Mechanism of the Enhanced Sintering and Chloride-Binding Capacity Caused by Magnesium Doping
Publication: Journal of Materials in Civil Engineering
Volume 36, Issue 11
Abstract
This work examined the impact of Mg doping on the sintering, hydration, and chloride-binding capacity of minerals and elucidated the role of Mg doping on reactivity mechanisms by experiments and calculations. Rietveld analysis determined the solid solubility limit of Mg in is 1.6% by weight. By the density functional theory (DFT), it revealed Mg preferentially substitutes Fe sites, followed by Ca sites in . Increasing Mg doping up to 4% by weight enhanced the chloride-binding capacity of hydrated pastes by more than 50%, attributed to the increased formation of Friedel’s salt. The introduction of Mg in promoted clinker sintering upon hydration and produced katoite, which reacted with chloride. Additionally, Mg facilitated the formation of layered double hydroxides that adsorb chlorides. The changes imparted by Mg doping served to increase microstructure porosity and optimize pore size distribution. The results provide insight into the role of Mg in high-Mg, high-Fe cement, demonstrating that phase change improves resistance to chloride intrusion. This has implications for the use of high-Mg limestone and the application of this cement in marine environments.
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Data Availability Statement
Some or all data, models, or code that support the findings of this study are available from the corresponding author upon reasonable request.
Acknowledgments
The authors appreciate the support from the National Natural Science Foundation of China (No. U1905216) and the fellowship of China Postdoctoral Science Foundation (No. 2020M682290).
Author contributions: Jiangwei Xue and Simei Li contributed equally to this work. Jiangwei Xue: Methodology, Investigation, Formal analysis, Writing – original draft, Validation. Simei Li: Methodology, Investigation, Formal analysis, Writing – original draft, Validation. Songhui Liu: Conceptualization, Methodology, Investigation, Formal analysis, Writing – review and editing. Xiaoe Ma: Conceptualization; Xuemao Guan: Conceptualization, Supervision, Funding acquisition.
References
Aretxabaleta, X. M., H. Manzano, and I. Etxebarria. 2020. “Electronic and elastic properties of brownmillerite.” Mater. Res. Express 7 (1): 015516. https://doi.org/10.1088/2053-1591/ab61a1.
Cao, L., J. Guo, J. Tian, Y. Xu, M. Hu, M. Wang, and J. Fan. 2018. “Preparation of Ca/Al-layered double hydroxide and the influence of their structure on early strength of cement.” Constr. Build. Mater. 184 (Sep): 203–214. https://doi.org/10.1016/j.conbuildmat.2018.06.186.
Colville, A. A., and S. Geller. 1971. “The crystal structure of brownmillerite, .” Acta. Crystallogr. B. 27 (12): 2311–2315. https://doi.org/10.1107/S056774087100579X.
Curtius, H., and Z. Kattilparampil. 2005. “Sorption of iodine on Mg-Al-layered double hydroxide.” Clay. Miner. 40 (4): 455–461. https://doi.org/10.1180/0009855054040183.
Dudarev, S. L., G. A. Botton, S. Y. Savrasov, C. J. Humphreys, and A. P. Sutton. 1998. “Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study.” Phys. Rev. B. 57 (3): 1505–1509. https://doi.org/10.1103/PhysRevB.57.1505.
Frey, S. T., S. L. Guilmet, R. G. Egan III, A. Bennett, S. R. Soltau, and R. C. Holz. 2010. “Immobilization of the aminopeptidase from Aeromonas proteolytica on layered double hydroxide particles.” ACS Appl. Mater. Interfaces 2 (10): 2828–2832. https://doi.org/10.1021/am1005095.
Frías, M., J. Cabrera, and WCA. 2000. “Pore size distribution and degree of hydration of metakaolin–cement pastes.” Cem. Concr. Res. 30 (4): 561–569. https://doi.org/10.1016/S0008-8846(00)00203-9.
Goh, K., T. Lim, and Z. Dong. 2008. “Application of layered double hydroxides for removal of oxyanions: A review.” Water Res. 42 (6): 1343–1368. https://doi.org/10.1016/j.watres.2007.10.043.
Gregg, J. M., D. L. Bish, S. E. Kaczmarek, H. G. Machel, and C. Hollis. 2015. “Mineralogy, nucleation and growth of dolomite in the laboratory and sedimentary environment: A review.” Sedimentology 62 (6): 1749–1769. https://doi.org/10.1111/sed.12202.
Guo, Y., T. Zhang, J. Du, W. Tian, A. Wang, J. Wei, and Q. Yu. 2022. “The chloride binding capacity and stability of gap-graded blended cement with calcined hydrotalcite and metakaolin.” J. Build. Eng. 49 (Mar): 104093. https://doi.org/10.1016/j.jobe.2022.104093.
