Phase Evolution of MgO-Nesquehonite Cements
Source abstract
Abstract
Magnesium-based cements, which combine MgO and nesquehonite (MgCO3·3H2O), are promising low-carbon binders which sequester CO2 and gain strength through the formation of hydrous carbonate-containing brucite (HCB). This study analyses the evolution of solid and liquid phases in MgO-nesquehonite suspensions (0 to 60% nesquehonite by mass, w/s = 10) over a year using XRD, TGA, FTIR, Raman spectroscopy and liquid analysis (pH, ionic composition), and compares them with previously studied paste systems (w/s = 1.25). The results show that HCB is the main hydrate after 28 days, while artinite forms in addition in blends with more than 30% nesquehonite after 91 days, consuming CO2 from HCB. Calculated saturation indices and the evolution of dissolved Mg and inorganic carbon confirm the dissolution of nesquehonite and the subsequent formation of HCB and artinite. Compared with paste systems, suspensions show faster phase evolution and artinite formation due to the higher water availability and continuous mixing. The findings confirm the metastability of HCB and provide data for the thermodynamic modelling of durable MgO-based binders.
Source: openalex_inverted_index · Quality: baseline
Research context
OpenAlex topics: Magnesium Oxide Properties and Applications · High-pressure geophysics and materials · Concrete and Cement Materials Research
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
Affiliations
Laboratory for Concrete & Asphalt, Swiss Federal Laboratories for Materials Science and Technology (Empa) 8600, Dübendorf, Switzerland.
University of Bern, Institute of Geological Sciences, Mineralogy Group, 3012 Bern, Switzerland.
Concrete & Asphalt, Swiss Federal Laboratories for Materials Science and Technology (Empa) 8600, Dübendorf, Switzerland.
References (74)
Show source-provided references
1. 1) Akao, M., & Iwai, S. (1977). The hydrogen bonding of artinite. Acta Crystallographica Section B, 33(12), 3951-3953. https://doi.org/10.1107/S056774087701257610.1107/S0567740877012576 ↗
2. 2) Badjatya, P., Akca, A. H., Fraga Alvarez, D. V., Chang, B., Ma, S., Pang, X., Wang, E., Van Hinsberg, Q., Esposito, D. V., & Kawashima, S. (2022). Carbon-negative cement manufacturing from seawater-derived magnesium feedstocks. Proceedings of the National Academy of Sciences, 119(34), e2114680119. https://doi.org/10.1073/pnas.211468011910.1073/pnas.2114680119 ↗
3. 3) Ballirano, P., De Vito, C., Mignardi, S., & Ferrini, V. (2013). Phase transitions in the Mg-CO2-H2O system and the thermal decomposition of dypingite, Mg5(CO3)4(OH)2·5H2O: Implications for geosequestration of carbon dioxide. Chemical Geology, 340, 59-67.10.1016/j.chemgeo.2012.12.005 ↗
4. 4) Bernard, E., Nguyen, H., Kawashima, S., Lothenbach, B., Manzano, H., Provis, J., Scott, A., Unluer, C., Winnefeld, F., & Kinnunen, P. (2023). MgO-based cements – Current status and opportunities. RILEM Technical Letters, 8, 65-78.10.21809/rilemtechlett.2023.177 ↗
5. 5) Botha, A., & Strydom, C. A. (2001). Preparation of a magnesium hydroxy carbonate from magnesium hydroxide. Hydrometallurgy, 62(3), 175-183.10.1016/S0304-386X(01)00197-9 ↗
6. 6) Botha, A., & Strydom, C. A. (2003). DTA and FT-IR analysis of the rehydration of basic magnesium carbonate. Journal of Thermal Analysis and Calorimetry, 71(3), 987-996. https://doi.org/10.1023/A:102335501620810.1023/A:1023355016208 ↗
7. 7) Chukanov, N. V. (2013). Infrared spectra of mineral species: Extended library. Dordrecht: Springer Science & Business Media.10.1007/978-94-007-7128-4 ↗
8. 8) Coelho, A. (2018). TOPAS and TOPAS-Academic: An optimization program integrating computer algebra and crystallographic objects written in C++. Journal of Applied Crystallography, 51(1), 210-218. https://doi.org/10.1107/S160057671800018310.1107/S1600576718000183 ↗
