Skip to Main Content
Skip Nav Destination
ASTM Selected Technical Papers
Zirconium in the Nuclear Industry: 20th International Symposium
Editor
Suresh K. Yagnik
Suresh K. Yagnik
Symposium Chairperson and STP Editor
1
Electric Power Research Institute (EPRI)
,
Palo Alto, CA,
US
Search for other works by this author on:
Michael Preuss
Michael Preuss
Symposium Chair and STP Editor
2
The University of Manchester Manchester
,
GB
;
Monash University
,
Clayton/Melbourne,
AU
Search for other works by this author on:
ISBN:
978-0-8031-7737-6
No. of Pages:
928
Publisher:
ASTM International
Publication date:
2023

Significant cost benefits through plant simplification can be achieved if a soluble boron-free lithiated primary water chemistry can be demonstrated to be viable for small modular reactor operation. However, the mechanisms of accelerated corrosion behavior of the zirconium alloy clad material under lithiated and boron-free autoclave conditions have yet to be fully identified. Advanced microstructural characterization of selected samples from the testing program, combined with atomistic simulation, have allowed for a significant development in the understanding of the mechanism of lithium-enhanced acceleration under boron-free conditions. Density functional theory has been used to identify the most stable accommodation mechanisms for lithium in tetragonal, monoclinic, and amorphous ZrO2 and its impact upon the defect population at an atomic scale. Atom probe tomography has confirmed that lithium predominantly segregates to oxide grain boundaries under elevated lithium conditions. The combination of modeling and advanced characterization has suggested that lithium-enhanced acceleration is linked to a local grain boundary effect caused by the segregation of lithium that increases the oxygen vacancy concentration within the usually protective barrier layer and leads to accelerated corrosion rates.

1.
Nordmann
F.
, “
PWR and BWR Chemistry Optimization
,” Nuclear Engineering International Magazine, (December
2011
): 24–29.
2.
Schrire
D.
,
Gabrielsson
P.
,
Hemlin
M.
,
Carling
K.
,
Nylén
H.
,
Ehrlén
F.
,
Johnson
K.
 et al
, “
Corrosion Hydrogen and Lithium Pickup of Optimized ZIRLO Cladding Operated at High Duty with High Lithium Levels
” (paper presentation, TopFuel 2021,
Santander, Spain
, October 24–28,
2021
).
3.
Garzarolli
F.
,
Pohlmeyer
J.
,
Trapp-Pritsching
S.
, and
Weidinger
H. G.
, “
Influence of Various Additions to Water on Zircaloy-4 Corrosion in Autoclave Tests at 350°C
,” in
Proceedings of the IAEA Technical Committee Meeting on Fundamental Aspects of Corrosion of Zr-Alloys in Water Reactor Environments
(
Vienna, Austria
:
International Atomic Energy Agency
,
1990
), 65–72.
4.
Bramwell
I. L.
,
Parsons
P. D.
, and
Tice
D.
, “
Corrosion of Zircaloy-4 PWR Fuel Cladding in Lithiated and Borated Water Environments
,” in
Zirconium in the Nuclear Industry: 9th International Symposium
, ed.
Eucken
C. M.
and
Garde
A. M.
(
West Conshohocken, PA
:
ASTM International
,
1991
), 628–642,
5.
Pêcheur
D.
,
Godlewski
J.
,
Peybernès
J.
,
Fayette
L.
,
Noé
M.
,
Frichet
A.
, and
Kerrec
O.
, “
Contribution to the Understanding of the Effect of the Water Chemistry on the Oxidation Kinetics of Zircaloy-4 Cladding
,” in
Zirconium in the Nuclear Industry: 12th International Symposium
, ed.
Sabol
G. P.
and
Moan
G. D.
(
West Conshohocken, PA
:
ASTM International
,
2000
), 793–811,
6.
Murgatroyd
R. A.
and
Winton
J.
, “
Hydriding Zircaloy-2 in Lithium Hydroxide Solutions
,”
Journal of Nuclear Materials
23
(
1967
): 249–256,
7.
