Hydrogen Induced Corrosion

Material Science 112 Group Research Paper

March 12th, 2001

Matthew Avery Benjamin Chui ! Gor"on #ariya #enneth $arson

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Introduction
&ne typically thin's o( corrosion as electrochemical reactions that "estroy metal sur(aces throu)h o*i"ation! +y"ro)en corrosion wor's throu)h mechanisms in which metals are wea'ene" internally! ,ue to its relatively small si-e, hy"ro)en is a.le to penetrate into metals an" a((ect properties such as stren)th an" "uctility! /his occurs throu)h em.rittlement, .listerin), precipitation, hy"ri"e (ormation, an" reaction with em.e""e" car.on! /his paper "escri.es the sources o( hy"ro)en corrosion, the "etails the mechanisms o( corrosion an" metho"s use" prevention!

Sources of Hydrogen Corrosion

+y"ro)en "ama)e o( metals occurs when hy"ro)en is a.sor.e" in metal an" thus wea'ens the loa"0carryin) capacity o( the metal! Metals a.sor. hy"ro)en when in an environment that contains or )enerates hy"ro)en! /his can .e "urin) the pro"uction, processin), an"1or the service o( the metal! +y"ro)en can .e a.sor.e" "urin) the pro"uction o( (or)e" steel! 2n steelma'in)/he sources o( hy"ro)en in steelma'in), hy"ro)en comes (rom is the 3moisture in the atmosphere an" in the(rom a""itives use" "urin) processin)!4 2t "issolves more in the hi)h0temperature 5CC austenite state 670iron8 than in the lower temperature BCC (errite state 690iron8! /here(ore, when hy"ro)en is a.sor.e" in the 70iron state an" su.se:uently coole", the in"ivi"ual hy"ro)en atoms precipitate in the 90iron at inclusions or micropores! /he pressure o( the hy"ro)en )as creates what are calle" 3(la'es4 in the metal, causin) em.rittlement! Similar "ama)e can occur when steel is wel"e" in an environment that contains hy"ro)en, which can .e intro"uce" throu)h atmospheric or sur(ace contamination! As the wel"e" metal containin) hy"ro)en cools, it .ecomes super0saturate", an" hy"ro)en "i((uses into the surroun"in) metal heate" "urin) the process! As a result, the area aroun" the wel" .ecomes em.rittle" .y su.se:uent corrosion! +y"ro)en can also .e a.sor.e" .y metal "urin) a:ueous corrosion or catho"ic char)in)! ;hen corrosion occurs in a low0p+ solution, some o( the re"uce" hy"ro)en "oes not (orm +2, .ut instea", "i((uses into the metal as atomic hy"ro)en! /his can happen "urin) pic'lin) an" electroplatin) o( metal! Su.stances such as arsenic, antimony, sul(ur, selenium, tellurium, an" cyani"e ions prevent the hy"ro)en atoms (rom (ormin) +2, an" are calle" catho"ic poisons! Catho"ic poisons (acilitate contamination .y 'eepin) hy"ro)en in atomic (orm, in which hy"ro)en more rea"ily "i((uses into the metal! <nvironments containin) hy"ro)en sul(i"e, which contains .oth hy"ro)en an" a catho"ic poison 6i!e! sul(ur8, are especially "an)erous (or alloys an" metals! +y"ro)en sul(i"e is o(ten encountere" in the petroleum in"ustry="urin) the "rillin) an" completion o( oil an" )as wells, an" "urin) the stora)e an" pipin) o( petroleum pro"ucts containin) hy"ro)en sul(i"e! 2( steel is in a hy"ro)en environment o( hi)h temperature an" pressure, hy"ro)en attac' can occur! +y"ro)en is a.sor.e" into the steel, an" althou)h the steel may appear (ine (or a while, it will su""enly lose its stren)th an" "uctility! /he hy"ro)en reacts with the car.i"es insi"e the steel! /his "elaye" attac' is encountere" in petrochemical plants, where hy"ro)en an" hy"rocar.on streams are at hi)h temperatures an" pressures!

