On the determination of trace impurities in carbon concentrates used in the spectrochemical analysis of extra-pure substances

The effects of concentration of NaCl, employed as the carrier substance in a carbon collector, on line excitation conditions for trace impurities and on other factors which determine detection limita in spectrochemical analysis with a d.c. arc have been studied. It was shown that over the range 4–0.5 per cent NaCl the change in excitation conditions has but a slight effect on the intensity of spectral lines. The major role in the marked lowering of detection limits for trace impurities (Ag, Be, Bi, Cd, Cu, Ga, Ge, In, Mn, Zn, down to n × 10⁻¹⁰ g; Au, Ba, Co, Cr, Ni, Pb, Sb, Sn, Tl—to n × 10⁻⁹ g and for As, B, Pt, Te—n × 10⁻⁸ g) is played by a decline in background intensity and a better coefficient of vapour utilization. For some trace impurities this limit may be improved still further by re-shaping the upper electrode.     

INAA of trace impurities in aluminium clads

As a contribution to nondestructive neutron assay of reactor grade aluminium, a number of elements have been investigated qualitatively and quantiatively using a vertical channel in the IRT-5000 reactor with a thermal neutron flux of 7.6·10¹²n·cm^–2·s^–1. The -ray spectra of irradiated samples were analysed with a 30 cm³ Ge(Li) detector connected to an HP-computer and a 4096 channel analyser. The following impurities have been determined: Sc, Ca, Cr, Fe, Ni, Co, Zn, As, Sb, W, Au, Th and U, while Lu and Hf have been determined qualitatively only.     

Neutron activation analysis of PbxSn1-xTe using extraction chromatography

A simple procedure of neutron activation analysis for the determination of 16 impurities in Pb_xSn_1–xTe with detection limits from 1×10^–4% for Ni and Zr to 2×10^–9% for Sc has been developed. The procedure is based on extraction chromatographic separation of impurities from the irradiated sample.     

Analysis of High-Purity Volatile Compounds

The current status of the analysis of high-purity volatile substances is considered. Two types of impurities in high-purity volatile substances were distinguished: molecularly dissolved substances and suspended particles. The main factors that restrict the limiting capabilities of analytical techniques were revealed. The attained detection limits were 10^–8–10^–10% for metal impurities, 10^–4–10^–8% for organic substances, 10^–5–10^–9% for water, and 10^–5–10^–7 for permanent gases. Suspended particles of 0.04–0.003 m in size were determined by light scattering.     

Investigation of uranium and thorium concentrations in the fluorite beds of Anatolia by using solid state nuclear track detectors

Uranium and thorium concentrations of fluorite samples taken from the main fluorite beds of Anatolia (Turkey) have been determined by fission fragment radiography using solid state nuclear track detectors (SSNTDs). The fissionable elements concentration of the fluorite samples were found to be 10^–4–10^–7 g/g. The Th/U ratio, obtained for all the fluorite samples, is found to be characteristic for the location of the samples. Some correlations between the concentration of Th and those of lanthanites and concentration of U and that of Mo or Zr are observed.     

Identification and determination of natural radioactive impurities in rare earth chlorides

²²⁷Ac,²²⁸Th,²²⁶Ra,²¹⁰Po and²¹⁰Pb can be present at rare earth chlorides. A radiochemical procedure is presented for the identification and determination of natural radioactive impurities in rare earth chlorides. The determination limits for these radionuclides were 1.5·10^–4 to 3·10^–1 Bq/g. The relative standard deviations for determining 10^–2 Bq/g radionuclides were usually less than ±7%.     

Analytical possibilities of the BOR 60 reactor

The analytical potential of a fast neutron reactor has been studied. The maximum density of the neutron flux is 2.5·10¹⁵ cm^–2·s^–1 at a maximum energy of 450 keV. The determining reaction for activation analysis at this reactor is an (n, n) reaction. The possibility of selectively determining Pb, Hg, Cd, Au, Ag and other elements at a level of 10^–5–10^–8% is demonstrated. This activation technique allows rapid determination of these elements.     

