Quality of electron probe X-ray microanalysis determinations obtained from laboratory reference materials of the coppery alloys and basaltic glasses

Nine coppery alloys and five basaltic glasses have been quantitatively evaluated as the reference materials to employ in electron probe X-ray microanalysis. The optimum conditions for measurements were selected considering the dependence of intensity and detection limit on the conditions of the X-ray radiation excitation and analytical signal recording. The homogeneity of basaltic glasses and coppery alloys has been examined. The dependence of electron probe X-ray microanalysis accuracy on the homogeneity of reference materials was studied in the reference materials of coppery alloys.Six data sets comprising the average concentrations, standard deviations, relative standard deviations, confidence interval and the z-score of data quality were calculated for 50 control samples: 10 alloys, 14 glasses, 2 metals, 24 minerals and oxides. The average compositions of every control sample were derived in 8–16 analyses. The measured values were corrected for matrix effects applying the original program. These series of concentrations have been compared with each other and with the certified/recommended values using 2-pair selective Student's t-test.The results gained from both laboratory reference materials and certified glass reference materials show comparable accuracy. The quality of all available results complies with the “applied geochemistry” category of performance (2nd category). The laboratory reference materials give comparable accuracy to certified reference materials and can be used for calibrating microprobe techniques, as well as data quality control. The application of laboratory reference materials in microanalysis of silicate minerals and coppery alloys allows reliable analytical data to be acquired. The applications in mineralogy and metallurgy can be extended successfully to the targets when certified reference materials are not available.     

Wavelength-dispersive spectral analysis and quantification of monazites by electron-probe microanalysis

The problem of determining the chemical composition of monazite grains through electron probe microanalysis is studied, by using a scanning electron microscope with a wavelength dispersive spectrometer. A careful qualitative analysis is performed with the purpose of determining all the elements present in the samples, the lines to be used in the quantifications trying to minimize interferences, the angular positions and the acquisition times for the measurement of peak and background intensities and the crystals to be used. Particular emphasis is devoted to the analysis of Th, U and Pb, which are used to determine the age of the rock by means of the U-Th-Pb method, commonly used in geochronology. Quantitative determinations of the chemical composition of monazite grains are performed, optimizing the experimental conditions on the basis of the qualitative analysis. The determinations were made under two different criteria of quantification of oxygen, and the dissimilar results obtained are discussed.     

Grazing-exit electron probe X-ray microanalysis (GE-EPMA): Fundamental and applications

Electron probe microanalysis (or Scanning electron microscope-energy dispersive X-ray spectrometry) has been studied under grazing-exit conditions. That is, characteristic X-rays are detected at a very small take-off (exit) angle; the technique is known as grazing-exit electron probe microanalysis (GE-EPMA). Fundamental aspects, instrumentation, and characteristics of grazing-exit electron probe X-ray microanalysis method are described here. Since the observation depth decreases as the exit angle decreases, theoretically to a few nanometers, surface analysis is possible in grazing-exit electron probe X-ray microanalysis. Of course, the size of the electron beam is also small—less than 1 μm, enabling localized surface analysis. In the case of total reflection X-ray spectrometry that allows surface analysis, the whole sample surface must be flat. However, the requirement for flatness is not as strict in grazing-exit electron probe X-ray microanalysis. Grazing-exit electron probe X-ray microanalysis measurements can easily be applied using a commercially available electron probe microanalysis (or Scanning electron microscope-energy dispersive X-ray spectrometry) instrument. To change and control the exit angle in grazing-exit electron probe X-ray microanalysis, the inclination of the sample stage or movement of the X-ray detector is all that is required. Theoretically, this study shows that grazing-exit electron probe X-ray microanalysis would be useful in improving the lateral resolution of the sample surface. In addition, the study demonstrates that grazing-exit electron probe X-ray microanalysis can be applied successfully for surface, thin-film, and particle analyses. As an optional method of electron probe microanalysis, grazing-exit electron probe X-ray microanalysis will be useful in expanding the research fields of normal electron probe microanalysis.     

