Audubert, F.

Geiger, E.

Hazemann, J.L.

Hunault, M.

Klosek, V.

Le Gall, C.

Léchelle, J.

Pontillon, Y.

Proux, O.

Riglet Martial, C.

Rovezzi, M.

Solari P, L.

English

Archive Ouverte en Sciences de l'Information et de la Communication

HAL Id: cea-02338951
https://hal-cea.archives-ouvertes.fr/cea-02338951
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Oxide phase characterization in simulated high burn-up
UO_2 fuels in the early stages of a nuclear severe
accident
C. Le Gall, E. Geiger, O. Proux, M. Rovezzi, P.L. Solari, M. Hunault, V.
Klosek, C. Riglet Martial, J. Léchelle, F. Audubert, et al.
To cite this version:
C. Le Gall, E. Geiger, O. Proux, M. Rovezzi, P.L. Solari, et al.. Oxide phase characterization in
simulated high burn-up UO_2 fuels in the early stages of a nuclear severe accident. The 2018 MRS
Spring Meeting & Exhibit, Apr 2018, Phoenix, United States. ￿cea-02338951￿
Oxide phase characterization in 
simulated high burn-up UO2 fuels in 
the early stages of a nuclear severe 
accident 
April 2-6, 2018 – Phoenix, Arizona 
MRS Spring Meeting 2018 | Claire Le Gall 
CEA Cadarache| DEN | DEC | SA3E | LAMIR  
 
 
C. Le Gall1, E. Geiger2, O. Proux3, M. Rovezzi3, P.L. Solari4, M. Hunault4, V. 
Klosek1, C. Riglet-Martial1, J. Léchelle1, F. Audubert1, Y. Pontillon1, 
J.-L. Hazemann5 
 
