.     

Production and evaluation of a reference material for moisture,ash, and total fat mass fractions,and titratable acidity in whole milk powder

Given the importance of reference materials (RM) in the structuring and maintenance of quality management systems for food analysis laboratories, RM were produced for the measurement of moisture, ash, total fat, and titratable acidity in whole milk powder. Two types of packaging and three storage temperatures were evaluated. The RM were considered homogeneous. The materials that were packaged in the pouches and those packaged in the amber glass bottles with screw caps (stored at room temperature) were not stable for moisture. Nevertheless, considering the four measurands, the amber glass bottles under refrigeration and freezing temperatures were the best packaging and storage conditions, respectively. Homogeneity and stability studies were carried out according to the ISO Guide 35, IUPAC harmonized protocol, and ISO 13528, considering the potential applicability of the produced materials as certified reference materials or even as RM for use in proficiency testing schemes. For homogeneity, despite the different criteria, there was agreement between the results. Considering the stability, the agreement depended on the evaluation of the regression assumptions, which is not required by the ISO Guide 35. The contribution of uncertainty associated with homogeneity was greater than that related to stability. The results indicated that the produced materials, i.e., the candidate certified RMs, were suitable for assessing trueness and could be submitted to further inter-laboratory characterization.     

Guidance on the contents of accompanying documentation for reference materials (RMs)

The use of reference materials (RMs) is a key activity for the improvement and maintenance of a worldwide coherent measurement system. As detailed in ISO Guide 33, RMs with different characteristics are used in measurement processes, for the purpose of precision control, bias assessment, calibration, assigning values to other materials, and maintaining conventional scales, to name a few. For the establishment of metrological traceability of measurement results to international scales or other measurement standards, proper use of certified reference materials (CRMs) is essential. From the perspective of a reference material producer, the documentation that is provided with an RM is the value-adding component of the material; for the user, the document is critical for the correct implementation and use of the RM in the measurement process. The ISO Committee on Reference Materials (ISO/REMCO) recognised the importance of the documentation that accompanies a reference material as early as 1981 when the first edition of ISO Guide 31 was published. The third edition of the Guide that was published recently considers the appropriate accompanying documentation for all types of reference materials, i.e. CRMs and non-certified RMs.     

Yields of rare earth fission products in the spontaneous fission of californium-252

Cumulative fission yields of rare earth isotopes have been determined in the spontaneous fission of²⁵²Cf by fast radiochemical separation and gamma-ray spectrometry. The determined yield values are compared with the available literature data. The yield values for¹⁴⁷Nd,¹⁵¹Nd and¹⁵¹Pm differ from the reported values. The yield for¹⁴⁵Ce is determined for the first time.     

Outline for the revision of ISO Guide 35

The production of reference materials (RMs) is a key activity for the improvement and maintenance of a worldwide coherent measurement system. As detailed in ISO Guide 33, RMs with different characteristics are used in measurements, such as calibration, quality control and method validation, as well as for the assignment of values to other materials. Currently, ISO Guide 35 is in its third edition after it was revised in 2006. The Guide was developed to support best practices in the value assignment to specified properties of Certified Reference Materials (CRMs). This Guide gives general guidance and explains concepts to assist the understanding and development of valid methods to assign values to the properties of a reference material, including the evaluation of their associated measurement uncertainties, and the establishment of their metrological traceability. From the outcome of a systematic review of ISO Guide 35 among the members of ISO/REMCO, the ISO Committee on Reference Materials, it followed that there is a need for revising the current edition of ISO Guide 35. The mandate for the revision is focused on editorial updates to explain the concepts in more detail. It is not envisaged that major technical changes will be introduced. This paper explains the approach and rationale for the revision of ISO Guide 35 and invites comments from the users of the current edition of ISO Guide 35.     