9. 9) Davies, P. J., & Bubela, B. (1973). The transformation of nesquehonite into hydromagnesite. Chemical Geology, 12(4), 289-300.10.1016/0009-2541(73)90006-5 ↗
10. 10) Dawson, P., Hadfield, C. D., & Wilkinson, G. R. (1973). The polarized infra-red and Raman spectra of Mg(OH)2 and Ca(OH)2. Journal of Physics and Chemistry of Solids, 34(7), 1217-1225.10.1016/S0022-3697(73)80212-4 ↗
11. 11) Dell, R. M., & Weller, S. W. (1959). The thermal decomposition of nesquehonite MgCO3·3H2O and magnesium ammonium carbonate MgCO3·(NH4)2CO3·4H2O. Transactions of the Faraday Society, 55(0), 2203-2220. https://doi.org/10.1039/TF959550220310.1039/TF9595502203 ↗
12. 12) Dendramis, A. L., Schwinn, E. W., & Sperline, R. P. (1983). A surface-enhanced Raman scattering study of CTAB adsorption on copper. Surface Science, 134(3), 675-688.10.1016/0039-6028(83)90065-1 ↗
13. 13) Dong, H., Unluer, C., Yang, E.-H., & Al-Tabbaa, A. (2017). Synthesis of reactive MgO from reject brine via the addition of NH4OH. Hydrometallurgy, 169, 165-172. https://doi.org/10.17863/CAM.906610.1016/j.hydromet.2017.01.010 ↗
14. 14) Dong, H., Unluer, C., Yang, E.-H., & Al-Tabbaa, A. (2018). Recovery of reactive MgO from reject brine via the addition of NaOH. Desalination, 429, 88-95. https://doi.org/10.1016/j.desal.2017.12.02110.1016/j.desal.2017.12.021 ↗
15. 15) Duffy, T. S., Meade, C., & Hemley, R. J. (1995). High-pressure phase transition in brucite, Mg(OH)2. American Mineralogist, 80(3-4), 222-230. https://doi.org/10.2138/am-1995-3-40310.2138/am-1995-3-403 ↗
16. 16) Edwards, H. G. M., Villar, S. E. J., Jehlicka, J., & Munshi, T. (2005). FT–Raman spectroscopic study of calcium-rich and magnesium-rich carbonate minerals. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 61(10), 2273-2280. https://doi.org/10.1016/j.saa.2005.02.02610.1016/j.saa.2005.02.026 ↗
17. 17) Farmer, V. C. (1974). The infrared spectra of minerals. London: The Mineralogical Society of Great Britain and Ireland.10.1180/mono-4 ↗
18. 18) Frost, R. L. (2011). Raman spectroscopic study of the magnesium carbonate mineral hydromagnesite (Mg5[(CO3)4(OH)2]·4H2O). Journal of Raman Spectroscopy, 42(8), 1690-1694.10.1002/jrs.2917 ↗
19. 19) Frost, R. L., & Palmer, S. J. (2011). Infrared and infrared emission spectroscopy of nesquehonite Mg(OH)(HCO3)·2H2O – Implications for the formula of nesquehonite. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 78(4), 1255-1260. https://doi.org/10.1016/j.saa.2010.12.05910.1016/j.saa.2010.12.059 ↗
20. 20) Frost, R. L., Bahfenne, S., & Graham, J. (2009). Raman spectroscopic study of the magnesium-carbonate minerals - Artinite and dypingite. Journal of Raman Spectroscopy, 40(8), 855-860. https://doi.org/10.1002/jrs.215210.1002/jrs.2152 ↗
21. 21) Frost, R. L., Bahfenne, S., Graham, J., & Martens, W. N. (2008a). Thermal stability of artinite, dypingite and brugnatellite—Implications for the geosequestration of greenhouse gases. Thermochimica Acta, 475(1), 39-43. https://doi.org/10.1016/j.tca.2008.06.00710.1016/j.tca.2008.06.007 ↗
22. 22) Frost, R. L., Bahfenne, S., Graham, J., & Reddy, B. J. (2008b). The structure of selected magnesium carbonate minerals. A near infrared and mid-infrared spectroscopic study. Polyhedron, 27(9), 2069-2076. https://doi.org/10.1016/j.poly.2008.03.01910.1016/j.poly.2008.03.019 ↗
23. 23) Gardeh, M. G., Kistanov, A. A., Nguyen, H., Manzano, H., Cao, W., & Kinnunen, P. (2022). Exploring mechanisms of hydration and carbonation of MgO and Mg(OH)2 in reactive magnesium oxide-based cements. The Journal of Physical Chemistry C, 126(14), 6196-6206.10.1021/acs.jpcc.1c10590 ↗
24. 24) Gartner, E., & Sui, T. (2018). Alternative cement clinkers. Cement and Concrete Research, 114, 27-39. https://doi.org/10.1016/j.cemconres.2017.02.00210.1016/j.cemconres.2017.02.002 ↗
25. 25) GCCA. (2021). Concrete future: The GCCA 2050 cement and concrete industry roadmap for net zero concrete. London: Global Cement and Concrete Association.
