This review examines the detailed chemical insights that have been generated through 150 years of work worldwide on magnesium-based inorganic cements, with a focus on both scientific and patent literature. Magnesium carbonate, phosphate, silicate-hydrate, and oxysalt (both chloride and sulfate) cements are all assessed. Many such cements are ideally suited to specialist applications in precast construction, road repair, and other fields including nuclear waste immobilization. The majority of MgO-based cements are more costly to produce than Portland cement because of the relatively high cost of reactive sources of MgO and do not have a sufficiently high internal pH to passivate mild steel reinforcing bars. This precludes MgO-based cements from providing a large-scale replacement for Portland cement in the production of steel-reinforced concretes for civil engineering applications, despite the potential for CO2 emissions reductions offered by some such systems. Nonetheless, in uses that do not require steel reinforcement, and in locations where the MgO can be sourced at a competitive price, a detailed understanding of these systems enables their specification, design, and selection as advanced engineering materials with a strongly defined chemical basis.

Magnesia-Based Cements: A Journey of 150 Years, and Cements for the Future?

The nucleation, growth, and orientation of lead zirconate titanate thin films prepared from organometallic precursor solutions by spin coating on (111) oriented platinum substrates and crystallized by rapid thermal annealing was investigated. The effects of pyrolysis temperature, post-pyrolysis thermal treatments, and excess lead addition are reported. The use of post-pyrolysis oxygen anneals at temperatures in the regime of 350–450 °C was found to strongly affect the kinetics of subsequent amorphous-pyrochlore-perovskite crystallization by rapid thermal annealing. The use of such post-pyrolysis anneals allowed films of reproducible microstructure and textures [both (100) and (111)] to be prepared by rapid thermal annealing. It is proposed that such anneals and pyrolysis temperature affect the oxygen concentration/average Pb valence in the amorphous films prior to annealing. Such changes in the Pb valence state then affect the stability of the transient pyrochlore phase and thus the kinetics of perovskite crystallization.

/pdf/orientation-of-rapid-thermally-annealed-lead-zirconate-3utfv7rnef.pdf

Orientation of rapid thermally annealed lead zirconate titanate thin films on (111) Pt substrates

Strategies for analyzing data from video fluorometric monitoring of liquid chromatographic effluents

Magnesium-based bioceramics in orthopedic applications.

Influence of molar ratios on properties of magnesium oxychloride cement

Thermal expansion and phase transformations of the U3O8−z phase in air☆

Solubilities of MgO in aqueous HC1 solutions at 23°±3°C were measured and combined with analyses of neat magnesium oxychloride cements, cured in sealed containers, to construct an equilibrium phase diagram for the system MgO-MgCl2-H2O. Specific gravities and acidities of solutions saturated with MgO and relative humidities of vapor phases over sealed samples were measured and combined with XRD data to define the compositions in equilibrium with two crystalline phases. Studies of relative reaction rates indicated that the 5–1–8 phase crystallizes more rapidly than the 3·1·8 phase and that cements near the 3·1·8 composition react rapidly with atmospheric CO2 to form the chlorocarbonate phase.

The System MgO‐MgCl2‐H2O at 23°C

Phase Relations in Magnesium Oxysulfate Cements

The irreversible reaction between zircon and alumina to form mullite and zirconia was observed to proceed very slowly at 1480°C, confirming the existence of a stable join between mullite and zirconia in addition to the join between mullite and zircon. Attempts to determine equilibrium assemblages in powder samples of several combinations of the constituents at 1300° and 1400°C were unsuccessful. Metastable tetragonal ZrO2 was observed in fired powder samples containing kaolinite, in fired zircon-alumina samples, and in calcined gels prepared from zirconyl nitrate, aluminum nitrate, and colloidal silica in water. Tetragonal ZrO2 was the dominant crystalline phase in gels fired for 24 h at 800°, 950°, and 1100°C; the thermal stability of the phase was enhanced by Al2O3 and by SiO2, but most effectively by mixtures of the two. Line broadening measurements and electron microscope observation indicate that the tetragonal ZrO2, with apparent crystallite sizes between 0.009 and 0.1 μm, develops as an intergrowth with, and is stabilized by, the amorphous matrix of Al2O3 and SiO2.

Charles A. Sorrell

Papers

Thermal expansion and phase transformations of the U3O8−z phase in air☆

The System MgO‐MgCl2‐H2O at 23°C

Phase Relations in Magnesium Oxysulfate Cements

Subsolidus Equilibria and Stabilization of Tetragonal ZrO2 in the System ZrO2‐Al2O3‐SiO2

Phase relations in magnesium oxysulfate cements