Flow Assisted Corrosion Introduction In this section, we consider principal varieties of related attack due to flow of a substance actoss a sucface “The surface may be ether stationary (@., a valve seat) or moving (eg, pump impeller or propeller), Definition Flow assisted corrasion is definod as the combined action ‘of corrosion and fluid flow. Types ‘The types of velocity phenomena we will discuss ae: + Exosion-corrosion Impingement = Cavitation Erosion-Corrosion Description Erosion-cortosion occurs when the velocity ofthe Muid is ent t0 remove protective films ffom the metal surface Recognition Erosion-corrosion often causes localized attack where surface discontinuities cause flow aberrations and turbulence, This phenomenon often occurs at weld beads, Mechanism Erosion-cortosion can eceur in lowing liquids or gases with oF without abrasive particles. In this form of atk, the velocity of the flow is sufficient to remove weakly- auhered corrosion products from the surface, redusing their protective effect, and may also remove substrate. This sults in an acceleration ofthe corrosion process The fluid dynamics in erosion-corrosion by liquids can be an important factor in determining the cate of material ‘GasicCovoson SwdowNanwal [BNACE International 200, oaevesForms of Carson: Recogniton Mechanisms and Contol removal. Turbulence of flow is also important. Velocity lone can explain a sudden inesease in surface damage. \When erosion-corrosion occurs, the effect of velocity on. the corrosion rate usually” exhibits a breakaway phenomenon, wherein a maximum velociy can be withstood without removal of the protective films. Above this limiting breakaway velocity, the eorrsion rates, increase very rapidly. The resistance of protective films to removal plays a significant role in deternining the breakaviay velocity for a given alloy-environment system, Erosion by particles ina corrosive medium may not proceed by complete removal of the corrosion product. At Clevatedtemperanures (eg, coal gasification fnvironments), the corrosion product may be ductile and fay How swith the particle impact, This results in the removal of a good deal of corrosion product and litle base metal. The erosion debris, if collected and examined, will ‘Show characteristic rounded particles eather than the flakes characteristic of metal debris. ‘Although not necessarily an electrochemical corrosion ‘mechanism, elements of mechanical erosion are often encountered; and the recognizable features should be defined. Mechanical erosion is caused by hard partieles impacting fon the surface and resulls in eratering ofthe meta surface. ‘The plastic deformation at each impact extudes metal around the particles, and the extrusions are broken off by tater impacts. Erosion by partile impact is influenced by the angle of impact. For ductile metals, the removal rate maximizes at an impingement angle of ahowt 20° to 30° Other factors contributing tO erosion rate are particle velocity, hardness and angularity and the temperature of the environment. The sensitivity of ductile materials 1 the angle of impingement causes localization of erosion damage along the flow path. As material is removed from the surface, the impingement angle changes locally, and small areas in which the erosion efficiency is highest erode faster than other areas. A characteristic ripple pattem is, shown, aie Coronon Sudore anoaT NAGE Iniorstonal, 2000, canvas 553Forms of Caronon: Rosagalon, Mechanisms and Control In some cases, it is difficult 10 discriminate between cerosion-corrosion and velocity effect corrosion resulting from nonuniform mass transfer effects which are due simply to the greater availability of reactive material and the reduction in dissolved metal ion concentration because of flow. If erosion-corrosion can be identified and ther is no evidence of particle impingement, one possible solution is to reduce the Mow rate, or remove flow-disturbing surface «discontinuities Erosion-Corrosion - Performance of Metals and Alloys Almost any material will be affected by the combined effects of velocity and corrosion if the velocity is high fenough, The discussion that follows concentrates on the performance of metals at velocities typically found in piping and heat exchanger tube environment. ‘Aluminum and Aluminum Alloys Aluminum and aluminum alloys, in general, are not very resistant to erosion-corrosion in environments where they fre subjeet 10 corrosion, such as in potable water and Seawater. Limiting velocities are usually on the order of 0.75 mis(2 fs) or less. Carbon and Low-Alloy Steels Carbon and low-alloy. steels, in general, are not very resistant te crosion-corrasion in environments where they’ fre subject 10 corrosion, such as in potable water and seawater. Limiting velocities are usually on the order of mis (3 108 or less Stainless Steels and Nickel-Based Alloys. Stainless steels and ckel-based alloys generlly. show good resistance to efosion-conwsion. Tt stould be remembered, however, that some alloys, particularly those in the stainless sleol group, are not very resistint under stagnant conditions, All flow conditions must be considered when soloeting materials for v Copper Alloys Copper alloys, generally, are fairly resistant te erosion: tcamosion attack. They are widely used For piping systems ‘ase Goronon Suen Nanost ‘SNAGE inaratona, 2000,Foxms of Coroson: Recogtion, Mechanisms and Contot and heat exchanger tubes. They do have limiting velocities ‘hich must not be exceeded. These velocities are usually fon the order of 210.4 m’s (6 to 12 fs). Impingement Description Impingement is localized erosion-corrusion caused by turbulence or impinging flow, Enirained air butbes tend 10 accelerate this aston, as do Suspended solids. This type of Corrosion oceurs in pumps, valves, and orifices, on heat ‘exchanger tubes, and at elbows and tees in pipelines. Recognition Impingement corrosion usually produces a_ pattem of localized attack with ditectional features. The pits or ‘grooves tend to be undercut on the side away from the Source of flow, in the same way that a sandy riverbank at a tend in the river is undercut by the oncoming water. Mechanism ‘The mechanism of impingement is similar to that of erosion-comrosion, a flow removes the protective films responsible for the corrosion resistance of the material. In impingement, however, the flow is either turbulent ot directed at roughly right angles to the materials, whereas, in erosion-corrosion, the flow is rougbly parallel to the ssrfaes. ‘When a liquid is Nowing over a surface (e.g, in a pipe), there is) usually a critical velocity below which impingement does not oecur and above whieh it increases rapidly. Impingement attack first received attention because of the poor behavior of some copper alloys in In practice, impingement and cavitation may occur together, and the resulting damage can be the result of both. Impingement may damage a protective oxide film land cause corrsion, of it may mechanically Wear away the e film to produce a deep groove. ‘Basie Coronion Suen anual [SHAE Inoraonal 2000 caer 555Forms of Camonon: Recaption, Mechanism Water Drop Impingement Water drop impingement is a form of mechanical erosion in which the eroding medium is high-velocity waer drops. “Analogous effects ean be procced by any liquid drops at high velocity. Usually, the source of the drops. is condensate, as is the case in steam turbines. Drops also ‘occur in natural atmospheres, such as by rain. Raindrop trosion is a practieal problem associated with high-speed jets re-entry vehicles, and helicopter rotor Blades. Some similarities exist between solid-particle and water- drop impact damage, The impact ereates sufficient contact sress f0 cause yielding of the surface and attendant crater formation. Impact can also cause disintegration and tateral jeting of fragments ofthe impacting particle, whether drop tr solid. Solid particles will tend to cut the surface and, therefore