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646
High Temperature Corrosion of Intermetallic Alloys 647
1638 C
1600 L
1455 C
1400
AlNi
1395 1385
(Ni)
Temperature (C)
1200
1133 C
1000
854 C
660.452
800
~700 C
639.9 C
600
Al3Ni
Al3Ni2
400
0 10 20 30 40 50 60 70 80 90 100
Al Atomic percent nickel Ni
Figure 2 NiAl phase diagram. Reproduced from Binary Alloy Phase Diagrams, 2nd ed., ASM International, Materials
Park OH, 1996, with permission from ASM International.
1400 L
1394 C
1310 C
( Fe) 1232
1200 1169 C ~1160 C
Temperature (C)
( Fe)
1102 C
1000
912 C
FeAl
800
Fe2Al5
FeAl3
FeAl2
770 C
655 C
660.452 C
600
Fe3Al (Al)
400
0 10 20 30 40 50 60 70 80 90 100
Fe Atomic percent aluminum Al
Figure 3 FeAl phase diagram. Reproduced from Binary Alloy Phase Diagrams, 2nd ed., ASM International, Materials
Park OH, 1996, with permission from ASM International.
nickel and iron oxides are much less stable than Al2O3, in the scale formed during oxidation. However, nickel
so the amount of aluminum in the alloy required for and iron oxides can also exist in the scale, either
the formation of an Al2O3 scale is much less in nickel as pure oxides (e.g., NiO, Fe2O3) or mixed oxides
and iron aluminides than in titanium aluminides. (e.g., NiAl2O4 spinel). In addition, with long-time
Because of this significant difference in oxide stabili- exposure, the growth of an Al2O3 scale depletes the
ties, nickel and iron aluminides have, in many ways, alloy of aluminum, so the amount of aluminum
similar oxidation behavior and will be discussed required to maintain a protective scale is higher
together in the next section. This will be followed by than the minimum for thermodynamic stability or
a section on titanium aluminides, and then a section on initial alumina formation. Pettit10 characterized the
some less commonly used aluminide alloys. oxidation behavior of nickelaluminum alloys and
found that Ni3Al alloys form a scale with alumina
and NiO or the NiAl2O4 spinel, whereas NiAl alloys
1.25.2.1 Nickel and Iron Aluminides
form a protective alumina scale. Once the critical
There are several general reviews of the oxidation of aluminum content for a protective alumina scale is
intermetallic alloys46 as well as reviews that focus on reached, additional aluminum has little effect on the
either the nickelaluminum7,8 or ironaluminum9 oxidation rate for short-term exposures. However,
system. with longer exposures, the aluminum content of the
alloy beneath the scale can decrease, which leads to
1.25.2.1.1 Scale properties/structure an increase in the oxidation rate. Changes in the
As a result of the large differences in oxide stability aluminum content can also affect the microstructure.
(Figure 5), Ni3Al, NiAl, Fe3Al, and FeAl are in For example, the decrease in the aluminum content
equilibrium with Al2O3, so Al2O3 is always present in FeAl can lead to a disordered structure (i.e., FeAl
High Temperature Corrosion of Intermetallic Alloys 651
1700
1670 C
1600 L
1500
1400
(b Ti)
1300 ~1285
Temperature (C)
d
TiAl
1200
~1125
1100
Superlattice structures
1000 Ti3Al
900
882 C TiAl3
800 (a Ti)
700 665 C
660.452 C
600
TiAl2
aTiAl3 (Al)
500
0 10 20 30 40 50 60 70 80 90 100
Ti Atomic percent aluminum Al
Figure 4 TiAl phase diagram. Reproduced from Binary Alloy Phase Diagrams, 2nd ed., ASM International, Materials Park
OH, 1996, with permission from ASM International.
to a-Fe in Figure 3) below the oxide scale. Such segregation of particular elements to the alloyscale
changes can affect the oxidation behavior, as diffusion interface can lead to weakening of the interface.
rates in the alloy will determine the magnitude of any Porosity is often formed beneath the scale formed on
changes in alloy composition at the alloyscale inter- nickel and iron aluminide alloys. The formation of poros-
face, which determines the oxide phases formed in ity is generally attributed to the coalescence of vacancies
the scale. formed during the growth of alumina. Figure 6 shows
In addition to alloy composition, microstructure the transport processes that occur during the growth of
also affects the oxidation behavior. For example, a an alumina scale on an aluminide alloy. Bulk alumina
finer alloy grain size can lead to reduced oxidation grows by the outward diffusion of aluminum through
rates, because the diffusion of aluminum to replenish the inward diffusion of aluminum vacancies, which are
the aluminum used to form the alumina scale can created at the oxide surface from oxygen in the gas
reach the scale faster by grain boundary diffusion. phase. The vacancies are filled by aluminum from the
A fine-grained microstructure has also been shown existing oxide, so that the new oxide is formed on the
to improve the adherence of an alumina scale on outer surface. The aluminum vacancies migrate to
NiAl.11 Scale adherence is particularly important dur- the alloy and are filled with aluminum from the alloy,
ing thermal cycling, as thermal stresses are generated which creates vacancies in the alloy. Once the concen-
in the scale due to differences between the coefficients tration of these vacancies exceeds the maximum con-
of thermal expansion of the scale and the alloy. How- centration in the alloy, pores will form.
ever, stresses can be generated in the scale even in The growth process at grain boundaries is gener-
isothermal oxidation due to growth or transforma- ally attributed to the inward migration of oxygen
tion stresses in the oxides. In addition, porosity or rather than to the outward migration of aluminum.
652 High Temperature Materials
100
1/3 Fe
2O3
NiO
150
Free energy of formation (kJ mol1) Fe3O4
FeO
200
250
300
1/
7Ti4O7
350 1/ Ti O
TiO2 5 3 5
1/
3Ti2O3
400
450 TiO
1/ Al O
3 2 3
500
600 700 800 900 1000 1100 1200 1300
Temperature (C)
Figure 5 Ellingham diagram for nickel, iron, titanium, and aluminum oxides. Data from Kubaschewski, O., Alcock, C.
B. Metallurgical Thermochemistry, 5th ed., Pergamon Press, 1979; Chase M.W., Jr. (Ed.), NIST-JANAF Thermochemical
Tables, 4th ed., J. Phys. Chem. Ref. Data, Monograph No. 9, 1998.
