Determination of light elements in metals and semiconductors by charged particle activation analysis

The determination of boron, carbon, nitrogen and oxygen in metals and semiconductors by charged particle activation analysis (CPAA) is reviewed. It is shown that CPAA is a sensitive and accurate method suitable for the analysis of reference materials.     

Multielement ultratrace analysis in tungsten using secondary ion mass spectrometry

Summary The ever increasing demands on properties of materials creates a trend also towards ultrapure products. Characterization of these materials is only possible with modern, highly sophisticated analytical techniques such as activation analysis and mass spectrometry, particularly SSMS, SIMS and GDMS [1].Analytical strategies were developed for the determination of about 40 elements in a tungsten matrix with high-performance SIMS. Difficulties like the elimination of interferences had to be overcome. Extrapolated detection limits were established in the range of pg/g (alkali metals, halides) to ng/g (e. g., Ta, Th).Depth profiling and ion imaging gave additional information about the lateral and the depth distribution of the elements.

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Multielementepurenanalyse in Wolfram mittels SIMS

     

Determination of the Stoichiometric Composition of High-Temperature Superconductors by ICP-OES for Production Control

 A procedure to dissolve and analyse different types of high-temperature superconducting materials in order to determine their stoichiometric com- position is described. As sample materials Y-Ba-Cu-O and (Pb)Bi-Sr-Ca-Cu-O were analysed. They were dissolved with hydrochloric acid and analysed by simultaneous ICP-OES, which fits best for this analytical task because of its multielement capacity, its high precision of determination and accuracy. Each of the relevant metals (Pb, Bi, Sr, Ca, Y, Ba, Cu) could be determined successfully. The precision of the determination was found to be better than 2% relative standard deviation and usually even below 1%. The sample preparation and determination procedure described allows a high sample throughput, which is essential for production control. Also precursors of the superconducting materials (e.g. nitrate solutions) could be analysed by the procedure described.     

Determination of sulfur in near-surface layers of materials by means of the32S(3He,p)34mCl nuclear reaction

The cross-sections of the³²S(³He, p)^34mCl nuclear reaction have been determined in the projectile energy region between 4.0 and 12.0 MeV with the aim of their use for the determination of sulfur in surface layers of materials by means of Charged Particle Activation Analysis (CPAA). The measured cross-sections indicate that the application of this reaction for the determination of ppm and sub-ppm concentrations of sulfur is possible depending on the matrix material (e.g. detection limit for S in GaAs is 2 ppm, whereas in Si 300 ppb).     

Multielement comparison of instrumental neutron activation analysis techniques using reference materials

Several instrumental neutron activation analysis techniques (parametric, comparative, and k_o-standardization) are evaluated using three reference materials. Each technique is applied to National Institute of Standards and Technology standard reference materials, SRM 1577a (Bovine Liver) and SRM 2704 (Buffalo River Sediment), and the United States Geological Survey standard BHVO-1 (Hawaiian Basalt Rock). Identical (but not optimum) irradiation, decay, and counting schemes are employed with each technique to provide a basis for comparison and to determine sensitivities in a routine irradiation scheme. Fifty-one elements are used in this comparison; however, several elements are not detected in the reference materials due to rigid analytical conditions (e.g., insufficient length of irradiation or activity for radioisotope of interest decaying below the lower limit of detection before counting interval). Most elements are normally distributed around certified or consensus values with a standard deviation of 10%. For some elements, discrepancies are observed and discussed. The accuracy, precision, and sensitivity of each technique are discussed by comparing the analytical results to consensus values for the Hawaiian Basalt Rock to demonstrate the diversity of multielement applications.     

