Insights on the effects of carbonates and phosphates on the hydration of magnesia (alumino-)silicate cements

Abstract

Cements based on magnesium oxide (MgO) and reactive (alumino-)silicates (xSiO2-yAl2O3) have drawn increasing attention owing to their potential to be produced using raw materials with low CO2 emissions. This study examines how the phase assemblages and compressive strengths of magnesia (alumino-)silicate cements are influenced by the addition of sodium hexametaphosphate (NaHMP) and sodium carbonate (Na2CO3). Cement paste samples with a Mg/Si molar ratio of 1.5 and Al/Si molar ratios of 0 and 1.0 were prepared using microsilica (SF) and metakaolin (MK), respectively, and investigated using SEM, TGA, XRD, and 29Si, 27Al, 31P, and 13C MAS NMR. The results showed that the addition of NaHMP and sodium carbonate enhanced the reactivity of the raw materials in the Al-free MgO-SF systems, with magnesium silicate hydrate (M-S-H) being the primary hydrated phase. After 91 days, the degrees of reaction of microsilica were ∼86% and 96% for systems containing 0 and 2.5 wt % Na2CO3, respectively. In contrast, the reactivity of metakaolin in the Al-containing MgO-MK systems was limited to ∼53%, irrespective of Na2CO3 addition, likely due to the excess sodium hexametaphosphate covering the surface of MK. Here, the main reaction products were magnesium aluminosilicate hydrate (M-A-S-H) and hydrotalcite (Mg6Al2CO3(OH)16·4(H2O))-like phases. Despite the MgO-SF systems displaying higher degree of reaction than the MgO-MK systems, the latter exhibited higher compressive strength. Sodium carbonate increased the compressive strength of the MgO-SF systems but decreased that of the MgO-MK systems. Thermodynamic modelling was also carried out and the results generally agreed with the phase formation observed with XRD and solid-state NMR.