April 2001

Document Type


Degree Name



Dept. of Materials Science and Engineering


Oregon Health & Science University


New formulations of castable refractory composite materials were studied. This technology is used to produce low cost composite concrete structures designed for high temperature stability, superior wear resistance and improved strength. An in situ fired, castable cement installation is a heterogeneous structure divided into three zones according to the temperature history and microstructure. The properties of each zone depend on the predominant bonding mode between constituents. Each zone has a characteristic microstructure that influences the integrity of the monolith. The hot side may have a highly dense and developed network of ceramic bonds between constituent particles while the cold side may never reach temperatures sufficient to drive off free water. The thermal, structural and tribological properties depend on the microstructure and the type of bonding that holds the monolith together. The phase distributions are defined by sets of metastable phase conditions driven by the local hydrated chemistry, nearest neighbor oxide compounds, impurities and sintering temperature. Equilibrium phase diagrams were used to select optimum compositions based on higher melting point phases. The phase diagrams were also used to target high temperature phase fields that are stable over wide temperature and stoichiometric ranges. Materials selection of candidate hydraulic clinkers, high temperature oxides, and reinforcement phases were based on requirements for high temperature stability. The calcium aluminate (CaO-Al2O3) and calcium dialuminate (CaO- (Al2O3) 2) are common refractory clinkers used in castable refractory cements. The thermodynamics and kinetics of cement hydrate formation are well studied and suited to become the building block of a design for a superior refractory castable cement. The inert oxides mixed with the calcium aluminate clinkers are magnesia (MgO), alumina (Al2O3), spinel (MgAl2O4) and chromia (Cr2O3). The bulk of the experiments concentrated in the Al2O3 - MgO - CaO ternary system. Materials selection criteria for reinforcement materials was based on improved high temperature stability, increased strength, reduced thermal expansion mismatch, low thermal conductivity and increasing wear resistance. The reinforcement phases selected for this investigation are zircon (ZrSiO4), zirconia (ZrO2), spinel (MgAl2O4) and dead burnt magnesia (MgO). Batches of the formulations were tested for thermal conductivity, wear resistance and mechanical strength. Relative rankings of the formulations against commercial products indicate improved or similar performance with increased maximum temperature limits and improved thermal insulating power. The new cement formulations proved to exhibit superior high temperature stability with an increasing volume fraction of high temperature oxides. The addition of reinforcement aggregates and powder sizing to offset the loss of strength. The room temperature compression strength and wear resistance of the optimized formulations exceeded the properties of conventional refractory brick and castable cement tested concurrently.




OGI School of Science and Engineering



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