He, Z., and Y. Li. 2018. “Synthesis mechanism and material characterization of obtained by the self-propagating combustion reaction method.” J. Wuhan Univ. Technol. 33 (5): 89–97.
Huang, X., S. Hu, F. Wang, L. Yang, M. Rao, and Y. Tao. 2019. “Enhanced sulfate resistance: The importance of iron in aluminate hydrates.” ACS Sustainable Chem. Eng. 7 (7): 6792–6801. https://doi.org/10.1021/acssuschemeng.8b06097.
Kameda, T., J. Oba, and T. Yoshioka. 2015. “New treatment method for boron in aqueous solutions using Mg−Al layered double hydroxide: Kinetics and equilibrium studies.” J. Hazard. Mater. 293 (Jun): 54–63. https://doi.org/10.1016/j.jhazmat.2015.03.015.
Kresse, G., and J. Hafner. 1993. “Ab initio molecular dynamics for liquid metals.” J. Non-Cryst. Solids 47 (1): 558.
Lee, J., G. Gwak, H. Kim, T. Kim, G. J. Lee, and J. Oh. 2016. “Synthesis of hydrotalcite type layered double hydroxide with various Mg/Al ratio and surface charge under controlled reaction condition.” Appl. Clay Sci. 134 (Sep): 44–49. https://doi.org/10.1016/j.clay.2016.03.029.
Li, S., J. Yang, and P. Zhang. 2022a. “Hydration and hardening properties of reactive magnesia and portland cement composite.” Constr. Build. Mater. 327 (Jun): 126779. https://doi.org/10.1016/j.conbuildmat.2022.126779.
Li, S., S. Zhang, and R. Zhao. 2022b. “Regulating the electronic and magnetic properties of 1T-ReS 2 by fabricating nanoribbons and transition-metal doping: A theoretical study.” Nanoscale 14 (Jan): 8454.
Li, X., H. Huang, J. Xu, S. Ma, and X. Shen. 2012. “Statistical research on phase formation and modification of alite polymorphs in cement clinker with and MgO.” Constr. Build. Mater. 37 (Aug): 548–555. https://doi.org/10.1016/j.conbuildmat.2012.07.099.
Li, X., W. Xu, S. Wang, M. Tang, and X. Shen. 2014. “Effect of and MgO on portland cement clinker: Formation of clinker phases and alite polymorphism.” Constr. Build. Mater. 58 (Dec): 182. https://doi.org/10.1016/j.conbuildmat.2014.02.029.
Liu, X., and Y. Li. 2005. “Effect of MgO on the composition and properties of alite-sulphoaluminate cement.” Cem. Concr. Res. 35 (9): 1685–1687. https://doi.org/10.1016/j.cemconres.2004.08.008.
Ma, L., Y. Qiang, and W. Zhao. 2021. “Designing novel organic inhibitor loaded MgAl-LDHs nanocontainer for enhanced corrosion resistance.” Chem. Eng. J. 408 (Feb): 127367.
Ma, X., H. Chen, and P. Wang. 2010. “Effect of CuO on the formation of clinker minerals and the hydration properties.” Cem. Concr. Res. 40 (12): 1681–1687. https://doi.org/10.1016/j.cemconres.2010.08.009.
Malherbe, F., C. Forano, and J. Besse. 1997. “Use of organic media to modify the surface and porosity properties of hydrotalcite-like compounds.” Microporous Mater. 10 (1): 67–84. https://doi.org/10.1016/S0927-6513(96)00123-X.
Malveiro, J., T. Ramos, L. P. Ferreira, J. C. Waerenborgh, M. R. Nunes, M. Godinho, and M. D. Carvalho. 2007. “Magnesium doping on brownmillerite .” J. Solid. State Chem. 180 (6): 1863–1874. https://doi.org/10.1016/j.jssc.2007.04.009.
Michalik, A., E. M. Serwicka, K. Bahranowski, A. Gaweł, M. Tokarz, and J. Nilsson. 2008. “Mg, Al-hydrotalcite-like compounds as traps for contaminants of paper furnishes.” Appl. Clay. Sci. 39 (1–2): 86–97. https://doi.org/10.1016/j.clay.2007.04.012.
Mittal, J. 2021. “Recent progress in the synthesis of layered double hydroxides and their application for the adsorptive removal of dyes: A review.” J. Environ. Manage. 295 (Jun): 113017. https://doi.org/10.1016/j.jenvman.2021.113017.
Mo, L., M. Deng, M. Tang, and A. Al-Tabbaa. 2014. “MgO expansive cement and concrete in China: Past, present and future.” Cem. Concr. Res. 57 (Mar): 1–12. https://doi.org/10.1016/j.cemconres.2013.12.007.
