Hydration reactivity difference between dicalcium silicate and tricalcium silicate revealed from structural and Bader charge analysis

Abstract

Cement hydration is the underlying mechanism for the strength development in cement-based materials. The structural and electronic properties of calcium silicates should be elucidated to reveal their difference in hydration reactivity. Here, we comprehensively compared β-C₂S and M3-C₃S and investigated their structural properties and Bader charge in the unit cell, during surface reconstruction and after single water adsorption via density functional theory. We identified different types of atoms in β-C₂S and M3-C₃S by considering the bonding characteristics and Bader charge. We then divided the atoms into the following groups: for β-C₂S, Ca and O atoms divided into two and four groups, respectively; for M3-C₃S, Ca, O, and Si atoms divided into four, four, and three groups, respectively. Results revealed that the valence electron distribution on the surface was more uniform than that on the unit cell, indicating that some atoms became more reactive after surface relaxation. During water adsorption, the electrons of β-C₂S and M3-C₃S were transferred from the surface to the adsorbed water molecules through position redistribution and bond formation/breaking. On this basis, we explained why β-C₂S and M3-C₃S had activity differences. A type of O atom with special bond characteristics (no O-Si bonds) and high reactivity existed in the unit cell of M3-C₃S. Bader charge analysis showed that the reactivity of Ca and O atoms was generally higher in M3-C₃S than in β-C₂S. Ca/O atoms had average valence electron numbers of 6.437/7.550 in β-C₂S and 6.481/7.537 in M3-C₃S. Moreover, the number of electrons gained by water molecules in M3-C₃S at the surface was higher than that in β-C₂S. The average variations in the valence electrons of H₂O on β-C₂S and M3-C₃S were 0.041 and 0.226, respectively. This study further explains the differences in the hydration reactivity of calcium silicates and would be also useful for the design of highly reactive and environmentally friendly cements.

Keywords

calcium silicates / Portland cement / hydration reactivity / first-principle calculations

References

[1] J.Y. Huo, Z.J. Wang, T.H. Zhang, R. He, and H.X. Chen, Influences of interaction between cement and ionic paraffin emulsion on cement hydration, Constr. Build. Mater., 299(2021), art. No. 123951.

[2] R. Li, L. Lei, T.B. Sui, and J. Plank, Effectiveness of PCE superplasticizers in calcined clay blended cements, Cem. Concr. Res., 141(2021), art. No. 106334.

[3] Yin SH, Wang LM, Chen X, Wu AX. Agglomeration and leaching behaviors of copper oxides with different chemical binders. Int. J. Miner. Metall. Mater., 2021, 28(7): 1127.

[4] Chen QS, Sun SY, Liu YK, Qi CC, Zhou HB, Zhang QL. Immobilization and leaching characteristics of fluoride from phosphogypsum-based cemented paste backfill. Int. J. Miner. Metall. Mater., 2021, 28(9): 1440.

[5] Taylor HF. Cement Chemistry, 1997, London, Thomas Telford, 1.

[6] Crow JM. The concrete conundrum. Chem. World, 2008, 5, 62

[7] J.P. Zhu, K. Yang, Y. Chen, G.X. Fan, L. Zhang, B.K. Guo, X.M. Guan, and R.Q. Zhao, Revealing the substitution preference of zinc in ordinary Portland cement clinker phases: A study from experiments and DFT calculations, J. Hazard. Mater., 409(2021), art. No. 124504.

[8] Ercikdi B, Yılmaz T, Külekci G. Strength and ultrasonic properties of cemented paste backfill. Ultrasonics, 2014, 54(1): 195.

[9] Cavusoglu I, Yilmaz E, Yilmaz AO. Sodium silicate effect on setting properties, strength behavior and microstructure of cemented coal fly ash backfill. Powder Technol., 2021, 384, 17.

[10] C.C. Qi and A. Fourie, Cemented paste backfill for mineral tailings management: Review and future perspectives, Miner. Eng., 144(2019), art. No. 106025.

[11] Y. Briki, M. Zajac, M.B. Haha, and K. Scrivener, Impact of limestone fineness on cement hydration at early age, Cem. Concr. Res., 147(2021), art. No. 106515.

[12] X.Y. Pang, W. Cuello Jimenez, and J. Singh, Measuring and modeling cement hydration kinetics at variable temperature conditions, Constr. Build. Mater., 262(2020), art. No. 120788.

[13] R.H. Yang and T.S. He, Influence of liquid accelerators combined with mineral admixtures on early hydration of cement pastes, Constr. Build. Mater., 295(2021), art. No. 123659.

[14] O. Linderoth, L. Wadsö, and D. Jansen, Long-term cement hydration studies with isothermal calorimetry, Cem. Concr. Res., 141(2021), art. No. 106344.

[15] Y.G. Zhang, C. Bouillon, N. Vlasopoulos, and J.J. Chen, Measuring and modeling hydration kinetics of well cements under elevated temperature and pressure using chemical shrinkage test method, Cem. Concr. Res., 123(2019), art. No. 105768.

