Toward a Comprehensive Mechanistic Understanding of Hydrogen Uptake in Zirconium Alloys by Combining Atom Probe Analysis With Electronic Structure Calculations
Paper in proceedings, 2015

The ability of a zirconium alloy to resist corrosion relies on a compromise between two opposing strategies. Minimizing the hydrogen pickup fraction (HPUF) by invoking metallic electron conduction in the barrier oxide results in rapid parabolic oxide growth. On the other hand, slow sub-parabolic barrier oxide growth, as reflected in rate limiting electron transport, may result in a high HPUF. The objective of the present study is to offer mechanistic insights as to how low concentrations of different alloying elements become decisive for the overall corrosion behavior. Combining atomistic microanalysis with first principles modeling by means of density functional theory, the speciation and redox properties of Fe and Ni towards hydrogen evolution are firstly explored. Complementary atom probe microanalysis at the metal–oxide interface provides evidence for Fe and Ni segregation to grain boundaries in Zircaloy-2 that propagates into the ZrO2 scale. Descriptors for how alloying elements in ZrO2 control electron transport as well as catalytic electron-proton recombination in grain boundaries to form H2 are determined by means of theory. The findings are generalized by further atomistic modeling, and are thus put in the context of early reports from autoclave experiments on HPUFs of zirconium with the alloying elements Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, and Nb. A shunting mechanism which combines inner and outer hydrogen evolution mechanisms is proposed. Properties of the transient zirconium sub-oxide are discussed. A plausible atomistic overall understanding emerges.

density functional theory

corrosion

zirconium

atom probe tomography

HPUF

hydride

alloys

hydrogen pickup

suboxide

HPU

Author

Mikaela Lindgren

Chalmers, Chemistry and Chemical Engineering, Energy and Material, Environmental Inorganic Chemistry

Gustav Sundell

Chalmers, Applied Physics, Materials Microstructure

Itai Panas

Chalmers, Chemistry and Chemical Engineering, Energy and Material, Environmental Inorganic Chemistry

Lars Hallstadius

Mattias Thuvander

Chalmers, Applied Physics, Materials Microstructure

Hans-Olof Andrén

Chalmers, Applied Physics, Materials Microstructure

ASTM 17th International Symposium on Zirconium in the Nuclear Industry, Hyderabad, Andhra Pradesh, India, 3-7 February 2013

0066-0558 (ISSN)

Vol. STP 1543 515-539

Driving Forces

Sustainable development

Subject Categories

Energy Engineering

Other Physics Topics

Other Materials Engineering

Theoretical Chemistry

Nano Technology

Corrosion Engineering

Condensed Matter Physics

Areas of Advance

Energy

Materials Science

Roots

Basic sciences

DOI

10.1520/STP154320120164

ISBN

978-0-8031-7529-7

More information

Created

10/7/2017