CSI SS Guide
CSI SS Guide
CSI SS Guide
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . page 2 What is Stainless Steel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . page 3 Stainless Steel Classifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . page 4
Austenitic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . page 4 Ferritic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . page 5 Duplex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . page 5 Martensitic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . page 6 Precipitation Hardening . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Page 6
Nickel Based Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . page 6 Strength & Heat Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . page 7 The Basics of Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . page 8
General or Uniform Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . page 9 Galvanic Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . page 11 Pitting Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . page 11 Crevice Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . page 13 Intergranular Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . page 14 Stress Corrosion Cracking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . page 15 Microbiologically Influence Corrosion . . . . . . . . . . . . . . . . . . . . . . . . page 17
We have strived in this document to provide engineers, purchasing agents, and plant personnel with a tool to enhance their knowledge of stainless steel and it uses as related to their present and future applications.
STEEL Stainless
What is stainless steel? Stainless steel is not a single alloy, but a large family of alloys with different properties for each member. There are hundreds of grades and sub grades in the stainless steel family, each designed for a special application. Chromium is the magic element that transforms iron into stainless steel. Stainless steel must contain at least 10.5% chromium to provide adequate resistance to rusting, and the more chromium the alloy contains, the better the corrosion resistance becomes. There is, however an upper limit to the amount of chromium the iron can hold. Therefore additional alloying elements are necessary to develop corrosion resistance to specific medias. We must remember that stainless steel is an alloy of iron. According to its definition, stainless steel must contain a minimum of 50% iron. If it contains less iron, the alloy system is named for the next major element. For example, if the iron is replaced with nickel-so that the iron is less than 50%-then it is called a nickel alloy.
Chromium imparts a special property to the iron that makes it corrosion resistant. When the chromium is in excess of 10.5%, the corrosion barrier changes from an active film to a passive film. While the active film continues to grow over time in the corroding solution until the base metal is consumed, the passive film will form and stop growing. This passive layer is extremely thin, in the order of 10 to 100 atoms thick, and is composed mainly of chromium oxide which prevents further diffusion of oxygen into the base metal. But, chromium also is stainless steels Achilles heel, and the chloride ion is stainless steels nemesis. The chloride ion combines with chromium in the passive layer, forming soluble chromium chloride. As the chromium dissolves, free iron is exposed on the surface and reacts with the environment forming rust. Alloying elements like molybdenum will minimize this reaction. Other elements, as illustrated in Table I (page 1), may be added for special purposes. These purposes include: high temperature oxidation resistance, sulfuric acid resistance, greater ductility, high temperature creep resistance, abrasion resistance, or high strength. Of all these elements, only chromium is required in order for stainless steel to be stainless.
Precipitation Hardening
Characteristics
Non-magnetic, Usually Very ductile Work hardenable Lower strength Not subject to 885F (475C) embrittlement Not subject to ductile brittle temperature range Not subject to hydrogen embrittlement Will chloride stress corrosion crack Type 304, 304L, 304H, 304N, 304LN, 321, 347 Type 316, 316L, 316H, 316N, 316LN, 316Ti Type 317, 317L, 317LM, 904L AL6XN, 254 SMO, 25-6Mo, 1925hMo Type 308, 309, 310
These are the most popular of the stainless steels because of their ductility, ease of working and good corrosion resistance. All were derived from the 18Cr-8Ni stainless steels. Their corrosion resistance may be compared to the rungs on a ladder with Type 304 on the first rung and the other grades occupying the successive rungs. The most common grade is
Examples
Type 304/304L, which makes up over 60% of all the stainless steel made in the United States today. The other grades are developed from the 188 base by adding alloying elements to provide special corrosion resistant properties or better weldability. For example, adding titanium to Type 304 makes Type 321, the workhorse of the intermediate temperature materials. Adding 2% molybdenum to Type 304 makes Type 316, which has better chloride corrosion resistance. Adding more chromium gives Type 310 the basis for high temperature applications. The major weakness of the austenitic stainless steels is their susceptibility to chloride stress corrosion cracking. Table III (page 2) lists characteristics, properties and examples of these alloys.