McDonald
S. G.
and
Sheppard
K. D.
, “
Effect of Lithium Hydroxide on the Corrosion Behavior of Zircaloy-4
,” in
Zirconium in the Nuclear Industry: 6th International Symposium
, ed.
Franklin
D. G.
and
Adamson
R. B.
(
West Conshohocken, PA
:
ASTM International
,
1984
), 519–530.
8.
Ramasubramanian
N.
,
Precoanin
N.
, and
Ling
V. C.
, “
Lithium Uptake and the Accelerated Corrosion of Zirconium Alloys
,” in
Zirconium in the Nuclear Industry: 8th International Symposium
, ed.
Van Swam
L. F.
P.
and
Eucken
C. M.
(
West Conshohocken, PA
:
ASTM International
,
1989
), 187–201,
9.
Jeong
Y. H.
,
Kim
K. H.
, and
Baek
J. H.
, “
Cation Incorporation into Zirconium Oxide in LiOH, NaOH and KOH Solutions
,”
Journal of Nuclear Materials
275
(
1999
): 171–177,
10.
Hulme
H.
,
Panteli
A.
,
Pickering
F.
,
Gass
M.
,
Cole-Baker
A.
,
Binks
P.
,
Fenwick
M.
,
Waters
M.
, and
Smith
J.
, “
Investigating the Corrosion Behavior of Zircaloy-4 in LiOH and under a Thermal Gradient and Two-Phase Flow Regime
,” in
Zirconium in the Nuclear Industry: 19th International Symposium
, ed.
Motta
A. T.
and
Yagnik
S. K.
(
West Conshohocken, PA
:
ASTM International
,
2021
), 537–563,
11.
Pan
C.
,
Jones
B. G.
, and
Machiels
A. J.
, “
Concentration Levels of Solutes in Porous Deposits with Chimneys under Wick Boiling Conditions
,”
Nuclear Engineering and Design
99
(
1987
): 317–327,
12.
Ramasubramanian
N.
, “
Lithium Uptake and the Corrosion of Zirconium Alloys in Aqueous Lithium Hydroxide Solutions
,” in
Zirconium in the Nuclear Industry: 9th International Symposium
, ed.
Eucken
C. M.
and
Garde
A. M.
(
West Conshohocken, PA
:
ASTM International
,
1991
), 613–627,
13.
Cox
B.
,
Ungurelu
M.
,
Wong
Y. M.
, and
Wu
C.
, “
Mechanisms of LiOH Degradation and H3BO3 Repair of ZrO2 Films
,” in
Zirconium in the Nuclear Industry: 11th International Symposium
, ed.
Bradley
E. R.
and
Sabol
G. P.
(
West Conshohocken, PA
:
ASTM International
,
1996
), 114–136,
14.
Zhou
B. X.
,
Li
Q.
,
Yao
M. Y.
,
Liu
W. Q.
, and
Chu
Y. L.
, “
Effect of Water Chemistry and Composition on Microstructural Evolution of Oxide on Zr Alloys
,” in
Zirconium in the Nuclear Industry: 15th Internional Symposium
, ed.
Kammenzind
B.
and
Limback
M.
(
West Conshohocken, PA
:
ASTM International
,
2009
), 360–383,
15.
Oskarsson
M.
,
Ahlberg
E.
, and
Pettersson
K.
, “
Oxidation of Zircaloy-2 and Zircaloy-4 in Water and Lithiated Water at 360°C
,”
Journal of Nuclear Materials
295
(
2001
): 97–108,
16.
Ramasubramanian
N.
and
Balakrishnan
P. V.
, “
Aqueous Chemistry of Lithium Hydroxide and Boric Acid and Corrosion of Zircaloy-4 and Zr-2.5Nb Alloys
,” in
Zirconium in the Nuclear Industry: 10th International Symposium
, ed.
Garde
A. M.
and
Bradley
E. R.
(
West Conshohocken, PA
:
ASTM International
,
1994
), 378–399,
17.
