Oxidation, high-temperature steel

J.R. Park, D.D. MacDonald, The fast-growth mechanism of magnetite on carbon steel in oxidizing high-temperature aqueous solutions. Corrosion 45 (1989) 563—571. 

Ferritic stainless steels depend on chromium for high temperature corrosion resistance. A Cr202 scale may form on an alloy above 600°C when the chromium content is ca 13 wt % (36,37). This scale has excellent protective properties and occurs iu the form of a very thin layer containing up to 2 wt % iron. At chromium contents above 19 wt % the metal loss owiag to oxidation at 950°C is quite small. Such alloys also are quite resistant to attack by water vapor at 600°C (38). Isothermal oxidation resistance for some ferritic stainless steels has been reported after 10,000 h at 815°C (39). Grades 410 and 430, with 11.5—13.5 wt % Cr and 14—18 wt % Cr, respectively, behaved significandy better than type 409 which has a chromium content of 11 wt %. 

Metallurgy. The strong affinity for oxygen and sulfur makes the rare-earth metals useflil in metallurgy (qv). Mischmetal acts as a trap for these Group 16 (VIA) elements, which are usually detrimental to the properties of steel (qv) or cast iron (qv). Resistance to high temperature oxidation and thermomechanical properties of several metals and alloys are thus significantly improved by the addition of small amounts of mischmetal or its siUcide (16,17). 

Under severe conditions and at high temperatures, noble metal films may fail by oxidation of the substrate base metal through pores in the film. Improved life may be achieved by first imposing a harder noble metal film, eg, rhodium or platinum—iridium, on the substrate metal. For maximum adhesion, the metal of the intermediate film should ahoy both with the substrate metal and the soft noble-metal lubricating film. This sometimes requires more than one intermediate layer. For example, silver does not ahoy to steel and tends to lack adhesion. A flash of hard nickel bonds weh to the steel but the nickel tends to oxidize and should be coated with rhodium before applying shver of 1—5 p.m thickness. This triplex film then provides better adhesion and gready increased corrosion protection. 

A simple, low cost steel for high temperature service in electric power generation (qv) is the C—0.5% Mo steel known as carbon—half moly, which was widely used for many years. The power industry and oil refineries have turned to 1.25% Cr—0.5% Mo and 2.25% Cr—1% Mo steels for high stress and high temperature service, because these steels have improved resistance to graphitization and oxidation, as weU as higher creep and mpture strength. 

The fifth component is the stmcture, a material selected for weak absorption for neutrons, and having adequate strength and resistance to corrosion. In thermal reactors, uranium oxide pellets are held and supported by metal tubes, called the cladding. The cladding is composed of zirconium, in the form of an alloy called Zircaloy. Some early reactors used aluminum fast reactors use stainless steel. Additional hardware is required to hold the bundles of fuel rods within a fuel assembly and to support the assembhes that are inserted and removed from the reactor core. Stainless steel is commonly used for such hardware. If the reactor is operated at high temperature and pressure, a thick-walled steel reactor vessel is needed. 

A good summary of the behavior of steels in high temperature steam is available (45). Calculated scale thickness for 10 years of exposure of ferritic steels in 593°C and 13.8 MPa (2000 psi) superheated steam is about 0.64 mm for 5 Cr—0.5 Mo steels, and 1 mm for 2.25 Cr—1 Mo steels. Steam pressure does not seem to have much influence. The steels form duplex layer scales of a uniform thickness. Scales on austenitic steels in the same test also form two layers but were irregular. Generally, the higher the alloy content, the thinner the oxide scale. Excessively thick oxide scale can exfoHate and be prone to under-the-scale concentration of corrodents and corrosion. ExfoHated scale can cause soHd particle erosion of the downstream equipment and clogging. Thick scale on boiler tubes impairs heat transfer and causes an increase in metal temperature. 

Sihcon carbide is comparatively stable. The only violent reaction occurs when SiC is heated with a mixture of potassium dichromate and lead chromate. Chemical reactions do, however, take place between sihcon carbide and a variety of compounds at relatively high temperatures. Sodium sihcate attacks SiC above 1300°C, and SiC reacts with calcium and magnesium oxides above 1000°C and with copper oxide at 800°C to form the metal sihcide. Sihcon carbide decomposes in fused alkahes such as potassium chromate or sodium chromate and in fused borax or cryohte, and reacts with carbon dioxide, hydrogen, ak, and steam. Sihcon carbide, resistant to chlorine below 700°C, reacts to form carbon and sihcon tetrachloride at high temperature. SiC dissociates in molten kon and the sihcon reacts with oxides present in the melt, a reaction of use in the metallurgy of kon and steel (qv). The dense, self-bonded type of SiC has good resistance to aluminum up to about 800°C, to bismuth and zinc at 600°C, and to tin up to 400°C a new sihcon nitride-bonded type exhibits improved resistance to cryohte. 

The contact ends of printed circuit boards are copper. Alloys of nickel and iron are used as substrates in hermetic connectors in which glass (qv) is the dielectric material. Terminals are fabricated from brass or copper from nickel, for high temperature appHcations from aluminum, when aluminum conductors are used and from steel when high strength is required. Because steel has poor corrosion resistance, it is always plated using a protective metal, such as tin (see Tin and tin alloys). Other substrates can be unplated when high contact normal forces, usually more than 5 N, are available to mechanically dismpt insulating oxide films on the surfaces and thereby assure metaUic contact (see Corrosion and corrosion control). 

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