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Carbon Dioxide Uptake by MOC-Based Materials

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Carbon Dioxide Uptake by MOC-Based Materials applied sciences Article Carbon Dioxide Uptake by MOC-Based Materials OndˇrejJankovský 1, Michal Lojka 1, Anna-Marie Lauermannová 1, Filip Antonˇcík 1, Milena Pavlíková 2, Zbyšek Pavlík 2 and David Sedmidubský 1,* 1 Department of Inorganic Chemistry, Faculty of Chemical Technology, University of Chemistry and Technology, Technická 5, 166 28 Prague 6, Czech Republic; [email protected] (O.J.); [email protected] (M.L.); [email protected] (A.-M.L.); fi[email protected] (F.A.) 2 Department of Materials Engineering and Chemistry, Faculty of Civil Engineering, Czech Technical University in Prague, Thákurova 7, 166 29 Prague 6, Czech Republic; [email protected] (M.P.); [email protected] (Z.P.) * Correspondence: [email protected]; Tel.: +420-2-2044-4122 Received: 6 March 2020; Accepted: 24 March 2020; Published: 26 March 2020 Featured Application: The highest potential of magnesium oxychloride cement (MOC) is its capability to be used as a component of low-energy building composite materials while acting as a CO2 sink. The results of this contribution also show that MOC can be used as a binder in advanced building materials that have particular properties, and therefore specific application potentials. Formation and hardening of this material are rather fast, so the material can be used in quick repairs as well as a protection layer. This property is also beneficial for use in prefabrication, due to the possibility of unmolding after a shorter time compared to Portland cement (PC) materials, so the whole production process can be considered more effective. Somewhat significant importance should be given to its ability to capture CO2, which not only makes it more eco-friendly, but also improves its mechanical properties. Abstract: In this work, carbon dioxide uptake by magnesium oxychloride cement (MOC) based materials is described. Both thermodynamically stable magnesium oxychloride phases with stoichiometry 3Mg(OH) MgCl 8H O (Phase 3) and 5Mg(OH) MgCl 8H O (Phase 5) were prepared. 2· 2· 2 2· 2· 2 X-ray diffraction (XRD) measurements were performed to confirm the purity of the studied phases after 7, 50, 100, 150, 200, and 250 days. Due to carbonation, chlorartinite was formed on the surface of the examined samples. The Rietveld analysis was performed to calculate the phase composition and evaluate the kinetics of carbonation. The SEM micrographs of the sample surfaces were compared with those of the bulk to prove XRD results. Both MOC phases exhibited fast mineral carbonation and high maximum theoretical values of CO2 uptake capacity. The materials based on MOC cement can thus find use in applications where a higher concentration of CO2 in the environment is expected (e.g., in flooring systems and wall panels), where they can partially mitigate the harmful effects of CO2 on indoor air quality and contribute to the sustainability of the construction industry by means of reducing the carbon footprints of alternative building materials and reducing CO2 concentrations in the environment overall. Keywords: magnesium oxychloride cement; MOC phases; carbonation; CO2 uptake; carbon footprint 1. Introduction Magnesium oxychloride cement (MOC), also known as Sorel cement, was discovered by French engineer Stanislas Sorel in 1867 [1]. Since then, it has often been compared to Portland cement (PC), which was discovered just a few years earlier. It is formed using a mixture of magnesium oxide with an aqueous solution of magnesium chloride in a certain ratio. The ratios in the system MgO-MgCl2-H2O Appl. Sci. 2020, 10, 2254; doi:10.3390/app10072254 www.mdpi.com/journal/applsci Appl. Sci. 2020, 10, 2254 2 of 11 are significant for each phase of MOC: Phase 2 (2Mg(OH) MgCl 4H O, MOC 2-1-4) and Phase 9 2· 2· 2 (9Mg(OH)Appl. Sci. 2020MgCl, 10, x FOR5H PEERO, REVIEW MOC 9-1-5), which are stable at elevated temperatures (~100 C); and2 of Phase11 2· 2· 2 ◦ 3 (3Mg(OH)2 MgCl2 8H2O, MOC 3-1-8) and Phase 5 (5Mg(OH)2 MgCl2 8H2O, MOC 5-1-8), which are 46 3 (3Mg(OH)·2∙MgCl2·∙8H2O, MOC 3-1-8) and Phase 5 (5Mg(OH)2∙MgCl· 2∙8H· 2O, MOC 5-1-8), which are stable at ambient temperature until they react with CO2 or H2O. [2–4] The crystal structures of Phase 3 47 stable at ambient temperature until they react with CO2 or H2O. [2–4] The crystal structures of Phase 3 and 5 formed by double and triple ribbons of edges shared MgO6 octahedra with water molecules 48 and 5 formed by double and triple ribbons of edges shared MgO6 octahedra with water molecules and and chloride anions in the interstitial region are shown in Figure1. The drawings were produced by 49 chloride anions in the interstitial region are shown in Figure 1. The drawings were produced by VESTA VESTA Software [5]. 50 Software [5]. 51 52 53 54 55 56 57 58 59 60 61 62 63 64 FigureFigure 1. 