1CEA / DEN / DEC, 2 DCCE / RMC Canada, 3OSUG-UGA, 4MARS / SOLEIL Synchrotron, 5Institut Néel / CNRS UGA 
MRS Spring Meeting 2018, Phoenix, Arizona, 
April 2-6, 2018 
NUCLEAR FUEL FISSION 
Fission products 
|  PAGE 2 MRS Spring Meeting 2018, Phoenix, Arizona, April 2-6, 2018 
D. Heinze Ph.D thesis (2010) 
Mo Ba 
Fission yield: FP most 
probably producted 
Fission occurs in nuclear fuel pellets 
UO2 or (U,Pu)O2 fuel in its Zr 
alloyed cladding 
Pressurized Water Reactor (PWR) Fuel assembly 
Zr 
SEVERE ACCIDENT PHENOMENA 
Source term 
|  PAGE 3 MRS Spring Meeting 2018, Phoenix, Arizona, April 2-6, 2018 
Source Term 
Nature and quantity of 
released radioactive 
materials 
FP 
FP release from the 
fuel 
J. P. Van Dorsselaere et al., NED 236 (2006) 
B. R. Sehgal, Nuclear safety in LWR (2012) 
Corium formation 
Loss of coolant 
Cladding 
oxidation 
BaMoO4(s) 
Oxide phase 
STUDY OF FPs BEHAVIOR 
Mechanism suggested in the literature 
|  PAGE 4 MRS Spring Meeting 2018, Phoenix, Arizona, April 2-6, 2018 
G. Nicaise, 8th International Conference on Candu Fuel (2003) 
G. Nicaise, NT DPAM/SEMIC 2004/37 (2004) 
E. Geiger, PhD thesis (2016) 
H. Kleykamp, J. Nucl. Mater. (1985) 
MoO2(g) MoO2(s) MoO2(g) 
BaZrO3(s) 
Oxide phase 
Zr(s) ZrO2(s) 
BaO(s) 
BaZrO3(s) 
BaO(g) 
Ba(g) 
Mo/Ru(s) 
Mo(g) 
Mo/Ru(s) 
Oxidation 
plateau 
(1100-1500°C) 
High temp. 
plateau 
(≥ 2300°C) 
Temperature 
ramp 
(400-1100°C) 
Temperature 
ramp 
(1500-2000°C) 
Initial State 
SIMFuels 
SIMFuels SAMPLES 
Fabrication data 
|  PAGE 5 MRS Spring Meeting 2018, Phoenix, Arizona, April 2-6, 2018 
Depleted UO2 + 11 oxides 
(FPs surrogates) 
Sintering at 1650°C 
during 2h under pure H2 
Elements Ba Ce La Mo Sr Y Zr Rh Pd Ru Nd 
Concentration 
(at%) 
0,26 0,61 0,20 0,51 0,13 0,06 0,60 0,03 0,42 0,64 0,91 
Concentrations representative of an irradiated fuel 
with a burn-up of 76 GWd.tHM
-1 
SIMFuels SAMPLES 
Thermal treatments 
|  PAGE 6 MRS Spring Meeting 2018, Phoenix, Arizona, April 2-6, 2018 
Mo
 (s
