Contribution a l’etude du dosage par radioactivation du soufre et du phosphore en tres faibles concentrations dans les metaux de tres haute purete (Aluminium,magnesium, cuivre,fer, nickel)

The analytical procedure for the determination of sulfur in copper by activation with thermal neutrons is given. The purifications necessary to obtain a radiochemically pure precipitate of baryum sulphate are described. The occurrence of some discrepant values in the determinations led to the observation, for the first time, of abnormally high contents of³⁵S^* at a relatively important depth in the samples of irradiated copper (as deep as about 300 μ). Therefore it is necessary to etch the samples to a depth of 300 μ at least on each surface, before doing the chemical separations. Owing to the great influence of the reaction³⁵Cl(n,p)³⁵S^*, the determination of sulfur by thermal neutrons is only possible at contents higher than 10⁻⁶, even if the chlorine concentration is very low (2·10⁻⁸ Cl introduces a correction in terms of sulfur of the order of 10⁻⁶). For sulfur contents lower than 10⁻⁶, the determination is made by irradiation in fast neutrons. The analytical procedure is described and the corrections in the presence of phosphorus and chlorine are discussed. At contents of the order of 10⁻⁸, the corrections are very small and the determination of some 10⁻⁷ of sulfur is easy. Finally, the determination of phosphorus in copper by activation in thermal neutrons is given. The chemical separations are the same as in the preceding case. Contents of the order of 10⁻⁸ phosphorus are determined without difficulty. The results of the determination of sulfur and phosphorus in many samples of copper are indicated: OFHC copper, High Purity copper (99.999%) and different samples of zone refined copper prepared at the Vitry’s Laboratory.      

Dosage du carbone dans quelques metaux purs par irradiation dans les photons γ

A method is described for the determination of carbon in iron, chromium, nickel, and molybdenum, using the¹²C (γ, n)¹¹C reaction. The samples are irradiated with the bremstrahlung from a 35 MeV electron beam impinging a platinum target. Two apparatuses for the separation of carbon are described. The¹¹C^* activity of the sample is compared with the activities of two graphite standards, counting the positron annihilation gamma rays. The limit of detection is 0.02 μg/g of carbon in high-purity iron.      

Production of58Co in a nuclear reactor under particular consideration of interfering nuclear reactions

A method for the discrimination of side reactions is described. This method of reducing interfering reactions is introduced by the special example of the⁵⁸Co production from natural nickel via the⁵⁸Ni/n,p/⁵⁸Co reaction. By this a coating of the target takes place with a material which has a higher cross section for certain neutron energies than the target material for the undesirable reaction. In this case the natural Ni-targets are coated with Cd and additionally with lead foil as suitable material for absorption of neutrons in the higher energy region. The⁵⁸Co yield indeed decreases to 60% but simultaneously the main contamination decreases by a factor of 8.3 /⁵⁷Co/ and 1.67 /⁶⁰Co/, respectively.     

Fast neutron activation analysis of silicon in aluminum alloys

The silicon content in an aluminum-silicon alloy was measured by nondestructive fast neutron activation analysis with fission spectrum neutrons. A boron nitride irradiation container reduced the flux of thermal and epithermal neutrons at the sample position, enhancing the²⁹Si (n, p)²⁹Al reaction. A detection limit of 0.4% silicon in a 0.5 g alloy sample was obtained.     

Effets de surface dans le dosage par activation neutronique du soufre

Surface effects in the determination of sulfur by neutron activation analysis Thermal neutron activation analysis leads to overestimated sulfur contents in some metals. This phenomenon was studied for samples of iron. It is attributed to ineffective chemical etching arising from dissolution of the metal through a surface layer which retains impurities, especially sulfur-35. Significant amounts of this isotope are produced at the surface through the ³⁵Cl(n, γ)³⁵S reaction. Experimental modifications which lead to the correct sulfur concentration are proposed.     