26. 26) German, A. (2024). Potential use of a low-carbon magnesia (MgO) binder for construction purposes. Thesis (Doctoral). ETH Zurich.
27. 27) German, A., Winnefeld, F., Lura, P., Rentsch, D., & Lothenbach, B. (2023). Hydrous carbonate-containing brucite (HCB) in MgO/hydromagnesite blends. Cement and Concrete Research, 173, 107304. https://doi.org/10.1016/j.cemconres.2023.10730410.1016/j.cemconres.2023.107304 ↗
28. 28) Hänchen, M., Prigiobbe, V., Baciocchi, R., & Mazzotti, M. (2008). Precipitation in the Mg-carbonate system—Effects of temperature and CO2 pressure. Chemical Engineering Science, 63(4), 1012-1028.10.1016/j.ces.2007.09.052 ↗
29. 29) Harrison, A. L., Mavromatis, V., Oelkers, E. H., & Bénézeth, P. (2019). Solubility of the hydrated Mg-carbonates nesquehonite and dypingite from 5 to 35 °C: Implications for CO2 storage and the relative stability of Mg-carbonates. Chemical Geology, 504, 123-135. https://doi.org/10.1016/j.chemgeo.2018.11.00310.1016/j.chemgeo.2018.11.003 ↗
30. 30) Hopkinson, L., Kristova, P., Rutt, K., & Cressey, G. (2012). Phase transitions in the system MgO-CO2-H2O during CO2 degassing of Mg-bearing solutions. Geochimica et Cosmochimica Acta, 76, 1-13. https://doi.org/10.1016/j.gca.2011.10.02310.1016/j.gca.2011.10.023 ↗
31. 31) Hopkinson, L., Rutt, K., & Cressey, G. (2008). The transformation of nesquehonite to hydromagnesite in the system CaO-MgO-H2O-CO2: An experimental spectroscopic study. The Journal of Geology, 116, 387-400. https://doi.org/10.1086/58883410.1086/588834 ↗
32. 32) Hu, Q., Lü, X., Lu, W., Chen, Y., & Liu, H. (2013). An extensive study on Raman spectra of water from 253 to 753 K at 30 MPa: A new insight into structure of water. Journal of Molecular Spectroscopy, 292, 23-27. https://doi.org/10.1016/j.jms.2013.09.00610.1016/j.jms.2013.09.006 ↗
33. 33) Hummel, W., & Thoenen, T. (2023). The PSI chemical thermodynamic database 2020 (Technical Report 21-03). Wettingen, Switzerland: National Co-operative for the Disposal of Radioactive Waste.
34. 34) IPCC. (2014). Climate change 2014: Mitigation of climate change: Working Group III contribution to the fifth assessment report of the Intergovernmental Panel on Climate Change. London: Cambridge University Press.
