Resistance to Corrosion

Sainte-Claire Deville observed that aluminium had good resistance to atmospheric corrosion, which included the particular atmosphere of gas lamps (used for street lighting in the Second Empire), an atmosphere laden with hydrogen sulphide (H2S). He also recognised the very good resistance of aluminium in contact with water. 

Many decades of experience with its use in buildings, pubfic works, shipbuilding, etc. have confirmed the observations of the 19th century chemists. Aluminium and the alloys of the 1000, 3000, 5000, 6000 and 8000 series have excellent resistance to atmospheric corrosion in the marine, luban and industrial environments (see Part C). 

This very good resistance to corrosion, as much as lightness, explains the development of numerous aluminium applications and offers users a number of major advantages  

The corrosion products of aluminium are white. They do not stain uncoated or coated metal surfaces, contrary to rust on steel. This is appreciated in certain areas of the chemical industry (textile fibres, etc.), because in case of a corrosive attack of the reactor, the corrosion products of aluminium do not alter the appearance of the products. 

Finally, it should be mentioned that anodising to a depth of a few micrometers helps to preserve optical properties, reflectance, and the decorative features of such products as luxury packaging for cosmetics and decorative panels for buildings. 

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Stainless steel. A group of Cr or Cr —Ni steels showing an unusually high resistance to corrosion by the atmosphere and many chemical reagents. In order to achieve this resistance to corrosion > 12% Cr is necessary. 

Sheet aluminium can be given a colour by a similar process. The aluminium is first made the anode in a bath of chromic acid (p. 377) when, instead of oxygen being evolved, the aluminium becomes coated with a very adherent film of aluminium oxide which is very adsorbent. If a dye is added to the bath the oxide film is coloured, this colour being incorporated in a film which also makes the remaining aluminium resistant to corrosion. This process is called anodising aluminium. 

Because of its resistance to corrosion, zinc may be used to coat iron. This may be done by dipping the iron into molten zinc or by spraying zinc on the iron articles, for example iron sheets. This is known as galvanising. Smaller iron articles may be coated by heating with zinc dust, a process known as sherardising, or suspensions of zinc may be used in paints. 

It is used as a protective agent, particularly for iron, and is more resistant to corrosion by sea water than, for example, zinc or nickel. 

Reactor-grade zirconium is essentially free of hafnium. Zircaloy(R) is an important alloy developed specifically for nuclear applications. Zirconium is exceptionally resistant to corrosion by many common acids and alkalis, by sea water, and by other agents. Alloyed with zinc, zirconium becomes magnetic at temperatures below 35oK. 

Lead is a bluish-white metal of bright luster, is very soft, highly malleable, ductile, and a poor conductor of electricity. It is very resistant to corrosion lead pipes bearing the insignia of Roman emperors, used as drains from the baths, are still in service. It is used in containers for corrosive liquids (such as sulfuric acid) and may be toughened by the addition of a small percentage of antimony or other metals. 

Praseodymium is soft, silvery, malleable, and ductile. It is somewhat more resistant to corrosion in air than europium, lanthanum, cerium, or neodymium, but it does develop a green oxide coating that spalls off when exposed to air. As with other rare-earth metals, it should be kept under a light mineral oil or sealed in plastic. 

Corrosion Resistant Fiber-Reinforced Plastic (FRP). Fiber glass reinforcement bonded with furfuryl alcohol thermosetting resias provides plastics with unique properties. Excellent resistance to corrosion and heat distortion coupled with low flame spread and low smoke emission are characteristics that make them valuable as laminating resins with fiber glass (75,76). Another valuable property of furan FRP is its strength at elevated temperature. Hand-layup, spray-up, and filament-win ding techniques are employed to produce an array of corrosion-resistant equipment, pipes, tanks, vats, ducts, scmbbers, stacks, and reaction vessels for industrial appHcations throughout the world. 

Gold [7440-57-5] Au, is presumably the first metal known and used by humans. It occurs ia nature as a highly pure metal and is treasured because of its color, its extraordinary ductility, and its resistance to corrosion. Early uses ia medicine and dentistry date to the ancient Chinese and Egyptians. In the Middle Ages the demand for gold led to the iatense, unsuccesshil efforts of alchemists to convert base metals iato gold. These pursuits became the basis for chemical science. The search for gold has been an important factor ia world exploration and the development of world trade. 

Chemically Resistant Fibers. Fibers with exceUent chemical resistance to corrosive and/or chemical warfare agents or extreme pH conditions (eg, very acidic or very alkaline) were initially used for protective clothing. However, appHcations for filtration of gases and Hquids in numerous industrial faciHties are now the more important. For example, PPS is suitable for use in filter fabrics for coal-fired boilers because of its outstanding chemical and heat resistance to acidic flue gases and its exceUent durabUity under these end use conditions. Many high tenacity fibers are also chemically inert or relatively unaffected under a variety of conditions. Aramids, gel spun polyethylene, polypropylene, fluorocarbon, and carbon fibers meet these criteria and have been used or are being considered for appHcations where chemical resistance is important. 

