Materials

Peter Elliott, Corrosion & Materials Consultancy, Inc.

High temperatures, stresses, and the presence of elements such as oxygen, sulfur, or the halogens can add up to trouble. Here is how to screen candidate alloys for such service.

M
aterials are selected on the basis of service requirements, notably strength, so corrosion resistance (stability) may not be the primary design consideration. Assemblies need to be strong and resilient to the unique loads and stresses imparted on them, which can include signicant temperature changes and thermal gradients for many high-temperature applications. In ma ing a choice, it is necessary to now what materials are available and to what e!tent they are suited to the specic application. "he decision is quite involved and the choice is signicantly affected by the environment and the intended use, be it a reactor vessel, tubes, supports, shields, springs, or others. #ome problems may occur because of distortion and crac ing caused by thermal e!pansion$contraction% typically, a high-temperature alloy might change 4 in.$ft from ambient to &,'''() (&,*+,(-). "he user or designer needs to properly understand that the environment dictates the materials selection process at all stages of the process or application. -or e!ample, an alloy that performs well at the service temperature may corrode because of aqueous (dew point) corrosion at lower temperatures during off-load periods, or through some lac of design detail or poor maintenance procedures that introduce local air draughts that cool the system (e.g., at access doors, inspection ports, etc.). "o provide as optimum performance as possible, it is necessary for a supplier to be aware of the application, and for the user to be aware of the general range of available materials. .therwise, severe problems can result. -or CEP ebruary !""# www.aiche.org$cep$ 75

Materials

tions to about /''() (&,01'(-) in continuous service, or *21() (&,11'(-) in intermittent (temperature cycling) service (1). "he failure occurred because of overheating with contributions from suldation (hot corrosion). "he true cause of failure was a material mi!-up, because "ype +'2 was not specied, but was inadvertently used.

Mechanical limits of materials In considering traditional alloys, it is important for the designer and user to be fully aware of the mechanical limits of a material. -or e!ample, the A#34 5ressure 6essel )odes advise that the ma!imum allowable stress shall not e!ceed whichever is the lowest of7 (i) &''8 of the average stress to produce a creep rate of '.'&8 in &,''' h% (ii) 098 of the average stress to cause rupture after &'',''' h% and (iii) *'8 of the minimum stress to cause rupture after &'',''' h. "hese recommendations may be better appreciated by e!tracting typical data for "ype +'2 intended for use in a pressure vessel up to *&1() (&,1''(-). :ased upon A#34 tables, for a load of &9 35a (,.1 si) at 90'() (&,2''(-), the e!pected design life would be ,2 yr% at 9**() (&,21'(-), the life falls to 9 yr% and at *&1() (&,1''(-), it is only ,., yr. "hus, a short-term temperature e!cursion can have a signicant effect on equipment life. Also to be noted is that a small increase in loading, for e!ample, from ,.1 to + si at 90'() (&,2''(-), can mar edly reduce the life e!pectancy, here, from ,2 to / yr. .verheating is the most common cause of high-temperature corrosion failure, but the temperature in;uence on mechanical properties is of equal or even more signicance in that many failures occur because of creep deformation (creep voids) and thermal fatigue. .verheating can arise for various reasons, including an une!pected accumulation of tenacious deposits that can foul tubes in a heat e!changer. Hightemperature

alloys and uses <igh-temperature alloys are typically iron-, nic el- or cobalt-based alloys containing =,'8 chromium (or +'8 for cobalt), which is sufficient to form a protective o!ide against further o!idation. "he basic alloys include various additional elements that aid in corrosion resistance, notably aluminum (typically =28 to develop an alumina scale), silicon (up to 18 to develop an amorphous (glass-li e) scale that is complementary to chromia), and rare earth elements (typically >&8, e.g., yttrium, cerium, and lanthanum, that improve scale adhesion). .ther additions, such as the reactive metals, the refractory metals, and carbon, primarily improve mechanical properties. "he benecial and detrimental roles of common alloying elements on the anticipated performance of alloys at high-temperatures is covered by Agarwal and :rill (2). Refractory metals ? 3olybdenum, which is a benecial addition for resisting aqueous chloride-induced pitting corrosion (found in "ypes +&0 and +&9 stainless steels, and the 083o alloys), is prone to catastrophic o!idation as temperatures e!ceed about 9''() (&,,/,(-), the point above which 3o. forms eutectic mi!tures with iron, nic el, and chromium o!ides. "he o!ide 3o. melts at 9/1() (&,20,(-(). )atastrophic o!idation rapidly renders a metal into a useless powdery o!ide. @amage is worse in stagnant conditions and appears to be e!acerbated when sodium o!ide is present (e.g., from insulation). All of the refractory metals (tungsten, tantalum, niobium, and molybdenum) may e!perience catastrophic o!idation. #ilicide coatings have shown some to offer some resistance to this catastrophic (ApestB) o!idation. Coatings ? <igh-temperature coatings or surface modications are generally based on chromium, aluminum, or silicon, which, at high temperatures, form protective o!ides rich in chromia, alumina, or silica, respectively. In more recent years, there have been developments in applying so-called alloy coatings, for e!ample, the use of 3)CADE (metal, chromium, aluminum, and yttrium) on steels or other high-temperature alloy sub+

strates. 4fforts have also continued in weld overlay wor , where a strong base metal can support a corrosionresistant surface-coated layer. Applications ? In considering materials options, a thorough nowledge of the service applications (stress-bearing service% cyclic loading or not% frequency of cycling% impact or erosion effects% thermal e!pansion and contraction) is needed. @ifferent high-temperature corrosion processes are simultaneously involved in many common service applications. #ome of these are synergistic, which creates a formidable challenge for users and alloy producers. #ome e!amples of the forms associated with various applications are given in "able & (3, 4).

Types of hightemperature corrosion "here are certain distinguishing features about the morphology of high-temperature corrosion that aid in deciding upon the cause of damage. #ome typical indications include thic scales, grossly thinned metal, burnt (blac ened) or charred surfaces, molten phases, deposits of various colors, distortion and crac ing, and magnetism in what was rst a nonmagnetic (e.g., austenitic) matri!. @amage varies signicantly based upon the environment, and will be most severe when a materialFs o!idation limits are e!ceeded, notably when an alloy sustains brea away attac by o!ygen$sulfur, halogen$o!ygen, low-melting ;u!ing salts, molten glasses, or molten metals, especially after res. Oxidation 3any industrial processes involve o!idation, i.e., a metal reacts in air to form and sustain a protective o!ide. 7 www.aiche.org$cep$ ebruary !""#
CEP

Ta!le "# Typical process conditio

Process or Components Temperature O %team reforming tubes %team crac)ing tubes* ethylene +inyl chloride crac)ers Hydrocrac)ers* heaters &o #,"""'C &o #,"""'C ,-"'C --".,""'C ( (

Co)e calcining recuperators Cat crac)ing regenerators lare0stac) tips C%! furnace tubes Melamine$urea reactors 2eactors in &i

/#-'C &o /""'C 1-". #,"/"'C /-"'C 4-".-""'C 1""'C

production 3itric acid* catalyst grids 5inings for 6l pyrohydrolysis 3uclear processing reactors H&829 :gas0cooled; reactors <il0=red

14"'C &o #,"""'C 7-"0./""'C 7-".1-"'C /-".1""'C

boilers$superheaters 8as0turbine blades ?aste incinerators luidi@ed0bed combustors 8lass* recuperators Hot0dip galvani@ing

1-">'C 47".-""'C A,""'C #,"1"'C 4--'C

( ( ( (

9 H&82 is high0temperature gas reactor.

"here can be several o!ide products, some of which are less desirable, for e!ample, wustite, a defective o!ide of iron that forms rapidly at about 12'() (&,'''(-) on steel. 3ost high-temperature alloys are o!idation resistant, so price, availability, e!perience, and the type of application usually dictate choice. "here are no signicant problems up to 2''() (91'(-), few up to 91'() (&,+*'(-), but the choice of successful alloys becomes somewhat limited above about *''() (&,29'(-). #imple iron-chromium (or ironchromium-molybdenum) alloys become less useful as service temperatures increase, which is where the "ype +'' series austenitic stainless steels, (+'2, +'/, +&', +&2, ++', +++, etc.) and certain ferritic stainless steels (2&' and 220) nd many applications. -or more arduous service conditions at higher temperatures, these alloys are surpassed by nic elor cobalt-based formulations, including many of the more robust alloys that are mechanically alloyed to im-

prove strength and to control (that is, minimiGe) grain growth at elevated temperatures. )ertain alloys (usually those with rare earth additions) are more resilient to o!idation under thermal cycling (shoc ) conditions. #ome applications do not allow an alloy to fully develop its steady-state condition, thus, performance is dictated by the transient (not-so-protective) surface scales. "ransient effects will become apparent should failure analysis be performed. )aution should be given to ironchromium-nic el alloys that can be prone to sigma-phase formation between 12'H*''() (&,'''H&,29'(-), which results in premature brittle failure. 3olybdenum-containing alloys ("ypes +&0 and +&9 stainless steels and the 08-3o alloys) can be prone to catastrophic o!idation above about 0*'() (&,,10(-).

$ul%dation #ulfurous gases are common to many applications, including fuel

combustion atmospheres, petrochemical processing, gas turbines, and coal gasication. #uldes (e.g., sulfur vapor, hydrogen sulde) can be very damaging, because metal suldes form at faster rates than do metal o!ides. #uldes have low melting points and produce voluminous scales (scale spallation). Iith mi!ed corrodant environments (o!ygen and sulfur), alloy performance is based upon a subtle interplay between o!ide and sulde formation. .!ides are more stable% suldes form more rapidly (due to inetics). "hus, o!ides, suldes, or both may form. If deposits are also present, then conditions at the metal surfaces are reducing compared to areas e!ternal to the deposits. @amage can be e!tensive. 3i!ed sulfur-and-o!ygen gases can invo e very high corrosion rates due to brea away attac , typically above about 0''() (&,&&'(-) for nic elbased alloys, /,'() (&,0**(-) for cobalt-based, and /2'() (&9,2(-) for iron-based formulations. :rea -

CEP ebruary !""# www.aiche.org$cep$

77

Materials

6bove* &ube failure due to 5eft* local Burst overheating. tube walls

due to overheating.

away attac is commonly associated with sulfur and e!cess air. .nce the rstformed o!ide is lost or destroyed, suldes can invade the chromium-depleted substrate, thus, causing accelerated attac to occur. #tainless steels and iron-based alloys are preferred over high-nic el alloys, because nic el is prone to forming the low-melting nic el-nic el sulde eutectic, Ji-Ji # , which melts at 0+1() (&,&91(-). 4utectics of cobalt and iron occur at higher temperatures, **'() (&,0&0(-) and /*1() (&,*'1(-), respectively. Alloys can be wea ened by internal corrosion, most noticeably when mobile species are present, such as low-melting suldes, which are typied by localiGed dull uniform gray phases within the alloy matri!. At times, liquid-appearing phases are found in the metallurgy. Alloys containing aluminum, silicon, and cobalt are useful in suldiGing environments. 3any alloys classied as candidates for suldation do well only if o!ides are rst able to form. 5reo!idation can be of value.
+ ,

Halogenation <alogen attac is commonly manifested as a combination of scale spallation with internal alloy damage including voids that form as a result of highly volatile species (5). 3aterial performance is dictated by the unique properties of the halides, including high vapor pressures, high volatility (vaporiGation), low melting points, mismatched e!pansion coefficients with metal substrates, and the effects of displacement reactions whereby o!ide or sulde are

thermodynamically favored over the halides. Alloy performance is greatly affected by o!idiGing or reducing conditions. -or o!idiGing atmospheres or for vapors Kointly present with o!ygen (or air), there is an opportunity for reduced corrosion rates ( inetics) associated with o!ide formation, although the scale may later be disrupted by the volatile halides, especially if iron-based alloys are used. Jic el alloys are generally favored for halogen atmospheres, since iron-based alloys are more vulnerable, due to their volatile products, e.g., -e)l . #ilicon additions are useful if o!idiGing environments prevail, but not for reducing conditions. 5reo!idation is not normally a benet for reducing halogen attac . Ihat ma es halogens different from other o!idants is their high mobility and diffusivity into a metal, resulting in internal damage of the alloy matri!. -luorine can penetrate twice the distance of chlorides, which means that the predominant mode of damage in ;uorine-containing gases is by means of internal attac . <alide products are also hygroscopic (3), so it is not unusual to discover local protrusions on a metal that have been removed during service. In laboratory studies, it is common to nd that a surface apparently free from chlorides (removed during metallographic preparation) is later found to show them. "his is because the chlorides have been leached out from deep under the voided areas in the metal.
+

Car!uri&ation #everal environments are synonymous with carburiGation, including pyrolysis and gas-crac ing processes, reforming plants, and heat-treating facilities that involve carbon mono!ide, methane, and hydrocarbon gases. @amage is usually manifested as internal carbides, notably in grain boundaries and is generally worst above &,'1'() (&,/,,(-). Ihen carburiGing conditions alternate with o!idiGing ones, carbides can become o!idiGed to o!ides, which yields carbon mono!ide that can wea en the grain boundaries in an alloy. #uch an alloy fails by Agreen rot,B a name that describes the green fractured surface that results (chromium o!ide). #trongly carburiGing atmospheres (i.e., those that have a carbon activity =&) can cause a metal to form co e-li e layers, often of a dusty form. "his form of attac , termed metal dusting, commonly occurs between 2,1H*''() (9/'H &,29'(-) and can be very rapid (in days not months). @amage is either general or localiGed (pitting), as dictated by the ability of the alloy to form a surface o!ide (6). 7' www.aiche.org$cep$ ebruary !""# CEP

6bove* &hermal fatigue crac) in boiler tube.

