1.

25 High Temperature Corrosion of Intermetallic Alloys

J. W. Fergus
Materials Research and Education Center, 275 Wilmore Laboratories, Auburn University, Auburn, AL 36849, USA

2010 Elsevier B.V. All rights reserved.

1.25.1 Introduction 647

1.25.1.1 General Uses of Intermetallic Alloys 647
1.25.1.2 Common Intermetallic Alloys 647
1.25.1.2.1 Nickel aluminides 647
1.25.1.2.2 Iron aluminides 648
1.25.1.2.3 Titanium aluminides 649
1.25.2 Oxidation 649
1.25.2.1 Nickel and Iron Aluminides 650
1.25.2.1.1 Scale properties/structure 650
1.25.2.1.2 Effect of atmospheres/impurities 654
1.25.2.1.3 Effect of alloying additions 655
1.25.2.2 Titanium Aluminides 656
1.25.2.2.1 Scale properties/structure 656
1.25.2.2.2 Effect of atmosphere and pretreatment 657
1.25.2.2.3 Effect of alloying additions 658
1.25.2.3 Other Aluminides 659
1.25.3 Hot Corrosion 660
1.25.3.1 Sulfur-Containing Environments 660
1.25.3.1.1 Gaseous 660
1.25.3.1.2 Molten salts 661
1.25.3.2 Chlorine-Containing Environments 661
1.25.3.2.1 Gaseous 661
1.25.3.2.2 Molten salts 662
1.25.3.3 Others 662
1.25.4 Coatings 662
1.25.4.1 Aluminide Coatings with Same Base as Substrate 663
1.25.4.1.1 Simple aluminide coatings 663
1.25.4.1.2 Alloyed aluminide coatings 663
1.25.4.2 Aluminide Coatings with Different Base as Substrate 665
1.25.5 Summary and Conclusions 666
References 666

Glossary Kirkendall effect Vacancy formation in a diffusion

B2 Crystal structure formed by NiAl and FeAl (see
Figure 1(a)).
Corundum Crystal structure formed by a-Al2O3.
D03 Crystal structure formed by Fe3Al (see
Figure 1(d)).
D019 Crystal structure formed by Ti3Al (see
Figure 1(e)).
Hot corrosion Corrosion in a high temperature
environment where molten salts are present.
couple because of differences in the
interdiffusion coefficients of the two atoms.
Laves phase Intermetallic crystal structure.
L10 Crystal structure formed by TiAl (see
Figure 1(b)).
L12 Crystal structure formed by Ni3Al (see
Figure 1(c)).
Pack cementation Chemical vapor deposition
process performed in a packed bed.

646
 High Temperature Corrosion of Intermetallic Alloys
Rutile Crystal structure formed by TiO2.
Spinel Crystal structure formed by NiAl2O4 and
other mixed oxides.
X-phase Mixed titaniumaluminum oxide phase.
Z-phase Mixed titaniumaluminum oxide phase.
Abbreviations
CVD Chemical vapor deposition
NCP New cubic phase (formed in TiAlO system)
TBC Thermal barrier coating
TCP Topographically close packed (phases)
TGO Thermally grown oxide
1.25.1 Introduction
Metal alloys, such as those discussed in the chapter on
High Temperature Corrosion of Alumina-forming
Iron, Nickel and Cobalt-base Alloys can be strength-
ened by the formation of intermetallic compounds, but
alloys consisting entirely of intermetallic compounds
are stronger. These intermetallic compounds typically
have higher melting temperatures compared with their
constituent metals, and are thus attractive materials for
high temperature applications. The most widely used
intermetallic compounds for high temperature appli-
cations are aluminides, because of their low densities
and their ability, or at least potential, to form a protec-
tive alumina scale. Silicides are also used for some high
temperature applications, but their oxidation behavior
is similar to that of nonoxide ceramics, such as silicon
carbide and silicon nitride, so they are discussed in the
chapter on High Temperature Corrosion of Cera-
mics and Refractory Materials. Thus, the focus of
this chapter is on the high temperature corrosion behav-
ior of aluminide intermetallic alloys.
1.25.1.1 General Uses of Intermetallic
Alloys
The low density of intermetallic aluminides is primar-
ily due to their high aluminum content, which also
promotes the formation of an aluminum scale for good
high temperature corrosion resistance. Intermetallic
compounds also have good high temperature strength
and creep resistance, but the mechanical properties at
low temperatures (including ambient room tempera-
ture) are inferior to those of metal alloys. In particular,
intermetallic compounds tend to have low ductility
647
because of the difficulty of slip in their ordered struc-
tures, which leads to low fracture toughness and cre-
ates challenges in the fabrication of intermetallic alloys
and their implementation in engineering structures.
The synthesis of intermetallic alloys is complicated
because of the larger differences in melting tempera-
ture among the constituent elements, which limits the
available fabrication processes. In addition, the proper-
ties of intermetallic alloys depend strongly on small
changes in composition, so compositional control dur-
ing synthesis and processing is particularly important.
Despite these significant engineering challenges,
the attractive high temperature properties of inter-
metallic alloys have led to their use in a variety of
high temperature applications.13 One of the most
promising applications of intermetallic alloys is for
components in aeroturbine engines, where increases
in operating temperature and decreases in weight
improve engine efficiency and performance. Although
low density is particularly important in aerospace
applications, intermetallic alloys have also been used
in other applications, such as valves and turbocharger
rotors in high-performance internal combustion
engines for automotive applications.
1.25.1.2 Common Intermetallic Alloys
Many of the promising intermetallic aluminide
alloys have been developed from the nickel- and
iron-based high temperature alloys described in the
chapter on High Temperature Corrosion of
Alumina-forming Iron, Nickel and Cobalt-base
Alloys. Intermetallic alloys have also been devel-
oped in the titaniumaluminum system. In all cases,
the intermetallic compounds form ordered crystal
structures, some examples of which are shown in
Figure 1. Plastic deformation by dislocation movement
in such ordered structures is more difficult than in
disordered metallic structures, so these compounds
have high strength and low ductility. Some of the char-
acteristics of these widely used systems are described in
the following sections.
1.25.1.2.1 Nickel aluminides
Alloys based on both NiAl and Ni3Al have been
developed. As shown in Figure 2, NiAl, which
forms the cubic B2 structure (Figure 1(a)), has a
much wider range of stoichiometry than Ni3Al,
which forms the cubic L12 structure (Figure 1(c)).
Ni3Al-based alloys exhibit an anomalous tempera-
ture dependence of flow stress, in which the strength
648 High Temperature Materials

increases with increasing temperature up to about

700
C and then decreases at higher temperatures.
Polycrystalline Ni3Al is difficult to fabricate because
a of its low deformability. Although their ductility can
be improved with boron, Ni3Al-based alloys have
relatively large densities and do not offer significant
advantages over nickel-based superalloys. NiAl-based
a
a alloys, however, have a higher aluminum content,
(a)
which decreases density and also improves oxidation
resistance. NiAl-based alloys have a higher melting
temperature and better creep resistance compared to
nickel-based superalloys. The strength can be
improved with the addition of niobium or tantalum,
c
which leads to the formation of Laves phases, and the
ductility can be improved with alloying additions
such as chromium, molybdenum, rhenium, and iron.
a However, the creep resistance of NiAl above 1000
C
(b) a is not good.

1.25.1.2.2 Iron aluminides

The ironaluminum system is similar to the nickel
a aluminum system, in that both Fe3Al and FeAl com-
pounds are formed. Like NiAl, FeAl forms the cubic
B2 structure (Figure 1(a)), but Fe3Al forms the D03
structure (Figure 1(d)). The tendency towards order-
a
a ing in the ironaluminum system is not as strong as
(c) that in the nickelaluminum system, as indicated by
the large disordered ferrite region shown in the phase
diagram in Figure 3. As in the nickelaluminum
system, the strengths of Fe3Al-based alloys increase
with increasing temperature to about 500
C and
a
then decrease at higher temperatures. However,
FeAl offers more advantages over superalloys than
NiAl. In particular, the fracture toughness and spe-
a
cific properties of FeAl-based alloys are better than
(d) a those of NiAl-based alloys, but ductility is low com-
pared to metal alloys. The ductility can be improved
with alloying additions such as zirconium. Another
y-120
difference between the ironaluminum and nickel
aluminum systems is that carbon is often used in the
ironaluminum system to improve strength through
c
carbide strengthening.

structure type AuCu, space Group P4/mmm. (c) L12 (Ni3Al),

Pearson symbol cP4, structure type Cu3Al, space group
a Pm3m. (d) D03 (Fe3Al), Pearson symbol cF16, structure type
a BiF3, space group Fm3m. (e) D019 (Ti3Al) Pearson symbol
(e)
hP8, structure type Ni3Sn, space group P63/mmc.
Figure 1 Crystal structures of selected intermetallic Reproduced from Villars P., Calvert L.D. (Eds.), Pearsons
compounds in the NiAl, FeAl, and TiAl systems. (a) B2 Handbook of Crystallographic Data for Intermetallic Phases,
(NiAl, FeAl), Pearson symbol cP2, structure type CsCl, 2nd ed., ASM International, Materials Park, OH, 1991, with
space group Pm3m. (b) L10 (TiAl), Pearson symbol tP4, permission from ASM International.
 High Temperature Corrosion of Intermetallic Alloys 649

Weight percent nickel

0 10 20 30 40 50 60 70 80 90 100
1800

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

(Al) Al3Ni5 AlNi3

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.

