Corrosion metallurgy

Many factors influence acid corrosion. Metallurgy, temperature, water turbulence, surface geometry, dissolved oxygen concentration, metal-ion concentration, surface fouling, corrosion-product formation, chemical treatment, and, of course, the kind of acid (oxidizing or nonoxidizing, strong or weak) may markedly alter corrosion. 

Physical Properties. An overview of the metallurgy (qv) and soUd-state physics of the rare earths is available (6). The rare earths form aUoys with most metals. They can be present interstitiaUy, in soUd solutions, or as intermetaUic compounds in a second phase. Alloying with other elements can make the rare earths either pyrophoric or corrosion resistant. It is extremely important, when determining physical constants, that the materials are very pure and weU characteri2ed. AU impurity levels in the sample should be known. Some properties of the lanthanides are Usted in Table 3. 

Niobium is also important in nonferrous metallurgy. Addition of niobium to tirconium reduces the corrosion resistance somewhat but increases the mechanical strength. Because niobium has a low thermal-neutron cross section, it can be alloyed with tirconium for use in the cladding of nuclear fuel rods. A Zr—l%Nb [11107-78-1] alloy has been used as primary cladding in the countries of the former USSR and in Canada. A Zr—2.5 wt % Nb alloy has been used to replace Zircaloy-2 as the cladding in Candu-PHW (pressurized hot water) reactors and has resulted in a 20% reduction in wall thickness of cladding (63) (see Nuclear reactors). 

The reaction is facilitated by elevated temperature necessitating pressure-capable, glass-lined reactors and exotic metallurgy for fittings to withstand the severely corrosive conditions. PAG product having 10—12% Al as AI2O2 can be produced. 

Chemical appHcations of Mn ssbauer spectroscopy are broad (291—293) determination of electron configurations and assignment of oxidation states in stmctural chemistry polymer properties studies of surface chemistry, corrosion, and catalysis and metal-atom bonding in biochemical systems. There are also important appHcations to materials science and metallurgy (294,295) (see Surface and interface analysis). 

W. D. Wilkinson, Uranium Metallurgy, Vol. 1, Trocess Metallurgy, Vol. 11, Uranium Corrosion and Alloys, Wdey-lnterscience, New York, 1962. 

Approximately 5% of the U.S. consumption of is in agriculture. Boron is a necessary trace nutrient for plants and is added in small quantities to a number of fertilizers. Borates are also used in crop sprays for fast rehef of boron deficiency. Borates, when apphed at relatively high concentration, act as nonselective herbicides. Small quantities of borates are used in the manufacture of alloys and refractories (qv). Molten borates readily dissolve other metal oxides usage as a flux in metallurgy is an important apphcation. Other important small volume apphcations for borates are in fire retardants for both plastics and ceUulosic materials, in hydrocarbon fuels for fungus control, and in automotive antifreeze for corrosion control (see Corrosion and corrosion inhibitors). Borates are used as neutron absorbers in nuclear reactors. Several borates, which are registered with the Environmental Protection Agency (EPA) can be used for insecticidal purposes, eg, TIM-BOR. 

The metallurgy of the cyclone equipment has in recent years focused primarily on type 304 H stainless steel. The 304 H material is durable and easy to fabricate and repair, withstands the high regenerator temperatures, and is oxidation- and corrosion-resistant. Essentially all internal surfaces of the cyclone that are subject to erosion are protected with a 2 cm layer of erosion-resistant lining. When installed and cured, most refractory linings are highly resistant to erosion. 

Ores are mined and are then refined in an energy intensive process to produce pure metals, which in turn are combined to make alloys (see Metallurgy Mineral RECOVERY and processing). Corrosion occurs because of the tendency of these refined materials to return to a more thermodynamically stable state (1—4). The key reaction in corrosion is the oxidation or anodic dissolution of the metal to produce metal ions and electrons... 

The most chemical-resistant plastic commercially available today is tetrafluoroethylene or TFE (Teflon). This thermoplastic is practically unaffected by all alkahes and acids except fluorine and chlorine gas at elevated temperatures and molten metals. It retains its properties up to 260°C (500°F). Chlorotrifluoroethylene or CTFE (Kel-F, Plaskon) also possesses excellent corrosion resistance to almost all acids and alkalies up to 180°C (350°F). A Teflon derivative has been developed from the copolymerization of tetrafluoroethylene and hexafluoropropylene. This resin, FEP, has similar properties to TFE except that it is not recommended for continuous exposures at temperatures above 200°C (400°F). Also, FEP can be extruded on conventional extrusion equipment, while TFE parts must be made by comphcated powder-metallurgy techniques. Another version is poly-vinylidene fluoride, or PVF2 (Kynar), which has excellent resistance to alkahes and acids to 150°C (300°F). It can be extruded. A more recent development is a copolymer of CTFE and ethylene (Halar). This material has excellent resistance to strong inorganic acids, bases, and salts up to 150°C. It also can be extruded. 