[16] Wyrzykowski M, Scrivener K, Lura P. Basic creep of cement paste at early age—The role of cement hydration. Cem. Concr. Res., 2019, 116, 191.

[17] Lalan P, Dauzères A, De Windt L, Bartier D, Sammaljärvi J, Barnichon JD, Techer I, Detilleux V. Impact of a 70°C temperature on an ordinary Portland cement paste/claystone interface: An in situ experiment. Cem. Concr. Res., 2016, 83, 164.

[18] Z.D. Zhang and G.W. Scherer, Physical and chemical effects of isopropanol exchange in cement-based materials, Cem. Concr. Res., 145(2021), art. No. 106461.

[19] S. Tontapha, N. Shinsuphan, W. Sang-Aroon, L. Temprom, S. Krongsuk, W. Jarernboon, P. Chindaprasirt, and V. Amornkitbamrung, A DFT study on electrocatalytic performance of 12CaO·7Al₂O₃ (C12A7) with electrolytic LiI applied in DSSCs, Surf. Sci., 711(2021), art. No. 121864.

[20] Durgun E, Manzano H, Kumar PV, Grossman JC. The characterization, stability, and reactivity of synthetic calcium silicate surfaces from first principles. J. Phys. Chem. C, 2014, 118(28): 15214.

[21] C.C. Qi, L. Liu, J.Y. He, Q.S. Chen, L.J. Yu, and P.F. Liu, Understanding cement hydration of cemented paste backfill: DFT study of water adsorption on tricalcium silicate (111) surface, Minerals, 9(2019), No. 4, art. No. 202.

[22] C.C. Qi, D. Spagnoli, and A. Fourie, DFT-D study of single water adsorption on low-index surfaces of calcium silicate phases in cement, Appl. Surf. Sci., 518(2020), art. No. 146255.

[23] Zhang Y, Lu XY, Song DS, Liu SB. The adsorption of a single water molecule on low-index C3S surfaces: A DFT approach. Appl. Surf. Sci., 2019, 471, 658.

[24] Zhang Y, Lu XY, He Z, Song DS. Molecular and dissociative adsorption of a single water molecule on a β-dicalcium silicate (100) surface explored by a DFT approach. J. Am. Ceram. Soc., 2018, 101(6): 2428.

[25] I.H. Svenum, I.G. Ringdalen, F.L. Bleken, J. Friis, D. Höche, and O. Swang, Structure, hydration, and chloride ingress in C—S—H: Insight from DFT calculations, Cem. Concr. Res., 129(2020), art. No. 105965.

[26] Qi CC, Fourie A, Chen QS, Liu PF. Application of first-principles theory in ferrite phases of cemented paste backfill. Miner. Eng., 2019, 133, 47.

[27] N.L. Mai, N.H. Hoang, H.T. Do, M. Pilz, and T.T. Trinh, Elastic and thermodynamic properties of the major clinker phases of Portland cement: Insights from first principles calculations, Constr. Build. Mater., 287(2021), art. No. 122873.

[28] C.C. Qi, Q.S. Chen, and A. Fourie, Role of Mg impurity in the water adsorption over low-index surfaces of calcium silicates: A DFT-D study, Minerals, 10(2020), No. 8, art. No. 665.

[29] Huang J, Wang B, Yu YT, Valenzano L, Bauchy M, Sant G. Electronic origin of doping-induced enhancements of reactivity: Case study of tricalcium silicate. J. Phys. Chem. C, 2015, 119(46): 25991.

[30] Kresse G, Hafner J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B, 1993, 47(1): 558.

[31] Kresse G, Furthmüller J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci., 1996, 6(1): 15.

[32] P. Giannozzi, S. Baroni, N. Bonini, M. Calandra, R. Car, C. Cavazzoni, D. Ceresoli, G.L. Chiarotti, M. Cococcioni, I. Dabo, A. dal Corso, S. de Gironcoli, S. Fabris, G. Fratesi, R. Gebauer, U. Gerstmann, C. Gougoussis, A. Kokalj, M. Lazzeri, L. Martin-Samos, N. Marzari, F. Mauri, R. Mazzarello, S. Paolini, A. Pasquarello, L. Paulatto, C. Sbraccia, S. Scandolo, G. Sclauzero, A.P. Seitsonen, A. Smogunov, P. Umari, and R.M. Wentzcovitch, QUANTUM ESPRESSO: A modular and open-source software project for quantum simulations of materials, J. Phys.: Condens. Matter, 21(2009), No. 39, art. No. 395502.

[33] Perdew JP, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Phys. Rev. Lett., 1996, 77(18): 3865.

[34] Jost KH, Ziemer B, Seydel R. Redetermination of the structure of β-dicalcium silicate. Acta Crystallogr. Sect. B Struct. Crystallogr. Cryst. Chem., 1977, 33(6): 1696.

[35] de Noirfontaine MN, Dunstetter F, Courtial M, Gasecki G, Signes-Frehel M. Polymorphism of tricalcium silicate, the major compound of Portland cement clinker: 2. Modelling alite for Rietveld analysis, an industrial challenge. Cem. Concr. Res., 2006, 36(1): 54.

