A graphic approach to the analysis of a large X‐ray microanalysis dataset obtained via SEM–EDS

A graphical method for phase analysis of advanced materials by EDS–SEM was developed and demonstrated on deformed superconducting Bi(Pb)2223 ceramics. Through visual representation, this method allows for the rapid and efficient analysis of large X‐ray microanalysis datasets and to identify phase composition of fine particles of secondary phases against a background of other phases. The graphical method can be applied using existing software and therefore does not require the development of new programs or complex computations.     

The application and programming of an image store for the SEM

The programming and use of a purposebuilt digital image store constructed for a SEM is described. The system is based on purpose designed circuitry controlled by a Motorola MC68000 and is capable of noise-averaging using multiple frames, colour look-up tables, high-resolution photographic recording, image processing using matrix functions, some image quantification, and x-ray spectrum acquisition. The way in which the FORTH language provided an efficient means of controlling the SEM is described and examples of each type of operation are presented.     

Secondary and backscattered electron imaging of weathered chromian spinel

Secondary (SE) and backscattered electron (BSE) imaging as well as x-ray microanalysis have demonstrated that the weathering of chromian spinel occurs as a progressive form of alteration. Numerous chemical discriminant analysis methods based on the composition of chromian spinel are used to locate valuable deposits of minerals. These methods will be misleading if the correct interpretation of the weathering of chromian spinel and the subsequent pattern of changes in its mineral chemistry are not properly assessed using scanning electron microscopy. This assessment is vital in understanding the geological processes involved and the economic potential of any indicated deposit. Minerals such as chromian spinel, pyrope garnet, and picroilmenite are considered to be highly resistant to weathering and abrasion and are therefore useful in the search for associated valuable deposits of diamond, nickel, platinum, and gold. Known as indicator minerals, they are usually present in relatively large concentrations compared with the target mineral (e.g., diamond) and form large and often subtle dispersion anomalies adjacent to the deposit. Chromian spinel has long been regarded as a stable indicator mineral; however, detailed SE and BSE imaging indicates that many of the chromian spinels that are routinely examined using scanning electron microscopes (SEM) and microprobes are extensively altered. Secondary electron and BSE imaging of weathered chromian spinel in a normal SEM provides valuable data on the form and chemical style of the alteration. Secondary electron imaging of weathered chromian spinel in the environmental SEM (ESEM) not only enhances the difference in atomic number between unaltered and altered areas but also allows high-resolution imaging of these very fine replacement textures.     

A method for determining the mass thickness of thin films using electron probe microanalysis

A method is proposed for easy determination of the mass thickness of thin films using electron-probe microanalysis. The model is based on the function of the depth distribution Ø(qz) of the characteristic x-ray production and emphasizes the treatment of the physical phenomena in the transition area between the film and the substrate. The method is applicable to a wide range of elements and element combinations (Z>5) and electron acceleration energies. It has been tested by comparing results obtained using this method with data taken from the literature. Errors are small, generally, not exceeding 5%.     

Investigation of foreign substances in food using scanning electron microscopy-x-ray microanalysis

Scanning electron microscopy (SEM) and x-ray microanalysis (EDS) were used to conduct forensic investigations on metal and glass foreign objects. SEM-EDS is an excellent method for identifying metal foreign objects in food, such as wire, dental fillings, bone, and metal packaging, based on their element composition. From a determination of the extent of corrosion of a metal foreign object using SEM-EDS, it is sometimes possible to determine whether the material has been processed with the food product. Case histories of processed aluminum, unprocessed nickel-coated steel, and corrosion resistant stainless steel foreign objects are discussed. A potential product-tampering problem involving a hole defect in a paperboard package was resolved using SEM-EDS. Blue fibers found in the hole were found to contain brass particles from a ball point pen rather than a syringe needle. SEM-EDS has been used to determine the elemental composition of glass foreign objects and is able to distinguish between many types of glass including container, electrical, and bakeware. A case history is presented to show that although container glasses cannot, in general, be distiguished from one another using SEM-ED S, they can be distinguished by trace element semiquantitative spectrograghic analysis. SEM-EDS can be used to distinguish glass-like foreign objects from glass. Case histories of struvite crystals found in salmon and cream of tartar crystals found in grape juice are discussed. Fourier transform infrared (FTIR) identified the cream of tartar crystal as calcium tartrate, and this complemented the calcium, carbon, and oxygen components of the compound found using SEM-EDS.     