)arbon steels and alloy steels are normally uniformly thinned by metal dusting% more highly alloyed materi als usually display local outgrowths of co e emerging through small pits that broaden with time. )ast iron-nic el-chromium alloys are widely used for carburiGing applications, including the more recent alloys containing &H,8 silicon and &.18 niobium (the <5 3od alloys) (4, 6). <igh-nic el alloys (with low solubility for carbon) nd many applications for carburiGing conditions. #tronger nic el-based alloys with high chromium and silicon contents are useful in more demanding environments. <ighly alloyed ferritic stainless steels (that are able to more rapidly form a thin o!ide lm) tend to outperform austenitic steels.

(itriding Celatively little is reported about nitridation other than material performance is wea ened (embrittlement) as a result of the formation of internal nitrides in the alloy (4). It is common to e!pect damage with nitrides at 9''H/''() (&,,/'H&,01'(-). Jitrides appear generally as needle-li e precipitates in the alloy matri!. Jic el- and cobalt-rich alloys appear to be rst-choice candidates for resisting nitride attac , because of the low solubility of nitrogen in these
&op* &ube fouling in an incinerator plant due to carryover of deposits. Bottom* &hrough0metal perforation in tubing from a carbon blac) plant.

base metals. Iron tends to be detrimental, as do aluminum and titanium in low concentrations. #ilicon forms a brittle intermetallic compound with nitrogen and can contribute to scale spallation, especially in applications at low o!ygen concentrations (potentials), where thin o!ides can form, and during thermal cycling.

Molten products @eposits are a common product in many high-temperature applications, including boilers, waste incinerators, ;uidiGed-bed combustors, and gas turbines. A whole series of reactions is possible should deposits become molten and no single mechanism can be applied generally to characteriGe such damage (7). "he mechanisms of molten product corrosion are comple!. "he types of damage include fuel-ash corrosion ? sulfates, including acid and basic ;u!ing reactions (8), and vanadic slag attac ( ) ? molten salt corrosion (chlorides, nitrates, and carbonates) (4), and molten glass corrosion. Diquid metal attac is yet another special category (4). !"el#as$ or as$%salt#&eposit cor rosion stems from high-temperature corrosion processes associated with fuel combustion products in boilers, waste incinerators, and gas turbines. "hus, products can include various deposits (o!idiGing or reducing) with active contributions from o!ygen, sulfur, halogens, carbon, and nitrogen (4, 7). "ypically, alloy matrices display intergranular attac (o!ides and chlorides) beneath disturbed o!ide layers possibly fused with molten deposits and internal suldes within the alloy-affected Gone. 'ot corrosion is generally regarded as attac in the Koint presence of sulfur and o!ygen. "ypically, attac is considered to be triggered by molten al ali metal salts that melt above 9''() (&,,/'(-). #odium sulfate, with a melting point of **2() (&,0,'(-), derived from sodium chloride and sulfur from the fuel, is considered to be closely involved in the mechanism of hot corrosion (8). "his mechanism is considered to have four stages7 o!idation (incubation)% mild suldation% o!ide failure% and catastrophic attac (internal suldes via a porous voluminous comple! o!ide$deposit layer). <ot corrosion is an irreversible autocatalytic process.

CEP ebruary !""# www.aiche.org$cep$

7)

Materials

Ta!le *# +uide to candidate materials#

Mat

erials

Peter Elliott, Corrosion & Materials Consultancy, Inc.

High temperatures, stresses, and the presence of elements such as oxygen, sulfur, or the halogens can add up to trouble. Here is how to screen candidate alloys for such service.

M
aterials are selected on the basis of service requirements, notably strength, so corrosion resistance (stability) may not be the primary design consideration. Assemblies need to be strong and resilient to the unique loads and stresses imparted on them, which can include signicant temperature changes and thermal gradients for many high-temperature applications. In ma ing a choice, it is necessary to now what materials are available and to what e!tent they are suited to the specic application. "he decision is quite involved and the choice is signicantly affected by the environment and the intended use, be it a reactor vessel, tubes, supports, shields, springs, or others. #ome problems may occur because of distortion and crac ing caused by thermal e!pansion$contraction% typically, a high-temperature alloy might change 4 in.$ft from ambient to &,'''() (&,*+,(-). "he user or designer needs to properly understand that the environment dictates the materials selection process at all stages of the process or application. -or e!ample, an alloy that performs well at the service temperature may corrode because of aqueous (dew point) corrosion at lower temperatures during off-load periods, or through some lac of design detail or poor maintenance procedures that introduce local air draughts that cool the system (e.g., at access doors, inspection ports, etc.). "o provide as optimum performance as possible, it is necessary for a supplier to be aware of the application, and for the

user to be aware of the general range of available materials. .therwise, severe problems can result. -or CEP ebruary !""# www.aiche.org$cep$ 75

Materials

tions to about /''() (&,01'(-) in continuous service, or *21() (&,11'(-) in intermittent (temperature cycling) service (1). "he failure occurred because of overheating with contributions from suldation (hot corrosion). "he true cause of failure was a material mi!-up, because "ype +'2 was not specied, but was inadvertently used.

Mechanical limits of materials In considering traditional alloys, it is important for the designer and user to be fully aware of the mechanical limits of a material. -or e!ample, the A#34 5ressure 6essel )odes advise that the ma!imum allowable stress shall not e!ceed whichever is the lowest of7 (i) &''8 of the average stress to produce a creep rate of '.'&8 in &,''' h% (ii) 098 of the average stress to cause rupture after &'',''' h% and (iii) *'8 of the minimum stress to cause rupture after &'',''' h. "hese recommendations may be better appreciated by e!tracting typical data for "ype +'2 intended for use in a pressure vessel up to *&1() (&,1''(-). :ased upon A#34 tables, for a load of &9 35a (,.1 si) at 90'() (&,2''(-), the e!pected design life would be ,2 yr% at 9**() (&,21'(-), the life falls to 9 yr% and at *&1() (&,1''(-), it is only ,., yr. "hus, a short-term temperature e!cursion can have a signicant effect on equipment life. Also to be noted is that a small increase in loading, for e!ample, from ,.1 to + si at 90'() (&,2''(-), can mar edly reduce the life e!pectancy, here, from ,2 to / yr. .verheating is the most common cause of high-temperature corrosion failure, but the temperature in;uence on mechanical properties is of equal or even more signicance in that many failures occur because of creep deformation (creep voids) and thermal fatigue. .verheating can arise for various reasons, including an une!pected accumulation of tenacious deposits that can foul tubes in a heat e!changer. Hightemperature

alloys and uses <igh-temperature alloys are typically iron-, nic el- or cobalt-based alloys containing =,'8 chromium (or +'8 for cobalt), which is sufficient to form a protective o!ide against further o!idation. "he basic alloys include various additional elements that aid in corrosion resistance, notably aluminum (typically =28 to develop an alumina scale), silicon (up to 18 to develop an amorphous (glass-li e) scale that is complementary to chromia), and rare earth elements (typically >&8, e.g., yttrium, cerium, and lanthanum, that improve scale adhesion). .ther additions, such as the reactive metals, the refractory metals, and carbon, primarily improve mechanical properties. "he benecial and detrimental roles of common alloying elements on the anticipated performance of alloys at high-temperatures is covered by Agarwal and :rill (2). Refractory metals ? 3olybdenum, which is a benecial addition for resisting aqueous chloride-induced pitting corrosion (found in "ypes +&0 and +&9 stainless steels, and the 083o alloys), is prone to catastrophic o!idation as temperatures e!ceed about 9''() (&,,/,(-), the point above which 3o. forms eutectic mi!tures with iron, nic el, and chromium o!ides. "he o!ide 3o. melts at 9/1() (&,20,(-(). )atastrophic o!idation rapidly renders a metal into a useless powdery o!ide. @amage is worse in stagnant conditions and appears to be e!acerbated when sodium o!ide is present (e.g., from insulation). All of the refractory metals (tungsten, tantalum, niobium, and molybdenum) may e!perience catastrophic o!idation. #ilicide coatings have shown some to offer some resistance to this catastrophic (ApestB) o!idation. Coatings ? <igh-temperature coatings or surface modications are generally based on chromium, aluminum, or silicon, which, at high temperatures, form protective o!ides rich in chromia, alumina, or silica, respectively. In more recent years, there have been developments in applying so-called alloy coatings, for e!ample, the use of 3)CADE (metal, chromium, aluminum, and yttrium) on steels or other high-temperature alloy sub+

strates. 4fforts have also continued in weld overlay wor , where a strong base metal can support a corrosionresistant surface-coated layer. Applications ? In considering materials options, a thorough nowledge of the service applications (stress-bearing service% cyclic loading or not% frequency of cycling% impact or erosion effects% thermal e!pansion and contraction) is needed. @ifferent high-temperature corrosion processes are simultaneously involved in many common service applications. #ome of these are synergistic, which creates a formidable challenge for users and alloy producers. #ome e!amples of the forms associated with various applications are given in "able & (3, 4).

Types of hightemperature corrosion "here are certain distinguishing features about the morphology of high-temperature corrosion that aid in deciding upon the cause of damage. #ome typical indications include thic scales, grossly thinned metal, burnt (blac ened) or charred surfaces, molten phases, deposits of various colors, distortion and crac ing, and magnetism in what was rst a nonmagnetic (e.g., austenitic) matri!. @amage varies signicantly based upon the environment, and will be most severe when a materialFs o!idation limits are e!ceeded, notably when an alloy sustains brea away attac by o!ygen$sulfur, halogen$o!ygen, low-melting ;u!ing salts, molten glasses, or molten metals, especially after res. Oxidation 3any industrial processes involve o!idation, i.e., a metal reacts in air to form and sustain a protective o!ide. 7 www.aiche.org$cep$ ebruary !""#
CEP

Ta!le "# Typical process conditio

Process or Components Temperature O %team reforming tubes %team crac)ing tubes* ethylene +inyl chloride crac)ers Hydrocrac)ers* heaters &o #,"""'C &o #,"""'C ,-"'C --".,""'C ( (

Co)e calcining recuperators Cat crac)ing regenerators lare0stac) tips C%! furnace tubes Melamine$urea reactors 2eactors in &i

/#-'C &o /""'C 1-". #,"/"'C /-"'C 4-".-""'C 1""'C

production 3itric acid* catalyst grids 5inings for 6l pyrohydrolysis 3uclear processing reactors H&829 :gas0cooled; reactors <il0=red

14"'C &o #,"""'C 7-"0./""'C 7-".1-"'C /-".1""'C

boilers$superheaters 8as0turbine blades ?aste incinerators luidi@ed0bed combustors 8lass* recuperators Hot0dip galvani@ing

1-">'C 47".-""'C A,""'C #,"1"'C 4--'C

( ( ( (

9 H&82 is high0temperature gas reactor.

"here can be several o!ide products, some of which are less desirable, for e!ample, wustite, a defective o!ide of iron that forms rapidly at about 12'() (&,'''(-) on steel. 3ost high-temperature alloys are o!idation resistant, so price, availability, e!perience, and the type of application usually dictate choice. "here are no signicant problems up to 2''() (91'(-), few up to 91'() (&,+*'(-), but the choice of successful alloys becomes somewhat limited above about *''() (&,29'(-). #imple iron-chromium (or ironchromium-molybdenum) alloys become less useful as service temperatures increase, which is where the "ype +'' series austenitic stainless steels, (+'2, +'/, +&', +&2, ++', +++, etc.) and certain ferritic stainless steels (2&' and 220) nd many applications. -or more arduous service conditions at higher temperatures, these alloys are surpassed by nic elor cobalt-based formulations, including many of the more robust alloys that are mechanically alloyed to im-

prove strength and to control (that is, minimiGe) grain growth at elevated temperatures. )ertain alloys (usually those with rare earth additions) are more resilient to o!idation under thermal cycling (shoc ) conditions. #ome applications do not allow an alloy to fully develop its steady-state condition, thus, performance is dictated by the transient (not-so-protective) surface scales. "ransient effects will become apparent should failure analysis be performed. )aution should be given to ironchromium-nic el alloys that can be prone to sigma-phase formation between 12'H*''() (&,'''H&,29'(-), which results in premature brittle failure. 3olybdenum-containing alloys ("ypes +&0 and +&9 stainless steels and the 08-3o alloys) can be prone to catastrophic o!idation above about 0*'() (&,,10(-).