JO Oi p Al2O3 V p JAl
Al
New oxide
Alalloy + V+ x
Al 3p = Al Al + Valloy
JAl
JAl NiAl JNi
JNi
Figure 6 Transport during growth of alumina scale on nickel aluminide alloys. The predominant inward diffusing oxygen
species has not been determined, so oxygen interstitials are used as an example.
Although the specific oxygen defect by which oxygen the Kirkendall effect, as, for nickel-rich compositions,
is transported is not well established, for illustrative the diffusion constant for aluminum in NiAl is smal-
purposes, oxygen interstitials are shown in Figure 6. ler than that for nickel in NiAl.12 Thus, the diffusion
Regardless of the specific predominant oxygen defect, of nickel away from the scale into the alloy is faster
however, inward migration of oxygen will lead to the than the diffusion of aluminum from the bulk toward
forming of new oxide at the alloyscale interface. the scale, which leads to a net movement of mass
Inward-growing scales generally contain less porosity away from the scale and the formation of vacancies
at the alloyscale interface as compared to outward- in the metal beneath the scale. The concentration of
growing scales. However, in the NiAl system, poros- vacancies continues to increase with increasing oxi-
ity can still form within the inward-growing scale. dation and eventually leads to the formation of pores.
The formation of porosity is generally attributed to The Kirkendall effect can occur regardless of where
High Temperature Corrosion of Intermetallic Alloys 653
the new oxide forms. However, the Kirkendall effect humidity. The transient alumina phases eventually
does not occur for aluminum-rich compositions of transform to the more stable a-Al2O3 phase, which
NiAl, because, in this case, the diffusion of aluminum leads to a reduction in the oxidation rate, but volu-
is not slower than that of nickel. This mechanism is metric changes associated with the phase transforma-
supported by the observation that the number of tion can generate stresses that can affect the
voids formed decreases with decreasing grain size, morphology of the oxide scale.
as the larger amount of grain boundary diffusion in The stresses generated in the a-Al2O3 are tensile,
the finer grained material would reduce the amount but relax with time.24 Relaxation can occur by defor-
of vacancies formed.13 mation in either the alloy or the oxide, and thus
The most important effect of the formation of depends on the microstructure. Fine grains in either
porosity at the alloyscale interface is that it weakens phase will enhance this deformation (i.e., creep of the
scale adhesion. The voids can act as stress concen- oxide or grain-boundary sliding in the alloy), and
trators and detachment of the oxide has been thus accelerate relaxation of the stresses. The stresses
observed at the pores.14 Pore formation does not, can also lead to convolution of the alloyscale inter-
however, appear to significantly affect the oxidation face, which is commonly referred to as rumpling.25
rate. Although the loss of contact between the alloy Although the interface of the rumpled scale is irregu-
and the scale at pores or voids might be expected to lar, contact is maintained between the alloy and the
affect the scale growth, the AlOx vapor pressure is scale. The rumpling is associated with swelling of the
large enough for vapor-phase transport of aluminum scale, which is attributed to the different diffusion rates
across the void to occur. The number and size of of nickel and aluminum in NiAl (i.e., the same Kirken-
voids increase with oxidation time and the growth dall effect that leads to void formation beneath the
of voids in directions parallel to the surface is faster scale).26 This has led to the suggestion that rumpling
than that perpendicular to the surface.15 Void forma- is initiated by swelling of individual grains in the alloy.
tion has been attributed to the growth of the oxide The a-Al2O3 forming from the transient oxides
around perturbations at the alloyscale interface.16 has been reported to nucleate at both the scalegas
Corundum (a-Al2O3) is the most stable form of interface27 and at the alloyscale interface.28 After
alumina and the scale formed on nickel- and iron nucleation, the transformation progresses in direc-
aluminide alloys is predominantly a-Al2O3. How- tions both perpendicular to the surface (inward or
ever, the first alumina phase to form is generally outward) and parallel to the alloy surface (lateral) and
one of the metastable alumina phases usually y or can lead to the formation of ridges as illustrated in
g, but occasionally d. These transient phases form on Figure 7.6 The lateral growth of a-Al2O3 from the
nickel and iron aluminide alloys, but are especially nucleation site results in low-angle grain boundaries,
prevalent on NiAl. The crystallographic orientation which are oriented radially from the nucleation site.
of the y- or g-Al2O3 phases is typically aligned with The transformation of the transient alumina phase
that of the alloy, and the oxides can grow epitaxially, creates tensile stresses in the a-Al2O3 that can lead to
as observed by transmission electron microscopy17 the formation of radial cracks with associated accel-
and low energy electron diffraction.18 Epitaxial erated growth, which can result in spokes along the
growth is maintained for a longer time on NiAl radial cracks (not shown in Figure 7). The outer
crystals with the (001) and (012) orientations as com- ridges form because the transient phases in this
pared to those with (011) and (111) orientations.19 region are the last to transform to a-Al2O3 and the
The transient phases grow by outward diffusion of higher growth rate of the transient oxides leads to a
aluminum, but at a higher growth rate (with lower thicker scale in the region. The ridges do eventually
activation energy) as compared with a-Al2O3.20,21 transform to a-Al2O3 and high-angle grain bound-
The transport of aluminum in y-Al2O3 is sufficiently aries are formed in the ridges at the boundaries
high for the overall growth rate of the scale to be between a-Al2O3 grown from adjacent nuclei. The
controlled in some cases by diffusion of aluminum high angle boundaries allow for more short-circuit
from the bulk of the alloy to the alloyscale interface, migration of oxygen (as shown in Figure 6), so the
rather than the diffusion of aluminum through the growth rate of the ridges can continue to be higher
scale to the surface.22 As expected for meta-stable than that inside the ridge, where only low-angle
phases, the transient alumina phases are more preva- boundaries are present. The transformation stresses
lent at lower temperatures.23 They are also more are relaxed with time and the scale eventually con-
prevalent at low oxygen partial pressures and high sists of columnar a-Al2O3 grains.