that of titanium. The most widely used ferritic stainless steel is Type 409, a 10.5% Ce alloy with no nickel, used for automotive exhaust systems. Ferritic stainless steels are resistant to chloride stress corrosion cracking, and have high strength. Grades like SEA-CURE stainless have the highest modulus of elasticity of the common engineering alloys, which makes them highly resistant to vibration. Table IV (page 3) lists characteristics, properties and types of these alloys.
resistance and good ductility characterize them. One alloy, Carpenter 7-Mo PLUS has the best corrosion resistance against nitric acid of any of the stainless steels because of its very high chromium content and duplex structure. Table V (page 3) lists the characteristics, properties and examples of these alloys.
Examples
but are infinitely better than the carbon steels they replace. Like carbon tool steels, martensitic stainless steels derive their excellent hardness from the carbon added to the alloy. Their ability to maintain a keen edge comes from their high hardness and corrosion resistance. Table VI (page 4) lists the characteristics and some examples of these alloys.
The alloy strength is controlled by the chemical composition and the metallurgical structure. Only the martensitic and precipitation hardening stainless steels can be heat treated to obtain higher strength. Strengthening, or an
increase in the ultimate and yield strengths, of the other grades must be achieved by cold working the structure. Heat treatment of the austenitic, martensitic and duplex grades is used to remove residual stress and, in the case of the austenitic stainless steels, to reduce the probability of chloride stress corrosion cracking. Heat treatment is also used to dissolve any undesirable metallurgical phases that may be present. Heating and cooling the various grades of stainless steel must be done with caution. Be very careful using acetylene, MAP or propane torches to heat the stainless steel. If a reducing flame is used, excessive carbon may be transferred to the metal resulting in the formation of chromium carbide and ultimately, failure of the part. Before attempting heat treatment of a particular grade of stainless steel, always refer to the heat
Table VIII: Properties of Stainless Steel Alloys, ASTM Minimums, Unless Otherwise Stated
Alloy UNS number Ultimate strength, psi Yield strength, psi 30,000 25,000 30,000 25,000 53,000 30,000 30,000 30,000 75,000 65,000 70,000 80,000 150,000 200,000 270,000 190,000 170,000 220,000 Elongation, percent minimum 35 35 30 35 50 20 20 20 25 25 20 15 15 5 2 5 8 10 Modulus of elasticity 29,000,000 29,000,000 28,000,000 28,000,000 27,000,000 29,000,000 29,000,000 29,000,000 31,500,000 29,000,000 29,000,000 30,500,000 29,000,000 29,000,000 29,000,000 32,500,000 28,500,000 29,000,000 Hardness typical 80 RB 75 RB 80 RB 80RB 90 RB 85 90 85 95 RB RB RB RB
Austenitic Stainless Steels Type 304 S30400 75,000 Type 304L S30403 70,000 Type 316 S31600 75,000 Type 316L S31603 70,000 AL-6XN N08367 112,000 Ferritic Stainless Steels Type 430 S43000 60,000 Type 439 S43035 60,000 Type 409 S40900 55,000 SEA-CURE S44660 90,000 Duplex Stainless Steels Alloy 2205 S31803 90,000 7Mo PLUS S32950 90,000 Alloy 255 S32550 110,000 Martensitic Stainless Steels, Maximum Strength Type 410 S41000 190,000 Type 420 S42000 240,000 Type 440C S44050 280,000 Precipitation Stainless Steels 17-7 PH S17700 210,000 17-4 PH S17400 190,000 Custom 455 S45500 230,000
30 RC 30 RC 32 RC 41 RC 55 RC 60 RC 48 RC 45 RC 48 RC
THEBASICS of Corrosion
from Type 304L stainless steel and it fails by chlo-
What is Corrosion?
