The O−Zr (Oxygen-Zirconium) system

Abriata, J. P.; Garcés, Jorge; Versaci, R.

doi:10.1007/bf02881546

Cited by 246 publications

(74 citation statements)

References 28 publications

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“…5(a) . This is consistent with the fact that M-ZrO 2 is the stable phase at ambient pressure up to 1205°C [46]. At P = 10.51 GPa H crosses zero and we enter the regime where T -ZrO 2 is stabilized by compressive stress.…”

Section: B Mechanical Effect Of Lithium Insertion Into Zrosupporting

confidence: 89%

Electro-chemo-mechanical effects of lithium incorporation in zirconium oxide

Yang¹,

Youssef²,

Yildiz³

2018

Phys. Rev. Materials

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Understanding the response of functional oxides to extrinsic ion insertion is important for technological applications including electrochemical energy storage and conversion, corrosion, and electronic materials in neuromorphic computing devices. Decoupling the complicated chemical and mechanical effects of ion insertion is difficult experimentally. In this work, we assessed the effect of lithium incorporation in zirconium oxide as a model system, by performing first-principles based calculations. The chemical effect of lithium is to change the equilibria of charged defects. Lithium exists in ZrO 2 as a positively charged interstitial defect, and raises the concentration of free electrons, negatively charged oxygen interstitials, and zirconium vacancies. As a result, oxygen diffusion becomes faster by five orders of magnitude, and the total electronic conduction increases by up to five orders of magnitude in the low oxygen partial pressure regime. In the context of Zr metal oxidation, this effect accelerates oxide growth kinetics. In the context of electronic materials, it has implications for resistance modulations via ion incorporation. The mechanical effect of lithium is in changing the volume and equilibrium phase of the oxide. Lithium interstitials together with zirconium vacancies shrink the volume of the oxide matrix, release the compressive stress that is needed for stabilizing the tetragonal phase ZrO 2 at low temperature, and promote tetragonal-to-monoclinic phase transformation. By identifying these factors, we are able to mechanistically interpret experimental results in the literature for zirconium alloy corrosion in different alkali-metal hydroxide solutions. These results provide a mechanistic and quantitative understanding of lithium-accelerated corrosion of zirconium alloy, as well as, and more broadly, show the importance of considering coupled electro-chemo-mechanical effects of cation insertion in functional oxides.

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Section: B Mechanical Effect Of Lithium Insertion Into Zrosupporting

confidence: 89%

Electro-chemo-mechanical effects of lithium incorporation in zirconium oxide

Yang¹,

Youssef²,

Yildiz³

2018

Phys. Rev. Materials

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“…In our previous work, we predicted oxygen selfdiffusion kinetics in tetragonal-ZrO 2 (t-ZrO 2 ) by combining first-principles calculations with random walk theory [21], resulting in good agreement with experimental measurements. Monoclinic-ZrO 2 (m-ZrO 2 ) is the stable phase below 1440 K [22] and is also relevant in the applications mentioned above. In m-ZrO 2 , the oxygen sublattice is distorted compared to the tetragonal phase, leading to two inequivalent sites for oxygen in the unit cell: one bonds with four zirconium atoms (O4) and one bonds with three zirconium atoms (O3).…”

Section: Introductionmentioning

confidence: 99%

Oxygen self-diffusion mechanisms in monoclinic ZrO2 revealed and quantified by density functional theory, random walk analysis, and kinetic Monte Carlo calculations

2018

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In this work, we quantify oxygen self-diffusion in monoclinic-phase zirconium oxide as a function of temperature and oxygen partial pressure. A migration barrier of each type of oxygen defect was obtained by first-principles calculations. Random walk theory was used to quantify the diffusivities of oxygen interstitials by using the calculated migration barriers. Kinetic Monte Carlo simulations were used to calculate diffusivities of oxygen vacancies by distinguishing the threefold-and fourfold-coordinated lattice oxygen. By combining the equilibrium defect concentrations obtained in our previous work together with the herein calculated diffusivity of each defect species, we present the resulting oxygen self-diffusion coefficients and the corresponding atomistically resolved transport mechanisms. The predicted effective migration barriers and diffusion prefactors are in reasonable agreement with the experimentally reported values. This work provides insights into oxygen diffusion engineering in ZrO 2 -related devices and parametrization for continuum transport modeling.

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“…This process is driven by the high solubility of oxygen in zirconium, i.e., *30 at% O [6,21]. Crucial is the distinction between neutral and oxidized oxygen vacancies, i.e., V O and V O 2?…”

Section: Resultsmentioning

confidence: 99%

Oxygen Vacancy Formation, Mobility, and Hydrogen Pick-up during Oxidation of Zirconium by Water

Lindgren

Panas

2017

Oxid Met

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A comprehensive first principles understanding of the oxidation of zirconium alloys by water was reiterated. Two channels were taken to jointly constitute to the oxidation process: one according to classical oxidation theory involving hydrogen evolution and the second reflected by inwards transport of protons causing hydrogen pick-up. The two were associated with charged and uncharged oxygen vacancies, respectively. The purpose of the present study was to clarify the nature of the effective anode during oxidation of zirconium as to the detailed role of the metal. Oxygen dissolution in the alloy resulted in a ''pre-anodic'' property associated with the formation of oxygen vacancy V O in the oxide, i.e., preceding V O 2? /2e -separation. Atomistic perspective on the metal/oxide interface before nucleation of V O was provided. The rapid convergence of the model interface to bulk properties in spite of the local structural variability provided new insight as to the nature of an amorphous metal/oxide interface.

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The O−Zr (Oxygen-Zirconium) system

Cited by 246 publications

References 28 publications

Electro-chemo-mechanical effects of lithium incorporation in zirconium oxide

Electro-chemo-mechanical effects of lithium incorporation in zirconium oxide

Oxygen self-diffusion mechanisms in monoclinic ZrO2 revealed and quantified by density functional theory, random walk analysis, and kinetic Monte Carlo calculations

Oxygen Vacancy Formation, Mobility, and Hydrogen Pick-up during Oxidation of Zirconium by Water

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