are more sensitive to impingement angle than are water drops, Water drop impact causes damage by the ‘momentary high-pressure pulse induced during collision ‘This pressure, Known as water hammer pressure, is a fanetion of the drop velocity relative fo the surface, the density of the Tiguid, and the velocity of sound in the ‘material being erodes. Water drop impingement damage on a ductile material prodiuces rounded erates of fairly uniform size and often raters within craters, The surface often looks something Tike a fracture surface, since it has ductile, dimpled charastertiee. Solid particle impingement causes angular pis conforming to the shape of the particle; and. mbeckled particles may be found in the surface. This is 2 positive Way 10 distinguish between water drop erosion and. hard particle erosion, Identifying differences between water frop impingement damage and cavitation erosien is very Giffcalty itis ofen impossible to distinguish beween the two. Impingement-Performance of Metals and Alloys ‘The interaction between the medium andthe surface ‘prodkces a film sshich either protoets the surface from the material removal process, of is Vulnerable (0 fracture ancl Shipping by impacting pacticles or liquid drops. Removal of protective oF passivating films by shear Basie Corrosion Student Manual ‘SNAGE International 2000, ‘soos ContForms of Conosion:Recogniton, Mechanisit and Cont high-velocity Nowing liquid or turbulence car accelerate galvanic action, especially when only a small area of Siifstrate is exposed. In this eas, the corrosion resistance Of alloys will be simile to that in Gime liquid immersion corrosion, The rate of corrosion may be accelerated by the flow, but the resistance to he specific corrosive environment will be the same for each metal or allo. Aluminum and Aluminum Alloys ‘Aluminum alloys, in general, are not very resistant 10 impingement in envitonments where they ae subject to corosion (@g. in potable water and seawater), Carbon and Low-Alloy Steels Carbon and low-alloy steels, in general, are not very resistant to impingement in environments where they are subject to comrasion (e., potable water and seawater) Stainless Steels and Nickel-Based Alloys Stainless steels and nickel-based alloys, in general, show {good resistance to impingement. Copper Alloys. Copper alloys, in general, are not very cesistant to impingement in environments where they may corrode, such a5 in potable water and seawater, Otherwise, they are fairly resistant to velocity attack, These alloys are widely used for piping systems and heat exchanger tbes, where impingement effects can be reduced through design. Titanium, Zirconium, Tantalum ‘Titanium, zirconium, and tantalum have good sistance to ‘velocity effees in general Cavitation Description Cavitation is a mechanical damage process caused by collapsing bubbles ina flowing liquid, Recognition Cavitation usually results in the formation of deep aligned! pits in arcas of turbulent flow. Base Orosen Scent tana NAGE ternational, 7000 aonFoims of Coroson: Recopation. Mech Mechanism Cavitation is eased when protective films are removed from a metal surface by the high pressures generared by the collapse of gas or vapor bubbles in a liguid. Where the energy input to produce cavitation is sufficiently high, there will be no significant contribution to the process either by hard particle impact or by corrosion. ‘The rrecessary high-energy inputs can be achievel in the laboratory with suitably-powered ultrasonic wansducers Under these conditions, extreme turbulence ean cause the ods in the liquid to disappear in a miceoseeond ion of a second) oF so and can generate Forees fm the order of about 700,000 kappa (100,000 psi) as the bubbles collapse. This prosess can literally tear the surface ‘apart, The aelion is somewhat similar to the water hammer effect in pipes when a valve is closed suddenly “The steps through which this process is thought to occur 1. Bubble formation ina area of low pressure 2. Bubbles move t higher pressure areas 53, Bubbles collapse, forming high-pressure waves Tiquie 4, Pressure waves impinge on the surface, removing the protective film 5. Corrosion occurs at the bare area {may or may not cceur) 6 Process ropeats Cavitation Corrosion - Performance of Metals and Alloys In genera, alloys with higher strength are more resistant to cavitation corrosion than lower-strength — materials, Cavitation damage should be considered as io separate phenomena. When cavitation damage is caused orimarily by corrosion following the removal of protective films, the corrosion portion of the damage may predomirate, The cavitation itself is incapable of mechanically dameging and emoving the uoderlying metal Under these conditions. the corrosion behavior ofthe ‘Basic Corson Stat Nanuat © NACE mnernaions, 200. 558Fors. of Consion Under extreme cavitation conditions, the cavitaion itself is ‘capable of damaging and removing the metal directly, and corrosion effects are insignificant Aluminum Alloys ‘Aluminum alloys, in general, are not very resistant cavitation damage because of their low strength. Carbon and Low-Alloy Steels, Carbon and low-alloy steels, in general, are not very resistant 10 cavitation damage unless the citation is incapable of directly damaging and removing te steel. In this ease, cathodic’ protection, or the use of corrosion Inhibitors, can reduce the effects of cavitation. Stainless Steols and Nickel-Based Alloys Stainless steels and nickel-based alloys, in general, show better resistance to cavitation than many materals because of their relatively-high strength and the relative resistance ff their protective films to mechanical damage, However they are susceptible o cavitation under extteme conditions. Copper Alloys Copper alloys, in general, are not very resistant 10 cavitation because of their Low strength, Impingement is tore likely in environments where they may corrode, such ts potable water and seawater, Otherveise, these materials are fairly resistant to velocity altack. They are widely used for piping systems and heat exchanger tubes, where impingement effects can be reduced through design Titanium, Zirconium, Tantalum Titanium, zirconium, and tantalum have good resistance to velocity effets in general Control of Flow Assisted Corrosion Flow assisted corrosion can be controlled in many ways, including: Design Materials selection Modification of environment Protective coatings Cathodic prowetion ‘ase Corson Sent Wenaal [BNAGE ntermtenal 2000,“Forms of Coroson: Recognition, Mechanisms and Cont Design Velocity effects can be controlled through design, primatily by controlling the flow velocity and flow pattems. Flow velocities should not exceed the limiting ‘elocites forthe materials selected. Smooth flow is always preferable to turbulent flow from the standpoint of velocity tffeet corrasion. Enirained gases and solids should be tliminated from flow whenever possible. Pressures should be considered when cavitation damage is possible, Materials Selection Selecting a material according to resistance to the expected flow velocity and flow regime is widely used 1» control velocity effect corrosion. As mentioned above, all conditions within the system (e.g. periods of stizmation) ‘must be considered when selecting material Modification of Environment In some eases, corrosion inhibitors ean effectively controt velocity effect corrosion. Some inhibitors ean reduce the ccorrasion rate ofthe areas from whieh the protective films have been removed. Another beneficial effeet of some inhibitors is that they can increase the resistance of the protective film to velocity effects. Protective Coatings Protective coatings can be used to control velocity effets. Robber linings aro particularly effective in reducing croslon-orrosion elTexis when solid matesals are contained within the flow stream. OF course, the bond of the protective coatings to the materials is an important tor in their