Oxidizing environments

Advanced Structural and Heating Materials. Molybdenum siHcide [12136-78-6] and composites of MoSi2 and siHcon carbide, SiC, have properties that allow use as high temperature stmctural materials that are stable in oxidizing environments (see Composite materials Metal-matrix composites). Molybdenum disiHcide also finds use in resistance heating elements (87,88). 

They show good to excellent resistance to highly aromatic solvents, polar solvents, water and salt solutions, aqueous acids, dilute alkaline solutions, oxidative environments, amines, and methyl alcohol. Care must be taken in choice of proper gum and compound. Hexafluoropropylene-containing polymers are not recommended for use in contact with ammonia, strong caustic (50% sodium hydroxide above 70°C), and certain polar solvents such as methyl ethyl ketone and low molecular weight esters. However, perfluoroelastomers can withstand these fluids. Propylene-containing fluorocarbon polymers can tolerate strong caustic. 

Actually, in many cases strength and mechanical properties become of secondaiy importance in process applications, compared with resistance to the corrosive surroundings. All common heat-resistant alloys form oxides when exposed to hot oxidizing environments. Whether the alloy is resistant depends upon whether the oxide is stable and forms a protective film. Thus, mild steel is seldom used above 480°C (900°F) because of excessive scaling rates. Higher temperatures require chromium (see Fig. 28-25). Thus, type 502 steel, with 4 to 6 percent Cr, is acceptable to 620°C (I,I50°F). A 9 to 12 percent Cr steel will handle 730°C (I,350°F) 14 to 18 percent Cr extends the limit to 800°C (I,500°F) and 27 percent Cr to I,I00°C (2,000°F). 

Substituting one alloy for another may be the only viable solution to a specific corrosion problem. However, caution should be exercised this is especially true in a cooling water environment containing deposits. Concentration cell corrosion is insidious. Corrosion-resistant materials in oxidizing environments such as stainless steels can be severely pitted when surfaces are shielded by deposits. Each deposit is unique, and nature can be perverse. Thus, replacement materials ideally should be tested in the specific service environment before substitution is accepted. 

Stainless steels contain 11% or more chromium. Table 5.1 lists common commercial grades and compositions of stainless steels. It is chromium that imparts the stainless character to steel. Oxygen combines with chromium and iron to form a highly adherent and protective oxide film. If the film is ruptured in certain oxidizing environments, it rapidly heals with no substantial corrosion. This film does not readily form until at least 11% chromium is dissolved in the alloy. Below 11% chromium, corrosion resistance to oxygenated water is almost the same as in unalloyed iron. 

CH2SH + 1/2 O2 -CH2-S-S-CH2 + H2O This reaction requires an oxidative environment, and such disulfide bridges are usually not found in intracellular proteins, which spend their lifetime in an essentially reductive environment. Disulfide bridges do, however, occur quite frequently among extracellular proteins that are secreted from cells, and in eucaryotes, formation of these bridges occurs within the lumen of the endoplasmic reticulum, the first compartment of the secretory pathway. 

CoiTosion may be uniform or be intensely localized, characterized by pitting. The mechanisms can be direct oxidation, e.g. when a metal is heated in an oxidizing environment, or electrochemical. Galvanic coiTosion may evolve sufficient hydrogen to cause a hazard, due to ... 

The formation of a layer of metal oxide on the surface of this steel provides better corrosion resistance in oxidizing environments than under reducing conditions. Common steels 304, 304L, 347, 316 and 316L are used for equipment exposed to aqueous solutions of acids and other low-temperature corrosive conditions. For high-temperature regimes involving... 

Impregnated carbon and grapliite can be used up to I80°C, and porous graphite can be used up to 400°C in oxidizing environments and 3000°C in a reducing atmosphere. Carbon and graphite bricks and tiles are used for... 

The mitomycins do not react directly with DNA, but require prior activation by reduction of the quinone. This property of bioreductive activation has inspired the design and development of synthetic anticancer drugs that are also activated by reduction, as this is expected to confer a degree of tumor selectivity [45, 46]. Many solid tumors are short of oxygen relative to normal tissue, so reductive activation of the mitomycins and other bioreductive drugs can proceed in tumors, while it is inhibited by the oxidizing environments in normal tissues. 

Price (Ref 39) compares the three principal quantitative models of ignition and concludes that there are serious deficiencies in the existing models, so much so that no one theory appears adequate to represent the complexity of ignition of composite solid proplnts. In the gas-phase model (Refs 22 36) the hot oxidizing environ-... 

McAlevy (M3, M4) developed an approximate mathematical analysis for the ignition of a pyrolyzing fuel in an oxidizing environment as shown in Fig. 5. Hermance (H4, H5) expanded the analysis by incorporating the contributions which were previously omitted. However, the effects of natural... 

To describe hypergolic heating, Anderson and Brown (A10) proposed a theoretical model based upon spontaneous exothermic heterogeneous reactions between the reactive oxidizer and a condensed phase at the gas-solid interface. In these studies, the least complex case was considered, i.e., the one in which the solid phase is instantaneously exposed to a stagnant (nonflowing) gaseous oxidizer environment. This situation can be achieved experimentally provided the sample to be tested is suddenly injected into the desired environment in a manner designed to minimize gas flow. 

Fig. 7. Best-fit agreement between experimental and calculated ignition data for PBAA/AN composite propellant (P8). Key O, pure-oxidizer environment A, oxidizer-nitrogen environment at 55 psia total pressure.

Davis, J. S. and Leckie, J. O. (1978). Effect of adsorbed complexing ligands on trace metal uptake by hydrous oxides. Environ. Sci. Technol. 12, 1309-1315. 

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