35. 35) Jansen, D., German, A., Ectors, D., & Winnefeld, F. (2024). Stacking faults of the hydrous carbonate-containing brucite (HCB) phase in hydrated magnesium carbonate cements. Cement and Concrete Research, 175, 107371. https://doi.org/10.1016/j.cemconres.2023.10737110.1016/j.cemconres.2023.107371 ↗
36. 36) Kuenzel, C., Zhang, F., Ferrándiz-Mas, V., Cheeseman, C. R., & Gartner, E. M. (2018). The mechanism of hydration of MgO-hydromagnesite blends. Cement and Concrete Research, 103, 123-129. https://doi.org/10.1016/j.cemconres.2017.10.00310.1016/j.cemconres.2017.10.003 ↗
37. 37) Kuhn, R., Lothenbach, B., Lura, P., Habert, G., & Bernard, E. (2026). Effects of carbonate and phosphate admixtures on MgO dissolution and Mg(OH)2 precipitation. Cement and Concrete Research, 204, 108207. https://doi.org/10.1016/j.cemconres.2026.10820710.1016/j.cemconres.2026.108207 ↗
38. 38) Kulik, D. A., Wagner, T., Dmytrieva, S. V., Kosakowski, G., Hingerl, F. F., Chudnenko, K. V., & Berner, U. R. (2013). GEM-Selektor geochemical modeling package: Revised algorithm and GEMS3K numerical kernel for coupled simulation codes. Computational Geosciences, 17(1), 1-24.10.1007/s10596-012-9310-6 ↗
39. 39) Li, Z., Mercken, J., Li, X., Riaño, S., & Binnemans, K. (2019). Efficient and sustainable removal of magnesium from brines for lithium/magnesium separation using binary extractants. ACS Sustainable Chemistry & Engineering, 7(23), 19225-19234.10.1021/acssuschemeng.9b05436 ↗
40. 40) Liu, C., Wang, D., Zheng, H., & Liu, T. (2017). A dehydroxylation kinetics study of brucite Mg(OH)2 at elevated pressure and temperature. Physics and Chemistry of Minerals, 44(4), 297-306.10.1007/s00269-016-0857-y ↗
41. 41) Loganathan, P., Naidu, G., & Vigneswaran, S. (2017). Mining valuable minerals from seawater: A critical review. Environmental Science: Water Research & Technology, 3(1), 37-53.10.1039/C6EW00268D ↗
42. 42) Lothenbach, B. (2010). Thermodynamic equilibrium calculations in cementitious systems. Materials and Structures, 43(10), 1413-1433. https://doi.org/10.1617/s11527-010-9592-x10.1617/s11527-010-9592-x ↗
43. 43) Lothenbach, B., Bernard, E., Zhou, Z., German, A., Montserrat-Torres, P., & Winnefeld, F. (2026a). Critical review of the properties of MgO-magnesium carbonate cements. Cement and Concrete Research, 200, 108092. https://doi.org/10.1016/j.cemconres.2025.10809210.1016/j.cemconres.2025.108092 ↗
44. 44) Lothenbach, B., Montserrat-Torres, P., Schreiner, C., & Winnefeld, F. (2026b). Solubility of artinite. Journal of Advanced Concrete Technology, 24(4), 174-190.10.3151/jact.24.174 ↗
45. 45) Madeddu, S., Priestnall, M., Godoy, E., Kumar, R. V., Raymahasay, S., Evans, M., Wang, R., Manenye, S., & Kinoshita, H. (2015). Extraction of Mg(OH)2 from Mg silicate minerals with NaOH assisted with H2O: implications for CO2 capture from exhaust flue gas. Faraday Discussions, 183, 369-387.10.1039/C5FD00047E ↗
46. 46) Mo, L., Deng, M., Tang, M., & Al-Tabbaa, A. (2014). MgO expansive cement and concrete in China: Past, present and future. Cement and Concrete Research, 57, 1-12. https://doi.org/10.1016/j.cemconres.2013.12.00710.1016/j.cemconres.2013.12.007 ↗
47. 47) Montserrat-Torres, P., Winnefeld, F., & Lothenbach, B. (2025). Impact of nesquehonite on hydration and strength of MgO-based cements. Cement and Concrete Research, 189, 107772. https://doi.org/10.1016/j.cemconres.2024.10777210.1016/j.cemconres.2024.107772 ↗
48. 48) Nduagu, E., Björklöf, T., Fagerlund, J., Wärnå, J., Geerlings, H., & Zevenhoven, R. (2012). Production of magnesium hydroxide from magnesium silicate for the purpose of CO2 mineralisation – Part 1: Application to Finnish serpentinite. Minerals Engineering, 30, 75-86.10.1016/j.mineng.2011.12.004 ↗
49. 49) Power, I. M., Kenward, P. A., Dipple, G. M., & Raudsepp, M. (2017). Room temperature magnesite precipitation. Crystal Growth & Design, 17(11), 5652-5659.10.1021/acs.cgd.7b00311 ↗
50. 50) Raade, G. (1970). Dypingite, a new hydrous basic carbonate of magnesium, from Norway. American Mineralogist, 55, 1457-1465.
