Influence of Chloride Transport Modes and Hydrated Cement Chemistry on Chloride Profile and Binding Mechanisms in Concrete
Publication: Journal of Materials in Civil Engineering
Volume 34, Issue 12
Abstract
A chloride binding model consisting of physical adsorption and chemical ion exchange was proposed. Chemical binding was quantified based on the thermodynamic equilibrium of the relevant hydrated phases while physical adsorption was modeled by a Freundlich-type isotherm. Comparison of the proposed model results with experimental chloride binding data in the literature was found to be satisfactory. The implementation of the model in the Nernst-Planck-Poisson (NPP) reactive transport NPP model accurately predicted the free and total chloride concentration profiles in the analyzed cement paste and concrete specimens. The results of the traditional chloride diffusion model based on Fick’s second law were compared with the NPP model and it was discovered that estimating the apparent diffusion coefficient by a well-established formula and using it in Fick’s model gave a significantly erroneous estimation of the free and total chloride profiles compared to the corresponding experimental data. Finally, in the NPP model it was determined that chloride transport by diffusion was limited to the region near the exposed surface while in the concrete bulk it was dominated by electromigration.
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Data Availability Statement
Some or all data, models, or code generated or used during the study are proprietary or confidential in nature and may only be provided with restrictions. The model or computer code cannot be provided but the output data can be provided upon request.
Acknowledgments
The first author gratefully acknowledges the financial support of McMaster University and the Natural Sciences and Engineering Research Council of Canada (NSERC) in support of this research. The second author wishes to thank NSERC for its financial support of the investigation through its Discovery Grant program, as well as the Tianjin government, the Ministry of Science and Technology of China, and Nankai University for financially supporting the preparation of this manuscript.
References
Alsheet, F. 2020. The Nernst-Planck-Poisson reactive transport model for concrete carbonation and chloride diffusion in carbonated and non-carbonated concrete. Hamilton, ON: McMaster Univ.
Alsheet, F., and A. G. Razaqpur. 2020. “Quantification of electromigration and chemical activity effects on reactive transport of chloride ions in concrete pore solution.” ACI Mater. J. 117 (6): 77–88. https://doi.org/10.14359/51728126.
Angst, U., B. Elsener, C. K. Larsen, and Ø. Vennesland. 2009. “Critical chloride content in reinforced concrete—A review.” Cem. Concr. Res. 39 (12): 1122–1138. https://doi.org/10.1016/j.cemconres.2009.08.006.
Angst, U., A. Rønnquist, B. Elsener, C. K. Larsen, and Ø. Vennesland. 2011. “Probabilistic considerations on the effect of specimen size on the critical chloride content in reinforced concrete.” Corros. Sci. 53 (1): 177–187. https://doi.org/10.1016/J.CORSCI.2010.09.017.
Ann, K. Y., and H. W. Song. 2007. “Chloride threshold level for corrosion of steel in concrete.” Corros. Sci. 49 (11): 4113–4133. https://doi.org/10.1016/j.corsci.2007.05.007.
Arya, C., N. R. Buenfeld, and J. B. Newman. 1990. “Factors influencing chloride-binding in concrete.” Cem. Concr. Res. 20 (2): 291–300. https://doi.org/10.1016/0008-8846(90)90083-A.
Arya, C., and J. B. Newman. 1990. “An assessment of four methods of determining the free chloride content of concrete.” Mater. Struct. 23 (5): 319–330. https://doi.org/10.1007/BF02472710.
Arya, C., and Y. Xu. 1995. “Effect of cement type on chloride binding and corrosion of steel in concrete.” Cem. Concr. Res. 25 (4): 893–902. https://doi.org/10.1016/0008-8846(95)00080-V.
Azad, V. J., and O. B. Isgor. 2017. “Modeling chloride ingress in concrete with thermodynamically calculated chemical binding.” Int. J. Adv. Eng. Sci. Appl. Math. 9 (2): 97–108. https://doi.org/10.1007/s12572-017-0189-2.
