Enhanced quantification for 3D SEM-EDS: using the full set of available X-ray lines.

An enhanced method to quantify energy dispersive spectra recorded in 3D with a scanning electron microscope (3D SEM-EDS) has been previously demonstrated. This paper presents an extension of this method using all the available X-ray lines generated by the beam. The extended method benefits from using high energy lines, that are more accurately quantified, and from using soft X-rays that are highly absorbed and thus more surface sensitive. The data used to assess the method are acquired with a dual beam FIB/SEM investigating a multi-element Ni-based superalloy. A high accelerating voltage, needed to excite the highest energy X-ray line, results in two available X-ray lines for several elements. The method shows an improved compositional quantification as well as an improved spatial resolution.This is the final version of the article. It first appeared from Elsevier via http://dx.doi.org/10.1016/j.ultramic.2014.10.01

Three Dimensional Microanalysis by Energy Dispersive Spectrometry:Improved Data Processing

This thesis is focused on a combined microscopy technique: energy dispersive spectrometry (EDS) is extended to a three dimensional (3D) microanalysis using a so-called "dual-beam microscope": a scanning electron microscope (SEM) equipped with a focused ion beam (FIB). In the sequential acquisition, the surface freshly milled by the FIB is characterised by SEM imaging and EDS mapping. A 3D elemental picture of the specimen is obtained this way. This technique suffers from the same limitations than the 2D EDS mapping, the major one being linked to the volume of X-ray emission that is large due to the required high accelerating voltage. Other limitations of 3D EDS microanalysis are more specific to FIB/SEM technique, such as the low acquisition time per spectrum due to the large number of spectra required in an acquisition. The goal of this thesis was to develop post-processing solutions to overcome the limitations of 3D EDS microanalysis. Three solutions have been developed. As the acquired data are composed of a high number of noisy spectra, multivariate statistic methods are appropriate. Such a technique is adapted to 3D EDS data and provides smoother spectra improving the quantification afterwards. When analysing a feature that is smaller than the volume of X-ray emission, the quantified composition is inaccurate as part of the X-rays are emitted from the feature’s surrounding. To take into account the influence of the neighbouring voxels, an enhanced quantification technique is developed. It is based on a recursive approach adapting an existing complex quantification. Another complementary approach is developed to resolve features too fine for EDS mapping: the segmentation technique is improved by using the higher spatial resolution of SEM images. A sample formed by laser welding of nickel-titanium (NiTi) and stainless-steel wires is characterised by 3D EDS microanalysis. The acquired data are used to demonstrate the gains and the limitations of the three developed processing techniques. With them, the noise-reduced spectra reveal further details of the fine microstructure. Their quantified composition is closer to the one predicted by the phase diagram. Furthermore, the segmented phases used for the 3D visualisation have a resolution close to the one of the SEM images. This visualisation allows a deeper comprehension of the formation of the phases and their morphologies during the implied solidification. This demonstrates the great potential of this technique to characterise samples with complex microstructure and complex composition

A novel 3D absorption correction method for quantitative EDX-STEM tomography.

This paper presents a novel 3D method to correct for absorption in energy dispersive X-ray (EDX) microanalysis of heterogeneous samples of unknown structure and composition. By using STEM-based tomography coupled with EDX, an initial 3D reconstruction is used to extract the location of generated X-rays as well as the X-ray path through the sample to the surface. The absorption correction needed to retrieve the generated X-ray intensity is then calculated voxel-by-voxel estimating the different compositions encountered by the X-ray. The method is applied to a core/shell nanowire containing carbon and oxygen, two elements generating highly absorbed low energy X-rays. Absorption is shown to cause major reconstruction artefacts, in the form of an incomplete recovery of the oxide and an erroneous presence of carbon in the shell. By applying the correction method, these artefacts are greatly reduced. The accuracy of the method is assessed using reference X-ray lines with low absorption.The research leading to these results has received funding from the European Union Seventh Framework Programme under Grant Agreement 312483 - ESTEEM2 (Integrated Infrastructure Initiative–I3), as well as from the European Research Council under the European Union’s Seventh Framework Programme (FP/2007-2013)/ERC grant agreement 291522 - 3DIMAGE. A.N.F. and A.B. acknowledge project MAT2013-42900-P from the Spanish Ministry of Economy and Competitiveness and REGPOT-CT-2011-285895-AlNANOFUNC.This is the final version of the article. It first appeared from Elsevier via http://dx.doi.org/10.1016/j.ultramic.2015.09.01

Enhanced Quantification for 3D Energy Dispersive Spectrometry: Going Beyond the Limitation of Large Volume of X-Ray Emission

This paper presents a method developed to quantify three-dimensional energy dispersive spectrometry (3D EDS) data with voxel size smaller than the volume from which X-rays are emitted. The influence of the neighboring voxels is corrected by applying recursively a complex quantification, improving thereby the accuracy of the quantification of critically small features. The enhanced quantification method is applied to simulated and measured data. A systematic improvement is obtained compared with classical quantification, proving the concept and the prospect of this metho

Interface flow process audit: using the patient's career as a tracer of quality of care and of system organisation