1.25.1.2.3 Titanium aluminides high reactivity of titanium creates challenges in attain-

Titanium aluminide alloys have the lowest densities
among the three common aluminide systems and
thus offer the best specific properties. The phase
diagram in Figure 4 shows that Ti3Al and TiAl have
similar ranges of stoichiometry. TiAl forms the tetrag-
onal L10 structure (Figure 1(b)), while Ti3Al forms
the hexagonal D019 structure (Figure 1(e)). Both
Ti3Al- and TiAl-based alloys have been developed,
but the best ductility is achieved with two-phase
(Ti3Al + TiAl) alloys. Production of the desirable
two-phase microstructure requires careful control of
both the chemical composition and the heat treatment
process. The aluminum content in Ti3Al is typically
not sufficient for good oxidation resistance, so the
most promising alloys consist entirely or mostly of
the g-phase (TiAl in the L10 structure). The mechan-
ical properties can be improved by adding substitu-
tional elements such as chromium, as well as
interstitial elements such as carbon and boron. The
ing corrosion resistance, as will be discussed later, as
well as in reliable alloy production.
1.25.2 Oxidation
A major difference between titanium aluminides and
the other two common aluminide systems (nickel and
iron) is that titanium is much more active than either
iron or nickel. This is illustrated in the Ellingham
diagram shown in Figure 5. Titanium can change
valence from Ti2+ to Ti4+, so there are several tita-
nium oxides, a few of which are included in Figure 5.
The two important titanium oxides are TiO, which is
in equilibrium with titanium metal, and TiO2, which
is stable in air. The free energy of TiO (per mole of
oxygen) is about the same as that of Al2O3, indicating
there is a strong competition between the formation of
titanium and aluminum oxides on TiAl. In comparison,
650 High Temperature Materials

Weight percent aluminum

0 10 20 30 40 50 60 70 80 90 100
1600
1538 C

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,
so the amount of aluminum in the alloy required for
the formation of an Al2O3 scale is much less in nickel
and iron aluminides than in titanium aluminides.
Because of this significant difference in oxide stabili-
ties, nickel and iron aluminides have, in many ways,
similar oxidation behavior and will be discussed
together in the next section. This will be followed by
a section on titanium aluminides, and then a section on
some less commonly used aluminide alloys.
1.25.2.1 Nickel and Iron Aluminides
There are several general reviews of the oxidation of
intermetallic alloys46 as well as reviews that focus on
either the nickelaluminum7,8 or ironaluminum9
system.
1.25.2.1.1 Scale properties/structure
As a result of the large differences in oxide stability
(Figure 5), Ni3Al, NiAl, Fe3Al, and FeAl are in
equilibrium with Al2O3, so Al2O3 is always present
in the scale formed during oxidation. However, nickel
and iron oxides can also exist in the scale, either
as pure oxides (e.g., NiO, Fe2O3) or mixed oxides
(e.g., NiAl2O4 spinel). In addition, with long-time
exposure, the growth of an Al2O3 scale depletes the
alloy of aluminum, so the amount of aluminum
required to maintain a protective scale is higher
than the minimum for thermodynamic stability or
initial alumina formation. Pettit10 characterized the
oxidation behavior of nickelaluminum alloys and
found that Ni3Al alloys form a scale with alumina
and NiO or the NiAl2O4 spinel, whereas NiAl alloys
form a protective alumina scale. Once the critical
aluminum content for a protective alumina scale is
reached, additional aluminum has little effect on the
oxidation rate for short-term exposures. However,
with longer exposures, the aluminum content of the
alloy beneath the scale can decrease, which leads to
an increase in the oxidation rate. Changes in the
aluminum content can also affect the microstructure.
For example, the decrease in the aluminum content
in FeAl can lead to a disordered structure (i.e., FeAl
 High Temperature Corrosion of Intermetallic Alloys 651

Weight percent aluminum

0 10 20 30 40 50 60 70 80 90 100
1800

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
changes can affect the oxidation behavior, as diffusion
rates in the alloy will determine the magnitude of any
changes in alloy composition at the alloyscale inter-
face, which determines the oxide phases formed in
the scale.
In addition to alloy composition, microstructure
also affects the oxidation behavior. For example, a
finer alloy grain size can lead to reduced oxidation
rates, because the diffusion of aluminum to replenish
the aluminum used to form the alumina scale can
reach the scale faster by grain boundary diffusion.
A fine-grained microstructure has also been shown
to improve the adherence of an alumina scale on
NiAl.11 Scale adherence is particularly important dur-
ing thermal cycling, as thermal stresses are generated
in the scale due to differences between the coefficients
of thermal expansion of the scale and the alloy. How-
ever, stresses can be generated in the scale even in
isothermal oxidation due to growth or transforma-
tion stresses in the oxides. In addition, porosity or
segregation of particular elements to the alloyscale
interface can lead to weakening of the interface.
Porosity is often formed beneath the scale formed on
nickel and iron aluminide alloys. The formation of poros-
ity is generally attributed to the coalescence of vacancies
formed during the growth of alumina. Figure 6 shows
the transport processes that occur during the growth of
an alumina scale on an aluminide alloy. Bulk alumina
grows by the outward diffusion of aluminum through
the inward diffusion of aluminum vacancies, which are
created at the oxide surface from oxygen in the gas
phase. The vacancies are filled by aluminum from the
existing oxide, so that the new oxide is formed on the
outer surface. The aluminum vacancies migrate to
the alloy and are filled with aluminum from the alloy,
which creates vacancies in the alloy. Once the concen-
tration of these vacancies exceeds the maximum con-
centration in the alloy, pores will form.
The growth process at grain boundaries is gener-
ally attributed to the inward migration of oxygen
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.