Baroghel-Bouny, V., X. Wang, M. Thiery, M. Saillio, and F. Barberon. 2012. “Prediction of chloride binding isotherms of cementitious materials by ‘analytical’ model or ‘numerical’ inverse analysis.” Cem. Concr. Res. 42 (9): 1207–1224. https://doi.org/10.1016/j.cemconres.2012.05.008.
Bazant, Z. P. 1979. “Physical model for steel corrosion in concrete sea structures—Theory.” ASCE J. Struct. Div. 105 (6): 1137–1153. https://doi.org/10.1061/JSDEAG.0005168.
Beaudoin, J., and I. Odler. 2019. “Hydration, setting and hardening of Portland cement.” In Lea’s chemistry of cement and concrete, 157–250. London: Butterworth-Heinemann.
Berner, U. R. 1992. “Evolution of pore water chemistry during degradation of cement in a radioactive waste repository environment.” Waste Manage. 12 (2): 201–219. https://doi.org/10.1016/0956-053X(92)90049-O.
Birnin-Yauri, U. A., and F. P. Glasser. 1998. “Friedel’s salt, Ca2Al(OH)6(Cl,OH) · 2H2O: Its solid solutions and their role in chloride binding.” Cem. Concr. Res. 28 (12): 1713–1723. https://doi.org/10.1016/S0008-8846(98)00162-8.
Bothe, J. V., and P. W. Brown. 2004. “PhreeqC modeling of Friedel’s salt equilibria at 23±1 °C.” Cem. Concr. Res. 34 (6): 1057–1063. https://doi.org/10.1016/j.cemconres.2003.11.016.
Brown, P., and J. Bothe. 2004. “The system CaO-Al2O3-CaCl2-H2O at 23±2 °C and the mechanisms of chloride binding in concrete.” Cem. Concr. Res. 34 (9): 1549–1553. https://doi.org/10.1016/j.cemconres.2004.03.011.
Brown, P. W., and S. Badger. 2000. “Distributions of bound sulfates and chlorides in concrete subjected to mixed NaCl, MgSO4, Na2SO4 attack.” Cem. Concr. Res. 30 (10): 1535–1542. https://doi.org/10.1016/S0008-8846(00)00386-0.
Chatterji, S. 1994. “Transportation of ions through cement based materials. Part 2. Adaptation of the fundamental equations and relevant comments.” Cem. Concr. Res. 24 (6): 1010–1014. https://doi.org/10.1016/0008-8846(94)90023-X.
Collepardi, M., A. Marcialis, and R. Turriziani. 1972. “Penetration of chloride ions into cement pastes and concretes.” J. Am. Ceram. Soc. 55 (10): 534–535. https://doi.org/10.1111/j.1151-2916.1972.tb13424.x.
Delagrave, A., J. Marchand, J. P. Ollivier, S. Julien, and K. Hazrati. 1997. “Chloride binding capacity of various hydrated cement paste systems.” Adv. Cem. Based Mater. 6 (1): 28–35. https://doi.org/10.1016/S1065-7355(97)90003-1.
De Weerdt, K., G. Plusquellec, A. Belda Revert, M. R. Geiker, and B. Lothenbach. 2019. “Effect of carbonation on the pore solution of mortar.” Cem. Concr. Res. 118 (Apr): 38–56. https://doi.org/10.1016/j.cemconres.2019.02.004.
Dilnesa, B. Z., E. Wieland, B. Lothenbach, R. Dähn, and K. L. Scrivener. 2014. “Fe-containing phases in hydrated cements.” Cem. Concr. Res. 58 (Apr): 45–55. https://doi.org/10.1016/j.cemconres.2013.12.012.
Ehlen, M. A., E. C. Bentz, and M. D. A. Thomas. 2009. “Life-365 service life prediction ModelTM Version 2.0.” Concr. Int. 31 (5): 41–46.
