Contribution of the Tricalcium Silicate Hydration Products to the Formation of Radiolytic H2: A Systemic Approach
Source abstract
Abstract
Because they contain residual water, cementitious materials produce radiolytic dihydrogen under irradiation, which can pose a safety concern for some nuclear applications. The estimation of H2 emissions by current models takes into account the contribution of pore water but not that of solid hydrates, which is considered negligible. Gamma irradiation (dose rate of 359 Gy h-1 up to 6 months in a closed system under Ar gas) of hydrated tricalcium silicate pastes, the main constituent of Portland cement, shows however an initial contribution of solid hydrates to H2 formation. A systemic study combining the source term of solid hydrates and the pore water radiolysis using simulation shows that the primary radiolytic yield devoted to portlandite and cementitious C-S-H (together) is of the order of 2.8 × 10-8 mol J-1, and that the contribution of the solid phases is decreasing and becomes negligible in the long term, suggesting a saturation effect with dose. Even if limited in time, the effect of the additional H2 source term is very sensitive on the radiolysis of the pore water with the very strong solicitation of the recycling reaction chain (equivalent to the Allen chain in basic medium) and leads to a frankly reducing medium (Eh ≈ − 470 mV NHE).
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Research context
OpenAlex topics: Concrete and Cement Materials Research · Nuclear materials and radiation effects · Concrete Properties and Behavior
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
Affiliations
Université Paris-Saclay, CEA, Service d’Etude du Comportement des Radionucléides, 91191, Gif-sur-Yvette, France.
References (31)
Show source-provided references
1. 1) Acher, L., (2017). “Etude du comportement sous irradiation γ et électronique de matrices cimentaires et de leurs hydrates constitutifs.” Thesis (PhD). Université Paris-Saclay. (in French)
2. 2) Aierken, Y., Sahin, H., Iyikanat, F., Horzum, S., Suslu, A., Chen, B., Senger, R. T., Tongay, S. and Peeters, F. M., (2015). “Portlandite crystal: Bulk, bilayer, and monolayer structures.” Physical Review B, 91, Article ID 245413.10.1103/PhysRevB.91.245413 ↗
3. 3) Allen, A. J., Thomas, J. J. and Jennings, H. M., (2007). “Composition and density of nanoscale calcium–silicate–hydrate in cement.” Nature Materials, 6(4), 311-316.10.1038/nmat1871 ↗
4. 4) Allen, A. O., (1948). “Radiation chemistry of aqueous solutions.” Journal of Physical and Colloid Chemistry, 52(3), 479-490.10.1021/j150459a009 ↗
5. 5) Bouniol, P., (2004). “Etat des connaissances sur la radiolyse de l’eau dans les colis de déchets cimentés et son approche par simulation (Report CEA-R-6069).” Saclay, France: Commissariat à l’Energie Atomique. (in French)
6. 6) Bouniol, P. and Aspart, A., (1998). “Disappearance of oxygen in concrete under irradiation: The role of peroxides in radiolysis.” Cement and Concrete Research, 28(11), 1669-1681.10.1016/S0008-8846(98)00138-0 ↗
7. 7) Bouniol, P. and Bjergbakke, E., (2008). “A comprehensive model to describe radiolytic processes in cement medium.” Journal of Nuclear Materials, 372(1), 1-15.10.1016/j.jnucmat.2006.10.004 ↗
8. 8) Bouniol, P., Guillot, W., Dauvois, V., Dridi, W. and Le Caër, S., (2018). “Original behavior of pore water radiolysis in cement-based materials containing sulfide: Coupling between experiments and simulations.” Radiation Physics and Chemistry, 150, 172-181.10.1016/j.radphyschem.2018.04.021 ↗
9. 9) Bouniol, P., Muzeau, B. and Dauvois, V., (2013). “Experimental evidence of the influence of iron on pore water radiolysis in cement-based materials.” Journal of Nuclear Materials, 437(1-3), 208-215.10.1016/j.jnucmat.2013.02.018 ↗
10. 10) Brouwers, H. J. H., (2004). “The work of Powers and Brownyard revisited: Part 1.” Cement and Concrete Research, 34(9), 1697-1716.10.1016/j.cemconres.2004.05.031 ↗
11. 11) Brouwers, H. J. H., (2005). “The work of Powers and Brownyard revisited: Part 2.” Cement and Concrete Research, 35(10), 1922-1936.10.1016/j.cemconres.2005.04.009 ↗
12. 12) Brun, E., Damian, F., Diop, C. M., Dumonteil, E., Hugot, F. X., Jouanne, C., Lee, Y. K., Malvagi, F., Mazzolo, A., Petit, O., Trama, J. C., Visonneau, T. and Zoia, A., (2015). “Tripoli-4, CEA, EDF and AREVA reference Monte Carlo code.” Annals of Nuclear Energy, 82, 151-160.10.1016/j.anucene.2014.07.053 ↗
13. 13) Chen, J. J., Thomas, J. J., Taylor, H. F. W. and Jennings, H. M., (2004). “Solubility and structure of calcium silicate hydrate.” Cement and Concrete Research, 34(98), 1499-1519.10.1016/j.cemconres.2004.04.034 ↗
14. 14) Christensen, H. and Bjergbakke, E., (1984). “Radiolysis of concrete (Report No. STUDSVIK/NW-83/434).” Nyköping, Sweden: Studsvik AB.