Grain boundary Bulk

O2

Al + 3V O } + 2 O2 = 2V+ 3VxO + 3p
3
{2V Al
1
O2 = Oi + 2p
2 New oxide

JO Oi p Al2O3 V p JAl
Al

New oxide
Alalloy + V+ x
Al 3p = Al Al + Valloy
JAl
JAl NiAl JNi
JNi

2Alalloy + 3Oi + 6p + {2V+

Al
3VO} = 2AlxAl + 3VxO + 2Valloy

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
the new oxide forms. However, the Kirkendall effect
does not occur for aluminum-rich compositions of
NiAl, because, in this case, the diffusion of aluminum
is not slower than that of nickel. This mechanism is
supported by the observation that the number of
voids formed decreases with decreasing grain size,
as the larger amount of grain boundary diffusion in
the finer grained material would reduce the amount
of vacancies formed.13
The most important effect of the formation of
porosity at the alloyscale interface is that it weakens
scale adhesion. The voids can act as stress concen-
trators and detachment of the oxide has been
observed at the pores.14 Pore formation does not,
however, appear to significantly affect the oxidation
rate. Although the loss of contact between the alloy
and the scale at pores or voids might be expected to
affect the scale growth, the AlOx vapor pressure is
large enough for vapor-phase transport of aluminum
across the void to occur. The number and size of
voids increase with oxidation time and the growth
of voids in directions parallel to the surface is faster
than that perpendicular to the surface.15 Void forma-
tion has been attributed to the growth of the oxide
around perturbations at the alloyscale interface.16
Corundum (a-Al2O3) is the most stable form of
alumina and the scale formed on nickel- and iron
aluminide alloys is predominantly a-Al2O3. How-
ever, the first alumina phase to form is generally
one of the metastable alumina phases usually y or
g, but occasionally d. These transient phases form on
nickel and iron aluminide alloys, but are especially
prevalent on NiAl. The crystallographic orientation
of the y- or g-Al2O3 phases is typically aligned with
that of the alloy, and the oxides can grow epitaxially,
as observed by transmission electron microscopy17
and low energy electron diffraction.18 Epitaxial
growth is maintained for a longer time on NiAl
crystals with the (001) and (012) orientations as com-
pared to those with (011) and (111) orientations.19
The transient phases grow by outward diffusion of
aluminum, but at a higher growth rate (with lower
activation energy) as compared with a-Al2O3.20,21
The transport of aluminum in y-Al2O3 is sufficiently
high for the overall growth rate of the scale to be
controlled in some cases by diffusion of aluminum
from the bulk of the alloy to the alloyscale interface,
rather than the diffusion of aluminum through the
scale to the surface.22 As expected for meta-stable
phases, the transient alumina phases are more preva-
lent at lower temperatures.23 They are also more
prevalent at low oxygen partial pressures and high
653
humidity. The transient alumina phases eventually
transform to the more stable a-Al2O3 phase, which
leads to a reduction in the oxidation rate, but volu-
metric changes associated with the phase transforma-
tion can generate stresses that can affect the
morphology of the oxide scale.
The stresses generated in the a-Al2O3 are tensile,
but relax with time.24 Relaxation can occur by defor-
mation in either the alloy or the oxide, and thus
depends on the microstructure. Fine grains in either
phase will enhance this deformation (i.e., creep of the
oxide or grain-boundary sliding in the alloy), and
thus accelerate relaxation of the stresses. The stresses
can also lead to convolution of the alloyscale inter-
face, which is commonly referred to as rumpling.25
Although the interface of the rumpled scale is irregu-
lar, contact is maintained between the alloy and the
scale. The rumpling is associated with swelling of the
scale, which is attributed to the different diffusion rates
of nickel and aluminum in NiAl (i.e., the same Kirken-
dall effect that leads to void formation beneath the
scale).26 This has led to the suggestion that rumpling
is initiated by swelling of individual grains in the alloy.
The a-Al2O3 forming from the transient oxides
has been reported to nucleate at both the scalegas
interface27 and at the alloyscale interface.28 After
nucleation, the transformation progresses in direc-
tions both perpendicular to the surface (inward or
outward) and parallel to the alloy surface (lateral) and
can lead to the formation of ridges as illustrated in
Figure 7.6 The lateral growth of a-Al2O3 from the
nucleation site results in low-angle grain boundaries,
which are oriented radially from the nucleation site.
The transformation of the transient alumina phase
creates tensile stresses in the a-Al2O3 that can lead to
the formation of radial cracks with associated accel-
erated growth, which can result in spokes along the
radial cracks (not shown in Figure 7). The outer
ridges form because the transient phases in this
region are the last to transform to a-Al2O3 and the
higher growth rate of the transient oxides leads to a
thicker scale in the region. The ridges do eventually
transform to a-Al2O3 and high-angle grain bound-
aries are formed in the ridges at the boundaries
between a-Al2O3 grown from adjacent nuclei. The
high angle boundaries allow for more short-circuit
migration of oxygen (as shown in Figure 6), so the
growth rate of the ridges can continue to be higher
than that inside the ridge, where only low-angle
boundaries are present. The transformation stresses
are relaxed with time and the scale eventually con-
sists of columnar a-Al2O3 grains.
654 High Temperature Materials

High-angle
grain boundaries -Al2O3 nucleation site
in center Low-angle
grain boundaries

Radial and inward growth of -Al2O3 from transient Al2O3

phases creates tensile stress and leads to radial cracking

Ridges: transient (/Y) Al2O3

growth by outward cation diffusion
Figure 7 Ridge formation in alumina scale formed on nickel aluminide alloys.6

