Materials Selection* Gregory Kobrin, E.1. Du Pont de Nemours & Company, Inc. FACTORS THAT INFLUENCE the service lie of equipment for example, # chemical pro cess heat exchanger or tank, 2 bridge, of an Avtomabile chassis, from a corrosion standpoint Include the following (Ref Vs © Desien 1 Materials of construction © Specification 1 Fubrizalion and quality control 1 Operation Maintenance 1 Environmental conditions In weighing the relative importance of these factors, design and moterials are of major sad ‘equal importance in achieving the desied.per formance and life. ‘The designer and materials engineer must work closely together to ensure that preaatuce failure Will not oscur becalse of design dlefeets oF improper material selection. I isalso inefficient and costly to use these elements Of design and material selection in a compen tory manner This article will discuss the step-by-step pr cess by Which materials are selected In oder 10 Sve! or minimize corrosion and wil inchade information on materials that are resistant to the ‘aris forms of corrosion Subsequent articles inthis Seetion wil diseuss design devs that ean he unplied to minimize corrosion, the application of fracture mechanics to equipment design, co rosion of Wweldments, and the economics of co The Material: Selection Process Review of Operating Conditions. The frst ‘sep in the materials selection process is thor ‘ough review of the corrosive eavironment and feqipment operating conditions. This review re- ‘quires input from knowledgeable process en neers, Preise definition ofthe chemical environ ‘ent, including the presence of race compounds, fh vila For example, the nickel molybdeoum alloy Hastelloy B-2 (UNS N1GGS) is highly re Sislant to. hydrochloric acid (HCD upto. the atmospheric boiling point. Hovtever, the pres tence of small quantities of oxidizing metal tons Sch as ferric lon (Fe), will result in severe corrosion. Other operating conditions. tht re ‘quire definition, especially for equipment used in the chemicalprocessing industry. include tem peratures, pressures, ow rates, iguid versus iseous phases, aqueous versus anhydrous ps £5, continuous versus inermuttent operation, me sre section ENS Pom de Nena nmaurs Company ie ia used for cooling or heating, external versus internal environment, and produel parity ‘Abnormal er upset conditions are often over looked during the selection process. For exam ple, plain carbon steel may be the optimum Choice for vessels and piping that must contain noncorrosive hyérocafbon gases. such as chylene, under pressure at normal temperatures. However. the cooling effect that occurs during ‘venting 1 the atmosphere, for whatever reason. may lower the temperature of vessels, piping. and relief valves to below the ductile-i-britte transition point and result ina catastrophic brite fracture. Thus, the selection of special steels ‘qualiied by impact testing atthe lowest expected {empersture, would be appropriate. Review of Design. Next. the type and design of the equipment and its various components ‘should be considered, slong with size. complex. fiy.and enticality in service. Selecting a material for 2 simple storage tank generally docs not require the same attention and effort ax chong the material of canstmuetion fr & highly sophis: licuted chemical process reactor. This is expecta Iy true when considering ertical_ unique pieees of ‘equipment in large, singe-eain, continuous pro. ess plants in which 2 failure would shut down the entre operation. In this case, great effort {expended to select rhe optimum material for safe Tow-maintenance service The materials used fo join the components into an assembly wil require as much atention as the ‘component materials themselves, Mony bolied ‘agitator assemblies in reactors, a8 well a8 riveted Wheels in centrifugal compressors, have fale! Calastrophically because the bolts or rivets did hot have atfeguate sticagih or costosion tess tance ‘When welding is the joining method, the mate als engineer is challenged t0 ensure that the welds are ss corrosion resistant as the Base Inetals. Generally, the weld metal must equal the bbase metal in chemictl composition nd must be Virtually fie of surface defects such as porosity slag inclusions. incomplete penetration oF lack of fusion, for long maintenance-free service. The challenge is even reater sehen isinr-metal elds are required. Improper selection bay allow Tocal attack die to weld metal dilation or my allow hydrogenassisted cracking duc to hard heatalfected zones (TAZ). More information ‘on preventing corrosion of welds is availabe in the article "Corrosion of Weldmente™ in this Volume: Selection of Candidate Materials. Once ‘the chemical environment, operating consitions and type and design of the equipment have been defined, consideration of materials uf construc: tioa is in order. Occasionally, the selection Is based on reliable, pertinent past experience and, ae such, i well defined. More often, hoviever, Selection is anything but straghiforwand for & fnumber of reasons, auch as complex chemical environments and sisingent code requirement "The list of materials to choose Irom is large and continues to inerwase. Ferrous and nonferrous metals and alloys. thermoplastics, reinforced thermoseting plastics (RTP), nonmetallic Hinings, lass. carbon and graphite, and catalyzed resin outings ate among the various matetals aval Able. Meny materials wil be immestiately exch fi because of service conditions, that is. pres Suites too high for RIP, temperatures 100 high for ‘honmetaic Hnings and costings such as rubber or epoxy resins, environment 100 aggressive for farbon steel, und 30 an. Remaining choices my Still be great in number. is always desirable to minimize the Hist of smaterials: hi allows in-depth evaluation, [9 oth: fr eases, the inital list_may be exceptionally Small because of limited knowledge shout the ‘operating conuliions or the complex. chemical fenvironment. A search of data sources should fallow in ether case Literature Surves. One aight begin with literature survey. using applicable sources sch ss Corrosion Abstracts (Re 2, son with the Corrosion Data Survevs (Ref 31 published by the [National "Association of” Coriesion Eniieets (NACE). This technical society. in conjunc ‘the National Brean of Standards, as in ated an on-going program