use in controlling velocity effects. Metal coatings, applied by cladding or weld overlay, are widely used to contra velocity effect comrosion. Cathodic Protection Cathodic protection cam effectively control the conosion of metals, even when the metals are not covered with protective tims. Thus, velocity effect corrosion can be Controlled by cathodic protection, The required electrical feurent fOr eathodic protcetion in high-velocity How is tually much grater than the current required a low-ow Basie Garona Student Manual BRACE Iterations, 2000Forms of Corson: Recagation, Mechanisms and Conta! Intergranular Corrosion Definition Intergranular corrosion is the preferential tack at, or adjacent to, the grain boundaries of a metal. Description [As described previously in this course, almost all tengincering metals are composed of individual erystals, oF trains, which mect at areas of relative impurity and misalignment called grain boundaries. Corosion that ‘cours. preferentially at, or adjacent to, these grain boundaries results in a very large effect compared 10 the actual amount of metal removed atthe grain boundaries, In Some cases, individual grains are loosened and lost from the material, In other cases, the localized lass of grain boundary material results in localized attack similar in appearance to cracking. Recognition Intertanlarconosion usually produces siesta aro granular in appearance. It may also take the form of Tocalized areas wth an appearance similar to cracking Mechanism Intergranular corrosion oceurs when the grain boundaries, or the areas directly adjacent to the grain boundaries, are anodic to the surounding grain materals. Grain boundaries may be anodic to the surrounding metal through many mechanisins. They may be anodic because Df diforences io impurity levels enwoen the grains and the ferain boundaries. They may be anodic because of the tffective strain energy ofthe misalignment of atoms inthe lean boundaries. The grain boundaries, of adjacent areas, may be anodic because ofthe formation of precipitates due to improper heat treatment “Base Govion Soon anual NAGE nematonal 2000, evaFarms of Covteson: Recogalton, Kt Jems and Conv Intergranular Corrosion- Performance of Materials Although several metals and alloy systems are subject 10 intergranular corrosion, we will concer ourselves primarily with stainless steels and aluminum alloy. Intergranular Corrosion of Stainless Steel Intergranutar corrosion of stainless steels is most Frequently caused by three types of metallurgical efTects that cause the grain boundaries or areas adjacent to the grain boundaries to become anodic relative to the surrounding material The three types of effects are: © General sensitization = Weld decay Knife line atack General Sensitization ‘Austenitic stainless steels, when they are cooled slowly through a temperature range of approximately SO0°C to 850°C (032°F to 1,562°F) or are otherwise mainained for some time in that range, can become susceptible 10 wr atack if subjected to specific eorrocents. The are Sid 10 be “sensitize.” This ion ib cated by the formation of cheominm ‘carbides, depleting grain boundaries and the areas adjacent to grain boundaries of chromium, A very small weight percentage of carbon combines with a relatively large Weight percent of chromium. The sensitized areas do not have sufficient chromium content t produce a stable passive film. They become anodic with respect 10 the Surrounding passive material, As will be desonbed later in more detail, sensitization of stainless steels canbe prevented by (1) avoiding heating in the sensitizing range, (2) heat treatment to eliminate chromium carbides, (3) use ‘ofa material with very low earbon content, and 4) use of stabilized” material Which contains alloy akliions tha preferentially combine with carbon rather than with the ‘mbinaticn of carbon with chromium intengra Basic Gaoson tose anual 562Fors of Corosion: Recognton, Mechanisms and Contol If ferric stainless stools are quenched rapidly, they ean also become sensitized, Weld Decay Weld decay oceurs in the heateffected zone sbout 6 mm from the actual weld and parallel to it. Weld decay is the same as sensitization, except it occurs lovally because of the effects of welding, rather than over the entire substa Weld decay results in uniform thinning adjacent 10 the ‘veld, where grains of metal have been removed because of iimorgramular atack, Knife Line Attack Knife line attack occurs in # narrow zone near te interface of the weld pool and base metal. Knife line atack occurs only in certain stabilized grades of stainless steel at the ‘veld temperature, which is higher than the terperature at which sensitization oecurs. In general sensitization and Weld decay, the chromium has higher affinity for carbon than for the titanium or niobium which has been added 10 Stabilize the material. Therefore, when the weld cools in the narrow weld zone, chromium carbide precipitates inthe fusion line, Resistance fo corrosion is lowered adjacent to the weld Aluminum and Aluminum Alloys ‘The chemical composition, mechanical working, and heat treatment of aluminum alloys have been developed to minimize intergranular corrosion, During welding this fareful balance can easily be upset, and the alloys can become susceptible to intergranular attack. Bath the weld filer materials and the welding process, paricularly the control of heat input, ust be carefully eontlled to mrinimize the adverse effects of welding on the intergranular corresion oF aluminum alloy. Cerin aluminum alloys are subject to a form of intergranular attack known as “exfoliation”. The ‘appearance of exfoliation is layered or leafed in character, consisting of alternating strata of corroded and uncorroded neta. Comrosion products resulting from the attack force the uncorroded layers upward from the surface, thus imparting the characteristic appearance of exfoliation Typically, the corrosive attack is parallel to he plane of “Basie Cororion Sud anual BNCE mernaions 2000, taoForms of rrosion: Recognition, Mechanisms and Cott plate in reduction, such a8 the rolling plane in sheet and Although many aluminum alloys are resistant to inter ssnular corrosion, others are not, particularly cluminu alloy systems containing magnesium, copper, or bot. Development of intergranular corrosion oF alumirum in an aqueous environment depends on the presence of ehlo Such conditions are a coneem, for example, in seawater tnd other chloride-containing environments Intergranular corrosion of aluminum is thought te occur in susceptible aluminum alloys asa result ofthe formation of precipitates along grain boundaries, For example, Sluminum-copper alloys (the 2XXX series), containing about 4% copper, exhibit incergranular attack under certain ‘After fabrication (welding) ofthese alloys, itis customary to solution heat treat the piece at approximately 490°C (020°F) and water quench it This elass of alloys will age harden at room temperature. If, however, the quench is incorrectly performed, CuAl, cat precipiale along. grain boundaries, leaving a zone adjacent to the grain boundaries that is depleted of copper. Copper and Copper Alloys Copper and many copper alloys are susceptible to Interzranular corrosion in euvironmvens contains amines for ammonia, Copper-nickel alloys are more resistant than tlhe copper alloy’ in these environments Nickel and Nickel-Based Alloys Commercially pure nickel is subject to intergranular ‘idation at elevated temperatures \Nickel-copper alloys have reportedly suffered intergranular corrosion in certain hydroflvoric acid and chrumie acid Solutions, The exact sensitization mechanism has not heen determined. ntergranular corrosion — can occur inthe nickel molybdenum alloys in hot hydrochloric acid and Basic Carson Student Manual ogotes 504Forms ot Corio: Reesonton, Machsnisns sulfuric seid, especially [due to precipitates of fmolybxlenum ‘rich consifuents) ecause these acics precipitate