654 High Temperature Materials
High-angle
grain boundaries -Al2O3 nucleation site
in center Low-angle
grain boundaries
In iron aluminides, the nucleation of a-Al2O3 can which, as discussed earlier, leads to higher growth
be enhanced by Fe2O3, which can be present in the rates. Nickel dissolves more readily in the transient
oxide scale and act as a template or nucleation site for oxides, so the outward diffusion of nickel is more
the a-Al2O3. This transformation of the transient prevalent in low oxygen partial pressures.29 The dis-
oxides to a-Al2O3 enhances rumpling or wrinkling solution of nickel has been postulated to increase the
of the scale. The degree of wrinkling increases with ionic transport number, but the effect on the para-
increasing temperature and aluminum content and bolic rate constant is not significant.30 At very low
also depends on the crystallographic structure oxygen partial pressures, the formation of nickel
(ordered or disordered) and orientation. Another dif- oxide can be completely eliminated. Although this
ference between iron- and nickel aluminide alloys is would seem to be beneficial, since alumina, rather
that the Fe2O3 formed on iron aluminides is often than NiO, provides the good oxidation resistance, the
mixed with the alumina, whereas the NiO or spinel absence of NiO can lead to higher stresses in the
formed on nickel aluminides is usually located on the oxide scale.31
outer scale surface. The presence of water vapor has less effect on the
oxidation of alumina-forming alloys compared with
1.25.2.1.2 Effect of atmospheres/impurities its effect on chromia-forming alloys. Although water
In systems in which the active component provides vapor often does not significantly affect the oxidation
the oxide for good corrosion resistance, such as nickel rate of aluminides, it can lead to increased spallation
and iron aluminides, a reduced oxygen partial pres- and oxidation rates for NiAl.32,33 The increased spall-
sure is typically beneficial to the corrosion resistance, ation has been attributed to the hydration of the
because it promotes the formation of the protective alumina scale. Hydrate phases are not stable at oxi-
scale. If the oxygen pressure is sufficiently low, the dation temperatures, but they can form during cool-
oxide of the base metal could become unstable. How- ing and generate stresses in the scale, which promote
ever, even if the oxide of the base metal is stable, scale spallation.32 Although water vapor generally has
the dissolution of oxygen into the alloy is reduced little effect on the oxidation rate of iron aluminides,
at lower oxygen partial pressures, which reduces increased rates have been observed in some experi-
the formation of internal oxidation and promotes the ments.34 Such variable results suggest that water
formation of an external protective scale. Because the vapor may influence transient phase transformations,
low oxygen partial pressure can promote a protective which can be affected by minor changes in scale
scale, preoxidation in low oxygen partial pressures is microstructure or morphology.
often used to improve the oxidation resistance. These The most important impurity for the oxidation of
trends apply to the nickel and ironaluminum sys- alumina-forming oxides is sulfur, which can increase
tems as the amount of alumina in the scale is typically porosity at the alloyscale interface and enhance
larger for oxidation in lower oxygen partial pressures, crack propagation.35,36 Sulfur diffuses to the scale and
but there are exceptions. For example, the lower initially adsorbs to the surface of pores. Once a contin-
oxygen partial pressure stabilizes the transient oxides, uous alumina scale is formed, the sulfur segregation
High Temperature Corrosion of Intermetallic Alloys 655
expands to the alloyscale interface. As increased observed at temperatures lower than those at which
porosity and sulfur segregation weaken the scale the general reactive element effects are observed, and
adherence, sulfur is detrimental to oxidation resis- is attributed to the formation of hafnium oxides that
tance. The diffusion rate of sulfur in NiAl decreases protrude into the scale and provide anchors, which
with increasing aluminum content; therefore the improve adhesion.44 Hafnium also improves the plas-
amount of segregation, and thus the associated detri- ticity of the scale, which increases the magnitude of
mental effects, are greater for lower aluminum con- stresses that can be accommodated without spall-
tents. In iron aluminides, sulfur initially adsorbs to the ation. The addition of hafnium can significantly
pore surface and subsequently cosegregates with alu- extend the lifetime of aluminide alloys, particularly
minum. The presence of sulfur increases the scale when exposed to cyclic oxidation.45
convolution, which, as discussed earlier, results from Zirconium is also a commonly added alloy, and,
growth and transformation stresses. like yttrium, can lead to the formation of an addi-
tional intermetallic compound, NiZr5, which can
1.25.2.1.3 Effect of alloying additions lead to the formation of ZrO2 in the scale; therefore,
The oxidation resistance of aluminide alloys can be the amount of zirconium added must be limited.
improved with alloying additions. Reactive elements Small amounts of zirconium can improve adherence
have been shown to be beneficial to the oxidation of and reduce oxide scale growth rate by increasing
aluminide alloys by reducing the amount of porosity grain size. However, zirconium can also be detrimen-
that forms at the alloyscale interface.37,38 One of the tal by impeding the formation of a-Al2O3 and pro-
mechanisms proposed for this beneficial effect of reac- moting outward scale growth, which increases growth
tive elements is that the reactive elements segregate to rates. Zirconium is a strong carbide former, so if
the grain boundaries in the oxide scale and form oxides zirconium is added with carbon, which is commonly
that block the outward diffusion of cations.36,38,39 added to iron aluminides, the ratio of zirconium to
Decreasing the outward diffusion of cations leads to carbon must be controlled, so that the appropriate
an increase in the proportion of growth by inward amount of zirconium is available to beneficially affect
diffusion of oxygen, which, as discussed earlier, the oxidation behavior.
reduces the amount of porosity formed at the alloy Other reactive elements, such as titanium and
scale interface and thus improves scale adherence. cerium, have also been shown to decrease the oxi-
This mechanism appears to be more prevalent in dation rate, either by decreasing the outward diffu-
nickel aluminides compared to iron aluminides. sion of aluminum or by increasing the grain size of
The reactive element most commonly added to the oxide. However, not all reactive elements are
aluminide alloys is yttrium, which can be added as a beneficial to oxidation behavior; e.g., lanthanum
metallic alloy or as an oxide in oxide dispersion leads to both a higher oxidation rate and lower scale
strengthened (ODS) alloys. In nickel aluminide adherence.
