Corrosion-resistance Decomposition

Silver reduces the oxygen evolution potential at the anode, which reduces the rate of corrosion and decreases lead contamination of the cathode. Lead—antimony—silver alloy anodes are used for the production of thin copper foil for use in electronics. Lead—silver (2 wt %), lead—silver (1 wt %)—tin (1 wt %), and lead—antimony (6 wt %)—silver (1—2 wt %) alloys ate used as anodes in cathodic protection of steel pipes and stmctures in fresh, brackish, or seawater. The lead dioxide layer is not only conductive, but also resists decomposition in chloride environments. Silver-free alloys rapidly become passivated and scale badly in seawater. Silver is also added to the positive grids of lead—acid batteries in small amounts (0.005—0.05 wt %) to reduce the rate of corrosion. 

The metal parts of the injection molder, ie, the liner, torpedo, and nozzle, that contact the hot molten resin must be of the noncatalytic type to prevent accelerated decomposition of the polymer. In addition, they must be resistant to corrosion by HCl. Iron, copper, and zinc are catalytic to the decomposition and caimot be used, even as components of alloys. Magnesium is noncatalytic but is subject to corrosive attack, as is chromium when used as plating. Nickel alloys such as Duranickel, HasteUoy B, and HasteUoy C are recommended as constmction materials for injection-molding metal parts. These and pure nickel are noncatalytic and corrosion-resistant however, pure nickel is rather soft and is not recommended. 

Oxychlorination of Ethylene or Dichloroethane. Ethylene or dichloroethane can be chlorinated to a mixture of tetrachoroethylene and trichloroethylene in the presence of oxygen and catalysts. The reaction is carried out in a fluidized-bed reactor at 425°C and 138—207 kPa (20—30 psi). The most common catalysts ate mixtures of potassium and cupric chlorides. Conversion to chlotocatbons ranges from 85—90%, with 10—15% lost as carbon monoxide and carbon dioxide (24). Temperature control is critical. Below 425°C, tetrachloroethane becomes the dominant product, 57.3 wt % of cmde product at 330°C (30). Above 480°C, excessive burning and decomposition reactions occur. Product ratios can be controlled but less readily than in the chlorination process. Reaction vessels must be constmcted of corrosion-resistant alloys. 

Because sulfuric acid and halogen are very corrosive, selection of the structural materials is an important issue. Screening tests have been carried out using test pieces of commercially available materials at GA [29], JAEA [30,31], etc. As for the gas-phase environment of the H2S04 decomposition step, some refractory alloys that have been used in conventional chemical plants showed good corrosion resistance. Figure 4.13 shows one of the experimental results of Alloys 800 and —600 obtained under gas-phase sulfuric acid decomposition environments at 850°C. Gas compositions in the upstream and downstream... 

Terephthalic Acid from Toluene. Both carbon monoxide and methanol can react with toluene to yield intermediates that can be oxidized to terephthalic acid. In work conducted mainly by Mitsubishi Gas Chemical Company (62,63), toluene reacts with carbon monoxide and molar excesses of HF and BF3 to yield a jtanz-tolualdehyde—HF—BF3 complex. Decomposition of this complex under carefully controlled conditions recovers HF and BF3 for recycle and ra-tolualdehyde, which can be oxidized in place of para-xyiene to yield terephthalic acid. One drawback of the process is the energy-intensive, and therefore high cost, decomplexing step. The need for corrosion-resistant materials for construction and the need for extra design features to handle the relatively hazardous HF and BF3 also add to the cost. This process can be advantageous where toluene is available and xylenes are in short supply. 

Materials investigations are directed toward establishing corrosion resistance to the various process fluids H2SO4 and its decomposition products and several solutions of HI, H2O and I2 [Trester and Liang, (6)]. 

At high concentrations, corrosion-resistant reactors and an effective acid recovery process are needed, raising the cost of the intermediate glucose. Dilute acid treatments minimize these problems, but a number of kinetic models indicate that the maximum conversion of cellulose to glucose under these conditions is 65 to 70 percent because subsequent degradation reactions of the glucose to HMF and lev-ulinic acid take place. The modem biorefinery is learning to exploit this reaction manifold, because these decomposition products can be manufactured as the primary product of polysaccharide hydrolysis (see below). 

Savitsky E.M., Arskaya, E.P., Lazarev, E.M., and Korotkov, N.A., Investigation of corrosion resistance of materials in the presence of sulfuric acid and its decomposition products applied in the thermochemical cycle of hydrogen production, International Journal of Hydrogen Energy, 1, 393-396, 1982. 

It should be noted that the products of this decomposition are water, carbon dioxide, and HF. While PFSA membrane FCs have been demonstrated for many thousands of hours, the flux of HF is significant enough so that uncoated metallic bipolar plates are precluded. Hard to machine graphite bipolar plates must be used or an electrically conducting corrosively resistive coating must be developed for easily fabricated metal bipolar plates. Lifetime studies of PEM... 

In early attempts to oxidize hydrocarbons electrochemically, organic solvents and corrosion-resistant electrodes (PbO, C, Pt) were used to overcome low reactant solubility and anode dissolution at extreme potentials, -I-1.8 V and up to 4.5 V (326, 327). The primary anodic reaction was usually oxygen evolution or solvent decomposition. The electrode material, nonetheless, affected the product even at the small attainable yields. Thus, toluene oxidized to traces of aldehydes on PbO2 (333), while on Pt it yielded up to 19% benzaldehyde (326). The catalytic efifect of the anode, however, on rate and selectivity was not realized. 

Au-Cu-Ag alloys based on the inter-metallic phases CuAu and CujAu have found applications in dentistry because of their extremely high corrosion resistance, their advantageous mechanical properties such as high strength and ductility, and their decorative gold color (Yasuda, 1991). These alloys age-harden as a result of complex ordering and decomposition reactions by which the phases CujAu I, CuAu I, CuAu II, and an Ag-rich tXj phase are formed, depending on the composition. 

Equilibrium values (decomposition pressure) therefore determine the existence of compounds in metal oxidation, but the rate at which they form is a kinetic problem. Because of the formation of layers of low porosity that separate metal and gaseous phase, the reaction rates of metals vary appreciably. Corrosion resistance in metals therefore means that the oxidation rates under the conditions in which they are used in practice are low. 

The polymer has a lower melting temperature (220°) than poly(tetra-fluoroethylene) (327° C), and so can be processed at 250-300° C on the usual plastics machines. But these machines must be corrosion resistant because of the decomposition already possible at these temperatures. 

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