to computcrize refer fice ata on tbe pesformance of materials fa ‘Oiher data sources include a wide variety of handbooks. conference proceedings, ad hters {ure compilations published by the American Society for Testing anil Materials (ASTM). ASM INTERNATIONAL, nd NACF. In addition, expert systems, which are computer programs Contnining methods and information developed Dy eaperts, are the latest tools available for ‘materia sclection (Ref #7), Such systems are designed to solve problems, make predictions ‘agent possible treatments, and oer materials nd corrosion advice with a degree of accimisy ‘equaling that of their human counterparts, Experience and data generated in-house often serve as the most reliable bases for materials Selection. Ideally, this is coupled with onside experience, when available, Irom materials ve ‘dors and equipment fabricators to complete this eas writen by George. Kerns, FE, Du Poa de Nemours & Compaay In. the seston “Erosion Cortesen™ was welt By LQ. Lackey322 / Designing to Minimize Corro: initial screening process: Contacts with clients referred by vendors should not be overiooked for added experience A this point, the lst of candidate materials should e narrowed to reasonable number Tot indepth evaluation. Final scletions should not he hase solely on the above dia sources, be fause in most eases the data provided are ins Fieient for the complete characterization of an caviroament oF sot of conditions. Evaluation of Materials. The in-depth eval- lustion of each candidate material should begin ‘sith a thorough understanding of the product forms available, along with the eave of fabreation iy standard methods, For example, it would be \astefal of Hime and money t0 evaluate an Fe- T4381 alloy for anything Dor a cast component suchas pimp easing or valve body. The slo 1s Sinavaible in any other form, Because of its poor weldsbility. this allay should ais be ruled ‘ur for applications involving welding ‘Comosion testing in representative environ nents generally the nex step. The estent ofthe Investigation fand determination af test-comdi- tions) depends on suct factors as (Ref 8) © Degree of uncertainty alter available informa tion has been considered 1 The consequences of ‘mam selection © The time available for evaluation Laboratory testing of candidate materials sco ion and in some cases may tee the only: mess valle for fal determination. Wherever por Sible. the actual process fhids shoul be Used. Otherwise, mintures simulating the actual envi ronment must be selected, There is considerable risk im using the later. because undefined com stituents can have significant effect on the performance ofa particular material Depending on the application, weighed and measured coupons of candidate materials are exposed fo the corrosive fis under variety of Conditions ranging from simple static immersion 0 a controlled temperature to eamplex testing Uinder combined heat transfer and velocity coo: Uitions: Guidance for conducting Iaboratory cor roston tess is avaiable in Ref 9 and 10, After exposure fora specified length of time (generally {minimum of f Week), the coupons are. in the ase of mots und alloys, cleaned and reweighed, fnd a corrosion rate i aieulated based om Weight Iund expaved surface ines, The rate i com ‘monly expressed ia millimeters of penetration per Year oF anches or mils (Lal = 0.001 in.) of Penetration per year. Te addition, coupons are examined under 1 microscope for evidence of local attack, sich 28 Pilling. ereviee corrosion, and exfoliation. Spe ial coupons, such as galvanic couples, welded, and stressed coupons, ute often expened 10 dee {ermine i other forms of corrosion may occur on tertain metals und alloys. These coupons may Fequire metallographic examination for evidence Df dealloying (parting) sirexs-coprasion racking SCC), intergranular corrosion. and other corr. ‘Sion phenamena "Nametale matcrils, such as thermoplastics coatings, reinforced thermosetting resins Clastomers, snd cersmies, are also evaluated in Tuorafory tests. but the criteria are different from those ised for metas, First, exposure ime rust generally be longer (oMten a minimum of Ito ‘mons before signticant changes occur. Ex: sue times of 6 months tI year are common, Also, corrosion rate calculations based on weight lose und surface aren are not applicable in mort eases, Of more importance ace changes in Weight, volume, hardness, strength, and appearance be- fore and after exposure. Corrosion testing and fvaluation are covered in detail im the Section ‘Coreosion Testing and Evaluation” in this Vol If possible, candidate materials should be test- cd under conditions more like the final applies: tion rather than it iaboratory glassware. that is Ina semmworks or pilot operation ori Fllscale equipment. Generally. the results are more reli able because test coupons are integrated into the ‘rocess ang are expased fo the same conditions as the actual equipment. Because of nonuniform Conditions Iflews, composition) within process ‘equipment. coupoa locations should be carefully “lected (sce the article “In-Service Monitoring” in this Volume. Reiiabilty is further enhanced when i is pos sible to est fll-size chempoments fabricated from andidate materia (ReF 11), Examples inch: nor (9 Flanged sections of selected alloys ronmetalis installed in a pipeline ‘» Experimental alloy impellers in pumps for cor fosfon and cavitation studies ‘© Tubirw installed ina fllsize operating or miniaire tes heat exchanger fo evaluate ma terials with optimum resistance 6 corrosion under beat wransfer conditions © Puddles of candidate materials bolted to a reactor agitator for erosion-corrosion studies The primary disadvantages of this method of testing are the cost of fabrication. installatio Femoval, aod evaluation; the doweiime resulting from equipment being taken out of service and lismantles for evaluation; and the fact thal test component could fail prematurely and eause a unit shutdown andor equipment damage ‘Specifications. At this point, all candidate materials have been thoroughly evaluated (along withthe econo tobe discussed later, ond the material of construction have been sel fer ihe pct appltion, Clear and cone specificstions must nos be prepared to easure ‘ha the materia is obtained as ordered sind that meets all the requirements of the