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Title: Oxygen interaction with hexagonal OsB 2 at high temperature

Abstract

The stability of ReB 2-type hexagonal OsB 2 powder at high temperature with oxygen presence has been studied by thermogravimetric analysis, differential scanning calorimetry, SEM, EDS, and high-temperature scanning transmission electron microscopy and XRD. Results of the study revealed that OsB 2 ceramics interact readily with oxygen present in reducing atmosphere, especially at high temperature and produces boric acid, which decomposes on the surface of the powder resulting in the formation of boron vacancies in the hexagonal OsB 2 lattice as well as changes in the stoichiometry of the compound. It was also found that under low oxygen partial pressure, sintering of OsB 2 powders occurred at a relatively low temperature (900°C). Finally, hexagonal OsB 2 ceramic is prone to oxidation and it is very sensitive to oxygen partial pressures, especially at high temperatures.

Authors:
 [1];  [1];  [1];  [2];  [3];  [3];  [3];  [4];  [4]
  1. Univ. of Central Florida, Orlando, FL (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. AGH Univ. of Science and Technology in Krakow, Krakow (Poland)
  4. Univ. of Central Florida, Cocoa, FL (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1345002
Grant/Contract Number:
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the American Ceramic Society
Additional Journal Information:
Journal Volume: 99; Journal Issue: 12; Journal ID: ISSN 0002-7820
Publisher:
American Ceramic Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; osmium diboride; ceramics; STEM; thermal analysis

