Grosse, Mirco

Kaestner, A.

Schillinger, B.

Steinbrueck, Martin

KITopen

KIT – University of the State of Baden-Wuerttemberg and  National Research Center of the Helmholtz Association  KIT / Institute for Applied Materials / Program NUSAFE     www.kit.edu In-situ Investigations of the Hydrogen Uptake of Zirconium Alloys during Steam Oxidation  M. Grosse, M. Steinbrueck, B. Schillinger, A. Kaestner Institute for Applied Materials  Program NUSAFE Mirco Grosse et al. / 18th Inten. Symposium on Zirconium in Nuclear Industries / Hilton Head Island / May 15 – 18 2016 2/22 Outline Introduction Neutron Imaging Results Examples In-situ Calibration  Analyse of the data Discussion Conclusions Institute for Applied Materials  Program NUSAFE Mirco Grosse et al. / 18th Inten. Symposium on Zirconium in Nuclear Industries / Hilton Head Island / May 15 – 18 2016 3/22 Introduction - Zirconium alloys absorb hydrogen during corrosion in water or steam oxidation at      higher temperatures  - Hydrogen uptake reduces the ductility of zirconium alloys  - Consequences for the thermo-shock stability during LOCA  - QUENCH-LOCA program was initiated at KIT to study the hydrogen uptake during     LOCA and its consequences on the mechanical properties Neutron radiograph of the balloning zone of rod #08 of the QUENCH-L0-test Institute for Applied Materials  Program NUSAFE Mirco Grosse et al. / 18th Inten. Symposium on Zirconium in Nuclear Industries / Hilton Head Island / May 15 – 18 2016 4/22 Neutron Imaging X-ray    Neutrons  iiiNsII)exp(0Beer-Lamberts law:  with )(ZfZrHZf )(Institute for Applied Materials  Program NUSAFE Mirco Grosse et al. / 18th Inten. Symposium on Zirconium in Nuclear Industries / Hilton Head Island / May 15 – 18 2016 5/22 Neutron Imaging OOHHZrZriiiBBtotalNNNNsIIIIZry...ln0Institute for Applied Materials  Program NUSAFE Mirco Grosse et al. / 18th Inten. Symposium on Zirconium in Nuclear Industries / Hilton Head Island / May 15 – 18 2016 6/22 Materials and Experiments Materials: Zry-4 and traditional E110  Temperatures:  Zry-4: 1273, 1373, 1473 and 1573 K  E110: (1123, 1173,) 1273,1373, 121473 and 1573 K  Neutron radiography measurements: ICON at SINQ, 120 and 20 s illumination per image ANTARES at FRM-2, 10 s illumination per image  INRRO furnace:      Institute for Applied Materials  Program NUSAFE Mirco Grosse et al. / 18th Inten. Symposium on Zirconium in Nuclear Industries / Hilton Head Island / May 15 – 18 2016 7/22 Results Examples Zry-4, 1373 K    E110, 1473 K Institute for Applied Materials  Program NUSAFE Mirco Grosse et al. / 18th Inten. Symposium on Zirconium in Nuclear Industries / Hilton Head Island / May 15 – 18 2016 8/22 Results Examples Zry-4, 1273 K Institute for Applied Materials  Program NUSAFE Mirco Grosse et al. / 18th Inten. Symposium on Zirconium in Nuclear Industries / Hilton Head Island / May 15 – 18 2016 9/22 Calibration – Effect of Hydrogen 2 l/h         4 l/h        8 l/h  H2,  50 l/h Ar  1273 K TRHRSKpKCSSSHSmHexp2)(Sieverts´ law: Institute for Applied Materials  Program NUSAFE Mirco Grosse et al. / 18th Inten. Symposium on Zirconium in Nuclear Industries / Hilton Head Island / May 15 – 18 2016 10/22 Calibration – Effect of Hydrogen 0,0 0,1 0,2 0,3 0,4 0,5 0,60,00,51,01,52,02,53,03,5     900°C 1000°C 1100°C 1200°C 1300°Ctotal, cm-1H/Zr atomic ratioFor in-situ NR experiments at SINQ:  Σtotal = 6.32 ± 0.12 H/Zr  For in-situ NR experiments at FRM2:  Σtotal = 5.61 ± 0.28 H/Zr  Institute for Applied Materials  Program NUSAFE Mirco Grosse et al. / 18th Inten. Symposium on Zirconium in Nuclear Industries / Hilton Head Island / May 15 – 18 2016 11/22 Calibration - Effect of Oxygen 0,00 0,05 0,10 0,15 0,20 0,25 0,300,00,10,20,30,40,5  cm-1m/mAnnealing in Ar/O2 at1200°C mmcmN OOO 1)04.098.0(mmcmN OOO 1)04.098.0(Institute for Applied Materials  Program NUSAFE Mirco Grosse et al. / 18th Inten. Symposium on Zirconium in Nuclear Industries / Hilton Head Island / May 15 – 18 2016 12/22 Results data correction Mirco Grosse et al. 0 2000 4000 6000 8000 100000,00,10,20,30,40,50,60,7  total, cm-1oxidation time t, s measured O HZry-4, 1473 K Institute for Applied Materials  Program NUSAFE Mirco Grosse et al. / 18th Inten. Symposium on Zirconium in Nuclear Industries / Hilton Head Island / May 15 – 18 2016 13/22 Results 0 3600 7200 10800 14400 180000250500750100012501500  1273 K  1373 K  1473 K  1573 KxH, wppmoxidation time, sVery fast hydrogen uptake at the beginning  Later the hydrogen concentration decreases with time  Enhanced hydrogen uptake due to breakaway Institute for Applied Materials  Program NUSAFE Mirco Grosse et al. / 