Cracking high-temperature corrosion

If the production of vinyl chloride could be reduced to a single step, such as dkect chlorine substitution for hydrogen in ethylene or oxychlorination/cracking of ethylene to vinyl chloride, a major improvement over the traditional balanced process would be realized. The Hterature is filled with a variety of catalysts and processes for single-step manufacture of vinyl chloride (136—138). None has been commercialized because of the high temperatures, corrosive environments, and insufficient reaction selectivities so far encountered. Substitution of lower cost ethane or methane for ethylene in the manufacture of vinyl chloride has also been investigated. The Lummus-Transcat process (139), for instance, proposes a molten oxychlorination catalyst at 450—500°C to react ethane with chlorine to make vinyl chloride dkecfly. However, ethane conversion and selectivity to vinyl chloride are too low (30% and less than 40%, respectively) to make this process competitive. Numerous other catalysts and processes have been patented as weU, but none has been commercialized owing to problems with temperature, corrosion, and/or product selectivity (140—144). Because of the potential payback, however, this is a very active area of research. 

If local stresses exceed the forces of cohesion between atoms or lattice molecules, the crystal cracks. Micro- and macrocracks have a pronounced influence on the course of chemical reactions. We mention three different examples of technical importance for illustration. 1) The spallation of metal oxide layers during the high temperature corrosion of metals, 2) hydrogen embrittlement of steel, and 3) transformation hardening of ceramic materials based on energy consuming phase transformations in the dilated zone of an advancing crack tip. 

A durable protective coating for high-temperature alloys can be achieved by CVD. Normally, we must consider alloy stabilization in addition to chemical reaction in a controlled environment. The results define the nature of coatings for high-temperature corrosion protection, namely, a thin (1-2 pm) diffused silicon layer that covers the surface and penetrates even the smallest defects, cracks, etc., on the alloy to be protected. This surface modification treatment by CVD can be adapted to other alloys and is technologically simple and relatively inexpensive. 

B.J. Smith, C.P. Erskine, R.J. Hartranft, A.R. Marde, High-temperature corrosion-fetigue (circumferential) cracking Hfe evaluation procedure for low alloy (Cr-Mo) boiler mbe steels. Mater. Charact. 34 (1995) 81-86. 

The presence of alumina is expected to provide enhanced high temperature corrosion resistance. Also, the introduction of Si02 into alumina based coatings has been found to form mullite and reduce the cracking within the coating (Marple et al., 2001). Mullite is known for its excellent creep resistance (Dokko et al., 1977 Lessing et al., 1975). 

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