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Metallic glass thin films (MGTFs) are a recently developed class of alloy coatings with potential applications ranging from biomedical devices to electrical components. Their tribological performance in service conditions is dictated by MGTF bulk composition but can be limited by the native oxide surface that inevitably forms upon exposure to atmosphere. Surface oxidation, thickness, and composition of ZrCuNiAl MGTFs were characterized using a combination of X-ray photoelectron microscopy (XPS) and electron probe microanalysis (EPMA). MGTF samples with nominal thicknesses of 50, 500, and 1500 nm were sputtered onto Si and SiN wafer substrates within a high vacuum deposition chamber and their amorphicity was confirmed by X-ray diffraction. XPS depth profiling identified the thin film composition and showed that the surface oxide was dominated by a mixed layer of mostly ZrO2, a little oxidized Al, and some metallic Zr. EPMA X-ray intensities were acquired as a function of beam energy to excite characteristic X-rays from different depths of the MGTFs and reconstructed using open-source thin film analysis software BadgerFilm, to determine the composition and thickness of sample layers. EPMA results constrain the composition to be Zr54Cu29Al10Ni7 within 0.7 at. % variation and total thicknesses to be 49, 470, and 1546 nm. Using the oxide composition identified from XPS depth profiling as an input for BadgerFilm analysis, EPMA results indicate the surface oxidation layer on each of the thin film samples was 6.5 ± 1.1 nm thick and uniform across a 0.25 mm region of the film. 

Electron probe microanalysis is a nondestructive technique widely used to determine the elemental composition of bulk samples. This was extended to layered specimens, with the development of appropriate software. The traditional quantification method requires the use of matrix correction procedures based upon models of the ionization depth distribution, the so-called ϕ ( ρz ) distribution. Most of these models have led to commercial quantification programs but only few of them allow the quantification of layered specimens. Therefore, we developed BadgerFilm, a free open-source thin film program available to the general public. This program implements a documented ϕ ( ρz ) model as well as algorithms to calculate fluorescence in bulk and thin film samples. Part 1 of the present work aims at describing the operation of the implemented ϕ ( ρz ) distribution model and validating its implementation against experimental measurements and Monte Carlo simulations on bulk samples. The program has the ability to predict absolute X-ray intensities that can be directly compared to Monte Carlo simulations. We demonstrate that the implemented model works very well for bulk materials. And as will be shown in Part 2, BadgerFilm predictions for thin film specimens are also shown to be in good agreements with experimental and Monte Carlo results. 

Since the 1960s, thicknesses and compositions of thin-film specimens have been determined by using the nondestructive technique of electron probe microanalysis. This approach, refined in the 1990s, is based upon models of the ionization depth distribution, the so-called ϕ ( ρz ) distribution, and is capable of analyzing layered specimens. Most of these quantification models have led to commercial programs. However, these programs may have possible limitations: some may not be directly compatible with modern computers, they often are “black boxes” making it difficult to assess the reliability of the results, and they are sometimes expensive enough to restrain many labs from purchasing them. We present a user-friendly, free, open-source program, BadgerFilm, implementing a documented ϕ ( ρz ) model and algorithms allowing the quantification of stratified samples. The program has the ability to calculate absolute X-ray intensities that can be directly compared with Monte Carlo simulations. We give a detailed explanation for the operation of the employed ϕ ( ρz ) model in thin films. A wide range of detailed Monte Carlo simulations and experimental data have been used to evaluate and validate the accuracy of the implemented algorithms. BadgerFilm demonstrated excellent quantification results for the films and in many cases for the substrates. 

Abstract Detrital chromites are commonly reported within Archean metasedimentary rocks, but have thus far garnered little attention for use in provenance studies. Systematic variations of Cr–Fe spinel mineral chemistry with changing tectonic setting have resulted in the extensive use of chromite as a petrogenetic indicator, and so detrital chromites represent good candidates to investigate the petrogenesis of eroded Archean mafic and ultramafic crust. Here, we report the compositions of detrital chromites within fuchsitic (Cr-muscovite rich) metasedimentary rocks from the Jack Hills, situated within the Narryer Terrane, Yilgarn Craton, Western Australia, which are geologically renowned for hosting Hadean (>4000 Ma) zircons. We highlight signatures of metamorphism, including highly elevated ZnO and MnO, coupled with lowered Mg# in comparison with magmatic chromites, development of pitted domains, and replacement of primary inclusions by phases that are part of the metamorphic assemblages within host metasedimentary rocks. Oxygen isotope compositions of detrital chromites record variable exchange with host metasedimentary rocks. The variability of metamorphic signatures between chromites sampled only meters apart further indicates that modification occurred in situ by interaction of detrital chromites with metamorphic fluids and secondary mineral assemblages. Alteration probably occurred during upper greenschist to lower amphibolite facies metamorphism and deformation of host metasedimentary rocks at ∼2650 Ma. Regardless of metamorphic signatures, sampling location or grain shape, chromite cores yield a consistent range in Cr#. Although other key petrogenetic indices, such as Fe2O3 and TiO2 contents, are complicated in Jack Hills chromites by mineral non-stoichiometry and secondary mobility within metasedimentary rocks, we demonstrate that the Cr# of chromite yields significant insights into their provenance. Importantly, moderate Cr# (typically 55–70) precludes a komatiitic origin for the bulk of chromites, reflecting a dearth of komatiites and intrusive equivalents within the erosional catchment of the Jack Hills metasedimentary units. We suggest that the Cr# of Jack Hills chromite fits well with chromites derived from layered intrusions, and that a single layered intrusion may account for the observed chemical compositions of Jack Hills detrital chromites. Where detailed characterization of key metamorphic signatures is undertaken, detrital chromites preserved within Archean metasedimentary rocks may therefore yield valuable information on the petrogenesis and geodynamic setting of poorly preserved mafic and ultramafic crust. 

Abstract The relatively recent entry of field emission electron microprobes into the field of microanalysis provides another tool for the study of small features of interest (e.g., mineral and melt inclusions, ex-solution lamellae, grain boundary phases, high-pressure experimental charges). However, the critical limitation for accurate quantitative analysis of these submicrometer- to micrometer-sized features is the relationship between electron beam potential and electron scattering within the sample. To achieve submicrometer analytical volumes from which X-rays are generated, the beam accelerating voltage must be reduced from 15–20 to ≤10 kV (often 5 to 7 kV) to reduce the electron interaction volume from ~3 to ~0.5 μm in common geological materials. At these low voltages, critical Kα X-ray lines of transition elements such as Fe are no longer generated, so L X-ray lines must be used. However, applying the necessary matrix corrections to these L lines is complicated by bonding and chemical peak shifts for soft X-ray transitions such as those producing the FeLα X-ray line. It is therefore extremely challenging to produce accurate values for Fe concentration with this approach. Two solutions have been suggested, both with limitations. We introduce here a new, simple, and accurate solution to this problem, using the common mineral olivine as an example. We also introduce, for the first time, olivine results from a new analytical device, the Extended Range Soft X-ray Emission Spectrometer.