$ul%dation #ulfurous gases are common to many applications, including fuel

combustion atmospheres, petrochemical processing, gas turbines, and coal gasication. #uldes (e.g., sulfur vapor, hydrogen sulde) can be very damaging, because metal suldes form at faster rates than do metal o!ides. #uldes have low melting points and produce voluminous scales (scale spallation). Iith mi!ed corrodant environments (o!ygen and sulfur), alloy performance is based upon a subtle interplay between o!ide and sulde formation. .!ides are more stable% suldes form more rapidly (due to inetics). "hus, o!ides, suldes, or both may form. If deposits are also present, then conditions at the metal surfaces are reducing compared to areas e!ternal to the deposits. @amage can be e!tensive. 3i!ed sulfur-and-o!ygen gases can invo e very high corrosion rates due to brea away attac , typically above about 0''() (&,&&'(-) for nic elbased alloys, /,'() (&,0**(-) for cobalt-based, and /2'() (&9,2(-) for iron-based formulations. :rea -

CEP ebruary !""# www.aiche.org$cep$

77

Materials

6bove* &ube failure due to 5eft* local Burst overheating. tube walls

due to overheating.

away attac is commonly associated with sulfur and e!cess air. .nce the rstformed o!ide is lost or destroyed, suldes can invade the chromium-depleted substrate, thus, causing accelerated attac to occur. #tainless steels and iron-based alloys are preferred over high-nic el alloys, because nic el is prone to forming the low-melting nic el-nic el sulde eutectic, Ji-Ji # , which melts at 0+1() (&,&91(-). 4utectics of cobalt and iron occur at higher temperatures, **'() (&,0&0(-) and /*1() (&,*'1(-), respectively. Alloys can be wea ened by internal corrosion, most noticeably when mobile species are present, such as low-melting suldes, which are typied by localiGed dull uniform gray phases within the alloy matri!. At times, liquid-appearing phases are found in the metallurgy. Alloys containing aluminum, silicon, and cobalt are useful in suldiGing environments. 3any alloys classied as candidates for suldation do well only if o!ides are rst able to form. 5reo!idation can be of value.
+ ,

Halogenation <alogen attac is commonly manifested as a combination of scale spallation with internal alloy damage including voids that form as a result of highly volatile species (5). 3aterial performance is dictated by the unique properties of the halides, including high vapor pressures, high volatility (vaporiGation), low melting points, mismatched e!pansion coefficients with metal substrates, and the effects of displacement reactions whereby o!ide or sulde are

thermodynamically favored over the halides. Alloy performance is greatly affected by o!idiGing or reducing conditions. -or o!idiGing atmospheres or for vapors Kointly present with o!ygen (or air), there is an opportunity for reduced corrosion rates ( inetics) associated with o!ide formation, although the scale may later be disrupted by the volatile halides, especially if iron-based alloys are used. Jic el alloys are generally favored for halogen atmospheres, since iron-based alloys are more vulnerable, due to their volatile products, e.g., -e)l . #ilicon additions are useful if o!idiGing environments prevail, but not for reducing conditions. 5reo!idation is not normally a benet for reducing halogen attac . Ihat ma es halogens different from other o!idants is their high mobility and diffusivity into a metal, resulting in internal damage of the alloy matri!. -luorine can penetrate twice the distance of chlorides, which means that the predominant mode of damage in ;uorine-containing gases is by means of internal attac . <alide products are also hygroscopic (3), so it is not unusual to discover local protrusions on a metal that have been removed during service. In laboratory studies, it is common to nd that a surface apparently free from chlorides (removed during metallographic preparation) is later found to show them. "his is because the chlorides have been leached out from deep under the voided areas in the metal.
+

Car!uri&ation #everal environments are synonymous with carburiGation, including pyrolysis and gas-crac ing processes, reforming plants, and heat-treating facilities that involve carbon mono!ide, methane, and hydrocarbon gases. @amage is usually manifested as internal carbides, notably in grain boundaries and is generally worst above &,'1'() (&,/,,(-). Ihen carburiGing conditions alternate with o!idiGing ones, carbides can become o!idiGed to o!ides, which yields carbon mono!ide that can wea en the grain boundaries in an alloy. #uch an alloy fails by Agreen rot,B a name that describes the green fractured surface that results (chromium o!ide). #trongly carburiGing atmospheres (i.e., those that have a carbon activity =&) can cause a metal to form co e-li e layers, often of a dusty form. "his form of attac , termed metal dusting, commonly occurs between 2,1H*''() (9/'H &,29'(-) and can be very rapid (in days not months). @amage is either general or localiGed (pitting), as dictated by the ability of the alloy to form a surface o!ide (6). 7' www.aiche.org$cep$ ebruary !""# CEP

6bove* &hermal fatigue crac) in boiler tube.

)arbon steels and alloy steels are normally uniformly thinned by metal dusting% more highly alloyed materi als usually display local outgrowths of co e emerging through small pits that broaden with time. )ast iron-nic el-chromium alloys are widely used for carburiGing applications, including the more recent alloys containing &H,8 silicon and &.18 niobium (the <5 3od alloys) (4, 6). <igh-nic el alloys (with low solubility for carbon) nd many applications for carburiGing conditions. #tronger nic el-based alloys with high chromium and silicon contents are useful in more demanding environments. <ighly alloyed ferritic stainless steels (that are able to more rapidly form a thin o!ide lm) tend to outperform austenitic steels.

(itriding Celatively little is reported about nitridation other than material performance is wea ened (embrittlement) as a result of the formation of internal nitrides in the alloy (4). It is common to e!pect damage with nitrides at 9''H/''() (&,,/'H&,01'(-). Jitrides appear generally as needle-li e precipitates in the alloy matri!. Jic el- and cobalt-rich alloys appear to be rst-choice candidates for resisting nitride attac , because of the low solubility of nitrogen in these
&op* &ube fouling in an incinerator plant due to carryover of deposits. Bottom* &hrough0metal perforation in tubing from a carbon blac) plant.

base metals. Iron tends to be detrimental, as do aluminum and titanium in low concentrations. #ilicon forms a brittle intermetallic compound with nitrogen and can contribute to scale spallation, especially in applications at low o!ygen concentrations (potentials), where thin o!ides can form, and during thermal cycling.

Molten products @eposits are a common product in many high-temperature applications, including boilers, waste incinerators, ;uidiGed-bed combustors, and gas turbines. A whole series of reactions is possible should deposits become molten and no single mechanism can be applied generally to characteriGe such damage (7). "he mechanisms of molten product corrosion are comple!. "he types of damage include fuel-ash corrosion ? sulfates, including acid and basic ;u!ing reactions (8), and vanadic slag attac ( ) ? molten salt corrosion (chlorides, nitrates, and carbonates) (4), and molten glass corrosion. Diquid metal attac is yet another special category (4). !"el#as$ or as$%salt#&eposit cor rosion stems from high-temperature corrosion processes associated with fuel combustion products in boilers, waste incinerators, and gas turbines. "hus, products can include various deposits (o!idiGing or reducing) with active contributions from o!ygen, sulfur, halogens, carbon, and nitrogen (4, 7). "ypically, alloy matrices display intergranular attac (o!ides and chlorides) beneath disturbed o!ide layers possibly fused with molten deposits and internal suldes within the alloy-affected Gone. 'ot corrosion is generally regarded as attac in the Koint presence of sulfur and o!ygen. "ypically, attac is considered to be triggered by molten al ali metal salts that melt above 9''() (&,,/'(-). #odium sulfate, with a melting point of **2() (&,0,'(-), derived from sodium chloride and sulfur from the fuel, is considered to be closely involved in the mechanism of hot corrosion (8). "his mechanism is considered to have four stages7 o!idation (incubation)% mild suldation% o!ide failure% and catastrophic attac (internal suldes via a porous voluminous comple! o!ide$deposit layer). <ot corrosion is an irreversible autocatalytic process.

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Materials

Ta!le *# +uide to candidate materials#

Corrosion Mode Oxidation ,asic -lloy Types e03i0:Co; A!"C :4"C; Cr. %tabili@ed to minimi@e sensiti@ation. 6l, %i bene=cial. 2are earth additions aid scale retention. Candidates. 4"4, 4!#,4"1, 4#", /"":H&;, /"4, 44", 44,,H2#!", 44", /-H, 444, ,"", ,"#:8C;, ,"!C6, ,#7, ,!-, !-4M6, 4-4M6, E%, !#4, M61-,, M67-4, F, etc. (otes and Cautions ?ide choice dictated by application and functionD Mechanical propertiesD &hermal cycle :shoc);D &ransient vs. steady stateD Internal oxides. Beware GD ?, Mo H catastrophic oxidation. %ulfur vapor, H!%, etc. H no oxides. Beware of 3i$3i4%! eutecticD coatings can help. %<!, %<4 , etc. H ris) of brea)away attac) with oxides and sul=desD 6l coatings. :%ee hot corrosion.; Internal carbides with intergranular attac)D Cast tubes bene=t from smooth I.E. surfaces. Metal dusting :at lower temperatures;. 8reen rot :with intermittent <!0C;. (itridation 3i0alloys rather than e. 6void high Cr levels. Kse low 6l and low &i levels :nitride formers;. %i promotes scale spalling. 3i alloys generally better than e. Bene=ts* Cr :not H ;, 6l, %i :with oxygen;. Ireoxidation not bene=cial. eCrMo alloys at lower temperaturesD C26sL for %, <, C H subMect to application. High Cr, 6l, %i useful :also as coatings;. Molten salts 3i alloys generally favoredD 6s with halogens, sul=dation* Intergranular attac), 4"1, 4#", /"":H&;, ,"", ,"#, ,"!C6, ,!-, /!-, !-4M6, 4-4M6, M67-4, M67-/, M61-,, I3,-7, ,7#, etc. 4"1, /"":H&;, 44", 44,, #//, !4", ,"", ,"!C6, ,!-, !-4M6, etc. Internal nitrides :e.g., 6l3; can wea)en alloyD &hin oxide at low oxygen partial pressure reduces nitridation. /""H, 444, !"", !"#, !"7, ,"", ,"#, ,"!C6, !#4, 3, H!4!, B4, etc. +olatile productsD Internal attac) with voidsD Hygroscopic products :e.g., chlorides;D %cale spallation. 6pplications dictate alloy, or coating* 8as turbines :strong > C26L;D vanadic slag :high0Cr > %i;.

$ul%dation /0educing gases no oxides1

e0 with high Cr :6l; alloys.

1.#!CCr steels* 4"1, 4#", 44", /"":H&;, /"4, H2#!", /-H, !-4M6, 4-4M6, M61-,, 44,, ,7#, ,B, #//, etc.

$ul%dation /Oxidi&ing gases1

e0Cr0based alloys. <xide formation a bene=t. Ireoxidi@ation may help.

6s above with #-4M6, ,"#, H2#,", M67-4, M61-,, 444, --,, etc.