Mohammed, T. U., and H. Hamada. 2003. “Relationship between free chloride and total chloride contents in concrete.” Cem. Concr. Res. 33 (9): 1487–1490. https://doi.org/10.1016/S0008-8846(03)00065-6.
Rekhi, S., S. K. Saxena, R. Ahuja, B. Johansson, and J. Hu. 2001. “Experimental and theoretical investigations on the compressibility of nanocrystalline nickel.” J. Mater. Sci. 36 (19): 4719–4721. https://doi.org/10.1023/A:1017974904559.
Rose, J., A. Bénard, S. El Mrabet, A. Masion, I. Moulin, V. Briois, L. Olivi, and J. Y. Bottero. 2006. “Evolution of iron speciation during hydration of .” Waste. Manage. 26 (7): 720–724. https://doi.org/10.1016/j.wasman.2006.01.021.
Seo, J., H. N. Yoon, S. Kim, Z. Wang, T. Kil, and H. K. Lee. 2021. “Characterization of reactive MgO-modified calcium sulfoaluminate cements upon carbonation.” Cem. Concr. Res. 146 (Jun): 106484. https://doi.org/10.1016/j.cemconres.2021.106484.
Shen, Y., S. Liu, Y. Wang, P. Shen, D. Xuan, X. Guan, and C. Shi. 2022. “Hydration-hardening properties of low-clinker composite cement incorporating carbonated waste sintering red mud and metakaolin.” Constr. Build. Mater. 354 (Dec): 129171. https://doi.org/10.1016/j.conbuildmat.2022.129171.
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.
Tang, L., 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.
Tao, Y., D. Wan, W. Zhang, F. Wang, and S. Hu. 2021. “Intrinsic reactivity and dissolution characteristics of tetracalcium aluminoferrite.” Cem. Concr. Res. 146 (Sep): 106485. https://doi.org/10.1016/j.cemconres.2021.106485.
Wang, H., D. D. Leon, and H. Farzam. 2014. “ reactivity—Chemistry and hydration of industrial cement.” ACI Mater. J. 111 (2): 201–210.
Wang, X., Z. Bai, D. Zhao, Y. Chai, M. Guo, and J. Zhang. 2013. “New synthetic route to Mg−Al−CO3 layered double hydroxide using magnesite.” Mater. Res. Bull. 48 (3): 1228–1232. https://doi.org/10.1016/j.materresbull.2012.11.096.
Wang, X. B., Z. M. Bai, Z. Y. He, Q. F. Zhang, and F. L. Qian. 2015. “The influence of synthesis conditions on the structure of Mg−Al layered double hydroxide.” Key Eng. Mater. 655 (Jun): 267–270. https://doi.org/10.4028/www.scientific.net/KEM.655.267.
Wei, J., J. Xu, Y. Mei, and Q. Tan. 2020. “Chloride adsorption on aminobenzoate intercalated layered double hydroxides: Kinetic, thermodynamic and equilibrium studies.” Appl. Clay. Sci. 187 (Aug): 105495. https://doi.org/10.1016/j.clay.2020.105495.
Xue, J., S. Liu, X. Ma, Y. Teng, and X. Guan. 2022. “Effect of different gypsum dosage on the chloride binding properties of hydrated paste.” Constr. Build. Mater. 315 (Feb): 125562. https://doi.org/10.1016/j.conbuildmat.2021.125562.
Yang, H. M., S. M. Zhang, L. Wang, P. Chen, D. K. Shao, S. W. Tang, and J. Z. Li. 2022. “High-ferrite portland cement with slag: Hydration, microstructure, and resistance to sulfate attack at elevated temperature.” Cem. Concr. Comp. 130 (Jan): 104560. https://doi.org/10.1016/j.cemconcomp.2022.104560.
Yang, P., Y. Xu, N. Yin, and Y. Ai. 2020. “Preparation of uniform high dispersed Mg−Al−LDHs and its adsorption performance for chloride ions.” Ind. Eng. Chem. Res. 22 (59): 10697–10704.
Yoon, H. N., S. M. Park, and H. K. Lee. 2018. “Effect of MgO on chloride penetration resistance of alkali-activated binder.” Constr. Build. Mater. 178 (Jun): 584–592. https://doi.org/10.1016/j.conbuildmat.2018.05.156.
Zhang, C., J. Wang, W. Song, and J. Fu. 2022a. “Pore structure, mechanical behavior and damage evolution of cemented paste backfill.” J. Mater. Res. Technol. 17 (Jan): 2864–2874. https://doi.org/10.1016/j.jmrt.2022.02.010.
Zhang, J. 2022. “Recent advance of MgO expansive agent in cement and concrete.” J. Build. Eng. 45 (Sep): 103633. https://doi.org/10.1016/j.jobe.2021.103633.
