Metallic alloys, high-temperature corrosion

Lai, G. Y., Carburization and Metal Dusting, High Temperature Corrosion of Engineering Alloys, ASM International, Materials Park, OH, 1990, pp. 47-72. 

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 %. 

The most common form of corrosion is uniform corrosion, in which the entire metal surface degrades at a near uniform rate (1 3). Often the surface is covered by the corrosion products. The msting of iron (qv) in a humid atmosphere or the tarnishing of copper (qv) or silver alloys in sulfur-containing environments are examples (see also SiLVERAND SILVER ALLOYS). High temperature, or dry, oxidation, is also usually uniform in character. Uniform corrosion, the most visible form of corrosion, is the least insidious because the weight lost by metal dissolution can be monitored and predicted. 

Mrowec et examined the resistance to high-temperature corrosion of Fe alloys with Cr contents between 0.35 and 74 at% Cr in 101 kPa S vapour. They found that the corrosion was parabolic, irrespective of the temperature or alloy composition, and noted that sulphidation takes place at a rate five orders of magnitude greater than oxidation at equivalent temperatures. At less than 2% Cr, the alloys formed Fe, j.,S growing by outward diffusion of Fe ions, with traces of FeCr2S4 near the metal core. 

T. A. Ramanarayanan and C. M. Chun, Chapter 6 Metal Dusting Corrosion of Metals and Alloys, New Development in High Temperature Corrosion and Protection of Materials, Ed. W. Gao and Z. Li, Woodhead Publishing Ltd., Cambridge, UK p.80-116 (2008). 

In selecting metals and alloys as materials of construction, one must have knowledge of how materials fail, for example is, how they corrode, become brittle with low-temperature operation, or degrade as a result of operating at high temperatures. Corrosion, embrittlement, and other degradation mechanisms such as creep will be described in terms of their threshold values. Transient or upset operating conditions are common causes of failure. Examples include start-ups and shutdowns, loss of coolant, the formation of dew point water, and hot spots due to the formation of scale deposits on heat transfer surfaces. Identification and documentation of all anticipated upset and transient conditions are required. 

The purpose of this review paper is to survey the principles of high temperature oxidation or high temperature corrosion. A typical situation is that of a metal exposed to a hot gas which can act as an oxidant. In many cases the oxidation product forms a layer which separates the reactants, the metal and the gas atmosphere. Under special conditions, the kinetics are diffusion controlled, i. e,, the rate of the reaction (the rate of oxide thickness growth) depends on the diffusion of species, ions and electrons, through the layer (sometimes called a tarnish layer). Actually when a metal or alloy is exposed to a corrosive gas, the reaction kinetics may be controlled by one or more of the following steps ... 

High-temperature corrosion is a practical problem in most applications of metals and alloys at elevated temperatures in corrosive environments. In power plants, chemical and petrochemical process industries, for aircraft engines, heat treatment and other metallurgical processes, and new technologies such as waste-incineration plants, high-temperature fuel cells, and so on, the metallic materials must he carefully selected, to allow sufficient lifetime and avoid premature failure. Sometimes processes are not possible since the materials would not withstand the process conditions that must he adapted to the available materials. 

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