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High temperatures,
stresses, and aterials are selected on the basis of service requirements, no-
tably strength, so corrosion resistance (stability) may not be
the presence of the primary design consideration. Assemblies need to be strong
elements such as and resilient to the unique loads and stresses imparted on them,
which can include significant temperature changes and thermal gradients for
oxygen, sulfur, or many high-temperature applications.
the halogens can In making a choice, it is necessary to know what materials are available
and to what extent they are suited to the specific application. The decision is
add up to trouble. quite involved and the choice is significantly affected by the environment
and the intended use, be it a reactor vessel, tubes, supports, shields, springs,
Here is how to or others. Some problems may occur because of distortion and cracking
screen candidate caused by thermal expansion/contraction; typically, a high-temperature alloy
might change 4 in./ft from ambient to 1,000°C (1,832°F).
alloys for such The user or designer needs to properly understand that the environment
service. dictates the materials selection process at all stages of the process or applica-
tion. For example, an alloy that performs well at the service temperature may
corrode because of aqueous (dew point) corrosion at lower temperatures dur-
< Discuss This Article! > ing off-load periods, or through some lack of design detail or poor mainte-
nance procedures that introduce local air draughts that cool the system (e.g.,
To join an online discussion about this article
with the author and other readers, go to the
at access doors, inspection ports, etc.).
ProcessCity Discussion Room for CEP articles To provide as optimum performance as possible, it is necessary for a sup-
at www.processcity.com/cep. plier to be aware of the application, and for the user to be aware of the gen-
eral range of available materials. Otherwise, severe problems can result. For
Based on a paper presented at CORROSION/2000 (NACE example, a catastrophic failure occurred within weeks for an ignitor, made
International 55th Annual Conference and Exhibition), Mar.
26–31, 2000, Orlando, FL, USA. © NACE International.
with Type 304 stainless steel (UNS S30400, iron, 19% Cr, 9% Ni, 0.08% C).
All rights reserved. Type 304 stainless steel would have been suitable for clean oxidizing condi-
tions to about 900°C (1,650°F) in High-temperature rich in chromia, alumina, or silica, re-
continuous service, or 845°C alloys and uses spectively. In more recent years, there
(1,550°F) in intermittent (temperature High-temperature alloys are typi- have been developments in applying
cycling) service (1). The failure oc- cally iron-, nickel- or cobalt-based al- so-called alloy coatings, for example,
curred because of overheating with loys containing >20% chromium (or the use of MCRALY (metal, chromi-
contributions from sulfidation (hot 30% for cobalt), which is sufficient to um, aluminum, and yttrium) on steels
corrosion). The true cause of failure form a protective oxide against fur- or other high-temperature alloy sub-
was a material mix-up, because Type ther oxidation. The basic alloys in- strates. Efforts have also continued in
304 was not specified, but was inad- clude various additional elements that weld overlay work, where a strong
vertently used. aid in corrosion resistance, notably base metal can support a corrosion-
aluminum (typically >4% to develop resistant surface-coated layer.
Mechanical limits of materials an alumina scale), silicon (up to 5% Applications — In considering
In considering traditional alloys, it to develop an amorphous (glass-like) materials options, a thorough knowl-
is important for the designer and user scale that is complementary to chro- edge of the service applications
to be fully aware of the mechanical mia), and rare earth elements (typi- (stress-bearing service; cyclic loading
limits of a material. For example, the cally <1%, e.g., yttrium, cerium, and or not; frequency of cycling; impact
ASME Pressure Vessel Codes advise lanthanum, that improve scale adhe- or erosion effects; thermal expansion
that the maximum allowable stress sion). Other additions, such as the re- and contraction) is needed.
shall not exceed whichever is the active metals, the refractory metals, Different high-temperature corro-
lowest of: (i) 100% of the average and carbon, primarily improve me- sion processes are simultaneously in-
stress to produce a creep rate of chanical properties. The beneficial volved in many common service ap-
0.01% in 1,000 h; (ii) 67% of the av- and detrimental roles of common al- plications. Some of these are syner-
erage stress to cause rupture after loying elements on the anticipated gistic, which creates a formidable
100,000 h; and (iii) 80% of the mini- performance of alloys at high-temper- challenge for users and alloy produc-
mum stress to cause rupture after atures is covered by Agarwal and ers. Some examples of the forms as-
100,000 h. Brill (2). sociated with various applications are
These recommendations may be Refractory metals — Molybde- given in Table 1 (3, 4).
better appreciated by extracting typi- num, which is a beneficial addition
cal data for Type 304 intended for use for resisting aqueous chloride-in- Types of high-temperature
in a pressure vessel up to 815°C duced pitting corrosion (found in corrosion
(1,500°F). Based upon ASME tables, Types 316 and 317 stainless steels, There are certain distinguishing
for a load of 17 MPa (2.5 ksi) at and the 6%-Mo alloys), is prone to features about the morphology of
760°C (1,400°F), the expected design catastrophic oxidation as tempera- high-temperature corrosion that aid in
life would be 24 yr; at 788°C tures exceed about 700°C (1,292°F), deciding upon the cause of damage.