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+y"ro)en can react "irectly with the metal to (orm hy"ri"es! /his can occur in metals such as titanium, -irconium, uranium, an" their alloys! /he (ormation o( hy"ri"es can severely wea'en these metals! 5or e*ample, -irconium hy"ri"e is so .rittle an" wea' that it can .e crushe" into pow"er! +y"ro)en can .e a.sor.e" "urin) meltin), wel"in), or pic'lin)? it can also .e a.sor.e" (rom water vapor an" hy"rocar.ons! Asi"e (rom hy"ro)en attac', which occurs at hi)h temperatures, the majority o( corrosion occurs at am.ient temperature! /his is .ecause at hi)h temperatures, the mo.ility o( hy"ro)en is )reat enou)h that there is little accumulation o( it at any one location in the lattice! &nce am.ient con"itions are met, solu.ility "ecreases an" causes poc'ets o( hy"ro)en to (orm! /his compoun"e" with the "ecrease in mo.ility traps the hy"ro)en within the metal lattice! /he process .y which hy"ro)en accumulation lea"s to corrosion is the topic o( the ne*t section

Principles of Hydrogen-Assisted Corrosion

Hydrogen Embrittlement
/he presence o( hy"ro)en in steel re"uces the tensile "uctility an" causes premature (ailure un"er static loa"s that "epen" on the stress an" time! /his phenomenon is 'nown as hy"ro)en em.rittlement! Althou)h many mechanisms o( hy"ro)en em.rittlement have .een propose", all can .e classi(ie" accor"in) to one o( three theories@ the planar pressure theory, the re"uce" sur(ace ener)y theory, an" the "ecohesion theory! All o( these theories are e*plore" .elow! /he .asic processes involve" in hy"ro)en em.rittlement are illustrate" in 5i)ure 1!

Steel can .e em.rittle" .y a very small amount o( hy"ro)en, on the level o( a (ew parts per million! /his hy"ro)en may come (rom some o( the many sources "escri.e" a.ove! Anli'e other mo"es o( environmentally0assiste" crac'in), such as stress corrosion crac'in), crac's cause" .y hy"ro)en em.rittlement usually "o not .ranch! Crac's can "evelop .y .oth trans)ranular an" inter)ranular paths! /he path o( crac' )rowth in hy"ro)en em.rittle" steels is a (unction o( the stress intensity (actor, # 6MPaBm8! <*amples o( crac' )rowth "ue to hy"ro)en em.rittlement are schematically shown in 5i)ure 2 .elow!

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5ailure cause" .y hy"ro)en em.rittlement is usually accompanie" .y very little plastic "e(ormation! /he (racture mo"e is usually .rittle cleava)e or :uasi0cleava)e (racture! 2n )eneral, materials .ecome more vulnera.le to hy"ro)en em.rittlement with increase" stren)th! /his .ehavior is supporte" .y the "ecohesion theory o( em.rittlement! ,ecohesion theory states that "issolve" hy"ro)en mi)rates into a tria*ially stresse" re)ion an" em.rittles the lattice .y lowerin) the cohesive stren)th .etween metal atoms! /his type o( (racture is shown in 5i)ure 2a a.ove! ,urin) stress crac'in), in (ront o( a crac' tip there is a locali-e" re)ion where stress is a ma*imum! &n the crac' sur(ace, hy"ro)en )as will physisor. near the crac' tip! /he hy"ro)en )as then .rea's into atomic hy"ro)en via chemia"sorption, an" the atomic hy"ro)en will pre(erentially mi)rate towar"s the re)ion o( locali-e" ma*imum stress in (ront o( the crac' tip! At this point, the hy"ro)en is suspecte" to wea'en the metal .on"s an" may coalesce to (orm microvoi"s lea"in) the crac' tip! Both possi.ilities re"uce the ener)y necessary to (orm .rittle crac' sur(aces! /his mechanism is very similar to the re"uce" sur(ace ener)y theory, which simply states that the a.sorption o( hy"ro)en "ecreases the sur(ace (ree ener)y o( the metal, enhancin) propa)ation o( the crac' tip! /his theory may e*plain the crac' propa)ation o( hi)h0 stren)th steels in low0pressure hy"ro)en environments! 5or a )iven hy"ro)en content, the ten"ency to em.rittle increases with "ecrease" strain rate, an" the em.rittlement is more prevalent at room temperature! Crac'in) "ue to hy"ro)en em.rittlement "ecreases with increasin) temperature, an" "isappears almost entirely in steels a.ove 200DC! At hi)h temperatures, hy"ro)en can .e "riven out o( soli" solution )iven a su((icient perio" o( time! 5or steels that are char)e" with a hi)h hy"ro)en content "urin) soli"i(ication, planar pressure theory is hel" to .e a vali" mechanism! ;hen steel saturate" with hy"ro)en at elevate" temperature is coole", )aseous hy"ro)en will precipitate in microvoi"s! <*tremely hi)h0pressure hy"ro)en can "evelop in these microvoi"s! /his mechanism appears vali" (or hy"ro)en0char)e" steels, .ut "oes not seem vali" (or steel in low0pressure hy"ro)en environments! 2n low0pressure hy"ro)en environments, it is thermo"ynamically un(avora.le (or an e*ternal low )as pressure to pro"uce a hi)h )as pressure within a soli"! /his theory is also use" to e*plain hy"ro)en in"uce" .listerin), which will .e "iscusse" .elow!

