Effect of grain refinement on the corrosion behavior of Zr alloys in fluorinated nitric acid

Abstract

The influence of grain size or grain refinement on the corrosion of Zr alloy is clarified by employing a series of electrochemical analyses and characterization techniques. The corrosion resistance, as a function of exposure time, F⁻ concentration, and solution temperatures, of Zr alloys with different grain sizes is ascertained. The results confirm that refining the grain size can effectively enhance the short-time corrosion properties of Zr alloy in HNO₃ with F⁻. The fine-grained Zr alloy (∼10 µm in diameter) consistently exhibits a lower corrosion current density, ranging from 18% to 46% lower than that of the coarse-grained Zr alloy (∼44 µm). The enhanced corrosion resistance is attributed to the high-density grain boundaries, which promote oxide stability, and accelerate the creation of the protective layer. The high corrosion rate and pseudo-passivation behavior of Zr alloys in fluorinated nitric acid originate from the accelerated “dissolution-passivation” of the oxide film. However, the grain refinement does not provide enduring anti-corrosion for Zr alloys. To meet the operation of spent fuel reprocessing, additional systematic efforts are required to evaluate the long-term effect of grain refinement.

Keywords

zirconium alloys / corrosion / grain size / fluoride ions / nitric acid

References

[1] GwinnerB, Balbaud-CélérierF, FauvetP, et al.. A step towards a better understanding of corrosion of zirconium in nitric acid with additions of fluorine: Focus on the role of the presence of an initial oxide film [J]. Corrosion Science, 2022, 201: 110284

[2] WangX-z, WangY, WangY-x, et al.. Corrosion of Zr-xTi-yNb alloys in concentrated nitric acid at elevated temperature [J]. Corrosion Science, 2023, 219: 111226

[3] KautzE, GwalaniB, YuZ-f, et al.. Investigating zirconium alloy corrosion with advanced experimental techniques: A review [J]. Journal of Nuclear Materials, 2023, 585: 154586

[4] FujiiT, BabaH. The effect of oxidizing ions on the passivity of the valve metals in boiling nitric acid solutions [J]. Corrosion Science, 1990, 31: 275-280

[5] YuanR, XieY-p, LiT, et al.. An origin of corrosion resistance changes of Zr alloys: Effects of Sn and Nb on grain boundary strength of surface oxide [J]. Acta Materialia, 2021, 209: 116804

[6] JayarajJ, KrishnaveniP, KrishnaD N G, et al.. Corrosion investigations on zircaloy-4 and titanium dissolver materials for MOX fuel dissolution in concentrated nitric acid containing fluoride ions [J]. Journal of Nuclear Materials, 2016, 473: 157-166

[7] GoncalvesZ, MünzelH. Dissolution kinetics of zircaloy in HNO₃/HF mixtures [J]. Journal of Nuclear Materials, 1990, 170(3): 261-269

[8] MeyerR E. The electrochemistry of the dissolution of zirconium in aqueous solutions of hydrofluoric acid [J]. Journal of the Electrochemical Society, 1964, 111(2): 147

[9] JayarajJ, Nanda Gopala KrishnaD, MallikaC, et al.. Electrochemical studies and XPS analysis of the surface of zirconium-702 in concentrated nitric acid with and without fluoride ions [J]. Transactions of the Indian Institute of Metals, 2018, 71(3): 521-531

[10] LohrengelM M. Thin anodic oxide layers on aluminium and other valve metals: High field regime [J]. Materials Science and Engineering R: Reports, 1993, 11(6): 243-294

[11] SuH-b, LiY-n, ZhaoY-q, et al.. Characteristics of oxide films on Zr702 and their corrosion performance in boiling fluorinated nitric acid [J]. Metals, 2024, 14(4): 479

[12] JiY-y, HuQ, XiaD-h, et al.. Corrosion susceptibility of passive films on 1060, 2024, and 5083 aluminum alloys: Experimental study and first-principles calculations [J]. Journal of the Electrochemical Society, 2023, 170(4): 041505

[13] HuJ, LinW-t, LvQ-y, et al.. Oxide formation mechanism of a corrosion-resistant CZ1 zirconium alloy [J]. Journal of Materials Science & Technology, 2023, 147: 6-15

[14] FigueiredoR B, KawasakiM, LangdonT G. Seventy years of Hall-Petch, ninety years of superplasticity and a generalized approach to the effect of grain size on flow stress [J]. Progress in Materials Science, 2023, 137: 101131

[15] RongX-d, LiY, ChenX-f, et al.. Plain interface strategy toward the high corrosion performance of Al matrix composites [J]. Science China Materials, 2023, 66(11): 4295-4305

[16] XueL, DingY, PradeepK G, et al.. The grain size effect on corrosion property of Al₂Cr₅Cu₅Fe₅₃Ni₃₅ high-entropy alloy in marine environment [J]. Corrosion Science, 2022, 208: 110625

[17] RalstonK D, BirbilisN, DaviesC H J. Revealing the relationship between grain size and corrosion rate of metals [J]. Scripta Materialia, 2010, 63(12): 1201-1204