alloys, the addition of yttrium can lead to the forma- Transition metals are often used as alloying additions
tion of a NiYx phase, which promotes spinel forma- for aluminide alloys. Chromium is commonly added to
tion and thus is detrimental to oxidation behavior. intermetallic alloys to improve ductility and minimize
The formation of NiYx is more likely when yttrium environmentally assisted crack embrittlement. Chro-
is added as a metallic alloy than when added as an mium is beneficial to the alumina-forming nickel-
oxide phase.40 As too large an addition of yttrium can and iron-based alloys, because it reduces the amount
increase stresses in the oxide,41 yttrium is most effec- of aluminum required to avoid internal oxidation and
tive when added in small amounts as an oxide phase. At form a protective scale. Chromium has a similar effect
low temperatures, yttrium additions promote a-Al2O3 in Ni3Al as it reduces the amount of aluminum
formation and thus decrease the oxidation rate. How- required to maintain an effectively rehealing scale
ever, at high temperatures, where a-Al2O3 forms easily for long oxidation exposures. Chromium affects the
with or without yttrium additions, yttrium is detrimen- transformation of y-Al2O3 to a-Al2O3, although the
tal by decreasing the grain size of the oxide scale, which reported effects are mixed as chromium has been
increases the amount of short-circuit grain-boundary reported to both inhibit42 and promote21 a-Al2O3
diffusion and thus increases the oxidation rate.42 formation. Chromium dissolves in y-Al2O3, which
Another common reactive element used with alu- would explain the inhibitive effect, as the chromium
minide alloys is hafnium, which improves the adhe- diffusion may be required for a-Al2O3 formation.46
sion of the oxide scale.43 The improvement is At the same time, chromium appears to accelerate
656 High Temperature Materials
nucleation of a-Al2O3. The effects of chromium on interface, and improves the long-term oxidation
the oxidation rate are likewise mixed as it has been resistance of the alloy.
reported to both increase and decrease the oxidation As mentioned earlier, carbon is used to strengthen
rate. Chromium can segregate to the alloyscale iron aluminide alloys. Carbon is generally detrimen-
interface and lead to additional phase formation, tal to oxidation resistance. The oxide scale formed on
which decreases adherence and is therefore detrimen- the carbide phase (Fe3AlCx) that strengthens the
tal to oxidation resistance. alloy is thicker than, but has the same morphology
The effects of niobium and tantalum are more as, the scale formed on the metal phase. As mentioned
consistent than those of chromium. Like chromium, earlier, when used with strong carbide formers (e.g.,
niobium and tantalum are added to improve the zirconium), the effects of carbide formation must be
mechanical properties. In both cases, a mixed oxide, considered in optimizing the alloy composition.45
NiTa2O6 or NiNb2O6, forms and is detrimental to Boron, another interstitial additional alloy, is also
oxidation resistance. However, if added in small generally detrimental to oxidation behavior, but can
amounts, niobium and tantalum improve the mechan- be beneficial when added with others, such as zirco-
ical properties with an acceptably minimal effect on nium or hafnium.
oxidation resistance. Although increasing the nio-
bium content is detrimental to the oxidation resis-
1.25.2.2 Titanium Aluminides
tance, very large niobium contents (i.e., NiAl + NbAl3
alloys) can lead to the formation of Laves phases, The high reactivity of titanium, relative to iron and
which promote the formation of a protective alumina nickel, creates additional challenges for the formation
scale during oxidation. and maintenance of an alumina scale, because of the
Refractory metals, such as molybdenum, tungsten, competition between aluminum and titanium for oxide
and vanadium, are generally detrimental because of formation. However, as mentioned earlier, titanium
the formation of liquid or gaseous oxides. For exam- aluminides have excellent specific properties and so
ple, although molybdenum does not significantly have been developed for aerospace application. There
affect short-term oxidation behavior, for longer expo- are several reviews of their oxidation behavior.4851
sures, the formation of molybdenum oxide vapor
phases is detrimental. 1.25.2.2.1 Scale properties/structure
Noble metals, such as Pt, Re, and Rh, can be The minimum aluminum content required for alu-
beneficial to the adherence of the oxide scale.6 For mina formation on titanium aluminide alloys is much
example, the beneficial effect of platinum to the higher than that for alumina formation on nickel or
oxidation behavior of NiAl is generally attributed to iron aluminide alloys. TiAl is in equilibrium with
its interaction with sulfur.47 Platinum, like sulfur, TiO and Al2O3, but any lower compositions are not
segregates to the pore surfaces and alloyscale inter- in equilibrium with Al2O3; so, even before any alu-
faces. Any platinum present at these locations dis- minum depletion occurs, TiAl is at the borderline
places sulfur, and thus decreases the detrimental aluminum composition for Al2O3 formation. Thus,
effects associated with sulfur segregation. Platinum scales formed on titanium aluminides generally con-
can also be detrimental by stabilizing y-Al2O3, which tain both aluminum and titanium oxides.
inhibits the formation of a-Al2O3, thus increasing The typical scale morphology of the scale formed
the oxidation rate.23 However, because of the cata- on TiAl is shown schematically in Figure 8.
strophic effects of scale spallation, the beneficial
effects of improved adherence can often outweigh Gas
the detrimental effects of increased growth rates.
Scale spallation is particularly critical when the alu- TiO2 outer layer
minide is used as a bond for thermal barrier coatings,
which will be discussed in a later section. Large
amounts of platinum additions can lead to the forma- Al2O3 + TiO2
tion of a platinum aluminide phase (PtAl2), which
N-rich inner layer
minimizes depletion of aluminum from the alloy
scale interface. Maintenance of a sufficient aluminum Alloy
level at the alloyscale interface prevents the forma- Figure 8 Schematic of scale formed during oxidation of
tion of Ni3Al, which can lead to local stresses at the titanium aluminide alloys.