Determination of nitrogen by neutron activation in meteorites and rocks

The results of determination of nitrogen content in meteorites by neutron activation are reported. The method is based on the¹⁴N(n,p)¹⁴C reaction, which occurs upon irradiation of the samples by neutrons. The use of proportional gas-filled countes for the recording of¹⁴C made it possible to obtain the low nitrogen detection limit of 0.001 g.     

Sulfur determination in coal by 14 MeV neutron activation analysis

A procedure involving the irradiation of coal samples with 14 MeV neutrons and subsequent gamma-ray spectrometry of the irradiated sample for the estimation of solfur in coal, has been outlined. The samples were irradiated with 14MeV neutrons from a Cockroft-Walton type generator for one minute and then subjected to gamma-ray spectrometry for another minute using an automated transfer cyclic system. Ten such cycles were repeated for accumulating events under the 2130 keV gamma ray photopeak belonging to³⁴P (T=12.4 s) produced by the³⁴S(n, p)³⁴P reaction for assessing the lower level of detection, LLD, of Sulfur. Interferences due to the presence of other elements in coal were also determined. Sulfur can be determined at LLD of 0.25% in coal provided a 5 g sample of the coal is irradiated with a neutron flux of 5·10⁹ n·cm⁻²·sec⁻¹ assayed with a gamma ray spectrometer having a large hollow core Ge(Li) detector and an anti-Compton shield.     

The determination of sulphur in copper,nickel and aluminium alloys by proton activation analysis

The ³⁴S(p, n)^34mCl reaction induced by 13-MeV protons is used for the determination of sulphur in copper, nickel and aluminium alloys. The ^34mCl is separated by repeated precipitation as silver chloride. The results obtained were 3.08 ± 0.47, 1.47 ± 0.17 and <1μg g^-1 for copper, nickel and aluminium alloys, respectively.     

Determination du fluor dans les milieux aqueux par activation au moyen de photons gamma

An apparatus ensuring identitical irradiation conditions for three samples and a standard of large volumes is reported. The interference caused by the protons originating from the¹⁶O(γ, p)¹⁵N reaction is determined. Results show that the secondary rection¹⁸O(p, n)¹⁸F induced by the protons of the former reaction gives an apparent fluorine content in natural waters of 0.015 μg/g for a maximum gamma photon beam energy of 21 MeV.      

Charged particle activation analysis of phosphorus in biological materials

Charged particle activation analysis of phosphorus in biological materials using the³¹P (α,n)^34mCl reaction has been studied. Since^34mCl is also produced by the³²S (α,pn) and the³⁵Cl (α, α′ n) reactions, the thick-target yield curves on phosphorus, sulfur and chlorine were determined in order to choose the optimum irradiation conditions. As a result, it was found that the activation analysis for phosphorus without interferences from surfur and chlorine is possible by bombarding with less than 17 MeV alphas. The applicability of this method to biological samples was then examined by irradiating several standard reference materals. It was confirmed that phosphorus can readily be determined at the detection limit of 1 μg free from interferences due to the matrix elements.     

Rapid determination of molar ratios in binary systems by 14 MeV neutron activation analysis

The magnetic characteristics of barium ferrite, a compound widely used for magnetic materials, depend on the molar ratio of iron(III) oxide to barium oxide. On account of this fact, activation analysis using 14 MeV neutrons was applied for the rapid and non-destructive determination of the molar ratio of iron(III) oxide to barium oxide in barium ferrite. Iron was detected as⁵⁶Mn produced from the⁵⁶Fe(n, p)⁵⁶Mn reaction, and barium as^137mBa originating from the¹³⁸Ba(n, 2n)^137mBa reaction. A linear relation was obtained between the ratio of counts of⁵⁶Mn and^137mBa and the molar ratio of iron(III) oxide to barium oxide; the corrected gradient of the experimental calibration curve, obtained with^137mBa internal standard, agreed well with the calculated value. The molar ratios of iron(III) oxide to barium oxide obtained by activation analysis and by chemical analysis were in good agreement.     