Technically, corrosion is the tendency of any metal to return to its most stable thermodynamic state. Namely, that is the state with the most negative free energy of formation. More simply stated, it is a chemical reaction of the metal with the environment to form an oxide, carbonate, sulfate, or other stable compound. In most cases, using a different alloy, material, proper coating, or impressed current can prevent corrosion problems. When a metal part fails in service, it is essential to determine the cause of the failure so that the replacement part can be manufactured from the proper alloy to prevent future failure. Many times a failed part is replaced with the same alloy. For example, if a piping system is made 6
ride stress corrosion cracking, replacing with the same alloy will assure failure within the same time frame. If a change of alloy is made, say to a 6%Mo stainless steel such as AL-6XN the piping may last for the lifetime of the system. Corrosion can be broadly classified in two forms: (1) chemical dissolution of the metal and (2) galvanic, or electrically driven. Abrasion, fretting and erosion sometimes are classified as corrosion mechanisms, but technically they are a mechanical metal removal process as compared to a chemical removal process. Chemical reaction may accompany the mechanical removal process to speed up the dissolution, but the chemical reaction will fit into the two basic forms. Some authorities list other
types of corrosion, but the other types generally are modifications of one of the existing corrosion forms. A correct alloy choice for one type of corrosion mechanism may be entirely the wrong choice for another. Therefore, a proper diagnosis of the failure is essential to make the correct material choice. Within these two basic classifications there are five types of corrosion: 1. General or uniform corrosion; 2. Intergranular corrosion; 3. Galvanic corrosion, including pitting and crevice corrosion; 4. Stress corrosion cracking; and, 5. Microbiologically induced corrosion (MIC). Many times, a metal starts to corrode by one mechanism, for example pitting corrosion, and then fails by a second mechanism, stress corrosion cracking.
A useful tool in determining corrosion resistance is the "Y" of corrosion shown in Figure 1 (page 8 ). This chart divides the alloys into three classes: those resistant to oxidizing acids on the left, those resistant to reducing acids on the right, and those resistant to a mixture of the two in the center. Oxidizing acids are those acids that oxidize the metals they come in contact with, and are themselves, reduced in the process. Reducing simply dissolves the metal without a change in valence or a release of hydrogen in the process. Corrosion resistance increases as you move up the chart. This chart indicates relative corrosion resistance.
By using the published tables of general corrosion rates, it is possible to determine the resistance of a given alloy to a given environment. The Corrosion Data Survey or the computer program, Corsur-both published by the National Association of Corrosion Engineers (NACE)-are excellent resources. Alloy selection can be simplified, or at least narrowed down, using these tables. Corrosion tables are based on isocorrosion curves. An isocorrosion curve for type 316 stainless steel in sulfuric acid is presented in Figure 2 (page 8). This curve shows the variation in corrosion rate with temperature and concentration. Similar curves are available for most alloys in many media, and generally are available from reputable material producers.
Figure 1: The Y of uniform corrosion. Increasing chromium content on the left means increasing corrosion resistance to oxidizing acids, such as nitric or citric. Increasing alloy content on the left indicates increasing resistance to the halide ions or reducing acids such as hydrochloric acid. When both the chromium and molybdenum content increase, as in the center, resistance to both types of acids increases.
Figure 2: Isocorrosion curve for Type 316 in sulfuric acid at temperatures up to 350F (175C) The boiling point curve represents the boiling point of the sulfuric acid -- water mixture. Mills per year is 0.001 x mpy = inches per year.
Galvanic corrosion occurs whenever two electrically different metals are connected in a circuit and are in an electrically conductive solution. This type of corrosion requires three conditions: two metals that differ in the galvanic or electromotive series, an electrically conductive path between the metals and both metals submerged in a conductive solution. A variation of galvanic corrosion can occur with passive film metals. If the alloy loses the passive film in one spot, then it becomes active in that area. Now the metal has both passive and active sites on the same surface. This is the mechanism for pitting and crevice corrosion. Table IX (page 9) is a list of materials and their relative position in the galvanic series.
