Nitridation, high-temperature corrosion

Lai, G. Y "Nitridation, High Temperature Corrosion of Engineering Alloys, ASM International, Materials Park, OH, 1990, pp. 73-84. 

Vanadium in a fuel forms various metal compounds with low melting points, and causes molten-salt corrosion of steel called vanadium attack. Another example of high temperature corrosion is sulfidation. Carbon monoxide, carbon dioxide, and hydrocarbons form metal carbides at high temperatures and this is called carburization. Nitriding involves chemical reaction of nitrogen with metal. 

Silicon nitride, however, has a problem with corrosion resistance in high-temperature corrosive environments such as acid or alkali, and therefore zirconia or silicon carbide is the best material for such applications. However,... 

The variables to be considered here include both the type of ceramic and the environment to which it is exposed. Non-oxide ceramics include borides, nitrides, and carbides. Most high temperature corrosion environments contain oxygen and hence the emphasis of this chapter will be on oxidation processes of the type (Shaw et al., 1987 Jacobson and Opila, 1999) ... 

Although all high-temperature corrosion is considered oxidation, there are other terms that are also encountered, such as oxidation-reduction, sulfidation, fuel ash corrosion, carburization, and nitridation, to name a few. 

The overall simulation of high-temperature corrosion processes under near-service conditions requires both a thermodynamic model to predict phase stabilities for given conditions and a mathematical description of the process kinetics, i.e. solid state diffusion. Such a simulation has been developed by integrating the thermodynamic program library, ChemApp, into a numerical finite-difference diffusion calculation, InCorr, to treat internal oxidation and nitridation of Ni-base alloys [10]. This simulation was intended to serve as a basis for an advanced computer model for internal oxidation and sulfidation of low-alloy boiler steels. 

SiHcon nitride (see Nitrides) is a key material for stmctural ceramic appHcations in environments of high mechanical and thermal stress such as in vehicular propulsion engines. Properties which make this material uniquely suitable are high mechanical strength at room and elevated temperatures, good oxidation and creep resistance at high temperatures, high thermal shock resistance, exceUent abrasion and corrosion resistance, low density, and, consequently, a low moment of inertia. Additionally, siHcon nitride is made from abundant raw materials. 

As noted, the oxidation resistance of silicon nitride ceramics depends on the type and concentration of the sintering aids. In materials designed for high temperature appHcations the specific weight gain resulting from oxidation upon a 500-h air exposure at 1200°C and 1350°C is about 1—2 g/m and 2—4 g/m, respectively. The kinetics of the oxidation process have been iavestigated (63,64) as has the corrosion resistance (65). Corrosion resistance is also dependent on material formulation and density. 

Carbon, Carbides, and Nitrides. Carbon (graphite) is a good thermal and electrical conductor. It is not easily wetted by chemical action, which is an important consideration for corrosion resistance. As an important stmctural material at high temperature, pyrolytic graphite has shown a strength of 280 MPa (40,600 psi). It tends to oxidize at high temperatures, but can be used up to 2760°C for short periods in neutral or reducing conditions. The use of new composite materials made of carbon fibers is expected, especially in the field of aerospace stmcture. When heated under... 

As a future alternative to glassed steel there is ceramics-coated steel which is resistant to abrasion, corrosion and high temperatures. The base metal is coated with silicon nitride formed in situ. Silicon nitride has resistance to both acid and alkali and it is durable at temperatures up to 1 000°C, suggesting a promising future coating in aggressive operating environments. 

Zirconium metal (mp 1855°C 15°C), like titanium, is hard and corrosion resistant, resembling stainless steel in appearance. It is made by the Kroll process (Section 17-A-l). Hafnium metal (mp 2222°C 30°C) is similar. Like titanium, these metals are fairly resistant to acids, and they are best dissolved in HF where the formation of anionic fluoro complexes is important in the stabilization of the solutions. Zirconium will burn in air at high temperatures, reacting more rapidly with nitrogen than with oxygen, to give a mixture of nitride, oxide, and oxide nitride (Zr2ON2). 

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