Synthetic TRPO<Subscript>4</Subscript> crystals as reference samples in the quantitative X-ray electron probe microanalysis of rare-earth elements

Crystals of 15 rare-earth element phosphates, which provide a set of standard reference samples in X-ray electron probe microanalysis, were synthesized and tested for homogeneity and stoichiometry. The phosphates were synthesized in two stages, the preparation of aqueous phosphates and crystal growth in a solution of potassium polymolybdate K₂Mo₃O₁₀. The tests of the synthesized crystals confirmed their reliability as reference samples.     

Investigation of soil mineral component in the Baikal Region by X-ray electron probe microanalysis

The procedure of X-ray electron probe microanalysis (EPMA) has been developed for the investigation of soil mineral component. In terms of reproducibility and accuracy, the suggested EPMA procedure satisfies the requirements of analysis of the second category. The phase and chemical composition of soil mineral component were investigated by X-ray electron probe microanalysis with the aim of environmental pollution estimation in Lake Baikal Region. The investigations of soil mineral component by EPMA from regions with various man-caused loading degrees allow identification of basic pollution sources and their influence on the environment and estimation of anthropogenic accumulation in clear background regions and regions with high man-caused loading degree.     

Practical aspects of carbon content determination in carburized steels by EPMA.

The carbon contents in carburized steels were investigated by electron probe microanalysis (EPMA) for a range of carbon levels in the solid solution less than 1 wt%. This article describes the difficulties encountered with the classic analytical procedure using the k ratio of X-ray intensities and the phi(rhoz) model. Here, a suitable calibration curve method is presented with emphasis on the metallographic study of standard specimens and on the carbon decontamination of samples.     

The determination of the efficiency of energy dispersive X-ray spectrometers by a new reference material.

A calibration procedure for the detection efficiency of energy dispersive X-ray spectrometers (EDS) used in combination with scanning electron microscopy (SEM) for standardless electron probe microanalysis (EPMA) is presented. The procedure is based on the comparison of X-ray spectra from a reference material (RM) measured with the EDS to be calibrated and a reference EDS. The RM is certified by the line intensities in the X-ray spectrum recorded with a reference EDS and by its composition. The calibration of the reference EDS is performed using synchrotron radiation at the radiometry laboratory of the Physikalisch-Technische Bundesanstalt. Measurement of RM spectra and comparison of the specified line intensities enables a rapid efficiency calibration on most SEMs. The article reports on studies to prepare such a RM and on EDS calibration and proposes a methodology that could be implemented in current spectrometer software to enable the calibration with a minimum of operator assistance.     

Potentials of Electron Probe Microanalysis in Studying Zircons

Potentials of electron probe microanalysis in determining hafnium, uranium, thorium, lead, niobium, titanium, manganese, iron, chromium, calcium, aluminum, tin, tungsten, yttrium, and lanthanide impurities in zircons have been studied. It was found that the background signal depends on the composition of the zircon crystal, including the concentration of hafnium. Methods have been proposed to improve the measurements of the background intensity and to optimize analytical conditions for attaining the lowest detection limits.     

Trace element characterization of medieval and post-medieval glass objects by means of INAA and EPMA

Instrumental neutron activation analysis (INAA) was applied to create a database for minor and trace elements in medieval and post-medieval glassware in order to establish a methodology for estimating the origin of the glass objects. First, general characterization of glass types was done on the basis of the results obtained by the use of electron probe microanalysis (EPMA). Information received by the use of INAA provided the additional valuable data reflecting to some extent the method of preparation or the differentiation of various sources of certain raw materials. Several glass samples and a set of various reference glass materials were used for our experiments.     

Determination of copper in urine by diffuse reflectance spectroscopy

A possibility of determining copper(II) after adsorption on polyacrylonitrile fiber filled with a KU-2 cation exchanger with immobilized 1-(2-pyridylazo)-2-naphthol (PANF–KU-2–PAN) is studied. The diffuse reflectance spectra of the carrier discs before and after the adsorption of copper in the batch mode are recorded. The dependences of the analytical signals of the copper complex on PANF–KU-2–PAN on adsorption conditions are studied. The conditions for determining 0.05–0.40 μg/mL of copper(II) by measuring diffuse reflection coefficient at 640 nm or visually by a color scale after the adsorption of copper from 20 mL of a solution containing 0.01 M of HCl are found. The determination of 0.1 μg/mL of copper does not interfered with equal amounts of Co, Zn, and Pb and double amounts of Ag, Fe(III), Cd, Mn(II), Bi(III), and Cr(III). The procedure is used for urine analysis. The following conditions of the preparation of urine samples for the determination of copper were selected: boiling with hydrogen peroxide followed by acidification to pH 2. A procedure for determining copper in urine with a limit of detection of 0.03 μg/mL was developed; the relative standard deviation does not exceed 25%; the duration of analysis of 5–6 samples is 30–35 min.     