Zhang, J., W. Zhu, Y. Zhang, D. Xiao, and Y. Yao. 2012. “Tailoring magnetic doping in the topological insulator .” Phys. Rev. Lett. 109 (26): 266405. https://doi.org/10.1103/PhysRevLett.109.266405.
Zhang, K., F. Wang, M. Rao, W. Zhang, and X. Huang. 2019. “Influence of ZnO-doping on the properties of high-ferrite cement clinker.” Constr. Build. Mater. 224 (Dec): 551–559. https://doi.org/10.1016/j.conbuildmat.2019.07.075.
Zhang, W., Z. Luan, X. Ren, J. Ye, D. Shi, and H. Zhang. 2022b. “Influence of alumina modulus on formation of high-magnesium clinker and morphological evolution of MgO.” Cem. Concr. Res. 162 (Dec): 106986. https://doi.org/10.1016/j.cemconres.2022.106986.
Zhao, J., G. Cai, D. Gao, and S. Zhao. 2014. “Influences of freeze–thaw cycle and curing time on chloride ion penetration resistance of sulphoaluminate cement concrete.” Constr. Build. Mater. 53 (Jan): 305–311. https://doi.org/10.1016/j.conbuildmat.2013.11.110.
Zhao, R., H. Liu, G. Fan, X. Guan, and J. Zhu. 2022. “Unraveling the doping preference of zinc ions in sulfoaluminate cement clinker minerals: A study combining experiments and DFT calculations.” Composites, Part B 242 (Dec): 110072. https://doi.org/10.1016/j.compositesb.2022.110072.
Zhao, R., L. Zhang, G. Fan, Y. Chen, G. Huang, H. Zhang, J. Zhu, and X. Guan. 2021a. “Probing the exact form and doping preference of magnesium in ordinary portland cement clinker phases: A study from experiments and DFT simulations.” Cem. Concr. Res. 144 (Aug): 106420. https://doi.org/10.1016/j.cemconres.2021.106420.
Zhao, R., L. Zhang, B. Guo, Y. Chen, G. Fan, Z. Jin, X. Guan, and J. Zhu. 2021b. “Unveiling substitution preference of chromium ions in sulphoaluminate cement clinker phases.” Composites, Part B 222 (Mar): 109092. https://doi.org/10.1016/j.compositesb.2021.109092.
Zheng, L., C. Xuehua, and T. Mingshu. 1992. “Hydration and setting time of MgO-type expansive cement.” Cem. Concr. Res. 22 (1): 1–5. https://doi.org/10.1016/0008-8846(92)90129-J.
Zhu, J., K. Yang, Y. Chen, G. Fan, L. Zhang, B. Guo, X. Guan, and R. Zhao. 2021a. “Revealing the substitution preference of zinc in ordinary portland cement clinker phases: A study from experiments and DFT calculations.” J. Hazard. Mater. 409 (Apr): 124504. https://doi.org/10.1016/j.jhazmat.2020.124504.
Zhu, J., K. Yang, X. Guan, R. Zhao, and W. Zhang. 2023. “Microstructure of cementitious materials under the coupling effects of and in a marine tidal environment.” Constr Build. Mater. 376 (May): 131003. https://doi.org/10.1016/j.conbuildmat.2023.131003.
Zhu, J., B. Zeng, L. Mo, F. Jin, M. Deng, and Q. Zhang. 2021b. “One-pot synthesis of Mg Al layered double hydroxide (LDH) using MgO and metakaolin (MK) as precursors.” Appl. Clay. Sci. 206 (Jun): 106070. https://doi.org/10.1016/j.clay.2021.106070.
Zivica, V., M. T. Palou, L. Bagel, and M. Krizma. 2013. “Low-porosity tricalcium aluminate hardened paste.” Constr. Build. Mater. 38 (Sep): 1191–1198. https://doi.org/10.1016/j.conbuildmat.2012.09.025.
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Published In
Journal of Materials in Civil Engineering
Volume 36 • Issue 11 • November 2024
Copyright
© 2024 American Society of Civil Engineers.
History
Received: Oct 17, 2023
Accepted: Apr 16, 2024
Published online: Sep 5, 2024
Published in print: Nov 1, 2024
Discussion open until: Feb 5, 2025
ASCE Technical Topics:
- Cement
- Chemical compounds
- Chemical elements
- Chemicals
- Chemistry
- Chloride
- Concrete
- Engineering materials (by type)
- Environmental engineering
- Geomechanics
- Geotechnical engineering
- Hydration
- Laminating
- Magnesium
- Materials engineering
- Materials processing
- Minerals
- Pollutants
- Pore size distribution
- Salts
- Soil mechanics
- Soil properties
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