Cast lead—calcium—tin alloys usually contain 0.06—0.11 wt % calcium and 0.3 wt % tin. These have excellent fluidity, harden rapidly, have a fine grain stmcture, and are resistant to corrosion. Table 4 Hsts the mechanical properties of cast lead—calcium—tin alloys and other alloys. 

Corrosion and Finishing. With few exceptions, magnesium exhibits good resistance to corrosion at normal ambient temperatures unless there is significant water content ia the environment ia combination with certain contaminants. The reaction which typically occurs is described by the equation... 

The only metals having good or excellent resistance to corrosion by amalgamation with mercury are vanadium, iron, niobium, molybdenum, cesium, tantalum, and tungsten (8). The diffusion rates of some metals in mercury are given in Table 5. 

Both zirconium hydride and zirconium metal powders compact to fairly high densities at conventional pressures. During sintering the zirconium hydride decomposes and at the temperature of decomposition, zirconium particles start to bond. Sintered zirconium is ductile and can be worked without difficulty. Pure zirconium is seldom used in reactor engineering, but the powder is used in conjunction with uranium powder to form uranium—zirconium aUoys by soHd-state diffusion. These aUoys are important in reactor design because they change less under irradiation and are more resistant to corrosion. 

Nickel—Copper. In the soHd state, nickel and copper form a continuous soHd solution. The nickel-rich, nickel—copper alloys are characterized by a good compromise of strength and ductihty and are resistant to corrosion and stress corrosion ia many environments, ia particular water and seawater, nonoxidizing acids, neutral and alkaline salts, and alkaUes. These alloys are weldable and are characterized by elevated and high temperature mechanical properties for certain appHcations. The copper content ia these alloys also easure improved thermal coaductivity for heat exchange. MONEL alloy 400 is a typical nickel-rich, nickel—copper alloy ia which the nickel content is ca 66 wt %. MONEL alloy K-500 is essentially alloy 400 with small additions of aluminum and titanium. Aging of alloy K-500 results in very fine y -precipitates and increased strength (see also Copper alloys). 

Another set of nickel aHoys, which have a high chromium content, a moderate molybdenum content, and some copper, are the ILLIUM aHoys. These cast aHoys are wear and erosion resistant and highly resistant to corrosion by acids and alkaHes under both oxidizing and reducing conditions. 

Resistance to Corrosion Inco Alloys International, Huntington, W. Va., 1985. 

Weak Acid. Stainless steels (SS) have exceUent corrosion resistance to weak nitric acid and are the primary materials of constmction for a weak acid process. Low carbon stainless steels are preferred because of their resistance to corrosion at weld points. However, higher grade materials of constmction are required for certain sections of the weak acid process. These are limited to high temperature areas around the gau2e (ca 900°G) and to places in which contact with hot Hquid nitric acid is likely to be experienced (the cooler condenser and tail gas preheater). 

Commercial-grade nitroparaftins are shipped and stored ia ordinary carbon steel. However, wet nitroparaftins containing more than 0.1—0.2% water may become discolored when stored ia steel for long periods, even though corrosion is not excessive. Aluminum and stainless steel are completely resistant to corrosion by wet nitroparaftins. Storage ia contact with lead (qv), copper, or alloys containing these metals should be avoided. Polymeric materials for gaskets, hoses, and connections should be tested for thek suitabiHty before exposure to nitroparaftins. 

The fifth component is the stmcture, a material selected for weak absorption for neutrons, and having adequate strength and resistance to corrosion. In thermal reactors, uranium oxide pellets are held and supported by metal tubes, called the cladding. The cladding is composed of zirconium, in the form of an alloy called Zircaloy. Some early reactors used aluminum fast reactors use stainless steel. Additional hardware is required to hold the bundles of fuel rods within a fuel assembly and to support the assembhes that are inserted and removed from the reactor core. Stainless steel is commonly used for such hardware. If the reactor is operated at high temperature and pressure, a thick-walled steel reactor vessel is needed. 

The principal advantage of plastic dmms and liners is their resistance to corrosion. This aspect of their performance requires the lading to be investigated in terms of capacity for chemical attack on the dmm. Stress-cracking tests should be performed in all instances where the compatibiUty of jading and dmm material has not been estabUshed (6). 

Copper is by far the most widely used conductor material. It has high electrical conductivity, thermal conductivity, solderabiUty, and resistance to corrosion, wear, and fatigue. Annealed copper conductors can withstand flex and vibration stresses normally encountered in use. 

Plating and Coatings. Thin surface coatings of platinum and platinum alloys are used as decorative finishes and in critical appHcations where it is necessary to provide finishes resistant to corrosion or high temperature, eg, coatings on jet-engine turbine components (258). Compounds used in the electro deposition of platinum are based on Pt(Il) and Pt(IV) and include H2[PtCl3] and its salts, eg, Pt—P—Salt, [Pt(NH3)2(N02)2] H2[Pt(S04)(N02)2] ... 

In dry air at room temperature this reaction is self-limiting, producing a highly impervious film of oxide ca 5 nm in thickness. The film provides both stabihty at ambient temperature and resistance to corrosion by seawater and other aqueous and chemical solutions. Thicker oxide films are formed at elevated temperatures and other conditions of exposure. Molten aluminum is also protected by an oxide film and oxidation of the Hquid proceeds very slowly in the absence of agitation. 

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