Title:
Chloride Adsorption of Cement Hydrates Combined with Chemical Evolution of Pore Solution
Author(s):
In-Seok Yoon and Tatsuhiko Saeki
Publication:
Materials Journal
Volume:
121
Issue:
5
Appears on pages(s):
51-62
Keywords:
alumina, ferric oxide, monosubstituted (AFm) phase; Ca/Si ratio; calcium-silicate-hydrate (C-S-H) phase; chloride adsorption; Friedel’s salt
DOI:
10.14359/51742037
Date:
9/1/2024
Abstract:
In this study, a chloride adsorption test was performed to depict
the chemical evolution of pore solution for cement hydration. It
was found that the amount of chloride adsorbed by the AFm phase
and the calcium-silicate-hydrate (C-S-H) phase decreased with
the increasing pH of the pore solution. The stability of Friedel’s
salt tended to decrease with the increasing pH of the pore solution.
Notably, in the C-S-H phase, the decrease in the amount of chloride
adsorption resulting from an increase in the pH level was larger
when the Ca/Si ratio was higher. Based on these works, multiple
regression analysis was performed to examine the correlation
between the chloride adsorption density of cement hydrates and
the experimental variables involved, including the pH of the pore
solution and the amount of chloride-ion penetration.
The pH of the pore solution was predicted based on cement hydration and pore-chemistry theories, and these results were combined with the experimental results, considering the changing chemical characteristics of the pore solution during each temporal stage of cement hydration. The amount of chloride-ion adsorption in fly ash (FA) and granulated blast-furnace slag (GBFS) was larger than in ordinary portland cement (OPC) due to the decreased pH of the pore solution resulting from the consumption of calcium hydroxide.
Related References:
1. Yoon, I.-S., and Chang, C., “Quantitative Relationship between Chloride Penetration Depth and Hydraulic Conductivity of Concrete under Hydrostatic Pressure,” Journal of Materials in Civil Engineering, ASCE, V. 34, No. 5, May 2022, p. 04022074. doi: 10.1061/(ASCE)MT.1943-5533.0004198
2. Yoon, I.-S., and Saeki, T., “Mechanism of Chloride Ion Adsorption in Cement Hydrates as per Time-Dependent Behavior,” ACI Materials Journal, V. 118, No. 1, Jan. 2021, pp. 41-53.
3. Florea, M. V. A., and Brouwers, H. J. H., “Chloride Binding Related to Hydration Products: Part I: Ordinary Portland Cement,” Cement and Concrete Research, V. 42, No. 2, Feb. 2012, pp. 282-290. doi: 10.1016/j.cemconres.2011.09.016
4. Hirao, H.; Yamada, K.; Takahashi, H.; and Zibara, H., “Chloride Binding of Cement Estimated by Binding Isotherms of Hydrates,” Journal of Advanced Concrete Technology, V. 3, No. 1, 2005, pp. 77-84. doi: 10.3151/jact.3.77
5. Andrade, C.; Merino, P.; Nóvoa, X. R.; Pérez, M. C.; and Soler, L., “Passivation of Reinforcing Steel in Concrete,” Materials Science Forum, V. 192-194, Aug. 1995, pp. 891-898.
6. Verink, E. D., and Pourbaix, M., “Pitting Potentials versus pH,” Corrosion, V. 27, 1971, p. 495.
7. McPolin, D. O.; Basheer, P. A.; and Long, A. E., “Carbonation and pH in Mortars Manufactured with Supplementary Cementitious Materials,” Journal of Materials in Civil Engineering, ASCE, V. 21, No. 5, May 2009, pp. 217-225. doi: 10.1061/(ASCE)0899-1561(2009)21:5(217)
8. Monteny, J.; Vincke, E.; Beeldens, A.; De Belie, N.; Taerwe, L.; Van Gemert, D.; and Verstraete, W., “Chemical, Microbiological, and In Situ Test Methods for Biogenic Sulfuric Acid Corrosion of Concrete,” Cement and Concrete Research, V. 30, No. 4, Apr. 2000, pp. 623-634. doi: 10.1016/S0008-8846(00)00219-2
9. Sumranwanich, T., and Tangtermsirikul, S., “A Model for Predicting Time-Dependent Chloride Binding Capacity of Cement-Fly Ash Cementitious System,” Materials and Structures, V. 37, No. 6, July 2004, pp. 387-396. doi: 10.1007/BF02479635
10. Shafigh, P.; Yousuf, S.; Ibrahim, Z.; Alsubari, B.; and Asadi, I., “Influence of Fly Ash and GGBFS on the pH Value of Cement Mortar in Different Curing Conditions,” Advances in Concrete Construction, V. 11, No. 5, May 2021, pp. 419-428.