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Hydrogen Induced Blistering

;hen hy"ro)en is a.sor.e" into metal an" "i((uses inwar", it can precipitate as molecular hy"ro)en, at laminations, or inclusion1matri* inter(aces! <ach (orm can .uil" up enou)h pressure to pro"uce internal crac's! 2( these crac's are just .elow the sur(ace, the hy"ro)en )as pressure in the crac's can li(t up an" .ul)e out the e*terior layer o( the metal so that it resem.les a .lister! /he e:uili.rium pressure o( the molecular hy"ro)en in the voi", which is in contact with the atomic hy"ro)en in the surroun"in) metal, is )reat enou)h to rupture any metal or alloy! /hus hy"ro)en in"uce" .listerin) can .e seen as a special case o( the plane pressure mechanism o( hy"ro)en em.rittlement, where hi)h pressure hy"ro)en (orms in microvoi"s near the materialFs sur(ace! +y"ro)en in"uce" .listerin) is most prevalent in low0 stren)th alloys, an" is o.serve" in metals that have .een e*pose" to hy"ro)en0char)in) con"itions!

Precipitation of Internal Hydrogen

/he process o( re(inin) steels o(ten intro"uces a hy"ro)en content o( G0> parts per million! +owever, the room temperature solu.ility o( hy"ro)en in steel is less than 0!1 parts per million! /his "istur.ance (rom e:uili.rium causes hy"ro)en to precipitate in the "iatomic (orm! +y"ro)en usually precipitates at previously esta.lishe" inclusions, an" the pressure (rom the precipitation causes the enlar)ement 6or (ormation8 o( hairline crac's! Such internal crac's lea" to an em.rittlement o( the steel! +y"ro)en is typically intro"uce" into the steel (rom e*cess atmospheric moisture, or contaminants that are alrea"y present! At temperatures a.ove 200DC, most o( the hy"ro)en can escape (rom the steel an" thus the inci"ence o( precipitation (la'in) is much lower! 5la'e (ormation is most (avora.le at temperatures .elow 200DC! 2nternal hy"ro)en "ama)e is also encountere" :uite (re:uently in parts that have .een wel"e"! +y"ro)en is intro"uce" (rom sources that inclu"e the surroun"in) atmosphere, sur(ace contaminants, an" the wel"in) ro" itsel(! +y"ro)en em.rittlement typically occurs in the metal .elow the wel" root, calle" the heat0a((ecte" -one 6+AH8! /his (orm o( "ama)e lea"s to re"uce" "uctility an" stren)th! /he (racture sur(ace reveals shiny spots that are re(erre" to as 3(ish eyes!4 Both (la'es an" (ish eyes can .e prevente" .y e*ten"e" annealin) in low hy"ro)en con"itions! /his allows the trappe" hy"ro)en to escape (rom the metal matri*! 2n the case o( wel"in), this is o(ten not economically (easi.le! Proper sample preparation to remove contaminants, plus the use o( clean inert )ases, can lower the ris' o( internal hy"ro)en "ama)e! A""itionally, hy"ro)en assiste" crac'in) can .e avoi"e" .y re"ucin) stress levels in the metal!

