Emmanuelle A. Marquis

Hydrogen production from formic acid decomposition at room temperature using a Ag–Pd core–shell nanocatalyst

Formic acid (HCOOH) has great potential as an in situ source of hydrogen for fuel cells, because it offers high energy density, is non-toxic and can be safely handled in aqueous solution. So far, there has been a lack of solid catalysts that are sufficiently active and/or selective for hydrogen production from formic acid at room temperature. Here, we report that Ag nanoparticles coated with a thin layer of Pd atoms can significantly enhance the production of H₂ from formic acid at ambient temperature. Atom probe tomography confirmed that the nanoparticles have a core-shell configuration, with the shell containing between 1 and 10 layers of Pd atoms. The Pd shell contains terrace sites and is electronically promoted by the Ag core, leading to significantly enhanced catalytic properties. Our nanocatalysts could be used in the development of micro polymer electrolyte membrane fuel cells for portable devices and could also be applied in the promotion of other catalytic reactions under mild conditions.

Precipitation strengthening at ambient and elevated temperatures of heat-treatable Al(Sc) alloys

Yield strength at ambient temperature and creep resistance between 225 and 300°C were investigated in dilute Al(Sc) alloys containing coherent Al3Sc precipitates, which were grown by heat-treatments to radii in the range 1.4–9.6 nm. The dependence of the ambient-temperature yield stress on precipitate size is explained using classical precipitation strengthening theory, which predicts a transition from precipitate shearing to Orowan dislocation looping mechanisms at a precipitate radius of 2.1 nm, in good agreement with experimental data. At 300°C creep threshold stresses are observed and found to be much lower than the yield stresses, indicative of a climb-controlled bypass mechanism. The threshold stress increases with increasing precipitate radius, in qualitative agreement with a climb model taking into account stiffness and lattice mismatches between matrix and precipitates [1].  2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

Nanoscale structural evolution of Al3Sc precipitates in Al(Sc) alloys

Precipitation of the Al3Sc (L12) phase in aluminum alloys, containing 0.1, 0.2 or 0.3 wt% Sc, is studied with conventional transmission and high-resolution (HREM) electron microscopies. The exact morphologies of the Al3Sc precipitates were determined for the first time by HREM, in Al-0.1 wt% Sc and Al-0.3 wt% Sc alloys. The experimentally determined equilibrium shape of the Al3Sc precipitates, at 300°C and 0.3 wt% Sc, has 26 facets, which are the 6 {100} (cube), 12 {110} (rhombic dodecahedron), and 8 {111} (octahedron) planes, a Great Rhombicuboctahedron. This equilibrium morphology had been predicted by first principles calculations of the pertinent interfacial energies. The coarsening kinetics obey the (time) 1/3 kinetic law of Lifshitz-Slyozov-Wagner theory and they yield an activation energy for diffusion, 164±9 kJ/mol, that is in agreement with the values obtained from tracer diffusion measurements of Sc in Al and first principles calculations, which implies diffusion-controlled coarsening.  2001 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

Advances in the reconstruction of atom probe tomography data

Key to the integrity of atom probe microanalysis, the tomographic reconstruction is built atom by atom following a simplistic protocol established for previous generations of instruments. In this paper, after a short review of the main reconstruction protocols, we describe recent improvements originating from the use of exact formulae enabling significant reduction of spatial distortions, especially near the edges of the reconstruction. We also show how predictive values for the reconstruction parameters can be derived from electrostatic simulations, and finally introduce parameters varying throughout the analysis.

Core/shell structures of oxygen-rich nanofeatures in oxide-dispersion strengthened Fe-Cr alloys

With the significant improvement in high temperature creep properties and resistance to radiation damage by addition of nanoscale oxide features, oxide-dispersion strengthened (ODS) ferritic/martensitic alloys are potential candidates for structural applications in nuclear fusion reactors. The structure of the oxygen-rich nanofeatures was analyzed by atom-probe tomography in three ODS alloys: MA957, ODS Fe–12wt%Cr, and ODS Eurofer-97. Although field evaporation and reconstruction of the precipitates suffer from artefacts, a core/shell structure is found even for very small precipitates. Precipitate cores are Y rich while shell regions are enriched in Ti, Cr, or V depending on alloy composition.