GALVANIC Corrosion
Metal Volts Corresponding Alloy Corroded end (anodic or least noble) -1.55 -1.33 -0.76 -0.44 -0.23 0.00 +0.34 Brass, copper, Monel, nickel (passive), alloy 600 (passive), stainless steel (passive) Silver Gold +0.80 +1.36 Silver Gold Magnesium Aluminum Zinc Steel, iron, stainless steel (active), alloy C (active) Nickel (active), Alloy 600 (active), Alloy B-2 Zinc Iron Nickel
Magnesium Aluminum
Hydrogen Copper
However, there is another factor called "area relaThis table allows selection of metal pairs that are galvanically compatible. In general, when an anode, for example aluminum, is connected to a cathode or noble metal in salt water, the anode will corrode and the cathode will be unaffected. tionship"; if the anode is very large, such as a vessel wall, and the cathode is small like a bolt head, the galvanic action is slight. But, if the anode is small and the cathode is large, the anode will corrode very rapidly.
Pitting corrosion is a form of galvanic corrosion in which the chromium in the passive layer is dissolved leaving only the corrosion prone iron. The voltage difference between the passive
PITTING Corrosion
and active layer on an austenitic stainless steel is +0.78 volts. Acid chlorides are the most common cause of pitting in stainless steel. Chlorides react with chromium to form the very soluble chromium chloride (CrCl3). Thus, chromium is removed from the passive layer leaving only the active iron. As the chromium is dissolved, the electrically driven chlorides bore into the stainless steel creating a spherical, smooth wall pit. The residual solution in the pit is ferric chloride (FeCl3), which is very corrosive to stainless steel. This is the reason ferric chloride is used in so many of the corrosion tests for stainless steel. When molybdenum and/or nitrogen is used as an alloying element in stainless steel, the pitting corrosion resistance improves. In an attempt to quantify the effect of alloying elements, a relationship of the various elements responsible for corrosion resistance was developed. The resulting equation is called the pitting resistance equivalent number, or PREN. It has a number of different coefficients of which the most commonly used form is detailed on the next page.
temperature and a higher pH reduce pitting. The worst conditions occur with acid chlorides, and less dangerous conditions occur with alkaline or high pH chlorides. Pitting can occur rapidly once it starts. For example, under the right conditions of chloride
Three factors influence pitting corrosion: chloride content, pH, and temperature. In general, the higher the temperature and chloride content and the lower the pH, the greater the probability of pitting. For a given chloride content, a higher temperature and lower pH encourage pitting. Conversely, a lower
content, pH and temperature, a type 304 tube with a .035" (0.89mm) wall thickness will pit through in less than 8 hours.
Increasing the molybdenum in the alloy produces greater resistance to pitting. Therefore high molybdenum high chromium alloys generally provide the best pitting resistance. Figure 3 (page 10) shows the relationship of pitting, molybdenum content, pH, and chloride content.
Figure 3: Pitting corrosion relationship as a function of chloride content, pH and molybdenum content of austenitic chromium alloys. Temperature range, 150180 F 965-80 C), Pitting is not a problem below the line, but may be severe above the line.
Table X (page 10) lists alloys within the molybdenum contents shown on the graph. The molybdenum line represents the threshold at which pitting starts. Above the line pitting can occur rapidly while below the line pitting corrosion will not take place. This chart is very helpful in determining the amount of chloride and pH that can be tolerated for a given alloy class.
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Crevice corrosion is another form of galvanic corrosion, which occurs when the corroding metal is in close contact with anything that makes a tight crevice. Crevice corrosion is usually the first to occur and is predictable as to when and where it will take place. Like pitting, a conductive solution must be present; and, the presence of chlorides makes the reaction proceed at a fast rate. Crevice corrosion depends on the environmental temperature, alloy content and metallurgical category of the alloy. Also, there is a relationship between the tightness of the crevice and the onset time and severity of corrosion. There is a "critical crevice corrosion temperature" (CCCT) below which corrosion will not occur. Figure 4 (page 11) is a plot of the PREN versus CCCT and metallurgical category. Table XI (page 10) lists the PREN for some of the more common alloys. These values are based on the lower composition value for each alloy addition; therefore, the results are
CREVICE Corrosion
Table XI: PREN number for Various Alloys
Metallurgical Category Austenitic Alloy Type 304, 304L Type 304N, 304LN Type 316, 316L Type 316N, 316LN Type 317, 317L Type 317LMN AL-6XN Alloy 625 Alloy C-276 20Cb-3 Duplex Alloy 2205 7-MoPLUS Ferritic SEA-CURE Stainless Type 430 Type 439 Type 444 PREN 18.0 19.6 22.6 24.2 27.9 31.8 42.7 46.4 73.9 25.6 30.5 31.7 49.5 16.0 17.0 23.3
conservative. The greater the difference between the CCCT and the operating temperature, the greater the probability that crevice corrosion will occur. This chart is very useful in determining the effect of temperature on corrosion by indicating the approximate temperature at which pitting corrosion begins. The effect of temperature on pitting corrosion is not as clear as that for crevice corrosion, but by adding approximately 100 F (60 C) to the CCCT, the approximate temperature at which pitting starts can be determined.
