Andrew London

Direct observation of individual hydrogen atoms at trapping sites in a ferritic steel

Heavy hydrogen gets frozen in place Hydrogen embrittlement contributes to the failure of steel in a wide variety of everyday applications. Various strategies to mitigate hydrogen embrittlement, such as adding carbides into the steel, are hard to validate because we are unable to map the hydrogen atoms. Chen et al. combined fluxing steel samples with deuterium and a cryogenic transfer protocol to minimize hydrogen diffusion, allowing for detailed structural analysis (see the Perspective by Cairney). Their findings revealed hydrogen trapped in the cores of the carbide precipitates. The technique will be applicable to a wide range of problems, including corrosion, catalysis, and hydrogen storage. Science, this issue p. 1196; see also p. 1128 The combination of deuteration and a cryogenic transfer protocol reveals hydrogen locations in high-strength steel. The design of atomic-scale microstructural traps to limit the diffusion of hydrogen is one key strategy in the development of hydrogen-embrittlement–resistant materials. In the case of bearing steels, an effective trapping mechanism may be the incorporation of finely dispersed V-Mo-Nb carbides in a ferrite matrix. First, we charged a ferritic steel with deuterium by means of electrolytic loading to achieve a high hydrogen concentration. We then immobilized it in the microstructure with a cryogenic transfer protocol before atom probe tomography (APT) analysis. Using APT, we show trapping of hydrogen within the core of these carbides with quantitative composition profiles. Furthermore, with this method the experiment can be feasibly replicated in any APT-equipped laboratory by using a simple cold chain.

Quantification of oxide particle composition in model oxide dispersion strengthened steel alloys.

Oxide dispersion strengthened ferritic steels (ODS) are being considered for structural components of future designs of fission and fusion reactors because of their impressive high-temperature mechanical properties and resistance to radiation damage, both of which arise from the nanoscale oxide particles they contain. Because of the critical importance of these nanoscale phases, significant research activity has been dedicated to analysing their precise size, shape and composition (Odette et al., Annu. Rev. Mater. Res. 38 (2008) 471-503 [1]; Miller et al., Mater. Sci. Technol. 29(10) (2013) 1174-1178 [2]). As part of a project to develop new fuel cladding alloys in India, model ODS alloys have been produced with the compositions, Fe-0.3Y2O3, Fe-0.2Ti-0.3Y2O3 and Fe-14Cr-0.2Ti-0.3Y2O3. The oxide particles in these three model alloys have been studied by APT in their as-received state and following ion irradiation (as a proxy for neutron irradiation) at various temperatures. In order to adequately quantify the composition of the oxide clusters, several difficulties must be managed, including issues relating to the chemical identification (ranging and variable peak-overlaps); trajectory aberrations and chemical structure; and particle sizing. This paper presents how these issues can be addressed by the application of bespoke data analysis tools and correlative microscopy. A discussion follows concerning the achievable precision in these measurements, with reference to the fundamental limiting factors.

Model-independent measurement of the charge density distribution along an Fe atom probe needle using off-axis electron holography without mean inner potential effects

The one-dimensional charge density distribution along an electrically biased Fe atom probe needle is measured using a model-independent approach based on off-axis electron holography in the transmission electron microscope. Both the mean inner potential and the magnetic contribution to the phase shift are subtracted by taking differences between electron-optical phase images recorded with different voltages applied to the needle. The measured one-dimensional charge density distribution along the needle is compared with a similar result obtained using model-based fitting of the phase shift surrounding the needle. On the assumption of cylindrical symmetry, it is then used to infer the three-dimensional electric field and electrostatic potential around the needle with ∼10 nm spatial resolution, without needing to consider either the influence of the perturbed reference wave or the extension of the projected potential outside the field of view of the electron hologram. The present study illustrates how a model-independent approach can be used to measure local variations in charge density in a material using electron holography in the presence of additional contributions to the phase, such as those arising from changes in mean inner potential and specimen thickness.

Nanoscale Stoichiometric Analysis of a High-Temperature Superconductor by Atom Probe Tomography

The functional properties of the high-temperature superconductor Y1Ba2Cu3O7-δ (Y-123) are closely correlated to the exact stoichiometry and oxygen content. Exceeding the critical value of 1 oxygen vacancy for every five unit cells (δ>0.2, which translates to a 1.5 at% deviation from the nominal oxygen stoichiometry of Y7.7Ba15.3Cu23O54-δ ) is sufficient to alter the superconducting properties. Stoichiometry at the nanometer scale, particularly of oxygen and other lighter elements, is extremely difficult to quantify in complex functional ceramics by most currently available analytical techniques. The present study is an analysis and optimization of the experimental conditions required to quantify the local nanoscale stoichiometry of single crystal yttrium barium copper oxide (YBCO) samples in three dimensions by atom probe tomography (APT). APT analysis required systematic exploration of a wide range of data acquisition and processing conditions to calibrate the measurements. Laser pulse energy, ion identification, and the choice of range widths were all found to influence composition measurements. The final composition obtained from melt-grown crystals with optimized superconducting properties was Y7.9Ba10.4Cu24.4O57.2.

Single-Ion Deconvolution of Mass Peak Overlaps for Atom Probe Microscopy

Due to the intrinsic evaporation properties of the material studied, insufficient mass-resolving power and lack of knowledge of the kinetic energy of incident ions, peaks in the atom probe mass-to-charge spectrum can overlap and result in incorrect composition measurements. Contributions to these peak overlaps can be deconvoluted globally, by simply examining adjacent peaks combined with knowledge of natural isotopic abundances. However, this strategy does not account for the fact that the relative contributions to this convoluted signal can often vary significantly in different regions of the analysis volume; e.g., across interfaces and within clusters. Some progress has been made with spatially localized deconvolution in cases where the discrete microstructural regions can be easily identified within the reconstruction, but this means no further point cloud analyses are possible. Hence, we present an ion-by-ion methodology where the identity of each ion, normally obscured by peak overlap, is resolved by examining the isotopic abundance of their immediate surroundings. The resulting peak-deconvoluted data are a point cloud and can be analyzed with any existing tools. We present two detailed case studies and discussion of the limitations of this new technique.