Absorption method for determination of pure beta-emitters in samples containing more than one beta-emitter

Absorption method is shown to be suitable for direct determination of pure β-emitting, isotopes in samples containing more than one β-emitter. This method consists of (1) measurement of the β-counting rate as a function of the thickness of the absorber placed in between the sample and the β-detector and (2) decomposition of the complex absorption curve by computation in order to obtain the contributions of the nuclides to the total counting rate one by one. The method is presented through two examples of its practical application in the field of environmental radioanalysis:⁹⁰Sr and¹⁴⁷Pm isotopes were determined in aerosol samples contaminated by Chernobyl radioactivity and in hot particles of Chernobyl origin using a simple end-window Geiger-Müller counter as a β-detector.     

Certification of reference materials and accreditation of reference material producers: Questionable terminology leads to confusion

In the view of the Deutscher Kalibrierdienst (DKD) , a certifying body for reference materials can be considered to be a calibration laboratory. Therefore, accreditation of calibration laboratories in accordance with ISO/IEC 17025 is the most appropriate way to establish confidence in certificates for reference materials. If necessary, the criteria of ISO/IEC 17025 can be tailored to specific cases. There is no need to provide any new kind of reference-material specific accreditation. However, in view of the variety of reference materials and the practice existing in other countries, accreditation of testing laboratories and product certification bodies may optionally be acceptable as long as the same stringent principles with respect to traceability and measurement uncertainty are applied. Such accreditations but not accreditations of reference material producers (ISO Guide 34) are also covered by existing international mutual recognition arrangements (MRA).     

Phase transformation of the periodic mesoporous organosilicas assisted by organotrialkoxysilane

A phase transformation of mesoporous organosilicas from 2D-hexagonal P6mm to cubic Pm3n phase can be induced by the organotrialkoxysilane with hydrophilic pendant group with the aid of methanol during the co-condensation of 1,2-bis(trimethoxysilyl)ethane (BTME) and (EtO)(3)Si-R (R = L-prolinamide, trans-(1R,2R)-diaminocyclohexane, and gamma-aminopropyl) using the cationic surfactant, octadecyltrimethylammonium chloride (C(18)TMACl), as template in basic medium. Under similar synthesis conditions, no cubic Pm3n phase could be formed in the absence of (EtO)(3)Si-R. Depending on the type of the pendant group, different amounts of methanol were needed for the formation of the cubic Pm3n phase. N-[(triethoxysilyl)propyl]-L-prolinamide (M(L-Pro)) could easily induce the phase changing from 2D-hexagonal P6mm to cubic Pm3n phase probably because L-proline could result in a decreasing of the surfactant packing factor (g) through formation of large architecture on the outer boundary of the surfactant micelles. The organotrialkoxysilane can also help the formation of spherical morphology of the resultant materials.     

Anion-directed self-organization of thermotropic liquid crystalline materials containing a guanidinium moiety

New wedge-shaped thermotropic liquid crystalline materials containing a guanidinium moiety at the apex organize into various supramolecular structures such as hexagonal columnar, rectangular columnar and Pm3n cubic mesophases depending on anions illustrating guest-directed self-organization in mesophases.     

Design and coordination behavior of the first selective recognition ligand of 147Pm(III)

A new amide tripodal ligand, 6-[2-(2-diethylamino-2-oxoethoxy)ethyl]-N,N,12-triethyl-11-oxo-3,9-dioxa-6,12-diazatetradecanamide (4) has been designed and synthesized for the recognition of rare earth ions. Three representative complexes of trivalent lighter (La), middle (Gd), and heavier (Er) rare earth ions with 4 were synthesized and characterized by X-ray crystallography. In the complex, the heptadentate forms a cup-like coordination cavity encapsulating the central ion. Different supramolecular complex dimers are constructed by pi-pi interaction and van der Waals forces in accordance with the lanthanide contraction. The differences of the cavity and dimer structures were investigated further by assessing the separation efficiency of in multitrace solvent extraction of rare earth ions from picrate acid solution and the ligand has the best separation factor for 147Pm(III).