Farnam, Y., S. Dick, A. Wiese, J. Davis, D. Bentz, and J. Weiss. 2015. “The influence of calcium chloride deicing salt on phase changes and damage development in cementitious materials.” Cem. Concr. Compos. 64 (Sep): 1–15. https://doi.org/10.1016/j.cemconcomp.2015.09.006.
Florea, M. V. A., and H. J. H. Brouwers. 2012. “Chloride binding related to hydration products: Part I: Ordinary Portland cement.” Cem. Concr. Res. 42 (2): 282–290. https://doi.org/10.1016/j.cemconres.2011.09.016.
Florea, M. V. A., and H. J. H. Brouwers. 2014. “Modelling of chloride binding related to hydration products in slag-blended cements.” Constr. Build. Mater. 64 (Aug): 421–430. https://doi.org/10.1016/j.conbuildmat.2014.04.038.
Georget, F., C. Bénier, W. Wilson, and K. Scrivener. 2021. “Chloride sorption by C-S-H quantified by SEM-EDX image analysis.” Cem. Concr. Res. 152 (Feb): 106656. https://doi.org/10.1016/j.cemconres.2021.106656.
Glass, G. K., and N. R. Buenfeld. 1997. “The presentation of the chloride threshold level for corrosion of steel in concrete.” Corros. Sci. 39 (5): 1001–1013. https://doi.org/10.1016/S0010-938X(97)00009-7.
Glosser, D., O. Burkan Isgor, and W. Jason Weiss. 2020. “Non-equilibrium thermodynamic modeling framework for ordinary portland cement/supplementary cementitious material systems.” ACI Mater. J. 117 (6): 111–123. https://doi.org/10.14359/51728127.
Heath, M. T. 2018. Scientific computing: An introductory survey. New York: McGraw-Hill.
Henocq, P. 2005. Modélisation des interactions ioniques à la surface des Silicates de Calcium Hydratés. Québec: Université Laval.
Hirao, H., K. Yamada, H. Takahashi, and H. Zibara. 2005. “Chloride binding of cement estimated by binding isotherms of hydrates.” J. Adv. Concr. Technol. 3 (1): 77–84. https://doi.org/10.3151/jact.3.77.
Isgor, B. O., and A. G. Razaqpur. 2004. “Finite element modeling of coupled heat transfer, moisture transport and carbonation processes in concrete structures.” Cem. Concr. Compos. 26 (1): 57–73. https://doi.org/10.1016/S0958-9465(02)00125-7.
Izquierdo, D., C. Alonso, C. Andrade, and M. Castellote. 2004. “Potentiostatic determination of chloride threshold values for rebar depassivation.” Electrochim. Acta 49 (17–18): 2731–2739. https://doi.org/10.1016/j.electacta.2004.01.034.
Jain, A., B. Gencturk, M. Pirbazari, M. Dawood, A. Belarbi, M. G. Sohail, and R. Kahraman. 2021. “Influence of pH on chloride binding isotherms for cement paste and its components.” Cem. Concr. Res. 143 (May): 106378. https://doi.org/10.1016/j.cemconres.2021.106378.
Jones, M. R., D. E. Macphee, J. A. Chudek, G. Hunter, R. Lannegrand, R. Talero, and S. N. Scrimgeour. 2003. “Studies using 27Al MAS NMR of AFm and AFt phases and the formation of Friedel’s salt.” Cem. Concr. Res. 33 (2): 177–182. https://doi.org/10.1016/S0008-8846(02)00901-8.
Kulik, D. A., T. Wagner, S. V. Dmytrieva, G. Kosakowski, F. F. Hingerl, K. V. Chudnenko, and U. R. Berner. 2013. “GEM-Selektor geochemical modeling package: Revised algorithm and GEMS3K numerical kernel for coupled simulation codes.” Comput. Geosci. 17 (1): 1–24. https://doi.org/10.1007/s10596-012-9310-6.