application. Perhaps the best known and most widely used Sspeciicaions are the stndards of ASTM. Thou: Sands of specifications for virally ll metal and nonmetal materials of construction are covered in 15 sections encompassing 65 volumes. Similar standards sn countries other than the United States include DIN (Germany), BS (Great Briain), AFNOR (France), UNI (ly), NBN (Belgium), and JIS Japan), Other materials spec icons that are well known but ure more im ited im application ate those of the Society of ‘Automotive Engineers (SAE) and its Aerospace Materials. Specifications (AMS), the American Welding Society (AWS), the American Petro leu Insite (APD, and the American National Standards Institute (ANSD, Fabrication requirements must also be spelled fot i detail to avo! mistakes that could shorten the life of the equipment and 10 satisfy the Feguirement of state and federal regulatory agen ies and insurance companies. ‘The American Society for Mechanical Engineers (ASME) code governs the fabrication of eaipment for the ‘chemical. power. and nuclear industries, and the API cow overns the fabrication of equinene for the refining industry. Piping for these inds- ties is generally fabricated per applicable ANSI codes. ln these codes, allowable stresses for ‘esign calculations have been determined for virial all metals and alloys that might be selected for corrosive (and noncorrosive) ser vice, Where welding is Uhe primary joining met od, wolding procedures and welders must be {qualified before fabrication begins. Vesting and quality assurance requirements, sich 96 tsdiog Fan, hydrostatic testing, and ultrasonic in Spection, are also covered in the codes and are specified where applicable (0 enstre com. pllance ‘The fabricator is generally required to provide etait drawings that Hist cimensions, tolersnc all pertinent materials specications. fabric: tion and welding details, and testing and qulily assurance fequirements for review, Prefabrica: tion meetings sire held for fil review of all lovgasketed pipe flanges oF under deposits some fabricated assemblies, it is possible and ‘cont elfecive (0 avoid crevices by careful design isequalto ‘a weld backing ssip atthe closing seam in type S041, stainlexs see! reactor handling hot HINO), A sunall amount of carresion by stagnant ac in ihe crevice created hexavalent chromium ons (Ci), which caused accelerated attack, other exposed surfaces in the vessel were unaffected The closing seam could have been welded from both sides or from one side with a consumable insert rig, Which would have avoided the prob- Jem. Simular tack has occurred in stainless shell and tube heat exchangers atthe rolled Lube-to- luesheet joints and has been solved by soal Welding the joints with appropriate ld filler ‘metal and proces. However, in many cases, crevices ate either too only or impossible to desig out of «system, 50 carefil selection of materials iy the answer ‘Thaniam is sasceptible to erevice corrosion in bot seawater and other ol aqueous chloride environments. ‘Theretore, for a. flanged and fasketed piping system in these Mus, commer ally pure titanium grade $5 (UNS RSQSSD) may bbe acceptable for piping, hut flanges will quire the more crevice Stack resistant grade 7 (UNS S240), sohich contains 0.185 (aominal Pd, of rade 13 (UNS RS3400), which contains small “amounts of molybdenum und nickel. This is more cost effective than selecting the more expensive falloys for the piping as well. Another approach that has been Successfully used in these Mads installation of nickelimpregnated gaskets with trade 55 ttanivm Aonges The austenitic stainless steels are susceptible to crevice corrosion in medin other than HNO: Solutions. For example, type 308L stainless stel exhibits borderline pasivity in hat acetic acid solutions, particularly in crevices. Accordingly the materials engineer will specity the more crev~ ice corrosion resistant type 316L stainless steel here etevices eannt be nvoided, sch land vessel Ranges, oF for the enti fassembly beemise the cost differential bevween materials inthis case may be neliibe. Preferential attack of weld metal is another form of localized corrosion thal can be avoided by idiclous selection of weld filler meta or weld324 / Desig srocess. Weld metal corrosion in high nickel: Chromuummolyodenum Hastelloy alloy C276 TUNS NI0276) in a hot oxidizing H:SOy process Stream contaiting chlorides was eliminated. OY fepair welding with Hateloy allay C-22 (UNS ‘NOi22). Im applications in’ which type 30L Stainless steel is selected for use in Bol HNO, Solutions, welds exposed to the process ae Ire: ‘quent!y made by an inert gas process, such 3s ss tungsten are or ges metal ais, rather than a Tus-utilizing process. sch ae shielded met are ‘This prevents weld corrosion by eliminating the minute particles of trapped slag that are the sites for initiation of local corrasion. Many other ex- anpes af preferential Weld metal attack and their Solutions are discussed in the anicle “Corrosion ‘of Weldments” in this Volume, "Nonmelalic materials of construction are wide- ly used where temperatures, pressures. and Slresses are not limiting. and in ‘such media as aqueous chloride Solutions, which cause local ized corrosion of metals sn alloys, Examples in Which lower-cost nonmetal constructions are Selected over expensive high alloys include the following ‘© Rubberlned steet for water treatment ion ex- change resin beds, which must be periodically regenerated with salt brine or dilute mineral acids or caustic solutions ‘© Giassined steel for reaction vessels in chlor: nated hydrocarbon service 1 Roid-proof brick and membrane lined steel for higher temperature, and. sold RTP polyester and viny-ester construction for lower temp ature, ue” yas and chlorine acutralization Scrubbers 1 should be apparent that an in-depth evaluation of candidate matenls for environments that can tense localized corrasion is imperative in order to select the optimum matenal of vonstruction. In particular, corresion fest coupons shold reflect the final fabricated componert—that is, include treviges snd weldments where applicable—and should be examined critically under the micro Scope for evidence of local attack. In cases in ‘hich the more common 300- and 40-seresstain- less seal fll short, the newer feritics, sch as 26Cr-IMo (UNS $4627) and 