Jeong
Y. H.
,
Baek
J. H.
,
Kim
S. J.
,
Kim
H. G.
, and
Ruhmann
H.
, “
Corrosion Characteristics and Oxide Microstructures of Zircaloy-4 in Aqueous Alkali Hydroxide Solutions
,”
Journal of Nuclear Materials
270
(
1999
): 322–333,
18.
Abram
T. J.
, “
Modelling the Waterside Corrosion of PWR Fuel Rods
,” in
Proceedings of the IAEA Technical Committee Meeting on Water Reactor Fuel Element Modelling at High Burnup
(
Vienna, Austria
:
International Atomic Energy Agency
,
1997
), 329–345.
19.
Billot
P.
,
Yagnik
S.
,
Ramasubramanian
N.
,
Peybernes
J.
, and
Pêcheur
D.
, “
The Role of Lithium and Boron on the Corrosion of Zircaloy-4 under Demanding PWR-Type Conditions
,” in
Zirconium in the Nuclear Industry: 13th International Symposium
, ed.
Moan
G. D.
and
Rudling
P.
(
West Conshohocken, PA
:
ASTM International
,
2002
), 169–189,
20.
Pêcheur
D.
,
Godlewski
J.
,
Billot
P.
, and
Thomazet
J.
, “
Microstructure of Oxide Films Formed during the Waterside Corrosion of Zircaloy-4 Cladding in Lithiated Environment
,” in
Zirconium in the Nuclear Industry: 11th International Symposium
, ed.
Bradley
E. R.
and
Sabol
G. P.
(
West Conshohocken, PA
:
ASTM International
,
1996
), 94–113,
21.
Stephens
G. F.
,
Than
Y. R.
,
Neilson
W.
,
Evitts
L. J.
,
Wenman
M. R.
,
Murphy
S. T.
,
Grimes
R. W.
 et al
, “
The Accomodation of Lithium in Bulk ZrO2
,”
Solid State Ionics
373
(
2021
): 115813,
22.
Cantwell
P. R.
,
Tang
M.
,
Dillon
S. J.
,
Luo
J.
,
Rohrer
G. S.
, and
Harmer
M. P.
, “
Grain Boundary Complexions
,”
Acta Materialia
62
(
2014
): 1–48,
23.
Thompson
A. P.
,
Atulga
H. M.
,
Berger
R.
,
Bolintineanu
D. S.
,
Brown
W. M.
,
Crozier
P. S.
,
in 't Veld
P. J.
 et al
, “
LAMMPS—A Flexible Simulation Tool for Particle-Based Materials Modeling at the Atomic, Meso, and Continuum Scales
,”
Computer Physics Communications
271
(
2022
): 108171,
24.
Middleburgh
S. C.
,
Lee
W. E.
, and
Rushton
M. J.
D.
, “
Structure and Properties of Amorphous Uranium Dioxide
,”
Acta Materialia
202
(
2021
): 366–375,
25.
Owen
M. W.
,
Rushton
M. J.
D.
,
Evitts
L. J.
,
Claisse
A.
,
Puide
M.
,
Lee
W. E.
, and
Middleburgh
S. C.
, “
Diffusion in Doped and Undoped Amorphous Zirconia
,”
Journal of Nuclear Materials
555
(
2021
): 153108,
26.
Cooper
M. W.
D.
,
Rushton
M. J.
D.
, and
Grimes
R. W.
, “
A Many-Body Potential Approach to Modelling the Thermomechanical Properties of Actinide Oxides
,”
Journal of Physics: Condensed Matter
26
(
2014
): 105401,
27.
Perdew
J. P.
,
Burke
K.
, and
Ernzerhof
M.
, “
Generalized Gradient Approximation Made Simple
,”
Physical Review Letters
77
(
1996
): 3865–3868,
28.
Youssef
M.
and
Yildiz
B.