51. 51) Saldi, G. D., Jordan, G., Schott, J., & Oelkers, E. H. (2009). Magnesite growth rates as a function of temperature and saturation state. Geochimica et Cosmochimica Acta, 73(19), 5646-5657.10.1016/j.gca.2009.06.035 ↗
52. 52) Scott, A., Oze, C., Shah, V., Yang, N., Shanks, B., Cheeseman, C., Marshall, A., & Watson, M. (2021). Transformation of abundant magnesium silicate minerals for enhanced CO2 sequestration. Communications Earth & Environment, 2(1), 25.10.1038/s43247-021-00099-6 ↗
53. 53) Scrivener, K. L., John, V. M., & Gartner, E. M. (2018). Eco-efficient cements: Potential economically viable solutions for a low-CO2 cement-based materials industry. Cement and Concrete Research, 114, 2-26. https://doi.org/10.1016/j.cemconres.2018.03.01510.1016/j.cemconres.2018.03.015 ↗
54. 54) Sednev-Lugovets, A., Lu, Y., Vistad, O., Carvalho, P. A., Missyul, A., Austrheim, H., Friis, H., & Guzik, M. N. (2025). The crystal structure of dypingite: understanding the long-range disorder. Journal of Applied Crystallography, 58(6), 1908-1919. https://doi.org/10.1107/S160057672500791510.1107/S1600576725007915 ↗
55. 55) Shi, R., Hao, Y., Chen, D., & Liu, W. (2023). Effect of low nesquehonite addition on the hydration product and pore structure of reactive magnesia paste. Materials, 16(6), 2445. https://doi.org/10.3390/ma1606244510.3390/ma16062445 ↗
56. 56) Snellings, R., Chwast, J., Cizer, Ö., De Belie, N., Dhandapani, Y., Durdzinski, P., Elsen, J., Haufe, J., Hooton, D., Patapy, C., Santhanam, M., Scrivener, K., Snoeck, D., Steger, L., Tongbo, S., Vollpracht, A., Winnefeld, F., & Lothenbach, B. (2018). RILEM TC-238 SCM recommendation on hydration stoppage by solvent exchange for the study of hydrate assemblages. Materials and Structures, 51(6), 172. https://doi.org/10.1617/s11527-018-1298-510.1617/s11527-018-1298-5 ↗
57. 57) Stephan, G. W., & MacGillavry, C. H. (1972). The crystal structure of nesquehonite, MgCO3·3H2O. Acta Crystallographica Section B: Structural Crystallography and Crystal Chemistry, 28(4), 1031-1033. https://doi.org/10.1107/S056774087200366810.1107/S0567740872003668 ↗
58. 58) Thasfiquzzaman, M., Singh, H., Nguyen, H., Patanen, M., Kinnunen, P., Selent, M., Ojala, S., Huttula, M., & Rani, E. (2025). Hydrated magnesium carbonates derived from brucite: Structural and vibrational analysis via synchrotron XRD and Raman spectroscopy. Results in Engineering, 27, 106109. https://doi.org/10.1016/j.rineng.2025.10610910.1016/j.rineng.2025.106109 ↗
59. 59) Traynor, B., Uvegi, H., Olivetti, E., Lothenbach, B., & Myers, R. J. (2020). Methodology for pH measurement in high alkali cementitious systems. Cement and Concrete Research, 135, 106122. https://doi.org/10.1016/j.cemconres.2020.10612210.1016/j.cemconres.2020.106122 ↗
60. 60) Unluer, C., & Al-Tabbaa, A. (2014). Characterization of light and heavy hydrated magnesium carbonates using thermal analysis. Journal of Thermal Analysis and Calorimetry, 115(1), 595-607.10.1007/s10973-013-3300-3 ↗
61. 61) Vlasopoulos, N., & Cheeseman, C. R. (2009). Binder composition. U.S. Patent No. US8496751B2.
