Effects of Aluminum Incorporation in Tobermorite Structure on Chloride Diffusion: A Molecular Dynamics Simulation Study

Document Type : Research Papers


Department of Civil Engineering, Shahid Rajaee Teacher Training University, Tehran, Iran


In this paper, the effects of different aluminum to silicon ratios in silicate chains of calcium silicate hydrates (C-S-H) are evaluated on the diffusion coefficient of chloride ions by molecular dynamics method. Tobermorite is a crystalline phase that is used for studying C-S-H properties in nano scale, because of its analogous chemical composition to C-S-H. Aluminum incorporation in C-S-H and the formation of calcium aluminosilicate hydrates (C-A-S-H) is due to both of hydration of tricalcium aluminate (C3A) in portland cement and aluminum oxides in pozzolans. There exist different Al/Si ratios in the tetrahedral chains of C-A-S-H depending on available aluminum oxides in cementitious raw materials. In order to compare the simulation results with previously-published experimental researches on cement pastes, a novel method is introduced here to calculate Al/Si ratio in tetrahedral chains of C-A-S-H using pozzolan replacement ratio in cementitious paste. MK (metakaolin) and FC3R (Fluid Catalytic Cracking Catalyst Residue) are the pozzolans that are used to validate the obtained results in this paper. Results showed that diffusion coefficients of chloride ions in C-A-S-H decrease by Al/Si ratio increasing in the tetrahedral chains as it was observed experimentally in previous researches.


Abdolhosseini Qomi, M.J., Ulm, F.J. and Pellenq, R.J.M. (2012). "Evidence on the dual nature of aluminum in the calcium‐silicate‐hydrates based on atomistic simulations", Journal of the American Ceramic Society, 95(3), 1128-1137.
Accelrys, I. (2012). Materials studio, Accelrys Software Inc.
Al-Ostaz, A., Wu, W., Cheng, A.-D. and Song, C. (2010). "A molecular dynamics and microporomechanics study on the mechanical properties of major constituents of hydrated cement", Composites Part B: Engineering, 41(7), 543-549.
Andersen, M.D., Jakobsen, H.J. and Skibsted, J. (2006). "A new aluminium-hydrate species in hydrated portland cements characterized by 27 al and 29 si mas nmr spectroscopy", Cement and Concrete Research, 36(1), 3-17.
Ann, K., Kim, T.-S., Kim, J. and Kim, S.-H. (2010). "The resistance of high alumina cement against corrosion of steel in concrete", Construction and Building Materials, 24(8), 1502-1510.
Balonis, M., Sant, G., and Isgor, O.B. (2019). "Mitigating steel corrosion in reinforced concrete using functional coatings, corrosion inhibitors, and atomistic simulations", Cement and Concrete Composites, 101, 15-23.
Bertolini, L., Elsener, B., Pedeferri, P., Redaelli, E. and Polder, R.B. (2013). Corrosion of steel in concrete: Prevention, diagnosis, repair, John Wiley & Sons.
Bonaccorsi, E., Merlino, S. and Kampf, A.R. (2005). "The crystal structure of tobermorite 14 å (plombierite), A C–S–H phase", Journal of the American Ceramic Society, 88(3), 505-512.
Caneda-Martínez, L., Frías, M., Medina, C., de Rojas, M.I.S., Rebolledo, N. and Sánchez, J. (2018). "Evaluation of chloride transport in blended cement mortars containing coal mining waste", Construction and Building Materials, 190, 200-210.
Ding, J.-T. and Li, Z. (2002). "Effects of metakaolin and silica fume on properties of concrete", ACI Materials Journal, 99(4), 393-398.
Einstein, A. (1956). Investigations on the theory of the brownian movement, Courier Corporation.
Farahani, A., Taghaddos, H. and Shekarchi, M. (2018). "Chloride diffusion modeling in pozzolanic concrete in marine site", ACI Materials Journal, 115(4), 509-518.
Faucon, P., Charpentier, T., Nonat, A. and Petit, J. (1998). "Triple-quantum two-dimensional 27 al magic angle nuclear magnetic resonance study of the aluminum incorporation in calcium silicate hydrates", Journal of the American Chemical Society, 120(46), 12075-12082.
