Oxidation Resistance
For the selection of ceramics in an oxidizing high-temperature environment and, as hard materials, for working or even simply contacting metals, the oxidation resistance is an important criterion. Unfortunately, the data reported in the literature about the oxidation velocity, in particular about the rate constant, are very unreliable and show a large scattering range. This fact can be explained by either the variations in microstructures or by the particular additives and dopants which may change the chemical behavior of the ceramics significantly. Furthermore, the characterization treatments are usually different and yield values that are not comparable. Accordingly, Figure 1.11 represents only tendencies of the oxidation resistance of various ceramics. The most insensitive materials are silicon compounds such as silicon borides, molybdenum disilicide (MoSi2), silicon carbide, and silicon nitride. These materials form a relatively dense silica layer on the surface exposed to air preventing oxygen diffusion to the bulk material beneath. The stability of this oxidation layer being proved efficient in laboratory experiments is, however, in question if it is exposed to aggressive atmospheres containing alkaline volatiles, exposed to alkaline solutions, or removed by abrasive or impact wear. In this case, the material is consumed by continuous oxidation and removal of the newly formed oxidation layer. Another example may show that the weight gain as a measure for oxidation resistance must be evaluated with great care. Boron carbide, (not presented in Figure 1.11) does not exhibit a significant weight gain or weight loss when exposed to air. In reality, the weight gain by the formation of boron oxide layers and the weight loss due to the evaporation of boron oxide balance each other causing the recorded weight to remain almost constant up to 1000 °C until all the boron carbide is transformed to boron oxide. Transition metal borides and carbides undergo severe oxidation during the very first time of exposure followed by more or less parabolic time dependence.
Figure 1.11.
Time dependent oxidation behavior of non-oxides exposed at 1000 °c to air
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Chemical Reactivity
In order to minimize chemical wear at higher temperatures, reactions between materials in contact with each other and work material must be generally excluded or at least run very slowly. This means that the materials are in a thermodynamic equilibrium throughout the expected temperature range or both materials possess a very low enthalpy of formation which is a measure of the stability of compounds. In Figure 1.12, the enthalpy of formation of some more important structural materials are shown. Accordingly, zirconia and alumina are the most stable compounds followed by titanium nitride, titanium carbide, silicon nitride when compared with hard metals: WC and Co which, as an element, has a zero enthalpy of formation by definition. According to this “figure of merit”, the hard metals are less suited for a series of applications due to their high chemical wear. If the enthalpy of formation of the contact materials are known, chemical reactions can be predicted by thermodynamic calculations. Many phase diagrams have already been assessed by experimental investigations together with computer-aided thermodynamic modeling. As an example, in Figure 1.13 the ternary system B-C-Fe is presented. The dashed line shows the considered contact between a boron carbide-based cutting tool during machining steel or a comparable wear-resistant boron carbide coating a steel. This line crosses more then six multicomponent equilibria involving iron borides and iron carbides. This means that boron carbide is not stable together with iron even below 1000 °C but decomposes to form FeB + C, FeB + Fe3C + C, or other borides being rich in iron. From the same phase diagram, it can be predicted that diamond grinding grits are partially dissolved in the iron work material forming cementite if the concentration of carbon gets high enough. This is a well-known problem from drilling steel-reinforced concrete with diamond tools.
Figure 1.12.
Enthalpy of formation of various hard materials
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Figure 1.13.
Isothermal section of the B-C-Fe system; the dashed line represents the contact between boron carbide and steel
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Alumina ceramics, silicon nitride, titanium nitride, and titanium carbide react minimally with steel whereas zirconia may undergo strong chemical wear during sliding contact in spite of its high chemical stability. This is because zirconia is an excellent oxygen ion conductor and suffers therefore from a rapid oxygen transfer to the steel, i.e., zirconia is reduced and iron is oxidized. This reaction may continue to a certain critical oxygen deficiency above which zirconia degrades and forms metallic zirconium. An additional risk for cutting steel with zirconia is the adhesive interaction with manganese sulfide which may result in a build-up of the cutting edges. In contact with metals under nitrogen atmosphere, zirconia may accommodate N instead of O in the crystal lattice and therefore change its transformation behavior.
Thermal Shock Resistance
The resistance against thermal shock describes the tolerance of a material against temperature-induced stresses in the microstructure. Both the isotropy of the thermal expansion of non-cubic crystalline phases as well as the variation of thermal expansion between different phases may give rise to a stress accumulation if the material is loaded with temperature gradients. The critical parameter for thermal shock is usually given as temperature difference ΔTC by which a material can be quenched without significant mechanical damage, e.g., decrease of fracture strength σc For some materials, so-called R-factors are available which give figures of merits for ranking the particular materials for certain applications. The R-factors involve elastic properties like Young’s modulus (E) Poisson ratio (v), the thermal expansion coefficient (a), the thermal conductivity (λ), and the fracture toughness (K1c). The R-factors can be calculated according to the following equations:
equation(1.2)
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equation(1.3)
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equation(1.4)
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Since most of the parameters are microstructure-dependent, they are more or less the critical values for ranking. The critical temperature difference ΔTC is measured by quenching experiments using bending bars and subsequent testing of the fracture strength. In this case, additional information is given by the residual fracture strength σr even if ΔTC is exceeded. The resistance against thermal shock is higher the larger the R-factors have been calculated or the higher the temperature difference is tolerated without decrease of strength. Table 1.4 shows calculated R-values for a series of ceramics and hard materials; this yields evidence that diamond is again the best material if the thermal conductivity is considered. As described before, fracture strength and toughness of diamond or related superhard materials are not adequately known, so these figures of merit give only a tendency. Metallically-behaving, hard materials like transition metal borides and carbides have a comparatively poor figure of merit due to their high thermal expansion and in spite of their high thermal conductivity.