High Temperature Corrosion of Intermetallic Alloys 657
Although TiO is the titanium oxide in equilibrium inferior to those of nickel and iron aluminides, so
with the alloy, TiO2 is stable in air. While there may titanium aluminide alloys are usually considered for
be some titanium oxides with valence lower than +4 lower temperature applications.
at the alloyscale interface, the major portion of the
titanium oxide is rutile TiO2. Rutile is an oxygen- 1.25.2.2.2 Effect of atmosphere
deficient oxide, for which the predominant ionic and pretreatment
point defects are oxygen vacancies at high oxygen The presence of a nitrogen-containing layer suggests
partial pressures and titanium interstitials at low oxy- that nitrogen may influence oxidation behavior.
gen partial pressures. Platinum marker experiments Nitrogen is often considered essentially inert for
on the oxidation of pure titanium have shown that the many oxidation processes. However, titanium, in par-
new oxide forms in the middle of the oxide, indicat- ticular, and aluminum to a lesser extent, are nitride
ing that the oxygen vacancies are predominant in the formers, so nitrogen does affect oxidation behavior.
outer scale and titanium interstitials are predominant The oxidation behavior of titanium aluminide alloys
in the inner scale. The oxidation of titanium alumi- in air is different from that in argonoxygen mix-
nide is further complicated, as the scale also contains tures.49,50 Although the results are somewhat varied,
aluminum oxides. As shown in Figure 8, the alumi- the oxygen rates in air are typically higher than those
num oxide is often dispersed in the rutile in the inner in oxygen without nitrogen for the same oxygen
portion of the scale. The outer portion of the scale is partial pressure. The detrimental effect of nitrogen
usually TiO2. Sometimes, as shown in Figure 8, there is attributed to the nitrogen-containing layer promot-
is a layer in the middle of the scale where the amount ing the formation of TiO2. Although the nitride layer
of alumina is higher than that in the inner portion of contains aluminum and titanium, the amount of tita-
the scale. These layers could be in part due to the nium is typically higher than that of aluminum.
oxygen partial pressure dependence of the ionic Nitrogen has also been shown to be beneficial to the
point defects in rutile as described earlier. Although oxidation behavior of some alloys particularly alloys
the defect chemistry has not been well established, with lower aluminum content. The beneficial effect of
platinum marker experiments have shown that, as in nitrogen is attributed to nitrogen doping the rutile and
the case of pure titanium, the new oxide forms in the decreasing the concentration of the mobile defect,
middle of the scale. There is typically an inner layer, which decreases transport through the scale. Nitrogen
which contains nitrogen if the oxidation is performed may also promote the formation of alumina in the
in air. This inner layer may also contain titanium in scale by reducing the titanium activity in the alloy.
a lower valence and/or mixed oxides. The mixed Because of the delicate balance between alumina
titaniumaluminum oxide phases (X-phase, Z-phase, and titania formation, small changes can determine
NCP) are not thermodynamically stable at the oxi- which phase nucleates and grows; subtle differences
dation temperature, but can form at the interface and can therefore affect oxidation behavior. For example,
affect the oxidation behavior. surface finish has been shown to significantly affect
The growth rate of rutile is much higher than that the oxidation rate in oxygen, but not in air.52 The
of alumina, so an alumina scale is desired for oxida- surface finish most likely affects nucleation, which
tion resistance. A continuous alumina layer would implies that the superior performance in oxygen is
provide the lowest oxidation rate and has been due to the formation of a phase that is inhibited by
achieved on some titanium aluminide alloys. How- either the presence of nitrogen or the surface rough-
ever, a mixed scale, as shown in Figure 8, is more ness. Such phenomena are difficult to characterize
typical and the growth rate of such a scale is between because they likely depend on transient phases and
the rates for alumina and titania growth. Although microstructures, which are not present when the
increasing the amount of alumina is beneficial for sample characterization is performed after the oxida-
oxidation resistance, the morphology is also important. tion experiment is completed.
For example, the more continuous the aluminum-rich The alloy microstructure also affects oxidation
layer in the middle of the scale (Figure 8), the slower behavior. For the same alloy composition, the oxida-
is the growth rate. Thus, control of the oxidation rate tion rate with a lamellar microstructure is lower than
of titanium aluminum alloys depends critically on the that for a duplex microstructure.53 One of the chal-
scale morphology. Because of the mixed scale that lenges in the application of titanium aluminide alloys
grows at a rate higher than pure alumina, the oxidation is control of the microstructure, as the microstructure
resistances of titanium aluminide alloys are generally also affects the mechanical properties. Production of
658 High Temperature Materials
parts with the same microstructure throughout the Another common alloying addition for titanium alu-
sample, as well as between samples, is a significant minide alloys is chromium, which is added primarily to
engineering challenge. Microstructural inhomogene- improve the mechanical properties of the alloy. Small
ities can lead to locally high corrosion rates or local amounts of chromium lead to an increase in the oxida-
mechanical weaknesses. tion rate. This increase is typically attributed to the
Water vapor in the atmosphere can increase the chromium doping the rutile scale and increasing the
oxidation rate. This increase is generally attributed to concentration of oxygen vacancies and/or titanium
increasing water vapor transport in the scale. interstitials. Larger amounts of chromium, however,
Although water vapor does not significantly affect are beneficial to oxidation resistance. The beneficial
the growth of alumina, it does affect transport in effect has been attributed to chromium increasing
rutile, which is generally the continuous phase in the aluminum activity in the alloy. While increases in
the oxidation scale and thus dominates the overall the aluminum activity have been measured, the mag-
scale growth rate. nitude of the increase is not sufficient to explain the
Preoxidation and presulfidation have been used to observed improvements. Another explanation is related
improve the oxidation resistance of titanium alumi- to the formation of Laves phases, which form in alloys
nide alloys. There are often conditions in which a with high chromium content. The Laves phases have
protective scale would not form, but could be main- low oxygen solubility and lower titanium activity, both
tained if it had already formed. Under such conditions, of which promote a more protective alumina scale.
a pretreatment in carefully controlled conditions can Niobium and chromium are sometimes added
be used to form a protective scale, which subsequently together and, fortunately, the oxidation behavior
grows at a slow rate. appears to be dominated by niobium rather than by
chromium. The oxidation rates of alloys with a
1.25.2.2.3 Effect of alloying additions combination of niobium and other alloying additions
The aluminum content in titanium aluminide alloys is such as manganese, zirconia, and hafnium are also
more critical than in nickel and iron aluminide alloys. similar to those of alloys with niobium as the only
The oxidation resistance of Ti3Al is generally poor, and alloying addition.