molybdenum-rich constituents. Nickel-chromium alloys of the Inconel variety are subject to intergranular corrosion because of Cry and ate not intended for service where this could be a problem. Some nickel-chromium alloys have been Stabilized against this type of attack and are hnommal welding-lype construction for corrosive service. ‘These alloys, however, are potentially subject w knife line attack (in the ease of titanium-stabilized alleys) and 10 attack of intermetallic phases in highly oxilizing acid solutions Inthe molybdenum-bearing grades, intergranular corrosion is caused! by molybdenum carbides and by molybdenum- rich intermetallic compounds, rather than by chromium {arbides. This problem has been countered by stabilization tnd by reduction of earbon content. These types of alloys have also experienced problems oxidizing chloride solutions (€g» ferric chloride, hypocklorites) and in Oxidizing and reducing acids Control of Intergranular Corrosion Intergranular corrosion ean be contrlled in several ways, including: ‘Matera selection Design’fabrication Modification of environment Use of proper welding procedures Heat treatment | Materials Selection Alloys ean be selected for ther resistance fo intergranular tortosion in the specific service environment. For the ess steels, alloy variations fow in carbon content (the SL grades) can be used, as well as grades containing stabilizing additions of such elements as titanium and niobium. “Boge Corton Soden Manual barons "Forms of Comosion: Rogaion. Design/Fabrication Ifthe material is not resistant to the effects of welding on intergranular corrosion, the welds may be eliminated by tusing another joining technique. In some eases, the joints themselves can be eliminated in the design. Other fabrication processes requiring heating of the metal must be properly controled, Modification of Environment In some eases, the environment can be modified s0 that the affected grain boundaries ae no longer anode wih respect to the adjacent material, This may be accompished by adding corrosion inhibitors, or by removing aggressive ions (such as ehlorides) where aluminum alloys are used. Use of Proper Welding Procedures Proper welding procedutes ean minimize or eliminate the effects at grain boundaries that lead 0 intergranular Compson, Welding procedures which — minimize intergranular corrosion, once developed, must be followed carefully to obtain the desired effets Heat Treatment Proper heat treatment ean eliminate intergranular coreosion cither by preventing getin boundary cffects in the first place, or by removing the adverse effeets of improper heat Ireatment or welding, This commonly consists of a heat treatment called a "solution heat treatment” which imulves the “undesirable constituents at the grin boundaries. This heating is usually followed by a rapid cooling f9 prevent reformation of undesirable precipitates, at the grain boundaries. Base Comox Sudan anual NACE interraona, 2000 ovrFexms of Corson: Resopation, Mechanisrs and Conta Dealloying Definition Dealloying is a corrosion process in which one constituent of an alloy is removed preferentially, leaving an altered residual structure Description Most engineering metals are alloys that consist of mixtures of elements, In some cases, such asin the ease of zine and topper alloyed to produce a brass, one element used is odie with respect 1 the other elements in the alloy and tan selectively corrode by galvanie action, The phenomenon was first reported in 1866 on brs (i. oppetcine) alloys thas been reported since in viwaly Sil Sopper based alioy systems, aswell a est ro and other ally systems Recognition Dealloying is commonly detscable a color change, o a {nate change im mechanical strength. Brass wll ti) ftom yell to red and ent tons, om silvery gry 1 dark fray, Gay iron that has sulle raphe corsion can Be faith pen ie Difficulties may be encountered where deposits, colored environments, oF accessibility make inspection had. Problems will be experienced in detecting dealloying in most methods of automated inspection, because no volume change oceurs and because the density difference ean be masked By precipitated salts, corrosion prudicis, ete, within the dealloyed region ‘Various laboratory techniques, such as eross-scetioning the part in question, will normally provide evidence of color Changes. Metallographic examination at high magnification find “Xeray spectroscopy (normally performed with a Specially-equipped seanning electron microscope or with fan electron microprobe) can provide positive igetiicaion “Basic Carona SusoruNanaal 'BNAGE hternatonal, 2000 tosForms of Corson: Recogniton, Meehan and Conte Mechanism ‘The dealloying mechanism can be ther a selective removal of one of more alloy constituents, Leaving a residual substrate, or dissolution of the entire alloy, with fone or more constituents redeposited. Laboratory investigations have shown that both processes can occur simultaneously under certain conditions. In either ease, the torrosion results in a residual metal with essentially the Same surface profile and volume as the parent metal. This is sometimes refered to as a "pscudomorph” ofthe original artifact. Typically, up t0 30% or more of the original metal will have corroded away, and the residual "sponge" or “plug” will have virally no mechanical strength, Dealloying - Performance of Metals and Alloys Copper Alloys Dealloying was orginally observe in brases ard termed ezinefcation™ to connote the Toss of zine from the original copper-zine alloy. Other terms, such as “Uestanification.” "deniekelifcaion." and “dealuminifia- tion" have been used to indiate the loss of other alloying constituents Brasses Red brsses of 15% zine or less ore sully resistant in {hele conventional applications i agucous of atsospherc Service Yellow brass, inlaling inhibited “aluminum brass" and admiralty bras, ae resistant in such moderate femvironments as potable or fesh cooling wate if they ontain tn plus arsenic, antimony, or phosphorus Bronzes Phosphor (tin) bronzes have been subject to destenification| (ie. dealloying of tin from the alloy) in severe chemical Aluminum bronzes (copper-aluminum alleys) Sometimes suhjeet to dealuminitieation rir 2000“Forms of Corsion: Recognition Mechanisms nd Gontol “There exist compositions that minimize this problem by avoiding the formation of 2 metastable high-lemperature phase, which is particularly subject t0 this form of Comosion, These alloys are normally used ss castings, ‘which make precise microstructural contrl difficult, Nonetheless, eat treatments have been suggested 0 minimize the problem. The weought alloys seem to be resistant except in certain severe chemical environments, such as phosphoric acid at elevated temperature Siicon bronzes have be’ isolated cases involving high-temperature steam plus acidic species Cupronickels have oocasionally been reported to suffer ealloying under conditions of localized corrosion. Cast Iron Dealloying of east ons usually proceeds unitonmly inward from the surface, leaving a porous matrix of carbon, Graphitic corrosion, oF graphitization, is a form of Uealloying caused by the selotive dissolution of iron from ‘some east ions, usually gray cast iron. In the dealloying of gray east iron, the iran corrodes, leaving the graphite matrix. In this instance, more than 90% of the original alloy may have been lost due (© corrosion, with no apparent change in volume or thickness ‘There is mo outward appearance of damage, but the effected metal loses weight and becomes porous and Deitle Depending on alloy composition, the porous residue may retain appreciable tensile strength and have moderate fesisumee to ermsion. Por example, a completely Ssraphitized buried cast icon pipe may continue to hold ‘water under pressure until jarred by a workman's shovel Graphitization occurs im salt waters, acidic mine waters, dilute acs, and soils, especially those contaaing sulfates and sulfate-reducing