In iron aluminides, the nucleation of a-Al2O3 can
be enhanced by Fe2O3, which can be present in the
oxide scale and act as a template or nucleation site for
the a-Al2O3. This transformation of the transient
oxides to a-Al2O3 enhances rumpling or wrinkling
of the scale. The degree of wrinkling increases with
increasing temperature and aluminum content and
also depends on the crystallographic structure
(ordered or disordered) and orientation. Another dif-
ference between iron- and nickel aluminide alloys is
that the Fe2O3 formed on iron aluminides is often
mixed with the alumina, whereas the NiO or spinel
formed on nickel aluminides is usually located on the
outer scale surface.
1.25.2.1.2 Effect of atmospheres/impurities
In systems in which the active component provides
the oxide for good corrosion resistance, such as nickel
and iron aluminides, a reduced oxygen partial pres-
sure is typically beneficial to the corrosion resistance,
because it promotes the formation of the protective
scale. If the oxygen pressure is sufficiently low, the
oxide of the base metal could become unstable. How-
ever, even if the oxide of the base metal is stable,
the dissolution of oxygen into the alloy is reduced
at lower oxygen partial pressures, which reduces
the formation of internal oxidation and promotes the
formation of an external protective scale. Because the
low oxygen partial pressure can promote a protective
scale, preoxidation in low oxygen partial pressures is
often used to improve the oxidation resistance. These
trends apply to the nickel and ironaluminum sys-
tems as the amount of alumina in the scale is typically
larger for oxidation in lower oxygen partial pressures,
but there are exceptions. For example, the lower
oxygen partial pressure stabilizes the transient oxides,
which, as discussed earlier, leads to higher growth
rates. Nickel dissolves more readily in the transient
oxides, so the outward diffusion of nickel is more
prevalent in low oxygen partial pressures.29 The dis-
solution of nickel has been postulated to increase the
ionic transport number, but the effect on the para-
bolic rate constant is not significant.30 At very low
oxygen partial pressures, the formation of nickel
oxide can be completely eliminated. Although this
would seem to be beneficial, since alumina, rather
than NiO, provides the good oxidation resistance, the
absence of NiO can lead to higher stresses in the
oxide scale.31
The presence of water vapor has less effect on the
oxidation of alumina-forming alloys compared with
its effect on chromia-forming alloys. Although water
vapor often does not significantly affect the oxidation
rate of aluminides, it can lead to increased spallation
and oxidation rates for NiAl.32,33 The increased spall-
ation has been attributed to the hydration of the
alumina scale. Hydrate phases are not stable at oxi-
dation temperatures, but they can form during cool-
ing and generate stresses in the scale, which promote
scale spallation.32 Although water vapor generally has
little effect on the oxidation rate of iron aluminides,
increased rates have been observed in some experi-
ments.34 Such variable results suggest that water
vapor may influence transient phase transformations,
which can be affected by minor changes in scale
microstructure or morphology.
The most important impurity for the oxidation of
alumina-forming oxides is sulfur, which can increase
porosity at the alloyscale interface and enhance
crack propagation.35,36 Sulfur diffuses to the scale and
initially adsorbs to the surface of pores. Once a contin-
uous alumina scale is formed, the sulfur segregation
 High Temperature Corrosion of Intermetallic Alloys
expands to the alloyscale interface. As increased
porosity and sulfur segregation weaken the scale
adherence, sulfur is detrimental to oxidation resis-
tance. The diffusion rate of sulfur in NiAl decreases
with increasing aluminum content; therefore the
amount of segregation, and thus the associated detri-
mental effects, are greater for lower aluminum con-
tents. In iron aluminides, sulfur initially adsorbs to the
pore surface and subsequently cosegregates with alu-
minum. The presence of sulfur increases the scale
convolution, which, as discussed earlier, results from
growth and transformation stresses.
1.25.2.1.3 Effect of alloying additions
The oxidation resistance of aluminide alloys can be
improved with alloying additions. Reactive elements
have been shown to be beneficial to the oxidation of
aluminide alloys by reducing the amount of porosity
that forms at the alloyscale interface.37,38 One of the
mechanisms proposed for this beneficial effect of reac-
tive elements is that the reactive elements segregate to
the grain boundaries in the oxide scale and form oxides
that block the outward diffusion of cations.36,38,39
Decreasing the outward diffusion of cations leads to
an increase in the proportion of growth by inward
diffusion of oxygen, which, as discussed earlier,
reduces the amount of porosity formed at the alloy
scale interface and thus improves scale adherence.
This mechanism appears to be more prevalent in
nickel aluminides compared to iron aluminides.
The reactive element most commonly added to
aluminide alloys is yttrium, which can be added as a
metallic alloy or as an oxide in oxide dispersion
strengthened (ODS) alloys. In nickel aluminide
alloys, the addition of yttrium can lead to the forma-
tion of a NiYx phase, which promotes spinel forma-
tion and thus is detrimental to oxidation behavior.
The formation of NiYx is more likely when yttrium
is added as a metallic alloy than when added as an
oxide phase.40 As too large an addition of yttrium can
increase stresses in the oxide,41 yttrium is most effec-
tive when added in small amounts as an oxide phase. At
low temperatures, yttrium additions promote a-Al2O3
formation and thus decrease the oxidation rate. How-
ever, at high temperatures, where a-Al2O3 forms easily
with or without yttrium additions, yttrium is detrimen-
tal by decreasing the grain size of the oxide scale, which
increases the amount of short-circuit grain-boundary
diffusion and thus increases the oxidation rate.42
Another common reactive element used with alu-
minide alloys is hafnium, which improves the adhe-
sion of the oxide scale.43 The improvement is
655
observed at temperatures lower than those at which
the general reactive element effects are observed, and
is attributed to the formation of hafnium oxides that
protrude into the scale and provide anchors, which
improve adhesion.44 Hafnium also improves the plas-
ticity of the scale, which increases the magnitude of
stresses that can be accommodated without spall-
ation. The addition of hafnium can significantly
extend the lifetime of aluminide alloys, particularly
when exposed to cyclic oxidation.45
Zirconium is also a commonly added alloy, and,
like yttrium, can lead to the formation of an addi-
tional intermetallic compound, NiZr5, which can
lead to the formation of ZrO2 in the scale; therefore,
the amount of zirconium added must be limited.
Small amounts of zirconium can improve adherence
and reduce oxide scale growth rate by increasing
grain size. However, zirconium can also be detrimen-
tal by impeding the formation of a-Al2O3 and pro-
moting outward scale growth, which increases growth
rates. Zirconium is a strong carbide former, so if
zirconium is added with carbon, which is commonly
added to iron aluminides, the ratio of zirconium to
carbon must be controlled, so that the appropriate
amount of zirconium is available to beneficially affect
the oxidation behavior.
Other reactive elements, such as titanium and
cerium, have also been shown to decrease the oxi-
dation rate, either by decreasing the outward diffu-
sion of aluminum or by increasing the grain size of
the oxide. However, not all reactive elements are
beneficial to oxidation behavior; e.g., lanthanum
leads to both a higher oxidation rate and lower scale
adherence.
Transition metals are often used as alloying additions
for aluminide alloys. Chromium is commonly added to
intermetallic alloys to improve ductility and minimize
environmentally assisted crack embrittlement. Chro-
mium is beneficial to the alumina-forming nickel-
and iron-based alloys, because it reduces the amount
of aluminum required to avoid internal oxidation and
form a protective scale. Chromium has a similar effect
in Ni3Al as it reduces the amount of aluminum
required to maintain an effectively rehealing scale
for long oxidation exposures. Chromium affects the
transformation of y-Al2O3 to a-Al2O3, although the
reported effects are mixed as chromium has been
reported to both inhibit42 and promote21 a-Al2O3
formation. Chromium dissolves in y-Al2O3, which
would explain the inhibitive effect, as the chromium
diffusion may be required for a-Al2O3 formation.46
At the same time, chromium appears to accelerate
656 High Temperature Materials
nucleation of a-Al2O3. The effects of chromium on
the oxidation rate are likewise mixed as it has been
reported to both increase and decrease the oxidation
rate. Chromium can segregate to the alloyscale
interface and lead to additional phase formation,
which decreases adherence and is therefore detrimen-
tal to oxidation resistance.
The effects of niobium and tantalum are more
consistent than those of chromium. Like chromium,
niobium and tantalum are added to improve the
mechanical properties. In both cases, a mixed oxide,
NiTa2O6 or NiNb2O6, forms and is detrimental to
oxidation resistance. However, if added in small
amounts, niobium and tantalum improve the mechan-
ical properties with an acceptably minimal effect on
oxidation resistance. Although increasing the nio-
bium content is detrimental to the oxidation resis-
tance, very large niobium contents (i.e., NiAl + NbAl3
alloys) can lead to the formation of Laves phases,
which promote the formation of a protective alumina
scale during oxidation.
Refractory metals, such as molybdenum, tungsten,
and vanadium, are generally detrimental because of
the formation of liquid or gaseous oxides. For exam-
ple, although molybdenum does not significantly
affect short-term oxidation behavior, for longer expo-
sures, the formation of molybdenum oxide vapor
phases is detrimental.
Noble metals, such as Pt, Re, and Rh, can be
beneficial to the adherence of the oxide scale.6 For
example, the beneficial effect of platinum to the
oxidation behavior of NiAl is generally attributed to
its interaction with sulfur.47 Platinum, like sulfur,
segregates to the pore surfaces and alloyscale inter-
faces. Any platinum present at these locations dis-
places sulfur, and thus decreases the detrimental
effects associated with sulfur segregation. Platinum
can also be detrimental by stabilizing y-Al2O3, which
inhibits the formation of a-Al2O3, thus increasing
the oxidation rate.23 However, because of the cata-
strophic effects of scale spallation, the beneficial
effects of improved adherence can often outweigh
the detrimental effects of increased growth rates.
Scale spallation is particularly critical when the alu-
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-
tion of a platinum aluminide phase (PtAl2), which
minimizes depletion of aluminum from the alloy
scale interface. Maintenance of a sufficient aluminum
level at the alloyscale interface prevents the forma-
tion of Ni3Al, which can lead to local stresses at the
