Search

Maya blue is a pigment found in different archaeological sites of different cultures from Mesoamerica, and also in colonial buildings in Mexico and Cuba. The pigment is made from a thermally treated mixture of indigo and palygorskite. Pigment samples from Aztec and non‐Aztec archaeological sites as well as reference Yucatecan palygorskites were studied in this paper to assess their differences. The characterization of the samples was carried out by a combination of a crystal–chemical‐point analyses using electron microscopy to obtain the structural formulae of the palygorskite crystals, and studied using high‐resolution X‐ray diffraction. The data show evidence that the palygorskite used by non‐Aztec cultures, such as the Maya, is compatible with palygorskite from known sources in the Yucatan Peninsula, while the palygorskite used by the Aztec culture is different in its structure and has an origin that is still unknown. [ABSTRACT FROM AUTHOR]

Neuromelanin (NM) is a compound which highly accumulates mainly in catecholamine neurons of the substantia nigra (SN), and is contained in organelles (NM-containing organelles) with lipid bodies and proteins. These neurons selectively degenerate in Parkinson's disease and NM can play either a protective or toxic role. NM-containing organelles of SN were investigated by Analytical Electron Microscopy (AEM) and Nano-Secondary Ion Mass Spectrometry (NanoSIMS) within human tissue sections with respect to ultrastructure and elemental composition. Within the NM-containing organelle, the single NM granules and lipid bodies had sizes of about 200-600 nm. Energy-Dispersive X-ray microanalysis spectra of the NM granules and lipid bodies were acquired with 100 nm beam diameter in AEM, NanoSIMS yielded elemental maps with a lateral resolution of about 150 nm. AEM yielded the quantitative elemental composition of NM granules and bound metals, e.g., iron with a mole fraction of about 0.15 atomic percent. Chemical analyses by AEM and NanoSIMS were consistent at the subcellular level so that nanoSIMS measurements have been quantitated. In NM granules of SN from healthy subjects, a significant amount of S, Fe, and Cu was found. In lipid bodies an amount of P consistent with the presence of phospholipids was measured. The improved detection limits of nanoSIMS offer new possibilities for chemical mapping, high-sensitivity trace element detection, and reduced acquisition times. Variations between individual NM granules can now be investigated effectively and quantitatively by NanoSIMS mapping Cu and Fe. This should yield new insight into the changes in chemical composition of NM pigments during healthy aging and disease. [ABSTRACT FROM AUTHOR]

Aluminum containing 4 wt.% magnesium was oxidized at a temperature for different oxidation times and analyzed by high-resolution electron microscopy. A thin oxidized layer of about 5 µm, which is composed of MgO, forms at short oxidation time and gradually increases. High-resolution microstructures reveal that the oxidized layers are porous regardless of oxidation time. After extended oxidation time, discrete MgAl2O4 particles formed as a result of the reaction of initially formed MgO, liquid aluminum, and oxygen introduced from air through the porous MgO. Furthermore, it is clear by high-resolution lattice images that MgAl2O4 particles are covered with thin Al2O3, whereas MgO is bonded intimately to aluminum. Therefore, MgAl2O4 particles that form naturally during oxidation are difficult to act as a direct substrate for nucleation of aluminum grains because of the coverage of Al2O3. In contrast, MgO shows the possibility of acting as a substrate for the aluminum nucleation. The formation mechanism of MgO and MgAl2O4 and their possibility of acting as substrates for nucleation of aluminum grains suggest that atomic level bonding and mismatches of nucleant/nucleus metal should be considered for correct evaluation of the possibility of heterogeneous nucleation of metallic matrix on a potent nucleant. Copyright © 2015 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

A method of analytical transmission electron microscopy is described that has been successfully applied to study dopant segregation to inversion domain boundaries in zinc oxide, to quantify the thicknesses of sub-nanometre thin epitaxial layers grown by molecular beam epitaxy of indium arsenide (InAs) on gallium arsenide (GaAs) or silicon/germanium on silicon and proved the absence of any gettering of As or Ga dopants at Sigma=3 {111} grain boundaries in silicon, with a precision of <1 atom/nm2 in each case. Here, the case study of InAs/GaAs is reviewed in detail and the procedure for quantification of full hyperspectral data sets is explained. (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [ABSTRACT FROM AUTHOR]

We applied the parametric bootstrap to the X-ray microanalysis of Si-Ge binary alloys, in order to assess the dependence of the Ge concentrations and the local film thickness, obtained by using previously described Monte Carlo methods, on the precision of the measured intensities. We show how it is possible by this method to determine the statistical errors associated with the quantitative analysis performed in sample regions of different composition and thickness, but by conducting only one measurement. We recommend the use of the bootstrap for a broad range of applications for quantitative microanalysis to estimate the precision of the final results and to compare the performances of different methods to each other. Finally, we exploited a test based on bootstrap confidence intervals to ascertain if, for given X-ray intensities, different values of the estimated composition in two points of the sample are indicative of an actual lack of homogeneity. [ABSTRACT FROM AUTHOR]