27Cr 3Mo-3Ni(UNS Sigs) und the duplex feritic-austeniti alloys, salchas 26Cr1 SN SMo (UNS $3290) and 26C Ni 2Cu3.3Mo (UNS S32590), should he evaluat fed as potentially lower-cost alternatives to higher alloys. Finally, proven nonmetallic materials (for example. the RPS), used seither as linings for Towercost metals such as plain carbon steel or fr solid construction, should not be overlooked, More Information on the mecksnisms of pitting, crevice corres, sad other forms cf localized stack Is fvallable in the atcte "Localized Corrosion” in this Volume; the aricles "Corrosion of Weld- ‘ments and "Metallurgical Infvenced. Como sion” contain information on the preferential cor- sion of weld metal Galvanic corrasion is quite possibly the only form of corrosion that can be beneficial as well 48 harmful. The materials engineer will frequently select galvanic eorrosion-—ihat is, cathode pros fection using saerificil metal anodes or coatings ‘of magnesiam, zine, or aluminam—o sie exist ing. oF prevent new. corrosion of structures fab ficated pmarily fram plain carbon oF laW-alloy Stecls—for example, bridges. underground and nerwater pipelines, auto trames, offshore dil Ingrigs and well casings. All too often, however. 1g to Minimize Corrosion ialvanic corrosion caused by contact between ‘issinlar metals in the same environment i= harmful, Examples ae © Unprotected underground pluin carbon steel pipelines connected to above-ground tanks and Other siactines that are electrically grounded with buried copper rods or cables 1 Stainless sleet shale in “canned” pumps ro singin carbon oF graphite bushings ina st10N§ electrolyte ‘© Copper nick! or stainless steel heat exchanger tubes rolled in plain carhon steel tubesheets exposed to river water for cooling ‘¢ Alumioum thermostat housings on cast iron tuto engine blocks in contact with glycol water mixtures Newer designs that require several different met als For various reasons sch as east und physics, ‘mechanical, and/or clecirical properties presen! a challenge t the materials engineer with regard 60 Sclection forthe avoidance of galvanic cortasion. Knowledge of the galvanie series of metals based ‘on the cleetochentical potential between a metal and a reference electrode ina given environment isessentil. A practical galvanic seis for metals And alloy’ in sealer is given in Table ‘A word of caution: Metals behave differeatly io diferent environments; thal is the relative pos lions of metals and alloys inthe galvanic series can vary significantly from one environment 60 ‘another, Infact. variations within the same en. ronment can occar with changes in such factors fs temperature, solution concentration, degree of agitation oF aeration, and metal surface condi tuon. ‘Thus, galvanic’ scricy that are based on Seawater of olher standard electrolytes are worth While for initial materials selection for multiple Ielallloy sysiems ina given environment, Hin ver, additional tests should be carried out in the Slated environment by using the anode poate ion measurements described in ASTM 5 (Ret 10), Suitable metal combinations can he deter Table 1 Practical galvanic series of metals and alloys in seawater [Least noble: most anodic; most susceptible to corrosion Magnesium an Ks alloys Zine ‘Aamir andi alloys satu fai canton et Ho alay sees (Gray sat ct ct ios Nickel cst ions Type 0 seats soe (atve) ‘Type and 316 likes tess (ave Lens Tin Mincz mot manganese owe naval ass Yell an ed Bees, laminom an sbicon {Copper ana eopersekel ley Nickel (pissive! Inconel 0 passive) Monel 0 Tana ‘Type Wt ad 36 sites tees (pnsve) Sirs god, latina ‘Must noble; mont cathodic; least susceptible to mined by examining and soperimponing polar tion curves of candidate metals and by estimating the mixed potential values (Ref 18) Tn conelision, the selection of dissimilar met als that ste far apart on any galvane series should be avoided unless provisions are made for sper Fela corrosion of one for another sin cathode protection. Otherwise, dissimilar metal app tions in corrosive environments should De 9 proached with extreme caution and should Be thoroughly investigated betore making the fra selections, The section “Galvanic Corrosion” of the aticle “General Corrosicn’ "in this Volunie ‘omnis more information om galvanic attack Intergranular corrosion is a selective form ‘of corrosion that proceeds slong iii rain boundaries, with the majority ofthe grain being tumlflected. Intergranular edrrosion can sec! fain alloys that are highly resistant co genera and Icalized attack: noteworthy are several of the 300- and 40Xi-series stainless sets and austenitic bighernicke alloys. These alloys ure mae si ‘cepitte to lnterpranular corrosion by sensitize: Hon—tha is, the precipitation of chromium & bides anor nitrides at grain boundaries during ‘expasre to temperatures from 450°C (840"F) 10 290°C [1600F), withthe maximum elect occur Fing neur 675 °C (1250 °F), Exposure 10 sich temperatures can occur ducing processing st the mill, welling and other fabrication operations. by plant service conditions, The resulting deple tom in chromium adjacent the ehromiarich ‘carbdesinitides provides & selective path for Intergranular corrosion by specific media, suchas hot oxidiing (nit. chromic) and hot organic (acetic. formic acids Suseepribie stainless stets are those that have normal carbon contents (generally 20.04%) and ‘d9:not contain carbide stabilizing elements (ie rium and niobium). Exumples are AISI types 302, 304, 309, 310, 315, 317, 430, and 46, Sus ‘cepible highee-nickel alloys include Inconel a Toys 60) (UNS NOGEiN0) and GOL (UNS Noes, Incoloy alloy 800 (UNS. NOSS0O) despite the presence of titanium, Ineoloy 00H. (UNS NOwB{0), Nickel 200 (UNS 02240). and Haste! Iny alloys B (UNS N10) and C (UNS 10002. Intergranular corrosion in these alloys is avoided by one or # combination of The following 1 Keep the alloy inthe solton Resttrested ‘© Limit interstitial slements, primarily carbon tnd nitrogen. to the lowest practical levels {© Ada carbide stabilizing elements, such a i ium, niobium. and antalum, slong with & Stabilizing heat wealment whore necessary 1m general, these alloys are purchased from the the’ solution hest-treated condition, {quirement of most specifications. With regard tn the austenitic stunless steels, solution heat teat- ing consists oF