in binary titaniumaluminum alloys, at least 4850 at% Like chromium, other transition metals, such as iron,
aluminum is generally required for good oxidation nickel, manganese, and vanadium, are generally detri-
resistance. The amount of aluminum required, how- mental to the oxidation of titanium aluminide alloys,
ever, can be reduced with alloying additions. while refractory metals, such as tungsten and molybde-
The alloying addition most widely used for improv- num, are beneficial. The beneficial effects of tungsten,
ing the oxidation resistance of titanium aluminide like those of niobium, are attributed to decreasing the
alloys is niobium. During oxidation, the alloy beneath oxygen solubility in the alloy (to inhibit internal oxida-
the scale is enriched with niobium, but niobium is also tion) and doping of the rutile (to reduce oxygen vacan-
incorporated in the scale. Several explanations for the cies and/or titanium interstitial concentrations).
beneficial effects of niobium additions have been pro- Silicon additions can be beneficial to the oxidation
posed. One explanation is that niobium increases the resistance of titanium aluminide alloys. If silicon is
activity of aluminum in the alloy, but this has not been present in the alloy, silica will usually form in the
supported by subsequent thermodynamic measure- scale. However, silica is often dispersed so that is it is
ments of the aluminum activity.49 Another explanation not effective for reducing the oxidation rate. In some
is that niobium increases the diffusion of aluminum cases, silicon additions lead to a continuous silica
and/or decreases the diffusion of oxygen in the alloy, layer, which provides a barrier to oxygen diffusion
which reduces the amount of internal oxidation of and thus improves the oxidation resistance. However,
aluminum and promotes a more continuous alumina this layer leads to stresses during thermal cycling and
scale. The beneficial effect of niobium has also been is thus detrimental to the cyclic oxidation resistance.
attributed to niobium doping the rutile scale and Noble metals have mixed effects on the oxidation
decreasing the concentration of oxygen vacancies of titanium aluminide alloys. Platinum and gold are
and/or titanium interstitials. Niobium has also been detrimental to oxidation resistance, but silver is ben-
reported to improve the mechanical integrity of the eficial.54 Silver promotes the formation of y-Al2O3,
scale, which improves the resistance to cyclic oxidation. which, as discussed earlier, grows at a faster rate than
Large amounts of niobium, however, can be detrimen- a-Al2O3 and thus would seem to be detrimental.
tal if a Nb2O5 phase forms in the oxide scale. However, the a-Al2O3 formed from transient alumina
High Temperature Corrosion of Intermetallic Alloys 659
of a platinum aluminide phase at the alloyscale inter- corrosion of intermetallic alloys. The corrosion can
face. Since platinum does not form a stable solid oxide, be enhanced if the additional species is in the gas
the only oxide that can form on a platinum aluminide phase, but corrosion is further accelerated if a
alloy is alumina. The microstructure of the alumina condensed molten salt phase is formed.
scale is similar to that formed on NiAl, but the adhesion
is better on platinum aluminide alloys.61 The scale
1.25.3.1 Sulfur-Containing Environments
growth occurs predominately through short-circuit
grain boundary diffusion, so the grain size of the The sulfidation behavior of intermetallic alloys has
oxide scale affects the oxidation rate. The adhesion recently been reviewed.67 The effects of sulfur on the
can be further improved with zirconia additions, corrosion rate depend on the oxygen partial pressure
which segregate to the alloyscale interface and lead and whether a condensed phase is formed.
to a convoluted, but strong, interface between the alloy
and the scale.62 A platinum aluminide coating is clearly 1.25.3.1.1 Gaseous
expensive and thus is used in applications where a small The addition of SO2 to an oxidizing environment
amount of material is required, such as in a bond coat, does not significantly affect corrosion behavior.
which will be discussed in a later section. While the scale formed in SO2 contains oxides and
Other noble metal aluminides include those of sulfides, scales formed in oxygen with SO2 contain
ruthenium and iridium. Ruthenium aluminide has mostly oxides with little or no sulfides.68 One notable
better ductility than most aluminide alloys and has difference between oxidation with and without sulfur
good oxidation resistance. The scale morphology is that silver, which as discussed earlier, is beneficial
suggests that the scale grows by outward diffusion of to the oxidation behavior of TiAl, is detrimental to the
aluminum, although voids are not formed beneath corrosion of TiAl in sulfur-containing atmospheres.
the scale.63 Two-phase Ru(Al) + RuAl are particu- The corrosion behavior changes as the oxygen par-
larly attractive because of their good ductility. How- tial pressure is reduced. In H2H2SH2O mixtures,
ever, the oxidation resistance decreases as the amount the oxygen partial pressure is typically sufficiently
of the metal phase increases, because the high oxygen high for alumina to form and alumina is present in
diffusivity of the metallic phase leads to internal the outer portion of the scale. However, the inner
oxidation.64 The oxidation resistance can be improved portion of the scale consists of sulfides, which can be
with platinum additions, but weight loss still occurs mixed, but usually contain little or no aluminum (e.g.,
during cyclic oxidation.65 Iridium aluminide is used TiS for TiAl69 or FeS for FeAl70). As expected from the
because iridium has very low oxygen permeability low aluminum content in the sulfides, increasing the
and thus is an excellent oxygen barrier. The oxidation aluminum content in the alloy increases the amount of
rates of iridiumaluminum alloys are representative alumina in the scale. For the corrosion of TiAl, TiO2 is
of pure alumina scale growth.66 also formed in the scale. In addition, the rapid transport
An aluminide alloy system that has been investi- of titanium in the inner TiS layer leads to depletion of
gated because of its high melting point and low titanium in the alloy, so phases with higher aluminum
density is niobium aluminide.6 However, niobium content, such as TiAl2 and TiAl3, form beneath the
aluminides, even with large aluminum concentra- scale. The addition of niobium improves the sulfidation
tions (e.g., NbAl3), form mixed oxide scales rather resistance of both FeAl and TiAl. Niobium oxides and
than alumina scales. In particular, the scales contain sulfides form in the scale and the scale adherence is
AlNbO4 and Nb2O5 and are thus not protective. improved with niobium additions.71
Zirconium aluminide has been investigated but has With further decrease in the oxygen partial pres-
poor oxidation resistance because of the formation of sure in H2H2S environments, the oxides become
ZrO2. ZrO2 not only has high oxygen permeability, less stable and the scale consists almost entirely of
but also undergoes phase transitions, which generate sulfides. For FeAl alloys, FeS and mixed (Fe,Al)S
stresses in the oxide scale. phases are formed in sulfidizing environments. The
predominant phase formed during sulfidation of
NiAl is Ni3S2, which can also contain Al2S3 or
1.25.3 Hot Corrosion NiAl2S4 inclusions. For low H2S levels the sulfidation
rate is reasonably low, but as the H2S content
The presence of other reactive species, such as sulfur increases a NiNi3S2 eutectic forms and leads to
and chlorine, in the environment can accelerate the large (4 orders of magnitude) increases in corrosion
High Temperature Corrosion of Intermetallic Alloys 661
In addition, aluminide coatings can be applied to and complicated alloy systems will be discussed. While
metallic alloys that have high ductility, but contain alloying additions from the substrate alloy can compli-
little or no aluminum and thus may have poor oxida- cate the coating process, the coating process can also
tion resistance. Coatings can be applied by a variety be used to introduce desired alloying additions for
of techniques, some of which will be discussed in improved coating performance.