Figure 4: Critical Crevice corrosion temperature as a function of the PRE Number. CCT will not occur below the temperature indicated. Tests made 6% ferric chloride.
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INTERGRANULAR Corrosion
All metals are composed of small grains that are normally oriented in a random fashion. These grains are each composed of orderly arrays of atoms with the same spacing between the atoms in every grain. Because of the random orientation of the grains, there is a mismatch between the atomic layers where the grains meet. This mismatch is called a "grain boundary." In a typical stainless steel product, there are about 1,000 grain boundaries that intersect a one-inch (25 mm) line drawn on the surface. Grain boundaries are regions of high-energy concentration. Therefore, chemical or metallurgical reactions usually occur at grain boundaries before they occur within the grains. The most common reaction is formation of chromium carbide in the heat-affected zone (HAZ) during welding. These carbides, formed along the grain boundaries, are called "sensitization." Because the carbides require more chromium than is locally available, the carbon pulls chromium from the area around the carbon. This leaves a low chromium grain boundary zone and creates a new low chromium alloy in that region. Now there is a mismatch in galvanic potential between the base metal and the grain boundary; so, galvanic corrosion begins. The grain boundaries corrode, allowing the central grain and the chromium carbides to drop out as if particles of rusty sand. The surface of the metal develops a "sugary" appearance as illustrated in Figure 5 (page 12). 12
Figure 5: Appearance of the surface of stainless steel (magnification 50X) that has undergone intergranular corrosion. This is sometimes called sugared.
Carbides are formed when heating occurs, such as welding, heat treatment or metal fabrication. Understanding how they form makes it relatively easy to control their formation. For example, always use a low carbon grade of stainless steel when welding is to be done. These grades are very common today since the development of argon oxygen decarburization (AOD) refining about 25 years ago. Almost all stainless steel is made using this method since it allows very precise control of the alloying elements, and it is possible to routinely obtain carbon levels of approximate 0.025%, a level at which no chromium carbide particles form in the HAZ during welding. These grades are normally designated as "L" grades such as Types 304L, 316L or 317L. Always use the "L" grades if there is any chance that the system will be welded. But if the part is to be used continuously at temperatures above 900 F, it will still sensitize over time. The only solution is to use a "stabilized" grade, one in which titanium, columbium (niobium) or both are added to react with the carbon forming stable grains of titanium or niobium carbide thus stabilizing the alloy. The type 304 equivalent stabilized with titanium is type 321, and the type 304 equivalent stabilized with niobium is type 347. Stabilized grades should be used whenever the steel is held for long periods in the temperature range of 800 to 1500 F (425 to 800 C). Sigma or "chi" phase may be minimized by avoiding the temperatures where they form, or by using alloys high in nickel and nitrogen.