Faucon, P., Delagrave, A., Petit, J., Richet, C., Marchand, J. and Zanni, H. (1999a). "Aluminum incorporation in calcium silicate hydrates (C−S−H) depending on their ca/si ratio", The Journal of Physical Chemistry B, 103(37), 7796-7802.
Faucon, P., Jacquinot, J.F., Delaue, J.M. and Virlet, J. (1997). "Molecular dynamics simulation of al3+ and na+ substitutions in the tobermorite structure", Philosophical Magazine B, 75(5), 769-783.
Faucon, P., Petit, J.C., Charpentier, T., Jacquinot, J.F. and Adenot, F. (1999b). "Silicon substitution for aluminum in calcium silicate hydrates", Journal of the American Ceramic Society, 82(5), 1307-1312.
Geng, G., Myers, R.J., Li, J., Maboudian, R., Carraro, C., Shapiro, D.A. and Monteiro, P.J. (2017). "Aluminum-induced dreierketten chain cross-links increase the mechanical properties of nanocrystalline calcium aluminosilicate hydrate", Scientific Reports, 7, 44032.
Hajilar, S. and Shafei, B. (2015). "Nano-scale investigation of elastic properties of hydrated cement paste constituents using molecular dynamics simulations", Computational Materials Science, 101, 216-226.
Hou, D. and Li, Z., (2014). "Molecular dynamics study of water and ions transport in nano-pore of layered structure: A case study of tobermorite", Microporous and Mmesoporous Materials, 195, 9-20.
Hou, D., Li, Z. and Zhao, T. (2015). "Reactive force field simulation on polymerization and hydrolytic reactions in calcium aluminate silicate hydrate (C–A–S–H) gel: Structure, dynamics and mechanical properties", RSC Advances, 5(1), 448-461.
Hou, D., Zhu, Y., Lu, Y. and Li, Z. (2014). "Mechanical properties of calcium silicate hydrate (C–S–H) at nano-scale: A molecular dynamics study", Materials Chemistry and Physics, 146(3), 503-511.
Jones, M., Macphee, D., Chudek, J., Hunter, G., Lannegrand, R., Talero, R. and Scrimgeour, S. (2003). "Studies using 27 al mas nmr of af m and af t phases and the formation of friedel's salt", Cement and Concrete Research, 33(2), 177-182.
Justnes, H. (1998). "A review of chloride binding in cementitious systems", Nordic Concrete Research-Publications, 21, 48-63.
Leach, A.R. (2001). Molecular modelling: Principles and applications, Pearson Education.
Madani, S. H. and Kooshafar, M. (2017). "Influential mechanisms and potential applications of nano-silicas in cement composites", Civil Engineering Infrastructures Journal, 50(2), 375-393.
Madani, H., Ramezanianpour, A.A., Shahbazinia, M., Bokaeian, V. and Ahari, S. (2016). "The influence of ultrafine filler materials on mechanical and durability characteristics of concrete", Civil Engineering Infrastructures Journal, 49(2), 251-262.
Manzano Moro, H. (2014). Atomistic simulation studies of the cement paste components, Servicio Editorial de la Universidad del País Vasco/Euskal Herriko Unibertsitatearen Argitalpen Zerbitzua.
Mehta, P.K. and Monteiro, P.J. (1993). Concrete structures, properties and materials, Englewood Cliffs, 9.
Merlino, S., Bonaccorsi, E. and Armbruster, T. (1999). "Tobermorites: Their real structure and order-disorder (od) character", American Mineralogist, 84(10), 1613-1621.
Mindess, S., Young, J.F. and Darwin, D. (2003). Concrete, Pearson Educations.
Payá, J., Monzó, J., Borrachero, M. and Velázquez, S. (2003). "Evaluation of the pozzolanic activity of fluid catalytic cracking catalyst residue (fc3r). Thermogravimetric analysis studies on fc3r-portland cement pastes", Cement and Concrete Research, 33(4), 603-609.