Hydrogen Attack
+y"ro)en attac' can occur in steel that has .een su.jecte" to a hi)h0temperature hi)h0 pressure hy"ro)en environment! /he term 3attac'4 is use" .ecause a((ecte" systems typically "o not e*hi.it any si)ns o( wea'enin) .e(ore (ailure occurs at si)ni(icantly .elow the yiel" stress! Anli'e hy"ro)en em.rittlement, hy"ro)en attac' is a hi)h0temperature phenomenon .ecause it "epen"s on hi)h concentrations o( a.sor.e" hy"ro)en! Car.i"es react with internal hy"ro)en to (orm methane, which precipitates in the )rain .oun"aries! Bu..les may (orm in the matri*, an" there may .e "ecar.uri-ation at )rain .oun"aries! /hese processes .ecome si)ni(icant at temperatures hi)her than 200DC! +owever, rapi" :uenchin) o( steel that has previously esta.lishe" e:uili.rium in a hi)h0pressure hi)h0 temperature hy"ro)en environment may cause rapi" precipitation an" crac'in)!
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Cracking From Hydride Formation

Metals that are suscepti.le to hy"ri"e (ormation inclu"e titanium, tantalum, -irconium, uranium, an" thorium! +y"ro)en is a.sor.e" into these metals at hi)h temperatures, with su.se:uent hy"ri"e (ormation upon coolin)! +y"ri"e particles ten" to increase the stren)th o( the host metal, while causin) a "ecrease in the "uctility! /hese particles typically e*hi.it lower "ensity than the surroun"in) matri*, with a pre(erre" orientation in the host matri*! An applie" stress can cause these hy"ri"e particles to ali)n!

Prevention of Hydrogen Corrosion

2n the pursuit to process metals an" alloys that are resistant to hy"ro)en "ama)e, there are two (orms o( prevention@ minimi-in) hy"ro)en content an" lowerin) internal stresses! <m.rittlement can .e reverse" with treatment that e((ectively ri"s the metal o( hy"ro)en! +owever, a majority o( the wor' a)ainst hy"ro)en "ama)e is in prevention! /he (irst approach is to improve processin) techni:ues to prevent trappin) hy"ro)en within the metal! /he secon" approach is to optimi-e the type o( metal accor"in) to the con"itions that the (inal pro"uct will .e su.ject to in operation! 5inally, there are certain harm(ul practices per(orme" on in0service metals that can .e curtaile" completely! 2n the (irst case, hy"ro)en in"uce" crac'in) 6+2C8 can e((ectively .e reverse" with heat treatment! +y"ro)en is not very solu.le in 0iron state! +owever, it is especially solu.le in the hi)h0temperature 0iron state a.ove the trans(ormation temperature, I2CDC! +y"ro)en mo.ility is increase" at hi)her temperatures as well! 2( steels reach hi)h temperatures an" hi)h partial pressures o( hy"ro)en, a )reat "eal o( hy"ro)en can penetrate the metal! 2( it is :uenche" to a lower temperature, the hy"ro)en can 3(ree-e4 within the metal, allowin) +2C to occur at these accumulation spots! Ba'in) .etween 100DC an" JG0DC un"er vacuum (or e*ten"e" perio"s o( time will )ive hy"ro)en the mo.ility to "i((use to the sur(ace! Kacuum con"itions create a pressure )ra"ient that "rives out any hy"ro)en on the interior! 2t most cases, it is not (easi.le to treat in0service metals! /he alternative is to maintain a low hy"ro)en content (rom the point o( processin) .e(ore it is put into service! As mentione" .e(ore, hi)h temperatures "urin) processin) can lea" to severe hy"ro)en contamination! Slow .a'in) while in the BCC (errite (orm is the (irst step to ma'in) a metal resistant to +2C! +eat treatment is also recommen"e" .e(ore an" a(ter wel"in)! +owever, lower temperatures are su((icient, at 2C0DC (or one hour per inch o( thic'ness! /he wel"in) ro" must have low hy"ro)en content as well! #eepin) wel" material in "ry places is essential to avoi" a.sorption (rom water vapor! Some (actors that can .e optimi-e" (or the service o( the steels inclu"e temperature ran)e, tensile stren)th, alloyin) a)ents, an" inhi.itors! A majority o( hy"ro)en "ama)e occurs at am.ient temperatures! As mentione" .e(ore, mo.ility increases with temperature, preventin) accumulation! +owever, at the same time, the metal is suscepti.le to hy"ro)en attac'! /his involves reactions .etween the hy"ro)en an" em.e""e" car.i"es to (orm methane or "ecar.uri-e" structures! ;hen operatin) at these hi)h temperatures, the amount o( car.on impurities shoul" .e minimi-e" to avoi" such e((ects! A common mista'e is to overcompensate with hi)h stren)th steels where lower stren)th will per(orm just as well! Pro.lems arise at hi)h tensile stren)ths which encoura)e +2C! A