bacteria “The presence of sulfates and sulfate-reducing bacteria in soil stimulates this form of attack, The additin of several percent of nickel to east iron greatly reduces susceptibility “Bae Govesion Sede anual SHAGE ineraonat 2000 ‘uot 599Forms of Comason: Resogeton, tech to graphitization. It is possible to produce graphitation in the laboratory by immersing gray cast iron in very dilute sulfur acid, Controls of Dealloying Control of dealloying can be accomplished in several ways, including Materials selection ‘Modification of environment Protective coatings Electrochemical techniques Design Materials Selection Control of dealloying is normally achieved by using an alloy that is more resistant to this form of corrosion, such ‘+ Inhibited brastes instoad of ordinary basses © Nicresist eat iron instead of gray east iron {Nodular or malleable cast iron instead of gray cast ion Control of Environment It is sometimes possible to control dealloying comosion by changing the environment, especially. im regal to the parameters of aeidity’alkalinity, For example, acidic waste waters that cause graphitic corrosion of east ren can be antral! by proper wwealent. Corrosion inhibitors can flo control “dealloying in some metal-environment systems Use of Protective Coatings Protective coatings may be useful in some specifi Electrochemical Techniques Cathode protection has been demonstrated to control dcalloying. Design Conirol of temperature is often used 10 contro dealloyin Minimizing hotwall effects in heat exch beneficial in conteoling dealloying of some mat Basic Certvon Sten Manual ‘oaD1i03, - ns Conte 570Forms of Conosion: Recogron, Mechanisms and Gott sn Fretting Corrosion Definition Fretting corrosion is defined as metal deterioration caused by repetitive slip at the interface between to surfaces in Description Frotting usually involves the relive motion of 0 Surfaces that were not intended to move i tha fashion Recognition Fretting corrosion occurs at the interface between (wo surfaces which can move with respect to each other. Surfaces effected by fretting corrosion are often free of corrosion products and show a burnished appearance. Mechanism Fretting corrosion occurs when motion between surfaces ther removes protective Films, of, combined with the Abrasive action of corrosion products, mechanically emoves material from surfaces in relative motion, For fretting corrosion to occur, the interface mast be under Joud and the motion (usually of small amplitale) must be sufficient for the surfaces to strike or ub rogetter. Results oF fretting include: 4 Metal loss in the area of contact inn af oxide and metal debris ‘Seizing, fatiguing, or cracking of the metal Loss of dimensional tolerances Loosening of bolted or riveted parts Destruction of bearing surfaces “The wear process in tretting is not well understood. It is knovin that the debris produced can be either an oxide, it oxidation conditions exist, oF very fine meal particles, if rho corrosive medium invades the contact region. The ‘Basic Conosion Student wana — (SHACE inemntcnal 2000, oveFons of Casi: Racognten,Meshnks and Cota sm debris an be abrasive and play a ole nthe ting wear eal Fretting Corrosion-Performance of Metals and Alloys Virtually all materials are subject to fretting corrosion if they are present Controls “Techniques for contro of fretting corrosion ine 1+ Materials selection + Design + Use of ubeicants Materials Selection ‘To control fretting corrosion when the motion between the surfaces cannot be eliminated, use mating surfaces of different materials, eSoft metal against harder metal Design In the design of systems, avoid situations in which there can be small relative motion between surfaces, This can be deeomplished by’ roughening the interface, inereasing the Toad, oF greatly increasing the relative motion besveen the surfaces. “The environment between the surfaces ean be eoniolted by the use of cements or sealants. These materials ean also reduce of eliminate abrasive serubbing between the surfaces Use of Lubricants Lubricants, such as molybdenum sulfide at te faying surfices, ean be used to control fretting corrosion. The use ‘of such low-friction materials as Auorocarbons, ether as fone surface in the system or as a lubricant, can also be effective in controling feting corrosion Base Gonosen Shdent Menus!Fons of Conmsion:Resogntion, Machanisms and Cont _ High-Temperature Corrosion Introduction High-temperature corrosion is a for of material gradation that oceurs at elevated temperatures. Direct chemical reactions, rather than the reacliens of the lectrochemical cell, are responsible for the deterioration ‘of metals by high-temperature corrosion, “The basis of high-temperature corrosion ressianee stems from vonsiderations of thermodynamics and kinetics of reactions at elevated temperatures. ‘Thermodynamics determines the tendency of metals to react in’ specific environments, considering both the femperature and species present in the environment (oxygen, water, sulfides, hydrogen, et). Ln the case of kinetics, whether or nota metal is considered ccorrosion-resistant is dependent not on "whether it torrodes”, but on "how fast it corrodes.” As to what factors Getermine whether a high-temperature corrosion reaction will occur slowly oF rapidly, we must consider the Characteristics of the corrosion product layer wich forms. ‘The behavior of motals at elevated tempestures, and especially their corrosion behavior, is a detailed and tompler subject. Cur diseussion of high-temperature corrosion will focus on its practical aspects Definition High-temperature corrosion is the deterioration of a metal at temperatures where direct chemical reactions between the metal and the environment cause the material to degrade ‘The avtual temperauure at which high-temperature corrosion becomes important depends upon the material ‘Gae Covodion Seam anual ‘SNACE Intemational 2000 ossFexms of Corson: Recogniton, Mecanims and Cool and the environment, but the corrosion usually begins to foceur when the temperature is about 30% to 40% of the ‘molting point of he alloy In is usually in this range that mechanical properties are governed by creep sirengl, and here the fist evdence of What we consider to. be high-temperature corrosion characteristies appears. Magnesium and aluminum alloys fre in high-temperature modes at torporatures 2s Low as 204°C (400°F), iron and steel at temperatures as low as 426°C (BO0°F), stainless steels in the range of 425° 10 870°C (800° t6 1,600°F), Titanium, on the oder hand, Toses strength at temperatures as low as 315°C (600°), despite its high melting point, .815°C @,300°F), Recognition High-temperature corrosion is usually associated with the formation of thick oxide or sulfide scales, or with internal reactions thal cause internal swelling of the metal at clevated temperatures Mechanisms High-temperature corrosion is dependent on several reaction, including: Oxygen reactions Sulfidation ‘rburization| Decarburization (hydrogen effects) Halide effects Molten-phase formation Oxygen Reactions ‘Oxygen reactions are the most common and mest widely stuclied high-temperature corosion reactions. Oxygen reaction concepts are diteetly applicable to most other gas-metal, high-temperature reactions in which a Seale is. formed, In fact, almost all high-temperature orrosion reactions can be classified as oxidation, whether the seale is an oxide, 9 sulfide, or a halide. because the walence eharge ofthe metal his been increased ‘isie Carosion Stade Nanoat ‘SNACE Imernatona, 2000Fox of Corsion: Resogniton, Mechansms and Cont! 7 575 Most metals will react directly with oxygen at high Temperatures. When a metal is oxidized at elevated Temperatures, an oxide or other compound may form. This corrosion product layer may act as a barrier between the Substrate snd the corrosive environment (air, Nue gas, molten salt, or any other corroden. ‘To be effective in controlling the rate