heating tos minimus temperate ‘of 1030 °C (1905 “F) to dissolve all the eaenes, Followed by rapid cooling im water or a to prevent sensitization roserving the olution-irested condition iv dif feult, except for certain applications in which rehesiing is nol a requirement of fabrication. One ‘example is 2 pump shaft auchined from forged or rolled and solution heat-treated har sock. HOS. ever. most applications for these alloys, such as Piping compements and pressure vessels, require hot rolling (for examples of pte) oF hot hensing Aor example, af pipe! and welding: these practi5, a5 discussed earlier, can cause sensitization. Soiution heat teating after fabrication is general Iylimpractical, because ofthe possibilty of rrep- arable damage due to distortion or excessive Scaling or because of the inability to cool rapidly Enough through the eritical sensitization temper ture ming, ‘Therefore, inmost applications involving ex- posure to environments that cise intergranular Eorrosion, the low caybon/nitiogen or stabilized alloy grades are specified. The new ferric stain- Tess steel UNS S4s800 with 0.0297 C maximum) Ds nitrogen is replacing the higher-curhon 446 [rode in applications in Which rosistance to Intergranalar corrosion ix 4 requirement. Tynes SOIL, 316L, and SI7L, with carbon and nitrogen ‘canfents ied fe 0.08% (maxima) aD 10" maximum), respectively, are used instead of theirhigher-carhom eounterpurts, The newer nick- fkchromium alloy OIL {UNS NOSvG%), with 9.42% maximum carbon. and. the high-nickel Hastelloy alloys C-22 (UNS. NOgI22) and B2 TUNS N10665). which have maximum carbon ‘contents of 0.018% and 0.01%, respectively. are now being used almost exclusively in the se (welded condition without intergranular corrosion problems. These low carbon levels are realy and eco nomieally achieved with the advent of the argon ‘oxygen decarburzation (AOD) refining process used by most alloy producers, By limiting the interstitial element content, sensitization is imi fed or avoided entirely during subsequent welding tnd other reheating operations. However. de= Sipners should be aware of the fact that lowering the carbomnintrogen cantent also lowers the mine mum allowaile design stresses, a8 noted in ap propriate sections of applicable fabrication codes, uch as ASME Section &, Division 1 for untired Dressire vessels and ANS R313 for process Piping ‘Commercially pure Nickel 200 is special case, Wih a maximum carbon content of 0.13%, Nickel 200 will precipitate elemental carbon of fraphite in the grain boundaries when leated ia the range of 315 to 76 °C (000 10 1400 "F). This results im embrittlement and susceptibiliv 10 interuranular corresion in certain environments, Such as high-temperature caustic. Where em Uement and intergranular corrosion must be avoided, Nickel 201 (UNS NOZ2O1) with a axe ‘mum carbon content of €.02% is specified “Titsaioa as a cacbide-stabilizing lene used in several Fertic and austeniic slunkess Steels including types 409, 439, 3167), and 321, fs well us the higher-nickel Incoloy illoy $25 TUNS NOHe25), at a minimums concentration of boat ive times the carbon plas nitrogen content Inthe same way, niobium, generally with tanta lum, is used in types 30OCh, 310Cb, and 347 Austonitie stainless stoos ta minimum combined Soncentration of about ten times the carbon com- tent ‘The higher-nickel alloys 20Cb-3, Inconel 625, and Hastelloy G contain even higher concent tions of niobium—up to @ maximum of about 4% inthe cave of alloy 625. In general, when stabi- lized alloys are heated in the sensitizing temper ature range, ehromtiam depletion at the grain boundaries does not occur, because the stabilz: ing elements have a greater ainity for carbon than does chron, ‘Under certain conditions, however, stailized siloys will sensitize especially during multipass ‘Welding or ross welding. They ate also suscep. tible 10 2 highly localized form of intergranular corrosion keown as knifed attack. which oc {Sars in se metal st the weld Faso ine. Tn some tases, these alloys are given stabilizing heat {reotments after solution heat treatment for mas {num resisanee to infergranular corrosion i the faswelded condition. Por extmpe, type 321 Tess steel i stabilize annealed at 990 °C (1650°F) for 2 hand alloys 828 and 20Ch:3 at 940°C (1725 "F) for Ih, before fabriation to avoid sensitize tion sind Knifeline attach, So treated, type 121 ‘may stil be suscoptible because titanium has & {ondeney to form an oxide during welings the fore, if role as a carbide stabilizer ‘may be Aiminished. For this reason, type 321 is aheuys ‘welded with a niobium stabilized weld fer met- al, such as type 347 stainless. ‘Some specialty alloys have low interstitial ee. iment content plus the addition of stabilizing ele ‘mats for resistance to intergranular corrosion. ‘These alloys include the higher nickel Hatelloy alloy G:3 (UNS N06985), which contains U.01872 CGraximum) and miobium plus tintin ap 19 (0.35, and the newer feritic stainless stots (Ref 19) ited below (© UNS 844607: 267 Cr, Ne Mo, 0.01% C (man), ISS N (man), 0.29 Nb Can) (© UNS S14635: 25% Cr, 9% Ni Mo, 0.02576 Ctra), 6.0355 N (na), 0.80% Ti+ Nb (max) (© UNS Se6oo: 26% Cr. 256 Ni, Mo. 0.0876 C (ra), 0.08% N fm), 05 Tit Nb (ma) © UNS S4a735: 29% Cr, D.55% Ni, 4% Mo, 0.0566 Ca, 0.0485 N (oa), L068 Ti+ Nb qa) ‘The new ferttic stainless steels were developed primarily for heat-exchanger tubing applications foruse in place of the higher-carbon unstablized type ip stainless steel. These ferrite stainless steels have many useful properties, ‘As eiscussed previosy, specific corrosion en vironments cause intergranular cortesion in spe cific metal and alloy systems. A wealth of infor ‘ation, both published (Ref 20) and unpublished, fhas been developed on corrodents that cise Intergranular cortosion in sensitized austenitic Sainless Steels; partial listing appears in Table 2. The low-eatboniniwogen or stabilized grades le specified for upplications. in ‘which the austeniics have satisfactory general and local led corvosion resistance in these environments i in which sensitization by such operations 23 ‘Welding and hot forming will undoubtedly occur. “Evaluation tests for intergranular cosrosion are eondacted to determine if purchased materials have the corzect chemical composition and ace in the properly. heatrested