Loser, R., B. Lothenbach, A. Leemann, and M. Tuchschmid. 2010. “Chloride resistance of concrete and its binding capacity—Comparison between experimental results and thermodynamic modeling.” Cem. Concr. Compos. 32 (1): 34–42. https://doi.org/10.1016/j.cemconcomp.2009.08.001.
Lothenbach, B., D. A. Kulik, T. Matschei, M. Balonis, L. Baquerizo, B. Dilnesa, G. D. Miron, and R. J. Myers. 2019. “Cemdata18: A chemical thermodynamic database for hydrated Portland cements and alkali-activated materials.” Cem. Concr. Res. 115 (Apr): 472–506. https://doi.org/10.1016/j.cemconres.2018.04.018.
Lothenbach, B., G. Le Saout, M. Ben Haha, R. Figi, and E. Wieland. 2012a. “Hydration of a low-alkali CEM III/B–SiO2 cement (LAC).” Cem. Concr. Res. 42 (2): 410–423. https://doi.org/10.1016/j.cemconres.2011.11.008.
Lothenbach, B., T. Matschei, G. Möschner, and F. P. Glasser. 2008. “Thermodynamic modelling of the effect of temperature on the hydration and porosity of Portland cement.” Cem. Concr. Res. 38 (1): 1–18. https://doi.org/10.1016/j.cemconres.2007.08.017.
Lothenbach, B., L. Pelletier-Chaignat, and F. Winnefeld. 2012b. “Stability in the system CaO–Al2O3–H2O.” Cem. Concr. Res. 42 (12): 1621–1634. https://doi.org/10.1016/j.cemconres.2012.09.002.
Lothenbach, B., and M. Zajac. 2019. “Application of thermodynamic modelling to hydrated cements.” Cem. Concr. Res. 123 (Sep): 105779. https://doi.org/10.1016/j.cemconres.2019.105779.
Luping, T., and L. O. Nilsson. 1993. “Chloride binding capacity and binding isotherms of OPC pastes and mortars.” Cem. Concr. Res. 23 (2): 247–253. https://doi.org/10.1016/0008-8846(93)90089-R.
Luping, T., and L.-O. Nilsson. 1997. “Chloride binding isotherms—An approach by applying the modified BET equation.” In Proc., RILEM Int. Workshop on Chloride Penetration into Concrete. Saint-Rémy-lès-Chevreuse, France: RILEM Publications SARL.
Martín-Pérez, B., S. J. Pantazopoulou, and M. D. A. Thomas. 2001. “Numerical solution of mass transport equations in concrete structures.” Comput. Struct. 79 (13): 1251–1264. https://doi.org/10.1016/S0045-7949(01)00018-9.
Masi, M., D. Colella, G. Radaelli, and L. Bertolini. 1997. “Simulation of chloride penetration in cement-based materials.” Cem. Concr. Res. 27 (10): 1591–1601. https://doi.org/10.1016/S0008-8846(97)00200-7.
Mohammed, T. U., T. Yamaji, and H. Hamada. 2002. “Chloride diffusion, microstructure, and mineralogy of concrete after 15 years of exposure in tidal environment.” ACI Mater. J. 99 (3): 256–263. https://doi.org/10.14359/11971.
Neville, A. 1995. “Chloride attack of reinforced concrete: An overview.” Mater. Struct. 28 (2): 63–70. https://doi.org/10.1007/BF02473172.
Papadakis, V. G. 1999. “Experimental investigation and theoretical modeling of silica fume activity in concrete.” Cem. Concr. Res. 29 (1): 79–86. https://doi.org/10.1016/S0008-8846(98)00171-9.
Papadakis, V. G. 2000. “Effect of supplementary cementing materials on concrete resistance against carbonation and chloride ingress.” Cem. Concr. Res. 30 (2): 291–299. https://doi.org/10.1016/S0008-8846(99)00249-5.
Parrot, L. J., and D. C. Killoh. 1984. Prediction of cement hydration. London: British Ceramic Soc.
Pitzer, K. S. 1991. Activity coefficients in electrolyte solutions. Boca Raton, FL: CRC Press.
