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Role of Magnesium-Stabilized Amorphous Calcium Carbonate in Mitigating the Extent of Carbonation in Alkali-Activated Slag

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Department of Civil and Environmental Engineering and the Andlinger Center for Energy and the Environment, Princeton University, Princeton, New Jersey 08544, United States
Ecole Supérieure d’Ingénieurs des Travaux de la Construction de Caen (ESITC-Caen), 1, rue Pierre et Marie Curie, 14610 Epron, France
*E-mail: [email protected]. Phone: +1 609 258 6263. Fax: +1 609 258 2799.
Cite this: Chem. Mater. 2015, 27, 19, 6625–6634
Publication Date (Web):September 9, 2015
Copyright © 2015 American Chemical Society

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    Oil well cements have received a significant amount of attention in recent years due to their use in high-risk conditions combined with their exposure to extremely aggressive environments. Adequate resistance to temperature, pressure, and carbonation is necessary to ensure the integrity of the well, with conventional cements prone to chemical degradation when exposed to CO2 molecules. Here, the local atomic structural changes occurring during the accelerated carbonation (100% CO2) of a sustainable cement, alkali-activated slag (AAS) have been investigated using in situ X-ray diffraction and pair distribution function analysis. The results reveal that the extent of carbonation-induced chemical degradation, which is governed by the removal of calcium from the calcium-alumino-silicate-hydrate (C-A-S-H) gel, can be reduced by tailoring the precursor chemistry; specifically the magnesium content. High-magnesium AAS pastes are seen to form stable magnesium-containing amorphous calcium carbonate phases, which prevents the removal of additional calcium from the C-A-S-H gel, thereby halting the progress of the carbonation reaction. On the other hand, lower-magnesium AAS pastes form amorphous calcium carbonate which is seen to quickly crystallize into calcite/vaterite, along with additional decalcification of the C-A-S-H gel. Hence, this behavior can be explained by considering (i) the solubility products of the various carbonate polymorphs and (ii) the stability of amorphous calcium/magnesium carbonate, where because of the higher solubility of amorphous calcium carbonate and associated saturation of solution with respect to calcium, additional C-A-S-H gel decalcification cannot proceed when this amorphous phase is present. These results may have important implications for the use of new cementitious materials in extremely aggressive conditions involving CO2 (e.g., enhanced oil recovery and geological storage of CO2), particularly because of the ability to optimize the durability of these materials by controlling the precursor (slag) chemistry.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.5b02382.

    • High-resolution X-ray diffraction patterns of the two slag precursors used in this investigation; evolution of the X-ray diffraction patterns of S-activated 7% MgO slag and H-activated 7% and 13% MgO slags as a function of the extent of carbonation; X-ray pair distribution functions for the noncarbonated control sample (H-activated 7% MgO slag); X-ray pair distribution functions for the carbonated control sample (H-activated 13% MgO slag); X-ray pair distribution functions of calcite, vaterite, and amorphous calcium carbonate, with associated major atom-atom correlations labeled (PDF)

