Being brittle and having low thermal conductivity, refractories suffer damage and sometimes fail in service as a result of thermal shock. While the approach of those making fine-grained technical ceramics is to make their products sufficiently strong to withstand thermal stresses; the refractory technologist is more cunning. He uses, often little known, devices to provide resistance to thermal shock that minimise but do not eliminate damage to the component. In this paper the basic equations of thermal conduction and elasticity are presented and followed by some immediate results that should guide the designer of components subject to severe thermal environments. The influence of size and shape of the refractory components is then discussed along with ways in which refractory producers can engineer the thermal and mechanical properties. In particular, the methods used to tailor fracture behavior to optimize the thermal shock resistance are treated in some detail.

Improved alkali resistant refractoriness are needed for biomass and black liquor gasification (BBLG). One particularly harsh application is linings for gasifiers used in the treatment of black liquor (BL). Black liquor is a water solution of the non-cellulose portion of the wood (mainly lignin) and the spent pulping chemicals (Na2CO3, K2C O3, and Na2S). Development of new refractory materials for the black liquor gasification (BLG) application is a critical issue for implementation of this technology. FactSage@ thermodynamic software was used to analyze the phases present in BL smelt and to predict the interaction of BL smelt with different refractory compounds. The modeling included prediction of the phases formed under the operating conditions of high temperature black liquor gasification (BLG) process. At the operating temperature of the BLG, Fact Sage@predicted that the water would evaporate from the BL and that the organic portion of BL would combust, leaving black liquor smelt composed of sodium carbonate (70-75%), potassium carbonate (2-5%), and sodium sulfide (20-25%). Exposure of aluminosilicates to this smelt leads to significant corrosion due to formation of expansive phases with subsequent cracking and spalling. Oxides (ZrO2, Ce O2, La2O2, Y2 O2, Li2O, MgO and CaO) were determined to be resistant to black liquor smelt but non-oxides (SiC and Si3N4) would oxidize and dissolve in the smelt. The other candidates such as MgAl2 O2 and BaAl2 O4 were resistant to sodium carbonate but not to potassium carbonate. LiAlO2 was stable with both sodium carbonate and potassium carbonate. Candidate materials selected on the basis of the thermodynamic calculations are being tested by sessile drop test for corrosion resistance to molten black liquor smelt. Sessile drop testing has confirmed the thermodynamic predictions for Al2O3, CeO2, MgO and CaO. Sessile drop testing showed that the thermodynamic predictions were incorrect for Zr O2.

Some of the scientific principles underlying the role of carbon and graphite in graphitic refractories are considered, with emphasis on the graphite phase. The highly anisotropic nature of graphite is a key factor in its ability to modify the properties of oxide refractories, resulting in the potential for anisotropy in the subsequent graphitic composite, depending upon the fabrication conditions. The thermal and mechanical properties are considered for model alumina-graphite composites first with no anti-oxidant additives in the formulation to reveal the intrinsic effect of the graphite phase and then effects of silicon as a typical additive are examined. The behaviour is modified considerably when the extent of ceramic bonding in the materials is increased through the reactions of silicon with the gaseous atmosphere and with the constituents in the refractory. Finally, a brief consideration of the structure and properties of typical binder phases is presented.

Improved structures of MgO carbon bonded materials due to new binder systems and due to the application of electrical currents during operation have been achieved for advanced applications in the secondary metallurgy and during near net shape metal casting.

Penetration and dissolution mechanisms are reviewed for predominantly single-phase oxide, two phase oxide and oxide-carbon composite refractories by liquid silicate slags. Theoretical models of these processes, as well as static (sessile drop, dipping and crucible) and dynamic (rotating finger and rotary slag) experimental tests, along with their practical limitations are considered. Direct (congruent or homogeneous) attack is controlled by the reaction rate at the slag-refractory interface or the rate of diffusive transport of species to it through the slag leading to active corrosion. Indirect (incongruent or heterogeneous) attack is controlled by diffusive transport through the slag or through a new solid phase, which forms at the original slagrefractory interface. This may lead to passive corrosion. Examples of direct and indirect attack in a range of refractory/slag systems are described highlighting the critical influence of the composition and hence viscosity of the local liquid slag adjacent the solid refractory. Penetration and corrosion can be controlled either through the local slag composition via the refractory or the bulk slag or by microstructural control of the refractory by e.g. internal generation of dense layers or external deposition/generation of passive coatings, so-called in situ refractories.