18th Inten. Symposium on Zirconium in Nuclear Industries / Hilton Head Island / May 15 – 18 2016 14/22 Results 0 3600 7200 10800 14400 18000 216000100200300400500600xH, wppmoxidation time, s 1273 K  1373 K   1473 K   1573 K  Very fast hydrogen uptake at the beginning  Later the hydrogen concentration decreases with time  Less influence of breakaway on the hydrogen concentration Institute for Applied Materials  Program NUSAFE Mirco Grosse et al. / 18th Inten. Symposium on Zirconium in Nuclear Industries / Hilton Head Island / May 15 – 18 2016 15/22 Discussion E110            Zry-4 1273 K, 4 h in steam Hydrogen pump effect during breakaway oxidation E110, 1273 K, 6 h in steam relative mass gain after 6 h at 1273 K during the in-situ experiments: Zry-4: 27.8 %, E110: -0.22% Institute for Applied Materials  Program NUSAFE Mirco Grosse et al. / 18th Inten. Symposium on Zirconium in Nuclear Industries / Hilton Head Island / May 15 – 18 2016 16/22 Discussion - very fast hydrogen uptake at the beginning  - during the first 20 s the whole hydrogen uptake occurs  - explains the results obtained from the QUENCH-LOCA tests 0 20 40 60 80 100 1200100200300400500600700xH, wppmoxidation time, sInstitute for Applied Materials  Program NUSAFE Mirco Grosse et al. / 18th Inten. Symposium on Zirconium in Nuclear Industries / Hilton Head Island / May 15 – 18 2016 17/22 Discussion Mirco Grosse et al. 6,0 6,2 6,4 6,6 6,8 7,0 7,2 7,4 7,6 7,8 8,05,05,25,45,65,86,06,26,46,66,87,0 E110 Zry-4ln(first maximum of xH, wppm)104/T, K-1Arrhenius type dependence   except values for 1573K  because of temporary steam starvation   Hydrogen concentration increases with temperature Institute for Applied Materials  Program NUSAFE Mirco Grosse et al. / 18th Inten. Symposium on Zirconium in Nuclear Industries / Hilton Head Island / May 15 – 18 2016 18/22 Discussion 0 3600 7200 10800 14400 18000 216000100200300400500600xH, wppmoxidation time, s 1273 K  1373 K   1473 K   1573 K  Hydrogen release according the model of Veshchunov and Berdyshev  with t-1/8 0 600 1200 1800 2400 3000 36000100200300400500600700xH, wppmoxidation time, s 1273 K  1373 K  1473 K  1573 K Institute for Applied Materials  Program NUSAFE Mirco Grosse et al. / 18th Inten. Symposium on Zirconium in Nuclear Industries / Hilton Head Island / May 15 – 18 2016 19/22 Discussion 6,0 6,5 7,0 7,5 8,06,06,57,07,5  Zry-4 E110ln(A/wppm)104/T, K-1Arrhenius type dependence   except values for 1573K  because of temporary steam starvation  Institute for Applied Materials  Program NUSAFE Mirco Grosse et al. / 18th Inten. Symposium on Zirconium in Nuclear Industries / Hilton Head Island / May 15 – 18 2016 20/22 Discussion Sieverts´ law:     RTHKtKdttKdnnnnnpRTHKpKxomOmOmOHArOHHHHsSHSmetalHexp~222exp~222  RTHHx OsmetalH2/exp~→ HO > HS → The hydrogen source term dominates the process not the Sieverts dependence Institute for Applied Materials  Program NUSAFE Mirco Grosse et al. / 18th Inten. Symposium on Zirconium in Nuclear Industries / Hilton Head Island / May 15 – 18 2016 21/22 Conclusions - Very fast hydrogen uptake as long as metallic surface exists or the oxide layer thickness is low enough. It explains the findings in the QUENCH-LOCA tests.  - The oxidation rate determines the amount of hydrogen absorbed, not the Sieverts´ law.  - After reaching maximal hydrogen concentrations, hydrogen will be released. The hydrogen concentration decreases according to the model of Veshchunov and Berdyshev  with t-1/8.  - Breakaway can enhance the hydrogen uptake significantly but only if the oxide is not spalled.   Institute for Applied Materials  Program NUSAFE Mirco Grosse et al. / 18th Inten. Symposium on Zirconium in Nuclear Industries / Hilton Head Island / May 15 – 18 2016 22/22 Thanks   We thank all involved in this investigations in particular our students Marius van den Berg and Camille Goulet.  Thanks to TU Munich (Germany) and PSI Villigen (Switzerland) for providing neutron beam time for these experiments.    KIT – University of the State of Baden-Wuerttemberg and  National Research Center of the Helmholtz Association  KIT / Institute for Applied Materials / Program NUSAFE     www.kit.edu In-situ Investigations of the Hydrogen Uptake of Zirconium Alloys during Steam Oxidation  M. Grosse, M. Steinbrueck, B. Schillinger, A. Kaestner 

In-situ Investigations of the Hydrogen Uptake of Zirconium Alloys during Steam Oxidation

https://publikationen.bibliothek.kit.edu/1000057793/3875492

In-situ Investigations of the Hydrogen Uptake of Zirconium Alloys during Steam Oxidation

Abstract

Similar works

Full text

Available Versions

KITopen