Stainless steel corrosive attack

Acidic pH helps break down protective oxides on stainless steels. Corrosion usually develops faster and is more severe as pH decreases. At very low pH, however, attack inside crevices may be no more severe than on regions outside the crevice. 

The amount of hydrogen partial pressure reduction depends upon the materials and the relative thickness of the cladding/ weld overlay and the base metal—the thicker the stainless barrier is relative to the base metal the better.32 Archakov and Grebeshkova33 mathematically considered how stainless steel corrosion barrier layers increase resistance of carbon and low alloy steels to high temperature hydrogen attack. 

Susceptibility to intergranular corrosion also can occur in ferritic stainless steels (Ref 86-90). As with the austenitic stainless steels, the extent of the susceptibility is a function of the chemical composition and the thermal history of the steel. Also, the mechanism of intergranular attack is essentially the same for both classes of stainless steels, specifically, attack of lowered-chromium-content regions adjacent to precipitated chromium-rich carbides and nitrides. However, there are... 

VM) significantly reduces the susceptibility of 316L stainless steel to attack, while titanium is practically immune. Corrosion, apart from affecting the mechanical performance of the implants, also results in contamination of the tissues with metallic ions. 

In unalloyed steel containers formamide discolors slowly during shipment and storage. Both copper and brass are also subject to corrosion, particularly in the presence of water. Lead is less readily attacked. Aluminum and stainless steel are resistant to attack by formamide and should be used for shipping and storage containers where the color of the product is important or when metallic impurities must be minimized. Formamide attacks natural mbber but not neoprene. As a result of the solvent action of formamide, most protective paints and finishes are unsatisfactory when in contact with formamide. Therefore, formamide is best shipped in containers made of stainless steel or in dmms made of, or coated with, polyethylene. Formamide supphed by BASF is packed in Lupolen dmms (230 kg) or Lupolen canisters (60 kg) both in continental Europe and overseas. 

Ferritic stainless steels depend on chromium for high temperature corrosion resistance. A Cr202 scale may form on an alloy above 600°C when the chromium content is ca 13 wt % (36,37). This scale has excellent protective properties and occurs iu the form of a very thin layer containing up to 2 wt % iron. At chromium contents above 19 wt % the metal loss owiag to oxidation at 950°C is quite small. Such alloys also are quite resistant to attack by water vapor at 600°C (38). Isothermal oxidation resistance for some ferritic stainless steels has been reported after 10,000 h at 815°C (39). Grades 410 and 430, with 11.5—13.5 wt % Cr and 14—18 wt % Cr, respectively, behaved significandy better than type 409 which has a chromium content of 11 wt %. 

Aniline is slightly corrosive to some metals. It attacks copper, brass, and other copper alloys, and use of these metals should be avoided in equipment that is used to handle aniline. For appHcations in which color retention is critical, the use of 400-series stainless steels is recommended. 

Shipment nd Stora.ge, Sulfur monochloride is minimally corrosive to carbon steel and iron when dry. If it is necessary to avoid discoloration caused by iron sulfide formation or chloride stress cracking, 310 stainless steel should be used. Sulfur monochloride is shipped in tank cars, tank tmcks, and steel dmms. When wet, it behaves like hydrochloric acid and attacks steel, cast iron, aluminum, stainless steels, copper and copper alloys, and many nickel-based materials. Alloys of 62 Ni—28 Mo and 54 Ni—15 Cr—16 Mo are useful under these conditions. Under DOT HM-181 sulfur monochloride is classified as a Poison Inhalation Hazard (PIH) Zone B, as well as a Corrosive Material (DOT Hazard Class B). Shipment information is available (140). 

Vanadium is resistant to attack by hydrochloric or dilute sulfuric acid and to alkali solutions. It is also quite resistant to corrosion by seawater but is reactive toward nitric, hydrofluoric, or concentrated sulfuric acids. Galvanic corrosion tests mn in simulated seawater indicate that vanadium is anodic with respect to stainless steel and copper but cathodic to aluminum and magnesium. Vanadium exhibits corrosion resistance to Hquid metals, eg, bismuth and low oxygen sodium. 

Crevice Corrosion. Crevice corrosion is intense locali2ed corrosion that occurs within a crevice or any area that is shielded from the bulk environment. Solutions within a crevice are similar to solutions within a pit in that they are highly concentrated and acidic. Because the mechanisms of corrosion in the two processes are virtually identical, conditions that promote pitting also promote crevice corrosion. Alloys that depend on oxide films for protection (eg, stainless steel and aluminum) are highly susceptible to crevice attack because the films are destroyed by high chloride ion concentrations and low pH. This is also tme of protective films induced by anodic inhibitors. 