Characterization and identification of local defects in glass

The most relevant defects in glasses are categorized and investigated by appropriate microanalytical techniques. Since these defects very often present a real challenge because of complex chemical and mineralogical properties, a multimethod approach is necessary to supplement or confirm the findings from scanning techniques. The combination of electron probe microanalysis/energy-dispersive x-ray (EPMA/EDX) and laser ablation inductively coupled plasma mass spectroscopy (LA-ICP-MS) allows the determination of element trace concentrations in a knot, a glassy defect, thus finally enabling the identification of a special source of the defect from otherwise nondistinguishable refractories. The type of crystals can be determined exactly by the use of EPMA and x-ray dispersion (XRD), stones (a crystalline agglomerate) are analyzed by EPMA/EDX pointing to a possible source for this defect; results on metallic inclusions, "filled bubbles," and surface defects are reported and defect sources are discussed. Since close cooperation with the production departments and knowledge of production techniques and conditions are necessary for the diagnosis to take appropriate countermeasures, an approach is presented which systematically accumulates all information into a data base. The structure of such "expert systems" is described, which leads to correlation of appearance, analytical data, and source of the defects for even more accurate diagnosis and faster reaction.     

One-shot spectrometer for several elements using an integrated conical crystal analyzer

Time-resolved x-ray spectrometry using an ultrastrong x-ray source such as an x-ray free electron laser is one of the new trends in the field of x-ray physics. To achieve such time-resolved measurement, the development of an one-shot spectrometer with a wide wavelength range, high efficiency, and good energy resolution is an essential prerequisite. Here we developed an integrated conical Ge crystal analyzer consisting of several conical rings, which were connected using spline surfaces to form a single body using our previously developed hot deformation technique, which can form a Si or Ge wafer into an arbitrary and accurate shape. We simultaneously focused several characteristic lines from an alloy sample onto different positions on a small x-ray charge-coupled device with very high image brightness (gain relative to planar analyzer: 100) and a good spatial resolution of 9-13 eV. The small radius of curvature of the crystal (28-50 mm) enabled us to realize a very short sample-detector distance of 214.4 mm. The present result shows the possibility of realizing a new focusing x-ray crystal spectrograph that can control the focal position as desired.     

Some theoretical considerations on X-ray microanalysis in the environmental or variable pressure scanning electron microscope

This paper presents a new correction procedure for quantitative x-ray microanalysis in the environmental or variable pressure scanning electron microscope (SEM). This method is based on a plot of the measured intensity as a function of the fraction of nonscattered beam intensity, f_p. The theory predicts that the plot should be linear and the corrected intensity is given for f_p = 1. The advantage is that such a plot is valid for any measured pressures, which is not the case with the usual pressure correction methods. To use this method, a simple equation is derived to compute f_p. Other variations of this correction procedure are also presented. Comparison with measurements performed by Mansfield (1999) show the great consistency of this method.     

Laser powered heating stage in a scanning electron microscope for microstructural investigations at elevated temperatures

A laser powered heating stage designed for application in high vacuum environment of a scanning electron microscope (SEM) is presented. It was developed to observe and characterize microstructural changes in crystalline materials at elevated temperatures up to 1000 degrees C. The approach utilizes the power output of a commercial infrared diode laser in order to heat up specimens without interference with the electronic system of the SEM. The heating stage can be used in combination with any standard characterization technique applicable for SEMs--electron backscatter diffraction, orientation contrast imaging, x-ray energy dispersive spectrometry, etc. The results of test measurements are presented.     

The continuum normalization method for quantification of X-ray spectra in biological microanalysis. 1. Generalized bremsstrahlung production cross-sections and analysis using standards

The thin self-supporting biological specimens used for quantitative X-ray microanalysis are problematical because the sections are most unlikely to be uniform in thickness or density, so the intensities of the characteristic lines alone are not a good measure of composition. The method developed to overcome these problems was introduced by T. A. Hall in 1971 and uses the bremsstrahlung or continuum intensity recorded in the X-ray spectrum to normalize each characteristic line, and hence is frequently referred to as the continuum normalization (CN) procedure.
  Reformulating the CN method of quantification in terms of generalized cross-sections and calculating more accurate values of bremsstrahlung production using a formula allows us a better understanding of the options open to the analyst of biological thin sections by which the errors in the measurement may be reduced. If one chooses to use the original Hall (1971 ) method using Kramers cross-sections, the window measuring the continuum for normalization should be set in the 4–7 keV region for typical scanning electron microscope and microprobe beam energies, 20–40 kV, and above 10 keV for transmission electron microscope energies of 80 kV and above. Although it is clear that peak counts must not contribute to the white count, the window should be as wide as possible to reduce statistical errors.     