Citation Formats

Xie, Zhilin, Blair, Richard G., Orlovskaya, Nina, Cullen, David A., Kata, Dariusz, Rutkowski, Pawel, Lis, Jerzy, Qin, Nan, and T-Raissi, Ali. Oxygen interaction with hexagonal OsB2 at high temperature. United States: N. p., 2016. Web. doi:10.1111/jace.14434.
Xie, Zhilin, Blair, Richard G., Orlovskaya, Nina, Cullen, David A., Kata, Dariusz, Rutkowski, Pawel, Lis, Jerzy, Qin, Nan, & T-Raissi, Ali. Oxygen interaction with hexagonal OsB2 at high temperature. United States. doi:10.1111/jace.14434.
Xie, Zhilin, Blair, Richard G., Orlovskaya, Nina, Cullen, David A., Kata, Dariusz, Rutkowski, Pawel, Lis, Jerzy, Qin, Nan, and T-Raissi, Ali. Wed . "Oxygen interaction with hexagonal OsB2 at high temperature". United States. doi:10.1111/jace.14434. https://www.osti.gov/servlets/purl/1345002.
@article{osti_1345002,
title = {Oxygen interaction with hexagonal OsB2 at high temperature},
author = {Xie, Zhilin and Blair, Richard G. and Orlovskaya, Nina and Cullen, David A. and Kata, Dariusz and Rutkowski, Pawel and Lis, Jerzy and Qin, Nan and T-Raissi, Ali},
abstractNote = {The stability of ReB2-type hexagonal OsB2 powder at high temperature with oxygen presence has been studied by thermogravimetric analysis, differential scanning calorimetry, SEM, EDS, and high-temperature scanning transmission electron microscopy and XRD. Results of the study revealed that OsB2 ceramics interact readily with oxygen present in reducing atmosphere, especially at high temperature and produces boric acid, which decomposes on the surface of the powder resulting in the formation of boron vacancies in the hexagonal OsB2 lattice as well as changes in the stoichiometry of the compound. It was also found that under low oxygen partial pressure, sintering of OsB2 powders occurred at a relatively low temperature (900°C). Finally, hexagonal OsB2 ceramic is prone to oxidation and it is very sensitive to oxygen partial pressures, especially at high temperatures.},
doi = {10.1111/jace.14434},
journal = {Journal of the American Ceramic Society},
number = 12,
volume = 99,
place = {United States},
year = {Wed Aug 10 00:00:00 EDT 2016},
month = {Wed Aug 10 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
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  • Hexagonal OsB{sub 2}, a theoretically predicted high-pressure phase, has been synthesized for the first time by a mechanochemical method, i.e., high energy ball milling. X-ray diffraction indicated that formation of hexagonal OsB{sub 2} begins after 2.5 h of milling, and the reaction reaches equilibrium after 18 h of milling. Rietveld refinement of the powder data indicated that hexagonal OsB{sub 2} crystallizes in the P63/mmc space group (No. 194) with lattice parameters of a=2.916 Å and c=7.376 Å. Transmission electron microscopy confirmed the appearance of the hexagonal OsB{sub 2} phase after high energy ball milling. in situ X-ray diffraction experiments showedmore » that the phase is stable from −225 °C to 1050 °C. The hexagonal OsB{sub 2} powder was annealed at 1050 °C for 6 days in vacuo to improve crystallinity and remove strain induced during the mechanochemical synthesis. The structure partially converted to the orthorhombic phase (20 wt%) after fast current assisted sintering of hexagonal OsB{sub 2} at 1500 °C for 5 min. Mechanochemical approaches to the synthesis of hard boride materials allow new phases to be produced that cannot be prepared using conventional methods. - Graphical abstract: High resolution transmission electron micrograph of hexagonal OsB{sub 2} nanocrystallite with corresponding fast Fourier transform and simulated diffraction pattern. - Highlights: • Hexagonal OsB{sub 2} has been synthesized for the first time by mechanochemical method. • Hexagonal OsB{sub 2} crystallizes in P63/mmc space group (No. 194), a=2.916 Å and c=7.376 Å. • The hexagonal structure was confirmed by a transmission electron microscope. • No phase transformation was observed after being annealed at 1050 °C for 6 days. • 20 wt% of h-OsB{sub 2} was transformed to o-OsB{sub 2} after being sintered at 1500 °C for 5 min.« less
  • The stability of hexagonal ReB 2 type OsB 2 powder upon heating under reforming gas was investigated. Pure Os metal particles were detected by powder X-ray diffraction starting at 375⁰ C and complete transformation of OsB 2 to metallic Os was observed at 725⁰ C. The mechanisms of precipitation of metallic Os is proposed and changes in the lattice parameters of OsB 2 upon heating are analysed in terms of the presence of oxygen or water vapour in the heating chamber. Previous studies suggested that Os atoms possess (0) valence, while B atoms possess both (+3) and ( 3) valencesmore » in the alternating boron/osmium sheet structure of hexagonal (P63/mmc, No. 194) OsB 2; if controllable method for Os removal from the lattice could be found, the opportunity would arise to form two-dimensional (2D) layers consisting of pure B atoms.« less
  • In this study, the metastable high pressure ReB 2-type hexagonal OsB 2 bulk ceramics was produced by spark plasma sintering. The phase composition, microstructure, and mechanical behavior of the sintered OsB 2 were studied by X-ray diffraction, optical microscopy, TEM, SEM, EDS, and nanoindentation. The produced ceramics was rather porous and contained a mixture of hexagonal (~80 wt.%) and orthorhombic (~20 wt.%) phases as identified by X-ray diffraction and EBSD analysis. Two boron-rich phases, which do not contain Os, were also identified by TEM and SEM/EDS analysis. Nanoindentation measurements yielded a hardness of 31 ± 9 GPa and Young’s modulusmore » of 574 ± 112 GPa, indicating that the material is rather hard and very stiff; but, it is very prone to crack formation and propagation, which is indicative of a very brittle nature of this material. Improvements in the sintering regime are required in order to produce dense, homogeneous and single phase hexagonal OsB 2 bulk ceramics.« less
  • The synthesis of novel hexagonal ReB{sub 2}-type OsB{sub 2} ceramic powder was performed by high energy ball milling of elemental Os and B powders. Two different sources of B powder have been used for this mechanochemical synthesis. One B powder consisted of a mixture of amorphous and crystalline phases and a mixture of {sup 10}B and {sup 11}B isotopes with a fine particle size, while another B powder was a purely crystalline (rhombohedral) material consisting of enriched {sup 11}B isotope with coarse particle size. The same Os powder was used for the synthesis in both cases. It was established that,more » in the first case, the hexagonal OsB{sub 2} phase was the main product of synthesis with a small quantity of Os{sub 2}B{sub 3} phase present after synthesis as an intermediate product. In the second case, where coarse crystalline {sup 11}B powder was used as a raw material, only Os{sub 2}B{sub 3} boride was synthesized mechanochemically. The thermal stability of hexagonal OsB{sub 2} powder was studied by heating under argon up to 876 °C and cooling in vacuo down to −225 °C. During the heating, the sacrificial reaction 2OsB{sub 2}+3O{sub 2}→2Os+2B{sub 2}O{sub 3} took place due to presence of O{sub 2}/water vapor molecules in the heating chamber, resulting in the oxidation of B atoms and formation of B{sub 2}O{sub 3} and precipitation of Os metal out of the OsB{sub 2} lattice. As a result of such phase changes during heating, the lattice parameters of hexagonal OsB{sub 2} changed significantly. The shrinkage of the a lattice parameter was recorded in 276–426 °C temperature range upon heating, which was attributed to the removal of B atoms from the OsB{sub 2} lattice due to oxidation followed by the precipitation of Os atoms and formation of Os metal. While significant structural changes occurred upon heating due to presence of O{sub 2}, the hexagonal OsB{sub 2} ceramic demonstrated good phase stability upon cooling in vacuo with linear shrinkage of the lattice parameters and no phase changes detected during cooling. - Graphical abstract: The in situ high temperature XRD contour plot (A) and XRD patterns (B) of h-OsB{sub 2} upon heating and cooling under an argon atmosphere. - Highlights: • Different boron sources were compared for the synthesis of h-OsB{sub 2}. • The phase stability and thermal behavior of h-OsB{sub 2} were studied by in situ XRD. • Shrinkage of the a lattice parameter was observed from 276 °C to 426 °C upon heating. • Oxidation of OsB{sub 2} produced B vacancies led to the shrinkage of a lattice parameter.« less