15. 15) Elliot, A. J. and Bartels, D. M., (2009). “The reaction set, rate constants and g-values for the simulation of the radiolysis of light water over the range 20° to 350°C based on information available in 2008 (Report No. AECL-153-127160-450-001).” Mississauga, Ontario,Canada: Atomic Energy of Canada Limited.
16. 16) Haïssinsky, M., (1967). “Rendements radiolytiques primaires en solution aqueuse, neutre ou alcaline.” In: Actions Chimiques et Biologiques Des Radiations. Paris: Masson et Cie, 131-179. (in French)
17. 17) Hayon, E., (1965). “Radical and molecular yields in the radiolysis of alkaline aqueous solutions.” Transactions of the Faraday Society, 61, 734-743.10.1039/tf9656100734 ↗
18. 18) Hubbell, J. H. and Seltzer, S. M., (2004). “Tables of x-ray mass attenuation coefficients and mass energy-absorption coefficients, v. 1.4 [online].” Gaithersburg, Maryland, USA, National Institute of Standards and Technology. Available from: .
19. 19) Ishikawa, S., Maruyama, I., Takizawa, M., Etoh, J., Kontani, O. and Sawada, S., (2019). “Hydrogen production and the stability of hardened cement paste under gamma irradiation.” Journal of Advanced Concrete Technology, 17(12), 673-685.10.3151/jact.17.673 ↗
20. 20) Jennings, H. M., (2008). “Refinements to colloid model of C-S-H in cement: CM-II.” Cement and Concrete Research, 38(3), 275-289.10.1016/j.cemconres.2007.10.006 ↗
21. 21) Jensen, O. M. and Hansen, P. F., (2001). “Water-entrained cement-based materials I: Principles and theoretical background.” Cement and Concrete Research, 31(4), 647-654.10.1016/S0008-8846(01)00463-X ↗
22. 22) Kirkegaard, P., Bjergbakke, E. and Olsen, J. V., (2008). “CHEMSIMUL: A chemical kinetics software package (Report No. Risø-R-1630EN).” Roksilde, Denmark: Risø National Laboratory for Sustainable Energy.
23. 23) Koppenol, W. H., Stanbury, D. M. and Bounds, P. L., (2010). “Electrode potentials of partially reduced oxygen species, from dioxygen to water.” Free Radical Biology and Medicine, 49(3), 317-322.10.1016/j.freeradbiomed.2010.04.011 ↗
24. 24) LaVerne, J. A. and Tandon, L., (2005). “H2 and Cl2 production in the radiolysis of calcium and magnesium chlorides and hydroxides.” Journal of Physical Chemistry A, 109(12), 2861-2865.10.1021/jp044166o ↗
25. 25) Le Caër, S., Dezerald, L., Boukari, K., Lainé, M., Taupin, S., Kavanagh, R. M., Johnston, C. S. N., Foy, E., Charpentier, T., Krakowiak, K. J., Pellenq, R. J. M., Ulm, F. J., Tribello, G. A., Kohanoff, J. and Saúl, A., (2017). “Production of H2 by water radiolysis in cement paste under electron irradiation: A joint experimental and theoretical study.” Cement and Concrete Research, 100, 110-118.10.1016/j.cemconres.2017.05.022 ↗
26. 26) Locher, F. W., (1966). “Stoichiometry of tricalcium silicate hydration.” In: Highway Research Board Special Report No. 90. Washington DC: US Highway Research Board, 300-308.
27. 27) Lothenbach, B. and Nonat, A., (2015). “Calcium silicate hydrates: Solid and liquid phase composition.” Cement and Concrete Research, 78A, 57-70.10.1016/j.cemconres.2015.03.019 ↗
28. 28) Offermann, P., (1988). “Calculation of the radiolytic gas production in cemented waste.” MRS Online Proceedings Library, 127, 461-468.10.1557/PROC-127-461 ↗
29. 29) Roosz, C., Gaboreau, S., Grangeon, S., Prêt, D., Montouillout, V., Maubec, N., Ory, S., Blanc, P., Vieillard, P. and Henocq, P., (2016). “Distribution of water in synthetic calcium silicate hydrates.” Langmuir, 32(27), 6794-6805.10.1021/acs.langmuir.6b00878 ↗
30. 30) Tajuelo Rodriguez, E., Hunnicutt, W. A., Mondal, P. and Le Pape, Y., (2019). “Examination of gamma-irradiated calcium silicate hydrates. Part I: Chemical-structural properties.” Journal of the American Ceramics Society, 103(1), 558-568.10.1111/jace.16515 ↗
31. 31) Yin, C., Dannoux-Papin, A., Haas, J. and Renault, J. P., (2019). “Influence of calcium to silica ratio on H2 gas production in calcium silicate hydrate.” Radiation Physics and Chemistry, 162, 66-71.10.1016/j.radphyschem.2019.04.035 ↗