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Effect of ion irradiation of the metal on the oxidation rate of the M5 Framatome alloy M. Tupin, R. Verlet, K. Colas, M. Jublot, G. Baldacchino, CEA Universit Paris Saclay K. Wolski Ecole des Mines de St Etienne I. Idarraga e DF D.

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  • M. TUPIN et al. – 19th International Symposium on

Zirconium in the Nuclear Industry

1

Effect of ion irradiation of the metal on the oxidation rate of the M5Framatome alloy

  • M. Tupin, R. Verlet, K. Colas, M. Jublot, G. Baldacchino,

CEA Université Paris Saclay

  • K. Wolski

Ecole des Mines de St Etienne

  • I. Idarraga

eDF

  • D. Kaczorowski

Framatome

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  • M. TUPIN et al. – 19th International Symposium on Zirconium in the Nuclear Industry

OUTLINE

2

  • Issue and Background
  • Aim of the study
  • Experimental results
  • Discussion
  • Conclusions
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  • M. TUPIN et al. – 19th International Symposium on Zirconium in the Nuclear Industry

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Comparison of M5Framatome

* and Zircaloy-4 performance in PWR

M5Framatome :

  • xidation

rate constant up to a high burn-up  Working hypothesis : irradiation effect contribution to the « High Burn-Up » good corrosion resistance of the M5Framatome alloy ?

Reaction of oxidation : Zr + 2 H20 ➔ ZrO2 + 2 H2

ISSUE AND BACKGROUND

RXA M5Framatome

*M5Framatome is a trademark or a registered trademark of Framatome or its affiliates, in the USA or other countries

[Kaczorowski et al. ASTM STP1543 (2015)]

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ISSUE AND BACKGROUND

➢ neutron irradiation effect on the corrosion rate of the Zr-2.5%Nb alloy in moist air at 300°C ➔ decrease of the corrosion rate after irradiation [Urbanic et al., AIEA (1990)] ➢ neutron irradiation effect on the corrosion rate of a pre-oxidized E110 alloy in PWR conditions at 350°C ➔ slight reduction of the corrosion rate after irradiation [Markelov et al., ASTM STP1597 (2016)]

Irradiation effect on the corrosion behavior of Zr-Nb type alloy : state of art

0,5 1 1,5 2 2,5 3 3,5 20 40 60 80 100 120 140

Oxide thickness (µm) t (days)

unirradiated specimen irradiated specimen

➢ ion irradiation effect of the oxide layer on the corrosion rate of the M5Framatome alloy in PWR conditions at 360°C ➔ significant decrease of the corrosion rate after irradiation

[Tupin et al., ASTM STP1597 (2016)]

 Focus on the change of the oxidation rate after irradiation of M5Framatome alloy

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  • M. TUPIN et al. – 19th International Symposium on Zirconium in the Nuclear Industry

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ISSUE AND BACKGROUND

Zr(Fe,Nb)2 SPP M5Framatome alloy

[Doriot et al., ASTM STP1597 (2016)] [AIEA (1998)]

  • wt. %

Fe Cr Sn Ni Nb O M5 <0.1 0.005

  • 1.03

0.13

b-Nb precipitate

dark field bright field

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  • M. TUPIN et al. – 19th International Symposium on Zirconium in the Nuclear Industry

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ISSUE AND BACKGROUND Neutron irradiation effect on the microstructure of the M5Framatome alloy

[S. Doriot et al., ASTM STP1467 (2005)]

microstructure evolution in PWR[1-4]

  • the nucleation of dislocation loops
  • growth of the initial b-Nb precipitates (same density)
  • increase of b-Nb volume fraction (x2)
  • Nb concentration decrease in the b-Nb particles
  • radiation–enhanced precipitation of b-Nb needles

nanometric β-Nb needles

1.Doriot et al., ASTM STP1467 (2005) 2.Doriot et al., ASTM STP1543 (2015) 3.Northwood et al., JNM 79 (1979) 4.M. Griffiths, JNM 159 (1988)

➔ metal hardening induced by neutron irradiation

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AIM OF THE STUDY Irradiation effect on the corrosion behavior of Zr-Nb alloy