Wastage was caused by crevice corrosion, accelerated by the difference in tube and tube sheet metallurgies. The brass tube, being more noble, was cathodically protected by corrosion of the surrounding mild steel tube sheet. However, the galvanic effect was secondary to the primary cause of failure, namely, crevice corrosion. 

Virtually all metallurgies can be attacked by corrosive bacteria. Cases of titanium corrosion are, however, rare. Copper alloys are not immune to bacterial attack however, corrosion morphologies on copper alloys are not well defined. Tubercles on carbon steel and common cast irons sometimes contain sulfate-reducing and acid-producing bacteria. Potentially corrosive anaerobic bacteria are often present beneath... 

Coupon tests involved a number of metallurgies and were done to evaluate precipitator-plate alloys. Test stainless steel plates failed, not only because of pitting but also because stress-corrosion cracks developed. 

Figure 8.1 Effect of pH on corrosion of 1100-H14 alloy (aluminum) by various chemical solutions. Observe the minimal corrosion in the pH range of 4-9. The low corrosion rates in acetic acid, nitric acid, and ammonium hydroxide demonstrate that the nature of the individual ions in solution is more important than the degree of acidity or alkalinity. (Courtesy of Alcoa Laboratories from Aluminum Properties and Physical Metallurgy, ed. John E. Hatch, American Society for Metals, Metals Park, Ohio, 1984, Figure 19, page 295.)...

Because alterations to equipment design can be cumbersome and expensive, a more economical approach may be to change the metallurgy of affected components. Metals used in typical cooling water environments vary in their resistance to erosion-corrosion. Listed in approximate order of increasing resistance to erosion-corrosion, these are copper, brass, aluminum brass, cupronickel, steel, low-chromium steel, stainless steel, and titanium. 

Occasionally, tubes affected by erosion-corrosion or erosion processes may be confined to specific regions of the equipment. In this case, only the metallurgy of affected tubes needs to be altered. For example,... 

When combating erosion-corrosion by changing tube metallurgy, caution must be exercised to ensure appropriate tube and baffle spacing so that vibration-associated cracking problems are not introduced. 

Changing the pump metallurgy to a more corrosion- and cavitation-resistant material, such as stainless steel, is a potential solution to this type of problem. Note, however, that all other cast iron pump components that have sustained graphitic corrosion should be replaced to avoid the possibility of galvanic corrosion (see Chap. 16) between retained graphitically corroded cast iron components and new components. 

Dealloying is influenced by many factors. In general, any process that increases general corrosion will promote dealloying. However, specific acceleration factors may be further classified into one of three categories metallurgy, environment, and water chemistry. 

Caution is also necessary when changing the metallurgy of tubes in a heat exchanger. Choosing more noble tubes may induce galvanic corrosion of the tube sheet. Problems can result if the tube sheet is not thick enough to accommodate the increased corrosion rate. 

Metallurgy is another cost versus operability factor for heat exchangers. For example, for seawater service some companies specify 90/10 Cu-Ni tubes as minimum and do not allow the cheaper, but more prone to corrosion, aluminum-brass. One can even consider going on up to 70/30 Cu-Ni, or to one of the modern, high-performance... 

Other examples of metallurgy decisions are red brass versus admiralty tubes with fresh water on the tubeside and suspected stress corrosion cracking conditions on the shellside, and stainless steel versus carbon steel with chlorides present. A good metallurgist should be brought in when these kinds of decisions are needed. 

Next to sales contract specifications, coiTosion protection ranks highest among the reasons for the removal of acid gases. The partial pressure ol the acid gases may be used as a measure to determine whether treatment IS required. The partial pressure of a gas is defined as the total pressure of the system times the mole % of the ga,seous component. Where ( 02 is present with free water, a partial pres.sure ot. hi psia or greater would indicate that CO2 corrosion should be expected. If CO2 is not removed, inhibition and special metallurgy may be required. Below 15 psia, COt corrosion is not normally a problem, although inhibition may be required. 

Hi.S may cause hydrogen embrittlement in certain metals. Figures 7-1 and 7 -2 show the H2S concentration at which the National Association of Corrosion Engineers (NACE) recommends special metallurgy to guard against H9S corrosion. 

Stressed, such as heat-affected zones near welds, in areas of high acid-gas concentration, or at a hot gas-liquid interface. Therefore, stress-relieving all equipment after manufacturing is necessary to reduce corrosion, and special metallurgy in specific areas such as the still overhead or the reboiler tubes may be required. 

Miscellaneous (nuclear shielding, metallurgy, corrosion control, leather tanning, flame-proofing, catalysts) 19% (26%)... 

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