Multielement-preconcentration for atomic spectroscopy by sorption of dithiocarbamate-metal complexes (e.g., HMDC) on cellulose collectors

Summary The analytical preconcentration of trace metals from saline solutions by sorption of their dithiocarbamates on reversed-phase cellulose is reported. Heavy metals [e.g., Bi, Cd, Co, Cr(III), Cu, Fe, Hg, In, Ni, Pb, Tl, Yb, Zn] dissolved at the ng/l to g/l level can be quantitatively fixed as dithiocarbamates (e.g., HMDC) on cellulose within a few minutes. In salt solutions and without use of any carriermetal the distribution coefficients K _d are of the order 10⁴ to 10⁵ (ml/g) in the pH range between 4 and 10. The K _d values of dithiocarbamates on RP cellulose (e.g., acetylated cellulose) are higher by a factor of 5 to 10 than those on conventional RP sorbents (e.g., C₁₈, C₆H₅). Moreover, the chemical blanks caused by the cellulose collector (batch and column procedure) are below the detection limits of the determination methods used (flame-AAS, graphite furnace-AAS, ICP-OES), Cu, Fe and Zn excepted. Combined with the above atomic spectroscopy methods, the multielement preconcentration with the aid of HMDC complexes is applied to the determination of trace metals in natural waters (including sea water), biological matters (e.g., urine, bovine liver) and high-purity metals (e.g., Al). The accuracy and precision of the developed analytical procedure are confirmed by trace determinations in standard reference materials (e.g., NBS 1577, Alusuisse 112/02).

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Multielement-Voranreicherung für die Atomspektroskopie durch Sorption von Dithiocarbamat-Metallkomplexen an Cellulose-Kollektoren

     

A novel approach to the explanation the effect of microwave heating on isothermal kinetic of crosslinking polymerization of acrylic acid

The effect of microwave heating (MWH) on the isothermal kinetic of crosslinking-polymerization of acrylic acid (CPAA) was investigated. The kinetic curves of CPAA were determined in the temperature range from 303 to 328 K. By applying the model-fitting method it was revealed that the isothermal kinetics of CPAA was described by the first order chemical reaction kinetics model under the MWH and by the second order chemical reaction rate model for the conventionally heated (CH) process. The values of the reaction rate constants of CPAA are about 40 times higher for the microwave heated system than for the conventional heating. The kinetic parameters (activation energy (E _a) and pre-exponential factor (lnA)) of the CPAA are significantly lower than the corresponding values for CH process. It was found that the increase in the reaction rate of CPAA for MWH was not a consequence of overheating neither the hot spots in the reaction system. Based on model of selective energy transfer between the reacting molecules and the heating bath a novel explanation of the established effects of MWH on the kinetics of CPAA is given. A quantized nature and value of activation energy was confirmed. The decrease in the value of activation energy of CPAA under microwave heating is explained by the increased value of energy of ground vibration level of resonant oscillator in the AA molecule (v = 1417 cm^?1) caused by the absorption of non-thermal energy of MW field.     

Analyse par activation aux photons gamma et aux particules chargees

The activation methods, nuclear reactions and chemical separation processes used to determine traces of carbon, nitrogen and oxygen in the metals and semiconductors considered are described briefly. The results obtained are reviewed. They mainly concern the following analyses: (1) determination of carbon and oxygen in alkaline metals; (2) determination of nitrogen and oxygen in refractory metals; (3) determination of carbon, nitrogen and particularly oxygen in various other metals; (4) determination of these same elements in semiconducting materials. In some cases the concentrations measured by γ photon or charged particle activation methods are compared with the results obtained by other techniques.     

Web-based spectrum analysis software for photon activation analysis

Photon activation analysis (PAA) includes extensive data evaluation that is sensitive to error. In order to save time and minimize human error, a new computer program—photon activation analysis system (PAAS)—was designed, built and implemented using the SQL language and Asp.net technology to analyze PAA data. Given peak information from PAA spectra and aided by a photonuclear data library, the program identifies the product isotopes, recognizes the possible nuclear reactions, and evaluates the concentration of target elements. Uncertainties of concentrations are estimated using standard error propagation techniques. The program can be accessed conveniently anywhere the internet is available and gives a fast and reliable determination of the trace elemental content of samples. Furthermore, this program also allow one to search its database for the information of general photonuclear reactions (e.g. energy lines, line intensities, target and product nuclides, photonuclear reactions, cross sections, natural abundance, etc.) and estimating the activity even before the activation begins. By switching the nuclide libraries, the program could also be expanded to neutron activation analysis and charged particle activation analysis (CPAA) without any difficulty. This program can be a versatile tool for the daily use of the nuclear and radiochemistry laboratories that conduct activation analysis.     

