X-Ray Mapping and Interpretation of Scatter Diagrams

Electron beam induced quantitative X-ray mapping has become a very useful characterisation tool for determining the elemental distribution in materials, whether using energy dispersive spectroscopy or wavelength dispersive spectroscopy. The X-ray intensity distributions of the elements from an X-ray map allow us to generate two dimensional and ternary scatter diagrams thus converting spatial information into concentration dimensions, which is an important tool for displaying the spatial relationships of elements or correlated elements (phases) in materials. To best understand how to use this tool, we need to understand the production and features of the scatter diagram. The type of clustering observed in the scatter diagram, whether oval, linear or spherical, can give the major and trace element distributions within phases as well as qualitative and quantitative phase information. This paper demonstrates the generation of scatter diagrams, properties of scatter diagrams, interpretation of scatter diagrams and the advantages of scatter diagrams through the use of examples.     

钢中Si、Mn的电子探针定量分析与标样

采用特制的Fe-Si、Fe-Mn合金系列标样，用电子探针测定了钢或铁基合金中低含量的Si和Mn元素、与用纯元素作标样、经ZAF修正的结果相比较，提高了分析准确度．     

Quantitative surface analysis by Auger and x-ray photoelectron spectroscopy

Recent developments in quantitative surface analysis by Auger (AES) and x-ray photoelectron (XPS) spectroscopies are reviewed and problems relating to a more accurate quantitative interpretation of AES/XPS experimental data are discussed. Special attention is paid to consideration of elementary physical processes involved and influence of multiple scattering effects on signal line intensities. In particular, the major features of core-shell ionization by electron impact, Auger transitions and photoionization are considered qualitatively and rigorous approaches used to calculate the respective transition probabilities are analysed. It is shown that, in amorphous and polycrystalline targets, incoherent scattering of primary and signal Auger and photoelectrons can be described by solving analytically a kinetic equation with appropriate boundary conditions. The analytical results for the angular and energy distribution, the mean escape depth, and the escape probability as a function of depth of origin of signal electrons as well as that for the backscattering factor in AES are in good agreement with the corresponding Mote Carlo simulation data. Methods for inelastic background subtraction, surface composition determination and depth-profile reconstructions by angle-resolved AES/XPS are discussed. Examples of novel techniques based on x-ray induced photoemission are considered.     

Characterization of high-temperature superconductors by electron microprobe analysis

In order to optimize the physical properties of HTSC small single crystals grown from a melt for basic studies of their physical properties the influence of the environment on their impurity content was investigated by EPMA. This requires quantitative analysis of all elements being present in the crystals. The accuracy of results was affected by problems with the choice and quality of standards, by contamination but also by malfunction of microprobe electronics. The HTSC materials were found to react with mills, milling balls, crucibles and the atmosphere. These problems are being discussed and some reactions being studied for Y₁Ba₂Cu₃O_6+x (0 < x < 1) HTSC in A1₂O₃ and ZrO₂ crucibles. The crystals grown contain reproducible amounts of impurities depending on boundary conditions and exhibit a zone structure in composition particularly for Y and Ba within their range of homogeneity.     

Preparation and Characterization of Compositions Based on PbO-MgO-Nb2O5 Using the Sol-Gel Method

Lead Magnesium Niobate, Pb(Mg_1/3Nb_2/3)O₃ (PMN), is an important relaxor ferroelectric material. A significant problem exists, however, in the preparation of this material: it is very difficult to prepare pure phase, without the presence of a pyrochlore impurity phase which degrades the dielectric properties. Depending on the processing conditions, the amount of pyrochlore phase varies.Considering the ternary diagram PbO-MgO-Nb₂O₅, different compositions have been prepared by a simple sol-gel method at room temperature using Pb(CH₃COO)₂, Mg(CH₃COO)₂, Nb(OC₂H₅)₅ as precursors. After the heat treatment, the samples obtained were analyzed by XRD and EPMA with the purpose of studying the compositions formed.From the analysis of these results, it seems to be that the appearance of pyrochlore can be related to the reactivity of the MgO and/or the presence of other phases of the binary system PbO-Nb₂O₅. An excess of Pb and Mg is necessary for compositions to be formed near the PMN. The control of the amount of these two elements is very important because an excess of MgO would lead to rich compositions in Mg as a secondary phase.     