Carbon disulfide is normally stored and handled in mild steel equipment. Tanks and pipes are usually made from steel. Valves are typically cast-steel bodies with chrome steel trim. Lead is sometimes used, particularly for pressure reUef disks. Copper and copper alloys are attacked by carbon disulfide and must be avoided. Carbon disulfide Hquid and vapor become very corrosive to iron and steel at temperatures above about 250°C. High chromium stainless steels, glass, and ceramics maybe suitable at elevated temperatures. 

Chlorosulfuric acid attacks brass, bronze, lead, and most other nonferrous metals. From a corrosion standpoint, carbon steel and cast Hon are acceptable below 35°C provided color and Hon content is not a concern. Stainless steels (300-series) and certain aluminum alloys are acceptable materials of constmction, as is HasteUoy. Glass, glass-lined steel, or Teflon-lined piping and equipment are the preferred materials at elevated temperatures and/or high velocities or where trace Hon contamination is a problem, such as in the synthetic detergent industry. 

An especially insidious type of corrosion is localized corrosion (1—3,5) which occurs at distinct sites on the surface of a metal while the remainder of the metal is either not attacked or attacked much more slowly. Localized corrosion is usually seen on metals that are passivated, ie, protected from corrosion by oxide films, and occurs as a result of the breakdown of the oxide film. Generally the oxide film breakdown requires the presence of an aggressive anion, the most common of which is chloride. Localized corrosion can cause considerable damage to a metal stmcture without the metal exhibiting any appreciable loss in weight. Localized corrosion occurs on a number of technologically important materials such as stainless steels, nickel-base alloys, aluminum, titanium, and copper (see Aluminumand ALUMINUM ALLOYS Nickel AND nickel alloys Steel and Titaniumand titanium alloys). 

Siace dimer acids, monomer acids, and trimer acids are unsaturated, they are susceptible to oxidative and thermal attack, and under certain conditions they are slightly corrosive to metals. Special precautions are necessary, therefore, to prevent product color development and equipment deterioration. Type 304 stainless steel is recommended for storage tanks for dimer acids. Eor heating coils and for agitators 316 stainless steel is preferred (heating coils with about 4s m (50 ft ) of heat transfer surface ia the form of a 5.1 cm schedule-10 U-bend scroU are recommended for a 37. 9-m (10,000-gal) tank. Dimer acid storage tanks should have an iaert gas blanket. 

Nickel and Nickel Alloys A wide range of ferrous and nonfer-rous nickel and nickel-bearing alloys are available. They are usually selected because of their improved resistance to chemical attack or their superior resistance to the effects of high temperature. In general terms their cost and corrosion resistance are somewhat a func tion of their nickel content. The 300 Series stainless steels are the most generally used. Some other frequently used alloys are hsted in Table 10-35 together with their nominal compositions. For metallurgical and corrosion resistance data, see Sec. 28. 

Liquid-Metal Corrosion Liquid metals can also cause corrosion failures. The most damaging are liqmd metals which penetrate the metal along grain boundaries to cause catastrophic failure. Examples include mercury attack on aluminum alloys and attack of stainless steels by molten zinc or aluminum. A fairly common problem occurs when galvanized-structural-steel attachments are welded to stainless piping or eqmpment. In such cases it is mandatoty to remove the galvanizing completely from the area which will be heated above 260°C (500°F). 

Short-time tests also can give misleading results on alloys that form passive films, such as stainless steels. With Borderline conditions, a prolonged test may be needed to permit breakdown of the passive film and subsequently more rapid attack. Consequently, tests run for long periods are considerably more reahstic than those conducted for short durations. This statement must be quahfied by stating that corrosion should not proceed to the point at which the original specimen size or the exposed area is drastic y reduced or the metal is perforated. 

Figure 2.7 Severe waterline attack in stainless steel beeiker. The beaker contained a chlorinated biocide tablet in water over a weekend. Perforations occurred in 40 hours or less, giving a minimum corrosion rate of 4380 mils (11.1 cm) per year at the perforations.

There is often a period before corrosion starts in a crevice in passivating metals. This so-called incubation period corresponds to the time necessary to establish a crevice environment aggressive enough to dissolve the passive oxide layer. The incubation period is well known in stainless steels exposed to waters containing chloride. After a time period in which crevice corrosion is negligible, attack begins, and the rate of metal loss increases (Fig. 2.8). 

The crevice shape markedly affects corrosion. Crevices so tight that water may not enter are entirely immune to attack. In misting environments or alternately wet-diy environments, the crevice holds water and may allow continued attack even when neeu by surfaces eire dry. In sea water, the severity of attack in stainless steel crevices depends on the ratio of the crevice area to the cathodic surface area outside the crevice. If the cathodic area is large relative to crevice eirea, corrosion is promoted. 

