Precipitation high-temperature alloys

Figure 5-13. Cross-sectional optical micrograph showing the subsurface region in a commercial, high-temperature alloy after long-term oxidation. The subsurface region consists of large voids and smaller oxide precipitates (courtesy of Haynes International).

Carburization involves the formation of internal carbide precipitates. For reasons discussed in Section 5.4, internal carburization is deleterious to the service life of a high-temperature alloy, particularly if the alloy is subjected to thermal cycling down to room temperature. Carburization is a problem mainly for components exposed to process environments above about 900 °C and containing a high content of CO, CH4, or other hydrocarbons. As an example, severe carburization occurs in the cracking tubes used in ethylene and other olefin plants (Kane and Cayard, 1995). Carburization can also be a problem in the heat-treatment of components associated with carbur-... 

Precipitation Hardening. With the exception of ferritic steels, which can be hardened either by the martensitic transformation or by eutectoid decomposition, most heat-treatable alloys are of the precipitation-hardening type. During heat treatment of these alloys, a controlled dispersion of submicroscopic particles is formed in the microstmeture. The final properties depend on the manner in which particles are dispersed, and on particle size and stabiUty. Because precipitation-hardening alloys can retain strength at temperatures above those at which martensitic steels become unstable, these alloys become an important, in fact pre-eminent, class of high temperature materials. 

Nickel—Copper. In the soHd state, nickel and copper form a continuous soHd solution. The nickel-rich, nickel—copper alloys are characterized by a good compromise of strength and ductihty and are resistant to corrosion and stress corrosion ia many environments, ia particular water and seawater, nonoxidizing acids, neutral and alkaline salts, and alkaUes. These alloys are weldable and are characterized by elevated and high temperature mechanical properties for certain appHcations. The copper content ia these alloys also easure improved thermal coaductivity for heat exchange. MONEL alloy 400 is a typical nickel-rich, nickel—copper alloy ia which the nickel content is ca 66 wt %. MONEL alloy K-500 is essentially alloy 400 with small additions of aluminum and titanium. Aging of alloy K-500 results in very fine y -precipitates and increased strength (see also Copper alloys). 

Because of constitutional complexity, the exact chemistries of nickel-base superalloys must be controlled carehiUy in order to avoid the precipitation of deleterious topologically close-packed (TCP) phases and extraneous carbides after long-term high temperature exposure. Heat-treatment schedules and thermomechanical treatments in the case of wrought alloys also are important to provide optimum strength and performance. 

Nickel sulfide, NiS, can be prepared by the fusion of nickel powder with molten sulfur or by precipitation usiag hydrogen sulfide treatment of a buffered solution of a nickel(II) salt. The behavior of nickel sulfides ia the pure state and ia mixtures with other sulfides is of iaterest ia the recovery of nickel from ores, ia the high temperature sulfide corrosion of nickel alloys, and ia the behavior of nickel-containing catalysts. 

The Tj-carbides are not specifically synthesized, but are of technical importance, occurring in alloy steels, stelUtes, or as embrittling phases in cemented carbides. Other complex carbides in the form of precipitates may form in multicomponent alloys or in high temperature reactor fuels by reaction between the fission products and the moderator graphite, ie, pyrographite-coated fuel kernels. 

If an impurity (copper, say) is dissolved in a metal or ceramic (aluminium, for instance) at a high temperature, and the alloy is cooled to room temperature, the impurity may precipitate as small particles, much as sugar will crystallise from a saturated solution when it is cooled. An alloy of A1 containing 4% Cu ( Duralumin ), treated in this way, gives very small, closely spaced precipitates of the hard compound CUAI2. Most steels are strengthened by precipitates of carbides, obtained in this way. ... 

Griess has observed crevice corrosion of titanium in hot concentrated solutions of Cl , SOj I ions, and considers that the formation of acid within the crevice is the major factor in the mechanism. He points out that at room temperature Ti(OH)3 precipitates at pH 3, and Ti(OH)4 at pH 0-7, and that at elevated temperatures and at the high concentrations of Cl ions that prevail within a crevice the activity of hydrogen ions could be even greater than that indicated by the equilibrium pH values at ambient temperatures. Alloys that remain passive in acid solutions of the same pH as that developed within a crevice should be more immune to crevice attack than pure titanium, and this appears to be the case with alloys containing 0-2% Pd, 2% Mo or 2[Pg.169]

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