Powers, T. C., and T. L. Brownyard. 1947. “Studies of the physical properties of hardened portland cement paste.” J. Am. Concr. Inst. 43 (9): 101–132.
Ratkowsky, D. A. 1990. Handbook of nonlinear regression models. New York: Marcel Dekker.
Saetta, A. V., R. V. Scotta, and R. V. Vitaliani. 1993. “Analysis of chloride diffusion into partially saturated concrete.” ACI Mater. J. 90 (5): 441–451.
Samson, E., G. Lemaire, J. Marchand, and J. J. Beaudoin. 1999. “Modeling chemical activity effects in strong ionic solutions.” Comput. Mater. Sci. 15 (3): 285–294. https://doi.org/10.1016/S0927-0256(99)00017-8.
Samson, E., and J. Marchand. 2006. “Multiionic approaches to model chloride binding in cementitious materials.” In Proc., 2nd Int. RILEM Symposium on Advances in Concrete through Science and Engineering, 101–122. Québec: RILEM Publication.
Samson, E., and J. Marchand. 2007. “Modeling the transport of ions in unsaturated cement-based materials.” Comput. Struct. 85 (23): 1740–1756. https://doi.org/10.1016/j.compstruc.2007.04.008.
Segerlind, L. J. 1984. Applied finite element analysis. New York: Wiley.
Sergi, G., S. W. Yu, and C. L. Page. 1992. “Diffusion of chloride and hydroxyl ions in cementitious materials exposed to a saline environment.” Mag. Concr. Res. 44 (158): 63–69. https://doi.org/10.1680/macr.1992.44.158.63.
Suraneni, P., J. Monical, E. Unal, Y. Farnam, and J. Weiss. 2017. “Calcium oxychloride formation potential in cementitious pastes exposed to blends of deicing salt.” ACI Mater. J. 114 (4): 631–641. https://doi.org/10.14359/51689607.
Suryavanshi, A. K., J. D. Scantlebury, and S. B. Lyon. 1996. “Mechanism of Friedel’s salt formation in cements rich in tri-calcium aluminate.” Cem. Concr. Res. 26 (5): 717–727. https://doi.org/10.1016/S0008-8846(96)85009-5.
Suryavanshi, A. K., J. D. Scantlebury, and S. B. Lyon. 1998. “Corrosion of reinforcement steel embedded in high water-cement ratio concrete contaminated with chloride.” Cem. Concr. Compos. 20 (4): 263–281. https://doi.org/10.1016/S0958-9465(98)00018-3.
Truc, O. 2000. “Prediction of chloride penetration into saturated concrete multi-species approach.” Doctoral dissertation, Dept. of Building Materials, Chalmers Univ. of Technology, Gothenburg, Sweden.
Tuutti, K. 1982. Corrosion of steel in concrete. Stockholm, Sweden: Swedish Cement and Concrete Research Institute.
Zhang, W., and H. Ba. 2012. “Effect of ground granulated blast-furnace slag (GGBFS) and silica fume (SF) on chloride migration through concrete subjected to repeated loading.” Sci. China Technol. Sci. 55 (11): 3102–3108. https://doi.org/10.1007/s11431-012-5027-y.
Zibara, H. 2001. Binding of external chlorides by cement pastes. Toronto: Univ. of Toronto.
Zuquan, J., S. Wei, Z. Yunsheng, J. Jinyang, and L. Jianzhong. 2007. “Interaction between sulfate and chloride solution attack of concretes with and without fly ash.” Cem. Concr. Res. 37 (8): 1223–1232. https://doi.org/10.1016/j.cemconres.2007.02.016.
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Journal of Materials in Civil Engineering
Volume 34 • Issue 12 • December 2022
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© 2022 American Society of Civil Engineers.
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Received: Oct 20, 2021
Accepted: Mar 30, 2022
Published online: Oct 10, 2022
Published in print: Dec 1, 2022
Discussion open until: Mar 10, 2023
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