The three-dimensional distribution of individual hydrogen atoms within a complex steel microstructure is characterized using isotopic doping and cryogenic-transfer atom probe tomography. AbstractThe design of atomic-scale microstructural traps to limit the diffusion of hydrogen is one key strategy in the development of hydrogen-

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There are many sources of random and systematic error in composition quantification by atom probe microscopy, often, however, only statistical error is reported. Significantly larger errors can occur from the misidentification of ions and overlaps or interferences of peaks in the mass spectrum. These overlaps can be solved using maximum likelihood estimation (MLE), improving the accuracy of the result, but with an unknown effect on the precision. An analytical expression for the uncertainty of the MLE solution is presented and it is demonstrated to be much more accurate than the existing methods. In one example, the commonly used error estimate was five times too small.Literature results containing overlaps most likely underestimate composition uncertainty because of the complexity of correctly dealing with stochastic effects and error propagation. The uncertainty depends on the amount of overlapped intensity, for example being ten times worse for the CO/Fe overlap than the Cr/Fe overlap. Using the methods described here, accurate estimation of error, and the minimization of this could be achieved, providing a key milestone in quantitative atom probe. Accurate estimation of the composition uncertainty in the presence of overlaps is crucial for planning experiments and scientific interpretation of the measurements.

Zirconium-based alloys are used in water-cooled nuclear reactors for both nuclear fuel cladding and structural components. Under this harsh environment, the main factor limiting the service life of zirconium cladding, and hence fuel burn-up efficiency, is water corrosion. This oxidation process has recently been linked to the presence of a sub-oxide phase with well-defined composition but unknown structure at the metal–oxide interface. In this paper, the combination of first-principles materials modeling and high-resolution electron microscopy is used to identify the structure of this sub-oxide phase, bringing us a step closer to developing strategies to mitigate aqueous oxidation in Zr alloys and prolong the operational lifetime of commercial fuel cladding alloys.

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.

a b s t r a c tThree model ODS alloys (Fe-0.3Y 2 O 3 , Fe-0.2Ti-0.3Y 2 O 3 and Fe-14Cr-0.2Ti-0.3Y 2 O 3 ) were prepared by ball milling and then hot extrusion to study the effect of Ti and Cr on the size, distribution, crystal structure and composition of the nano-oxide particles. All alloys were characterized by high resolution transmission electron microscopy (HRTEM), atom probe tomography (APT) and synchrotron-X-ray diffraction (S-XRD) to determine the distribution, structure and composition of the oxide nanoparticles samples. The median particle sizes were 9.6 nm, 7.7 nm and 3.7 nm for the Fe-Y 2 O 3 , Fe-Ti-Y 2 O 3 and Fe-Cr-Ti-Y 2 O 3 alloys, respectively, so the presence of Ti resulted in a significant reduction in oxide particle diameter and the addition of Cr gave a further reduction in size. In the Fe-0.3Y 2 O 3 alloy, the particles are found to be bcc Y 2 O 3 , whereas in the other two alloys (Fe-Ti-0.3Y 2 O 3 and Fe-Cr-Ti-Y 2 O 3 ), the oxide particles were found to be structurally consistent with both orthorhombic Y 2 TiO 5 and fcc Y 2 Ti 2 O 7 . Detailed APT studies showed Cr shells around oxide particles of all sizes in the Fe-Cr-Ti-Y 2 O 3 alloy, that a range of cluster compositions are present and that the particle chemistry varies with cluster size. We show that the addition of Cr has a strong effect on both the size and stoichiometry of the particles.

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.

Towards quantitative off-axis electron holographic mapping of the electric field around the tip of a sharp biased metallic needle J. Appl. Phys. 116, 024305 (2014) 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.