(1,450°F), the life falls to 7 yr; and at the point above which MoO3 forms Some typical indications include
815°C (1,500°F), it is only 2.2 yr. eutectic mixtures with iron, nickel, thick scales, grossly thinned metal,
Thus, a short-term temperature excur- and chromium oxides. The oxide burnt (blackened) or charred surfaces,
sion can have a significant effect on MoO3 melts at 795°C (1,462°F°). molten phases, deposits of various
equipment life. Also to be noted is Catastrophic oxidation rapidly ren- colors, distortion and cracking, and
that a small increase in loading, for ders a metal into a useless powdery magnetism in what was first a non-
example, from 2.5 to 3 ksi at 760°C oxide. Damage is worse in stagnant magnetic (e.g., austenitic) matrix.
(1,400°F), can markedly reduce the conditions and appears to be exacer- Damage varies significantly based
life expectancy, here, from 24 to 9 yr. bated when sodium oxide is present upon the environment, and will be
Overheating is the most common (e.g., from insulation). All of the re- most severe when a material’s oxida-
cause of high-temperature corrosion fractory metals (tungsten, tantalum, tion limits are exceeded, notably
failure, but the temperature influence niobium, and molybdenum) may ex- when an alloy sustains breakaway at-
on mechanical properties is of equal perience catastrophic oxidation. Sili- tack by oxygen/sulfur, halogen/oxy-
or even more significance in that cide coatings have shown some to gen, low-melting fluxing salts, molten
many failures occur because of creep offer some resistance to this catas- glasses, or molten metals, especially
deformation (creep voids) and ther- trophic (“pest”) oxidation. after fires.
mal fatigue. Overheating can arise for Coatings — High-temperature
various reasons, including an unex- coatings or surface modifications are Oxidation
pected accumulation of tenacious de- generally based on chromium, alu- Many industrial processes involve
posits that can foul tubes in a heat minum, or silicon, which, at high oxidation, i.e., a metal reacts in air to
exchanger. temperatures, form protective oxides form and sustain a protective oxide.
There can be several oxide products, prove strength and to control (that is, combustion atmospheres, petrochemi-
some of which are less desirable, for minimize) grain growth at elevated cal processing, gas turbines, and coal
example, wustite, a defective oxide of temperatures. gasification. Sulfides (e.g., sulfur
iron that forms rapidly at about Certain alloys (usually those with vapor, hydrogen sulfide) can be very
540°C (1,000°F) on steel. rare earth additions) are more re- damaging, because metal sulfides
Most high-temperature alloys are silient to oxidation under thermal cy- form at faster rates than do metal ox-
oxidation resistant, so price, availabil- cling (shock) conditions. Some appli- ides. Sulfides have low melting points
ity, experience, and the type of appli- cations do not allow an alloy to fully and produce voluminous scales (scale
cation usually dictate choice. There develop its steady-state condition, spallation).
are no significant problems up to thus, performance is dictated by the With mixed corrodant environ-
400°C (750°F), few up to 750°C transient (not-so-protective) surface ments (oxygen and sulfur), alloy per-
(1,380°F), but the choice of success- scales. Transient effects will become formance is based upon a subtle inter-
ful alloys becomes somewhat limited apparent should failure analysis be play between oxide and sulfide for-
above about 800°C (1,470°F). performed. mation. Oxides are more stable; sul-
Simple iron-chromium (or iron- Caution should be given to iron- fides form more rapidly (due to kinet-
chromium-molybdenum) alloys be- chromium-nickel alloys that can be ics). Thus, oxides, sulfides, or both
come less useful as service tempera- prone to sigma-phase formation be- may form. If deposits are also pre-
tures increase, which is where the tween 540–800°C (1,000–1,470°F), sent, then conditions at the metal sur-
Type 300 series austenitic stainless which results in premature brittle fail- faces are reducing compared to areas
steels, (304, 309, 310, 314, 330, 333, ure. Molybdenum-containing alloys external to the deposits. Damage can
etc.) and certain ferritic stainless (Types 316 and 317 stainless steels be extensive.