A new mechanism of cleaving-healing of garnet in metamorphic rocks during exhumation is reported. Almandine garnet with submicron multiple-phase inclusions characteristic of the GRAIL reaction, garnet + rutile = kyanite + ilmenite + low-quartz, was found by analytical electron microscopy to have non-epitaxial rutile nanoparticles distributed along internal {110} microcrack trails at the acute corner of submicron multiple-phase inclusions defined by the intersecting (110) and (011) mould surfaces. Such garnet microcracks were formed during lithostatic decompression due to a relatively high compressibility of quartz in the inclusion pockets and stress concentration at the acute corner. Spontaneous healing with accompanied formation of non-epitaxial rutile nanoparticles was activated predominantly via the GRAIL reaction due to high surface tension at the tip of microcracks and, to a lesser extent, decreasing lithostatic pressure or increasing inclusion pressure upon exhumation. This new mechanism of microcracking and healing involves stress build up, fracture propagation, mineral reaction, transport of elements to the reaction site and lowering of reaction boundaries by capillarity effect, all under the influence of thermodynamic and kinetic factors at the submicron-scale. Thus, TiO2 nanoparticle trails in garnet provide additional information on the P–T path and may shed light on exhumation rates/mechanisms and metamorphic reactions/processes. Careful scrutiny of host minerals on the submicron scale is required to tell whether there are other metamorphic-reaction facilitated healing processes being overlooked by inappropriate techniques or being obliterated by the predominant healing processes of fluid infiltration and resorption zoning. [ABSTRACT FROM AUTHOR]

Although oriented rutile needles in garnet have been reported from several ultrahigh-pressure (UHP) rocks and considered to be important UHP indicators, their crystallographic features including growth habit and lattice correspondences with garnet host have never been properly characterized. This paper presents a detailed analytical electron microscopic (AEM) study on evenly distributed oriented rutile needles in garnet of two eclogitic rocks from Sulu. Some garnet in one UHP diamondiferous quartzofeldspathic rock from the Saxonian Erzgebirge, and in one high-pressure (HP) felsic granulite from Bohemia also contain a few unevenly distributed oriented rutile needles. They have also been studied for the purpose of comparison. Despite different distribution patterns, AEM revealed that all rutile needles are oriented along the 〈111〉 directions of garnet with their lateral sides surrounded by the {110} planes of garnet, and that the growth directions of most needles are close to the normal of the {101} planes of rutile. No other specific crystallographic orientation relationships between rutile and garnet host were observed, and there is no pyroxene associated with rutile, as necessitated by the precipitation reaction of rutile in garnet as previously proposed. A simple solid-state precipitation scenario for the formation of the rutile needles in garnet in these two eclogitic rocks is not justified. Three alternative mechanisms are considered for the formation of oriented rutile needles: (i) the rutile needles may be inherited from precursor minerals; (ii) the rutile needles may be formed by a dissolution–reprecipitation mechanism; and (iii) the rutile needles may be formed by cleaving and healing of garnet with rutile deposition. None of these mechanisms can fully explain the observations, although the first one is less likely and the third one is preferred. This study presents an example where the presence of oriented/aligned inclusions in minerals does not necessarily imply a precipitation origin. [ABSTRACT FROM AUTHOR]

Qualitative and quantitative electron energy-loss spectroscopy analyses have been performed on niobium and stable niobium oxides (NbO, NbO2 and Nb2O5). At integration windows (Δ) greater than 75 eV, k-factor analysis can be used to distinguish between the stoichiometry of the three oxides within 5.7% error. As seen in other metal oxides, with increasing oxidation state the metal ionization edges shift to higher energies relative to the O-K edge. Normalized M2,3 white-line intensities show a strong correlation with 4 d occupancy for each compound. The data are in correspondence with that observed in the literature for 4 d transition metals using normalized L2,3 white lines. Lastly, a distinctive energy-loss near-edge, structure of the O-K edge was observed for each oxide, which could be used as a fingerprint for analysis of unknowns. [ABSTRACT FROM AUTHOR]

Summary Analytical electron microscopy was used to characterize aquatic iron-rich colloids. We focused our attention on a redox transition medium in the drainage water of a peat soil. In the anoxic peat water, observations by transmission electron microscopy and associated energy dispersive analyses (TEM-EDS) highlight the presence of spherical entities (∼100–600 nm), containing only traces of iron. The increase of dissolved oxygen concentration favours the formation of iron oxy(hydr)oxides. In the oxygenated drain, particles with the same morphology and size range are present. Statistical TEM-EDS analyses show that they represent the only colloidal form of iron in the drain samples. Nevertheless, although Fe–K peaks appear clearly on EDS spectra, the proportion of iron in these colloids reaches at most 4% at. (whereas C + O > 90% at.). Structural information completes this study. Both electron spectroscopic imaging (ESI) and electron energy-loss spectroscopy (EELS) reveal the disparity between element distributions within the drain entities. Iron and calcium are preferably distributed on the outer sphere of the particle, whereas carbon and oxygen follow the theoretical variation of the signal intensity within a plain sphere. The implication of organic matter as nucleation site for iron precipitation is spectacularly demonstrated by the presence of nanometre-sized iron-rich phases highlighted by EELS line scans. [ABSTRACT FROM AUTHOR]