Car!uri&atio n

?ide use of cast alloys. or worse conditions, use high03i alloys with Cr, %i. :5ow solubility of C in 3i is bene=t for 3i alloys.;

HH, HJ, HIMod, 4"1, 4#", 44", 444, /-H, /"":H&;, /"4, E%, H2#,", ,"", ,"#, !-4M6, ,"!C6, ,#7, ,!-, ,1", M67-4, M61-,, F, --,, 7",, 7#/, 7-", etc.

Halogenatio n2 chlorination , 3uorination, etc# 4uel ash corrosion

some high0Cr alloysD 3iCrMo? alloys for molten chlorides. Molten glass 3i0 or some Co0$high0Cr alloysD %ome refractories.

depends on nature of salts :acidic$basic;.

internal voids, and probable embrittlement.

,"", ,"#, ,"!C6, ,7#, ,1", M67-/, etc.

Complex Nuxing reactionsD oxidationD sul=dationD chlorinationD Nuorination, etc. Eissolution or alloying effectsD Intergranular attac)D Eepends on system.

5i6uid metals

e0alloys with Cr, 6l, %i usual =rst choices :subMect to liOuid metal, e.g,. 5iO. 3a, J, molten Pn, Ib, etc.; %ynergy of processes.

4"1, 4#", /-H, !-4M6, etc.

Complex En7ironmen ts

C26sL or coatings

%ee) input from suppliersD Consider online tests$monitoring.

3ote* &his is a general, not exhaustive, guide. 9 3ot in any preferred order. L C26s are corrosion0resistant alloys.

'8

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ebruary !""# CEP

(ana&ic slag corrosion occurs following combustion of certain lowgrade or residual fuel oils that are of high vanadium, sulfur, and al ali metals. "he molten sodium vanadyl vanadates typically ;u! away protective o!ides and then rapidly dissolve the metal. 3any high-temperature alloys cannot survive &'' h at /''() (&,01,(-) in vanadic slags ( ). 6anadic attac can be managed by lowering temperatures (if possible), using fuel-oil additives (such as magnesium and calcium o!ides), or by specifying high-chromium alloys. #ilicon-rich coatings are benecial and appear to complement the role of chromium ( ). )olten glass typically induces intergranular attac with voids (from volatile halides) and suldes. .!ides are generally fused into the glass. Attac is commonly rapid, and high chromium-nic el-based alloys are usually employed. Iron-rich alloys can be prone to severe attac due to their ability to form low-melting halides (e.g., -e)l ). )olten salts, used for heat treating applications, nuclear engineering, solar cells, and metal e!traction, generally promote intergranular attac in alloys, often with voids and internal low-melting products (halides). A common feature in most hightemperature aggressive environments is the synergy of the reactants one with each other ("able &). Iastage can be easily measured, but the mechanism(s) are not as easy to determine. As a minimum, a rigorous study and analysis of the morphologies should help to establish the rate-controlling process, which should help to better dene the type of alloy that could be considered as a candidate. "he broad e!pertise of the material suppliers should be fully e!plored in the quest for a suitable choice. 3onitoring trials using test spools are recommended wherever they can be used.
+

sel. As might be e!pected, there are many candidates, yet, from these the choice is often reduced to one of two, once the total range of properties is fully e!plored. -actors to be considered include mechanical properties (strength, ;e!ibility, fatigue life), physical properties (e!pansion and contraction, re;ectivity, magnetism, etc.), availability (shape and form), and price (economic decision based on overall costs and fabrication, etc.). As a convenience, some generally

for various high-temperature environments are summariGed in "able ,. "his table is intended only as a guide% no order of merit is to be interpreted from the sequence of listings (or omissions) in this table. Also, the alloy lists are not meant to be inclusive, but, rather, merely typical e!amples of what has wor ed in the eld.

5iterature Cited
1. Rothman, M. F., ed., A<igh "emperature 5roperty @ata7 -errous Alloys,B A#3 International, 3etals 5ar , .<, p. /.,0 (&/*/). 2. Agarwal, D. C., and U. Brill, A3aterial @egradation 5roblems in <igh "emperature 4nvironments,B *n&"strial 'eating, p. 10 (.ct. &//2).

#. !. 4.

Elliott, P., A5ractical Luide to <igh"emperature Alloys,B )aterials +erfor# mance, 29 (2), p. 19 (Apr. &/*/). Lai, G. A., A<igh-"emperature )orrosion of 4ngineering Alloys,B A#3 International, 3etals 5ar , .< (&//'). !""ain, M. #., AAspects of <ot )orrosion Attac on <igh-"emperature 3aterials,B 5h@ thesis, Mniversity of 3anchester (&/*2)% C. $. %&reman, A"he <igh "emperature )orrosion of 3etals and Alloys in <--containing 4nvironments,B 5h@ thesis, Mniversity of 3anchester (&/*0). Gra'(e, . $., A)arburiGation ? A <igh "emperature )orrosion 5henomenon,B 5ublication Jo 1,, 3aterials "echnology Institute of the )hemical 5rocess Industries, Inc., #t. Douis (&//*). Elliott, P., A3aterials 5erformance in <igh "emperature Iaste )ombustion #ystems,B )aterials +erformance, )) (,), p. *, (&//+). Goe'el, $. A., et al., A3echanism for <ot )orrosion of Jic el :ase Alloys,B )et. ,rans., * (&), p. ,0& (&/9+). Elliott P., and %. $. %a&lor, A#ome Aspects of #ilicon )oatings Mnder 6anadic Attac ,B in A3aterials and )oatings to Cesist <igh "emperature .!idation and )orrosion,B A. Cahmel and @. C. <olmes, eds., Applied #cience 5ublishers, Dondon, p. +1+ (&/9*).

To sum up Ideally, the material choice is based on nown data and e!perience, which implies communication between a user and a supplier. A better nowledge of anticipated component requirements in addition to corrosion behavior provides for a better choice and the e!pectation of more reliable service. 5roper identication and recording of damage from prior systems is a positive benet in deciding upon an alternative alloy or coated system. Iherever possible, and certainly for new and comple! environments, testing is to be recommended. Q
P# E559OTT is president of Corrosion & Materials Consultancy, Inc., Colts 3ec), 3R ::74!; 4"40"-4/D ax* :74!; 4"40 "-1#D S0mail* pelliottTmonmouth.com;. &he company provides professional engineering services, notably in materials utili@ation and corrosion control. C&MC offers a wide range of technical support, including metallurgical, analytical, corrosion testing, and evaluation services. Slliott has 4" yearsU experience as a corrosion and materials engineer, especially in troubleshooting and failure analysis. He is the author of over 1" technical papers dealing with materials performance, high0temperature corrosion, environmental corrosion, ris) assessment, and technology transfer. He is a 36CS International ellow and Corrosion %pecialist, and serves on several 36CS committeesD he also presents a 36CS seminar on high0 temperature corrosion. He is a ellow and past chairman of the Institute of Corrosion, a ellow of the Institute of Materials, a chartered engineer, and a member of 6%M International. He has also presented over #"" lectures to international conferences and professional societies. Slliott holds a B%c in metallurgy, and an M%c and IhE in chemical metallurgy from the Kniversity of Manchester, K.J.

4.

-. ,. 7.

Candidate alloys )hoice should be based on careful considerations, including, primarily, the function of the component or ves-

recommended alloys and alloy types

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Materials

Peter

High temperatures, stresses, and the presence of elements such as oxygen, sulfur, or the halogens can add up to trouble. Here is how to screen candidate alloys for such service.

Elliott, Corrosion & Materials Consultancy, Inc.

M
aterials are selected on the basis of service requirements, notably strength, so corrosion resistance (stability) may not be the primary design consideration. Assemblies need to be strong and resilient to the unique loads and stresses imparted on them, which can include signicant temperature changes and thermal gradients for many high-temperature applications. In ma ing a choice, it is necessary to now what materials are available and to what e!tent they are suited to the specic application. "he decision is quite involved and the choice is signicantly affected by the environment and the intended use, be it a reactor vessel, tubes, supports, shields, springs, or others. #ome problems may occur because of distortion and crac ing caused by thermal e!pansion$contraction% typically, a high-temperature alloy might change 4 in.$ft from ambient to &,'''() (&,*+,(-). "he user or designer needs to properly understand that the environment dictates the materials selection process at all stages of the process or application. -or e!ample, an alloy that performs well at the service temperature may corrode because of aqueous (dew point) corrosion at lower temperatures during off-load periods, or through some lac of design detail or poor maintenance procedures that introduce local air draughts that cool the system (e.g., at access doors, inspection ports, etc.). "o provide as optimum performance as possible, it is necessary for a supplier to be aware of the application, and for the user to be aware of the general range of available materials. .therwise, severe problems can result. -or CEP ebruary !""# www.aiche.org$cep$ 75

Materials

tions to about /''() (&,01'(-) in continuous service, or *21() (&,11'(-) in intermittent (temperature cycling) service (1). "he failure occurred because of overheating with contributions from suldation (hot corrosion). "he true cause of failure was a material mi!-up, because "ype +'2 was not specied, but was inadvertently used.

Mechanical limits of materials In considering traditional alloys, it is important for the designer and user to be fully aware of the mechanical limits of a material. -or e!ample, the A#34 5ressure 6essel )odes advise that the ma!imum allowable stress shall not e!ceed whichever is the lowest of7 (i) &''8 of the average stress to produce a creep rate of '.'&8 in &,''' h% (ii) 098 of the average stress to cause rupture after &'',''' h% and (iii) *'8 of the minimum stress to cause rupture after &'',''' h. "hese recommendations may be better appreciated by e!tracting typical data for "ype +'2 intended for use in a pressure vessel up to *&1() (&,1''(-). :ased upon A#34 tables, for a load of &9 35a (,.1 si) at 90'() (&,2''(-), the e!pected design life would be ,2 yr% at 9**() (&,21'(-), the life falls to 9 yr% and at *&1() (&,1''(-), it is only ,., yr. "hus, a short-term temperature e!cursion can have a signicant effect on equipment life. Also to be noted is that a small increase in loading, for e!ample, from ,.1 to + si at 90'() (&,2''(-), can mar edly reduce the life e!pectancy, here, from ,2 to / yr. .verheating is the most common cause of high-temperature corrosion failure, but the temperature in;uence on mechanical properties is of equal or even more signicance in that many failures occur because of creep deformation (creep voids) and thermal fatigue. .verheating can arise for various reasons, including an une!pected accumulation of tenacious deposits that can foul tubes in a heat e!changer. Hightemperature

alloys and uses <igh-temperature alloys are typically iron-, nic el- or cobalt-based alloys containing =,'8 chromium (or +'8 for cobalt), which is sufficient to form a protective o!ide against further o!idation. "he basic alloys include various additional elements that aid in corrosion resistance, notably aluminum (typically =28 to develop an alumina scale), silicon (up to 18 to develop an amorphous (glass-li e) scale that is complementary to chromia), and rare earth elements (typically >&8, e.g., yttrium, cerium, and lanthanum, that improve scale adhesion). .ther additions, such as the reactive metals, the refractory metals, and carbon, primarily improve mechanical properties. "he benecial and detrimental roles of common alloying elements on the anticipated performance of alloys at high-temperatures is covered by Agarwal and :rill (2). Refractory metals ? 3olybdenum, which is a benecial addition for resisting aqueous chloride-induced pitting corrosion (found in "ypes +&0 and +&9 stainless steels, and the 083o alloys), is prone to catastrophic o!idation as temperatures e!ceed about 9''() (&,,/,(-), the point above which 3o. forms eutectic mi!tures with iron, nic el, and chromium o!ides. "he o!ide 3o. melts at 9/1() (&,20,(-(). )atastrophic o!idation rapidly renders a metal into a useless powdery o!ide. @amage is worse in stagnant conditions and appears to be e!acerbated when sodium o!ide is present (e.g., from insulation). All of the refractory metals (tungsten, tantalum, niobium, and molybdenum) may e!perience catastrophic o!idation. #ilicide coatings have shown some to offer some resistance to this catastrophic (ApestB) o!idation. Coatings ? <igh-temperature coatings or surface modications are generally based on chromium, aluminum, or silicon, which, at high temperatures, form protective o!ides rich in chromia, alumina, or silica, respectively. In more recent years, there have been developments in applying so-called alloy coatings, for e!ample, the use of 3)CADE (metal, chromium, aluminum, and yttrium) on steels or other high-temperature alloy sub+

strates. 4fforts have also continued in weld overlay wor , where a strong base metal can support a corrosionresistant surface-coated layer. Applications ? In considering materials options, a thorough nowledge of the service applications (stress-bearing service% cyclic loading or not% frequency of cycling% impact or erosion effects% thermal e!pansion and contraction) is needed. @ifferent high-temperature corrosion processes are simultaneously involved in many common service applications. #ome of these are synergistic, which creates a formidable challenge for users and alloy producers. #ome e!amples of the forms associated with various applications are given in "able & (3, 4).