steels (410 and 446) find many appli- and the 6%-Mo alloys) can be prone Mixed sulfur-and-oxygen gases
cations. For more arduous service to catastrophic oxidation above about can invoke very high corrosion rates
conditions at higher temperatures, 680°C (1,256°F). due to breakaway attack, typically
these alloys are surpassed by nickel- above about 600°C (1,110°F) for
or cobalt-based formulations, includ- Sulfidation nickel-based alloys, 920°C (1,688°F)
ing many of the more robust alloys Sulfurous gases are common to for cobalt-based, and 940°C (1724°F)
that are mechanically alloyed to im- many applications, including fuel for iron-based formulations. Break-
Oxidation Fe-Ni-(Co) >20% (30%) Cr. 304, 321,309, 310, 800(HT), 803, Wide choice dictated by
Stabilized to minimize 430, 446,HR120, 330, 85H, 333, application and function;
sensitization. Al, Si beneficial. 600, 601(GC), 602CA, 617, 625, Mechanical properties;
Rare earth additions aid scale 253MA, 353MA, DS, 214, MA956, Thermal cycle (shock);
retention. MA754, X, etc. Transient vs. steady state;
Internal oxides. Beware σ;
W, Mo — catastrophic oxidation.
Sulfidation Fe- with high Cr (Al) alloys. 9–12%Cr steels: 309, 310, 330, Sulfur vapor, H2S, etc. —
(Reducing gases 800(HT), 803, HR120, 85H, no oxides. Beware of Ni/Ni3S2
no oxides) 253MA, 353MA, MA956, 446, 671, eutectic; coatings can help.
6B, 188, etc.
Sulfidation Fe-Cr-based alloys. Oxide As above with 153MA, 601, HR160, SO2, SO3 , etc. — risk of
(Oxidizing gases) formation a benefit. MA754, MA956, 333, 556, etc. breakaway attack with oxides
Preoxidization may help. and sulfides; Al coatings. (See
hot corrosion.)
Carburization Wide use of cast alloys. HH, HK, HPMod, 309, 310, 330, 333, Internal carbides with
For worse conditions, use 85H, 800(HT), 803, DS, HR160, 600, intergranular attack; Cast
high-Ni alloys with Cr, Si. 601, 253MA, 602CA, 617, 625, 690, tubes benefit from smooth
(Low solubility of C in Ni is MA754, MA956, X, 556, 706, 718, I.D. surfaces.
benefit for Ni alloys.) 750, etc. Metal dusting (at lower
temperatures). Green rot
(with intermittent O2-C).
Nitridation Ni-alloys rather than Fe. Avoid 309, 800(HT), 330, 446, 188, 230, Internal nitrides (e.g., AlN) can
high Cr levels. Use low Al and 600, 602CA, 625, 253MA, etc. weaken alloy; Thin oxide at low
low Ti levels (nitride formers). oxygen partial pressure
Si promotes scale spalling. reduces nitridation.
Halogenation: Ni alloys generally better 800H, 333, 200, 201, 207, 600, Volatile products; Internal
chlorination, than Fe. Benefits: Cr (not HF), 601, 602CA, 214, N, H242, B3, etc. attack with voids;
fluorination, etc. Al, Si (with oxygen). Hygroscopic products
Preoxidation not beneficial. (e.g., chlorides); Scale spallation.
Fuel ash corrosion FeCrMo alloys at lower 309, 310, 800(HT), 600, 601, 602CA, Applications dictate alloy,
temperatures; CRAs† for S, O, 625, 825, 253MA, 353MA, MA754, or coating: Gas turbines
C — subject to application. MA758, MA956, IN657, 671, etc. (strong + CRA†); vanadic
High Cr, Al, Si useful (also slag (high-Cr + Si).
as coatings).
Molten salts Ni alloys generally favored; As with halogens, sulfidation: Intergranular attack,
some high-Cr alloys; depends on nature of salts internal voids, and
NiCrMoW alloys for molten (acidic/basic). probable embrittlement.
chlorides.
Molten glass Ni- or some Co-/high-Cr 600, 601, 602CA, 671, 690, Complex fluxing reactions;
alloys; Some refractories. MA758, etc. oxidation; sulfidation;
chlorination; fluorination, etc.
Liquid metals Fe-alloys with Cr, Al, Si 309, 310, 85H, 253MA, etc. Dissolution or alloying effects;
usual first choices (subject to Intergranular attack;
liquid metal, e.g,. Liq. Na, K, Depends on system.
molten Zn, Pb, etc.)