PWR Ions

  • nucleation of dislocation loop
  • growth the b-Nb precipitates
  • increase of b-Nb volume fraction (x2)
  • Nb concentration decrease in the b-Nb

particles

  • radiation–enhanced precipitation of b-Nb

needles (ten nanometers)

Aim of the study : reproduce (if possible separatly) each metallurgical change observed in- core using ion irradiation test in order to study their effect on the oxidation rate of M5Framatome alloy ➢ nuclear damage :

  • Frenkel pairs
  • dislocation loops

+ metal hardening H+/350°C

Zu et al., Philos. Mag 85 (2005)

?

➢ radiation-induced precipitation of nanometric β-Nb needles

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  • M. TUPIN et al. – 19th International Symposium on Zirconium in the Nuclear Industry

SRIM Simulation irradiation Sample characterization TEM Oxidation kinetics

  • 1. weight gain
  • 2. isotopic exposure +

SIMS analyses post-oxidation characterization TEM & XPS

  • Oxidation

: 50 days at 360°C, 18.7 MPa in H2

16O with Li, B.

Ion and energy choice

  • defect distribution
  • nuclear damage
  • Isotopic exposure

H2

18O / D2 16O

(20/80%) JANNUS Orsay Facilities

8

Tecnai 300 kV Microscope

1 10 4 2 10 4 3 10 4 4 10 4 5 10 4 6 10 4 0.2 0.4 0.6 0.8 I(cps/s) X (µm)

EXPERIMENTAL APPROACH

Tecnai 300 kV Microscope

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1 2 3 4 5 1 2 3  (dpa) metal depth (µm)

H+/300 keV 1018cm-2

Aim of the irradiation test : corrosion monitoring up to 3 µm oxide thickness ➔ metal irradiated depth of around 2 µm (Pillig-Bedworth Ratio = 1.56)

Ion Ion energy Temperature (°C) Fluence (ions/cm²) Flux (ions/cm²/s) dpa (on the plateau) dose (dpa/s) Target

H+ 300 keV 350 °C 1018 8.1013 ~0.7 3.9 10-4

<a>-Dislocation loops + b-Nb-needles particles ?

EXPERIMENTAL

SRIM SIMULATION

2 µm irradiated area 3 µm oxide layer

PBR = 1.56

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  • M. TUPIN et al. – 19th International Symposium on Zirconium in the Nuclear Industry

SRIM Simulation irradiation Sample characterization TEM Oxidation kinetics

  • 1. weight gain
  • 2. isotopic exposure +

SIMS analyses post-oxidation characterization TEM & XPS

  • Oxidation

: 50 days at 360°C, 18.7 MPa in H2

16O with Li, B.

Ion and energy choice

  • Defect distribution
  • Defect contents

(dpa, Se)

  • Isotopic exposure

H2

18O / D2 16O

(20/80%) JANNUS Orsay and Saclay Facilities

10

1 10 4 2 10 4 3 10 4 4 10 4 5 10 4 6 10 4 0.2 0.4 0.6 0.8 I(cps/s) X (µm)

Tecnai 300 kV Microscope Tecnai 300 kV Microscope

EXPERIMENTAL

METAL CHARACTERIZATION AFTER IRRADIATION TEST

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TEM observations

  • precipitation of long nanometric particles

➔ b-Nb needles found in neutron irradiated fuel cladding ?

Particles :

  • length : 10-100 nm
  • width : 2-20nm

EXPERIMENTAL

METAL CHARACTERIZATION AFTER IRRADIATION TEST

b-Nb (~50 nm) reference material proton irradiated material

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12 Long niobium-enriched precipitates looking like b-Nb needles

2 n m 2 n m

EDX profiles b-Nb ~8%

EXPERIMENTAL

METAL CHARACTERIZATION AFTER IRRADIATION TEST

TEM observation of proton irradiated material

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  • M. TUPIN et al. – 19th International Symposium on Zirconium in the Nuclear Industry

SRIM Simulation irradiation Sample characterization TEM Oxidation kinetics

  • 1. weight gain
  • 2. isotopic exposure +

SIMS analyses post-oxidation characterization TEM & XPS

  • Oxidation

: 50 days at 360°C, 18.7 MPa in H2

16O with Li, B.