interface, and improves the long-term oxidation
resistance of the alloy.
As mentioned earlier, carbon is used to strengthen
iron aluminide alloys. Carbon is generally detrimen-
tal to oxidation resistance. The oxide scale formed on
the carbide phase (Fe3AlCx) that strengthens the
alloy is thicker than, but has the same morphology
as, the scale formed on the metal phase. As mentioned
earlier, when used with strong carbide formers (e.g.,
zirconium), the effects of carbide formation must be
considered in optimizing the alloy composition.45
Boron, another interstitial additional alloy, is also
generally detrimental to oxidation behavior, but can
be beneficial when added with others, such as zirco-
nium or hafnium.
1.25.2.2 Titanium Aluminides
The high reactivity of titanium, relative to iron and
nickel, creates additional challenges for the formation
and maintenance of an alumina scale, because of the
competition between aluminum and titanium for oxide
formation. However, as mentioned earlier, titanium
aluminides have excellent specific properties and so
have been developed for aerospace application. There
are several reviews of their oxidation behavior.4851
1.25.2.2.1 Scale properties/structure
The minimum aluminum content required for alu-
mina formation on titanium aluminide alloys is much
higher than that for alumina formation on nickel or
iron aluminide alloys. TiAl is in equilibrium with
TiO and Al2O3, but any lower compositions are not
in equilibrium with Al2O3; so, even before any alu-
minum depletion occurs, TiAl is at the borderline
aluminum composition for Al2O3 formation. Thus,
scales formed on titanium aluminides generally con-
tain both aluminum and titanium oxides.
The typical scale morphology of the scale formed
on TiAl is shown schematically in Figure 8.
Gas
TiO2 outer layer
Al2O3 + TiO2
N-rich inner layer
Alloy
Figure 8 Schematic of scale formed during oxidation of
titanium aluminide alloys.
 High Temperature Corrosion of Intermetallic Alloys
Although TiO is the titanium oxide in equilibrium
with the alloy, TiO2 is stable in air. While there may
be some titanium oxides with valence lower than +4
at the alloyscale interface, the major portion of the
titanium oxide is rutile TiO2. Rutile is an oxygen-
deficient oxide, for which the predominant ionic
point defects are oxygen vacancies at high oxygen
partial pressures and titanium interstitials at low oxy-
gen partial pressures. Platinum marker experiments
on the oxidation of pure titanium have shown that the
new oxide forms in the middle of the oxide, indicat-
ing that the oxygen vacancies are predominant in the
outer scale and titanium interstitials are predominant
in the inner scale. The oxidation of titanium alumi-
nide is further complicated, as the scale also contains
aluminum oxides. As shown in Figure 8, the alumi-
num oxide is often dispersed in the rutile in the inner
portion of the scale. The outer portion of the scale is
usually TiO2. Sometimes, as shown in Figure 8, there
is a layer in the middle of the scale where the amount
of alumina is higher than that in the inner portion of
the scale. These layers could be in part due to the
oxygen partial pressure dependence of the ionic
point defects in rutile as described earlier. Although
the defect chemistry has not been well established,
platinum marker experiments have shown that, as in
the case of pure titanium, the new oxide forms in the
middle of the scale. There is typically an inner layer,
which contains nitrogen if the oxidation is performed
in air. This inner layer may also contain titanium in
a lower valence and/or mixed oxides. The mixed
titaniumaluminum oxide phases (X-phase, Z-phase,
NCP) are not thermodynamically stable at the oxi-
dation temperature, but can form at the interface and
affect the oxidation behavior.
The growth rate of rutile is much higher than that
of alumina, so an alumina scale is desired for oxida-
tion resistance. A continuous alumina layer would
provide the lowest oxidation rate and has been
achieved on some titanium aluminide alloys. How-
ever, a mixed scale, as shown in Figure 8, is more
typical and the growth rate of such a scale is between
the rates for alumina and titania growth. Although
increasing the amount of alumina is beneficial for
oxidation resistance, the morphology is also important.
For example, the more continuous the aluminum-rich
layer in the middle of the scale (Figure 8), the slower
is the growth rate. Thus, control of the oxidation rate
of titanium aluminum alloys depends critically on the
scale morphology. Because of the mixed scale that
grows at a rate higher than pure alumina, the oxidation
resistances of titanium aluminide alloys are generally
657
inferior to those of nickel and iron aluminides, so
titanium aluminide alloys are usually considered for
lower temperature applications.
1.25.2.2.2 Effect of atmosphere
and pretreatment
The presence of a nitrogen-containing layer suggests
that nitrogen may influence oxidation behavior.
Nitrogen is often considered essentially inert for
many oxidation processes. However, titanium, in par-
ticular, and aluminum to a lesser extent, are nitride
formers, so nitrogen does affect oxidation behavior.
The oxidation behavior of titanium aluminide alloys
in air is different from that in argonoxygen mix-
tures.49,50 Although the results are somewhat varied,
the oxygen rates in air are typically higher than those
in oxygen without nitrogen for the same oxygen
partial pressure. The detrimental effect of nitrogen
is attributed to the nitrogen-containing layer promot-
ing the formation of TiO2. Although the nitride layer
contains aluminum and titanium, the amount of tita-
nium is typically higher than that of aluminum.
Nitrogen has also been shown to be beneficial to the
oxidation behavior of some alloys particularly alloys
with lower aluminum content. The beneficial effect of
nitrogen is attributed to nitrogen doping the rutile and
decreasing the concentration of the mobile defect,
which decreases transport through the scale. Nitrogen
may also promote the formation of alumina in the
scale by reducing the titanium activity in the alloy.
Because of the delicate balance between alumina
and titania formation, small changes can determine
which phase nucleates and grows; subtle differences
can therefore affect oxidation behavior. For example,
surface finish has been shown to significantly affect
the oxidation rate in oxygen, but not in air.52 The
surface finish most likely affects nucleation, which
implies that the superior performance in oxygen is
due to the formation of a phase that is inhibited by
either the presence of nitrogen or the surface rough-
ness. Such phenomena are difficult to characterize
because they likely depend on transient phases and
microstructures, which are not present when the
sample characterization is performed after the oxida-
tion experiment is completed.
The alloy microstructure also affects oxidation
behavior. For the same alloy composition, the oxida-
tion rate with a lamellar microstructure is lower than
that for a duplex microstructure.53 One of the chal-
lenges in the application of titanium aluminide alloys
is control of the microstructure, as the microstructure
also affects the mechanical properties. Production of
658 High Temperature Materials
parts with the same microstructure throughout the
sample, as well as between samples, is a significant
engineering challenge. Microstructural inhomogene-
ities can lead to locally high corrosion rates or local
mechanical weaknesses.
Water vapor in the atmosphere can increase the
oxidation rate. This increase is generally attributed to
increasing water vapor transport in the scale.
Although water vapor does not significantly affect
the growth of alumina, it does affect transport in
rutile, which is generally the continuous phase in
the oxidation scale and thus dominates the overall
scale growth rate.
Preoxidation and presulfidation have been used to
improve the oxidation resistance of titanium alumi-
nide alloys. There are often conditions in which a
protective scale would not form, but could be main-
tained if it had already formed. Under such conditions,
a pretreatment in carefully controlled conditions can
be used to form a protective scale, which subsequently
grows at a slow rate.
1.25.2.2.3 Effect of alloying additions
The aluminum content in titanium aluminide alloys is
more critical than in nickel and iron aluminide alloys.
The oxidation resistance of Ti3Al is generally poor, and
in binary titaniumaluminum alloys, at least 4850 at%
aluminum is generally required for good oxidation
resistance. The amount of aluminum required, how-
ever, can be reduced with alloying additions.
The alloying addition most widely used for improv-
ing the oxidation resistance of titanium aluminide
alloys is niobium. During oxidation, the alloy beneath
the scale is enriched with niobium, but niobium is also
incorporated in the scale. Several explanations for the
beneficial effects of niobium additions have been pro-
posed. One explanation is that niobium increases the
activity of aluminum in the alloy, but this has not been
supported by subsequent thermodynamic measure-
ments of the aluminum activity.49 Another explanation
is that niobium increases the diffusion of aluminum
and/or decreases the diffusion of oxygen in the alloy,
which reduces the amount of internal oxidation of
aluminum and promotes a more continuous alumina
scale. The beneficial effect of niobium has also been
attributed to niobium doping the rutile scale and
decreasing the concentration of oxygen vacancies
and/or titanium interstitials. Niobium has also been
reported to improve the mechanical integrity of the
scale, which improves the resistance to cyclic oxidation.
Large amounts of niobium, however, can be detrimen-
tal if a Nb2O5 phase forms in the oxide scale.
Another common alloying addition for titanium alu-
minide alloys is chromium, which is added primarily to
improve the mechanical properties of the alloy. Small
amounts of chromium lead to an increase in the oxida-
tion rate. This increase is typically attributed to the
chromium doping the rutile scale and increasing the
concentration of oxygen vacancies and/or titanium
interstitials. Larger amounts of chromium, however,
are beneficial to oxidation resistance. The beneficial
effect has been attributed to chromium increasing
the aluminum activity in the alloy. While increases in
the aluminum activity have been measured, the mag-
nitude of the increase is not sufficient to explain the
observed improvements. Another explanation is related
to the formation of Laves phases, which form in alloys
with high chromium content. The Laves phases have
low oxygen solubility and lower titanium activity, both
of which promote a more protective alumina scale.
Niobium and chromium are sometimes added
together and, fortunately, the oxidation behavior
appears to be dominated by niobium rather than by
chromium. The oxidation rates of alloys with a
combination of niobium and other alloying additions
such as manganese, zirconia, and hafnium are also
similar to those of alloys with niobium as the only
alloying addition.
Like chromium, other transition metals, such as iron,
nickel, manganese, and vanadium, are generally detri-
mental to the oxidation of titanium aluminide alloys,