Evolution of tip shape during field evaporation of complex multilayer structures.

Atom‐probe tomography analysis of complex multilayer structures is a promising avenue for studying interfacial properties. However, significant artefacts in the three‐dimensional reconstructed data arise due to the field evaporation process. To clarify the origin and impact of these artefacts for a FeCoB/FeCo/MgO/FeCo/IrMn multilayer, tip shapes were observed by transmission electron microscopy and compared to those obtained by finite difference modelling of electric fields and evaporation processes. It was found that the emitter shape is not spherical and its surface morphology evolves during successive evaporation of the different layers. This evolving morphology contributes to the artefacts generally observed in the reconstructed atom‐probe data for multilayer structures because algorithms for three‐dimensional reconstruction are based on the assumption that the shape of the emitter during field evaporation is spherical. Some proposed improvements to data reconstruction are proposed.

Effect of Mg addition on the creep and yield behavior of an Al–Sc alloy

The relationships between microstructure and strength were studied at room temperature and 300 °C in an Al–2 wt% Mg–0.2 wt% Sc alloy, containing Mg in solid-solution and Al3Sc (L12 structure) as nanosize precipitates. At room temperature, the yield strength is controlled by the superposition of solid-solution and precipitation strengthening. At 300 °C and at large applied stresses, the creep strength, which is characterized by a stress exponent of ~5, is significantly improved compared to binary Al–Sc alloys, and is independent of the size of the Al 3Sc precipitates. At small applied stress, a threshold stress exists, increasing from 9% to 70% of the Orowan stress with increasing Al 3Sc precipitate radius from 2 to 25 nm. An existing model based on a climb-controlled bypass mechanism is in semiquantitative agreement with the precipitate radius dependence of the threshold stress. The model is, however, only valid for coherent precipitates, and the Al 3Sc precipitates lose coherency for radii larger than 11 nm. For semi-coherent precipitates with radii greater than 15 nm, the threshold stress remains high, most likely because of the presence of interfacial misfit dislocations.

Atom probe tomography today

This review aims to describe and illustrate the advances in the application of atom probe tomography that have been made possible by recent developments, particularly in specimen preparation techniques (using dual-beam focused-ion beam instruments) but also of the more routine use of laser pulsing. The combination of these two developments now permits atomic-scale investigation of site-specific regions within engineering alloys (e.g. at grain boundaries and in the vicinity of cracks) and also the atomic-level characterization of interfaces in multilayers, oxide films, and semiconductor materials and devices.

Probing the improbable: imaging C atoms in alumina

The ability to probe the three-dimensional atomic structure of materials is an essential tool for material design and failure analysis. Atom-probe tomography has proven very powerful to analyze the detailed structure and chemistry of metallic alloys and semiconductor structures while ceramic materials have remained outside its standard purview. In the current work, we demonstrate that bulk alumina can be quantitatively analyzed and microstructural features observed. The analysis of grain boundary carbon segregation – barely achievable by electron microscopy – opens the possibility of understanding the mechanistic effects of dopants on mechanical properties, fracture and wear properties of bulk oxides.

Towards better 3-D reconstructions by combining electron tomography and atom-probe tomography

Scanning transmission electron microscope tomography and atom-probe tomography are both three-dimensional techniques on the nanoscale. We demonstrate here the combination of the techniques by analyzing the very same volume of an Al-Ag alloy specimen. This comparison allows us to directly visualize the theoretically known artifacts of each technique experimentally, providing insight into the optimal parameters to use for reconstructions and assessing the quality of each reconstruction. The combination of the techniques for accurate morphology and compositional information in three dimensions at the nanoscale provides a route for a new level of materials characterization and understanding.