Types of hightemperature corrosion "here are certain distinguishing features about the morphology of high-temperature corrosion that aid in deciding upon the cause of damage. #ome typical indications include thic scales, grossly thinned metal, burnt (blac ened) or charred surfaces, molten phases, deposits of various colors, distortion and crac ing, and magnetism in what was rst a nonmagnetic (e.g., austenitic) matri!. @amage varies signicantly based upon the environment, and will be most severe when a materialFs o!idation limits are e!ceeded, notably when an alloy sustains brea away attac by o!ygen$sulfur, halogen$o!ygen, low-melting ;u!ing salts, molten glasses, or molten metals, especially after res. Oxidation 3any industrial processes involve o!idation, i.e., a metal reacts in air to form and sustain a protective o!ide. 7 www.aiche.org$cep$ ebruary !""#
CEP

Ta!le "# Typical process conditio

Process or Components Temperature O %team reforming tubes %team crac)ing tubes* ethylene +inyl chloride crac)ers Hydrocrac)ers* heaters &o #,"""'C &o #,"""'C ,-"'C --".,""'C ( (

Co)e calcining recuperators Cat crac)ing regenerators lare0stac) tips C%! furnace tubes Melamine$urea reactors 2eactors in &i

/#-'C &o /""'C 1-". #,"/"'C /-"'C 4-".-""'C 1""'C

production 3itric acid* catalyst grids 5inings for 6l pyrohydrolysis 3uclear processing reactors H&829 :gas0cooled; reactors <il0=red

14"'C &o #,"""'C 7-"0./""'C 7-".1-"'C /-".1""'C

boilers$superheaters 8as0turbine blades ?aste incinerators luidi@ed0bed combustors 8lass* recuperators Hot0dip galvani@ing

1-">'C 47".-""'C A,""'C #,"1"'C 4--'C

( ( ( (

9 H&82 is high0temperature gas reactor.

"here can be several o!ide products, some of which are less desirable, for e!ample, wustite, a defective o!ide of iron that forms rapidly at about 12'() (&,'''(-) on steel. 3ost high-temperature alloys are o!idation resistant, so price, availability, e!perience, and the type of application usually dictate choice. "here are no signicant problems up to 2''() (91'(-), few up to 91'() (&,+*'(-), but the choice of successful alloys becomes somewhat limited above about *''() (&,29'(-). #imple iron-chromium (or ironchromium-molybdenum) alloys become less useful as service temperatures increase, which is where the "ype +'' series austenitic stainless steels, (+'2, +'/, +&', +&2, ++', +++, etc.) and certain ferritic stainless steels (2&' and 220) nd many applications. -or more arduous service conditions at higher temperatures, these alloys are surpassed by nic elor cobalt-based formulations, including many of the more robust alloys that are mechanically alloyed to im-

prove strength and to control (that is, minimiGe) grain growth at elevated temperatures. )ertain alloys (usually those with rare earth additions) are more resilient to o!idation under thermal cycling (shoc ) conditions. #ome applications do not allow an alloy to fully develop its steady-state condition, thus, performance is dictated by the transient (not-so-protective) surface scales. "ransient effects will become apparent should failure analysis be performed. )aution should be given to ironchromium-nic el alloys that can be prone to sigma-phase formation between 12'H*''() (&,'''H&,29'(-), which results in premature brittle failure. 3olybdenum-containing alloys ("ypes +&0 and +&9 stainless steels and the 08-3o alloys) can be prone to catastrophic o!idation above about 0*'() (&,,10(-).

$ul%dation #ulfurous gases are common to many applications, including fuel

combustion atmospheres, petrochemical processing, gas turbines, and coal gasication. #uldes (e.g., sulfur vapor, hydrogen sulde) can be very damaging, because metal suldes form at faster rates than do metal o!ides. #uldes have low melting points and produce voluminous scales (scale spallation). Iith mi!ed corrodant environments (o!ygen and sulfur), alloy performance is based upon a subtle interplay between o!ide and sulde formation. .!ides are more stable% suldes form more rapidly (due to inetics). "hus, o!ides, suldes, or both may form. If deposits are also present, then conditions at the metal surfaces are reducing compared to areas e!ternal to the deposits. @amage can be e!tensive. 3i!ed sulfur-and-o!ygen gases can invo e very high corrosion rates due to brea away attac , typically above about 0''() (&,&&'(-) for nic elbased alloys, /,'() (&,0**(-) for cobalt-based, and /2'() (&9,2(-) for iron-based formulations. :rea -

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Materials

6bove* &ube failure due to 5eft* local Burst overheating. tube walls

due to overheating.

away attac is commonly associated with sulfur and e!cess air. .nce the rstformed o!ide is lost or destroyed, suldes can invade the chromium-depleted substrate, thus, causing accelerated attac to occur. #tainless steels and iron-based alloys are preferred over high-nic el alloys, because nic el is prone to forming the low-melting nic el-nic el sulde eutectic, Ji-Ji # , which melts at 0+1() (&,&91(-). 4utectics of cobalt and iron occur at higher temperatures, **'() (&,0&0(-) and /*1() (&,*'1(-), respectively. Alloys can be wea ened by internal corrosion, most noticeably when mobile species are present, such as low-melting suldes, which are typied by localiGed dull uniform gray phases within the alloy matri!. At times, liquid-appearing phases are found in the metallurgy. Alloys containing aluminum, silicon, and cobalt are useful in suldiGing environments. 3any alloys classied as candidates for suldation do well only if o!ides are rst able to form. 5reo!idation can be of value.
+ ,

Halogenation <alogen attac is commonly manifested as a combination of scale spallation with internal alloy damage including voids that form as a result of highly volatile species (5). 3aterial performance is dictated by the unique properties of the halides, including high vapor pressures, high volatility (vaporiGation), low melting points, mismatched e!pansion coefficients with metal substrates, and the effects of displacement reactions whereby o!ide or sulde are

thermodynamically favored over the halides. Alloy performance is greatly affected by o!idiGing or reducing conditions. -or o!idiGing atmospheres or for vapors Kointly present with o!ygen (or air), there is an opportunity for reduced corrosion rates ( inetics) associated with o!ide formation, although the scale may later be disrupted by the volatile halides, especially if iron-based alloys are used. Jic el alloys are generally favored for halogen atmospheres, since iron-based alloys are more vulnerable, due to their volatile products, e.g., -e)l . #ilicon additions are useful if o!idiGing environments prevail, but not for reducing conditions. 5reo!idation is not normally a benet for reducing halogen attac . Ihat ma es halogens different from other o!idants is their high mobility and diffusivity into a metal, resulting in internal damage of the alloy matri!. -luorine can penetrate twice the distance of chlorides, which means that the predominant mode of damage in ;uorine-containing gases is by means of internal attac . <alide products are also hygroscopic (3), so it is not unusual to discover local protrusions on a metal that have been removed during service. In laboratory studies, it is common to nd that a surface apparently free from chlorides (removed during metallographic preparation) is later found to show them. "his is because the chlorides have been leached out from deep under the voided areas in the metal.
+

Car!uri&ation #everal environments are synonymous with carburiGation, including pyrolysis and gas-crac ing processes, reforming plants, and heat-treating facilities that involve carbon mono!ide, methane, and hydrocarbon gases. @amage is usually manifested as internal carbides, notably in grain boundaries and is generally worst above &,'1'() (&,/,,(-). Ihen carburiGing conditions alternate with o!idiGing ones, carbides can become o!idiGed to o!ides, which yields carbon mono!ide that can wea en the grain boundaries in an alloy. #uch an alloy fails by Agreen rot,B a name that describes the green fractured surface that results (chromium o!ide). #trongly carburiGing atmospheres (i.e., those that have a carbon activity =&) can cause a metal to form co e-li e layers, often of a dusty form. "his form of attac , termed metal dusting, commonly occurs between 2,1H*''() (9/'H &,29'(-) and can be very rapid (in days not months). @amage is either general or localiGed (pitting), as dictated by the ability of the alloy to form a surface o!ide (6). 7' www.aiche.org$cep$ ebruary !""# CEP

6bove* &hermal fatigue crac) in boiler tube.

)arbon steels and alloy steels are normally uniformly thinned by metal dusting% more highly alloyed materi als usually display local outgrowths of co e emerging through small pits that broaden with time. )ast iron-nic el-chromium alloys are widely used for carburiGing applications, including the more recent alloys containing &H,8 silicon and &.18 niobium (the <5 3od alloys) (4, 6). <igh-nic el alloys (with low solubility for carbon) nd many applications for carburiGing conditions. #tronger nic el-based alloys with high chromium and silicon contents are useful in more demanding environments. <ighly alloyed ferritic stainless steels (that are able to more rapidly form a thin o!ide lm) tend to outperform austenitic steels.

(itriding Celatively little is reported about nitridation other than material performance is wea ened (embrittlement) as a result of the formation of internal nitrides in the alloy (4). It is common to e!pect damage with nitrides at 9''H/''() (&,,/'H&,01'(-). Jitrides appear generally as needle-li e precipitates in the alloy matri!. Jic el- and cobalt-rich alloys appear to be rst-choice candidates for resisting nitride attac , because of the low solubility of nitrogen in these
&op* &ube fouling in an incinerator plant due to carryover of deposits. Bottom* &hrough0metal perforation in tubing from a carbon blac) plant.

base metals. Iron tends to be detrimental, as do aluminum and titanium in low concentrations. #ilicon forms a brittle intermetallic compound with nitrogen and can contribute to scale spallation, especially in applications at low o!ygen concentrations (potentials), where thin o!ides can form, and during thermal cycling.

Molten products @eposits are a common product in many high-temperature applications, including boilers, waste incinerators, ;uidiGed-bed combustors, and gas turbines. A whole series of reactions is possible should deposits become molten and no single mechanism can be applied generally to characteriGe such damage (7). "he mechanisms of molten product corrosion are comple!. "he types of damage include fuel-ash corrosion ? sulfates, including acid and basic ;u!ing reactions (8), and vanadic slag attac ( ) ? molten salt corrosion (chlorides, nitrates, and carbonates) (4), and molten glass corrosion. Diquid metal attac is yet another special category (4). !"el#as$ or as$%salt#&eposit cor rosion stems from high-temperature corrosion processes associated with fuel combustion products in boilers, waste incinerators, and gas turbines. "hus, products can include various deposits (o!idiGing or reducing) with active contributions from o!ygen, sulfur, halogens, carbon, and nitrogen (4, 7). "ypically, alloy matrices display intergranular attac (o!ides and chlorides) beneath disturbed o!ide layers possibly fused with molten deposits and internal suldes within the alloy-affected Gone. 'ot corrosion is generally regarded as attac in the Koint presence of sulfur and o!ygen. "ypically, attac is considered to be triggered by molten al ali metal salts that melt above 9''() (&,,/'(-). #odium sulfate, with a melting point of **2() (&,0,'(-), derived from sodium chloride and sulfur from the fuel, is considered to be closely involved in the mechanism of hot corrosion (8). "his mechanism is considered to have four stages7 o!idation (incubation)% mild suldation% o!ide failure% and catastrophic attac (internal suldes via a porous voluminous comple! o!ide$deposit layer). <ot corrosion is an irreversible autocatalytic process.