Pivonka, P., Hellmich, C. and Smith, D. (2004). "Microscopic effects on chloride diffusivity of cement pastes, A scale-transition analysis", Cement and Concrete Research, 34(12), 2251-2260.
Powers, T.C., Copeland, L.E. and Mann, H. (1959). Capillary continuity or discontinuity in cement pastes, Portland Cement Association.
Qomi, M.A., Krakowiak, K.J., Bauchy, M., Stewart, K., Shahsavari, R., Jagannathan, D., Brommer, D.B., Baronnet, A., Buehler, M.J. and Yip, S. (2014). "Combinatorial molecular optimization of cement hydrates", Nature Communications, 5, 4960.
Ramezanianpour, A. and Jovein, H.B. (2012). "Influence of metakaolin as supplementary cementing material on strength and durability of concretes", Construction and Building Materials, 30, 470-479.
Richardson, I.G., Brough, A.R., Brydson, R., Groves, G.W. and Dobson, C.M. (1993). "Location of aluminum in substituted calcium silicate hydrate (C-S-H) gels as determined by 29 Si and 27 Al nmr and eels", Journal of the American Ceramic Society, 76(9), 2285-2288.
Shekarchi, M., Bonakdar, A., Bakhshi, M., Mirdamadi, A. and Mobasher, B. (2010). "Transport properties in metakaolin blended concrete", Construction and Building Materials, 24(11), 2217-2223.
Sun, G., Young, J.F. and Kirkpatrick, R.J. (2006). "The role of al in C–S–H: Nmr, xrd, and compositional results for precipitated samples", Cement and Concrete Research, 36(1), 18-29.
Sun, H. (1998). "Compass: An ab initio force-field optimized for condensed-phase applications overview with details on alkane and benzene compounds", The Journal of Physical Chemistry B, 102(38), 7338-7364.
Tadayon, M.H., Shekarchi, M. and Tadayon, M. (2016). "Long-term field study of chloride ingress in concretes containing pozzolans exposed to severe marine tidal zone", Construction and Building Materials, 123, 611-616.
Tarighat, A. and Zehtab, B. (2016). "Structural reliability of reinforced concrete beams/columns under simultaneous static loads and steel reinforcement corrosion", Arabian Journal for Science and Engineering, 41(10), 3945-3958.
Ukpata, J. O., Basheer, P. A. M., and Black, L. (2019). "Slag hydration and chloride binding in slag cements exposed to a combined chloride-sulphate solution", Construction and Building Materials, 195, 238-248.
Yang, J., Mohseni, E., Behforouz, B. and Khotbehsara, M.M. (2015). "An experimental investigation into the effects of Cr2O3 and ZnO2 nanoparticles on the mechanical properties and durability of self-compacting mortar", International Journal of Materials Research, 106(8), 886-892.
Zehtab, B. and Tarighat, A. (2016). "Diffusion study for chloride ions and water molecules in csh gel in nano-scale using molecular dynamics: Case study of tobermorite", Advances in Concrete Construction, 4(4), 305-317.
Zehtab, B. and Tarighat A. (2018). "Molecular dynamics simulation to assess the effect of temperature on diffusion coefficients of different ions and water molecules in C-S-H", Mechanics of Time-Dependent Materials, 22(4), 483-497.
Zhang, T., Tian, W., Guo, Y., Bogush, A., Khayrulina, E., Wei, J. and Yu, Q. (2019). "The volumetric stability, chloride binding capacity and stability of the portland cement-GBFS pastes: An approach from the viewpoint of hydration products", Construction and Building Materials, 205, 357-367.
Zhang, Y. and Ye, G. (2015). "Chloride transport in partially saturated mortar made of blended cement", Proceedings of the 14th International Congress on The Chemistry of Cement (ICCC2015), Beijing, China.
Zornoza, E., Payá, J. and Garcés, P. (2008). "Chloride-induced corrosion of steel embedded in mortars containing fly ash and spent cracking catalyst", Corrosion Science, 50(6), 1567-1575.
Volume 53, Issue 1
June 2020
Pages 1-13
  • Receive Date: 25 March 2018
  • Revise Date: 24 October 2019
  • Accept Date: 26 November 2019
  • First Publish Date: 01 June 2020