[18] WangY, JinJ-s, ZhangM, et al.. Effect of the grain size on the corrosion behavior of CoCrFeMnNi HEAs in a 0.5 M H₂SO₄ solution [J]. Journal of Alloys and Compounds, 2021, 858: 157712

[19] RittenhouseJ, LuebbeM, HoffmanA, et al.. Effect of grain refinement on high temperature steam oxidation of an FeCrAl alloy [J]. Corrosion Science, 2024, 226: 111688

[20] LuK-j, LeiZ-r, DengS, et al.. Synergistic effects of grain sizes on the corrosion behavior and mechanical properties in a metastable high-entropy alloy [J]. Corrosion Science, 2023, 225: 111588

[21] XuJ, BaiX-d, HeF, et al.. Influence of Ar ion bombardment on the uniform corrosion resistance of laser-surface-melted Zircaloy-4 [J]. Journal of Nuclear Materials, 1999, 265(3): 240-244

[22] WangP-j, ChengX-q, ZhangZ-y, et al.. Roles of grain refinement in the rust formation and corrosion resistance of weathering steels [J]. Corrosion Science, 2023, 224: 111561

[23] MiyamotoH, HaradaK, MimakiT, et al.. Corrosion of ultra-fine grained copper fabricated by equal-channel angular pressing [J]. Corrosion Science, 2008, 50(5): 1215-1220

[24] WangP-j, MaL-w, ChengX-q, et al.. Effect of grain size and crystallographic orientation on the corrosion behaviors of low alloy steel [J]. Journal of Alloys and Compounds, 2021, 857: 158258

[25] LiS-x, HeY-n, YuS-r, et al.. Evaluation of the effect of grain size on chromium carbide precipitation and intergranular corrosion of 316L stainless steel [J]. Corrosion Science, 2013, 66: 211-216

[26] KaithwasC K, BhuyanP, PradhanS K, et al.. ‘Hall-Petch’ type of relationship between the extent of intergranular corrosion and grain size in a Ni-based superalloy [J]. Corrosion Science, 2020, 175: 108868

[27] FengJ-h, MaoL, YuanG-c, et al.. Grain size effect on corrosion behavior of Inconel 625 film against molten MgCl₂-NaCl-KCl salt [J]. Corrosion Science, 2022, 197: 110097

[28] SinhaP K, KainV. Investigations of cathodic reactions using cyclic voltammetry and electrochemical behavior of Ti-Al-Zr alloy in nitric acid using electrochemical impedance spectroscopy [J]. Journal of Applied Electrochemistry, 2022, 52(2): 375-394

[29] AminM A, Abd El-RehimS S, El-SherbiniE E F, et al.. Pitting corrosion studies on Al and Al-Zn alloys in SCN-solutions [J]. Electrochimica Acta, 2009, 54(18): 4288-4296

[30] WangZ, FengZ, FanX-h, et al.. Pseudo-passivation mechanism of CoCrFeNiMo_0.01 high-entropy alloy in H₂S-containing acid solutions [J]. Corrosion Science, 2021, 179: 109146

[31] CouetA, MottaA T, AmbardA. The coupled current charge compensation model for zirconium alloy fuel cladding oxidation: I. Parabolic oxidation of zirconium alloys [J]. Corrosion Science, 2015, 100: 73-84

[32] ZhangH-l, KimT, SwartsJ, et al.. Nano-porosity effects on corrosion rate of Zr alloys using nanoscale microscopy coupled to machine learning [J]. Corrosion Science, 2022, 208: 110660

[33] MorantC, SanzJ M, GalánL, et al.. An XPS study of the interaction of oxygen with zirconium [J]. Surface Science, 1989, 218(23): 331-345

[34] BespalovI, DatlerM, BuhrS, et al.. Initial stages of oxide formation on the Zr surface at low oxygen pressure: An in situ FIM and XPS study [J]. Ultramicroscopy, 2015, 159: 147-151

[35] De GaboryB, DongY, MottaA T, et al.. EELS and atom probe tomography study of the evolution of the metal/oxide interface during zirconium alloy oxidation [J]. Journal of Nuclear Materials, 2015, 462: 304-309

[36] KleinR. Dissolution of zirconium in nitric-hydrofluoric acid mixtures [J]. Corrosion, 1997, 53(4): 327-332

[37] LeeS, WhiteH S. Dissolution of the native oxide film on polycrystalline and single-crystal aluminum in NaCl solutions [J]. Journal of the Electrochemical Society, 2004, 151(8): B479

[38] LiaoJ-j, YangZ-b, QiuS-y, et al.. The correlation between tetragonal phase and the undulated metal/oxide interface in the oxide films of zirconium alloys [J]. Journal of Nuclear Materials, 2019, 524: 101-110

[39] BouvierP, GodlewskiJ, LucazeauG. A Raman study of the nanocrystallite size effect on the pressure-temperature phase diagram of zirconia grown by zirconium-based alloys oxidation [J]. Journal of Nuclear Materials, 2002, 300(23): 118-126

[40] LiaoJ-j, ZhangJ-s, ZhangW, et al.. Critical behavior of interfacial t-ZrO₂ and other oxide features of zirconium alloy reaching critical transition condition [J]. Journal of Nuclear Materials, 2021, 543: 152474

RIGHTS & PERMISSIONS

Central South University