condition to resist intergranular corrosion ia service (Ref 21), Eval lustion testing i amperative for a umber of 1 The stainless steels and nickel-base alloys 10 which these tests ate applied are relatively expensive ‘© These materials are trequently specified for critical uppications inthe petrochemicl, pr ess, and power industries ‘6 The principal cost associated with a corrosion fale seer ht of production oss. not replacement ‘# For maximum cost effectiveness, these mate rials should be used) in their best possible rietallargical and corrosion-resstant™ condi fone Most of the evaluation tests are described in etal in ASTM standards. Appropriate evalua Materials Selection | 325 Table 2 Partial listing of environments known to cause intergranular corrosion in sensitized austenitic stainless steals Nie wi 1 fev ed Bowing {WI c9 bosing 5 Room tobosne SR Room ta hone Lactic ai, sess Rowtog Salaried "0 Roo Forms ck > Bowne Chromic ac be) eting Geshe cid opis Fe) Bese Phosppone seid oss,’ Botae ydrftore ach 2 play FO") 77130) Fes conde < Roling miscre Unkaown —ropt40 212-210) Mile amiyarse |! Unknown 140) Comsiech Slory eH 1.5... Unknown 49120) seawate Room Sonar hon athe abyaide ene Unknow 28250 tion tests and acceptance criteria for wrought alloys are listed in Table | in the article “Ex ion of Intergranular Corrosion” inthis Volume. Intergranular corrosion is rare in ronsensiized ferrite and austenitic stainless stels aun nickel base alloys, but one environment knovin 10 be an exception i boiling HINO, containug an oxidize ing ion such as dichromate (Ref 22). vanadate anior cupric. Intergranular corrosion hus also becurred in low-carbon, stabilized andlor pewper= ly solution heat reated alloys cast in resin sand molds (Ref 23). Carbon pickup on the surface of the castings trom metal-resin eactions has result ed in severe inleranular cormosion in certain environments. Suscepubility goes undetected in the evaluation tests mentioned above because test samples obiained Irom castings generally have the carbon-rich layers removed. This prob lem is avowed by casting these alloys in ceramic oncartonaceous molds Other metals. such as magnesium, aluminum, lead, zine, copper, and certain alloys. are suscep ible to intergranular corrosion under ver¥ spe cific conditions. Very few ease histories ure fe ported in the literature. An unusual form of ftlergranular corrosion. known as_exfoiation, ‘which occurs in aluminum copper alloys, i dis. cussed in the section "Other Types of Corto sion” in this article. Intergranular SCC. is di ussed i the following section. More information bn intergranular corrosion is available in the nice" Metallargically Influenced Corrosion” in this Volante ‘Strase-corrosion cracking is a type of eavi ronmental eracking caused By the simultaneous ction of corrodent and sustained tensile stress. ‘The following diseussion deals primarily with anodic SCC. Anodic SCC is believed 10 be 3 ‘elayed eracking phenomenon tht occurs in nor326 | Designing to Mi mally ductile materials under the stress resulting from wecelerated electrochemical corrosion it snodie sites of the material ns well sat the crack tip iter types af enviconmental eracking, such Sf hydrogen stress cracking and. iguid metal femavitlement, ate discussed later in this article (see also the article “Eavironmentally Induced Cracking” in this Volume) The National Association of Corrosion Engi neers the Materials Technology Instat of the Caemicsl Process Industries, and others have published tables of eorrodenis known to cause SCC of various metal alloy systems (Ref 22-25). Table 3 lists these data in condensed form aad covers the SCC environments of major impor- tance 10 the materials engineer, This table. as Sell us those published inthe literature, should De used only 3s a guide for sereening candidate materials for further indepth investigation, tes- ing, and evasion. Siress-corrosion cracking is not a certainty in thelisted environments under all conditions. Met alan alloys thal are indicated us being suscer Tike can give good service under specific condi- lions. For example. refering t0 Table 3 1 Anhydrous arimonia will cause SCC in carbon steels. but rarely at temperatures below 0 °C G2°F} and only when such impurities as air oF ‘oxygen are present: addition of @ minimum of 0.2% H.0 will inhibit SCC ‘# Aqucous Mhorides and hytrofluori acid (HF) Primarily affect Mone! alloy 400 (UNS ND#00) In the aickel alloys system others are re- Steant is known to cause SCC only in alumi ‘num bronzes and silicon bronzes inthe copper alloys system ‘© Polythionic acid only cracks sensitized austenitic stainless steels and nickel alloys SCC is avoided by. solution annealing, heat lucatments oF selection of stabilized oF low carbon alloys Table 3 Some environment-alloy combi ize Corrosion Stress.corrosion cracking is often sudden and tinpredictabie, occurring afters litle as Few outs exposure or after months or even years of satisfactory service. Cracking aoeursIrequently In the absence of other forms of corrosion, such a6 general aflack or crevice allack. Virwilly all alloy systems sre susceptible 0 SCC by a specific orrodent under a specific set of coneitions, that 's, concentration, temperature, stress level, and 0.0m, Only the ferrite stsinless steels sv cls fre fesistant to many of the environments that ause SCC in other alloy systems, bul they are Stsceplible to other forms af corrosion by some of these environments, The combination of aqueous chlorides snd austenitic sainles steels 1s probably the most Important from the standroints of occurrence, economics. and investigation, Although the ‘mechanism and boundary conditions for chloride SCC ate sill not fully defined. i is reasonably Safe 10 slate that ebloride SCC of austenitic Stainless steels f Seldom occurs at metal temperatures below 60 °C (140 “Fan above 200 °C 390 °F) © Requires an aqueous environment containing dissolved air or oxygen of other oxidizing agent 1 Occurs at very low tensile stress levels such that stessreieving heat treatmentsare seldom elective as a preventive measure © Afcts al the austenite Siinless steels wbout equally with regard To susceptibility, time to Tila, and so-o Is characterized by transgranular Dranchlike cracking as seen under # metalursical micto= scope ‘So many materials and environments