[36] Tasker PW. The stability of ionic crystal surfaces. J. Phys. C: Solid State Phys., 1979, 12(22): 4977.

[37] Noguera C. Polar oxide surfaces. J. Phys.: Condens. Matter, 2000, 12(31): R367

[38] Tjung SJ, Zhang Q, Repicky JJ, Yuk SF, Nie XW, Santagata NM, Asthagiri A, Gupta JA. STM and DFT studies of CO₂ adsorption on O-Cu(100) surface. Surf. Sci., 2019, 679, 50.

[39] Jiang Z, Qin P, Fang T. Investigation on adsorption and decomposition of H₂S on Pd (100) surface: A DFT study. Surf. Sci., 2015, 632, 195.

[40] Lloyd A, Cornil D, van Duin ACT, van Duin D, Smith R, Kenny SD, Cornil J, Beljonne D. Development of a ReaxFF potential for Ag/Zn/O and application to Ag deposition on ZnO. Surf. Sci., 2016, 645, 67.

[41] Tereshchuk P, da Silva JLF. Ethanol and water adsorption on close-packed 3d, 4d, and 5d transition-metal surfaces: A density functional theory investigation with van der Waals correction. J. Phys. Chem. C, 2012, 116(46): 24695.

[42] Shepard R, Shepard S, Smeu M. Ab initio investigation into the physisorption of noble gases on graphene. Surf. Sci., 2019, 682, 38.

[43] Peng CL, Min FF, Liu LY, Chen J. A periodic DFT study of adsorption of water on sodium-montmorillonite (001) basal and (010) edge surface. Appl. Surf. Sci., 2016, 387, 308.

[44] Xin Y, Hou SC, Xiang L, Yu YX. Adsorption and sub-stitution effects of Mg on the growth of calcium sulfate hemihydrate: An ab initio DFT study. Appl. Surf. Sci., 2015, 357, 1552.

[45] Liu J, Wen SM, Deng JS, Chen XM, Feng QC. DFT study of ethyl xanthate interaction with sphalerite (110) surface in the absence and presence of copper. Appl. Surf. Sci., 2014, 311, 258.

[46] C.X. Cai, S.S. Wei, Z.P. Yin, J. Bai, W.W. Xie, Y. Li, F.W. Qin, Y. Su, and D.J. Wang, Oxygen vacancy formation and uniformity of conductive filaments in Si-doped Ta₂O₅ RRAM, Appl. Surf. Sci., 560(2021), art. No. 149960.

[47] Bader RFW. A quantum theory of molecular structure and its applications. Chem. Rev., 1991, 91(5): 893.

[48] W. Tang, E. Sanville, and G. Henkelman, A grid-based Bader analysis algorithm without lattice bias, J. Phys.: Condens. Matter, 21(2009), No. 8, art. No. 084204.

[49] Scherson YD, Aboud SJ, Wilcox J, Cantwell BJ. Surface structure and reactivity of rhodium oxide. J. Phys. Chem. C, 2011, 115(22): 11036.

[50] Henkelman G, Arnaldsson A, Jónsson H. A fast and robust algorithm for Bader decomposition of charge density. Comput. Mater. Sci., 2006, 36(3): 354.

[51] Z. Cheng, B.J. Sherman, and C.S. Lo, Carbon dioxide activation and dissociation on ceria (110): A density functional theory study, J. Chem. Phys., 138(2013), No. 1, art. No. 014702.

[52] N. Kuriakose, A. Mohan T, and P. Ghosh, Coverage dependent CO₂ activation on Ti₂C(111) surface: Effect of intrinsic subsurface Carbon vacancies, Surf. Sci., 706(2021), art. No. 121798.

[53] Durgun E, Manzano H, Pellenq RJM, Grossman JC. Understanding and controlling the reactivity of the calcium silicate phases from first principles. Chem. Mater., 2012, 24(7): 1262.

[54] M. Laanaiya, A. Bouibes, and A. Zaoui, Understanding why Alite is responsible of the main mechanical characteristics in Portland cement, Cem. Concr. Res., 126(2019), art. No. 105916.

[55] Li GJ, Hu WG, Sun YN, Xu JY, Cai X, Cheng XL, Zhang YY, Tang AC, Liu X, Chen MY, Ding WP, Zhu Y. Reactivity and lability modulated by a valence electron moving in and out of 25-atom gold nanoclusters. Angew. Chem., 2020, 132(47): 21321.

[56] Sarugaku S, Arakawa M, Kawano T, Terasaki A. Electronic and geometric effects on chemical reactivity of 3d-transition-metal-doped silver cluster cations toward oxygen molecules. J. Phys. Chem. C, 2019, 123(42): 25890.

[57] Mascaraque A, Garza LM, Michel EG. Electronic structure and reactivity of the Co/MoS₂(0001) interface. Surf. Sci., 2001, 482–485, 664.