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Materials

Ta!le *# +uide to candidate materials#

Corrosion Mode Oxidation ,asic -lloy Types e03i0:Co; A!"C :4"C; Cr. %tabili@ed to minimi@e sensiti@ation. 6l, %i bene=cial. 2are earth additions aid scale retention. Candidates. 4"4, 4!#,4"1, 4#", /"":H&;, /"4, 44", 44,,H2#!", 44", /-H, 444, ,"", ,"#:8C;, ,"!C6, ,#7, ,!-, !-4M6, 4-4M6, E%, !#4, M61-,, M67-4, F, etc. (otes and Cautions ?ide choice dictated by application and functionD Mechanical propertiesD &hermal cycle :shoc);D &ransient vs. steady stateD Internal oxides. Beware GD ?, Mo H catastrophic oxidation. %ulfur vapor, H!%, etc. H no oxides. Beware of 3i$3i4%! eutecticD coatings can help. %<!, %<4 , etc. H ris) of brea)away attac) with oxides and sul=desD 6l coatings. :%ee hot corrosion.; Internal carbides with intergranular attac)D Cast tubes bene=t from smooth I.E. surfaces. Metal dusting :at lower temperatures;. 8reen rot :with intermittent <!0C;. (itridation 3i0alloys rather than e. 6void high Cr levels. Kse low 6l and low &i levels :nitride formers;. %i promotes scale spalling. 3i alloys generally better than e. Bene=ts* Cr :not H ;, 6l, %i :with oxygen;. Ireoxidation not bene=cial. eCrMo alloys at lower temperaturesD C26sL for %, <, C H subMect to application. High Cr, 6l, %i useful :also as coatings;. Molten salts 3i alloys generally favoredD 6s with halogens, sul=dation* Intergranular attac), 4"1, 4#", /"":H&;, ,"", ,"#, ,"!C6, ,!-, /!-, !-4M6, 4-4M6, M67-4, M67-/, M61-,, I3,-7, ,7#, etc. 4"1, /"":H&;, 44", 44,, #//, !4", ,"", ,"!C6, ,!-, !-4M6, etc. Internal nitrides :e.g., 6l3; can wea)en alloyD &hin oxide at low oxygen partial pressure reduces nitridation. /""H, 444, !"", !"#, !"7, ,"", ,"#, ,"!C6, !#4, 3, H!4!, B4, etc. +olatile productsD Internal attac) with voidsD Hygroscopic products :e.g., chlorides;D %cale spallation. 6pplications dictate alloy, or coating* 8as turbines :strong > C26L;D vanadic slag :high0Cr > %i;.

$ul%dation /0educing gases no oxides1

e0 with high Cr :6l; alloys.

1.#!CCr steels* 4"1, 4#", 44", /"":H&;, /"4, H2#!", /-H, !-4M6, 4-4M6, M61-,, 44,, ,7#, ,B, #//, etc.

$ul%dation /Oxidi&ing gases1

e0Cr0based alloys. <xide formation a bene=t. Ireoxidi@ation may help.

6s above with #-4M6, ,"#, H2#,", M67-4, M61-,, 444, --,, etc.

Car!uri&atio n

?ide use of cast alloys. or worse conditions, use high03i alloys with Cr, %i. :5ow solubility of C in 3i is bene=t for 3i alloys.;

HH, HJ, HIMod, 4"1, 4#", 44", 444, /-H, /"":H&;, /"4, E%, H2#,", ,"", ,"#, !-4M6, ,"!C6, ,#7, ,!-, ,1", M67-4, M61-,, F, --,, 7",, 7#/, 7-", etc.

Halogenatio n2 chlorination , 3uorination, etc# 4uel ash corrosion

some high0Cr alloysD 3iCrMo? alloys for molten chlorides. Molten glass 3i0 or some Co0$high0Cr alloysD %ome refractories.

depends on nature of salts :acidic$basic;.

internal voids, and probable embrittlement.

,"", ,"#, ,"!C6, ,7#, ,1", M67-/, etc.

Complex Nuxing reactionsD oxidationD sul=dationD chlorinationD Nuorination, etc. Eissolution or alloying effectsD Intergranular attac)D Eepends on system.

5i6uid metals

e0alloys with Cr, 6l, %i usual =rst choices :subMect to liOuid metal, e.g,. 5iO. 3a, J, molten Pn, Ib, etc.; %ynergy of processes.

4"1, 4#", /-H, !-4M6, etc.

Complex En7ironmen ts

C26sL or coatings

%ee) input from suppliersD Consider online tests$monitoring.

3ote* &his is a general, not exhaustive, guide. 9 3ot in any preferred order. L C26s are corrosion0resistant alloys.

'8

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ebruary !""# CEP

(ana&ic slag corrosion occurs following combustion of certain lowgrade or residual fuel oils that are of high vanadium, sulfur, and al ali metals. "he molten sodium vanadyl vanadates typically ;u! away protective o!ides and then rapidly dissolve the metal. 3any high-temperature alloys cannot survive &'' h at /''() (&,01,(-) in vanadic slags ( ). 6anadic attac can be managed by lowering temperatures (if possible), using fuel-oil additives (such as magnesium and calcium o!ides), or by specifying high-chromium alloys. #ilicon-rich coatings are benecial and appear to complement the role of chromium ( ). )olten glass typically induces intergranular attac with voids (from volatile halides) and suldes. .!ides are generally fused into the glass. Attac is commonly rapid, and high chromium-nic el-based alloys are usually employed. Iron-rich alloys can be prone to severe attac due to their ability to form low-melting halides (e.g., -e)l ). )olten salts, used for heat treating applications, nuclear engineering, solar cells, and metal e!traction, generally promote intergranular attac in alloys, often with voids and internal low-melting products (halides). A common feature in most hightemperature aggressive environments is the synergy of the reactants one with each other ("able &). Iastage can be easily measured, but the mechanism(s) are not as easy to determine. As a minimum, a rigorous study and analysis of the morphologies should help to establish the rate-controlling process, which should help to better dene the type of alloy that could be considered as a candidate. "he broad e!pertise of the material suppliers should be fully e!plored in the quest for a suitable choice. 3onitoring trials using test spools are recommended wherever they can be used.
+

sel. As might be e!pected, there are many candidates, yet, from these the choice is often reduced to one of two, once the total range of properties is fully e!plored. -actors to be considered include mechanical properties (strength, ;e!ibility, fatigue life), physical properties (e!pansion and contraction, re;ectivity, magnetism, etc.), availability (shape and form), and price (economic decision based on overall costs and fabrication, etc.). As a convenience, some generally

for various high-temperature environments are summariGed in "able ,. "his table is intended only as a guide% no order of merit is to be interpreted from the sequence of listings (or omissions) in this table. Also, the alloy lists are not meant to be inclusive, but, rather, merely typical e!amples of what has wor ed in the eld.

5iterature Cited
1. Rothman, M. F., ed., A<igh "emperature 5roperty @ata7 -errous Alloys,B A#3 International, 3etals 5ar , .<, p. /.,0 (&/*/). 2. Agarwal, D. C., and U. Brill, A3aterial @egradation 5roblems in <igh "emperature 4nvironments,B *n&"strial 'eating, p. 10 (.ct. &//2).

/. 1.

Elliott, P., A5ractical Luide to <igh"emperature Alloys,B )aterials +erfor# mance, 29 (2), p. 19 (Apr. &/*/). Lai, G. A., A<igh-"emperature )orrosion of 4ngineering Alloys,B A#3 International, 3etals 5ar , .< (&//'). !""ain, M. #., AAspects of <ot )orrosion Attac on <igh-"emperature 3aterials,B 5h@ thesis, Mniversity of 3anchester (&/*2)% C. $. %&reman, A"he <igh "emperature )orrosion of 3etals and Alloys in <--containing 4nvironments,B 5h@ thesis, Mniversity of 3anchester (&/*0). Gra'(e, . $., A)arburiGation ? A <igh "emperature )orrosion 5henomenon,B 5ublication Jo 1,, 3aterials "echnology Institute of the )hemical 5rocess Industries, Inc., #t. Douis (&//*). Elliott, P., A3aterials 5erformance in <igh "emperature Iaste )ombustion #ystems,B )aterials +erformance, )) (,), p. *, (&//+). Goe'el, $. A., et al., A3echanism for <ot )orrosion of Jic el :ase Alloys,B )et. ,rans., * (&), p. ,0& (&/9+). Elliott P., and %. $. %a&lor, A#ome Aspects of #ilicon )oatings Mnder 6anadic Attac ,B in A3aterials and )oatings to Cesist <igh "emperature .!idation and )orrosion,B A. Cahmel and @. C. <olmes, eds., Applied #cience 5ublishers, Dondon, p. +1+ (&/9*).

To sum up Ideally, the material choice is based on nown data and e!perience, which implies communication between a user and a supplier. A better nowledge of anticipated component requirements in addition to corrosion behavior provides for a better choice and the e!pectation of more reliable service. 5roper identication and recording of damage from prior systems is a positive benet in deciding upon an alternative alloy or coated system. Iherever possible, and certainly for new and comple! environments, testing is to be recommended. Q
P# E559OTT is president of Corrosion & Materials Consultancy, Inc., Colts 3ec), 3R ::74!; 4"40"-4/D ax* :74!; 4"40 "-1#D S0mail* pelliottTmonmouth.com;. &he company provides professional engineering services, notably in materials utili@ation and corrosion control. C&MC offers a wide range of technical support, including metallurgical, analytical, corrosion testing, and evaluation services. Slliott has 4" yearsU experience as a corrosion and materials engineer, especially in troubleshooting and failure analysis. He is the author of over 1" technical papers dealing with materials performance, high0temperature corrosion, environmental corrosion, ris) assessment, and technology transfer. He is a 36CS International ellow and Corrosion %pecialist, and serves on several 36CS committeesD he also presents a 36CS seminar on high0 temperature corrosion. He is a ellow and past chairman of the Institute of Corrosion, a ellow of the Institute of Materials, a chartered engineer, and a member of 6%M International. He has also presented over #"" lectures to international conferences and professional societies. Slliott holds a B%c in metallurgy, and an M%c and IhE in chemical metallurgy from the Kniversity of Manchester, K.J.

#".

##.

#!. #4. #4.

Candidate alloys )hoice should be based on careful considerations, including, primarily, the function of the component or ves-

recommended alloys and alloy types

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Materials

Peter

High temperatures, stresses, and the presence of elements such as oxygen, sulfur, or the halogens can add up to trouble. Here is how to screen candidate alloys for such service.

Elliott, Corrosion & Materials Consultancy, Inc.

M
aterials are selected on the basis of service requirements, notably strength, so corrosion resistance (stability) may not be the primary design consideration. Assemblies need to be strong and resilient to the unique loads and stresses imparted on them, which can include signicant temperature changes and thermal gradients for many high-temperature applications. In ma ing a choice, it is necessary to now what materials are available and to what e!tent they are suited to the specic application. "he decision is quite involved and the choice is signicantly affected by the environment and the intended use, be it a reactor vessel, tubes, supports, shields, springs, or others. #ome problems may occur because of distortion and crac ing caused by thermal e!pansion$contraction% typically, a high-temperature alloy might change 4 in.$ft from ambient to &,'''() (&,*+,(-). "he user or designer needs to properly understand that the environment dictates the materials selection process at all stages of the process or application. -or e!ample, an alloy that performs well at the service temperature may corrode because of aqueous (dew point) corrosion at lower temperatures during off-load periods, or through some lac of design detail or poor maintenance procedures that introduce local air draughts that cool the system (e.g., at access doors, inspection ports, etc.). "o provide as optimum performance as possible, it is necessary for a supplier to be aware of the application, and for the user to be aware of the general range of available materials. .therwise, severe problems can result. -or CEP ebruary !""# www.aiche.org$cep$ 75

Materials

tions to about /''() (&,01'(-) in continuous service, or *21() (&,11'(-) in intermittent (temperature cycling) service (1). "he failure occurred because of overheating with contributions from suldation (hot corrosion). "he true cause of failure was a material mi!-up, because "ype +'2 was not specied, but was inadvertently used.