OBJECTIVES: This case study aims to demonstrate the method's feasibility and capacity to improve quality of care. Several drawbacks attached to tracer condition and selected procedure audits oblige clinicians to rely on external evaluators. Interface flow process audit is an alternative method, which also favours integration of health care across institutions divide. METHODS: An action research study was carried out to test the feasibility of interface flow process audit and its impact on quality improvement. An anonymous questionnaire was carried out to assess the participants' perception of the process. RESULTS: In this study, interface flow process audit brought together general practitioners and hospital doctors to analyse the co-ordination of their activities across the primary-secondary interface. Human factors and organisational characteristics had a clear influence on implementation of the solutions. In general, the participants confirmed that the interface flow process audit helped them to analyse the quality of case management both at primary and secondary care level. CONCLUSIONS: The interface flow process audit appears a useful method for regular in-service self-evaluation. Its practice enabled to address a wide scope of clinical, managerial and economical problems. Bridging the primary-secondary care gap, interface flow process audit's focus on the patient's career combined with the broad scope of problems that can be analysed are particularly powerful features. The methodology would benefit from an evaluation of its practice on larger scale

Multicomponent signal unmixing from nanoheterostructures: overcoming the traditional challenges of nanoscale X-ray analysis via machine learning.

The chemical composition of core-shell nanoparticle clusters have been determined through principal component analysis (PCA) and independent component analysis (ICA) of an energy-dispersive X-ray (EDX) spectrum image (SI) acquired in a scanning transmission electron microscope (STEM). The method blindly decomposes the SI into three components, which are found to accurately represent the isolated and unmixed X-ray signals originating from the supporting carbon film, the shell, and the bimetallic core. The composition of the latter is verified by and is in excellent agreement with the separate quantification of bare bimetallic seed nanoparticles.D.R. acknowledges support from the Royal Society’s Newton International Fellowship scheme. B.R.K. thanks the U.K. EPSRC for financial support (EP/J500380/1). F.d.l.P. and C.D. acknowledge funding from the ERC under grant no. 259619 PHOTO EM. P.A.M and P.B. acknowledges financial support from the European Research Council under the European Union’s Seventh Framework Programme (FP7/ 2007-2013)/ERC grant agreement 291522-3DIMAGE. P.A.M. also acknowledges financial support from the European Union’s Seventh Framework Programme of the European Commission: ESTEEM2, contract number 312483.This is the final published version. It first appeared at http://pubs.acs.org/doi/abs/10.1021/acs.nanolett.5b00449

Magnetic-Field Induced Strains in Ferromagnetic Shape Memory Alloy Ni55Mn23Ga22 Deposited by RF-Magnetron Sputtering

1.5mm–Ni55Mn23Ga22 ferromagnetic thin films were deposited onto silicon substrates and silicon single beam cantilever using radio-frequency magnetron sputtering. As-deposited sample and heat-treated thin films were studied on their silicon substrates and peeled off to determine the influence of the stress. Post-heat treatment process allows at the films to achieve the shape memory effect (SME). Vibrating sample magnetometer (VSM) and deflection measurement of the sample annealed at 873 K during 36 ks exhibit ferromagnetic martensitic structure with a typical SME response to the magnetic field induced strains which match the values of the bulk material

Vacuum template synthesis of multifunctional nanotubes with tailored nanostructured walls

A three-step vacuum procedure for the fabrication of vertical TiO2 and ZnO nanotubes with three dimensional walls is presented. The method combines physical vapor deposition of small-molecules, plasma enhanced chemical vapor deposition of inorganic functional thin films and layers and a postannealing process in vacuum in order to remove the organic template. As a result, an ample variety of inorganic nanotubes are made with tunable length, hole dimensions and shapes and tailored wall composition, microstructure, porosity and structure. The fabrication of multishell nanotubes combining different semiconducting oxides and metal nanoparticles is as well explored. This method provides a feasible and reproducible route for the fabrication of high density arrays of vertically alligned nanotubes on processable substrates. The emptying mechanism and microstructure of the nanotubes have been elucidated through SEM, STEM, HAADF-STEM tomography and energy dispersive X-ray spectroscopy. In this article, as a proof of concept, it is presented the straightforward integration of ZnO nanotubes as photoanode in a photovoltaic cell and as a photonic oxygen gas sensorPeer reviewe

Characterization and Functional Identification of a Novel Plant 4,5-Extradiol Dioxygenase Involved in Betalain Pigment Biosynthesis in Portulaca grandiflora

Betalains are pigments that replace anthocyanins in the majority of families of the plant order Caryophyllales. Betalamic acid is the common chromophore of betalains. The key enzyme of the betalain biosynthetic pathway is an extradiol dioxygenase that opens the cyclic ring of dihydroxy-phenylalanine (DOPA) between carbons 4 and 5, thus producing an unstable seco-DOPA that rearranges nonenzymatically to betalamic acid. A gene for a 4,5-DOPA-dioxygenase has already been isolated from the fungus Amanita muscaria, but no homolog was ever found in plants. To identify the plant gene, we constructed subtractive libraries between different colored phenotypes of isogenic lines of Portulaca grandiflora (Portulacaceae) and between different stages of flower bud formation. Using in silico analysis of differentially expressed cDNAs, we identified a candidate showing strong homology at the level of translated protein with the LigB domain present in several bacterial extradiol 4,5-dioxygenases. The gene was expressed only in colored flower petals. The function of this gene in the betalain biosynthetic pathway was confirmed by biolistic genetic complementation in white petals of P. grandiflora genotypes lacking the gene for color formation. This gene named DODA is the first characterized member of a novel family of plant dioxygenases phylogenetically distinct from Amanita sp. DOPA-dioxygenase. Homologs of DODA are present not only in betalain-producing plants but also, albeit with some changes near the catalytic site, in other angiosperms and in the bryophyte Physcomitrella patens. These homologs are part of a novel conserved plant gene family probably involved in aromatic compound metabolism