Increasing the solid angle of X-ray collection is a major factor in improving the analytical sensitivity of X-ray energy-dispersive spectrometry (XEDS) in the analytical electron microscope (AEM). A new scanning transmission electron microscope, the VG HB 603, is equipped with two XEDS detectors with the largest collection angles (0.30 and 0.17 sr) available in commercial AEMs. However, large collection angles result in a large range of take-off angles, from ~ 4° to 36°, and the low angles can cause strong X-ray absorption. In order to investigate possible detrimental effects of the low (and of the range of) take-off angles on quantitative microanalysis of specimens exhibiting significant absorption, a stoichiometric Ni3Al thin-film, in which the Al Kα line is significantly absorbed, was analysed. Furthermore, the effect of different values of the collection angle on X-ray intensities was theoretically evaluated by numerical calculations and spectral simulation. These theoretical approaches permitted correlation of changes in the X-ray take-off angle (and hence X-ray absorption) with changes in the collection angle. It is demonstrated that ~ 0.30 sr detectors, with minimum take-off angles as small as 4°, only result in maximum errors of 4% in the quantification of Al in Ni3Al and, therefore, further increases in collection angle can be pursued while maintaining current levels of accuracy of quantification. [ABSTRACT FROM AUTHOR]

The interpretation of highly resolved elemental maps is not straightforward: one has to consider the quantum mechanical nature of the scattering process as well as the influence of the microscope. Existing calculations of the contrast in elemental maps are based on a non-relativistic approach, while in most of the currently installed electron microscopes, the electrons penetrate the specimen with relativistic energies ≥ 200 keV. Therefore, we have recalculated the intensity distribution in elemental maps based on a fully relativistic theory. Using the concept of contrast transfer functions, the simulations account for lens aberrations as well as the defocus. Surprisingly, the results exhibit considerable deviations between the relativistic and non-relativistic calculations even in the region of low acceleration voltages such as 100 kV. These differences increase with increasing acceleration voltage and are strongly dependent on aperture and energy loss. Quantitative simulations and evaluations of highly resolved elemental maps should therefore make use of a fully relativistic theory. [ABSTRACT FROM AUTHOR]

SUMMARY A new procedure has been developed to produce thin foils of uranium and its alloys for transmission electron microscopy. The procedure is a two-step electrochemical cleaning-thinning process which produces self-supporting discs. This procedure was used to produce thin foils of the most important alloys of uranium. [ABSTRACT FROM AUTHOR]

Using analytical electron microscopy. we directly tested the hypothesis that transition metals and sulfur are the cause of chlorhexidine-induced tooth stain. Plaque scraped from the teeth of water-treated individuals or chlorhexidine-treated "non-stainers" was non- or lightly-stained and contained low concentrations of sulfur and transition metals. Tooth scrapings from heavily-staining chlorhexidine-treated individuals consisted of distinct unstained and stained regions. The stained regions were organic but were in close proximity to mineralized areas. Enhanced levels of sulfur and transition metals, particularly iron, were found in stained regions, whereas unstained regions contained low sulfur and metal levels similar to the water-treated or non-staining individuals. Excluding decreased mineralization, the major elemental change in heavily-stained plaque was an increase in sulfur, and to a lesser extent, iron and other transition metals. Sulphur and iron levels were directly correlated. Following chlorhexidine treatment with iron supplementation, staining was enhanced. the Fe/S ratio increased, and sulfur and iron remained correlated. These data support the hypothesis that transition metals and sulfur are the cause of chlorhexidine-induced tooth stain. The data are consistent with chlorhexidine treatment altering the incorporation into plaque of a natural sulfur-containing organic component of saliva or bacteria. This natural component appears to readily interact with transition metals, particularly iron, producing stained material. [ABSTRACT FROM AUTHOR]

Core−rim structures are found as a general microstructural feature in SiC ceramics gas–pressure sintered with AlN−Y2O3 additives in different ratio, combined with a range of α/β‐SiC seeding to control the phase transformation. Using analytical electron microscopy, the authors investigate the re‐distribution of additives to detect uniform level of AlN solution into SiC rims, independent to the seeding ratio, and also not proportional to additives. The behavior of AlN solution reveals the presence of sintering melt based on nitro‐carbide to start the reprecipitation of SiC rims, while the cores are remnants from starting powders to control the phase transformation as well as the grain growth behavior. Among various intergranular phases, Y10Al2‐zSi3+zO18+zN4‐z is observed as common hence the secondary phase, while its Al level changes in an opposite trend to AlN solution in SiC rims. This oxynitride phase precipitates from the Y‐rich oxynitride melt, which extends and regulates the solution−reprecipitation process and develops into the Y−Si−O−(C) melt to create a series of residual intergranular oxides. Post‐annealing can fully devitrify the viscous intergranular glass to reach complete crystallization of ceramic body, which leads to improved creep resistance at high temperature for this SiC ceramic system. [ABSTRACT FROM AUTHOR]