Comparison of atom probe tomography and transmission electron microscopy analysis of oxide dispersion strengthened steels

Oxide dispersion strengthened steels owe part of their high temperature stability to the nano-scale oxides they contain. These yttrium-titanium oxides are notoriously difficult to characterise since they are embedded in a magnetic-ferritic matrix and often <10 nm across. This study uses correlated transmission electron microscopy and atom probe tomography on the same material to explore the kind of information that can be gained on the character of the oxide particles. The influence of chromium in these alloys is of interest, therefore two model ODS steels Fe-(14Cr)-0.2Ti-0.3Y2O3 are compared. TEM is shown to accurately measure the size of the oxide particles and atom probe tomography is necessary to observe the smallest sub-1.5 nm particles. Larger Y2Ti2O7 and Y2TiO5 structured particles were identified by high-resolution transmission electron microscopy, but the smallest oxides remain difficult to index. Chemical data from energy-filtered TEM agreed qualitatively with the atom probe findings. It was found that the majority of the oxide particles exhibit an unoxidised chromium shell which may be responsible for reducing the ultimate size of the oxide particles.

A Round Robin Experiment: Analysis of Solute Clustering from Atom Probe Tomography Data.

1. Department of Materials Science and Engineering, University of Michigan, Ann Arbor, MI, U.S.A. 2. Groupe de Physique des Matériaux, UMR CNRS 6634, Université de Rouen, Saint Etienne du Rouvray Cedex, France 4. NRC “Kurchatov Institute”, Moscow, Russia 3. Institute of Nuclear Safety System, Inc., Kyoto, Japan 5. Commissariat à l’Energie Atomique (CEA), Saclay, France 6. Department of Materials, University of Oxford, U.K. 7. Institute for Materials Research, Tohoku University, Oarai Japan 8. Materials Science Research Laboratory, Central Research Institute of Electric Power Industry, Nagasaka, Japan 9. Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, WA, U.S.A. 10. Department of Physics, Chalmers University of Technology, Chalmers, Sweden 11. Departement Métallurgie, EDF, Moret sur Loing, France 12. Electric Power Research Institute, Palo Alto, CA, U.S.A.

New Approaches for Measuring Electrostatic Potentials and Charge Density Distributions in Working Devices Using Off-Axis and In-Line Electron Holography

1 Ernst Ruska Centre for Microscopy and Spectroscopy with Electrons and Peter Gruenberg Institute, Forschungszentrum Juelich, Juelich, Germany 2 Department of Materials, University of Oxford, Parks Road, Oxford, United Kingdom 3 Fakultaet fuer Physik & Center of Nanointegration, Universitaet Duisburg-Essen, Duisburg, Germany 4 Department of Physics and Astronomy, University of Bologna, Viale B. Pichat 6/2, Bologna, Italy

Determining EDS and EELS partial cross-sections from multiple calibration standards to accurately quantify bi-metallic nanoparticles using STEM

Spectroscopic signals such as EDS and EELS provide an effective way of characterising multi-element samples such as Pt-Co nanoparticles in STEM. The advantage of spectroscopy over imaging is the ability to decouple composition and mass-thickness effects for thin samples, into the number of various types of atoms in a sample. This is currently not possible for multi element samples using conventional ADF quantification techniques alone. With recent developments in microscope hardware and software, it is now possible to acquire the ADF, EDS and EELS signals simultaneously and at high speed. However, the methods of quantifying the signals emitted from the sample vary greatly. Most approaches use pure-element standards in the form of needles, nanoparticles and wedges to quantify the spectroscopic signal into either partial scattering cross-sections, zeta-factors or k-factors. But self-consistency between the different methods has not been verified and the units of the quantification are not standardised. We present a robust approach for measuring and combining ADF, EDS and EELS signals using needle and nanoparticle standards in units of the partial scattering cross-section. The partial scattering cross-section allows an easy interpretation of the signals emitted from the sample and enables accurate atom-counting of the sample.

On the Use of Density-Based Algorithms for the Analysis of Solute Clustering in Atom Probe Tomography Data

Because atom probe tomography (APT) provides three-dimensional reconstructions of small volumes by resolving atomic chemical identities and positions, it is uniquely suited to analyze solute clustering phenomena in materials. A number of approaches have been developed to extract clustering information from the 3D reconstructed dataset, and numerous reports can be found applying these methods to a wide variety of materials questions. However, results from clustering analyses can differ significantly from one report to another, even when performed on similar microstructures, raising questions about the reliability of APT to quantitatively describe solute clustering. In addition, analysis details are often not provided, preventing independent confirmation of the results. With the number of APT research groups growing quickly, the APT community recognizes the need for educating new users about common methods and artefacts, and for developing analysis and data reporting protocols that address issues of reproducibility, errors, and variability. To this end, a round robin experiment was organized among ten different international institutions. The goal is to provide a consistent framework for the analysis of irradiated stainless steels using APT. Through the development of more reliable and reproducible data analysis and through communication, this project also aims to advance the understanding between irradiated microstructure and materials performance by providing more complete quantitative microstructural input for modeling. The results, methods, and findings of this round robin will also apply to other clustering phenomena studied using APT, beyond the theme of radiation damage.