Preparation and characterization of copper/silver bimetallic nanowires with core‐shell structure

Core‐shell copper/silver bimetallic nanowires were prepared by replacement reaction with citric acid and polyvinylpyrollidone at room temperature. A uniform silver coating was obtained by strictly controlling the molar ratio of Ag/Cu. The copper/silver composite was characterized by X‐ray diffraction, scanning electron microscopy, electron probe microanalysis and X‐ray photoelectron spectroscopy. Microscopic analysis shows that a well‐copper/silver core‐shell structure was formed. Thermo‐gravimetry and differential thermal analysis to the composite nanowires show that the silver coatings efficiently inhibit the oxidation of Cu. Copyright © 2015 John Wiley & Sons, Ltd.     

Electron probe microanalysis of dried biological substances

In the present study electron probe X-ray microanalysis (EPMA) was used to examine the elemental contents in samples of biological molecules from aqueous solutions and of cultured cells. To preserve the contents of diffusible elements the freeze-drying technique was applied as a preparative procedure. The resulting powders were then formed into small tablets, weighing about 0.1 mg, which were analyzed with a wavelength-dispersive spectrometer (WDS). Using tablets, the total concentration of different elements was measured in biological substances isolated fromGalleria mellonella, and cells taken from a culture ofChlorella vulgaris treated with uranium nitrate.     

Fast determination of lead and copper in dairy products by graphite furnace atomic absorption spectrometry

A rapid and direct procedure for determining lead and copper in dairy products by electrothermal atomic absorption spectrometry (ETAAS) is described. Samples are slurried in a medium containing 50% v/v hydrogen peroxide, 1% v/v nitric acid, 0.5% w/v dihydrogen phosphate, and 20% v/v ethanol and directly injected into the furnace with no previous mineralization. Calibration is performed with aqueous standards. Limits of determination were 0.4 and 2.4 ng/mL for copper and lead, respectively. The reliability of the procedure was checked by comparison with the acid mineralization procedure and by analyzing 3 certified reference milk samples.     

Determination of Chloroacetic Acids in Drinking Water by Reaction Gas Chromatography

A procedure was developed for determining chloroacetic acids in drinking water. The procedure is based on solid-phase extraction followed by the conversion of chloroacetic acids to trifluoroacetic esters and their separation and determination by gas–liquid chromatography with an electron capture detector. Esterification conditions were optimized. The procedure was used for analyzing samples of drinking water.     

A pre-concentration procedure employing a new imprinted polymer for the determination of copper in water

This work describes the development by response surface methodology (RSM) of a procedure for copper determination by inductively coupled plasma optical emission spectrometry (ICP OES) in water samples after extraction by copper imprinted polymer. Results of the two-level full factorial design (2⁴) based on an analysis of variance demonstrated that only the solution pH; amount of polymer and adsorption time were statistically significant. Optimal conditions for the extraction of copper samples were obtained by using Box-Behnken design. Solution pH; amount of polymer and adsorption time were regarded as factors in the optimisation study. The working conditions were 4.6, 0.03?g and 3.5?h, for solution pH, amount of polymer; and adsorption time, respectively. Under the optimised experimental conditions, the detection limit of the proposed method followed by ICP OES was found to be 0.8?µg?L^?1. The relative standard deviation (RSD) was found to less than 0.81%. The pre-concentration factor was 22.5. The accuracy of the optimised procedure was evaluated by analysis of certified reference material. The method was applied to the determination of copper in water samples.     