of oxidation, oxide scales must Be physically stable Maintain good mochanicalintesrity Be adherent to substrate Possess slow-growth kit Have low volatility Reaction Rates Depending on the degree to which the stale formed prevents attack of the base metal, the corroson reaction can be either a linear oF a parabolic function of time. Other fate behaviors with respect fo time are also possible. igh temperature Onénton tes cove igre 58 High Tompertare Corson Linear Behavior If the oxide film or scale eracks or is pomus and the conusive environment can continue 1 penetrate readily 1 react with the base metal, protection wil be limited Bacic Croan Sivdert Menu! ceoForms of Crosion: Reegation, Mechanisms and Contoh and attack will proceed at arate determined essentially by the availablity of the corrosive species. In this ease, the rato willbe linear. Parabolic Behavior Ifthe seale formed is continuous, adherent, and prevents easy access of the corrosive gas to the underling base ‘eial, a considerable measure of protection may occur and the extent of protection will increase as the scale thickens. In this ease, the availability of the corrosive gas will not determine the reaction mate Ditfusion through the scale will be the slowest ard, hence, the rate-contralling stop. The diffusing element that controls the reaction cate may be either the oxygen moving inward oF the metal moving outward. The fatter is more kely in alloys possessing good corrosion resisiince. As the scale thickens, everything else remaining the same, the diffasion rate will decrease, s0 the rate of scale growth will decrease anid be inversely proportional to its thickness at any point in time, Oxide Scale Characteristics [As briefly mentioned, important characteristics of scales With respect t0 their ability to control high-temperature corrosion include seale thickness and scale adhesion ‘Scale Thickness Seale thickness eon be ait important factor. In eal stages. the seal i thin and comparatively elastic. I also will have Tittle intéinsie strength and usually will remain tightly adherent to the base metal. As it thickens, however, its [ess sirable properties may become manifest. Hewy scales tend to be brite and, therefore, tend (0 rupture and spall from the surface. ‘The volume of scale formed, relative to the volume of the metal reacting, often has been cited 3s a principle factor Controlling seale continuity. It has been postulated that for ‘maximum performance, the scale Volume should exceed thatof the metal consumed, n this eas, the surface scale is tunder some compressive sttess, which is desirable for most brittle materials, and the teleney to crack is minimized asic Garson Son Manual aForms of Conesion: Recaghiton, Mechanisms and Conkoh Certainly, if the seale volume were considerably less and tensile stresses existed, the opportunity for eupture would bbe much greater. Scale Adhesion ‘The matter of scale adhesion is important, particularly it temperature variations occur. A weakly adherent scale is likely to separate. locally fom the base metal, a phenomenon sometimes termed lstering. Seales ‘can Eventually ‘apnire and spall because they have litle intrinsic strength, ‘Adhesion may be affected by differences in thermal ccooffcients of expansion between scale and base metal “The nature of the interface between the scale and hase metal also affects scale adhesion If the interface is smooth, it is easy to conceive of a shear erick initiating at the interface and propagating rapidly aeross the surfoce. the interface is rough and incipient grain bourdary attack ‘occurs beneath the scale, a keying action may prevent rapid track propagation and, thereby, may improve scale adherence It is thought by some shat reactive rare earth sitions to heat-resistant alloys exert their jamor effect nol by entering the scale and lowering diffusion rates, but by azcumulating in grain boundaries, thus ensuring a small amount of grain ‘poundary attack to provide the keying action Internal Oxidation It is also possible for oxidation 0 proceed without an extemal sede, provided certain conditions exis: ‘The alloy must contain, 38 a minor ingredient, an element that is considerably ‘more reactive than the major constituent. Silicon in copper is one example; chromium in nickel is another. The concentration of the mnor element Thus be less than a certain ertical value “The rate at which the minor element diffuses toward the surface must be less than that at which the corrosive species diffuses inva aie Coresion Sudo Manual ‘BWAGE iernaona 2000, rorInternal oxidation is controlled by the concentration of oxygen in surface layers. This quanity must be insufficient fo oxidize the nobler major constituent, but sufficient to ie the reactive minor constituent External scale will form only when the effective pressure fof oxygen atthe metal-gas interface exceeds this range for the more noble component, or when the concentation of the less noble component exceeds some critic value. Conversely, failure of surface scale to form ean indicate thatthe oxygen partial pressure atthe interface is at such a level that the oxygen will not react with the major constituent. ‘An early example of destructive intemal oxidstion was found in failures of the chromel alumel therwocouples used to measure the temperature of a hydrogenich gas. The hydrogen was able fo penetrate the protectior tube and set up an atmosphere within the tube of 90% nickel-10% Chromium-chromel alloy; this atmosphere was reducing to the nickel, but oxidizing to the chromium. Thus, no nickeloxide surface scale formed, and the chromium oncentraion was not sufficient to form an external ‘chromium oxide seale, Instead, islands of C03 formed within the alloy, giving the facture surfices their characteristic green color ("green cot"), One method to tcoreet situations ofthis sort isto clude in the assembly fan aotive “getter” for oxygen, such as a strip of titanium, Which by removing the oxygen will leave an atmosphere thats reducing to Bott constituents ofthe alloy, Sulfidation ‘When the sulfur activity (partial pressure, concentration) of | the environment is sufficiently high, Sulfide phases (in dalton t oxide phases) can be formed. In the majority of environments encountered, sluriina or chromium sesquioxide should form in preference 10 any sulfides, and destntive sulfidation attack occurs mainly at Sites where the protective oxide has broken down. Sulfur tan be transported through seales. Onee it has entered the alloy, slfur appeaes to tie up the chromium and alutninu ‘as sulfides, effectively redistributing the protective scale for jing clements near the alloy surfiee and inverfering osicGarosion Sudont Marva NACE Inemationl 2000, agorios S70“Fess of Conosion: Recopition, Mechanisms and Conral = with the process of scale formation or reformation. If Sufficient sulfur enters the alloy so that all immediately- available chromium of aluminum is converted to sulfides, the less stable sulfides ofthe base metal ean then form, It's these base metal sulfides that are often responsible for the observed accelerated attack because they grow much fasier than the oxides of sulfides of chromium or slyminum. They have relatively low melting points, so molten slag phases are often possible, Sulfur can be transported across continuous protective scales of alumina and chromium sesquioxide under certain conditions, withthe result that discrete sulfide precipitates ‘can be observed immediately beneath the scales on alloys behaving in # protective manner. For reasons indicated above, a fong as the amount of sulfur present as sulfides is Small there is litle danger of accelerated attack. However, fonce sulfides have formed inthe alloy, there isa tendeney far the sulfide phases to be preferentially oxidized by the feneroaching reaction front (oxides are more stable than Sulfdes) and for the sulfur to be displaced inward. This process prompts the formation of new sulfides deeper