In situ\textit{In situ} hydride breathing during the template-assisted electrodeposition of Pd nanowires

We investigated the structural evolution of electrochemically fabricated Pd nanowires $\textit{in situ}$ by means of grazing-incidence transmission small- and wide-angle x-ray scattering (GTSAXS and GTWAXS), x-ray fluorescence (XRF) and 2-dimensional surface optical reflectance (2D-SOR). This shows how electrodeposition and the hydrogen evolution reaction (HER) compete and interact during Pd electrodepositon. During the bottom-up growth of the nanowires, we show that $\beta$-phase Pd hydride is formed. Suspending the electrodeposition then leads to a phase transition from $\beta$- to $\alpha$-phase Pd hydride. Additionally, we find that grain coalescence later hinders the incorporation of hydrogen in the Pd unit cell. GTSAXS and 2D-SOR provide complementary information on the volume fraction of the pores occupied by Pd, while XRF was used to monitor the amount of Pd electrodeposited.Comment: 17 pages, 11 figures, 4 appendice

Texture evolution during room temperature ageing of silver processed by equal-channel angular pressing

The evolution of texture was investigated using silver samples processed by equal-channel angular pressing for different numbers of passes and stored at room temperature for up to 4 months. For 1 and 4 passes, only a slight texture intensity change was detected during storage. For 8 and 16 passes, there was a weakening of components A*(20) and C-0 and the development of a strong A*(10) component due to significant recrystallization in the severely deformed samples. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserve

High-resolution reciprocal space mapping reveals dislocation structure evolution during 3D printing

International audienceDislocation structures are ubiquitous in any 3D printed alloy and they play a primary role in determining the mechanical response of an alloy. While it is understood that these structures form due to rapid solidification during 3D printing, there is no consensus on whether they evolve due to the subsequent solid-state thermal cycling that occurs with further addition of layers. In order to design alloy microstructures with desired mechanical responses, it is crucial to first answer this outstanding question. To that end, a novel experiment has been conducted by employing high resolution reciprocal space mapping, a synchrotron-based X-ray diffraction technique, in situ during 3D printing of an austenitic stainless steel. It reveals that dislocation structures formed during rapid solidification undergo significant evolution during subsequent solid-state thermal cycling, in particular during addition of the first few (up to 5) layers above the layer of interest

Stress partitioning in harmonic structure materials at the early stages of tensile loading studied in situ by synchrotron X-ray diffraction

In situ X-ray diffraction was employed to gain insight into the tensile deformation behavior of harmonic structure (HS) nickel. HS consists of a continuous network of fine grains encompassing islands of coarse grains. With the aid of a newly developed separation algorithm, the X-ray diffraction signals from coarse and fine grains were analyzed separately. Using line profile analysis, the evolution of local stresses and microstrains in the respective grain fractions were examined. Several stages were identified during yielding and the onset of plastic deformation in HS nickel. The mechanical behavior of the individual fractions was related to the macroscopic behavior of the HS and compared to that of homogeneous counterparts with similar average grain sizes as the grain fractions. The analysis reveals that the stress partitions between the grain fractions and that the plastic deformation of coarse grains within the HS are constrained by the network of fine grains

Grain-level mechanism of plastic deformation in harmonic structure materials revealed by high resolution X-ray diffraction

Materials with heterogeneous microstructures have been reported to have an attractive combination of strength and ductility. This is attributed to synergistic strengthening effects from the difference in strength of fine- and coarse-grained regions. Understanding the interaction of the regions is crucial for further optimization of the microstructures. In this work, we fabricated nickel of harmonic structure (HS) and a reference with homogenous coarse grains. The HS constitutes of an interconnected fine-grained network that surrounds regions of coarse grains. The interplay of the regions was studied by monitoring Bragg reflections from individual grains in situ during tensile deformation until approximately 2 % strain through synchrotron X-ray diffraction. The technique allows grain-level assessment of the degree of plastic deformation. Two grains were followed in the reference and two small grains (fine-grained region) and two large grains (coarse-grained region) in the HS. Three deformation regimes were identified: elastic deformation, onset of plastic deformation and significant plastic deformation. Our results reveal that the large grains in the harmonic structure onset plastic deformation during the macroscopic elastic stage. With increasing applied stress, the small grains yield plastically also and once a large fraction of the fine-grained network deforms plastically the large grains undergo significant plastic deformation. Notably, the onset of significant plastic deformation of large grains in the HS occurs at approximately 100 MPa higher applied stress than in the grains in the reference. This shows that fine grains constrain the large grains from deforming plastically in the HS

Stress partitioning in harmonic structure materials at the early stages of tensile loading studied in situ by synchrotron X-ray diffraction