Zur Bestimmung des Chloridgehalts von Zinksulfidluminophoren

Zusammenfassung Zur Bestimmung chloridischer Verunreinigungen in Zinksulfidluminophoren wird eine potentiometrische Titrationsmethode vorgeschlagen. Verluste bei der Auflösung der Proben werden durch die Verwendung einer geschlossenen Apparatur vermieden. Die untere Erfassungsgrenze liegt bei etwa 10^–5 g Cl/g ZnS. Die Chloridgehalte von ZnS-Luminophoren, welche mit chloridischen Mineralisatoren hergestellt wurden, ergaben sich zu 10^–5 bis 2,5 · 10^–4 g Cl/g ZnS. Eine Diskussion der Ergebnisse ist an anderer Stelle vorgesehen.

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Summary A potentiometric method is proposed for the determination of impurities of chloride in ZnS phosphors. Any losses during the dissolution of the samples have been avoided by use of a closed apparatus. The lower limit of detection is 10 ppm Cl with a sample size of 1 g. ZnS phosphors prepared with chloride fluxes contain between 10 and 250 ppm Cl per 1 g ZnS. A discussion of the results will appear in another paper.

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Dem Leiter des Bereiches Luminescenzforschung, Herrn Dr. H. Ortmann, danke ich für die Förderung dieser Arbeit.     

Bestimmung von Spuren Titan und Zirkonium in Molybd?n und Wolfram bzw. deren Sauerstoffverbindungen durch R?ntgenfluorescenz-Spektralanalyse (RFA)

Zusammenfassung Eine Methode zur Bestimmung von Mikrogramm-Mengen Titan und Zirkonium in metallischem Molybdän und Wolfram bzw. in den Ausgangsstoffen MoO₃ bzw. WO₃ und H₂WO₄ wird vorgestellt. Die Methode beruht auf der Trennung der Titan- und Zirkoniumspuren von der Molybdänbzw. Wolframmatrix, wobei die Trennung durch Mitfällung der Spurenverunreinigungen erfolgt; als Kollektor findet Kobalthydroxid Verwendung. Die so erhaltenen Hydroxidniederschläge werden auf Filterpapier gesammelt und nach Trocknen derselben durch RFA vermessen. Mit dieser Arbeitstechnik erhält man bis zu 1 · 10^–4 g Titan bzw. Zirkonium Eichgeraden; die Erfassungsgrenze für Titan kann mit 3,4 · 10^–8 g, die für Zirkonium mit 5,0 · 10^–7 g angegeben werden. Die Gesamtdauer für eine Einzelanalyse beträgt etwa 45 min, wobei aber mehrere Proben gleichzeitig analysiert werden können.

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Determination of trace impurities of titanium and zirconium in molybdenum and tungsten and their oxygen compounds by X-ray fluorescence spectrometry

A method for the determination of trace impurities of titanium and zirconium in metallic molybdenum and tungsten or in their basic products MoO₃, WO₃ and H₂WO₄ is presented. The method is based on coprecipitation of the trace impurities titanium and zirconium with cobalt hydroxide as carrier from molybdenum and tungsten matrices. The hydroxide precipitates are collected on filter paper and measured by XRF after drying. In that way it is possible to get linear calibration curves up to 1 · 10^–4 g; the limits of detection are determined to be 3.4 · 10^–3 g for titanium and 5.0 · 10^–7 g for zirconium. About 45 min are necessary for one analysis, but several samples can be analysed simultaneously.

     

Determination of Rare-Earth Elements in Sulfide Minerals by Inductively Coupled Plasma Mass Spectrometry with Ion-Exchange Preconcentration

A procedure was developed for determining ultratrace rare-earth elements in sulfide minerals by inductively coupled plasma mass spectrometry with ion-exchange preconcentration. The concentration factor was 200. The found concentrations of rare-earth elements were 6–30 times lower than those in chondrites. For lanthanum and praseodymium, RSD < 10%; for other rare-earth elements, RSD < 6%. The accuracy of the results was verified by the addition of known amounts of Eu, Tb, Tm, and Lu to a chalcopyrite sample at the stage of decomposition with HCl and HNO₃. The calculated yield of rare-earth elements was 94–96%. The detection limit was from 0.06 ng/g (6 × 10^–9%) for lutetium to 5 ng/g (5 × 10^–7%) for cerium. The procedure was used for the determination of rare-earth elements in chalcopyrites, pyrites, and sphalerites.     