the chapter on High Temperature Coatings: Pro-
tection and Breakdown. However, diffusion coatings 1.25.4.1.1 Simple aluminide coatings
are widely used for aluminide intermetallic alloys The aluminum for growth of the aluminide coating
and will be discussed in this chapter. Aluminum is can be introduced through several different methods.
typically supplied in a gaseous or liquid phase, but One method is to sputter an aluminum, or aluminum-
solid-state diffusion is required for the growth of the containing, layer on the surface of the alloy. The
coating. For aluminide coatings of the same base alloy sputtering process is typically followed by a high
(e.g., NiAl on nickel-based alloys), only aluminum temperature anneal for diffusion of the aluminum
need be added to form an aluminide phase, although into the alloy. Another method is to place the sub-
other elements are often added for improved proper- strate in molten aluminum, which provides good
ties. However, for aluminide coatings with a different contact with the alloy as well as protection from
base than the substrate (e.g., NiAl on steel), both oxidation. The most common method for producing
elements of the aluminide phase (e.g., nickel and aluminide coatings, however, is pack cementation.
aluminum for NiAl on steel), must be provided, The pack in the pack cementation process consists
which complicates the coating process. of 1030% of an aluminum source (aluminum metal
or aluminum-containing alloy) and a few percent of
an activator (typically a halide species), which are
1.25.4.1 Aluminide Coatings with Same
dispersed in an inert filler (typically alumina). Upon
Base as Substrate
heating, aluminum halide gaseous species are formed
Increasing the aluminum concentration at the surface and transport aluminum to the substrate material.
is especially useful in the titaniumaluminum sys- Pure aluminum can be used as the aluminum source
tem, since, as discussed earlier, TiAl is a borderline for process temperatures below the melting point
alumina-former. The formation of TiAl3 coatings on of aluminum, while aluminum-containing alloys
TiAl-based alloys can improve oxidation resistance.83 must be used for higher temperature deposition.
A similar approach can be used in the nickel or iron Pack cementation processes are referred to as high
systems, but an increase in the aluminum content of activity or low activity, based on the aluminum activ-
NiAl- or FeAl-based alloys is less critical, because, ity in the aluminum source. Coatings formed in a
with the lower stability of the nickel- and iron-oxide high-activity process are inward-growing as alumi-
phases, the alumina phase is more stable and the num diffuses into the alloy. Low-activity processes
additional aluminum content only provides signifi- (e.g., Al/Ni < 1), however, result in the outward
cant benefit for long exposure times when aluminum growth as both elements (e.g., Ni and Al) are depos-
depletion occurs. However, aluminide coatings can ited. The low-activity process is commonly referred
significantly improve the oxidation resistance of to as chemical vapor deposition (CVD), as both, or
metallic alloys with little or no aluminum. For exam- all, components of the coating are deposited. One of
ple, aluminide coatings have been used for more than the advantages of a low-activity process is that impu-
30 years to improve the oxidation resistance of super- rity elements, such as sulfur and phosphorus, are
alloys.84 Such alloys contain several alloying additions, removed during the process, so that high-quality
the concentrations of which can change during the coatings are produced. The low-activity CVD pro-
diffusion process, and can lead to undesired micro- cess is more complicated, but provides flexibility to
structural changes, such as the formation of topo- deposit a variety of coatings.87
graphically close packed (TCP) phases.85 Similarly,
the corrosion resistance of steel can be improved by 1.25.4.1.2 Alloyed aluminide coatings
aluminization to form an iron aluminide coating. In As with bulk materials, the corrosion resistance of
this case, the presence of carbon, which can lead to aluminide coatings can be improved with alloying
undesired carbide precipitation, places restrictions on additions, so the coating processes are often modified
the coating process.86 In the following sections, the to incorporate other elements in the coating. One
application of aluminide coating processes to simple example is the introduction of chromium to improve
664 High Temperature Materials
the resistance to corrosion in chlorine-containing envir- formation of silica, which provides excellent oxidation
onments. Chromium, as well as reactive element addi- resistance because of its low oxygen permeability and is
tions, can be deposited simultaneously with aluminum particularly resistant to acidic melts. Like chromium,
in a pack cementation process by using an alloy con- silicon can be added in the pack cementation process,
taining the desired elements as the source.88 This and, also like chromium, a two-step process can be
process is complicated when steel is used as the sub- used to produce a coating with the desired composition
strate, because carbon in the steel reacts with chro- distribution.91 Although silicon can be introduced
mium to form chromium carbides. For low carbon through the vapor phase, the eutectic in the alumi-
contents, the carbide particles form separate precipi- numsilicon system provides an opportunity for the
tates, but for higher carbon contents, even as low as introduction of silicon and aluminum through liquid-
0.2%, a chromium carbide layer forms and disrupts the phase processes. This includes simple dipping pro-
coating process. This problem can be overcome by cesses as well as surface melting processes, such as
using a two-step process, which is illustrated in Figure laser surface melting. Siliconizing is most widely used
12.89 In the first step, the pack is heated to a relatively for titanium aluminide alloys. Although such processes
low temperature where there is a significant partial can result in an outer titanium silicide layer, the scale
pressure of the aluminum chloride vapor species, but formed during oxidation is similar to that formed on
the vapor species of the chromium chloride species is uncoated titanium aluminide alloys. The outer scales
low, so that aluminum, but not chromium, is deposited. consist of titanium and aluminum oxides, but a silica
Aluminum stabilizes the ferrite structure, so dissolu- layer is formed in the inner portion of the scale and
tion of aluminum causes a phase change in the iron improves the oxidation resistance.92
from austenite to ferrite. Because of the low carbon Aluminide coatings can also be used as the bond