Mechanical limits of materials In considering traditional alloys, it is important for the designer and user to be fully aware of the mechanical limits of a material. -or e!ample, the A#34 5ressure 6essel )odes advise that the ma!imum allowable stress shall not e!ceed whichever is the lowest of7 (i) &''8 of the average stress to produce a creep rate of '.'&8 in &,''' h% (ii) 098 of the average stress to cause rupture after &'',''' h% and (iii) *'8 of the minimum stress to cause rupture after &'',''' h. "hese recommendations may be better appreciated by e!tracting typical data for "ype +'2 intended for use in a pressure vessel up to *&1() (&,1''(-). :ased upon A#34 tables, for a load of &9 35a (,.1 si) at 90'() (&,2''(-), the e!pected design life would be ,2 yr% at 9**() (&,21'(-), the life falls to 9 yr% and at *&1() (&,1''(-), it is only ,., yr. "hus, a short-term temperature e!cursion can have a signicant effect on equipment life. Also to be noted is that a small increase in loading, for e!ample, from ,.1 to + si at 90'() (&,2''(-), can mar edly reduce the life e!pectancy, here, from ,2 to / yr. .verheating is the most common cause of high-temperature corrosion failure, but the temperature in;uence on mechanical properties is of equal or even more signicance in that many failures occur because of creep deformation (creep voids) and thermal fatigue. .verheating can arise for various reasons, including an une!pected accumulation of tenacious deposits that can foul tubes in a heat e!changer. Hightemperature

alloys and uses <igh-temperature alloys are typically iron-, nic el- or cobalt-based alloys containing =,'8 chromium (or +'8 for cobalt), which is sufficient to form a protective o!ide against further o!idation. "he basic alloys include various additional elements that aid in corrosion resistance, notably aluminum (typically =28 to develop an alumina scale), silicon (up to 18 to develop an amorphous (glass-li e) scale that is complementary to chromia), and rare earth elements (typically >&8, e.g., yttrium, cerium, and lanthanum, that improve scale adhesion). .ther additions, such as the reactive metals, the refractory metals, and carbon, primarily improve mechanical properties. "he benecial and detrimental roles of common alloying elements on the anticipated performance of alloys at high-temperatures is covered by Agarwal and :rill (2). Refractory metals ? 3olybdenum, which is a benecial addition for resisting aqueous chloride-induced pitting corrosion (found in "ypes +&0 and +&9 stainless steels, and the 083o alloys), is prone to catastrophic o!idation as temperatures e!ceed about 9''() (&,,/,(-), the point above which 3o. forms eutectic mi!tures with iron, nic el, and chromium o!ides. "he o!ide 3o. melts at 9/1() (&,20,(-(). )atastrophic o!idation rapidly renders a metal into a useless powdery o!ide. @amage is worse in stagnant conditions and appears to be e!acerbated when sodium o!ide is present (e.g., from insulation). All of the refractory metals (tungsten, tantalum, niobium, and molybdenum) may e!perience catastrophic o!idation. #ilicide coatings have shown some to offer some resistance to this catastrophic (ApestB) o!idation. Coatings ? <igh-temperature coatings or surface modications are generally based on chromium, aluminum, or silicon, which, at high temperatures, form protective o!ides rich in chromia, alumina, or silica, respectively. In more recent years, there have been developments in applying so-called alloy coatings, for e!ample, the use of 3)CADE (metal, chromium, aluminum, and yttrium) on steels or other high-temperature alloy sub+

strates. 4fforts have also continued in weld overlay wor , where a strong base metal can support a corrosionresistant surface-coated layer. Applications ? In considering materials options, a thorough nowledge of the service applications (stress-bearing service% cyclic loading or not% frequency of cycling% impact or erosion effects% thermal e!pansion and contraction) is needed. @ifferent high-temperature corrosion processes are simultaneously involved in many common service applications. #ome of these are synergistic, which creates a formidable challenge for users and alloy producers. #ome e!amples of the forms associated with various applications are given in "able & (3, 4).

Types of hightemperature corrosion "here are certain distinguishing features about the morphology of high-temperature corrosion that aid in deciding upon the cause of damage. #ome typical indications include thic scales, grossly thinned metal, burnt (blac ened) or charred surfaces, molten phases, deposits of various colors, distortion and crac ing, and magnetism in what was rst a nonmagnetic (e.g., austenitic) matri!. @amage varies signicantly based upon the environment, and will be most severe when a materialFs o!idation limits are e!ceeded, notably when an alloy sustains brea away attac by o!ygen$sulfur, halogen$o!ygen, low-melting ;u!ing salts, molten glasses, or molten metals, especially after res. Oxidation 3any industrial processes involve o!idation, i.e., a metal reacts in air to form and sustain a protective o!ide. 7 www.aiche.org$cep$ ebruary !""#
CEP

Ta!le "# Typical process conditio

Process or Components Temperature O %team reforming tubes %team crac)ing tubes* ethylene +inyl chloride crac)ers Hydrocrac)ers* heaters &o #,"""'C &o #,"""'C ,-"'C --".,""'C ( (

Co)e calcining recuperators Cat crac)ing regenerators lare0stac) tips C%! furnace tubes Melamine$urea reactors 2eactors in &i

/#-'C &o /""'C 1-". #,"/"'C /-"'C 4-".-""'C 1""'C

production 3itric acid* catalyst grids 5inings for 6l pyrohydrolysis 3uclear processing reactors H&829 :gas0cooled; reactors <il0=red

14"'C &o #,"""'C 7-"0./""'C 7-".1-"'C /-".1""'C

boilers$superheaters 8as0turbine blades ?aste incinerators luidi@ed0bed combustors 8lass* recuperators Hot0dip galvani@ing

1-">'C 47".-""'C A,""'C #,"1"'C 4--'C

( ( ( (

9 H&82 is high0temperature gas reactor.

"here can be several o!ide products, some of which are less desirable, for e!ample, wustite, a defective o!ide of iron that forms rapidly at about 12'() (&,'''(-) on steel. 3ost high-temperature alloys are o!idation resistant, so price, availability, e!perience, and the type of application usually dictate choice. "here are no signicant problems up to 2''() (91'(-), few up to 91'() (&,+*'(-), but the choice of successful alloys becomes somewhat limited above about *''() (&,29'(-). #imple iron-chromium (or ironchromium-molybdenum) alloys become less useful as service temperatures increase, which is where the "ype +'' series austenitic stainless steels, (+'2, +'/, +&', +&2, ++', +++, etc.) and certain ferritic stainless steels (2&' and 220) nd many applications. -or more arduous service conditions at higher temperatures, these alloys are surpassed by nic elor cobalt-based formulations, including many of the more robust alloys that are mechanically alloyed to im-

prove strength and to control (that is, minimiGe) grain growth at elevated temperatures. )ertain alloys (usually those with rare earth additions) are more resilient to o!idation under thermal cycling (shoc ) conditions. #ome applications do not allow an alloy to fully develop its steady-state condition, thus, performance is dictated by the transient (not-so-protective) surface scales. "ransient effects will become apparent should failure analysis be performed. )aution should be given to ironchromium-nic el alloys that can be prone to sigma-phase formation between 12'H*''() (&,'''H&,29'(-), which results in premature brittle failure. 3olybdenum-containing alloys ("ypes +&0 and +&9 stainless steels and the 08-3o alloys) can be prone to catastrophic o!idation above about 0*'() (&,,10(-).

$ul%dation #ulfurous gases are common to many applications, including fuel

combustion atmospheres, petrochemical processing, gas turbines, and coal gasication. #uldes (e.g., sulfur vapor, hydrogen sulde) can be very damaging, because metal suldes form at faster rates than do metal o!ides. #uldes have low melting points and produce voluminous scales (scale spallation). Iith mi!ed corrodant environments (o!ygen and sulfur), alloy performance is based upon a subtle interplay between o!ide and sulde formation. .!ides are more stable% suldes form more rapidly (due to inetics). "hus, o!ides, suldes, or both may form. If deposits are also present, then conditions at the metal surfaces are reducing compared to areas e!ternal to the deposits. @amage can be e!tensive. 3i!ed sulfur-and-o!ygen gases can invo e very high corrosion rates due to brea away attac , typically above about 0''() (&,&&'(-) for nic elbased alloys, /,'() (&,0**(-) for cobalt-based, and /2'() (&9,2(-) for iron-based formulations. :rea -

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Materials

6bove* &ube failure due to 5eft* local Burst overheating. tube walls

due to overheating.

away attac is commonly associated with sulfur and e!cess air. .nce the rstformed o!ide is lost or destroyed, suldes can invade the chromium-depleted substrate, thus, causing accelerated attac to occur. #tainless steels and iron-based alloys are preferred over high-nic el alloys, because nic el is prone to forming the low-melting nic el-nic el sulde eutectic, Ji-Ji # , which melts at 0+1() (&,&91(-). 4utectics of cobalt and iron occur at higher temperatures, **'() (&,0&0(-) and /*1() (&,*'1(-), respectively. Alloys can be wea ened by internal corrosion, most noticeably when mobile species are present, such as low-melting suldes, which are typied by localiGed dull uniform gray phases within the alloy matri!. At times, liquid-appearing phases are found in the metallurgy. Alloys containing aluminum, silicon, and cobalt are useful in suldiGing environments. 3any alloys classied as candidates for suldation do well only if o!ides are rst able to form. 5reo!idation can be of value.
+ ,

Halogenation <alogen attac is commonly manifested as a combination of scale spallation with internal alloy damage including voids that form as a result of highly volatile species (5). 3aterial performance is dictated by the unique properties of the halides, including high vapor pressures, high volatility (vaporiGation), low melting points, mismatched e!pansion coefficients with metal substrates, and the effects of displacement reactions whereby o!ide or sulde are

thermodynamically favored over the halides. Alloy performance is greatly affected by o!idiGing or reducing conditions. -or o!idiGing atmospheres or for vapors Kointly present with o!ygen (or air), there is an opportunity for reduced corrosion rates ( inetics) associated with o!ide formation, although the scale may later be disrupted by the volatile halides, especially if iron-based alloys are used. Jic el alloys are generally favored for halogen atmospheres, since iron-based alloys are more vulnerable, due to their volatile products, e.g., -e)l . #ilicon additions are useful if o!idiGing environments prevail, but not for reducing conditions. 5reo!idation is not normally a benet for reducing halogen attac . Ihat ma es halogens different from other o!idants is their high mobility and diffusivity into a metal, resulting in internal damage of the alloy matri!. -luorine can penetrate twice the distance of chlorides, which means that the predominant mode of damage in ;uorine-containing gases is by means of internal attac . <alide products are also hygroscopic (3), so it is not unusual to discover local protrusions on a metal that have been removed during service. In laboratory studies, it is common to nd that a surface apparently free from chlorides (removed during metallographic preparation) is later found to show them. "his is because the chlorides have been leached out from deep under the voided areas in the metal.
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Car!uri&ation #everal environments are synonymous with carburiGation, including pyrolysis and gas-crac ing processes, reforming plants, and heat-treating facilities that involve carbon mono!ide, methane, and hydrocarbon gases. @amage is usually manifested as internal carbides, notably in grain boundaries and is generally worst above &,'1'() (&,/,,(-). Ihen carburiGing conditions alternate with o!idiGing ones, carbides can become o!idiGed to o!ides, which yields carbon mono!ide that can wea en the grain boundaries in an alloy. #uch an alloy fails by Agreen rot,B a name that describes the green fractured surface that results (chromium o!ide). #trongly carburiGing atmospheres (i.e., those that have a carbon activity =&) can cause a metal to form co e-li e layers, often of a dusty form. "his form of attac , termed metal dusting, commonly occurs between 2,1H*''() (9/'H &,29'(-) and can be very rapid (in days not months). @amage is either general or localiGed (pitting), as dictated by the ability of the alloy to form a surface o!ide (6). 7' www.aiche.org$cep$ ebruary !""# CEP

6bove* &hermal fatigue crac) in boiler tube.

)arbon steels and alloy steels are normally uniformly thinned by metal dusting% more highly alloyed materi als usually display local outgrowths of co e emerging through small pits that broaden with time. )ast iron-nic el-chromium alloys are widely used for carburiGing applications, including the more recent alloys containing &H,8 silicon and &.18 niobium (the <5 3od alloys) (4, 6). <igh-nic el alloys (with low solubility for carbon) nd many applications for carburiGing conditions. #tronger nic el-based alloys with high chromium and silicon contents are useful in more demanding environments. <ighly alloyed ferritic stainless steels (that are able to more rapidly form a thin o!ide lm) tend to outperform austenitic steels.

(itriding Celatively little is reported about nitridation other than material performance is wea ened (embrittlement) as a result of the formation of internal nitrides in the alloy (4). It is common to e!pect damage with nitrides at 9''H/''() (&,,/'H&,01'(-). Jitrides appear generally as needle-li e precipitates in the alloy matri!. Jic el- and cobalt-rich alloys appear to be rst-choice candidates for resisting nitride attac , because of the low solubility of nitrogen in these
&op* &ube fouling in an incinerator plant due to carryover of deposits. Bottom* &hrough0metal perforation in tubing from a carbon blac) plant.

base metals. Iron tends to be detrimental, as do aluminum and titanium in low concentrations. #ilicon forms a brittle intermetallic compound with nitrogen and can contribute to scale spallation, especially in applications at low o!ygen concentrations (potentials), where thin o!ides can form, and during thermal cycling.