, “
Intrinsic Point-Defect Equilibria in Tetragonal ZrO2: Density Functional Theory Analysis with Finite-Temperature Effects
,”
Physical Review
B 86
, no.
14
(
2012
): 144109,
29.
Neilson
W. D.
,
Steele
H.
, and
Murphy
S. T.
, “
Evolving Defect Chemistry of (Pu,Am)Ox
,”
Journal of Physical Chemistry C
125
(
2021
): 15560–15568,
30.
Armson
S. A.
J.
,
Garner
A.
,
Baxter
F.
,
Yankova
M. S.
,
Race
C. P.
,
Cole-Baker
A.
,
Riley
C.
,
Preuss
M.
, and
Frankel
P.
, “
The Importance of Substrate Grain Orientation on Local Oxide Texture and Corrosion Performance in α-Zr Alloys
,” in
Zirconium in the Nuclear Industry: 19th International Symposium
, ed.
Motta
A. T.
and
Yagnik
S. K.
(
West Conshohocken, PA
:
ASTM International
,
2021
), 878–903,
31.
Hielscher
R.
and
Schaeben
H.
, “
A Novel Pole Figure Inversion Method: Specification of the MTEX Algorithm
,”
Journal of Applied Crystallography
41
(
2008
): 63–68,
32.
Garner
A.
,
Gholinia
G.
,
Frankel
P.
,
Gass
M.
,
MacLaren
I.
, and
Preuss
M.
, “
The Microstructure and Microtexture of Zirconium Oxide Films Studied by Transmission Electron Backscatter Diffraction and Automated Crystal Orientation Mapping with Transmission Electron Microscopy
,”
Acta Materialia
80
(
2014
): 159–171,
33.
Garner
A.
, “
Investigating the Effect of Oxide Texture on the Corrosion Performance of Zirconium Alloys
” (PhD thesis,
University of Manchester
,
2015
).
34.
Hu
J.
,
Liu
J.
,
Lozano-Perez
S.
,
Grovenor
C. R.
M.
,
Christensen
M.
,
Wolf
W.
,
Wimmer
E.
, and
Mader
E. V.
, “
Hydrogen Pickup during Oxidation in Aqueous Environments: The Role of Nano-Pores and Nano-Pipes in Zirconium Oxide Films
,”
Acta Materialia
180
(
2019
): 105–115,
35.
Ni
N.
,
Lozano-Perez
S.
,
Jenkins
M. L.
,
English
C.
,
Smith
G. D.
W.
,
Sykes
J. M.
, and
Grovenor
C. R.
M.
, “
Porosity in Oxides on Zirconium Fuel Cladding Alloys, and Its Importance in Controlling Oxidation Rates
,”
Scripta Materialia
62
(
2010
): 564–567,
36.
Xie
S.
,
Zhou
B.
,
Liang
X.
,
Li
Q.
,
Liu
W.
,
Yao
M.
, and
Zhang
J.
, “
The Distribution of Li Ions in the Oxide Film Formed on Zircaloy-4 Corroded in Lithiated Water at 633 K
,”
Materials
13
(
2020
): 873,
37.
Thompson
K.
,
Lawrence
D.
,
Larson
D. J.
,
Olson
J. D.
,
Kelly
T. F.
, and
Gorman
B.
, “
In Situ Site-Specific Specimen Preparation for Atom Probe Tomography
,”
Ultramicroscopy
107
(
2007
): 131–139,
38.
Hillner
E.
, “
Corrosion of Zr Base Alloys—An Overview
,” in
Zirconium in the Nuclear Industry
, ed.
Lowe Jr.
A. L.
and
Parry
G. W.
(
West Conshohocken, PA
:
ASTM International
,
1977
), 211–235.
39.
Gass
M.
,
Fenwick
M.
,
Hulme
H.
,
Waters
M.
,
Binks
P.
,
Panteli
A.
,
Chatterton
M.
,
Allen
V.
, and
Cole-Baker
A.