Figure 6 (page 13) shows the effect of temperature, time and carbon content on the formation of chromium carbide. It is critical to get past the nose of the carbon content curve as fast as possible. If it is not possible to cool fast enough to get past the nose of the curve, carbide precipitation will occur. Additionally if a part operates within the maximum upper and lower limits of the curve carbide precipitation will also occur. Chromium carbide is not the only compound that can cause intergranular corrosion. Other compounds are delta ferrite, sigma phase (a chromium-
iron compound), chi phase (a chromium-iron-molybdenum compound), and several other compounds that are found less often. Special mention should be made concerning delta ferrite. All stainless steels are compounded to have a certain amount of delta ferrite in the microstructure to minimize micro cracking during cooling of the weld. The Welding Research Council recommends a range of 2-5%, with most welds measuring at 2%. However, when delta ferrite is exposed to high chloride waters including many hot water systems-the chloride begins to attack the delta ferrite corroding it preferentially and leakage occurs.
Figure 6: Effect of carbon on the time required for formation of harmful chromium carbide. Carbide precipitation occurs inside the loop to the right of the various carbon content curves.
Corrosion Cracking
Stress corrosion cracking (SCC) is one of the most common and dangerous forms of corrosion. Usually it is associated with other types of corrosion that create a stress concentrator that leads to cracking failure. Nickel containing stainless steel is especially susceptible to chloride induced SCC. Figure 7 (page 14) indicates the maximum susceptibility is in the nickel range of about 5-35% and that pure ferritics, such as Types 430, 439, and 409 are immune. The point of maximum susceptibility occurs between 7-20% nickel. This makes types 304/304L, 316/316L, 321, 347, etc., very prone to such failure.
STRESS
Stress corrosion cracking (SCC) has three components: alloy composition, environment and the presence of tensile stress. All metals are susceptible to stress corrosion cracking, as Table XII (page 14) indicates. 13
Figure 7: Probability of chloride stress corrosion cracking occuring as a function of the nickel content of the alloy. Cracking will not occur below the stress corrosion cracking threshold temperature, but will above.
Chlorides, both organic and inorganic, Caustic solutions, Sulfurous and polythionic acid Caustic above 600F (315C), Fused caustic, Hydrofluoric acid Seawater, Salt atmospheres, Fused salt
It doesnt take much chloride to cause failure (a few parts per million will do the job) providing that the pH is low and oxygen is present. Temperature is important, and there is a threshold temperature below which the steel will not crack. This is related to the critical pitting temperature; therefore, the 14
threshold temperature increases as the molybdenum content increases. Type 304 may SCC at room temperature, whereas the six percent Mo alloys have a threshold temperature in the range of 450 F (239 C).
The stress component is more subtle. First the stress must be tensile, and it must exceed the yield strength of the component. This sounds simple enough, but any time a component is bent or straightened, or when any physical exertion is made to place the material into a fixed shape, the yield strength is exceeded. Next, matters can be complicated by stress multiplication factors. If a pit or other sharp notch is present, the residual stress is multiplied several times resulting in a stress far in excess of the tensile yield strength. Thus, SCC usually starts with pitting or crevice corrosion as a precursor to forming a stress concentrator. istic that distinguishes SCC from other types of cracking. Using microprobe analysis, or electron When the cracks form, they usually are transgranular as illustrated in Figure 8 (page 15). That is, they crack through the grain. Cracking occurs rapidly progressing through the grain, terminating in a feathery cluster of small cracks. This is a characterdispersive spectroscopy (EDS), on the crack surface to look for the presence of chlorine, we can observe conclusive evidence that SCC has occurred.
Figure 8: Polished and etched crosssection of stress corrosion cracked stainless steel (magnification 250X) showing the transgranular cracks and feathery appearance of crack tips.
One of the most common forms of MIC is the metabolic byproduct of the sulfur-fixing bacteria that produces sulfurous or sulfuric acid. These bacteria cause rapid corrosion of the lower alloy stainless steels, like Types 304L or 316L, resulting in through wall crevice corrosion under the bacteria colonies.