Ion and energy choice

  • Defect distribution
  • Defect contents

(dpa, Se)

  • Isotopic exposure

H2

18O / D2 16O

(20/80%) JANNUS Orsay and Saclay Facilities

13

1 10 4 2 10 4 3 10 4 4 10 4 5 10 4 6 10 4 0.2 0.4 0.6 0.8 I(cps/s) X (µm)

Tecnai 300 kV Microscope Tecnai 300 kV Microscope

EXPERIMENTAL

OXIDATION KINETICS

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  • M. TUPIN et al. – 19th International Symposium on Zirconium in the Nuclear Industry

0.5 1 1.5 2 2.5 10 20 30 40 50 60

  • xide thickness (µm)

time (days)

y = m1*m0^0.5 Error Value 0.0057049 0.32051 m1 NA 0.025548 Chisq NA 0.99613 R y = m1*m0^0.5 Error Value 0.00027292 0.24574 m1 NA 4.767e-6 Chisq NA 1 R

14

➔strong effet of the proton irradiation on the oxidation rate of the M5Framatome alloy : 1. around 25 % reduction of the corrosion rate up to 20 days : R=0.78

  • xide thickness vs exposure time

Fitting with power law

eox = 0.25xt0.5 eox = 0.32xt0.5

𝑙𝑞_𝑗𝑠𝑠 𝑙𝑞_𝑣𝑜𝑗𝑠𝑠 = 0.78

EXPERIMENTAL

OXIDATION KINETICS

T=360°C P=19MPa B/Li : 1000/2 wt ppm

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➔strong effet of the proton irradiation on the oxidation rate of the M5Framatome alloy : 1. around 25 % reduction of the corrosion rate up to 20 days : R=0.78 2. around 95 % reduction of the corrosion rate beyond 20 days : R=0.05

  • xide thickness vs exposure time

Fitting with power law

𝑠

𝑗𝑠𝑠

𝑠

𝑣𝑜𝑗𝑠𝑠

~0.05

EXPERIMENTAL

OXIDATION KINETICS

samples for SIMS analyses

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5 10

5

1 10

6

1.5 10

6

2 10

6

2.5 10

6

3 10

6

0.1 0.2 0.3 0.4 0.5

18O SIMS intensity (cs/s)

  • xide depth (µm)

unirradiated alloy proton irradiated specimen

18O SIMS profiles after 24 hours of isotopic exposure in 18O enriched primary water

18O absorbed amount ratio :

R=

R= 0.75 ➔ close to the parabolic constant ratio at the beginning of the oxidation process ➢ decrease of 18O surface concentration ➢ decrease of the 18O amount absorbed within the oxide layer after irradiation ➔consistent with the oxidation kinetics EXPERIMENTAL

OXYGEN DIFFUSION PROFILE

 

x x

= dx I dx I

NI O O 18 18  

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  • M. TUPIN et al. – 19th International Symposium on Zirconium in the Nuclear Industry

SRIM Simulation irradiation Sample characterization TEM post-oxidation characterization TEM & XPS Oxidation kinetics

  • 1. weight gain
  • 2. isotopic exposure +

SIMS analyses

  • Oxidation

: 50 days at 360°C, 18.7 MPa in H2

16O with Li, B.

Ion and energy choice

  • Defect distribution
  • Defect contents

(dpa, Se)

  • Isotopic exposure

H2

18O / D2 16O

(20/80%) JANNUS Orsay Facilities

17

CAMECA X-rays Photoelectron Spectroscopy

1 10 4 2 10 4 3 10 4 4 10 4 5 10 4 6 10 4 0.2 0.4 0.6 0.8 I(cps/s) X (µm)