in the alloy, often in grain boundaries or atthe sites of other chromium or aluminum-rich phases, such as earbides. In this way, Fingerke protrusions of oxidelsu fide can be farmed ffom the alloy surface inward, which may act to localize stress or otherwise reduce the load-bearing section Carburization Metals, such as steel, when exposed to a suitable carbonaceous gas or liquid at high temperature, nay absorb Some of the carbo atoms that reach the metal surface. The orfive, bueause of its higher carhon content, will respond better to heat treatment and develop a higher surface hardness, while the interior will be softer but tougher, a desirable characteristic for many applications ‘Most metals have a significant solubility for erbon, that is, they can absorb large amounts of carbon without undergoing any drastic physical change, alough some properties (e-2 response to heat treatment) may be altered ‘measurably “Base Corson SisentWanual [SNAGE inertial 2000,Forms of Comason: Resognitn, If carbon continues to be driven into the metal, its solubility can be exceeded and more dramatic ehenges will ‘Occur. [n pure nickel, Which forms no stable carbide at high Temperatures, embritlement from graphite pre:ipitaion may oceur, and in the more commonly used heat-resistant alloys of the iron-nickel-chromium system, precipitation of| ‘chrornium-tich carbides will occur. Initially, such carbides will have Title effet on the chemical or physical behavior of the alloy. In fact, most commercial chromium-containing alloys, suck as the Stainless steels, have a small quantity. of chromium carbides present, However, as carburization continues and the quantity of carbides. inereases, the situaion will change. Because chromium forms carbides more readily than the other constituents of stainless steels, the matrix of | the alloy will be depleted of chromium. [As discussed previously, chromium is the element that contributes most to a resistance to oxidaiion and sulfidation, The ehromium-depleted matrix will be unable to develop adequate protective scales and wil become quite susceptible to these and other types of attack, Furthermore, the presence of continuous rain boundary carbides will Both increase the rate of intergranular attack because the carbides are more reactive than the matrix) tnd deteriorate mechanical properties (because eracks ean ‘propagate more readily). Another possible ettest of earbuetzation is met dusting ‘This phenomenon occurs in process operations where oxidizing and reducing conditions alternate. When the tenvironment is on the reducing side (CO predominant), shallow carburization of the metal ean occur at breaks in the protective oxide film, When the exposure then changes to oxidizing, the high-carbon area of the metal is bumed fot and the underlying. metal is reacted to become new ‘oxide, A depression is left in the metal surface where the ceaurized area exised, and the metal oxide is. swept Alownstream as metal dust Decarburization (Hydrogen Effects) Decarburization, of high-temperature hyilrogen effect attack is also high-temperature phenomenon. ft should be esx Caisson Sten Manual NACE Intatonal 2000, oanForms of Conosion’ Recognition, Mechanisms and Conrol clearly distinguished from hydrogen-induced cracking, which occurs at nea-ambient lemperatures ant is usually “sociated with an aqueous environment as the source of the hydrogen. At temperatures above the dew point, high- pressure hydrogen is the usual souree The attack relates tothe reaction of hydrogen, with readily reducible carbides, or in some cases oxides, within the alloy to form methane or steam. These gascoas products, under high pressure, will cause small local ruptures whi ‘vill impair the structural integrity ofthe metal and lead to carly failure. Hydrogen is a difficult_gas to cope with at elevated temperatures because of ils ability to diffuse rapidly through metas in atomic form and because of its extreme reactivity. Ifthe hydrogen, during its passage through the ‘metal, encounters such readily-reducible compounds asthe carbides previously mentioned, an ireversibleweaction will Because the movement of hydrogen through metals cannot be prevented, the principle means of contol is to ensure that the carbides formed are sufficiently stable to resist reaction with hydrogen. Such clements as chromium and molybdenum form carbides considerably more stable than iron carbides, 0 steels containing additions of these ‘lements have been quite successful in resisting hydrogen tack. Note, however, that blistering can be caused by such defects as seams and inclusions and will not be iminated merely by selecting a stabilized alley Romember, atomic hydrogen penetrates throwwh common inclu Inaclad vessel (2g. conper-nickel, or stailess- Clad ste, the substrate steel must be alloyed to resist the process side-conuitions of temperature and patial pressure ff hydrogen, Otherwise, the steel substrate wil be attacked by atomie hydrogen passing through the corresion-resistant cladding. Halide Effects Halogen gas can form volatile halide layers on metal subsirates, When & critical temperature is reached, the ‘ace Coveon Sudan Manual SNAGE nenatona, 2000 owenFes of Cmosion: Racagniton, Mechaigns and Control halide layer evaporates, leaving the metal substrate exposed to further rapid reaction In industrial service, the principle halides of imerest are chlorine and fluorine, together with hydrochbric and hydrofluoric acid vapors. Bromine and iodine are of secondary importance, but relatively few data exist even forthe gases of major significance. Despite the small amount of data, it is of interest to consider halide attack because it introduces a new mode of Seale breakdown, In principle, corrosion by halogens proceeds in essentially the same fashion as corrosion by fxyzen, sulfur, or nitrogen. The gas, upon contscting the ‘surfice, will oxidize the metal atoms there ant form a halide layer “The halide seal, while it remains in place, will offer some ‘measure of protection against continuing attack. The major Gifference is that metal halide compounds all have very high vapor pressures, so that when some critical temperature is exceeded, the scale will volatize and leave the metal surface exposed for further rapid reacticn Although a few oxides (eg, MoOs) ate volatile at felatively low temperatures and others (©. C03) may teach significant vapor pressures at very high temperatures, Yolatization of oxides can be ignored in most cases. It Cannot for halides. Many metal halides. such as chlorides, fluorides, and bromules, Rave high vapor pressures: and scales formed by these halides vaporize quickly above a certain critical temperature, leaving the metal exposed for ‘continuing attack Molten-phases Formation In all environments considered up to this point, we have ignored the possibilty of corrosion product fasion and. have limited the discussion to gas-metal reactions with solid, or in the case of halides, gaseous reaction product. Tn many situations a clear distinetion eannot be made. The corrosion product itself my avelt, oF contamirants may Tower the melting point into the service temperature range ‘aie Cavosion Stet Manual NACE Inertial. 