Salt doping in electronprobe microanalysis

A new method of electronprobe microanalysis (EPMA) is suggested. It is based on creating ionic conductivity in frozen water solutions and in polymer films by doping them with a salt. This procedure is effective to prevent surface charging and allows imaging of nonconducting samples by scanning electron microscopy (SEM) as well as X-ray microanalysis. Specifically, this procedure makes it possible to perform EPMA of samples with xerogel matrices, which were used for molecular laser microprobe mass spectrometry analysis, and consequently to provide complex microprobe examination of samples. Received: 24 January 1996 / Revised: 4 July 1996 / Accepted: 16 July 1996     

Phase relationships in the SiO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> system

Phase equilibria in a miscibility gap of the SiO₂-TiO₂ system were studied. A visual polythermal analysis and annealing of samples were performed in a Galakhov microfurnace. The microstructure and composition of the obtained samples were investigated by scanning electron microscopy and electron probe microanalysis. A critical analysis of the experimental data was made. Thermodynamically optimized based on the sub-regular solution model, a phase diagram of the SiO₂-TiO₂ system was constructed.     

Determination of cadmium,aluminium, and copper in beer and products used in its manufacture by electrothermal atomic absorption spectrometry

Procedures were developed for determining cadmium, aluminium, and copper in beer and the products used in its manufacture by electrothermal atomic absorption spectrometry. Beer samples were injected into the furnace and solid samples were introduced as suspensions after preparation in a medium containing hydrogen peroxide, nitric acid, and ammonium dihydrogen phosphate for cadmium atomization. Calibration was performed with aqueous standards, and characteristic masses and detection limits were, respectively, 1 and 0.3 pg for cadmium, 18 and 5.4 pg for aluminium, and 5.6 and 6.8 pg for copper. Different samples of beer, wort, brewer's yeast, malt, raw grain, and hops were analyzed by the proposed procedures. Cadmium was found in low concentrations (0.001-0.08 microg/g and 0-1.3 ng/mL); copper (3-13 microg/g and 25-137 ng/mL) and aluminium (0.6-9 microg/g and 0.1-2 microg/mL) were found at higher levels. The reliability of the procedure was confirmed by comparing the results obtained with others based on microwave oven sample digestion, and by analyzing several certified reference materials.     

Multianalytical study of corrosion layers in some archaeological copper alloy artefacts

Corrosion layers in some copper and bronze archaeological objects from Haft Tappeh archaeological site, southwest Iran, were studied. For this purpose, optical microscopy, scanning electron microscopy with energy dispersive X‐ray microanalysis, micro‐Raman spectroscopy and X‐ray diffraction methods were applied to observe corrosion stratigraphy and their characteristics as well as identification of chemical composition and phase determination of different corrosion layers. Based on optical and electron microscopy, three different corrosion strata were identified in cross section of different metallic objects including various red, green, white‐grey powdery and dark internal compact layers. Scanning electron microscopy with energy dispersive X‐ray microanalysis on different corrosion layers revealed that Cu, Sn and Cl are the main elements in the chemical composition of different layers. Tin‐rich phases were detected in white‐grey and dark layers that may be formed because of the internal oxidation of tin as well as the decuprification (selective dissolution of copper) phenomena occurring during long‐term burial period in the soil. Also, the XRD and micro‐Raman spectroscopy results proved that the main corrosion products are nantokite (CuCl), copper trihydroxychlorides and copper oxides. The combination of these analytical methods allows us to explore the surface and internal corrosion layers of the archaeological copper and bronze samples, and major interest is on studying their chemistry, microstructural properties and corrosion stratigraphy. Copyright © 2015 John Wiley & Sons, Ltd.     

Influence of different correction models on investigations of carbonaceous insulating films by electron beam X-ray microanalysis

Normally quantitative investigations of insulators by electron beam X-ray microanalysis are made possible by coating special samples with thin evaporated carbon films. This, however, will fail if the samples themselves contain carbon as polysilastyrene {[(CH₃)₂Si]_x (CH₃)C₆H₅Si}_n, which is used for the preparation of silicon carbide. Samples of polysilastyrene, together with reference layers (pure silicon) were investigated using different equipment (JEOL, CAMECA) and with varying correction procedures (ZAF, PAP). Compared with the results of reference measurements (elementary analysis, NMR) it appears that the PAP correction procedure is better suited for solving this problem than the classical ZAF correction procedure.