Molten products @eposits are a common product in many high-temperature applications, including boilers, waste incinerators, ;uidiGed-bed combustors, and gas turbines. A whole series of reactions is possible should deposits become molten and no single mechanism can be applied generally to characteriGe such damage (7). "he mechanisms of molten product corrosion are comple!. "he types of damage include fuel-ash corrosion ? sulfates, including acid and basic ;u!ing reactions (8), and vanadic slag attac ( ) ? molten salt corrosion (chlorides, nitrates, and carbonates) (4), and molten glass corrosion. Diquid metal attac is yet another special category (4). !"el#as$ or as$%salt#&eposit cor rosion stems from high-temperature corrosion processes associated with fuel combustion products in boilers, waste incinerators, and gas turbines. "hus, products can include various deposits (o!idiGing or reducing) with active contributions from o!ygen, sulfur, halogens, carbon, and nitrogen (4, 7). "ypically, alloy matrices display intergranular attac (o!ides and chlorides) beneath disturbed o!ide layers possibly fused with molten deposits and internal suldes within the alloy-affected Gone. 'ot corrosion is generally regarded as attac in the Koint presence of sulfur and o!ygen. "ypically, attac is considered to be triggered by molten al ali metal salts that melt above 9''() (&,,/'(-). #odium sulfate, with a melting point of **2() (&,0,'(-), derived from sodium chloride and sulfur from the fuel, is considered to be closely involved in the mechanism of hot corrosion (8). "his mechanism is considered to have four stages7 o!idation (incubation)% mild suldation% o!ide failure% and catastrophic attac (internal suldes via a porous voluminous comple! o!ide$deposit layer). <ot corrosion is an irreversible autocatalytic process.

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Materials

Ta!le *# +uide to candidate materials#

Corrosion Mode Oxidation ,asic -lloy Types e03i0:Co; A!"C :4"C; Cr. %tabili@ed to minimi@e sensiti@ation. 6l, %i bene=cial. 2are earth additions aid scale retention. Candidates. 4"4, 4!#,4"1, 4#", /"":H&;, /"4, 44", 44,,H2#!", 44", /-H, 444, ,"", ,"#:8C;, ,"!C6, ,#7, ,!-, !-4M6, 4-4M6, E%, !#4, M61-,, M67-4, F, etc. (otes and Cautions ?ide choice dictated by application and functionD Mechanical propertiesD &hermal cycle :shoc);D &ransient vs. steady stateD Internal oxides. Beware GD ?, Mo H catastrophic oxidation. %ulfur vapor, H!%, etc. H no oxides. Beware of 3i$3i4%! eutecticD coatings can help. %<!, %<4 , etc. H ris) of brea)away attac) with oxides and sul=desD 6l coatings. :%ee hot corrosion.; Internal carbides with intergranular attac)D Cast tubes bene=t from smooth I.E. surfaces. Metal dusting :at lower temperatures;. 8reen rot :with intermittent <!0C;. (itridation 3i0alloys rather than e. 6void high Cr levels. Kse low 6l and low &i levels :nitride formers;. %i promotes scale spalling. 3i alloys generally better than e. Bene=ts* Cr :not H ;, 6l, %i :with oxygen;. Ireoxidation not bene=cial. eCrMo alloys at lower temperaturesD C26sL for %, <, C H subMect to application. High Cr, 6l, %i useful :also as coatings;. Molten salts 3i alloys generally favoredD 6s with halogens, sul=dation* Intergranular attac), 4"1, 4#", /"":H&;, ,"", ,"#, ,"!C6, ,!-, /!-, !-4M6, 4-4M6, M67-4, M67-/, M61-,, I3,-7, ,7#, etc. 4"1, /"":H&;, 44", 44,, #//, !4", ,"", ,"!C6, ,!-, !-4M6, etc. Internal nitrides :e.g., 6l3; can wea)en alloyD &hin oxide at low oxygen partial pressure reduces nitridation. /""H, 444, !"", !"#, !"7, ,"", ,"#, ,"!C6, !#4, 3, H!4!, B4, etc. +olatile productsD Internal attac) with voidsD Hygroscopic products :e.g., chlorides;D %cale spallation. 6pplications dictate alloy, or coating* 8as turbines :strong > C26L;D vanadic slag :high0Cr > %i;.

$ul%dation /0educing gases no oxides1

e0 with high Cr :6l; alloys.

1.#!CCr steels* 4"1, 4#", 44", /"":H&;, /"4, H2#!", /-H, !-4M6, 4-4M6, M61-,, 44,, ,7#, ,B, #//, etc.

$ul%dation /Oxidi&ing gases1

e0Cr0based alloys. <xide formation a bene=t. Ireoxidi@ation may help.

6s above with #-4M6, ,"#, H2#,", M67-4, M61-,, 444, --,, etc.

Car!uri&atio n

?ide use of cast alloys. or worse conditions, use high03i alloys with Cr, %i. :5ow solubility of C in 3i is bene=t for 3i alloys.;

HH, HJ, HIMod, 4"1, 4#", 44", 444, /-H, /"":H&;, /"4, E%, H2#,", ,"", ,"#, !-4M6, ,"!C6, ,#7, ,!-, ,1", M67-4, M61-,, F, --,, 7",, 7#/, 7-", etc.

Halogenatio n2 chlorination , 3uorination, etc# 4uel ash corrosion

some high0Cr alloysD 3iCrMo? alloys for molten chlorides. Molten glass 3i0 or some Co0$high0Cr alloysD %ome refractories.

depends on nature of salts :acidic$basic;.

internal voids, and probable embrittlement.

,"", ,"#, ,"!C6, ,7#, ,1", M67-/, etc.

Complex Nuxing reactionsD oxidationD sul=dationD chlorinationD Nuorination, etc. Eissolution or alloying effectsD Intergranular attac)D Eepends on system.

5i6uid metals

e0alloys with Cr, 6l, %i usual =rst choices :subMect to liOuid metal, e.g,. 5iO. 3a, J, molten Pn, Ib, etc.; %ynergy of processes.

4"1, 4#", /-H, !-4M6, etc.

Complex En7ironmen ts

C26sL or coatings

%ee) input from suppliersD Consider online tests$monitoring.

3ote* &his is a general, not exhaustive, guide. 9 3ot in any preferred order. L C26s are corrosion0resistant alloys.

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(ana&ic slag corrosion occurs following combustion of certain lowgrade or residual fuel oils that are of high vanadium, sulfur, and al ali metals. "he molten sodium vanadyl vanadates typically ;u! away protective o!ides and then rapidly dissolve the metal. 3any high-temperature alloys cannot survive &'' h at /''() (&,01,(-) in vanadic slags ( ). 6anadic attac can be managed by lowering temperatures (if possible), using fuel-oil additives (such as magnesium and calcium o!ides), or by specifying high-chromium alloys. #ilicon-rich coatings are benecial and appear to complement the role of chromium ( ). )olten glass typically induces intergranular attac with voids (from volatile halides) and suldes. .!ides are generally fused into the glass. Attac is commonly rapid, and high chromium-nic el-based alloys are usually employed. Iron-rich alloys can be prone to severe attac due to their ability to form low-melting halides (e.g., -e)l ). )olten salts, used for heat treating applications, nuclear engineering, solar cells, and metal e!traction, generally promote intergranular attac in alloys, often with voids and internal low-melting products (halides). A common feature in most hightemperature aggressive environments is the synergy of the reactants one with each other ("able &). Iastage can be easily measured, but the mechanism(s) are not as easy to determine. As a minimum, a rigorous study and analysis of the morphologies should help to establish the rate-controlling process, which should help to better dene the type of alloy that could be considered as a candidate. "he broad e!pertise of the material suppliers should be fully e!plored in the quest for a suitable choice. 3onitoring trials using test spools are recommended wherever they can be used.
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sel. As might be e!pected, there are many candidates, yet, from these the choice is often reduced to one of two, once the total range of properties is fully e!plored. -actors to be considered include mechanical properties (strength, ;e!ibility, fatigue life), physical properties (e!pansion and contraction, re;ectivity, magnetism, etc.), availability (shape and form), and price (economic decision based on overall costs and fabrication, etc.). As a convenience, some generally

for various high-temperature environments are summariGed in "able ,. "his table is intended only as a guide% no order of merit is to be interpreted from the sequence of listings (or omissions) in this table. Also, the alloy lists are not meant to be inclusive, but, rather, merely typical e!amples of what has wor ed in the eld.

5iterature Cited
1. Rothman, M. F., ed., A<igh "emperature 5roperty @ata7 -errous Alloys,B A#3 International, 3etals 5ar , .<, p. /.,0 (&/*/). 2. Agarwal, D. C., and U. Brill, A3aterial @egradation 5roblems in <igh "emperature 4nvironments,B *n&"strial 'eating, p. 10 (.ct. &//2).

#-. #,. #7.

Elliott, P., A5ractical Luide to <igh-"emperature Alloys,B )aterials +erformance, 29 (2), p. 19 (Apr. &/*/). Lai, G. A., A<igh-"emperature )orrosion of 4ngineering Alloys,B A#3 International, 3etals 5ar , .< (&//'). !""ain, M. #., AAspects of <ot )orrosion Attac on <igh-"emperature 3aterials,B 5h@ thesis, Mniversity of 3anchester (&/*2)% C. $. %&reman, A"he <igh "emperature )orrosion of 3etals and Alloys in <--containing 4nvironments,B 5h@ thesis, Mniversity of 3anchester (&/*0). Gra'(e, . $., A)arburiGation ? A <igh "emperature )orrosion 5henomenon,B 5ublication Jo 1,, 3aterials "echnology Institute of the )hemical 5rocess Industries, Inc., #t. Douis (&//*). Elliott, P., A3aterials 5erformance in <igh "emperature Iaste )ombustion #ystems,B )aterials +erformance, )) (,), p. *, (&//+). Goe'el, $. A., et al., A3echanism for <ot )orrosion of Jic el :ase Alloys,B )et. ,rans., * (&), p. ,0& (&/9+). Elliott P., and %. $. %a&lor, A#ome Aspects of #ilicon )oatings Mnder 6anadic Attac ,B in A3aterials and )oatings to Cesist <igh "emperature .!idation and )orrosion,B A. Cahmel and @. C. <olmes, eds., Applied #cience 5ublishers, Dondon, p. +1+ (&/9*).

To sum up Ideally, the material choice is based on nown data and e!perience, which implies communication between a user and a supplier. A better nowledge of anticipated component requirements in addition to corrosion behavior provides for a better choice and the e!pectation of more reliable service. 5roper identication and recording of damage from prior systems is a positive benet in deciding upon an alternative alloy or coated system. Iherever possible, and certainly for new and comple! environments, testing is to be recommended. Q
P# E559OTT is president of Corrosion & Materials Consultancy, Inc., Colts 3ec), 3R ::74!; 4"40"-4/D ax* :74!; 4"40 "-1#D S0mail* pelliottTmonmouth.com;. &he company provides professional engineering services, notably in materials utili@ation and corrosion control. C&MC offers a wide range of technical support, including metallurgical, analytical, corrosion testing, and evaluation services. Slliott has 4" yearsU experience as a corrosion and materials engineer, especially in troubleshooting and failure analysis. He is the author of over 1" technical papers dealing with materials performance, high0temperature corrosion, environmental corrosion, ris) assessment, and technology transfer. He is a 36CS International ellow and Corrosion %pecialist, and serves on several 36CS committeesD he also presents a 36CS seminar on high0 temperature corrosion. He is a ellow and past chairman of the Institute of Corrosion, a ellow of the Institute of Materials, a chartered engineer, and a member of 6%M International. He has also presented over #"" lectures to international conferences and professional societies. Slliott holds a B%c in metallurgy, and an M%c and IhE in chemical metallurgy from the Kniversity of Manchester, K.J.

#/.

#1. !". !#.

Candidate alloys )hoice should be based on careful considerations, including, primarily, the function of the component or ves-

recommended alloys and alloy types

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