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    12. Tao Liu, Shaohua Li, Yuxuan Chen, H.J.H. Brouwers, Qingliang Yu. In-situ formation of layered double hydroxides in MgO–NaAlO2-activated GGBS / MSWI BA: Impact of Mg2+ on reaction mechanism and leaching behavior. Cement and Concrete Composites 2023, 140 , 105114.
    13. Rakibul I. Khan, Muhammad Intesarul Haque, Salman Siddique, Eric N. Landis, Warda Ashraf. Effects of amino acids on the multiscale properties of carbonated wollastonite composites. Construction and Building Materials 2023, 374 , 130816.
    14. Muhammad Intesarul Haque, Ishrat Baki Borno, Rakibul I. Khan, Warda Ashraf. Reducing carbonation degradation and enhancing elastic properties of calcium silicate hydrates using biomimetic molecules. Cement and Concrete Composites 2023, 136 , 104888.
    15. Yuelin Li, Jian Yin, Qiang Yuan, Linchong Huang, Jiabin Li. Greener strain-hardening cementitious composites (SHCC) with a novel alkali-activated cement. Cement and Concrete Composites 2022, 134 , 104735.
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    17. Xin Zhang, Alan S. Lea, Anne M. Chaka, John S. Loring, Sebastian T. Mergelsberg, Elias Nakouzi, Odeta Qafoku, James J. De Yoreo, Herbert T. Schaef, Kevin M. Rosso. In situ imaging of amorphous intermediates during brucite carbonation in supercritical CO2. Nature Materials 2022, 21 (3) , 345-351.
    18. Xiaogang Sun, Yingliang Zhao, Jingping Qiu, Jun Xing. Review: alkali-activated blast furnace slag for eco-friendly binders. Journal of Materials Science 2022, 57 (3) , 1599-1622.
    19. Kai Gong, Claire E. White. Time-dependent phase quantification and local structure analysis of hydroxide-activated slag via X-ray total scattering and molecular modeling. Cement and Concrete Research 2022, 151 , 106642.
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    22. Joonho Seo, H.N. Yoon, Seonhyeok Kim, Zhen Wang, Taegeon Kil, H.K. Lee. Characterization of reactive MgO-modified calcium sulfoaluminate cements upon carbonation. Cement and Concrete Research 2021, 146 , 106484.
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    25. Ana Cuesta, Angeles G. De la Torre, Miguel A. G. Aranda. X-ray Total Scattering Study of Phases Formed from Cement Phases Carbonation. Minerals 2021, 11 (5) , 519.
    26. Jian Zhang, Caijun Shi, Zuhua Zhang. Effect of Na2O concentration and water/binder ratio on carbonation of alkali-activated slag/fly ash cements. Construction and Building Materials 2021, 269 , 121258.
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    30. Sarah Y. Wang, Eric McCaslin, Claire E. White. Effects of magnesium content and carbonation on the multiscale pore structure of alkali-activated slags. Cement and Concrete Research 2020, 130 , 105979.
    31. Fei Jin, Abir Al-Tabbaa. Magnesia in alkali activated cements. 2020, 213-241.
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    34. Humad, Habermehl-Cwirzen, Cwirzen. Effects of Fineness and Chemical Composition of Blast Furnace Slag on Properties of Alkali‐Activated Binder. Materials 2019, 12 (20) , 3447.
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    40. Lei Wang, Daniel C.W. Tsang. Carbon dioxide sequestration on composites based on waste wood. 2018, 431-450.
    41. Warda Ashraf, Jan Olek. Elucidating the accelerated carbonation products of calcium silicates using multi-technique approach. Journal of CO2 Utilization 2018, 23 , 61-74.
    42. Kengran Yang, V. Ongun Özçelik, Nishant Garg, Kai Gong, Claire E. White. Drying-induced atomic structural rearrangements in sodium-based calcium-alumino-silicate-hydrate gel and the mitigating effects of ZrO 2 nanoparticles. Physical Chemistry Chemical Physics 2018, 20 (13) , 8593-8606.
    43. S. M. Park, J. G. Jang, H. K. Lee. Unlocking the role of MgO in the carbonation of alkali-activated slag cement. Inorganic Chemistry Frontiers 2018, 5 (7) , 1661-1670.
    44. Harisankar Sreenivasan, Paivo Kinnunen, Eetu-Pekka Heikkinen, Mirja Illikainen. Thermally treated phlogopite as magnesium-rich precursor for alkali activation purpose. Minerals Engineering 2017, 113 , 47-54.
    45. Nam Kon Lee, Kyung Taek Koh, Min Ook Kim, Gi Hong An, Gum Sung Ryu. Physicochemical changes caused by reactive MgO in alkali-activated fly ash/slag blends under accelerated carbonation. Ceramics International 2017, 43 (15) , 12490-12496.
    46. Lei Wang, Tiffany L.K. Yeung, Abbe Y.T. Lau, Daniel C.W. Tsang, Chi-Sun Poon. Recycling contaminated sediment into eco-friendly paving blocks by a combination of binary cement and carbon dioxide curing. Journal of Cleaner Production 2017, 164 , 1279-1288.
    47. Ribooga Chang, Semin Kim, Seungin Lee, Soyoung Choi, Minhee Kim, Youngjune Park. Calcium Carbonate Precipitation for CO2 Storage and Utilization: A Review of the Carbonate Crystallization and Polymorphism. Frontiers in Energy Research 2017, 5
    48. Nishant Garg, Claire E. White. Mechanism of zinc oxide retardation in alkali-activated materials: an in situ X-ray pair distribution function investigation. Journal of Materials Chemistry A 2017, 5 (23) , 11794-11804.
    49. Kai Gong, Claire E. White. Impact of chemical variability of ground granulated blast-furnace slag on the phase formation in alkali-activated slag pastes. Cement and Concrete Research 2016, 89 , 310-319.
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