1. CrystalCrystal structures of Phase 3 3 (left) (left) and and Phase Phase 5 5(right). (right). Mg Mg atoms atoms are are located located in inthe the centers centers of of 65 distorteddistorted octahedra octahedra formedformed by oxygen atoms. Cl Cl at atoms—green;oms – green; O O atoms atoms—blue. – blue. Green-blue Green-blue spheres spheres in in 66 thethe Phase Phase 55 structures structures correspondcorrespond to a mixed site site occupied occupied by by chloride chloride anions anions and and water water molecules molecules 67 (hydrogen(hydrogen atoms atoms areare notnot shown). 68 MOCMOC phases phases and and MOC-based MOC-based composites composites have have been been intensively intensively studied studied in recent in years.recent Synthesis,years. 69 structure,Synthesis, and structure, the thermal and the stability thermal of magnesiumstability of magnesium oxychlorides oxychlorides in particular in were particular studied were in detailstudied [6, 7]. 70 MOCin detail is a [6,7]. non-hydraulic MOC is a non-hydraulic versatile binder versatile with binder specific with properties, specific properties, which make which it superior make it tosuperior PC. One 71 ofto the PC. most One significantof the most propertiessignificant isproperties its specific is it density,s specific which density, is considerablywhich is considerably lower and lower possesses and 72 materiallypossesses materially high compressive high compressive and flexural and flexural strength. strength. Other Other superior superior properties properties are are its its elevated elevated fire 73 resistance,fire resistance, resistance resistance to abrasion, to abrasion, and and low low thermal thermal conductivity. conductivity. All of of these these properties properties develop develop in in 74 quitequite a a short short curing curing time,time, soso the material is is suitable suitable for for quick quick repairs. repairs. Further, Further, MOC MOC is isnot not affected affected by by 75 oils,oils, grease, grease, or or paint paint [[8–11],8–11], andand it is less alkaline (pH~10) (pH~10) than than PC, PC, making making it itappropriate appropriate for for use use with with 76 glassglass fibers fibers andand preventingpreventing the aging process as as well well as as with with other other fillers fillers and and aggregates aggregates such such as astire tire 77 rubber,rubber, synthetic synthetic resin, resin, and and wood wood particles particles [[12].12]. The advantageadvantage of MOC MOC also also lies lies in in the the fact fact that that it it has has a 78 higha high bonding bonding capacity capacity with with di differentfferent types types ofof filersfilers including secondary secondary raw raw materials materials coming coming from from 79 industrial processes. industrial processes. 80 The versatility and functional performance of MOC-based materials have spurred considerable The versatility and functional performance of MOC-based materials have spurred considerable 81 research into product design, development, and characterization [13–15]. Properties of MOC cement- research into product design, development, and characterization [13–15]. Properties of MOC 82 based materials make them applicable in many ways—primarily as a flooring material, but also in fire cement-based materials make them applicable in many ways—primarily as a flooring material, 83 protective systems, grinding wheels, decoration, wall insulation, and others [16,17]. 84 but alsoAt inthe fire same protective time, these systems, materials grinding have also wheels, some decoration, disadvantages, wall especially insulation, when and they others come [16 ,into17]. 85 contactAt the with same water time, [18,19]. these MOC materials has a have low alsowater some resistance disadvantages, due to magnesium especially chloride when they leaching, come intoa 86 contactcorrosive with compound water [18 that,19 ].causes MOC seve hasre a damage low water when resistance it comes duein contact to magnesium with metals chloride [20–22]. leaching, The rest a 87 corrosiveof the material compound is then that left causesin the form severe of hydrated damage when brucite it (Mg(OH) comes in2 contact) as the binding with metals phase. [20 This–22 ].process The rest 88 ofcan the be material prevented is then by leftimproving in the form the ofstability hydrated of MOC brucite in (Mg(OH) humid conditions,2) as the binding which phase.can be Thisachieved process 89 cannaturally be prevented by letting by the improving surface of the Sorel stability cement of react MOC with in humid CO2 from conditions, the air. The which reaction can be provides achieved 90 naturallymagnesium by lettingchlorocarbonates the surface to ofthe Sorel surface cement of the react original with material. CO2 from Another the air. method The reaction of improving provides 91 magnesiumMOC is to use chlorocarbonates a very small amount to the of surfaceadditives of such the as original phosphoric material. acid or Another soluble methodphosphates of improving of alkali 92 MOCmetals, is alkaline to use a earth very metals, small amountaluminum, of additivesammonia, suchor iron.
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