anodicreactiontoproducethecorrosionteaction product, This product may bea film ora deal loyed layer but the at of formation and there- fore the brite crack growth ate are dependent ontheeracktipeurent density. Material Chemistry and Microstructure “The relationship between material chemistry and microstructure and SCC is qualy as complex ‘5 the relationship between the envifonment and ‘SCC. Bulk alloy composition can affect passive ‘ilo staat and phase dstabaton (or example, chromium in stainless steel), minor alloying ele ‘ments can cause local changes in passive film form- Ingelements (or example. carbon in stainless tec! ‘using senization), impuriy elements can sep- ‘gate o grain boundries and cause local erack ip hhmtry charges asthe crack mtecets them (ot example, manganese slide in sel) Als, alloys ‘an undergo dealloying, whi i thought vo be a Primary method by which brite SOC ints. The following summary willbe divided nt srg Jar and tansgranulreffecs because some ofthe primary factors can be best deseribed in his way: Feever, tis mporant to recognize tht many of the material chemistry factors ean affect both in- ‘ergranular and tansgranular racking. Intergranular Stress-Corrosion Cracking. ‘Material chemistry and microstructure effects on ltergranar SCC can generally be divided io the following two eategories: grain-boundary precipitation and grain-boundary segregation Grain-boundary precipitation effects include ‘carbide precipitation in austenitic stainles tals ‘and nicke-base alloys, which causes a depletion ‘of chromium adjacent to the gain boundary and imermetallic precipitation in aluminum alloys, Which are-anodicaly active. Grain-boundary ‘segregation of impanties such as phosphors, sulfur, carbon, and silicon can produce 8 grain ‘boundary thats up 30% impurity within a I-10 nm thick region. These impure can ae he ‘orosion and mechanical properties of the grain ‘boundary and can therefore cause cracking by a- ‘ic dissolution and preps mechanical rate ‘Grain-Boundary Precipitation in Stantess Steels: Chromium carbide precipitation in stin- lese steels occurs in the temperate range from ‘500 to 850 °C (930 to 1560 “F, with the rate of precipitation contolled by chromium diffusion For intermediate times, such as occurs with heat tweating and welding. chromium depletion occurs adjacent tothe gran boundary during chromium ‘arbi growth. This depletion can be described by the minimum chromium concenttation adja- ‘cent othe carbide andthe width ofthe depleted ‘o0e. Minimum chromium concentrations oF 810 10a. 5 have been measuted by analytical elec. ‘eon microscopy, while the width of he depleted zone has been measured to range From 10 hm 19 hhandreds of nanometers After times longenough for atbie growth wo reach completion, the chro- ‘miu profile i eliminated, and the chromium Concentration retusa the blk vale, ‘The intergranular SCC of austenitic stainless steel is primarily dependent on the nature of the chromium-depleted zone, which s generally ex- plained bythe depletion ofa passive film form- Ing clement along a continuous path through the . Sean ‘material The stress-corosion susceptibility and rack growth rate of austenitic stainless steel can bbe described by the degree of sensitization (DOS) as measuredby cortosion ests suchas the ‘Straus or electrochemical potcatokineticreac- tivation (EPR) tests. Quantcatve comparisons ‘berween suseepbiliy as measured by the pres- tence or absence of infergranular SCC in an’ SCC testorthe rack growth ate and the DOS o chro ‘ium depletion parameters have been successful ‘mcases in which sufficient data have ben avail able but these cortelatons ae limited to specific alloy, environments, and stess conditions. Seamiguantiative in which inter {granular SCC is predicted for DOS values greater ‘than some critical valve ae less costly 10 obtain land have been used more extensive: ‘An example of the time/temperature/DOS ‘curves at several carbon concentrations i show fn Fig. 77. The curves represent the conditions necessary forthe development of a constant de gree of sensitization, withthe strong effect of balk carhon concentration onthe Gime needed © evelop a sensitized microstuctre. Therefore, ‘he most common method for reducing the possi bility of developing asensitized microsuctoreis to redace the ca-bon concentration orto control the thermal history of the materiel Given that the ‘materials sensitized, contol ofthe environment find atess conditions ean be use to reduce the ‘crac propagation rate Clearly, chromium and carbon arethetwomos important elements involved in he development of sensitization: however, other elements can play a role. Molybdenum hasan effect similar t that of ‘reasesin nickel concentration can enhance ses ration for a given carbon concentration and thermal history: Manganese silicon, and itn hhave also been shown o affect sensitization. bat the dats thai available on these elements om om mo ww ope cones 5 SL | pee ; . i |_| a } ra i wel bi 3 T [ | | ed a a ; oe ae gen seem Toneeoen {tenn gcc peg iid 3 a en ar 28°65") Fig, 76 fm ee oe Senna eae a ee Soanernt sos Fig. 7548 / Corrosion in the Petrochemical Industry ‘. ——alee * x i b] oe Kewse | y Soe ee Fig-77 inca tacivcnype 30 sats sla SEs paratively sparse. Silicon hasbeen shown Se Frese fo gram Doundarcs when present in l= ent quantities or by the nonequilibrium pocesses ha cur when the mater sia ‘ted wih neurons. The presence of silicon inthe ‘rain boundaries hasbeen found to be delete ‘usin oxidizing environmen. ‘Grain-Boundary Precipitation in Nickel AL {oy The ease of intergranular SCC in nickel tase alloy s more complex than in austenitic stunless see. Chromium carbide preciptation alloys, sucha alloy 60, as they do in austen tic stainless sees, but a clear connection De- ttecem the presen ‘microstracture and intergranular SCC has not been made. Carbon folobility is considerably Tomer and chromium ‘iffusion i faster in nickel-Dase alloys tha in fustenitic stainless sels: therefor, the nose it the earbide precipitation or sensitization curves shown in Fig 77s shifted to shore times and ‘500 have been observed fora piven heat reat ‘ment. This variation faribued to the seasiiv- ity of alloy 600 to carbon concentration and 10 the variability in mil-anneal heat treatment ‘conditions. Chromium depletion is thought to accelerate cracking in oxygenated water but tas nt been identified as acontrolling factor deaerated water or caustic environmen at 300 *C(510"F). The rapid carbide precipitation ki- netics in nckel-base alloys allows the develop- iment of a heated microstructure in which carbide growth is complete and the chromium profile i eliminated with relatively short heat ‘Some significant differences between tein Aergranlar SCC of nicke-base alloys and that of tustentic sailes stecls elude the postive ef- {eet ofa semicontinuous dsinbution of carbides atthe grain boundary in single-phase mera] sult from a galvanic couple that polaris the" phase anodicall elaive tothe phase. Grain Boundary Precipitation ia Aluminum Alloys Amin alloys ae also noted forthe ‘currence of intergralar SCC in agueous en ronments including sodium chloride (NaCI so- lations. The details of th itergranalar SCC process in aluminum alloys ae very complex and ‘ary with alloy compesitio, but some features an be summarized. Grain boundary precipita fn hs een Menta aconebatng factor the imterpranalar SCC in aluminum alloys: gal- ‘ani elects between the precipitates and mais ‘re considered tobe imporant In sme cases he precipitates are anodic, and in others, they ate fathoic the mari, Peac-agedaerals tha give ‘atin Rirdnesce and microtractorsich flip bands re prced pon training se consi ‘redo be vlcrable to SCC. Overaged stctes ‘re considered o he les sascepubie The mech rismofcrack growths thought bea combination ‘foal ani dation tt hyogen cite tment Whebercackertenson by ae da "in ory hydogenemsitement emus an ope "uss! however mavens ons, ena Source of hydrogen sancti discon, ‘Graia-Boundary Segregation in Aluminum Alloy: Gran- boundary enrichment of magne- ‘ium without precipitation of a magnesium Fich phase has recently been identified asa w factor in he intergranular SCC of sumioum a toys(Ref 140,141) Thsenrichmestisassociated with increased corosion activity at the graia boundary and he possible formation of magne slumbydide MgH)orenhancedhydrogenentry long the grain boundaries. Crack advance thoaght o car by dscontinuoes crack jumps {posibly nucleated by hydrides) anderackarest afersbout8010380amofadvancefellowedby Fepetiionotehixprocess Gran: Boundary Segregation in Ferrous and Wicket Alloy Grin toundary enechment off ports ean contut othe imergranolarSCC of fron-base alloys, austenitic stanes steel, and ickel-base alloys. The extent of their effect de pets on he elecrochemical pote the pres ‘ce of other sres-coronon proveses suchas thromium depletion. and thet concentration in the gin boundary. The enrichment of impurities to grain Boundaries by equilibrium segregation an be described by the enrichment ratio a8 shown in Fig 78 for a variety of impurty-alloy combinations (Ref 142). The enrichment rato de Fines the upper bound othe grain-boundary con- ‘enirton that willbe achieved under equim anditins, which an be very Tog times at ow temperature Itcan be sen fog ig 78 that richment ratios a high as 10° are posible for ‘ome soe wedi, Fig. 78 Comat nen meson pinta richness, The Syl Xan represent tcl concer aon tbe specs bande neesere impuries nd tat rain greater than 10? trevotunconmon Forde ul mpuryconcen- toms preset mostenginecring aloe wound iu consenaon 03035 fe ponble