EXPERIMENTAL

OXIDE CHARACTERIZATION

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➢ reduction of the surface niobium content associated with : ➔ decrease of the 18O surface concentration and the oxygen diffusion flux ➔ oxidation rate reduction at the start of the corrosion process (~25 %)

specimen

  • at. % of Nb at

the surface Niobium content ratio

18O surface

concentration ratio

  • xygen

diffusion flux ratio parabolic constant ratio (kp_irr/kp_unirr) unirradiated

4.3 (+/- 0.3)

  • proton

irradiated 3 (+/- 0.3) 0.7 0.74 0.75 0.78

XPS analyses : specimens with the same thicknesses as SIMS samples ➔ charge (or oxidation) state of niobium : +V ➔ measurement of the surface niobium concentration

EXPERIMENTAL

OXIDE CHARACTERIZATION / XPS ANALYSES

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dense and protective oxide layer very damaged oxide with many cracks unirradiated material

Difference of the stress distribution within the oxide between reference and irradiated material due to metal hardening by irradiation ?

proton irradiated material Zr ZrO2 Pt Zr ZrO2

EXPERIMENTAL

OXIDE CHARACTERIZATION / TEM OBSERVATIONS

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Effect of irradiation on the start of the oxidation kinetics

DISCUSSION

CHEMICAL EFFECT

Precipitation of niobium rich particles (TEM) reduction of niobium concentration in solid solution in the M5 alloy (needs to be confirmed) decrease of surface niobium concentration (XPS) reduction of available electron density due to eletro-neutrality decrease of 18O surface concentration and oxygen diffusion flux

What’s going on beyond 20 days of oxidation time ?

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𝐾𝑃 = −𝐸𝜏0 exp 𝑊

𝐵

𝑙𝑈 𝜏𝐼 𝜖𝐷𝑃 𝜖𝑦 + 𝛻𝑂

𝐵

𝑆𝑈 𝜖𝜏𝐼 𝜖𝑦 𝐷𝑃

𝐵 − 𝐷𝑃

(Eq. 1)

  • 2. Diffusion model considering the Dollins (D dependent on stress) and the

Stephenson (stress gradient effect) effects on the oxygen diffusion flux :

[Zumpicchiat et al., Corr. Sci.(2015)]

  • 1. Diffusion model taking into account an electric field (Fromhold equation) :

→ Diffusion flux of the OH- species : → Analytical solution for a constant and homogeneous electric field

𝐾𝑃𝐼 = −𝐸𝑃𝐼 𝜖𝐷𝑃𝐼 𝜖𝑦 − 𝐺 𝑆𝑈 𝐷𝑃𝐼 𝜖𝜒 𝜖𝑦

Oxygen concentration gradient electrical potential gradient Oxygen concentration gradient stress gradient DISCUSSION

MECHANICAL EFFECT

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➔ Good simulation

  • f the kinetics of the

irradiated material

Castem code :

𝐾𝑃 = −𝐸𝜏0 exp 𝑊

𝐵

𝑙𝑈 𝜏𝐼 𝜖𝐷𝑃 𝜖𝑦 + 𝛻𝑂

𝐵

𝑆𝑈 𝜖𝜏𝐼 𝜖𝑦 𝐷𝑃

𝐵 − 𝐷𝑃

set stress gradient [2]:

𝝐𝝉𝑰 𝝐𝒚 = - 0.6 GPa. µm-1

10-13cm2.s-1 DISCUSSION

MECHANICAL EFFECT

(Eq. 1) [1] Anisotropic strain tensor ➔ Parise et al., JNM 256 (1998) [2] Compressive stress gradient ➔ Godlewski et al. ASTM STP 1354 (2000)

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18 juin 2019

CONCLUSIONS

  • proton irradiation effect

➔long niobium rich precipitates similar to b-Nb needles ➔reduction of the niobium surface concentration associated with the decrease of the 18O surface concentration ➔strong decrease of the oxidation rate

  • interpretation of the irradiation effect on the corrosion behavior
  • f M5Framatome alloy

➔A chemical effect linked to the precipitation of the niobium rich particles ➔ a mechanical effect due to the matrix hardening induced by ion irradiation

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This work is funded by the project GAINE from the French nuclear tripartite institute CEA EDF Framatome.

Thank you for your attention