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simple reme"y is to "etermine the hi)hest stren)th nee"e" (or service an" match the metal accor"in)ly, leavin) no e*tra chance (or +2C to occur! Metallic alloyin) a)ents can create 3traps4 (or the hy"ro)en! 5or instance, the a""ition o( 1!GL /i to iron can increase the time ta'en (or the "i((usion o( hy"ro)en to reach its ma*imum! /his is .ecause the hy"ro)en accumulates at these 3traps4 .e(ore "i((usin) onwar"! /hese traps also re"uce the ma*imum "i((usion rate, .ecause they .uil" up micro0)ra"ients that slow "i((usion! Another type o( a""itive is the use o( corrosion inhi.itors! ;hen a""e" to process (lui"s, they re"uce the )eneral corrosion rate! 2n turn, they slow the )eneration o( hy"ro)en ions at the sur(ace, re"ucin) the concentration )ra"ient that "rives the hy"ro)en inwar"! Some )eneral practices that ai" hy"ro)en "ama)e can .e curtaile"! 5or instance, catho"ic protection techni:ues create a source o( hy"ro)en that can "i((use into the protecte" metal! Stray currents an" )alvanic couples can create hy"ro)en as well! 2( at all possi.le, supplementin) these techni:ues with other metho"s that minimi-e hy"ro)en creation can prevent corrosion!

Conclusions
/he possi.ility o( hy"ro)en "ama)e shoul" .e consi"ere" in the "esi)n o( mechanical systems! 2n many situations, hy"ro)en "ama)e is a result o( the processin) history o( the metal? an" not necessarily the service con"itions in which the metal is place"! +y"ro)en attac', however, is a hi)h temperature phenomenon that is usually associate" with hostile service con"itions! ,i((usional mechanisms play a major role in all (orms o( hy"ro)en "ama)e! 2n almost all cases, it is the precipitation o( hy"ro)en that lea"s to "ama)e!

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References
Crai), Bruce! Metals +an".oo', Kol! 1C, Corrosion, Mth <"ition! Metals Par', &+! ASM 2nternational, p! 1JC, 1M>J! +ert-.er), Richar" ;! ,e(ormation an" 5racture Mechanics o( <n)ineerin) Materials! New or'@ Oohn ;iley % Sons, 2nc!, 1MMJ! Oones, ,enny A! Principles an" Prevention o( Corrosion! New Oersey@ Prentice +all, 1MMJ! #im, C!,! Metals +an".oo', Kol! 11, 5ailure Analysis, Mth <"ition! Metals Par', &+@ ASM 2nternational, p! 2EG, 1M>J! #o.rin, G! Metals +an".oo', Kol! 1C, Corrosion, Mth <"ition! Metals Par', &+! ASM 2nternational, p! C21, 1M>J! Ritchie, R!&! 3Su.critical Crac' Growth4! Material Science 11C $ecture, Novem.er Mth, 2000! Raymon", $ouis! +y"ro)en <m.rittlement@ Prevention an" Control! Phila"elphia, PA! AS/M, 1M>>! /urn.ull, Alan! +y"ro)en /ransport % Crac'in) in Metals! Cam.ri")e, A#! /he 2nstitute o( Materials, 1MMG!

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