) +
 R
u(s
) +
 Pd
(s)
 + 
Rh
(s)
 + 
ZrO
 2(s
) +
 Ba
ZrO
 3(s
) +
 U
O2(
s)
Ru
(s)
 + 
Pd
(s)
 + 
Rh
(s)
 + 
ZrO
 2(s
) +
 Ba
ZrO
 3(s
) +
 M
oO2
(s)
 + 
UO
2(s
)
Ru(
s) +
 Pd
(s) +
 Rh
(s) +
 ZrO
 2(s
) + 
BaM
oO 4
(s) 
+ M
oO2
(s) 
+ U
O 2(
s)
ZrO
 2(s
) + 
BaM
oO 4
(s) 
+ M
oO 2
(s) 
+ U4
O9(
s2)
Pd(liq) + MoO2(s) + ZrO2(s)
Pd(liq) + UO2(s) +
Ru(
s) +
 Pd
(s) 
+ R
h(s
) +
+ Rh(s) + Ru(s) + UO2(s)
Ru(s) + Mo(s) + Rh3U(s)
H2
O/
H2
 = 
50
H2O/H
2 = 0.0
2 P
d
(l
iq
) 
+
 R
h
(s
) 
+
 R
u
(s
) 
+
 M
o
(s
) 
+
Z
rO
 2
(s
) 
+
 B
a
Z
rO
 3
(s
) 
+
 U
O
 2
(s
)
Ba
ZrO
 3(s
)
Ba
Mo
O4(
s)
Ba - O2 - Mo - Zr - Ru - Rh - Pd - U
Temperature (°C)
R
T
ln
 p
(O
2
) 
(k
J
/m
o
l 
O
2
)
400 600 800 1000 1200 1400 1600 1800 2000
-500
-450
-400
-350
-300
-250
-200
-150
Mo
 (s
) +
 Ru
(s)
 + 
Pd
(s)
 + 
Rh
(s)
 + 
ZrO
 2(s
) +
 Ba
ZrO
 3(s
) +
 UO
2(s
)
Ru
(s)
 + 
Pd
(s)
 + 
Rh
(s)
 + 
ZrO
 2(s
) +
 Ba
Zr
 3(s
) 
Mo
O2
(s)
 + 
UO
2(s
)
Ru(
s) +
 Pd
(s) +
 Rh
(s) +
 ZrO
 2(s
) + 
BaM
oO 4
(s) 
+ M
oO2
(s) 
+ U
O 2(
s)
ZrO
 2(s
) + 
BaM
oO 4
(s) 
+ M
oO 2
(s) 
+ U4
O9(
s2)
Pd(liq) MoO2(s) + ZrO2(s)
Pd(liq) + UO2(s) +
Ru(
s) +
 Pd
(s) 
+ R
h(s
) +
+ Rh(s) + Ru(s) + UO2(s)
Ru(s) + Mo(s) + Rh3U(s)
H2
O/
H2
 = 
50
H2O/H
2 = 0.0
2 P
d
(l
iq
) 
+
 R
h
(s
) 
+
 R
u
(s
) 
+
 M
o
(s
) 
+
Z
rO
 2
(s
) 
+
 B
a
Z
rO
 3
(s
) 
+
 U
O
 2
(s
)
Ba
ZrO
 3(s
)
Ba
Mo
O4(
s)
Ba - O2 - Mo - Zr - Ru - Rh - Pd - U
Temperature (°C)
R
T
ln
 p
(O
2
) 
(k
J
/m
o
l 
O
2
)
400 600 800 1000 1200 1400 1600 1800 2000
-500
-450
-400
-350
-300
-250
-200
-150
R1700 
R1000 
R900 R700 
R400 
O1000 
O900 
O700 
O400 
BaZrO3(s) + MoO2(s) + ½O2(g)      BaMoO4(s) + ZrO2(s) 
Mo(s) + H2O(l)      MoO2(s) +H2(g) 
(Ba+Sr)/Mo ≈ 1 
(Ba+Sr)/Zr ≈ 0.6 
O/Zr ≈ 4 
CHARACTERIZATIONS 
SEM-EDX 
|  PAGE 7 MRS Spring Meeting 2018, Phoenix, Arizona, April 2-6, 2018 
C. Thouzellier internship (2017), H. Kleykamp, J. Nucl. Mater. (1985); E. Geiger et al. ERMSAR proceedings (2015); E Geiger et al. J. Nucl. Mater. (accepted) 
 