solubility of ferrite, carbon is rejected into the austen- coating between superalloys and thermal barrier
ite layer below the ferrite. In the second step, the pack coatings (TBC). In this application, in addition to the
is heated to a higher temperature where the partial inherent oxidation behavior, the interface between the
pressure of the chromium vapor species increases, so thermally grown oxide (TGO) on the bond coating
chromium is now deposited and diffuses in the ferrite. and the TBC must be strong, so that the TBC
Because of the low concentration of carbon in the remains attached to the alloy during use (particularly
ferrite, chromium carbides do not form and a high- during thermal cycling). Thus, the adherence of the
quality coating is produced. A similar process has been scale is of greater importance than the growth rate,
used with a nickel-based superalloy to produce a coat- because a thicker TGO is less of a problem than the
ing with an outer high-chromium layer, which pro- loss of the TBC. Because of the importance of adher-
vides good hot corrosion resistance.90 Chromium, in ence, one of the common additions to NiAl bond
larger amounts, can also improve the oxidation resis- coating is platinum.93,94 Platinum-containing coat-
tance of titanium aluminide alloys and is often ings maintain good scale adherence even with signif-
incorporated in titanium aluminide coatings. icant amounts of sulfur, which, as discussed earlier,
Another element that is commonly added to alumi- generally degrades scale adherence. Platinum is typi-
nide coatings is silicon. Silicon additions result in the cally added as a coating prior to aluminization. There
are several commercial pack cementation processes for
producing platinum-containing coatings, including
Step 1 (low temperature) Gas (high AlCl, low CrCl2)
high-activity inward-growing coating with the sub-
Ferrite (low C stabilized by Al) C Al strate in the pack (e.g., Chromalloy RT22), high-activ-
C-enriched austenite (C rejected from ferrite) ity inward-growing coating with the substrate above
the pack (e.g., Howmet SS82A), and low-activity out-
Steel
ward-growing coating (e.g., Thermatech MDC150L).95
Step 2 (high temperature) Gas (reduce AlCl, increase CrCl2)
The addition of platinum eliminates void formation at
Al Cr the coatingTGO interface, but voids are observed at
Ferrite (low C stabilized by Al)
C the alloycoating interface, as shown schematically in
Figure 13.96 Void formation beneath the scale can lead
C-enriched austenite (C rejected from ferrite)
to spallation of the scale during thermal cycling, which
Steel is especially critical if the coating is used as a bond coat,
Figure 12 Two-step process for codeposition of since such spallation will lead to loss of the TBC. Void
aluminum and chromium on steel.89 formation at the coatingscale interface has been
High Temperature Corrosion of Intermetallic Alloys 665
attributed to both the Kirkendall effect and stresses more complicated than simply increasing the alumi-
associated with the transformation of b-NiAl to num content of the surface. For example, as discussed
g0 -Ni3Al.97 The void formation at the alloycoating earlier, alumina is more stable on NiAl than on TiAl,
interface is less critical than that at the coatingscale so NiAl can provide improved long-term corrosion
interface; as both NiAl and Ni3Al are more ductile than protection, but TiAl is less dense and has better
alumina, crack propagation is less likely. specific strength. Titanium aluminide coated with
As mentioned earlier, large amounts of platinum NiAl combines the advantages of the two materials
additions can lead to the formation of PtAl2, which in and can be produced by first electroplating the TiAl
addition to improving the supply of aluminum with nickel and then aluminizing the nickel layer by
needed to maintain an a-Al2O3 layer, also limits the pack cementation.99 The same process can be used
transport of transition metal impurities outward from for applying a NiAl coating to steel and allows for a
the aluminide coating into the scale. This is particu- reduction in the processing temperature to avoid
larly important in coatings for superalloys, which grain growth or carbide formation in the steel sub-
contain elements that can degrade the corrosion pro- strate.100 Similarly, steel, and other non-titanium
tection provided by the coating. alloys, can be coated with titanium aluminide by
Other noble metals used in NiAl bond coatings first depositing a layer of titanium and then aluminiz-
include rhenium and palladium. Rhenium acts ing the titanium to form the corrosion resistant tita-
like platinum in that it promotes the formation of nium aluminide coating.
an a-Al2O3 layer and forms a compound that acts as a An analogous process can be used to produce a
diffusion barrier. Palladium helps to stabilize the ruthenium aluminide coating on a nickel-base super-
NiAl phase and maintain sufficient aluminum in the alloy.101 In this case, the coating microstructure
scale. Noble metals can also be used with reactive depends on whether the ruthenium layer is alumi-
elements. For example, hafnium and platinum have nized using a high-activity pack cementation process
been used together, where, in addition to improving or a low-activity CVD process. As shown schemati-
the oxidation resistance, the formation of a HfPt cally in Figure 14, in a high-activity process, the
layer provides a diffusion barrier to prevent loss of coating grows by inward diffusion of aluminum,
aluminum and incorporation of transition metals in which results in an outer layer of RuAl and an inner
the coating and scale. layer of NiAl that are separated by a zone containing
Titanium aluminide alloys can also be used with Ru(Al,Ta) precipitates. In a low-activity process, the
TBCs. The TBC has relatively good adherence to the coating grows by outward diffusion of aluminum,
alloy, which is attributed to the better match in the which results in an outer layer of NiAl. The coating
coefficients of thermal expansion as compared to with the outer NiAl layer has superior oxidation
nickel-based superalloys. However, a bond coat, such resistance. However, the presence of the inner RuAl
as TiAlCr or TiAl3, is needed for long lifetimes.98 layer is beneficial as it acts as a diffusion barrier,
which can prevent undesired elements from the sub-
strate from entering the outer coating and oxidation
1.25.4.2 Aluminide Coatings with Different
scale.
Base as Substrate
Deposition of an aluminide phase of an element not Low activity CVD
in the substrate can provide useful properties, but is aluminization
NiAl
Ru
Al2O3scale (TGO) Al-rich layer JNi RuAl
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