Hostname: page-component-586b7cd67f-dlnhk Total loading time: 0 Render date: 2024-11-26T20:55:21.040Z Has data issue: false hasContentIssue false
  • English
  • Français

Study of SIMFUEL corrosion under hyper-alkaline conditions in the presence of silicate and calcium

Published online by Cambridge University Press:  15 December 2016

Alexandra Espriu-Gascon ,
David W. Shoesmith ,
Javier Giménez ,
Ignasi Casas  and
Joan de Pablo
Alexandra Espriu-Gascon*
Affiliation:
Escola d’Enginyeria de Barcelona Est (EEBE), Carrer d’Eduard Maristrany, 10-14, 08019 Barcelona, Spain.
David W. Shoesmith
Affiliation:
Department of Chemistry, The University of Western Ontario, 1151 Richmond Street, London, Ontario, Canada N6A 5B7
Javier Giménez
Affiliation:
Escola d’Enginyeria de Barcelona Est (EEBE), Carrer d’Eduard Maristrany, 10-14, 08019 Barcelona, Spain.
Ignasi Casas
Affiliation:
Escola d’Enginyeria de Barcelona Est (EEBE), Carrer d’Eduard Maristrany, 10-14, 08019 Barcelona, Spain.
Joan de Pablo
Affiliation:
Escola d’Enginyeria de Barcelona Est (EEBE), Carrer d’Eduard Maristrany, 10-14, 08019 Barcelona, Spain. Fundació CTM Centre Tecnològic, Plaça de la Ciència 2, 08243 Manresa, Barcelona, Spain
*
*(Email: [email protected])
Get access

Abstract

Cement has been considered as a possible material present in the Deep Geological Disposal (DGD) [1] . In order to determine the effect of cementitious waters on the oxidation of the surface of Spent Fuel (SF), a series of electrochemical experiments were performed, to study the influence of two main components of cementitious water: calcium and silicate.

Test solutions with Na2SiO3 and/or CaCl2 were prepared at pH 12 and NaCl 0.1 mol·dm-3 as ionic medium. A 3 at.% doped SIMFUEL was used to perform cyclic voltammetric (CV), potentiostatic and corrosion potential (ECORR) experiments. After potentiostatic and ECORR experiments, the SIMFUEL surface was analyzed using X-Ray Photoelecton Spectroscopy (XPS).

The results showed that the presence of silicate decreased the SIMFUEL oxidation between -100 mV and 300 mV. When Ca2+ was added, the whole oxidation process was shifted to higher potentials which indicated a protective effect of the combination of Ca2+ and SiO32- . The XPS results obtained after potentiostatic experiments at 200 mV showed that the presence of silicate partially suppressed the oxidation of SIMFUEL, as indicated by the contribution of both U(IV) and U(V) XPS to the U 4f7/2 band (∼ 38%). After the addition of calcium, the predominant uranium oxidized state contribution on the surface was U(V) (40%). After the ECORR experiments, the ECORR values were similar either with or without silicate in solution (-80 mV and -70 mV respectively). The resulting surface also exhibited a similar composition. When calcium was added to the electrolyte, the ECORR value was suppressed to -105 mV, and XPS showed that the surface was less oxidized than with the other two electrolytes.

Keywords

corrosionx-ray photoelectron spectroscopy (XPS)oxidation
Type
Articles
Information
MRS Advances , Volume 2 , Issue 10: Scientific Basis for Nuclear Waste Management XL , 2017 , pp. 543 - 548
Copyright
Copyright © Materials Research Society 2016 

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

ENRESA, 7 o Plan Nacional De I + D. 2014-2018, First edit. Madrid (Spain): TransEdit, 2014.Google Scholar
Shoesmith, D. W., “The Role of Dissolved Hydrogen on the Corrosion / Dissolution of Spent Nuclear Fuel,” Ontario, Canada, 2008.Google Scholar
Wu, L. and Shoesmith, D. W., “An Electrochemical Study of H2O2 Oxidation and Decomposition on Simulated Nuclear Fuel (SIMFUEL),” Electrochim. Acta, vol. 137, pp. 83–90, 2014.CrossRefGoogle Scholar
Chung, D.-Y., Seo, H.-S., Lee, J.-W., Yang, H.-B., Lee, E.-H., and Kim, K.-W., “Oxidative leaching of uranium from SIMFUEL using Na2CO3–H2O2 solution,” J. Radioanal. Nucl. Chem., vol. 284, no. 1, pp. 123–129, Jan. 2010.Google Scholar
Berner, U. R., “Evolution of pore water chemistry during degradation of cement in a radioactive waste repository environment,” Waste Manag., vol. 12, no. 2–3, pp. 201–219, Jan. 1992.Google Scholar
Rojo, I., Rovira, M., and de Pablo, J., “Selenate Diffusion Through Mortar and Concrete,” Environ. Eng. Sci., vol. 31, no. 8, pp. 469–473, Aug. 2014.Google Scholar
De Pablo, J., Casas, I., Giménez, J., Clarens, F., Duro, L., and Bruno, J., “The oxidative dissolution mechanism of uranium dioxide. The effect of pH and oxygen partial pressure,” in Materials Research Society Symposium Proceedings, 2004, vol. 807, pp. 83–88.Google Scholar
Meca, S., Martí, V., De Pablo, J., Giménez, J., and Casas, I., “UO2 dissolution in the presence of hydrogen peroxide at pH > 11,” Radiochim. Acta, vol. 96, no. 9–11, pp. 535–539, 2008.Google Scholar
Santos, B. G., Noël, J. J., and Shoesmith, D. W., “The effect of pH on the anodic dissolution of SIMFUEL (UO2),” J. Electroanal. Chem., vol. 586, no. 1, pp. 1–11, Jan. 2006.Google Scholar
Santos, B. G., Noël, J. J., and Shoesmith, D. W., “The influence of silicate on the development of acidity in corrosion product deposits on SIMFUEL (UO2),” Corros. Sci., vol. 48, no. 11, pp. 3852–3868, Nov. 2006.CrossRefGoogle Scholar
Santos, B. G., Noël, J. J., and Shoesmith, D. W., “The influence of calcium ions on the development of acidity in corrosion product deposits on SIMFUEL, UO2,” J. Nucl. Mater., vol. 350, no. 3, pp. 320–331, May 2006.CrossRefGoogle Scholar
Ofori, D., Keech, P. G., Noël, J. J., and Shoesmith, D. W., “The influence of deposited films on the anodic dissolution of uranium dioxide,” J. Nucl. Mater., vol. 400, no. 1, pp. 84–93, May 2010.CrossRefGoogle Scholar
Shoesmith, D. W., “Fuel corrosion processes under waste disposal conditions,” J. Nucl. Mater., vol. 282, no. 1, pp. 1–31, Nov. 2000.Google Scholar
Broczkowski, M. E., Noël, J. J., and Shoesmith, D. W., “The influence of dissolved hydrogen on the surface composition of doped uranium dioxide under aqueous corrosion conditions,” J. Electroanal. Chem., vol. 602, no. 1, pp. 8–16, Apr. 2007.Google Scholar