Other than the use of bactericides, such as chlorine or ozone, the usual solution to this type of corrosion is to use a 6% molybdenum alloy such as AL-6XN (a superaustenitic stainless steel) or the highly alloyed nickel alloys. Therefore, if MIC corrosion is taking place, it is best to use one of these alloys. 15
Thiobacillus
Converts soluble ferrous ions to insoluble ferric oxide Converts soluble manganese ions to insoluble manganese dioxide
Produces iron oxides and forms crevices Produces manganese dioxide that can form crevices, or can react with chlorine to produce hydrochloric acid
Figure 9: Crevice corrosion under bacteria colony on the inside of a stainless steel tube (magnidication 5X)
3. Always clean the surfaces prior to welding to remove all organic materials, moisture and dirt. These contaminants will react either with the chromium to produce chromium carbide or decompose during welding to create hydrogen gas resulting in porosity. 4. Always use oxide-grinding wheels, not silicon carbide for any dressing of weld surfaces. The carbide may react with the chromium, which decreases the corrosion resistance of the weld metal. 5. Because stainless steel has lower heat conductivity than carbon steel, 30% less heat input generally is required. Also, the welds take longer to cool. Maintain short arc length and use staggered beads for very long welds to reduce heat input. 6. The coefficient of thermal expansion for austenitic stainless steel is higher than for carbon steels and ferritic or martensitic stainless steels. Therefore, keep the base metal restraint to a minimum to prevent distortion of the system. 7. If multiple weld passes are required, maintain the interpass temperatures at less than 200 F (100 C) to prevent cracking and distortion of the system. 8. Avoid crater cracks by controlling the size of the termination weld pool. If crater cracks occur, remove by grinding with an aluminum oxide wheel before proceeding.
cleaning/passivation. A poorly cleaned surface may be just as susceptible to attack as the original heat tint.
Use an inert gas for both the weld and shield gas. Either helium or argon may be used, although argon is normally used. Where possible use 3 5% nitrogen additions to both the torch and shielding gas. This added nitrogen compensates for the nitrogen lost from the alloy during welding.
begins. The grain boundaries corrode, allowing the central grain and the chromium carbides to drop out as so many particles of rusty sand. The surface of the metal develops a "sugary" appearance. Several compounds may cause intergranular corrosion in addition to chi phase and chromium carbide. Another compound is sigma phase, a chromiumiron compound. Note, these are compounds, not a random mixture or alloy.
These compounds usually are formed when some type of heating occurs, such as welding, heat treatment, or metal fabrication. Understanding how they form makes it relatively easy to control their formation. For example, always use a low carbon grade of stainless steel when welding is to be done. Today these grades are very common ever since the invention of argon - oxygen - decarburization (AOD) refining about 25 years ago. Almost all stainless steel is made by this method since it allows very precise control of the alloying elements, and it is possible to obtain routinely carbon levels in the range of 0.025 percent, a level at which no chromium carbide particles form in the HAZ during welding. These grades normally are designated as "L" grades, like Types 304L, 316L or 317L. Always use the "L" grades if there is any chance that the
Grain boundaries are regions of high-energy concentration. Therefore, chemical or metallurgical reactions usually occur at grain boundaries before they occur within the grains. The most common reaction is formation of chromium carbide in the heat-affected zone (HAZ) during welding. These carbides form along the grain boundaries. Because the carbides require more chromium than is locally available, the carbon pulls chromium from the area around the carbon. This leaves a grain boundary zone, low in chromium, creating a new, low chromium alloy in that region. Now there is a mismatch in galvanic potential between the base metal and the grain boundary, so galvanic corrosion
system will be welded. Another way of controlling the formation of chromium carbide is to use a stabilizing element addition to the stainless steel. These are titanium and niobium (columbium). The Type 304 equivalent with titanium is Type 321, and the Type 304 equivalent with niobium is Type 347. Stabilized grades should be used whenever the steel is held for long periods in the temperature range of 800 to 1500F (425 to 800C). Sigma or chi phase may be minimized by avoiding the temperature range where they form, or by using alloys high in nickel and nitrogen.