Highly Sensitive Determination of Carbon- and Hydrogen-Containing Impurities in Silicon Tetrachloride by Gas Chromatography

Procedures were developed for the direct gas-chromatographic determination of impurities of organochlorine substances, chlorosilane, and alkylchlorosilane in silicon tetrachloride and for the gas-chromatographic analysis with matrix subtraction by preliminary hydrolysis of silicon tetrachloride and subsequent extraction of organochlorine impurities with an organic solvent. It was found that the major impurities in high-purity silicon tetrachloride obtained by the rectification of the by-product in the production of trichlorosilane are trichlorosilane, methyltrichlorosilane, methyldichlorosilane, chloroform, and carbon tetrachloride. Detection limits of impurities are 10^–5–10^–7wt %, which is lower than those reported in the literature by 1–2 orders of magnitude.     

Structural investigations of electrical conducting plasma polymerized films from 2-iodothiophene

Summary Thin plasma polymerized films were produced in a microwave (2.45 GHz) plasma discharge using 2-iodothiophene as the initial monomer. The structure of these electrically conducting films (10^–6–10^–1 S/cm), the chemical state of the doping element iodine and the elemental homogeneity at the surface and in the films have been investigated by XPS, FTIR and AES. An interesting relationship was found that indicates some similarity to conventional polythiophene, prepared by electrodeposition. Besides covalently bound iodine, considerable amounts of I ₃ ^– and I ₅ ^– were detected and also a small number of O-I bonds were identified.     

Verfahren zur Spurenanalyse aus metallischen Proben

Zusammenfassung Ein neues lösungsspektrographisches Zerstäubungsverfahren wird beschrieben, bei dem die Lösung so zerstäubt wird, daß sie die Graphitelektroden nicht berührt. Mit diesem Verfahren könnten 10^–3 bis 10^–5 % Al, B, Cr, Cu, Mg, Mn, Mo, Ni, Si, Sn, Ti, V und Zr in Eisen und Stahl bestimmt werden.Zur Bestimmung von Verunreinigungen oder Einschlüssen in Stahl wird ein spektrographisches Verfahren mit Preßlingselektroden empfohlen, das nur 0,1–1 mg Rückstand benötigt. Oxide von Al, B, Ca, Co, Cu, Cr, Fe, Mg, Mn, Mo, Nb, Ni, Pb, Si, Sn, Sr, Ti, V, Zn und Zr konnten bis herab zu etwa 10^–7 g erfaßt werden.

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Methods for the determination of trace elements from metallic samples

The principles of a new spectrographical atomizing-method of solution are described. The solution has to be atomized into a gap without contacting the surface of the graphite electrodes. In this way the exact determination of 10^–3 to 10^–5 % of Al, B, Cr, Cu, Mg, Mn, Mo, Ni, Si, Sn, Ti, V and Zr in iron and steel is possible.The microanalytical determination of impurities or inclusions in steel has been achieved by a spectrographical method with briquette electrodes. The necessary amount of isolation residue is only 0.1–1 mg. The oxides of Al, B, Ca, Co, Cu, Cr, Fe, Mg, Mn, Mo, Nb, Ni, Pb, Si, Sn, Sr, Ti, V, Zn and Zr can be accurately determined by this procedure. The limit of determination is about 10^–7 g.