while refractory metals, such as tungsten and molybde-
num, are beneficial. The beneficial effects of tungsten,
like those of niobium, are attributed to decreasing the
oxygen solubility in the alloy (to inhibit internal oxida-
tion) and doping of the rutile (to reduce oxygen vacan-
cies and/or titanium interstitial concentrations).
Silicon additions can be beneficial to the oxidation
resistance of titanium aluminide alloys. If silicon is
present in the alloy, silica will usually form in the
scale. However, silica is often dispersed so that is it is
not effective for reducing the oxidation rate. In some
cases, silicon additions lead to a continuous silica
layer, which provides a barrier to oxygen diffusion
and thus improves the oxidation resistance. However,
this layer leads to stresses during thermal cycling and
is thus detrimental to the cyclic oxidation resistance.
Noble metals have mixed effects on the oxidation
of titanium aluminide alloys. Platinum and gold are
detrimental to oxidation resistance, but silver is ben-
eficial.54 Silver promotes the formation of y-Al2O3,
which, as discussed earlier, grows at a faster rate than
a-Al2O3 and thus would seem to be detrimental.
However, the a-Al2O3 formed from transient alumina
 High Temperature Corrosion of Intermetallic Alloys
is continuous and the oxidation rate of the alloy is the
same as that for the growth of an alumina scale. The
beneficial effect of silver decreases with increasing
temperature, presumably because it results from the
transient formation of y-Al2O3, which is metastable
and thus becomes less prevalent with increasing tem-
perature. The addition of small amounts (13%) of
chromium to silver-doped alloys is detrimental to
oxidation resistance, but with larger amounts (57%)
the oxidation rate is reduced to that of an alumina-
forming alloy.55 The excellent oxidation resistance of
these alloys, like the high-chromium-content alloys
described earlier, is attributed to the presence of
Laves phases in the alloy microstructure.
Reactive elements are used as alloying additions in
titanium aluminide alloys, but not to the extent, or to
the same beneficial effect, as in nickel and iron alu-
minide. Small amounts of reactive elements, such as
zirconium, hafnium, and yttrium, are beneficial to
oxidation resistance. Hafnium has been shown to
improve scale adherence. Zirconium, while beneficial
for short oxidation exposures, eventually leads to the
formation of zirconia, the transformation of which
creates stresses in the oxide scale.
One of the most successful recent approaches for
improving the oxidation resistance of TiAl-based
alloys is the addition of halogen elements, such as
fluorine, chlorine, or bromine. The addition of the
appropriate amount of a halogen element can lead to
a continuous alumina scale and kinetics following the
growth of an alumina scale. Various explanations
have been proposed for the beneficial effect of halo-
gen additions. One explanation is that chlorine
doping of the scale decreases the oxygen vacancy
and/or titanium interstitial concentration (i.e., the
same as that of niobium and tungsten doping).56
Other explanations are that the formation of TiO2
is inhibited by the presence of the halogen element57
or by a reduction in titanium activity due to volatili-
zation of titanium. The explanation that best illus-
trates the long-term effect is shown in Figure 9.58,59
In this model, aluminum is transported from the alloy
to the scalegas interface in a gas phase that diffuses
through pores or microcracks in the scale. Once the
aluminum-containing vapor reaches the scale surface,
it reacts with oxygen to form alumina and evolves
chlorine, which can diffuse back to the alloy and
form more of the aluminum-containing species. The
chlorine that evolves is thus recycled and provides a
mechanism for the transport of aluminum to heal
pores and/or cracks in the scale. For this mechanism
to work, chlorine partial pressure must be in a critical
659
Gas
4AlCl(g) + 3O2(g) = 2Al2O3(s) + 2Cl2(g)
Scale
Cl2(g) AlCl(g)
2Al(alloy) + Cl2(g) = 2AlCl(g)
Alloy
Figure 9 Vapor transport mechanism for beneficial effect
of halogen additions on the oxidation of titanium aluminide
alloys.58,59
range: it must be high enough to transport sufficient
aluminum to maintain the protective scale, but if it is
too high, the partial pressure of a titanium chloride
species may exceed that of the aluminum-containing
species. When the pressure of the titanium species is
too high the alumina forms in a whisker-like morphol-
ogy, which does not provide adequate protection.
To impart its beneficial effect on oxidation resis-
tance, the halogen element is needed only at the
surface, so ion implantation is often used to add halo-
gen elements to titanium aluminide alloys. The same
is true for other alloying elements added for improved
corrosion resistance, especially those which may have
detrimental properties on the mechanical properties of
the alloy. Thus, ion implantation is used to alloy tita-
nium aluminide alloys with other metallic elements, as
well as nonmetallic elements, such as phosphorous.60
This technique minimizes the amount of alloying ele-
ments used by localizing the addition to the location at
which the element is needed. This technique would not
be effective for an element that is consumed during
oxidation, as there is a limited source, which could
become depleted after long exposures. However, in the
case of halogen additions, the halogen element appears
to be recycled, and ion implantation has been shown to
improve oxidation resistance for long periods of time.
1.25.2.3 Other Aluminides
Most of the aluminide alloys used are from the nickel,
iron, or titaniumaluminum system. However, there
are a few other systems that have been developed,
including aluminides of noble and active metals.
As described earlier, the beneficial effect of plati-
num additions to NiAl is due, in part, to the formation
660 High Temperature Materials
of a platinum aluminide phase at the alloyscale inter-
face. Since platinum does not form a stable solid oxide,
the only oxide that can form on a platinum aluminide
alloy is alumina. The microstructure of the alumina
scale is similar to that formed on NiAl, but the adhesion
is better on platinum aluminide alloys.61 The scale
growth occurs predominately through short-circuit
grain boundary diffusion, so the grain size of the
oxide scale affects the oxidation rate. The adhesion
can be further improved with zirconia additions,
which segregate to the alloyscale interface and lead
to a convoluted, but strong, interface between the alloy
and the scale.62 A platinum aluminide coating is clearly
expensive and thus is used in applications where a small
amount of material is required, such as in a bond coat,
which will be discussed in a later section.
Other noble metal aluminides include those of
ruthenium and iridium. Ruthenium aluminide has
better ductility than most aluminide alloys and has
good oxidation resistance. The scale morphology
suggests that the scale grows by outward diffusion of
aluminum, although voids are not formed beneath
the scale.63 Two-phase Ru(Al) + RuAl are particu-
larly attractive because of their good ductility. How-
ever, the oxidation resistance decreases as the amount
of the metal phase increases, because the high oxygen
diffusivity of the metallic phase leads to internal
oxidation.64 The oxidation resistance can be improved
with platinum additions, but weight loss still occurs
during cyclic oxidation.65 Iridium aluminide is used
because iridium has very low oxygen permeability
and thus is an excellent oxygen barrier. The oxidation
rates of iridiumaluminum alloys are representative
of pure alumina scale growth.66
An aluminide alloy system that has been investi-
gated because of its high melting point and low
density is niobium aluminide.6 However, niobium
aluminides, even with large aluminum concentra-
tions (e.g., NbAl3), form mixed oxide scales rather
than alumina scales. In particular, the scales contain
AlNbO4 and Nb2O5 and are thus not protective.
Zirconium aluminide has been investigated but has
poor oxidation resistance because of the formation of
ZrO2. ZrO2 not only has high oxygen permeability,
but also undergoes phase transitions, which generate
stresses in the oxide scale.
1.25.3 Hot Corrosion
The presence of other reactive species, such as sulfur
and chlorine, in the environment can accelerate the
corrosion of intermetallic alloys. The corrosion can
be enhanced if the additional species is in the gas
phase, but corrosion is further accelerated if a
condensed molten salt phase is formed.
1.25.3.1 Sulfur-Containing Environments
The sulfidation behavior of intermetallic alloys has
recently been reviewed.67 The effects of sulfur on the
corrosion rate depend on the oxygen partial pressure
and whether a condensed phase is formed.
1.25.3.1.1 Gaseous
The addition of SO2 to an oxidizing environment
does not significantly affect corrosion behavior.
While the scale formed in SO2 contains oxides and
sulfides, scales formed in oxygen with SO2 contain
mostly oxides with little or no sulfides.68 One notable
difference between oxidation with and without sulfur
is that silver, which as discussed earlier, is beneficial
to the oxidation behavior of TiAl, is detrimental to the
corrosion of TiAl in sulfur-containing atmospheres.
The corrosion behavior changes as the oxygen par-
tial pressure is reduced. In H2H2SH2O mixtures,
the oxygen partial pressure is typically sufficiently
high for alumina to form and alumina is present in
the outer portion of the scale. However, the inner
portion of the scale consists of sulfides, which can be
mixed, but usually contain little or no aluminum (e.g.,
TiS for TiAl69 or FeS for FeAl70). As expected from the
low aluminum content in the sulfides, increasing the
aluminum content in the alloy increases the amount of
alumina in the scale. For the corrosion of TiAl, TiO2 is
also formed in the scale. In addition, the rapid transport
of titanium in the inner TiS layer leads to depletion of
titanium in the alloy, so phases with higher aluminum
content, such as TiAl2 and TiAl3, form beneath the
scale. The addition of niobium improves the sulfidation
resistance of both FeAl and TiAl. Niobium oxides and
sulfides form in the scale and the scale adherence is
improved with niobium additions.71
With further decrease in the oxygen partial pres-
sure in H2H2S environments, the oxides become
less stable and the scale consists almost entirely of
sulfides. For FeAl alloys, FeS and mixed (Fe,Al)S
phases are formed in sulfidizing environments. The
predominant phase formed during sulfidation of
NiAl is Ni3S2, which can also contain Al2S3 or
NiAl2S4 inclusions. For low H2S levels the sulfidation
rate is reasonably low, but as the H2S content
increases a NiNi3S2 eutectic forms and leads to
large (4 orders of magnitude) increases in corrosion
 High Temperature Corrosion of Intermetallic Alloys
rates. The addition of chromium leads to the forma-
tion of (Cr,Al)3S4 and further degrades the sulfidation
resistance.72 Similarly, zirconium additions increase
the amount of internal corrosion and increase the
sulfidation rate. In general, nickel aluminides have
poor sulfidation resistance.
TiAl forms a layered sulfide structure in low
oxygen-partial-pressure sulfidizing atmospheres.73