Applications of inductively coupled plasma mass spectrometry and laser ablation inductively coupled plasma mass spectrometry in materials science

Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) have been applied as the most important inorganic mass spectrometric techniques having multielemental capability for the characterization of solid samples in materials science. ICP-MS is used for the sensitive determination of trace and ultratrace elements in digested solutions of solid samples or of process chemicals (ultrapure water, acids and organic solutions) for the semiconductor industry with detection limits down to sub-picogram per liter levels. Whereas ICP-MS on solid samples (e.g. high-purity ceramics) sometimes requires time-consuming sample preparation for its application in materials science, and the risk of contamination is a serious drawback, a fast, direct determination of trace elements in solid materials without any sample preparation by LA-ICP-MS is possible. The detection limits for the direct analysis of solid samples by LA-ICP-MS have been determined for many elements down to the nanogram per gram range. A deterioration of detection limits was observed for elements where interferences with polyatomic ions occur. The inherent interference problem can often be solved by applying a double-focusing sector field mass spectrometer at higher mass resolution or by collision-induced reactions of polyatomic ions with a collision gas using an ICP-MS fitted with collision cell. The main problem of LA-ICP-MS is quantification if no suitable standard reference materials with a similar matrix composition are available. The calibration problem in LA-ICP-MS can be solved using on-line solution-based calibration, and different procedures, such as external calibration and standard addition, have been discussed with respect to their application in materials science. The application of isotope dilution in solution-based calibration for trace metal determination in small amounts of noble metals has been developed as a new calibration strategy. This review discusses new analytical developments and possible applications of ICP-MS and LA-ICP-MS for the quantitative determination of trace elements and in surface analysis for materials science.     

Elemental characterization of coal ash and its leachates using sequential extraction techniques

Over 50 million tons of coal ash are produced annually in North America. Technological improvements in air pollution control have decreased stack emissions but have also increased contaminant concentrations in the ash of coal-fired boiler applications. The leaching of heavy metals and other elements during regulatory tests may cause coal ash ro be classified as hazardous waste, complicating land disposal. The hazardous nature of coal ash remains unclear because current toxicity tests fail to effectively characterize the elemental distribution and chemical solubility of trace metals in the landfill environment. Leaching characteristics of ash samples can be investigated with various laboratory extraction procedures in association with multi-elemental analytical techniques (e.g., neutron activation analysis and inductively coupled plasma-atomic emission spectroscopy). Such methods provide more thorough analyses of coal ash leaching dynamics than the regulatory assessments can demonstrate. Regulatory elements including Ag, As, Ba, Cd, Cr, Hg, Pb, and Se were shown to remain in largely insoluble forms while elements such as B and S leached at higher levels. Experimental results may assist operators of coal-fired boiler industries in selecting coal types and disposal options to curtail the leaching of potentially toxic inorganic contaminants.     

Accurate determination of the noble metals II. Determination methods

As was shown in the first part of this contribution, accurate analytical determination of the noble metals in rocks, ores and alloys needs a sophisticated sample pretreatment prior to the final determination step of the preconcentrated elements. For this many instrumental and classical methods are available, the choice of which is usually dictated by levels of precious metal to be handled, nature of sample matrix and availability of the instruments. For trace levels (μg/g range) flame atomic absorption and inductively coupled plasma (ICP) emission spectrometry can be used. ICP emission is favoured because of ease of multi-element operation. At the sub-μg/g level furnace atomic absorption and nuclear techniques (mainly neutron activation) are favoured. Minor and % concentrations are best handled by X-ray fluorescence. The use of standard reference samples and internal and external laboratory control schemes are essential to the accurate determination of precious metals.     