In situ X-ray diffraction was employed to gain insight into the tensile deformation behavior of harmonic structure (HS) nickel. HS consists of a continuous network of fine grains encompassing islands of coarse grains. With the aid of a newly developed separation algorithm, the X-ray diffraction signals from coarse and fine grains were analyzed separately. Using line profile analysis, the evolution of local stresses and microstrains in the respective grain fractions were examined. Several stages were identified during yielding and the onset of plastic deformation in HS nickel. The mechanical behavior of the individual fractions was related to the macroscopic behavior of the HS and compared to that of homogeneous counterparts with similar average grain sizes as the grain fractions. The analysis reveals that the stress partitions between the grain fractions and that the plastic deformation of coarse grains within the HS are constrained by the network of fine grains

Improvement of Left Ventricular Graft Function Using an Iron-Chelator-Supplemented Bretschneider Solution in a Canine Model of Orthotopic Heart Transplantation

Demand for organs is increasing while the number of donors remains constant. Nevertheless, not all organs are utilized due to the limited time window for heart transplantation (HTX). Therefore, we aimed to evaluate whether an iron-chelator-supplemented Bretschneider solution could protect the graft in a clinically relevant canine model of HTX with prolonged ischemic storage. HTX was performed in foxhounds. The ischemic time was standardized to 4 h, 8 h, 12 h or 16 h, depending on the experimental group. Left ventricular (LV) and vascular function were measured. Additionally, the myocardial high energy phosphate and iron content and the in-vitro myocyte force were evaluated. Iron chelator supplementation proved superior at a routine preservation time of 4 h, as well as for prolonged times of 8 h and longer. The supplementation groups recovered quickly compared to their controls. The LV function was preserved and coronary blood flow increased. This was also confirmed by in vitro myocyte force and vasorelaxation experiments. Additionally, the biochemical results showed significantly higher adenosine triphosphate content in the supplementation groups. The iron chelator LK614 played an important role in this mechanism by reducing the chelatable iron content. This study shows that an iron-chelator-supplemented Bretschneider solution effectively prevents myocardial/endothelial damage during short- as well as long-term conservation

Thickness and composition of native oxides and near-surface regions of Ni superalloys

The surface chemistry and thickness of the native oxide, hydroxide, and modified sub-surface layer of three Ni superalloys (alloy 59, 625, and 718) were determined by synchrotron X-ray Photoelectron Spectroscopy (XPS) and X-ray Reflectivity (XRR). Taking advantage of the synchrotron radiation techniques, a procedure for normalizing the photoelectron intensity was employed, which allowed for accurate quantitative analysis revealing a total oxide thickness for all samples of 12–13 Å, a hydroxide layer of 2–3 Å, and a thickness of the sub-surface alloy layer of 20–35 Å. The thickness results were compared to structural atomic models suggesting that the oxide thickness corresponds to four planes of metal cations in the oxide matrix. The XPS data revealed that the native oxides were enriched in Cr3+, Mo(4,5,6)+, and Nb5+, while no Ni oxide was detected. The hydroxide layer mainly contained Ni2+ and Cr3+ hydroxide. The sub-surface layer was enriched in Ni and depleted in Cr, Fe, Mo, and Nb. The obtained oxide composition can be explained using thermodynamics, and it was found that the oxide composition correlates with the enthalpy of oxide formation for the metal elements in the alloys. Finally, the advantages of synchrotron radiation for composition and thickness determination are discussed

The Oxygen Evolution Reaction Drives Passivity Breakdown for Ni–Cr–Mo Alloys

Corrosion is the main factor limiting the lifetime of metallic materials, and a fundamental understanding of the governing mechanism and surface processes is difficult to achieve since the thin oxide films at the metal-liquid interface governing passivity are notoriously challenging to study. In this work, a combination of synchrotron-based techniques and electrochemical methods is used to investigate the passive film breakdown of a Ni-Cr-Mo alloy, which is used in many industrial applications. This alloy is found to be active toward oxygen evolution reaction (OER), and the OER onset coincides with the loss of passivity and severe metal dissolution. The OER mechanism involves the oxidation of Mo4+ sites in the oxide film to Mo6+ that can be dissolved, which results in passivity breakdown. This is fundamentally different from typical transpassive breakdown of Cr-containing alloys where Cr6+ is postulated to be dissolved at high anodic potentials, which is not observed here. At high current densities, OER also leads to acidification of the solution near the surface, further triggering metal dissolution. The OER plays an important role in the mechanism of passivity breakdown of Ni-Cr-Mo alloys due to their catalytic activity, and this effect needs to be considered when studying the corrosion of catalytically active alloys