 
Sample as sintered 
 
 
1000°C, -292 kJ.mol-1 
 
 
1700°C, -426 kJ.mol-1 
 
O/Zr ≈ 2 (Sr+Ba)/Zr ≈ 1 
O/Zr ≈ 2.5 
Ba0,8Sr0,2ZrO3 
ZrO2 
Ba0,9Sr0,1ZrO3 
Mo 
Oxide 
phase 
O/Mo ≈ 5 
Ba0,8Sr0,2ZrO3 
ZrO2 
(Ba, Sr)(Zr, Mo)Ox 
CHARACTERIZATIONS 
SEM-EDX 
|  PAGE 8 MRS Spring Meeting 2018, Phoenix, Arizona, April 2-6, 2018 
C. Thouzellier internship (2017), H. Kleykamp, J. Nucl. Mater. (1985); E. Geiger et al. ERMSAR proceedings (2015); E Geiger et al. J. Nucl. Mater. (accepted) 
 
 
Sample as sintered 
 
 
1000°C, -292 kJ.mol-1 
 
 
1700°C, -426 kJ.mol-1 
 
O/Mo ≈ 2 
Oxide 
phase 
Metallic 
phase 
100% Mo 100% Mo 100% Mo 
MoO2 
01
2
3
4
5
6
7
8
9
10
11
19975 20025 20075
N
o
rm
(E
)
Energy (eV)
0
1
2
3
4
5
6
7
8
9
10
11
12
19975 20025 20075
N
o
rm
(E
)
Energy (eV)
R1700
T0
SrMoO4
BaMoO4
MoO3
O1000
O900
T0
MoO2
Mo
SrMoO4
BaMoO4
MoO3
MoO2
Mo
N
o
rm
(E
)
N
o
rm
(E
)
CHARACTERIZATIONS 
X-ray Absorption Spectroscopy at Mo K-edge 
|  PAGE 9 MRS Spring Meeting 2018, Phoenix, Arizona, April 2-6, 2018 
No strong evolution of Mo 
XANES reducing conditions 
Metallic Mo 
0
1
2
3
4
5
6
7
8
9
10
1
1 975 2 025 2 075
N
o
rm
(E
)
Energy (eV)
0
1
2
3
4
5
6
7
8
9
10
1
12
1 975 2 025 2 075
N
o
rm
(E
)
Energy (eV)
R17 0
T0
SrMoO4
BaMoO4
MoO3
O1 0
O9 0
T0
MoO2
Mo
SrMoO4
BaMoO4
MoO3
MoO2
Mo
Evolution of Mo local 
environment from 900°C in 
oxidizing conditions 
Consistent with Mo oxidation, 
MoO2 formation and the oxide 
phase evolution 
01
2
3
4
5
6
7
8
9
10
17975 18025 18075
N
o
rm
(E
)
Energy (eV)
0
1
2
3
4
5
6
7
8
9
17975 18025 18075
N
o
rm
(E
)
Energy (eV)
BaZrO3
ZrO2
R1700
T0
Zr
BaZrO3
ZrO2
Zr
O1000
T0
0
1
2
3
4
5
6
7
8
9
10
17975 18025 18075
N
o
rm
(E
)
Energy (eV)
0
1
2
3
4
5
6
7
8
9
17975 18025 18075
N
o
rm
(E
)
Energy (eV)
BaZrO3
ZrO2
R170
T0
BaZrO3
ZrO2
O10
T0
N
o
rm
(E
)
N
o
rm
(E
)
|  PAGE 10 MRS Spring Meeting 2018, Phoenix, Arizona, April 2-6, 2018 
Zr XANES evolution at 1700°C 
in reducing conditions 
Consistent with the  
continuous BaZrO3 
formation and stabilization 
N
o
rm
(E
)
N
o
rm
(E
)
Zr
Zr
N
o
rm
(E
)
N
o
rm
(E
) Zr XANES evolution from 
1000°C in oxidizing conditions 
Destruction of part of the 
BaZrO3 phase and formation of 
ZrO2 ? 
Consistent with the oxide phase 
evolution (Mo reacts with Ba) 
CHARACTERIZATIONS 
X-ray Absorption Spectroscopy at Zr K-edge 
05
10
15
20
25
5 220 5 250 5 280 5 310 5 340
N
o
rm
(E
)
Energy (eV)
BaMoO4
BaZrO3
BaCO3
BaO
1700°C, 10-
27
N
o
rm
(E
)
|  PAGE 11 MRS Spring Meeting 2018, Phoenix, Arizona, April 2-6, 2018 
No Ba XANES evolution at 
1700°C in reducing conditions 
BaZrO3 
XANES analyses of the O-
samples scheduled in April 
2018 
CHARACTERIZATIONS 
HERFD-XANES at Ba L3-edge 
BaZrO3 
BaMoO4 
BaCO3 
BaO 
R1700 
T0 
BaZrO3(s) 
Oxide phase 
BaZrO3(s) 
ZrO2(s) 
Mo/Ru(s) 
Mo/Ru(s) 
BaMoO4(s) 
Oxide phase 
|  PAGE 12 MRS Spring Meeting 2018, Phoenix, Arizona, April 2-6, 2018 
MoO2(g) 
ZrO2(s) 
BaZrO3(s) 
Mo/Ru(s) 
1000°C 400°C – 900°C 1700°C Initial State 
CONCLUSIONS 
Evolution of the oxide phase 
Oxidizing 
atmosphere 
Reducing 
atmosphere 
ZrO2(s) 
To be confirmed 
ESRF:  
P. Colomp, O. Proux, M. Rovezzi, J. L. Hazemann 
 
MARS/SOLEIL:  
M. Hunault, P. L. Solari 
 
CEA/LLCC:  
C. Riglet Martial, D. Drouan, C. Tanguy, V. Klosek, J. Léchelle, G. Jomard 
 
CEA/LCU:  
F. Garel, P. Matheron, N. Tarisien, X. Itlis, H. Rouquette, J. Raynal, 
 J. Lamontagne 
 
CEA/LAMIR:  
C. Thouzellier, J.C. Richaud, M. Pontillon, G. Volle, A. Gallais During, Y. 
Pontillon, F. Audubert, I. Moysan 
Commissariat à l’énergie atomique et aux énergies alternatives 
Centre de Cadarache |  13108 Saint Paul lez Durance 
T. +33 (0)4 42 25 70 00  
Etablissement public à caractère industriel et commercial | R.C.S Paris B 775 685 019 
MRS Spring Meeting 2018, Phoenix, Arizona, 
April 2-6, 2018 
|  PAGE 14 MRS Spring Meeting 2018, Phoenix, Arizona, April 2-6, 2018 
5/6 X-RAY ABSORPTION SPECTROSCOPY 
Principle 
0 
1 
2 
3 
4 
5 
6 
7 
5200 5250 5300 5350 5400 
N
o
rm
 µ
(E
) 
Energy (eV) 
XANES EXAFS 
Geometry and 
oxidation state 
Interatomic distances, 
coordination, nature 
of nearest neighboors 
Incident beam 
X-ray fluorescence 
Fluorescence 
detector 


Oxide phase characterization in simulated high burn-up UO2 fuels in the early stages of a nuclear severe accident

https://hal-cea.archives-ouvertes.fr/cea-02338951/document

Oxide phase characterization in simulated high burn-up UO2 fuels in the early stages of a nuclear severe accident

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