Determination of metal-cofactors in respiratory chain complexes by total-reflection X-ray fluorescence spectrometry (TXRF)

Total Reflection X-Ray Fluorescence Spectrometry (TXRF) offers many advantages for the detection of trace elements in enzymes as compared to other well known analytical techniques like flame-AAS or ICP-AES because of the significantly smaller amounts of sample required. Without any decomposition, elements like Fe, Ni, Cu, Zn, Mn and Mo could be determined with high accuracy, in spite of the large bio-organic matrix. Besides the metals also sulfur can be determined in protein samples. The two terminal oxidases, cytochrome c oxidase and quinol oxidase, isolated from the soil bacterium Paracoccus denitrificans, were transferred from their usual salt buffer into a solution of 100 mmol/L tris(hydroxymethyl)aminomethane (TRIS) acetate containing an appropriate detergent. By this procedure an improved signal/noise ratio is attained. The data for cytochrome c oxidase are in good agreement with values obtained by ICP-AES. Further results of quinol oxidase, which has different element ratios, also fit the expected values. The investigations lead to the conclusion that the method is well suited for the quantitative determination of metals in enzymes, and in particular their molar ratios, and requires only small amounts of the biological sample without any extensive pretreatment.     

Gold and silver determination in Waters by SPHERON® Thiol 1000 preconcentration and ETAAS

A reliable procedure for the electrothermal atomic absorption spectrometry (ETAAS) determination of gold and silver in waters at trace level is described. The method is based on prior separation and preconcentration of the metals using a chelating sorbent SPHERON® Thiol 1000 after acidification of water samples (pH < 3) with nitric acid. Optimization of analytical variables during enrichment and ETAAS determination of the metals are discussed. The accuracy of the method is verified by analysis of certified reference materials. The limits of determinations based on 10 σ definition were 0.005 ng cm^?3 for Au and 0.02 ng cm^?3 for Ag. Precision of studied elements determination expressed by relative standard deviation varied in the range from 2.9 % to 16.4 %.     

Inorganic trace analysis by mass spectrometry

Mass spectrometric methods for the trace analysis of inorganic materials with their ability to provide a very sensitive multielemental analysis have been established for the determination of trace and ultratrace elements in high-purity materials (metals, semiconductors and insulators), in different technical samples (e.g. alloys, pure chemicals, ceramics, thin films, ion-implanted semiconductors), in environmental samples (waters, soils, biological and medical materials) and geological samples. Whereas such techniques as spark source mass spectrometry (SSMS), laser ionization mass spectrometry (LIMS), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), glow discharge mass spectrometry (GDMS), secondary ion mass spectrometry (SIMS) and inductively coupled plasma mass spectrometry (ICP-MS) have multielemental capability, other methods such as thermal ionization mass spectrometry (TIMS), accelerator mass spectrometry (AMS) and resonance ionization mass spectrometry (RIMS) have been used for sensitive mono- or oligoelemental ultratrace analysis (and precise determination of isotopic ratios) in solid samples. The limits of detection for chemical elements using these mass spectrometric techniques are in the low ng g⁻¹ concentration range. The quantification of the analytical results of mass spectrometric methods is sometimes difficult due to a lack of matrix-fitted multielement standard reference materials (SRMs) for many solid samples. Therefore, owing to the simple quantification procedure of the aqueous solution, inductively coupled plasma mass spectrometry (ICP-MS) is being increasingly used for the characterization of solid samples after sample dissolution. ICP-MS is often combined with special sample introduction equipment (e.g. flow injection, hydride generation, high performance liquid chromatography (HPLC) or electrothermal vaporization) or an off-line matrix separation and enrichment of trace impurities (especially for characterization of high-purity materials and environmental samples) is used in order to improve the detection limits of trace elements. Furthermore, the determination of chemical elements in the trace and ultratrace concentration range is often difficult and can be disturbed through mass interferences of analyte ions by molecular ions at the same nominal mass. By applying double-focusing sector field mass spectrometry at the required mass resolution—by the mass spectrometric separation of molecular ions from the analyte ions—it is often possible to overcome these interference problems. Commercial instrumental equipment, the capability (detection limits, accuracy, precision) and the analytical application fields of mass spectrometric methods for the determination of trace and ultratrace elements and for surface analysis are discussed.     