The scale typically contains Ti3S4, TiS, and Al2S3.
The sulfide scale typically contains more titanium
than aluminum, so the alloy beneath the scale is
depleted in titanium, and aluminum-rich phases,
such as TiAl2 and TiAl3, form. Alloying addition
affect the specific sulfide phases formed, but in most
cases do not significantly affect the overall sulfidation
rate. Silver and copper additions, however, increase
the amount of sulfidation.
1.25.3.1.2 Molten salts
The corrosion behavior changes when sulfur is pres-
ent in a condensed salt on the alloy surface. An oxide
scale that is relatively stable in a gaseous environment
may dissolve in the salt and lead to increased corro-
sion rates.
The reaction between FeAl and Na2SO4 produces
a complex mixture of oxygen- and sulfur-containing
compounds (e.g., NaAlO2, NaAl(SO4)2, Fe2O3, Al2O3).
The corrosion of the alloy occurs by dissolution of
the oxide in the molten salt and internal sulfidation
of the alloy. Corrosion resistance can improve with
increasing temperature as the more rapid growth of
the alumina results in a more protective scale.74 Simi-
larly, the addition of dispersed Al2O3 to the alloy
improves the corrosion resistance by stabilizing the
Al2O3 in the scale. Carbon additions have been shown
to improve the corrosion resistance of FeAl by form-
ing carbides that inhibit sulfur diffusion into the alloy.
Boron additions, however, have mixed effects as they
have been shown to be both beneficial and detrimen-
tal to hot corrosion resistance.
Aluminization of nickel-based superalloys has been
used to improve hot corrosion resistance. The oxide
scale formed on nickel aluminide alloys during hot
corrosion in molten sulfates contains an outer layer of
NiO or NiAl2O4. The latter has better hot corrosion
resistance because of the lower solubility of the spinel,
as compared to NiO, in the molten salt.75 The resis-
tance to molten sulfate corrosion can be improved with
the addition of platinum, palladium, or chromium.
The oxide formed during the corrosion of tita-
nium aluminide alloys in molten sulfates contains
TiO2 and Al2O3 with an inner layer of sulfides as
661
(Na,K)2SO4
TiO2 outer layer
Al2O3 + TiO2
TiS
TiAl3
TiAl
Figure 10 Schematic of scale formed during corrosion of
Ti50Al in (Na,K)2SO4 at 900
C.76
shown schematically in Figure 10.76 As with sulfida-
tion in a gaseous environment, the scale contains
more titanium than aluminum, so the alloy beneath
the scale is depleted in titanium and a layer of TiAl3
is formed. Also, as with other sulfidation and oxida-
tion processes, increasing the amount of aluminum in
the alloy increases the amount of alumina in the scale
and improves corrosion resistance. Niobium is bene-
ficial to the oxidation resistance as it improves scale
adherence.76 Chromium aids the hot corrosion resis-
tance, and, as will be discussed later, is often added to
protect aluminide coatings. Vanadium additions,
however, increase the amount of scale spallation and
are thus detrimental.
1.25.3.2 Chlorine-Containing Environments
Chlorine enhances the corrosion rate of most materi-
als and intermetallic alloys are no exception. Chlo-
rine can be present in the gas phase or in a molten
salt either a chloride or mixed salt.
1.25.3.2.1 Gaseous
The primary effect of chlorine in the gas-phase cor-
rosion of aluminide alloys is the formation of volatile
chloride species.77 In particular, the vapor pressure
of AlCl3 is relatively high and can lead to loss of
aluminum and/or void formation in the scale, both
of which are detrimental, as loss of aluminum
decreases the amount of alumina in the scale, and
void formation degrades scale adherence. The addi-
tion of zirconium has been shown to reduce the loss of
aluminum and thus improve corrosion resistance. In
some cases, the liquid chlorides can form from reac-
tion with the chlorine in the gas and can enhance the
corrosion rate.
662 High Temperature Materials
1.25.3.2.2 Molten salts
Molten chlorides can also be formed from salts
deposited on the alloy surface. For example, the
reaction of titanium aluminides with sodium chloride
results in the formation of TiO2, Al2O3, and NaTiO2.
The increase in corrosion rate due to the presence of
sodium chloride is generally attributed to vapor
phase transport via chloride gas species.78 As dis-
cussed earlier, controlled amounts of chlorine, or
other halogens, can improve the oxidation of titanium
aluminide alloys, but for this beneficial effect to
occur, the chlorine content must be limited so that
transport of aluminum, but not titanium, occurs. The
chlorine levels present during hot corrosion in NaCl
are high enough for the transport of both titanium
and aluminum from the alloy to the scale surface.
Under these conditions, the alumina forms as whis-
kers, rather than as a protective layer, so the corrosion
rate is increased.
Hot corrosion in lithium-containing chloride salts,
such as LiClLi2O or KClLi2O, results in the forma-
tion of multiple mixed oxides. For TiAl, in addition to
TiO2 and Al2O3, LiAlO2 forms in the outer portion of
the scale, while Li2TiO3 forms in the inner portion
of the scale. LiAlO2 also forms during corrosion of
NiAl and FeAl in lithium-containing salts, but NiAl
is more resistant than FeAl to chloride attack.79
The corrosion of titanium aluminide alloys in
mixed sulfidechloride molten salts is similar to
that in chloride salts, although in some cases the
corrosion in a molten chloride is faster than that in
a mixed salt. The chloride vapor transport mecha-
nism described above is active in the corrosion of
TiAl in a mixed chloridesulfide salt. Chromium
and silver additions to TiAl improve the hot corro-
sion resistance by improving the adherence of the
mixed oxide phase (Z-phase) formed at the alloy
scale interface.76,80 The morphology of the scale
formed on titanium aluminide containing 13% sil-
ver is shown in Figure 11.80 Niobium, which, as
discussed earlier, is generally beneficial to the corro-
sion of TiAl, can be detrimental when added in large
amounts because of sulfide phase formation.
The corrosion of nickel aluminide alloys in mixed
sulfidechloride molten salts is similar to that in
sulfide melts, presumably due to the absence of sig-
nificant partial pressures of nickel chloride gas spe-
cies to provide vapor phase transport analogous to
that which occurs in titanium aluminide alloys. The
oxide scale formed on nickel aluminide alloys con-
sists of a layer of NiO and Al2O3 above an inner layer
of sulfides. The alloy beneath the scale is depleted in
Na2SO4 + NaCl
Al2O3 + TiO2
Z-phase
Ag
TiAl(Ag)
Figure 11 Schematic of scale formed during corrosion of
Ti48Al(13)Ag in Na2SO4 + NaCl at 800
C.80
aluminum and the scale is generally not protective.
Silicon additions increase the amount of alumina, and
thus improve the oxidation resistance. Oxide (Y2O3)
dispersions can also improve the corrosion resistance
by improving scale adherence.81
1.25.3.3 Others
Molten carbonates can also lead to enhanced corro-
sion of aluminide alloys. Corrosion in lithium-
containing carbonates is similar to that in other
lithium-containing salts in that LiAlO2 is present in
the corrosion scale. Because of their high aluminum
content, NiAl and FeAl, are used as replacements or
coatings on stainless steels and superalloys in molten
carbonate environments.
As mentioned earlier, vanadium is detrimental to
the corrosion of TiAl in sulfate salts. Vanadium is also
detrimental when present in a corrosive salt. Vanadium-
containing salts are more corrosive than sodium
chloride to iron aluminides. The scale formed in
V2O5-containing salts consists of several mixed oxi-
des and can be quite complex. For example, the
weight loss of FeAl in a V2O5Na2SO4 mixture
increases with increasing temperature up to about
700
C and then decreases at higher temperatures
due to the formation of a more protective scale. The
addition of Al2O3 to the alloy provides some
improvement in scale adherence.82
1.25.4 Coatings
Aluminide alloys are attractive as oxidation resistant
coatings, because ductility, while desirable, is less
critical in a coating than it is in a structural load-
bearing member. Aluminide coatings can be used as
coatings for other aluminide alloys with inferior oxi-
dation resistance, but superior mechanical properties.
 High Temperature Corrosion of Intermetallic Alloys
In addition, aluminide coatings can be applied to
metallic alloys that have high ductility, but contain
little or no aluminum and thus may have poor oxida-
tion resistance. Coatings can be applied by a variety
of techniques, some of which will be discussed in
the chapter on High Temperature Coatings: Pro-
tection and Breakdown. However, diffusion coatings
are widely used for aluminide intermetallic alloys
and will be discussed in this chapter. Aluminum is
typically supplied in a gaseous or liquid phase, but
solid-state diffusion is required for the growth of the
coating. For aluminide coatings of the same base alloy
(e.g., NiAl on nickel-based alloys), only aluminum
need be added to form an aluminide phase, although
other elements are often added for improved proper-
ties. However, for aluminide coatings with a different
base than the substrate (e.g., NiAl on steel), both
elements of the aluminide phase (e.g., nickel and
aluminum for NiAl on steel), must be provided,
which complicates the coating process.
1.25.4.1 Aluminide Coatings with Same
Base as Substrate
Increasing the aluminum concentration at the surface
is especially useful in the titaniumaluminum sys-
tem, since, as discussed earlier, TiAl is a borderline
alumina-former. The formation of TiAl3 coatings on
TiAl-based alloys can improve oxidation resistance.83
A similar approach can be used in the nickel or iron
systems, but an increase in the aluminum content of
NiAl- or FeAl-based alloys is less critical, because,
with the lower stability of the nickel- and iron-oxide
phases, the alumina phase is more stable and the
additional aluminum content only provides signifi-
cant benefit for long exposure times when aluminum
depletion occurs. However, aluminide coatings can
significantly improve the oxidation resistance of
metallic alloys with little or no aluminum. For exam-
ple, aluminide coatings have been used for more than
30 years to improve the oxidation resistance of super-
alloys.84 Such alloys contain several alloying additions,
the concentrations of which can change during the
diffusion process, and can lead to undesired micro-
structural changes, such as the formation of topo-
graphically close packed (TCP) phases.85 Similarly,
the corrosion resistance of steel can be improved by
aluminization to form an iron aluminide coating. In
this case, the presence of carbon, which can lead to
undesired carbide precipitation, places restrictions on
the coating process.86 In the following sections, the
application of aluminide coating processes to simple
663
and complicated alloy systems will be discussed. While
alloying additions from the substrate alloy can compli-
cate the coating process, the coating process can also
be used to introduce desired alloying additions for
improved coating performance.
1.25.4.1.1 Simple aluminide coatings
The aluminum for growth of the aluminide coating
can be introduced through several different methods.
One method is to sputter an aluminum, or aluminum-
containing, layer on the surface of the alloy. The