62. 62) Wagner, T., Kulik, D. A., Hingerl, F. F., & Dmytrieva, S. V. (2012). GEM-Selektor geochemical modeling package: TSolMod library and data interface for multicomponent phase models. The Canadian Mineralogist, 50(5), 1173-1195.10.3749/canmin.50.5.1173 ↗
63. 63) Walling, S. A., & Provis, J. L. (2016). Magnesia-based cements: A journey of 150 years, and cements for the future? Chemical Reviews, 116(7), 4170-4204.10.1021/acs.chemrev.5b00463 ↗
64. 64) White, W. B. (1971). Infrared characterization of water and hydroxyl ion in the basic magnesium carbonate minerals. American Mineralogist, 56(1-2), 46-53.
65. 65) White, W. B. (1974). The carbonate minerals. In: V. C. Farmer, Ed. The Infrared Spectra of Minerals. London: The Mineralogical Society of Great Britain and Ireland, Vol. 4, 227-285.10.1180/mono-4.12 ↗
66. 66) Winnefeld, F., Epifania, E., Montagnaro, F., & Gartner, E. M. (2019). Further studies of the hydration of MgO-hydromagnesite blends. Cement and Concrete Research, 126, 105912. https://doi.org/10.1016/j.cemconres.2019.10591210.1016/j.cemconres.2019.105912 ↗
67. 67) Wyrzykowski, M., Bernard, E., Toropovs, N., & Lura, P. (2025). Pore structure and sorption of MgO-hydromagnesite cement pastes – On the mechanisms of moisture-induced weakening. Cement and Concrete Research, 206, 108249.10.1016/j.cemconres.2026.108249 ↗
68. 68) Yamamoto, G., Kyono, A., Abe, J., Sano-Furukawa, A., & Hattori, T. (2021). Crystal structure of nesquehonite, MgCO3·3H(D)2O by neutron diffraction and effect of pH on structural formulas of nesquehonite. Journal of Mineralogical and Petrological Sciences, 116, 96-103. https://doi.org/10.2465/jmps.20011710.2465/jmps.200117 ↗
69. 69) Yamamoto, G., Kyono, A., & Okada, S. (2022). Thermal decomposition process of dypingite Mg5(CO3)4(OH)2·5H2O. Materials Letters, 308, 131125. https://doi.org/10.1016/j.matlet.2021.13112510.1016/j.matlet.2021.131125 ↗
70. 70) Yang, B., Cao, X., Wang, S., & Sun, C. (2020). Exploring molecular association of isopropanol-water binary solution by Raman spectroscopy. Optik, 204, 163544. https://doi.org/10.1016/j.ijleo.2019.16354410.1016/j.ijleo.2019.163544 ↗
71. 71) Zajac, M., Skocek, J., Lothenbach, B., & Mohsen, B. H. (2020). Late hydration kinetics: Indications from thermodynamic analysis of pore solution data. Cement and Concrete Research, 129, 105975.10.1016/j.cemconres.2020.105975 ↗
72. 72) Zhang, J., Zhang, W., Wang, W., Liu, C., Deng, T., & Yu, X. (2025). Separation and production of metallic magnesium from salt lake brine by extraction-electrodeposition technology. Separation and Purification Technology, 357, 130062.10.1016/j.seppur.2024.130062 ↗
73. 73) Zhou, Z., Bernard, E., & Lothenbach, B. (2025). Effect of nesquehonite and silica on magnesia-silicate-carbonate cements. Cement and Concrete Research, 194, 107892. https://doi.org/10.1016/j.cemconres.2025.10789210.1016/j.cemconres.2025.107892 ↗
74. 74) Zhu, Y., German, A., Wyrzykowski, M., Toropovs, N., Winnefeld, F., Lura, P., & Griffa, M. (2025). Low-carbon MgO/hydromagnesite binders – Effect of moisture state on the evolution of mechanical properties. Cement and Concrete Research, 197, 107966. https://doi.org/10.1016/j.cemconres.2025.10796610.1016/j.cemconres.2025.107966 ↗