Direct diffusion through interpenetrating networks: Oxygen in titanium

How impurity atoms move through a crystal is a fundamental and recurrent question in materials. The previous understanding of oxygen diffusion in titanium relied on interstitial lattice sites that were recently found to be unstable, making the diffusion pathways for oxygen unknown. Using first-principles quantum-mechanical methods, we find three oxygen interstitial sites in titanium, and quantify the multiple interpenetrating networks for oxygen diffusion. Surprisingly, no single transition dominates, but all contribute to diffusion.Comment: 10 pages, 3 figures; additional supporting materia

Hydrogen isotope exchange in proton-conducting oxides during proton and deuteron irradiation

It has been found that during accelerator beam deuteron irradiation of a proton-conducting oxide containing protium H/D isotope exchange between beam ions and dissolved ions takes place. This isotope exchange was also observed during high-energy proton irradiation of the oxide containing dissolved deuterium atoms. These results provide evidence to a new type of hydrogen isotope exchange. Any appreciable effects of conjugate diffusion of hydrogen and oxygen ions and of the interface processes on the isotope exchange rate were eliminated. In this type of exchange the rate of replacement of H+ by D+ and of D+ by H+ was determined only by the properties of the crystal. The discovered effect was used in our study to obtain experimental data characterizing the dynamic and equilibrium behavior of hydrogen isotopes in the oxide BaZr0.9Y0.1O3 - δ. © 2013 Pleiades Publishing, Ltd

Synthesis, Structure and Electrical Properties of Li+-doped Pyrochlore Gd2Zr2O7

Received: 08.04.2020. Accepted: 20.05.2020. Published: 30.06.2020.The pyrochlore Gd1.55Li0.45Zr2O6.55 was prepared by the solution and solidstate methods. The introduction of lithium in the Gd-sublattice led to decrease in the lattice parameter a = 10.4830(8) Å in comparison with Gd2Zr2O7 (a =10.5346(2) Å). Monitoring of the lithium content in the sample during heat treatments showed a loss of lithium at temperatures above 1100 °C, so, to maintain the stoichiometry of lithium the low temperature sintering methods are required. The sample Gd1.55Li0.45Zr2O6.55 exhibited a predominant oxygen-ion transport over a wide range of temperatures. Although doping did not lead to an increase in the oxygen-ion conductivity compared to Gd2Zr2O7, it caused the suppression of the hole conductivity.The reported study was funded by RFBR and Sverdlovsk region, project number 20‑43‑660033a

Electrical Properties of Li+-Substituted Solid Solutions Based on Gd2Zr2O7

Abstract: Solid solution (Formula presented.) with a pyrochlore structure is synthesized for the first time. The cationic composition is confirmed via chemical analysis and nuclear reactions. It is found that the stoichiometry with respect to lithium is retained up to 1100°C. The lattice parameter diminishes in the homogeneity range 0 ≤ x ≤ 0.30, while the free volume of migration grows. Introducing lithium into the Gd sublattice raises oxygen–ion conductivity, due to the emergence of oxygen vacancies and enhancement of their mobility. Maximum conductivity is reached for composition with х = 0.10 (~1 × 10−3 Ω−1 cm−1, 650°C). An assumption is made about the formation of associates of the type (Formula presented.) at high contents of the dopant (x = 0.30), accompanied by an increase in the activation energy of conductivity. © 2021, The Author(s).This work was performed with a grant from the Russian Foundation for Basic Research, project no. 20-43-660033, and financial support from the State Atomic Energy Corporation ROSATOM (State Contract no. Н.4о.241.19.21.1070 of April 16, 2021; electronic identifier 07731000003210000330001)

CVD growth of carbon nanostructures from zirconia: mechanisms and a method for enhancing yield.

By excluding metals from synthesis, growth of carbon nanostructures via unreduced oxide nanoparticle catalysts offers wide technological potential. We report new observations of the mechanisms underlying chemical vapor deposition (CVD) growth of fibrous carbon nanostructures from zirconia nanoparticles. Transmission electron microscope (TEM) observation reveals distinct differences in morphological features of carbon nanotubes and nanofibers (CNTs and CNFs) grown from zirconia nanoparticle catalysts versus typical oxide-supported metal nanoparticle catalysts. Nanofibers borne from zirconia lack an observable graphitic cage consistently found with nanotube-bearing metal nanoparticle catalysts. We observe two distinct growth modalities for zirconia: (1) turbostratic CNTs 2-3 times smaller in diameter than the nanoparticle localized at a nanoparticle corner, and (2) nonhollow CNFs with approximately the same diameter as the nanoparticle. Unlike metal nanoparticle catalysts, zirconia-based growth should proceed via surface-bound kinetics, and we propose a growth model where initiation occurs at nanoparticle corners. Utilizing these mechanistic insights, we further demonstrate that preannealing of zirconia nanoparticles with a solid-state amorphous carbon substrate enhances growth yield.This material is based upon work supported by the National Science Foundation under Grant No. 1007793 and was also supported by Airbus group, Boeing, Embraer, Lockheed Martin, Saab AB, Hexcel, and TohoTenax through MIT’s Nano- Engineered Composite aerospace STructures (NECST) Consortium. This research was supported (in part) by the U.S. Army Research Office under Contract W911NF-13-D-0001. This work was performed in part at the Center for Nanoscale Systems (CNS), a member of the National Nanotechnology Infrastructure Network (NNIN), which is supported by the National Science Foundation under NSF Award No. ECS-0335765. CNS is part of Harvard University. This work was carried out in part through the use of MIT Microsystems Technology Laboratories. Stephan Hofmann acknowledges funding from EPSRC under grant EP/H047565/1. Piran Kidambi acknowledges the Lindemann Trust Fellowship.This is the final published version. It first appeared at http://pubs.acs.org/doi/abs/10.1021/ja509872y

Disks of Oxygen Vacancies on the Surface of TiO₂ Nanoparticles

Oxide nanopowders are widely used in engineering, and their properties are largely controlled by the defect structure of nanoparticles. Experimental data on the spatial distribution of defects in oxide nanoparticles are unavailable in the literature, and in the work presented, to gain such information, methods of nuclear reactions and deuterium probes were employed. The object of study was oxygen-deficient defects in TiO2 nanoparticles. Nanopowders were synthesized by the sol–gel method and laser evaporation of ceramic targets. To modify the defect structure in nanoparticles, nanopowders were subjected to vacuum annealings. It was established that in TiO2 nanoparticles there form two-dimensional defects consisting of six titanium atoms that occupy the nanoparticle surface and result in a remarkable deviation of the chemical composition from the stoichiometry. The presence of such defects was observed in two cases: in TiO2 nanoparticles alloyed with cobalt, which were synthesized by the sol–gel method, and in nonalloyed TiO2 nanoparticles synthesized by laser evaporation of ceramic target. The concentration of the defects under study can be varied in wide limits via vacuum annealings of nanopowders which can provide formation on the surface of oxide nanoparticles of a solid film of titanium atoms 1–2 monolayers in thickness

Isotopic exchange of gaseous oxygen with mechanoactivated manganese oxides

Isotope exchange of oxygen 18O 2 with oxides Mn 2O 3 and Mn 3O 4 was investigated in the temperature range of 300-700° C. It was established that the content of the isotope O 18 in mechanically activated powders was noticeably higher than in the initial ones. Already at relatively low annealing temperatures isotope exchange leads to nearly the maximum possible under the given conditions replacement of atoms 16O to 18O. The isotope exchange parameters connected with the processes at the boundaries of the particles of mechanoactivated powder and within their volume were determined. © (2012) Trans Tech Publications