Determination of sulfur in steels by radiochemical neutron activation analysis with liquid scintillation counting

A method has been developed for the determination of low-level sulfur in steels by radiochemical neutron activation analysis. During sample irradiation, ³⁵S is produced by the ³⁴S(n,γ)³⁵S reaction. Irradiated steels are mixed with sulfur carrier and dissolved in HCl/HNO₃. Sulfur is reduced to H₂S by reaction with HI/H₃PO₂/HCl. The evolved H₂S is absorbed in dilute NaOH, which is mixed with scintillation cocktail for the measurement of ³⁵S by liquid scintillation counting. Sulfur carrier yield is determined by iodometric titration. Chlorine is also determined by RNAA in order to correct for ³⁵S produced via the ³⁵Cl(n,p)³⁵S reaction. Sulfur has been determined at mass fractions as low as ≈5 mg/kg in ultra-high-purity iron using this method.     

Determining trace amounts of nickel in plant samples by neutron activation analysis

Neutron activation analysis of plant samples for trace amounts of nickel has applications in various fields. Landsberger and Robinson (Trans Am Nucl Soc 102:187–188, 2010) found their measurement of the concentrations of nickel for different NIST reference materials to be significantly greater than the certified values when measuring nickel from the 810.8 keV gamma ray that comes from ⁵⁸Co from the ⁵⁸Ni(n,p) reaction. They determined that this overestimation was due to a significant interference by the presence of ¹⁵²Eu at 810.5 keV, and presented a method for correcting this interference. Their method involved a long thermal irradiation and correction of gamma ray counts based on the 1,408 keV belonging to ¹⁵²Eu. This paper presents an alternative approach, which involves irradiating the samples with epithermal neutrons, which suppressed the ¹⁵²Eu to the point of being negligible for samples with low levels of europium. Both methods were determined to work well for the identification of nickel concentrations by neutron activation analysis.     

Neutron activation analysis of zeolite catalysts

A new method for the determination of aluminum and silicon has been developed for zeolite catalysts. In contrast to previous methods, thermal neutrons are used for the analysis of both elements, and cadmium absorbers are not needed. The silicon determination utilizes a one-hour irradiation to observe the³¹Si produced by the (n, ) reaction of³⁰Si. A 15-second irradiation is used for the²⁷Al(n, )²⁸Al reaction. The²⁸Al activity is corrected for the contribution from the²⁸Si(n,p)²⁸Al reaction by using the analyzed weight of silicon in the sample and the data for a silicon standard irradiated simultaneously with the zeolite and the aluminum standard. The quantitation limits are 0.012 g for silicon and 3.3×10^–5 g for aluminum. Sodium presents a significant interference, but this element can be removed by taking advantage of the ion exchange properties of these materials.     

Die Bestimmung von53Mn,Welches in Meteoritischem Material Durch Kosmische Strahlung Erzeugt Wurde,mit Hilfe der Neutronenaktivierung

Among a number of stable and unstable nuclides formed in material exposed to cosmic radiation the spallation nuclide⁵³Mn (T=2·10⁶ a) is investigated in meteoritic manganese by combined techniques of neutron activation and advanced γ-spectrometry. The need for an economic use of precious meteorites is so ensured best. Intense neutron bombardment transforms the long-livedK-emitter⁵³Mn into⁵⁴Mn, which is detected by its 0.84 MeV γ-rays. Using the (n,γ) cross section—recently derived byMillard—⁵³Mn-values in the range of 60–600 dpm/kg (10⁻¹¹ g/g) are found in a larger number of iron meteorite samples, which are only 1–3 g in weight. The determination is very specific and under appropriate conditions unaffected by side reactions. The attempt to use the⁴⁴Ti (n,γ)⁴⁵Ti reactions for the analysis of spallogenic titanium failed, because the σ_therm of⁴⁴Ti was found to be unexpectedly low (10 barns). Additionally,⁴⁵Sc was determined after (n,γ) reaction by the⁴⁶Sc γ,γ-cascades.      

Determination du bore dans le zirconium,par activation au moyen de deutons

The determination of boron in zirconium by activation analysis using the¹⁰B(d, n)¹²C reaction with the chemical separation of¹¹C is described. The method was applied to industrial zirconium samples as zircalloy.