     

Quantitative analysis of W-C:H coatings by EPMA,RBS (ERD) and SIMS

Several analytical techniques have been used to characterize homogeneous films of tungsten-containing hydrogenated carbon (W-C: H), deposited on Si with a film thickness of 1–1.5 m. Electron probe microanalysis (EPMA) enables one to determine the major components W (3–43 at %) and C, impurities (< 2 at %) of Ar and O, and the mass thickness (300–1800 g/cm²) of the films. The agreement between the results of EPMA and the data (W-content, mass thickness) provided by Rutherford backscattering spectrometry (RBS) is 5–10% relative. Quantitative analysis of hydrogen in W-C:H films (1–16 at %) is carried out by the technique of elastic recoil detection (ERD). A suitable scheme for the determination of H in W-C: H films by SIMS is proposed, based on monitoring the intensity ratio of HCs⁺/CCs⁺ secondary ions.     

Trace element determination in high-purity scandium by neutron activation analysis and pre-irradiation matrix separation

A pre-irradiation separation procedure has been developed for the determination of trace elements in high-purity scandium by neutron activation analysis. The sample is dissolved in high-purity concentrated hydrochloric acid and scandium is extracted with the same volume of a solution of 50 vol.% bis(2-ethyl hexyl)-orthophosphoric acid (HDEHP) in toluene. The scandium matrix is removed from the most important trace impurities and the residual amount of Sc is in the range of 0.001%. The separation is carried out in the vial to be used in irradiation to prevent sample contamination. Detection limits in the ppb range were achieved with a sample of 10 mg, a thermal neutron flux of 2 · 10¹³ n · cm^–2 · s^–1 and an irradiation time of 48 hours. Most of the elements sought in two samples of high-purity scandium were below the detection limits.     

Solubility of Solid 2,3-Dimethylbutane and Cyclopentane in Liquid Argon and Nitrogen at the Standard Boiling Points of the Solvents

The solubilities of solid 2,3-dimethylbutane and cyclopentene in liquid argon at a temperature of 87.3 K and in liquid nitrogen at 77.4 K have been measured by the filtration method. The hydrocarbon contents in solutions were determined using gas chromatography. GC–MS was used to identify impurities in solutes. The experimental value of the mole fraction solubility of solid 2,3-dimethyl-butane in liquid argon at 87.3 K is (8.26 ± 1.60) × 10^–6 and (2.77 ± 0.94) × 10^–8 in liquid nitrogen at 77.4 K. The experimental value of the mole fraction solubility of solid cyclopentene in liquid argon at 87.3 K is (5.11 ± 0.44) × 10^–6 and (4.60 ± 0.76) × 10^–8 in liquid nitrogen at 77.4 K. The Preston–Prausnitz method was used for calculation of the solubilities of solid hydrocarbons in liquid argon in the temperature range 84.0–110.0 K and in liquid nitrogen from 64.0 to 90.0 K. The solvent–solute interaction parameters l ₁₂ were also calculated. At 90.0 K liquid argon is a better solvent for investigated solid hydrocarbons than is liquid nitrogen.     

Determination of trace scandium by ion-exchanger phase spectrophotometry withp-nitrochlorophosphonazo

Ion-exchanger phase Spectrophotometry withp-nitrochlorophosphonazo (CPApN) has been developed for the determination of scandium. The linear range is 1–8 g of scandium in 50 ml of solution, using 0.8 g of resin, with an apparent molar absorptivity of 2.76 × 10⁵ 1 mol^–1 cm^–1. Aluminum and rare earth elements in reasonable amounts do not interfere. The method has been applied successfully to the determination of scandium in alloys, with relative standard deviations of 2–4%.     

Adsorption behaviour of microamounts of cesium on manganese dioxide

The adsorption of cesium on manganese dioxide from aqueous solutions has been studied in relation to pertinent variables such as shaking time, pH, composition of aqueous solutions, mass of adsorbent (10 mg–1 g) and concentration of adsorbate (10^–6–5·10^–3 M), using a radiotracer technique. The influence of various anions and cations on cesium adsorption was examined. The distribution coefficient of a variety of other elements was determined under similar conditions. The adsorption of cesium obeys a Freundlich-type isotherm over the entire concentration range investigated, whereas the Langmuir-type isotherm is followed only at moderate concentrations.     