sputtering process is typically followed by a high
temperature anneal for diffusion of the aluminum
into the alloy. Another method is to place the sub-
strate in molten aluminum, which provides good
contact with the alloy as well as protection from
oxidation. The most common method for producing
aluminide coatings, however, is pack cementation.
The pack in the pack cementation process consists
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
dispersed in an inert filler (typically alumina). Upon
heating, aluminum halide gaseous species are formed
and transport aluminum to the substrate material.
Pure aluminum can be used as the aluminum source
for process temperatures below the melting point
of aluminum, while aluminum-containing alloys
must be used for higher temperature deposition.
Pack cementation processes are referred to as high
activity or low activity, based on the aluminum activ-
ity in the aluminum source. Coatings formed in a
high-activity process are inward-growing as alumi-
num diffuses into the alloy. Low-activity processes
(e.g., Al/Ni < 1), however, result in the outward
growth as both elements (e.g., Ni and Al) are depos-
ited. The low-activity process is commonly referred
to as chemical vapor deposition (CVD), as both, or
all, components of the coating are deposited. One of
the advantages of a low-activity process is that impu-
rity elements, such as sulfur and phosphorus, are
removed during the process, so that high-quality
coatings are produced. The low-activity CVD pro-
cess is more complicated, but provides flexibility to
deposit a variety of coatings.87
1.25.4.1.2 Alloyed aluminide coatings
As with bulk materials, the corrosion resistance of
aluminide coatings can be improved with alloying
additions, so the coating processes are often modified
to incorporate other elements in the coating. One
example is the introduction of chromium to improve
664 High Temperature Materials
the resistance to corrosion in chlorine-containing envir-
onments. Chromium, as well as reactive element addi-
tions, can be deposited simultaneously with aluminum
in a pack cementation process by using an alloy con-
taining the desired elements as the source.88 This
process is complicated when steel is used as the sub-
strate, because carbon in the steel reacts with chro-
mium to form chromium carbides. For low carbon
contents, the carbide particles form separate precipi-
tates, but for higher carbon contents, even as low as
0.2%, a chromium carbide layer forms and disrupts the
coating process. This problem can be overcome by
using a two-step process, which is illustrated in Figure
12.89 In the first step, the pack is heated to a relatively
low temperature where there is a significant partial
pressure of the aluminum chloride vapor species, but
the vapor species of the chromium chloride species is
low, so that aluminum, but not chromium, is deposited.
Aluminum stabilizes the ferrite structure, so dissolu-
tion of aluminum causes a phase change in the iron
from austenite to ferrite. Because of the low carbon
solubility of ferrite, carbon is rejected into the austen-
ite layer below the ferrite. In the second step, the pack
is heated to a higher temperature where the partial
pressure of the chromium vapor species increases, so
chromium is now deposited and diffuses in the ferrite.
Because of the low concentration of carbon in the
ferrite, chromium carbides do not form and a high-
quality coating is produced. A similar process has been
used with a nickel-based superalloy to produce a coat-
ing with an outer high-chromium layer, which pro-
vides good hot corrosion resistance.90 Chromium, in
larger amounts, can also improve the oxidation resis-
tance of titanium aluminide alloys and is often
incorporated in titanium aluminide coatings.
Another element that is commonly added to alumi-
nide coatings is silicon. Silicon additions result in the
Step 1 (low temperature) Gas (high AlCl, low CrCl2)
Ferrite (low C stabilized by Al) C Al
C-enriched austenite (C rejected from ferrite)
Steel
Step 2 (high temperature) Gas (reduce AlCl, increase CrCl2)
Al
Ferrite (low C stabilized by Al)
C the alloycoating interface, as shown schematically in
C-enriched austenite (C rejected from ferrite)
Steel
Figure 12 Two-step process for codeposition of
aluminum and chromium on steel.89
formation of silica, which provides excellent oxidation
resistance because of its low oxygen permeability and is
particularly resistant to acidic melts. Like chromium,
silicon can be added in the pack cementation process,
and, also like chromium, a two-step process can be
used to produce a coating with the desired composition
distribution.91 Although silicon can be introduced
through the vapor phase, the eutectic in the alumi-
numsilicon system provides an opportunity for the
introduction of silicon and aluminum through liquid-
phase processes. This includes simple dipping pro-
cesses as well as surface melting processes, such as
laser surface melting. Siliconizing is most widely used
for titanium aluminide alloys. Although such processes
can result in an outer titanium silicide layer, the scale
formed during oxidation is similar to that formed on
uncoated titanium aluminide alloys. The outer scales
consist of titanium and aluminum oxides, but a silica
layer is formed in the inner portion of the scale and
improves the oxidation resistance.92
Aluminide coatings can also be used as the bond
coating between superalloys and thermal barrier
coatings (TBC). In this application, in addition to the
inherent oxidation behavior, the interface between the
thermally grown oxide (TGO) on the bond coating
and the TBC must be strong, so that the TBC
remains attached to the alloy during use (particularly
during thermal cycling). Thus, the adherence of the
scale is of greater importance than the growth rate,
because a thicker TGO is less of a problem than the
loss of the TBC. Because of the importance of adher-
ence, one of the common additions to NiAl bond
coating is platinum.93,94 Platinum-containing coat-
ings maintain good scale adherence even with signif-
icant amounts of sulfur, which, as discussed earlier,
generally degrades scale adherence. Platinum is typi-
cally added as a coating prior to aluminization. There
are several commercial pack cementation processes for
producing platinum-containing coatings, including
high-activity inward-growing coating with the sub-
strate in the pack (e.g., Chromalloy RT22), high-activ-
ity inward-growing coating with the substrate above
the pack (e.g., Howmet SS82A), and low-activity out-
ward-growing coating (e.g., Thermatech MDC150L).95
The addition of platinum eliminates void formation at
Cr the coatingTGO interface, but voids are observed at
Figure 13.96 Void formation beneath the scale can lead
to spallation of the scale during thermal cycling, which
is especially critical if the coating is used as a bond coat,
since such spallation will lead to loss of the TBC. Void
formation at the coatingscale interface has been
 High Temperature Corrosion of Intermetallic Alloys
attributed to both the Kirkendall effect and stresses
associated with the transformation of b-NiAl to
g0 -Ni3Al.97 The void formation at the alloycoating
interface is less critical than that at the coatingscale
interface; as both NiAl and Ni3Al are more ductile than
alumina, crack propagation is less likely.
As mentioned earlier, large amounts of platinum
additions can lead to the formation of PtAl2, which in
addition to improving the supply of aluminum
needed to maintain an a-Al2O3 layer, also limits the
transport of transition metal impurities outward from
the aluminide coating into the scale. This is particu-
larly important in coatings for superalloys, which
contain elements that can degrade the corrosion pro-
tection provided by the coating.
Other noble metals used in NiAl bond coatings
include rhenium and palladium. Rhenium acts
like platinum in that it promotes the formation of
an a-Al2O3 layer and forms a compound that acts as a
diffusion barrier. Palladium helps to stabilize the
NiAl phase and maintain sufficient aluminum in the
scale. Noble metals can also be used with reactive
elements. For example, hafnium and platinum have
been used together, where, in addition to improving
the oxidation resistance, the formation of a HfPt
layer provides a diffusion barrier to prevent loss of
aluminum and incorporation of transition metals in
the coating and scale.
Titanium aluminide alloys can also be used with
TBCs. The TBC has relatively good adherence to the
alloy, which is attributed to the better match in the
coefficients of thermal expansion as compared to
nickel-based superalloys. However, a bond coat, such
as TiAlCr or TiAl3, is needed for long lifetimes.98
1.25.4.2 Aluminide Coatings with Different
Base as Substrate
Deposition of an aluminide phase of an element not
in the substrate can provide useful properties, but is
Al2O3scale (TGO)
Location
-NiAl coating of voids -(Ni,Pt)Al coating
Y(interdiffusion zone) Y(interdiffusion zone)
Superalloy substrate Superalloy substrate
Figure 13 Effect of platinum additions on pore formation
in b-nickel aluminide coating after oxidation at 1150
C.96
665
more complicated than simply increasing the alumi-
num content of the surface. For example, as discussed
earlier, alumina is more stable on NiAl than on TiAl,
so NiAl can provide improved long-term corrosion
protection, but TiAl is less dense and has better
specific strength. Titanium aluminide coated with
NiAl combines the advantages of the two materials
and can be produced by first electroplating the TiAl
with nickel and then aluminizing the nickel layer by
pack cementation.99 The same process can be used
for applying a NiAl coating to steel and allows for a
reduction in the processing temperature to avoid
grain growth or carbide formation in the steel sub-
strate.100 Similarly, steel, and other non-titanium
alloys, can be coated with titanium aluminide by
first depositing a layer of titanium and then aluminiz-
ing the titanium to form the corrosion resistant tita-
nium aluminide coating.
An analogous process can be used to produce a
ruthenium aluminide coating on a nickel-base super-
alloy.101 In this case, the coating microstructure
depends on whether the ruthenium layer is alumi-
nized using a high-activity pack cementation process
or a low-activity CVD process. As shown schemati-
cally in Figure 14, in a high-activity process, the
coating grows by inward diffusion of aluminum,
which results in an outer layer of RuAl and an inner
layer of NiAl that are separated by a zone containing
Ru(Al,Ta) precipitates. In a low-activity process, the
coating grows by outward diffusion of aluminum,
which results in an outer layer of NiAl. The coating
with the outer NiAl layer has superior oxidation
resistance. However, the presence of the inner RuAl
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
scale.
Low activity CVD
aluminization
NiAl
Ru
Al-rich layer JNi RuAl
Superalloy substrate Superalloy substrate
High activity pack
aluminization
Ru JAl RuAl Ru(Al,Ta)
Al-rich layer ppt.
NiAl
Superalloy substrate Interdiffusion
zone
Superalloy substrate
Figure 14 Ruthenium-modified coatings by low-activity
CVD aluminization and high-activity pack aluminization.101
666 High Temperature Materials

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