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Collaborateur temporaire de thèse au CEA.     

Correction of interferences by fast neutrons for determination of sodium in silicon

The interferences caused by reactions with fast neutrons may be corrected with the help of substances containing the interfering element, which are irradiated together with samples and standards. For the correction of the apparent sodium content caused by the²⁸Si(n,p)-reaction we need silicon with an extremely low sodium content. Irradiation without such a standard needs calculation for interference with the help of flux monitors. Because of the highly effective threshold energy of the reaction an additional correction factor taking into account various neutron spectra in different irradiation positions is necessary.     

Contribution a l’etude du dosage par radioactivation du sourfe et du phosphore en tres faibles concentrations dans les metaux de tres haute purete (Aluminium,magnesium, cuivre,fer, nickel)

The determination of sulphur and phosphor by means of activation analysis in high purity aluminium and magnesium is described. The irradiations were performed both with thermal and with fast neutrons. A detailed procedure is given and errors not considered so far are discussed.     

Dating of mineral samples through activation analysis of argon

Mass Spectrometry has been the usual method to determine Ar concentrations in mineral samples for dating them through the⁴⁰Ar/⁴⁰K ratio. This technique has been replaced since 1966 by measurement of⁴⁰Ar/³⁹Ar ratio, after artificial production of³⁹Ar from the³⁹K(n,p)³⁹Ar reaction produced in the fast neutron flux of a nuclear reactor. This method requires the fusion of the sample by incremental heating until reaching a temperature of 1000°C in order to get the total release of both argon isotopes. In principle, it should be possible to determine the⁴⁰Ar/⁴⁰K ratio by activation analysis in an easier, non-destructive way, but it presents the following drawbacks: manufacture of argon standards; usual low ratio peak/Compton distribution for both peaks: 1.29 Mev and 1.52 Mev (⁴¹Ar and⁴²K respectively), since potassium minerals are usually very rich in sodium, manganese and chlorine; reaction⁴¹K(n,p)⁴¹Ar induced by fast neutrons present in the thermal flux; and possible contamination of the samples and standards with atmospheric⁴⁰Ar (99.6% of elementary Ar, whose proportion in the atmosphere at sea level is 0.93%). This paper describes how these problems may be solved, also determining the limits of Ar and K concentration related to Compton distribution, in our experimental conditions.     

Aktivierungsanalytische Sauerstoffbestimmung mit schnellen Reaktorneutronen

Summary Oxygen can be determined by the nuclear reaction ¹⁶O (n, p) ¹⁶N initiated by fast reactor neutrons. The automatic irradiation and counting system which is used in the Munich research reactor for non-destructive oxygen determination is described. The activation by thermal neutrons is suppressed by the installation of a cadmium shield around the pneumatic tube at the irradiation position. Oxygen has been determined in the presence of many elements to find out which elements disturb the oxygen activation analysis.Zusammenfassung Sauerstoff läßt sich aktivierungsanalytisch mit schnellen Reaktorneutronen über die Kernreaktion ¹⁶O (n, p) ¹⁶N bestimmen. Die automatische Bestrahlungs- und Meßanlage, die die Durchführung solcher zerstörungsfreier Sauerstoffanalysen am Forschungsreaktor München erlaubt, wird beschrieben. Die Aktivierung durch thermische Neutronen wurde durch Einbau eines Cadmiumschildes am Bestrahlungsort unterdrückt. Sauerstoffanalysen wurden in Gegenwart zahlreicher Matrixelemente durchgeführt, um zu ermitteln, welche Elemente die aktivierungsanalytische Sauerstoffbestimmung mit schnellen Reaktorneutronen erschweren oder unmöglich machen.Wir danken der Betriebsleitung und der Bestrahlungsgruppe des FRM für deren verständnisvolles Eingehen auf unsere Wünsche, Herrn Dr. Köhler für seine wertvollen Hinweise beim Aufbau der schnellen Rohrpost und Herrn E. Pfeffermann für seine Mithilfe bei einem Teil der Messungen.