2000 592Forms af Conosin: Recognon, Machanisins and Cont! “The reaction products or harmful contaminants have one thing in common: Whether they themselves are solid, Tiguid, or gaseous, they react with the metal a corrosion pradicts 0 Form a used! phase. This phase will destroy the integrity of the protective scale by Muxing or dissolving it ‘and leaving the underlying metal available for further corrosion. Frequently the fused phase will atiract and concentrate potent corrodents at the place where they do the maximum amount of damage: where the seale is disrupted, Ideally, the contaminating phase is removed and the problem is eliminated. However, this correction is frequently not possible Because of the numbers of contaminants which may inerlere with the normal development ofa protsctive scale during high-temperature serviee, itis virtually impossible to present a complete list. Some familiar examples inelude: ‘Leaded gasoline (lead oxide) Residual oils Sea salt ‘Welding slag “The combustion of leaded gasoline leaves depesits of lead ‘oxide and other compounds on exhaust valves. which ean shorten their lives. Due to the introduction of unleaded fasolines, it was discovered that lead oxide cating has a fenefiial effect in reducing valve wear, and valve and Valve seat materials with improved wear resistance are now require. Combustion of residual oils may interfore with the normal evelopment of protective scale, because the ash contains, among other things, vanadium pentoxide. This feompound, in pace form, melts at 690°C (1,274°F), but its melting temperature may be lowered further by the presence of other compounds, “The small amount of sea salt that may enter a reaetor oF was turbine with the combustion air ean initiate a sequence of ‘events culminating in catastrophically high cormsion rates “Basie Corson Stent areal ‘SNAGE ntrminal, 2000,“Forms of Carosion: Recogran, Mechanisms and Control Welding slag, improperly or incompletely removed, also ray cause difficulty and frequently premature faire However, no attempt will be made to discuss even a representative sampling of such contaminants. We shall ‘merely try to show how they affect corrosion behavior. High-Temperature Corrosion- Performance of Metals and Alloys Carbon and Low-Alloy Steels Ordinary carbon and low-alloy steels have been used successfully from room temperature up to tempertures of About 480°C (900°F) and for short periods of time up to 590°C (1,100°E). At temperatures beyond this, ordinary steels tend to corrode rather heavily. There is a trend 10 fesort to cementation (Surlace diffusion treatrents) on tearbon and low-alloy steels to render them more resistant {o corrosion. Depending on the comrosiveness of the ‘medium involved and the exposure temperature one oF Several of the following may be used: silvonizing, Aluminizing, chromizing. or special treatments such as plating, plasma spraying, or cladding Alloy Additions Aclitions of alloying elements to steels can greatly increase their resistance f© some high-temperature Additions of chromium to steel can cause a sharp decrease in. iton corrosion (oxidation) by air at elevated Temperatures. However, additions of chromium beyond 20% have litle effect, particularly at the lower temperatures, On the negative side, chromium additions fan make iron less resisiant to halide attack. Nickel Additions to ion-chromium alloys not only improve the Corrosion resistance, 38 deseribed in the following section, bout their mechanical strength, as wel Nickel is not alloyed to ordinary iron t improve highs temperature corrosion properties. It is effective, however, in alloys containing 11% chromium, Its beneficial effects, Tike those of chromium, tek! 10 become less elTetive after Some specific amount, The amount of nickel Base seFons of Comesion: Recagniton Mechanisms and Cont required to achieve a low-corrosion rate is greater than th Of chromium, and the necded amount also increases for higher exposure temperatures, “The beneficial effect of aluminum additions in suppressing, high-temperature corrosion of iron alloys is stprisingly sisong. When amounts of up to 12% aluminum are added, a considerable reduction in high-temperature corrosion is lachieved. However, mechanical properties siffer, ths tmaking this approach to corrosion resistance less attractive. ‘Where lower mechanical properties can be tolerated, the Use of limited amounts of aluminum can be considered, ‘One approach to simulating. sluminum-alloying while ‘causing relatively litle effect on mechanical properties is Spray metallizing of aluminizing, This high-temperature ementation process diffuses aluminum inte iron and produces an effective surface for exposure in a, or sulfur Gioxide fumes fo temperatures in the neighborhood of 1,095°C (2,000°F). Stainless Steels “The most common alloys used for exposure at high temperatures are the stainless steel 1f medium oF high-alloy steels are used, ehromium- bearing stainless stecls are generally recommended. Both Staight chromium steels and chromium-nickel stainless Steels are used up t© approximately 870°C (1,600°F). At Sill higher temperatures, higher nickel and higher chromium alloys afe used. At temperatures. somewhat in excess of 1,0939C (2,000°F), only alloys with more than 30% Cr can be used. These alloys are relatively safe for “hort or intermediate periods of Him During long-term use at high temperatures, a phenomenon known as ereep is experienced, during whieh relatively low Toads may cause a metal 10 deform very slowly and possibly fal. This is & Factor that must be considered by “anyone considering or recommending alloys for use at very high temperatures ‘Fei Corson Sudeninewal ‘S NAGE ntrnatona, 000 eon 585Forms of Conlon: Recogniton, Mechanisms and Cotol Nickel-Based Alloys Many nickel-based alloys have excellent resistanc: to high- temperature corrasion, and many have been specifically developed for high-temperature application such as blades for gas turbine engines. Refractory Metals [At temperatures higher than can be tolerated by other alloys, it may be necessary to use refractory metals ~those that have good high-temperature mechanical properties and melting temperatures well above 1,650°C (3,000°F), Thus, Slloys of chromium, niobium, molybdenum, tantalum, Thenium, oF tungsten are usually considered for very high temperature serviee, Although titanium and zirconium melt above 1,650°C (3,000°F), their _high-temperaure ‘mechanical properties are rather unsatisfactory, so they are hhot generally considered in the cateyory oF refractory metals. Similarly, vanadium is not a popular cowender for high-temperature applications. Unfortunately, all the above-named refractory metals, wit the exception of chromium, have poor high-temperature conosion resistance in ait of olher oxidizing atmospheres, ‘Some success has been obtained in developing wseful life at high temperatares with proteetive coatings on the other feftactory metas. Ina few cases, corrosion resistance has been improved by alloying Control of High-Temperature Corrosion Methods of corrasion control in high-temperature applications are largely confined to materials selection and design, although limited modification of the environment fean be achieved and the use of protective coatings can be effective. Materials Selection The selection of materials compatible with the chemical makeup of the environment at the specific service Temperature conditions isthe most commonly used method for controlling high-temperauure corrosion. Becase ofthe complex nature of high-temperature corrosion, materials ‘NACE Intational, 2000selection usually requires the services of an expert inhi temperature corrosion. Design Design can be used to reduce some factors related to high- temperature corrosion, Stress reduction can reduce the creep that affects scale adhesion and dimensional stability ff the metal itself Good design can also reduce the effect Of the high-temperature corrosion in a manne” similar to the use of a corrosion allowance. Reduction of thermal teyeling and thermal differentials can also be used 10 ‘control high-temperature corrosion. Modification of the Environment In some eases, environmental contaminan's can be controlled to reduce high-temperature corrosion. tn other teases, materials stich as oxygen can be added to improve ‘Seale formation (¢., oxygen ean be added) when the Scales are mote stable in high-oxygen environments), Protective Coatings Protective coatings of high-temperature-resistant metals and alloys applied by weld overlay or electoplating, as Well as ceramic coatings, have been successfully used to ‘control high-temperature corrosion in some eas. “Basis Caroson Suaent Waraal NAGE Intron 2000, sania 537ye