are sour: 5 of chlorides that they are hurd to avon (Ret 120). Significant costs for repairs and replace iments, as well as lest ullity, have occurred through the vears in the petrochemical industry asa result of chloride SCC: tions known to result in SCC In water-cooled heat exchangers from chlo des in the cooling water ‘© Under thermal insulation allowed 10 deterio. rile and hecome soaked with water that leached chlorides from the insulation ‘© Under chlorde-bearing plstics, elastomers, and adhesives on tapes In the case of shell and tbe heat exchangers, ia which ehloride-bearing waters are used for coe)- lng, 8 number of preventive measures ae avai thle. In vertical urs with water om the shel side, tracking occurs most often a the external surtae: 26 of the tubes under the top tubesheet (Ref 28). This is a deat space (air pocket) at which chlo- rides are allowed to concentrate by’ alleraate wetting and drying of tubing surfaces. Adding vents to the top tubesheet sometimes alleviates this problem by eliminating the deud space und allowing complete water flooding of all tubing Surfaces (Ref 29) However. in many cases, this approach resus, inonly a nominal increase in time to failure 7 0 benelt whatsoever. because of other inhere deficiencies, such ts low water flows or throting ‘water flow toconuol process temperatures. Thus 4 material more resistant (0 chloride SCC. is fequited, such a8 the austenitic highernickel Tacoloy loys 80 (UNS NO8800) und 825 (UNS. NOS825): Inconel G00 [UNS NO66O0}: fevitic Stainfess steels such us 1ype 430 (UNS $43008), 2Cr-IMe {UNS S44627), and SC-1 (UNS ‘SA4660); duplex stainless stews sucin ay Fer tallum 255. (UNS.$32550) and “AISI type 329 (UNS $2500); o titanium. In this case, selection ‘depends primarily on econemics, that i. the least expensive material that will revit processside ‘corrosion as well as water side SCC. ‘Alloys are said be either resistant or immune to chloride SCC, depending oa hew they perform jn accelerated. laboratory tests. In geneva, an alloy is imane if it passes the boiling, 12% ‘magnesium chloride test conducted according to Snes, aque ‘Stn snp meni saucous ‘Bromine Cartman: ous ‘Girton monoid, carbon dnd Clones aes ° CGhones canentaed, hong hones dey bo (Carina solvents (Gand, aquenan sce Histroenione cud Hyreorc ac Uplrondes concent Ba Methanol pio aes. Nivates, aqueous. Nirgen tetroxide Patio acs Suis pi hiss eau ifr a1. Water hpi. fot . ° : . ° :ASTM G 36, Examples are Incore! alley 60 26Cr-IMo, and grade 3 commercially pe titan tum (UNS'RSVS50), Industry hus recognized the severity of this test and has devised other acce! trated Inboratory tests, such av hug 25% so ‘lium chloride and the Wick Test (ASTM C 692). that are more representative of clus condifions ‘nthe ld (Ref 30). Thus, alloys tht fal the G 36 test bot pass the C 692 test, such us Incoloy 8 slioy”2205 (UNS 31803), and. 20-Mos (UNS 'Nos026), typically provide many years of service as tubes in water-cooled heat exchangers. (The Sustenitic 4O(-reries stainless steel, v1 lass {ail ofthe secelerated laboratory chloride SCC texts mentioned above.) Unfortunately all of the immune and resistant alloys are more expensive than most of the Austenitic stainless steels, A more cost-effective nplicalion of some of these alloys involves a procedure known as safe ending, in Which short Tengths, (for example, 0.349 0.m, 0" 120 248) are Ut, welded to the austenitic stainless steel lubes. The SCC-resistant ends are positioned in the exchanger atthe pont of peatest exposure 10 'SCC conditions, that's, under the up tuhesheet. Salecended tubes have extended the life of austenitic stainless ste! wing several-fold, with ‘oly nominal increase in east. OF course. the Uissimir metals mast he weld compa: this ‘eliminates the use of Uranium for safe ending ‘Anuther coseffective answer to chloride SCC In heat exchangers is bimetallic tubing. in which the austenitic stainless steel required for process side corrosion resistance is clad witha waterside SCC und corrosion-resistant material such as Cu: 10Ni (UNS CT0600) (Ref 31). Sill snother answer is cathodic protection with a sacrificial ‘etal coating such a8 lead containing 2% Sn and 2 Sb applied by hot dipping or fame spraying ‘ket 3 Chloride SCC under insulation can be prevent ed by Keeping it dry, but this fs easier sid than Alone in many cases. Its particularly dificult in hum, high annual rainfall elimates, such as the Gulf Coast area of the United States, and were inaulated equipment must be washed down per odically or is exposed to fire control deluge ‘Systems that ane periodically activated (Ref 33) Under these conditions, three preventive mea sures are applied, 3s follows ‘The fist preventive measure is the ation of sodium metisilieate as an SCC inhibitor te the Insulation at’ a-minimutt conceatration ot ten times the chloride content. The inhibitor i acti vated when the insulation becomes wet and is fective only when it wets the stunless steel Surface. For maximum protection, metasilicate is painted on the vessel oF piping before the instal Iation of inhibited insulation. However, SCC has boeeurredafier many yeursof service under iahib- ited insulation that was allowed fo become so wet thatthe water-soluble inhibitor was leached ox te a point below the minimum concentration required for prevention of SCC Second is protective coating of the vessel or piping before insulation. Catalyzed high build epoxy pants are effective co abst 100 °C O12 °F), catalyzed coal tarepoxy enamels to about 150 °C 300 °F), and silconestase coatings 10 out 200 °C (390 "F). These coatings are even toro effective ifthe stainless steel surfaces are heavily sandblasted before coating, Sandblasting eens the surface wa depth of 0.0110 0.1 mm 4 fo 4 mils), and this results in a layer under compressive stesses that courteraet the tensile siresies requied for SCC (peening will be dis {ussed later inthis article). "The third preventive measure is cathodic pro tection of the vessel or piping with aluminurn foi tunder insulation (Ref 84, This method is claimed to provide both a physical barrier to chloride ‘migration to stainless steel surfaces as well a5 {atk protection shen the insulation becomes Wet, and it is effective at vessel temperatures Between 60 and S00°C (140 to 980 “F). However. the foil is attacked by