The Sialons MLn[Si4−xAlxOxN7−x] with M = Eu,Sr, Ba and Ln = Ho‐Yb – Twelve Substitution Variants with the MYb[Si4N7] Structure Type

The oxonitridoalumosilicates (so‐called sialons) MLn[Si_4?xAl_xO_xN_7?x] with M = Eu, Sr, Ba and Ln =Ho, Er, Tm, Yb were obtained by the reaction of the respective lanthanoid metal, the alkaline earth carbonates or europium carbonate, resp., AlN, “Si(NH)₂” and MCl₂ as a flux in a radiofrequency furnace at temperatures around 2100 °C. The compounds MLn[Si_4?xAl_xO_xN_7?x] are relevant for the investigation of substitutional effects on the materials properties due to their ability of tolerating a comparatively large phase width up to x ≈ 2.0(5). The crystal structures of the twelve compounds were refined from X‐ray single crystal data and X‐ray powder data and are found to be isotypic to the MYb[Si₄N₇] structure type. The compounds crystallize in space group P6₃mc (no. 186, hexagonal) and are made up of chains of so‐called starlike units [N^[4](SiN₃)₄] or [N^[4]((Si,Al)(O,N)₃)₄], respectively. These units are formed by four (Si,Al)(N/O)₄ tetrahedra sharing a common central nitrogen atom. The structure refinement was performed utilizing an O/N‐distribution model according to Paulings rules, i.e. nitrogen was positioned on the four‐fold bridging site and nitrogen and oxygen were distributed equally on both of the two‐fold bridging sites, resulting in charge neutrality of the compound. The Si and Al atoms were distributed equally on their two crystallographic sites, referring to their elemental proportion in the compound, due to being poorly distinguishable by X‐ray methods. The chemical compositions of the compounds were derived from electron probe micro analyses (EPMA).     

Study of the winter and summer changes of the air composition in the church of Szalowa, Poland, related to conservation

The St. Michael Archangel’s Church in Szalowa, Poland, was selected for closer investigation with respect to the indoor/outdoor air exchange and its influence on the air quality and work arts preservation. Chemical composition, size and abundance of particulate matter and concentration of gases NO₂, SO₂, O₃ inside and outside the church were determined. To study seasonal variation of the weather condition (temperature, inversion level, wind direction) and the influence of seasonal sources of the air pollution (like heating of the nearby houses), samples were collected in winter and summer time. It was stated that suspended particulate matter inside the wooden church has in general an outdoor source. Several groups of particles were distinguished such as the organic ones, soil dust, nitrates and sulphates. In case of organic and soil dust particles, the concentration inside was higher than outside. From the results, in comparison to literature data, one can conclude that accumulation of particulate suspended matter in the church is more intense than in other types of buildings. Gaseous pollutants were detected but their concentration was negligible.     

Comparison of sediment pollution in the rivers of the Hungarian Upper Tisza Region using non-destructive analytical techniques

The rivers in the Hungarian Upper Tisza Region are frequently polluted mainly due to mining activities in the catchment area. At the beginning of 2000, two major mining accidents occurred in the Romanian part of the catchment area due to the failure of a tailings dam releasing huge amounts of cyanide and heavy metals to the rivers. Surface sediment as well as water samples were collected at six sites in the years 2000–2003, from the northeast-Hungarian section of the Tisza, Szamos and Túr rivers. The sediment pollution of the rivers was compared based on measurements of bulk material and selected single particles, in order to relate the observed compositions and chemical states of metals to the possible sources and weathering of pollution. Non-destructive X-ray analytical methods were applied in order to obtain different kinds of information from the same samples or particles. In order to identify the pollution sources, their magnitude and fate, complementary analyses were carried out. Heterogeneous particulate samples were analyzed from a large geographical territory and a 4-year time period. Individual particles were analyzed only from the “hot” samples that showed elevated concentrations of heavy metals. Particles that were classified as anthropogenic were finally analyzed to identify trace concentrations and chemical states of heavy metals.     

Characterisation of Sugar Cane Combustion Particles in the Araraquara Region, Southeast Brazil

Biomass burning is an important primary and secondary source of aerosol particles. The presence of carbonaceous particles in the respirable size range makes the study of this fraction important in view of possible health and climatic effects. The annual burning of sugar cane plantations causes emission of huge amounts of pyrogenic particles. Aerosol samples were collected in Araraquara city, São Paulo state, Brazil, during the harvest season for fine and coarse particles and bulk; they were analysed by electron-probe microanalysis, including facilities for low-Z element determination (low-Z EPMA) and by energy-dispersive X-ray fluorescence (EDXRF), in order to investigate the elemental composition of individual particles and bulk samples, respectively. Numerical analysis of the EPMA results by hierarchical clustering shows high contributions of carbonaceous particles that can be distinguished mainly in two different types: biogenic and carbon-rich. Additionally, two significant contributions of aluminosilicate particles were identified: as rather pure aluminosilicates or mixed with carbonaceous species. The EDXRF results are compatible with those of aerosol particles in Amazon, which is nowadays one of the main sources of biogenic particles in the world.     

The Legacy of Raimond Castaing

 In April 1998 Raimond Castaing left the world of electrons, of ions and others particles, his wife and his family, his numerous students, for the world of stars. Raimond Castaing (Fig. 1) had a very strong personality. No one will forget their first meeting with him and all his students remember how brilliant he was as a teacher. A lot of anecdotes about his famous hot temper are still circulating among his friends and his former students. But in this paper, we would like to evoke Castaing’s memory through his achievements in Instrumental Physics, from the time of his doctoral thesis to later developments with his students, which were all centred on the imaging of the microstructures of materials and their quantitative chemical analysis.