Fine structure of hepatocytes during the etiology of several common pathologies

Hepatocytes respond to injury by a few basic pathological reactions that are reflected in cell death, different types of degeneration, regeneration, or tumorous transformation. At the ultrastructural level, alterations of cell organelles can be observed in different combinations as a result of the injury, depending on the etiological agent(s) or pathological conditions developed. Nuclear bodies, dilation and fragmentation of rough endoplasmic reticulum (rer), swelling of mitochondria, and an increased number of lysosomes occur during acute viral hepatitis. The core and surface components of the hepatitis B virus can be localized in the liver cells in chronic hepatitis and in carriers. Close contact of hepatocytic and lymphocytic cell membranes were observed in chronic active hepatitis. Hepatocytes surrounded by an increased amount of collagen fibers are characteristic of cirrhosis. Loosely arranged, fine fibrils or condensed forms of Mallory bodies are pathognomic for alcoholic injury. A wide spectrum of alterations are noted after drug treatment: the proliferation of smooth endoplasmic reticulum (ser) as an adaptive phenomenon, focal or complete necrosis of the cell, inflammation, and the like. The fine structural analysis of hepatocytic inclusions in storage diseases has a differential diagnostic value. The storage of copper and other elements can be measured by x-ray microanalysis. The study of the hepatocytic differentiation in liver tumors is highly important in establishing the diagnosis and in proving the hepatocytic origin of the tumor.     

Observation of impurities in ice.

This paper presents a new method for determining the microstructural location of impurities in polycrystalline ice, which involves allowing the ice to sublimate under vacuum and then identifying the concentrated impurities using energy dispersive X-ray microanalysis in a low-vacuum scanning electron microscope. The method allows the presence of impurities in both the grain boundaries and the lattice of natural polycrystalline ice to be observed. Using this technique on natural ice, filaments consisting chiefly of NaCl were observed in some grain boundaries, small amounts of sulfur and chlorine were found in the grain interiors of the ice, and large concentrations of sulfur were observed in inclusions.     

Morphology of rat exocrine pancreas prepared by anhydrous cryo-procedures

This paper describes and compares the morphology of a relatively complex tissue, the exocrine pancreas, prepared by state-of-the-art anhydrous cryoprocedures. Cryopreparative procedures are being used increasingly for a wide range of applications, for example, electron-probe x-ray microanalysis and immunocytochemical localization of antigenic molecules, because they preserve the composition of the specimen better than procedures involving aqueous media. Some doubts have remained concerning the morphology of cryosections and the precise identification of subcellular structures. We show that thin and sufficiently large cryosections of fresh biological tissues can be produced using commercially available hardware. The freeze-dried cryosections display high intrinsic contrast, are stable under the beam, and allow identification of intracellular fine structure.     

Acquisition and processing of scanning electron microscope images using a PC and a framestore

A versatile, low-cost data acquisition and processing system for scanning electron microscope (SEM) images has been successfully developed and demonstrated. This is based on an Amstrad PC and a framestore interfaced to the SEM, and is an upgrade of an earlier BBC microbased system. In addition to supporting colour x-ray mapping, as reported previously, the PC-based unit incorporates new features which enhance the system's performance, flexibility, and overall user friendliness. An example of the system's capabilities in a very large-scale integrated circuit application is presented. This relates to the processing and analysis of a series of images taken on the surface of a Motorola MC 68000 microprocessor, with and without a voltage stimulus.     

Pulsed laser atom probe analysis of semiconductor materials

As the size of semiconductor devices is reduced the active volumes of material in each device is also decreased. Under these circumstances it becomes more important to understand the microchemistry of semiconducting materials, as small fluctuations in composition can dramatically affect both the operation of the devices, and of the contacts to semiconductors. Atom probe microanalysis has been shown to be able to analyse the microchemistry of metallic materials with plane-by-plane resolution, and by using a pulsed laser to replace the more conventional voltage pulses the analysis of semiconducting and insulating materials becomes possible. The pulsed laser atom probe has been shown to give very accurate chemical analysis of the stoichiometry of extremely small volumes of III-V compound semiconductors, and the composition of the interfacial layer between silicon dioxide and silicon has been identified as SiO of thickness about 0.3 nm. It has been shown to be possible to prepare specimens for analysis from thin films of semiconductors, thus allowing the microanalysis of a wide range of materials that are deposited in thin film form.     

