The influence of composition and temperature on hydrated phase assemblages in magnesium oxychloride cements

Due to their nonhydraulic nature, magnesium oxychloride cements (MOCs) are susceptible to degradation following contact with water. Improving the water resistance of these materials requires better understanding of hydrated phase relations and the sensitivity of hydrated phases to water. Toward this end, a series of targeted experiments and complementary thermodynamic calculations were carried out to assess hydrated phase assemblages in the system MgO-MgCl2-H2O across a range of compositions. Focus is placed on appraising the effects of composition and reaction temperature. In broad agreement with literature data, under ambient conditions, hydrated MOCs are noted to contain Phase 3 (P3), Phase 5 (P5), and brucite, but the mass partitioning of these phases is highly dependent on H2O/MgCl2 and MgO/MgCl2 molar ratio as well as curing temperature and age. At room temperature, P3 is favored at lower water contents, however, P5 and/or brucite are favored to form as water availability increases. Thermodynamic calculations indicate that P3 is more stable than P5 at lower temperaturesan outcome which impacts the engineering properties, for example, strength and volume stability. The impacts of the accuracy and self-consistency of currently available thermodynamic data and their implications on predicted phase assemblages are discussed.