Pitting is also promoted by low pH. Thus, acidic deposits contribute to attack on stainless steels. Amphoteric alloys such as aluminum are harmed by both acidic and alkaline deposits (Fig. 4.4). Other passive metals (those that form protective corrosion product layers spontaneously) are similarly affected. 

Corrosion resistance of stainless steel is reduced in deaerated solutions. This behavior is opposite to the behavior of iron, low-alloy steel, and most nonferrous metals in oxygenated waters. Stainless steels exhibit very low corrosion rates in oxidizing media until the solution oxidizing power becomes great enough to breach the protective oxide locally. The solution pH alone does not control attack (see Chap. 4, Underdeposit Corrosion ). The presence of chloride and other strong depassivating chemicals deteriorates corrosion resistance. 

Oxygen corrosion only occurs on metal surfaces exposed to oxygenated waters. Many commonly used industrial alloys react with dissolved oxygen in water, forming a variety of oxides and hydroxides. However, alloys most seriously affected are cast irons, galvanized steel, and non-stainless steels. Attack occurs in locations where tuberculation also occurs (see Chap. 3). Often, oxygen corrosion is a precursor to tubercle development. 

Corrosion morphologies. Sulfate-reducing bacteria frequently cause intense localized attack (Figs. 6.2 through 6.7). Discrete hemispherical depressions form on most alloys, including stainless steels, aluminum. Carpenter 20, and carbon steels. Few cases occur on titanium. Copper alloy attack is not well defined. 

Attack at welds due to bacteria is possible, but it is not nearly so common as is often supposed. Because of residual stresses, microstruc-tural irregularities, compositional variation, and surface irregularities, welds show a predisposition to corrode preferentially by most corrosion mechanisms. Attack is common along incompletely closed weld seams such as at butt welds in light-gauge stainless steel tubing (Fig. 6.9A and B). Attack at carbon steel welds may occur. Figure 6.10 shows a severely corroded carbon steel pipe from a service water sys-... 

Figure 6.9 Irregular deposit and corrosion-product mounds containing concentrations of sulfate-reducing bacteria on the internal surface of a 316 stainless steel transfer line carrying a starch-clay mixture used to coat paper material. Attack only occurred along incompletely closed weld seams, with many perforations. Note the heat tint, partially obscured by the deposit mounds, along the circumferential weld.

Stainless steels attacked by sulfate reducers show well-defined pits containing relatively little deposit and corrosion product. On freshly corroded surfaces, however, black metal sulfides are present within pits. Rust stains may surround pits or form streaks running in the direction of gravity or flow from attack sites. Carbon steel pits are usually capped with voluminous, brown friable rust mounds, sometimes containing black iron sulfide plugs fFig. 6.10). 

Acidic attack on stainless steels differs from corrosion on nonsteunless steels in two important respects. First, nonoxidizing acid corrosion is usually more severe in deaerated solutions second, oxidizing acids attack stainless steel far less strongly than carbon steel. Hence, nitric acid solutions at low temperatures cause only superficial damage, but hydrochloric acid causes truly catastrophic damage. 

Stainless steels tend to pit in acid solutions. Pits form local areas of metal loss associated with breakdown of a protective oxide layer. Breakdown is stimulated by low pH as well as by the decrease of dissolved oxygen in occluded regions. Small, active pit sites form and remain stable because of the large ratio of cathodic surface area (unattacked metal surface) to the pit area. Active corrosion in the pit cathodically protects immediately adjacent areas. If conditions become very severe, pitting will give way to general attack as more and more of the surface becomes actively involved in corrosion. 

Alloys whose corrosion resistance depends on forming a protective oxide layer, such as stainless steel, are susceptible to severe localized attack when pH falls as a result of nonoxidizing acid excursions. How-... 

Fresh acid attack is recognized by the absence of corrosion product in wasted areas and the sharpness of attack. Oxide layers are usually easily stripped by a test drop of hydrochloric acid in freshly corroded areas. Deposits are almost always absent. Edges of attacked areas are sharp and angular, as intervening corrosion has not recently occurred. In stainless steels such distinctions blur, as corrosion in intervening periods is usually slight. 

Corrosion of industrial alloys in alkaline waters is not as common or as severe as attack associated with acidic conditions. Caustic solutions produce little corrosion on steel, stainless steel, cast iron, nickel, and nickel alloys under most cooling water conditions. Ammonia produces wastage and cracking mainly on copper and copper alloys. Most other alloys are not attacked at cooling water temperatures. This is at least in part explained by inherent alloy corrosion behavior and the interaction of specific ions on the metal surface. Further, many dissolved minerals have normal pH solubility and thus deposit at faster rates when pH increases. Precipitated minerals such as phosphates, carbonates, and silicates, for example, tend to reduce corrosion on many alloys. 

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