Ionic composition of rat airway surface liquid determined by X-ray microanalysis

The thin layer of liquid that lines the conducting airway epithelium, the airway surface liquid (ASL), is important for mucociliary clearance. Altered ionic composition and/ or volume of the ASL play a major role in the pathology of airway diseases such as cystic fibrosis. Since the ASL is a thin layer, it has been difficult to exactly determine its composition. The present paper describes two techniques that have been developed and used to study ASL composition: X-ray microanalysis of frozen hydrated rat trachea, and an ion-exchange (dextran) bead method, where dextran beads were placed on the airway epithelium to equilibrate with the ASL; the beads were then collected under silicone oil, dried and analyzed by X-ray microanalysis. The results from both frozen-hydrated specimens and from the dextran beads showed that ASL from rat trachea is hypotonic. Concentrations of Na, P, S, and K were higher in the frozen-hydrated ASL, in which mainly the mucus layer is analyzed, compared with the dextran bead method, in which mainly the periciliary liquid is sampled. Also the composition of rat nasal fluid was investigated by the dextran bead method. This fluid was somewhat hypertonic because of a high K concentration. The ionic composition of the nasal and tracheal fluid can be manipulated by cholinergic or alpha- or beta-adrenergic stimulation. Collecting ASL with dextran beads did not disturb the integrity of the airway epithelium. The ionic composition of the collected beads remained stable for several days during storage in silicone oil. It is concluded that X-ray microanalysis is a suitable method to determine the ionic composition of ASL.     

Three-colour x-ray mapping using digital storage

Computer-controlled scanning of a scanning electron microscope (SEM) fitted with an energy-dispersive x-ray analyser has been carried out. This has been achieved by building an SEM interface module which controls the scanning of the electron beam and also provides a communication link between the x-ray analyser and an enhanced BBC micro. The digitised x-ray data pulses can be collected from three elements simultaneously to produce colour-coded x-ray distribution maps. Some such maps from two different specimens are presented and an effect of x-ray shadowing is clearly demonstrated. A comparison between images acquired using a frame size with 256 × 256 pixels and those with 128 × 128 pixels is made.     

Effect of grain refinement and modification on the dry sliding wear behaviour of eutectic Al-Si alloys

The present study deals with an investigation of dry sliding wear behaviour of grain refined and or modified eutectic (Al-12Si) Al-Si alloy by using a Pin-On-Disc machine. The indigenously developed Al-1Ti-3B and Al-10Sr master alloys were used as grain refiner and modifier for the grain refinement of α-Al dendrites and modification of eutectic Si, respectively. Various parameters have been studied such as alloy composition, sliding speed, sliding distance and normal pressure. The cast alloys, master alloys and worn surfaces were characterized by SEM/EDX microanalysis. Results suggest that, the wear resistance of eutectic Al-Si alloys increases with the addition of grain refiner (Al-1Ti-3B) and or modifier (Al-10Sr). Further, the worn surface studies show that adhesive wear was observed in Al-12Si alloy in the absence of grain refiner and modifier. However, an abrasive and oxidative wear was observed when the grain refiner and modifier are added to the same alloy. Commercially available LM-6 (12.5%Si) alloy was used for comparison.     

Diagnostics of heterogeneous chemical reactions by cathodoluminescence

A scheme is developed for establishing the mechanism of heterogeneous chemical reactions by scanning electron microscopy (SEM) using cathodoluminescent markers (or flares CLF). Diagnostic formulas are found for the distribution function of product crystals with respect to their states under different reaction conditions. The diagnostic scheme is checked for the reaction of F-apatite with phosphoric acid.     

Quantitative electron probe microanalysis of rough targets: testing the peak-to-local background method

Rough samples with topography on a scale that is much greater than the micrometer dimensions of the electron interaction volume present an extreme challenge to quantitative electron beam x-ray microanalysis with energy-dispersive x-ray spectrometry. Conventional quantitative analysis procedures for flat, bulk specimens become subject to large systematic errors due to the action of geometric effects on electron scattering and the x-ray absorption path compared with the ideal flat sample. The best practical approach is to minimize geometric effects through specimen reorientation using a multiaxis sample stage to obtain the least compromised spectrum. When rough samples must be analyzed, corrections for geometric factors are possible by the peak-to-local background (P/B) method. Correction factors as a function of photon energy can be determined by the use of reference background spectra that are either measured locally or calculated from pure element spectra and estimated compositions. Significant improvements in accuracy can be achieved with the P/B method over conventional analysis with simple normalization.