Therefore an nergranular ses onosion cack can propagate slong gain ‘oundary tah cmmponton vet iret frm bof bu oy, emi tech exhib interpanar SCC in toc nate, casi carbone tnd avy of ‘ther crvionnets: The presence of ier IaeSCC sopndet on he ccewochom po ua ee inerpamale SCC redomian st pte inthe ace pave ration ary ses of hi tect semis ‘carbon segregation as the primary element of oncrn wir theca ns were said po. Side sual perfection ste for drm of ‘tue ian sooo indaced cack roeth mechani (Re a9), Moe rece, phospho. fs segregation hs bon altel wh te ‘Saran SCC of ton alts i hire and ‘tc solions (Ref 1,143) gr body cacenratom as low a 2103 at have bec ‘stent esr te psy of ro a ht trae sluons. A complesty of SCC in eric ‘esis the ncepebiny of och set winter Forms of Corrosion in the Petrochemical Industry / 49. _ranalar SCC and to hydrogen-inducedsubcriti- al erack growth. The temperatires and electro. ‘chemical potential at whieh intergranular SCC and cathodic induced sberiical rack ‘growth occur are generally not the same Stress ‘orrosion tends to dominate at temperatures ‘Sbove about 50°C (120 °F) and a potentials in the stive-passve transition: hydrogen effects are predominant attemperaures Below #0°C (120 *F), a more cate potentials, and at lower pH ‘ales. Examples ofthe effect of sulfr and phos- pret ee tdacy rman rise Bc {ree gen nig. 79nd, from whichitcan be ‘ents lf morefeciv thin phosphors ergranlar fracture of iron at cathodic potentials (Ref 14,147). Frthe conons of this {es.asulfurconcesratonofabout 3a. wassut tic stainless stools (Ref 148): however, no diect effect on imergranular SCC has been iden fn high-temperature water, Phosphorus sepre tontas Been shown tocause intergranola corr son in highly oxidizing solutions, and impurity ‘iain noundary compotion menelnars eres Ys Peco Fig, 79 Sion 1 cn fae. ae ain ulead. ton phoschonsae in «pho ical wvanan cade pera segregation of phosphorus and perhaps silicon hasbeen sugested as a primary factor in iradia- ‘on-asisted SCC, which occurs inthe oxidizing {in core envionment of light water reactors Ref 149), Phosphorus segregation can apparently ‘contribute othe intergranular SCC of aus ‘Saintes sels i hightemperature water the Carbon concentration ofthe alloy is lower than 0.0024. Atthis ow concemwation, there is viru ally no sensitization therefor, the phosphors Segregationeffectis observed. Phosphorus i also he primary grain-bound- ary segregant in alloy 600 and has been shown 10 Sepregate by an equilibrium process (Ref 150). ‘The grain-boundary composition versus tem- erate curves for alloy 600 and type 304 stain- fess steel are shown in Fig. 81, along with 9 ‘alulated curve for equilibrium segregation in nickel (Ref 151) Iteanbe sen that grain-bound- fry phosphorus concentrations {0.15 at are possible. Grain- boundary segregation of sulfur, boron, nitrogen, and titanium has also been ob- served in alloy 600; however, x clear connection between the impurity segregation and intr- sramular SCC in icke-bate alloys has not been ‘bserved to date, In contrast 10 the hightemperature water sults for alloy 600 a clear effect of phosphorus sceepaion on th inerranlr SCC of ick lions ac 23°C (77°F) (Ret 131), as shown in Fig #2 Intergranular SCC was observed ata ‘dic potentials ranging from the active-passive transition to tanspassive potentials i nickel ‘th phosphorus-enriched grain oundaries but ‘ot slfarenriched grain boundaries. The role of ‘phosphorus was idenied with degradation of the passive film formed on nickel in acidic s0- lutions. This example isa clear ease of active path corrosion; however, the cracking. was Clearly stess dependent, as evidenced by a threshold stress intensity below which inter: {ranular SCC did not occur and an alignment ‘of eracks withthe applied tensile stress. Be- ‘cause there were no grain-boundary carbides ‘or chromium depletion inthe nickel these re Salts illustrate the potential eect of impurities when oer grain-boundary processes ae absent. ‘ep ce of 9 4 stainless tel citedearler tha impunity sarc ton may induce ergarlar SCC nthe 8 ‘ence of cirhides and chromium depletion. Like fer materials, nickel base alloys and austenitic stainless stels are suscepible to hy: ‘drogen induced intergranular suberitical crack ov imperiysarzaonthousht tpl 2 ey role in this hydrogen-induced fracture, teal or michel shown in Tig. 89 tsa ‘These results show the combined effec of slur segregation and. cathodic hydrogen on the ‘amount of intergranular fracture in nick. For the conditions ofthese test, a given amount of intergranular facture resulted fr diferent com- binations of grain-boundary sulfurand hydrogen reduction ae, A decreas nthe amount of sulfur could be compensated fr by an increased hydro- igen activity fo give the same amount of inter- ‘ranula fracture,