11. Chang, Q., “Electrical Properties,” Colloid and Interface Chemistry for Water Quality Control, Academic Press, Cambridge, MA, 2016, pp. 79-136.
12. van Eijk, R. J., and Brouwers, H. J. H., “Prediction of Hydroxyl Concentrations in Cement Pore Water Using a Numerical Cement Hydration Model,” Cement and Concrete Research, V. 30, No. 11, Nov. 2000, pp. 1801-1806. doi: 10.1016/S0008-8846(00)00413-0
13. Atkins, M.; Glasser, F. P.; and Kindness, A., “Cement Hydrate Phases: Solubility at 25°C,” Cement and Concrete Research, V. 22, No. 2-3, Mar.-May 1992, pp. 241-246.
14. Hosokawa, Y.; Yamada, K.; Johannesson, B. F.; and Nilsson, L.-O., “Reproduction of Chloride Ion Binding in Hardened Cement Paste Using Thermodynamic Equilibrium Models,” Taiheiyo Cement Kenkyu Hokoku, V. 151, 2005, pp. 1-12.
15. Yamaguchi, G., and Takagi, S., “The Analysis of Portland Cement Clinker,” Proceedings of the Fifth International Symposium on the Chemistry of Cement, V. 1, Tokyo, Japan, 1969, pp. 181-218.
16. van Breugel, K., “Simulation of Hydration and Formation of Structure in Hardening Cement-Based Materials,” PhD thesis, Delft University of Technology (TU Delft), Delft, the Netherlands, 1991, 328 pp.
17. Taylor, H. F. W., “A Method for Predicting Alkali Ion Concentrations in Cement Pore Solutions,” Advances in Cement Research, V. 1, No. 1, Oct. 1987, pp. 5-17. doi: 10.1680/adcr.1987.1.1.5
18. Sirisawat, I.; Saengsoy, W.; Baingam, L.; Krammart, P.; and Tangtermsirikul, S., “Durability and Testing of Mortar with Interground Fly Ash and Limestone Cements in Sulfate Solutions,” Construction and Building Materials, V. 64, Aug. 2014, pp. 39-46. doi: 10.1016/j.conbuildmat.2014.04.083
19. Glasser, F. P.; Kindness, A.; and Stronach, S. A., “Stability and Solubility Relationships in AFm Phase: Part I. Chloride, Sulfate and Hydroxide,” Cement and Concrete Research, V. 29, No. 6, June 1999, pp. 861-866. doi: 10.1016/S0008-8846(99)00055-1
20. Bothe, J. V. Jr., and Brown, P. W., “PhreeqC Modeling of Friedel’s Salt Equilibria at 23±1°C,” Cement and Concrete Research, V. 34, No. 6, June 2004, pp. 1057-1063. doi: 10.1016/j.cemconres.2003.11.016
21. Nielsen, E. P.; Herfort, D.; Geiker, M. R.; and Hooton, R. D., “Effect of Solid Solution of AFm Phases on Chloride Binding,” Proceedings of the 11th International Congress on the Chemistry of Cement (ICCC), G. Grieve and G. Owens, eds., Durban, South Africa, 2003, pp. 1497-1505.
22. Nielsen, E. P.; Herfort, D.; and Geiker, M. R., “Binding of Chloride and Alkalis in Portland Cement Systems,” Cement and Concrete Research, V. 35, No. 1, Jan. 2005, pp. 117-123. doi: 10.1016/j.cemconres.2004.05.026
23. Labbez, C.; Nonat, A.; Pochard, I.; and Jönsson, B., “Experimental and Theoretical Evidence of Overcharging of Calcium Silicate Hydrate,” Journal of Colloid and Interface Science, V. 309, No. 2, May 2007, pp. 303-307. doi: 10.1016/j.jcis.2007.02.048
24. Haas, J., “Etude Expérimentale et Modélisation Thermodynamique du Système CaO-SiO2-(Al2O3)-H2O,” PhD thesis, University of Burgundy, Dijon, France, 2012, 199 pp.