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Welds may be done with standard orbital welding equipment consisting of a solid-state DC power supply, associated cables, and an enclosed weld head. The weld head contains an internal rotor which holds a tungsten elec-
Welding Equipment
ORBITAL
trode, which rotates around the work to do the weld. The portable power supply, which plugs into 115V VAC, controls the entire weld sequence including an inert-gas pre-purge arc strike, rotation delay, rotational speed (RPM), and multiple timed levels of welding current with pulsation. This is followed by a downslope which gradually terminates the current, and a postpurge to prevent oxidation of the heated material. These weld parameters are dialed into the power supply from a weld schedule sheet after determination of the proper parameters from test welds done on tubing samples. Fusion welds with automatic orbital TIG welding equipment is practical on tubing or small diameter pipe in sizes from 1/8 inch OD tubing to 6" schedule 10 pipe, and on wall thicknesses up to 0.154 wall.
AL-6XN is easily weldable with weld parameters, including travel speed (RPM) and weld currents, comparable to 316L stainless steel. Weld appearance is excellent with a smooth, shiny, flat weld bead on both the OD and ID. For welds with weld insert rings, the inserts are simply placed between the two sections to be welded and fusion welded as usual, except for a slight increase in welding current to compensate for the increased thickness of material contributed by the insert ring. These welds also have a pleasing appearance, with a slight crown on the OD and some inner-bead reinforcement.
In many applications, a post-weld anneal and pickle may not be possible, as in large vessel fabrication or field welding of piping systems. In these cases, the exposure conditions must be carefully reviewed to determine if autogenous welds are satisfactory. Autogenous AL-6XN welds are more resistant to corrosion than similar welds of types 316L, 317L and 904L. Their corrosion resistance is approximately that of alloy 904L base metal and superior to that of types 316L and 317L base metal. 19
SELECTION Alloy
When a corrosion problem is encountered, review the solution chemistry to determine if a change can be made to eliminate the corroding condition. For example, if carbon steel is rapidly oxidizing in steam, is it possible to adjust the pH upward and add hydrazine, or one of its derivatives, to combat the dissolved oxygen? If the system is being cleaned with muriatic acid, which is dangerous to stainless steel, can the acid be changed to one more friendly to the stainless steel such as nitric, citric or sulfamic? If the pH is being lowered using carbon dioxide sparging and chloride pitting occurs, can a mineral acid such as sulfuric or phosphoric acid be substituted to prevent acid bubbles from forming on the surface causing crevice corrosion?
If it is not possible to modify the environment, the alloy must be changed. Use the following selection process to narrow down the alloy options. This same procedure can be used in selecting an alloy for the initial design. 1. Review the nature of the environment with respect to chemical composition, temperature, pH, and velocity. Always assume the worst-case scenario. Use the corrosion rate charts or tables to determine those alloys with the best uniform corrosion resistance. If the solution is a single composition, selection will be rather easy. If it is a complex solution of two or more components, determine the corrosion rates in each component individually. Keep in mind the corrosion rates may be accelerated or slowed down in each environment. Many complex solutions require the use of corrosion racks with different alloys exposed to a test environment to determine the best alloy. 2. Always determine if chlorides are present. If they are-and they usually are-select the best alloy for pitting resistance as a function of pH and chloride content, using the chart in Figure 3 (page 9). 3. Next, pick the proper alloy using its PREN number for the temperature based on crevice corrosion; see Figure 4 (page 11). 4. Determine the best carbon range to prevent intergranular corrosion using Figure 6 (page 13), or use a low carbon grade as a general rule. 5. Finally, pick the best alloy that will not stress corrosion crack based on Figure 7 (page 14). 6. Consider the metallurgical and mechanical characteristics of each candidate alloy. If you are not that familiar with each alloy and its limitations, contact a reputable and qualified material producer for assistance. Many tests have been conducted in many environments, and a wealth of information is available. There is an alloy, material or design modification out there that will solve your problem.
Conclusion
The correlation between metallurgical factors and corrosion resistance is straightforward. Inclusion of corrosion control and the correct material selection in the design process is the most efficient means of controlling corrosion and therefore high replacement costs, or catastrophic system failure. If corrosion control is not considered in the design stage, the subsequent costs are usually much greater than the initial investment at the onset.
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Copyright 2002 Central States Industrial Equipment & Service, Inc. All rights reserved. No reproduction without permission of the author.