the alkaline (generally) leachates from the insultion snd must he re- newed periodically, ‘Other important environments that cause SCC of stainless steels are hydroxide (caustic) sob tions, sulfurous acid polythionie acids. Caus- tie SCU of austenite stalmlessstees can be Both ‘ransgranular and intergranular and isa function ‘of solution concentration and temperature. Tt Seldom gecurs at temperatures below 120°C 250 SE), At higher temperatures, the newer ferric stainless stee's, nickel, and_high-nickel alloys prove outstanding service: 26¢'-IMo stainless Sieel has four widespread application in he ‘exchanger tuby bundles secving caustic evapor Tors ut 170 to 200 °C (340 to 390P), Nickel 200 and 201 as weil as Inconel alloy 600 are resistant to 300°C (570 "F) in caustic concentrations to 70%, olytbionie acid and sulfurous acid will cause SCC in sensitized nonstabilized austenitic Stit= less steels and nickel-base alloys. Cracking Is always intergranular and requires relatively low Temile stresses for initiation and. propagation. Aswelded, normal eatbon grades, such a8 types Sv and 316 and Incoloy ally 800, are particular iy susceptible to SCC in weld HAZs, Low-carbon (0.038 C) and stabilized grades, such as types 301 and 347, are resistant, especially after receiv ing stabilizing heat treatment. The normal car thon grades in the solution heat treated condition are also resistant. Susceptibility 0 polythionic Acid SCC can be determined by laboratory cor ‘osion texting acconding to ASTM G 35. Polvthionie acid and sulfirous acid SCC are major considerations. in the. petroleum reiaing industry, especially in desulfurizer, hydrocrack- fer, and relarmer processes (Ref 35, 36). These fcids form in process units during shutdowas ‘when equipment and piping containing sulfide posits and scales are Opened and expaved to air land moisture, Preventive measures inelude sh- ing wth alkane solutions to neutralize sulhdes before shutdown and purging with dry aitzogen luring shutdown according (0. recommended practices established by NACE (Ret 37) Cast austenitic stainless steels such as Alloy Casting Institute (ACH) types CF 8 (UNS 392600) ‘and CF-8M (UNS 192900) are inherently more Fesistant (But not immune) to ehloride SCC than their wrought counterparts (Iypes Mb6 and 316, respectively) for severat reasons. Castings gener ally have lower resilul stresses than Wrought Alloys affer soluton-annealing heat treatments, nll serviceapplied stresses are often lower be ‘use of heavy section thicknesses. However the principal reason for improved SCC resistance isthe presence of varying amounts of free fernite singin duplex austenitic teritie microstruc. me. Bree ferite te primarily atributet (ost tions of 110.2% Sita improve Mudity during pouring and to resist hor cracking during cooling OF the casting, During work conducted some years ago on the evelopinent oF the duplex cast ACT alloy CD- Materials Selection / 327 4MCu (UNS 393370), researchers noted improved resitance 10 chloride SCC in cst alloys contain ing high ferrite; (his confirmed observations the fleld by materials engineers (Ref 38). A sie nificant improvement in SCC resistance occurred Wah ferite contents in the range 13 to 20 vol% find greater. This led tothe development of alloys ‘with contelledfenite content by balancing cher teal composition. Fernie formation is promoted by chromium and by elements that 3c like che rium, such as silicon. nishium, and molybde tum, Nickel and elements that act Hike nickel (carbon, manganese. rion) retard ferite for mation. When specified. fersite is typically cor trolled at the foundry by susting chromium toward the upper end of the specifeation range find nickel toward the fower end, along Wit the SMlicoa addition, Resistance to SCC in these alloys is believed to bbe a result of che Keying action of ferrite particles (Ref 39), This uct blocks direct propagation of SCC throug the austenitic matrix. Along wiih this benefit, however, are improvements in Strength, weldabiliy, and resistance to general corrosion, particularly in bx concentrated nite, acetic, phosphosic. and sulfuric acids and mixed hivich¥drofuoric acid (Ref 40). The American Society for Testing and Materials has recognized alloys produced with contrlled ferrite content in specification A 351, However, users are cus tioned to limit upplications to 2 maximum tem perature of 425°C (00°F) because of the thermal Instability ofthese grades. “A nuniber of measures for preventing SCC of suistenfe stainless steels have already been dis cussed, Two additonal meusures warty of con Sietation are stres-relieving heat eatments and shot peening. The typed! sires-relieving tipper ature for plain carbon steels—995 °C (1100 is only slightly effective for the sustenities, which require slow cooling from about 900 °C (1680 °F) for effective relic of residual stresses from such ‘operations as welding. However, such treatments not prevent, bat only prolong. the time to fe: chloride SCC of austenitic stainless seals can ooeur at vory Tow stress levels Also, these Slevated temperatures may cause unwanted dis tion of complex andior highly stressed strc tures and will sensitize suscoptibe alloys. This ‘sensitization will esul im intergranular corrosion or intergranular SCC ‘Shet peening is the controlled bombardment of 4 metal Surface with round. nar ste! shot forthe purpose of infroducing compressive Sresses in Surtace ayers. These compressive stresses cus {eract the tensile stesses required for SCC. The {depth ofthe resultant coldworked fayers erally in the range 0.1 10.0.5 im (410 20 TWA? coverage is required. In laDoratory tests in boiling 42° magnesium chloride, shot-peened type 4 stainless steel U-bend stipes showed no SCC ailer more th 1000 fof exposure, but nonpeened control samples all cracked in appx imately 1h (Ret 41), Successful applications in the chemicarpracessing industries clade a 19D 16 stainless Meel ceotriuge exposed t9 an OF tanic chloride process stream (Re? 42) and merous storage tanks exposed 10 a variety of SCC conditions (Ref 43), “The exposure of shot peened surfaces 10 ex cessive temperatures of 10 environments that fase excessive general oF pitting. corrosion should be avoided. Temperatures above 565.°C {1030 °F) wil relieve the beneficial compressive Stresses and reduce the overall heneis Of shot