Semiquantitative Analysis of Biological Materials by Inductively Coupled Plasma–Mass Spectrometry

Semiquantitative analysis with accuracy of ±30 to 50% is a valuable tool for rapid screening of samples prior to quantitative determination of trace metals. In this study semiquantitative analysis software available with commercial inductively coupled plasma–mass spectrometry (ICP-MS) instrumentation is applied for rapid multielemental analysis, and the accuracy and precision of this semiquantitative analysis approach is evaluated with biological certified reference materials. Samples were prepared by high-pressure, high-temperature nitric acid vapor-phase digestion. For most elements the measured semiquantitative results are in the range of the certified values. With appropriate analyte solution dilution, the measured concentrations of the major elements (e.g., Ca) also agree with certified values. The accuracy is within ±10% for 28 element determinations that include 16 individual elements (Ag, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Rb, Sb, Sr, Tl, and Zn) and ±20% for 54 element determinations that include three more elements (Mg, V, and U) in eight certified reference materials including water. The method precision is 11 ± 11% (relative standard deviation,n= 65).     

Introduction of multiple γ-ray detection to charged particle activation analysis

Charged particle activation analysis (CPAA) is a rapid method with high accuracy which can analyze multi-elements simultaneously. Since multiple γ-ray detection method is expected to improve the detection efficiency and the signal-to-noise ratio, we study what design of the γ-ray detector array is the most suitable for CPAA. We take up four design candidates and investigated the responses by the radiation simulation code Geant 4. From the results, we have deduced the best design with 5 germanium detectors in close geometry. By inspecting the sensitivity in CPAA, the method is proved to be useful and applicable to 116 nuclides.

     

Application of neutron activation analysis to determine the contents and isotopic ratios of elements in rocks and minerals

Data on the applicability of neutron activation analysis to determine various rare and trace elements and the isotopic abundance of some of them in natural samples are discussed as relevant to the solution of various geological and geochemical problems. For the determination of minute amounts of elements from small weighed quantities of rocks and minerals a number of modifications of neutron activation analysis are used: analysis with the radiochemical separation of individual elements—RNAA (tantalum, tungsten, antimony, arsenic, molybdenum, rhenium, osmium, etc.) and analysis with semiconductor—Ge (Li)—gamma-spectrometry, which is multi-element and non-destructuve—INAA (scandium, europium, tantalum, iron caesium, rubidium, cobalt, antimony, etc.) or the combination of the latter with group radiochemical separation—IRNAA (alkaline, alkaline-earth, rare-earth elements, etc.). First steps have been made towards developing techniques for the determination of the isotopic rations of some elements by means of neutron activation method, e.g., the isotopic ratio of⁵⁸Fe/⁵⁴Fe. The accuracy of isotopic ratio determination is 1 to 3 relative per cent.     

Spectral Interferences in the Determination of REEs in Samarium and Dysprosium Matrices by High Resolution Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES)

There is an increasing need for sensitive, accurate and convenient analytical techniques for rare earth elements (REEs) analysis and determination with their expanding applications. Rare earth elements (REEs) are widely used in the areas of industry, agriculture and modern technologies, e.g., as growth promotion agent in agriculture,catalyst in oil refining, additives in new ceramic material and special steels, etc. It is also finding important application in nuclear industry.     

Challenges for INAA in Studies of Materials from Advanced Material Research Including Rare Earth Concentrates and Carbon Based Ceramics

Rare-earth elements are increasingly applied in advanced materials to be used, e.g., in electronic industry, automobile catalysts, or lamps and optical devices. Trace element analysis of these materials might be an interesting niche for NAA because of the intrinsic high accuracy of this technique, and the shortage of matrix matching reference materials with other methods for elemental analysis. The carbon composite materials form another category of advanced materials, where sometimes a very high degree of purity is required. Also for these materials, NAA has favorable analytical characteristics. Examples are given of the use of NAA in the analysis of both categories of materials.