25. Tritthart, J., “Chloride Binding in Cement II. The Influence of the Hydroxide Concentration in the Pore Solution of Hardened Cement Paste on Chloride Binding,” Cement and Concrete Research, V. 19, No. 5, Sept. 1989, pp. 683-691. doi: 10.1016/0008-8846(89)90039-2
26. Masel, R. I., Principles of Adsorption and Reaction on Solid Surfaces, John Wiley & Sons, Inc., New York, 1996, 818 pp.
27. De Weerdt, K.; Colombo, A.; Coppola, L.; Justnes, H.; and Geiker, M. R., “Impact of the Associated Cation on Chloride Binding of Portland Cement Paste,” Cement and Concrete Research, V. 68, Feb. 2015, pp. 196-202. doi: 10.1016/j.cemconres.2014.01.027
28. Hansson, C. M.; Frølund, T.; and Markussen, J. B., “The Effect of Chloride Cation Type on the Corrosion of Steel in Concrete by Chloride Salts,” Cement and Concrete Research, V. 15, No. 1, Jan. 1985, pp. 65-73. doi: 10.1016/0008-8846(85)90009-2
29. Plusquellec, G., and Nonat, A., “Interactions between Calcium Silicate Hydrate (C-S-H) and Calcium Chloride, Bromide and Nitrate,” Cement and Concrete Research, V. 90, Dec. 2016, pp. 89-96. doi: 10.1016/j.cemconres.2016.08.002
30. Dhir, R. K., and Jones, M. R., “Development of Chloride-Resisting Concrete Using Fly Ash,” Fuel, V. 78, No. 2, Jan. 1999, pp. 137-142. doi: 10.1016/S0016-2361(98)00149-5
31. Thomas, M. D. A.; Hooton, R. D.; Scott, A.; and Zibara, H., “The Effects of Supplementary Cementitious Materials on Chloride Binding in Hardened Cement Paste,” Cement and Concrete Research, V. 42, No. 1, Jan. 2012, pp. 1-7. doi: 10.1016/j.cemconres.2011.01.001
32. Franco-Luján, V. A.; Mendoza-Rangel, J. M.; Jiménez-Quero, V. G.; and Montes-García, P., “Chloride-Binding Capacity of Ternary Concretes Containing Fly Ash and Untreated Sugarcane Bagasse Ash,” Cement and Concrete Composites, V. 120, July 2021, Article No. 104040. doi: 10.1016/j.cemconcomp.2021.104040
33. Ramezanianpour, A. A., “Natural Pozzolans,” Cement Replacement Materials: Properties, Durability, Sustainability, Springer-Verlag, Berlin, Germany, 2014, pp. 10-46
34. Liu, J.; Ou, G.; Qiu, Q.; Chen, X.; Hong, J.; and Xing, F., “Chloride Transport and Microstructure of Concrete with/without Fly Ash under Atmospheric Chloride Condition,” Construction and Building Materials, V. 146, Aug. 2017, pp. 493-501. doi: 10.1016/j.conbuildmat.2017.04.018
35. Wilson, W.; Gonthier, J. N.; Georget, F.; and Scrivener, K. L., “Insights on Chemical and Physical Chloride Binding in Blended Cement Pastes,” Cement and Concrete Research, V. 156, June 2022, Article No. 106747. doi: 10.1016/j.cemconres.2022.106747
36. Ishida, T.; Miyahara, S.; and Maruya, T., “Chloride Binding Capacity of Mortars Made with Various Portland Cements and Mineral Admixtures,” Journal of Advanced Concrete Technology, V. 6, No. 2, 2008, pp. 287-301. doi: 10.3151/jact.6.287
37. Muthulingam, S., and Rao, B. N., “Chloride Binding and Time-
Dependent Surface Chloride Content Models for Fly Ash Concrete,” Frontiers of Structural and Civil Engineering, V. 10, No. 1, Mar. 2016, pp. 112-120. doi: 10.1007/s11709-015-0322-x