Sulfidation of metallic materials

Z GRZESIK and K PRZYBYLSKI AGH University of Science and Technology, Poland 

Metal sulfides are characterized by lower thermodynamic stabilities in comparison with those of corresponding oxides. Thus, the dissociation pressures of sulfides are much higher and do not differ so significantly as in the case of metal oxides (Table 20.1). Another feature of transition metal sulfides which distinguishes them from oxides is their lower melting points (Table 20.2). In addition, metal sulfides are much more numerous than the 

Sulfide Melting point Oxide Melting point 

Tafo/e 20.3 Sulfides and oxides in some metal-oxidant systems 

1 Collective plot of maximum nonstoichiometry in several metal sulfides and oxides as a function of temperature. 

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Ceramic materials can be made from the oxides, nitrides, carbides, or sulfides of metals. The precursor solution must contain both the metal and the requisite O, N, C, or S in close liaison. Three broad... 

Total Sulfur and Sulfide Sulfur. Total sulfur is predominately in the form of metal sulfate, and because sulfates act as inerts, these materials have htde impact on the process. Sulfide sulfur compounds, on the other hand, react and leave the furnace as a sulfur vapor, which may deposit in the gas handling system. A possible mechanism for this is the partial reaction of SO2 to H2S, followed by... 

At elevated temperatures SF forms the respective fluorides and sulfides with many metals (25). In quart2, it starts to decompose at 500°C (1) in copper or stainless steel, it is less stable (26). The stabiUty of SF at 200 and 250°C in the presence of aluminum, copper, siUcon steel, and mild steel is shown in Table 2 (14). Careful exclusion of moisture from the system improves the stabiUty of sulfur hexafluoride in the presence of most materials. 

Material Protection. The graft copolymers of ethylene sulfide on polyethyleneimine can be used as an antifouHng anticorrosion substrate for iron (439). PEIs or their derivatives are also used in electrolysis baths as brighteners in the electrochemical deposition of metals (440,441). 

AH metals come originally from natural deposits present in the earth s cmst. These ore deposits result from a geological concentration process, and consist mainly of metallic oxides and sulfides from which metals can be extracted. Seawater and brines are another natural source of metals, eg, magnesium (see Chemicals frombrine Magnesium and magnesium alloys Ocean raw materials). Metal extracted from a natural source is called primary metal. 

Heterogeneous Photocatalysis. Heterogeneous photocatalysis is a technology based on the irradiation of a semiconductor (SC) photocatalyst, for example, titanium dioxide [13463-67-7] Ti02, zinc oxide [1314-13-2] ZnO, or cadmium sulfide [1306-23-6] CdS. Semiconductor materials have electrical conductivity properties between those of metals and insulators, and have narrow energy gaps (band gap) between the filled valence band and the conduction band (see Electronic materials Semiconductors). 

Various methods can be used to analy2e succinic acid and succinic anhydride, depending on the characteristics of the material. Methods generally used to control specifications of pure products include acidimetric titration for total acidity or purity comparison with Pt—Co standard calibrated solutions for color oxidation with potassium permanganate for unsaturated compounds subtracting from the total acidity the anhydride content measured by titration with morpholine for content of free acid in the anhydride atomic absorption or plasma spectroscopy for metals titration with AgNO or BaCl2 for chlorides and sulfates, respectively and comparison of the color of the sulfide solution of the metals with that of a solution with a known Pb content for heavy metals. 

The principal direct raw materials used to make sulfuric acid are elemental sulfur, spent (contaminated and diluted) sulfuric acid, and hydrogen sulfide. Elemental sulfur is by far the most widely used. In the past, iron pyrites or related compounds were often used but as of the mid-1990s this type of raw material is not common except in southern Africa, China, Ka2akhstan, Spain, Russia, and Ukraine (96). A large amount of sulfuric acid is also produced as a by-product of nonferrous metal smelting, ie, roasting sulfide ores of copper, lead, molybdenum, nickel, 2inc, or others. 

Many of the by-products of microbial metaboHsm, including organic acids and hydrogen sulfide, are corrosive. These materials can concentrate in the biofilm, causing accelerated metal attack. Corrosion tends to be self-limiting due to the buildup of corrosion reaction products. However, microbes can absorb some of these materials in their metaboHsm, thereby removing them from the anodic or cathodic site. The removal of reaction products, termed depolari tion stimulates further corrosion. Figure 10 shows a typical result of microbial corrosion. The surface exhibits scattered areas of localized corrosion, unrelated to flow pattern. The corrosion appears to spread in a somewhat circular pattern from the site of initial colonization. 

Corrosion products and deposits. All sulfate reducers produce metal sulfides as corrosion products. Sulfide usually lines pits or is entrapped in material just above the pit surface. When freshly corroded surfaces are exposed to hydrochloric acid, the rotten-egg odor of hydrogen sulfide is easily detected. Rapid, spontaneous decomposition of metal sulfides occurs after sample removal, as water vapor in the air adsorbs onto metal surfaces and reacts with the metal sulfide. The metal sulfides are slowly converted to hydrogen sulfide gas, eventually removing all traces of sulfide (Fig. 6.11). Therefore, only freshly corroded surfaces contain appreciable sulfide. More sensitive spot tests using sodium azide are often successful at detecting metal sulfides at very low concentrations on surfaces. 

Raw material input to petroleum refineries is primarily crude oil however, petroleum refineries use and generate an enormous number of chemicals, many of which leave the facilities as discharges of air emissions, wastewater, or solid waste. Pollutants generated typically include VOCs, carbon monoxide (CO), sulfur oxides (SOJ, nitrogen oxides (NOJ, particulates, ammonia (NH3), hydrogen sulfide (HjS) metals, spent acids, and numerous toxic organic compounds. 

The principal constituents of the paniculate matter are lead/zinc and iron oxides, but oxides of metals such as arsenic, antimony, cadmium, copper, and mercury are also present, along with metallic sulfates. Dust from raw materials handling contains metals, mainly in sulfidic form, although chlorides, fluorides, and metals in other chemical forms may be present. Off-gases contain fine dust panicles and volatile impurities such as arsenic, fluorine, and mercury. 

Material requirements for sulfide stress cracking resistant metallic material for oil field equipment, MR-01-75, National Association of Corrosion Engineers, Houston, 1975. 

Sulfur compounds, whether organic or inorganic in nature, cause sulfidation in susceptible materials. The sulfide film, which forms on the surface of much con-stmction materials at low temperatures, becomes friable and melts at higher temperatures. The presence of molten sulfides (especially nickel sulfide) on a metal surface promotes the rapid conversion to metal sulfides at temperatures where these sulfides are thermodynamically stable. High-alloy materials such as 25% Cr, 20% Ni alloys are widely used, but these represent a compromise between sulfidation resistance and mechanical properties. Aluminum and similar diffusion coatings can be of use. 

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