Bestimmung von Spurenverunreinigungen in Gallium und Galliumarsenid durch Neutronenaktivierungsanalyse

Zusammenfassung Bei der Neutronenbestrahlung von Gallium und Galliumarsenid werden recht hohe spezifische Aktivitäten der Radionuklide ⁷²Ga und ⁷⁶As gebildet. Ihre ziemlich kurzen Halbwertszeiten von 14,1 bzw. 26,5 h ermöglichen erne relativ ungestörte Bestimmung aller Fremdelemente mit langlebigen Radionukliden nach weitgehendem Abklingen der Matrixaktivitäten; zu diesen Elementen gehören u. a. Ag, Cd, Co, Cr, Fe, Hg, Ni, Zn. Für die Bestimmung von Elementen mit kurzlebigen Radionukliden, wie Mn, Cu, Ge u. a. muß dagegen die hochradioaktive Probe (Aktivität 1–10 Ci) möglichst frühzeitig nach Bestrahlungsende hinter entsprechend starken Abschirmungen aufgearbeitet werden. Sowohl für die Bestimmung der langlebigen als auch der kurzlebigen Radionuklide wurden chemische Trennungsgänge ausgearbeitet, die leicht in bezug auf Zahl und Art der zu bestimmenden Verunreinigungselemente variiert werden können. Die bei Einsatz optimaler Bestrahlungsbedingungen erreichbaren unteren Bestimmungsgrenzen liegen zwischen 2·10^–3 und 2·10^–6 ppm. Mögliche Störungen der Bestimmung durch Nebenreaktionen sowie durch Kontamination des während der Bestrahlung flüssigen Galliums durch im Verpackungsmaterial vorhandene Verunreinigungen werden diskutiert.

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Determination of trace impurities in gallium and gallium-arsenide by neutron activation analysis

In neutron activation of gallium and gallium arsenide very high specific activities of the radionuclides ⁷²Ga and ⁷⁶As are formed. Their rather short half-life values of 14.1 and 26.5 h respectively permit relatively undisturbed determination of all foreign elements with long-lived radionuclides after a certain degree of decay of the matrix activities. These elements include Ag, Cd, Co, Cr, Fe, Hg, Ni, Zn and others. However, for the determination of elements with short-lived radionuclides, such as Mn, Cu, and Ge, it is necessary to radiochemically process the highly radioactive sample (activity 1 to 10 Ci) behind suitable shielding as soon as possible after irradiation. Chemical separating schemes have been developed for the determination of both long-lived and short-lived radionuclides. These can be varied easily according to the number and nature of the impurity elements to be determined. The sensitivity attainable under optimal irradiation conditions lies between 2×10^–3 and 2×10^–6 ppm. The authors discuss possible disturbance of the analysis due to side reactions and contamination of the liquid gallium by impurities in the packing material during irradiation.

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Vortrag bei der Tagung Analytische Probleme der Reindarstellung von Halbleitern, Wiesbaden 24/25.9.1968.

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Wir danken Herrn Dr. Sirtl, Forschungslaboratorium München der Siemens AG.. und Herrn Dr. Raab, Forschungslaboratorium Erlangen der Siemens A.G. für die Überlassung der Analysenproben sowie Herrn Prof. Dr. Gebauhr für anregende Diskussionen.     

Preconcentration of neptunium by supported liquid membranes for luminescent analysis of environmental samples

The possibilities of liquid membrane preconcentration of neptunium from environmental samples of different nature have been studied. The use the solid-supported liquid membrane containing a trioctylmethylammonium nitrate carrier allows to achieve preconcentration factors of 10²–5×10². The teflon solid support does not interact with the luminescent matrix (CaF₂, PbMoO₄) during calcination at 900 °C, so it makes practical to measure the neptunium content by luminescence without reextraction to aqueous solution. As a result, the detection limit of neptunium is lowed down to 10^–13 g ml^–1 and 5×10^–13 g g^–1 for pure solutions and soils, respectively.