, “
Corrosion of Zircaloys: Relating the Microstructural Observations to the Corrosion Kinetics
,”
Journal of Nuclear Materials
509
(
2018
): 343–354,
40.
Li
H.
and
Glavicic
M. G. S. J.
A.
, “
A Model of Texture Formation in ZrO2 Films
,”
Materials Science and Engineering: A
366
(
2004
): 164–174,
41.
Hu
J.
,
Garner
A.
,
Ni
N. G.
A.
,
Nicholls
R.
,
Lozano-Perez
S.
,
Frankel
P.
,
Preuss
M.
, and
Grovenor
C. R.
M.
, “
Identifying Suboxide Grains at the Metal-Oxide Interface of a Corroded Zr-1.0%Nb Alloy Using (S)TEM, Transmission-EBSD and EELS
,”
Micron
69
(
2015
): 35–42,
42.
Hu
J.
,
Setiadinata
B.
,
Aarholt
T.
,
Garner
A.
,
Vilalta-Clemente
A.
,
Partezana
J. M.
,
Frankel
P.
 et al
, “
Understanding Corrosion and Hydrogen Pickup of Zirconium Fuel Cladding Alloys: The Role Oxide Microstructure, Porosity, Suboxides, and Second-Phase Particles
,” in
Zirconium in the Nuclear Industry: 18th International Symposium
, ed.
Comstock
R.
and
Motta
A.
(
West Conshohocken, PA
:
ASTM International
,
2018
), 93–126,
43.
Billot
P.
,
Robin
J. C.
,
Giordano
A.
,
Peybernès
J.
,
Thomazet
J.
, and
Amanrich
H.
, “
Experimental and Theoretical Studies of Parameters That Influence Corrosion of Zircaloy-4
,” in
Zirconium in the Nuclear Industry: 10th International Symposium
, ed.
Garde
A. M.
and
Bradley
E. R.
(
West Conshohocken, PA
:
ASTM International
,
1994
), 351–377,
44.
Beie
H. J.
,
Mitwalsky
A.
,
Garzarolli
F.
,
Ruhmann
H.
, and
Sell
H. J.
, “
Examinations of the Corrosion Mechanism of Zirconium Alloys
,” in
Zirconium in the Nuclear Industry: 10th International Symposium
,
Garde
A. M.
and
Bradley
E. R.
(
West Conshohocken, PA
:
ASTM International
,
1994
), 615–643,
45.
Garvie
R. C.
, “
The Occurrence of Metastable Tetragonal Zirconia as a Crystallite Size Effect
,”
Journal of Physical Chemistry
69
(
1965
): 1238–1243,
46.
Barberis
P.
, “
Zirconia Powders and Zircaloy Oxide Films: Tetragonal Phase Evolution during 400°C Autoclave Tests
,”
Journal of Nuclear Materials
226
(
1995
): 34–43,
47.
Palmer
D. A.
,
Machesky
M. L.
,
Bénézeth
P.
,
Wesolowsky
D. J.
,
Anovitz
L. M.
, and
Deshon
J. C.
, “
Adsorption of Ions on Zirconium Oxide Surfaces from Aqueous Solutions at High Temperatures
,”
Journal of Solution Chemistry
38
(
2009
): 907–924,
48.
Cox
B.
and
Sheikh
H. I.
, “
Redistribution of the Alloying Elements during Zircaloy-2 Oxidation
,”
Journal of Nuclear Materials
249
(
1997
): 17–32,
49.
Ramasubramanian
N.
,
Billot
P.
, and
Yagnik
S.
, “
Hydrogen Evolution and Pickup during the Corrosion of Zirconium Alloys: A Critical Evaluation of the Solid State and Porous Oxide Electrochemistry
,” in
Zirconium in the Nuclear Industry: 13th International Symposium
, ed.
Moan
G. D.
and
Rudling
P.
(
West Conshohocken, PA
:
ASTM International
,
2002
), 222–244,
This content is only available via PDF.
You do not currently have access to this chapter.
Close Modal

or Create an Account

Close Modal
Close Modal