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temperature oxidation and corrosion processes may deviate from these rate-law kinetics, or the high-

temperature reactions may be a combination of more than one rate.


Linear kinetics are typically associated with either a surface reaction step being rate controlling or
nonprotective scaling. In the case of the latter, the corroding material may form a scale that is porous,
crackprone, or nonadherent. The integrated rate equation describing linear kinetics is:
x = kLt (Eq 8)
where x is the scale thickness or mass gain per unit area, kL is the linear rate constant, and t is time. The units of
kL depend on the test parameters used in measuring the kinetics: if the scale thickness is measured, kL has units
of centimeters per second, while if mass gain is measured, the rate constant has the units of g/cm2 · s. Figure 5
shows the linear relationship between mass gain versus oxidation time.

Fig. 5 Linear oxidation kinetics showing relationship between oxide mass and time

Parabolic kinetics describe high-temperature corrosion reactions where the rate-determining step is the
diffusion of ions, either inward toward or outward from the substrate, with a chemical potential gradient as the
driving force. Integrated, the parabolic rate equation is:
x2 = kpt (Eq 9)
where kp is the parabolic rate constant, and x is the thickness (centimeters per second) or mass gain per unit area
(g/cm2 · s). Figure 6 shows the parabolic relationship between mass gain versus oxidation time. The high-
temperature corrosion resistance of most chromia (Cr2O3) and alumina (Al2O3) scale-forming alloys follows
parabolic rate kinetics.

Fig. 6 Parabolic oxidation kinetics

Periodic cracking of a protective oxide results in the parabolic oxidation being interrupted by a sudden increase
in rate, when the gas can react directly with the bare metal surface. As oxide begins to cover the metal surface
again, parabolic oxidation is resumed. The time periods between successive parabolic steps are sometimes
fairly uniform, because a critical scale thickness is reached that causes cracks to be initiated. The overall
oxidation of the metal becomes approximately a slow linear process.
Internal penetration and attack often can be described by parabolic kinetics (Ref 9). This characterizes the
formation of precipitates (either intra- or intergranular) by the interaction of one or more species from the
environment with the substrate. Internal penetration occurs when the reactive substrate component diffuses
outwardly more slowly than the gaseous species diffuses inwardly. A simplified equation to describe internal
attack in the absence of any external scale formation has been proposed (Ref 11):

(Eq 10)

where X is the depth of internal penetration at time, t, Ns is the mole fraction of reactive gaseous species in the
substrate at the surface, D is the diffusion coefficient of the oxidant in the substrate, ν is the atom ratio of
oxidant to metal for the internally precipitating phase BOν, and is the mole fraction of reactive component
in the bulk substrate.
Logarithmic kinetics are often associated with the initial stages of oxidation, low-temperature service tests, or
conditions where cavities and precipitates in a thick scale interfere with ion or vacancy diffusion mechanisms.
Logarithmic scaling behavior on alloys is affected by precipitates that grow slowly within the scale or at the
scale-substrate interface and restrict the growth of a scaling constituent (Ref 9). Growth stresses in the scale
may cause development of cracks in the scale parallel to the substrate, thus leading to logarithmic or inverse
logarithmic kinetics from the transport of electrons or ions. The rate equations describing logarithmic reaction
kinetics are:
Logarithmic x = klog log(t + to) + A (Eq 11)
Inverse logarithmic 1/x = B - kinv log t (Eq 12)
where A, B, klog, and kinv are constants at isothermal temperatures. Figure 7 shows the variation of direct
logarithmic and inverse logarithmic kinetics.

Fig. 7 Logarithmic and inverse logarithmic oxidation kinetics

Cubic Kinetics. In certain situations, scales form on some metals according to a cubic rate law:
x3 = kct (Eq 13)
where kc is the cubic rate constant. Usually, such behavior is limited to short exposures (Ref 10). The cubic
kinetics reported for the oxidation of zirconium or hafnium are explained as a combination of diffusion-limited
scale formation and oxygen dissolution into the metal (Ref 12). In other cases, cubic kinetics have been
explained as a superposition of a morphological complication and ionic diffusion through the scale (Ref 12).
Figure 8 shows the comparison of the cubic rate kinetics with linear, parabolic, and logarithmic rate kinetics.
Fig. 8 Comparison of linear, logarithmic, parabolic, and cubic kinetics found in various thermal
degradation processes. Source: Ref 13

Some high-temperature corrosion reactions cannot be described by the simple rate equations discussed
previously. Occasionally, a metal oxidizes parabolically until the scale cracks or spalls off, and from that time
on, until a new scale is formed, the oxidation is linear. Breakaway corrosion often occurs when numerous
cracks continuously form through the scale to the substrate or when the principal component for forming the
most stable scale is either effectively depleted at the alloy surface through repeated scale formation and
spallation cycles or through selective internal compound formation.
Catastrophic corrosion occurs when a liquid phase is a product of a corrosion process. This may happen as a
result of metal or alloy exposure to vapors of a low-melting compound or during the substrate corrosion, when
one or more components of the material forms a low-melting compound with one or more corrosive species of a
test or service gaseous environment. The liquid phase first forms at the scale/atmosphere interface and
permeates through the scale to the substrate along defects such as grain boundaries and pores. Once at the
substrate/scale interface, the molten phase spreads by capillary action and destroys scale adhesion (Ref 9).
Table 1 lists oxides, sulfides, and chlorides that may lead to catastrophic corrosion.

Table 1 Low-melting compounds and eutectics that may lead to catastrophic corrosion

Potentially catastrophic corrosion species Melting point


°C °F
Oxides
V2O5 674 1245
MoO3 795 1463
Bi2O3 817 1503
PbO 885 1625
WO3 1470 2678
Chlorides
MoCl5 194 381
WCl5 240 464
MnCl2 652 1206
FeCl2 676 1249
CoCl2 740 1364
NiCl2 1030 1886
Metal-sulfide eutectics
Ni-Ni3S2 645 1193
Co-Co4S3 877 1611
Fe-FeS 988 1810
Cu-Cu2S 1067 1953
Source: Ref 9

Diffusion

Diffusion occurs due to the differences in chemical potential to the extent that a component always diffuses
down its potential gradient. Note that by this definition, it is possible in multi- component systems for a given
component to diffuse up its concentration gradient. When two isolated chambers kept at different temperatures
are suddenly connected, the temperature in each chamber rises or falls to a common, equilibrated temperature
that is driven by thermodynamics. Chemical, compositional, or defect differences in materials exposed to high-
temperature gaseous environments will attempt to equilibrate via diffusion to form oxides, sulfides, and other
metal-anion species or to level compositional differences.
Diffusion processes in solids play a key role in oxidation and other gaseous reactions with metals. Mass transfer
may be the result of metal ion diffusion from the metal surface through the oxide, nitride, sulfide, or chloride
(and other such metal compounds) layer to the absorbed anions at the oxide, nitride, sulfide, or chloride/gas
interface or the result of diffusion of anions inward through the scale to the metal or alloy. Within the alloy, the
diffusion of reacting metal atoms toward the surface and the back diffusion of unreactive atoms from the metal
surface inward to the unaltered alloy can occur. The diffusion of interstitial atoms such as carbon, nitrogen,
hydrogen, and oxygen can also be involved.
Atoms or ions can diffuse through solids by several mechanisms. The most common is vacancy diffusion,
because a metal crystal always contains a high concentration of point defects, such as atomic vacancies, while
ionic oxides contain Schottky and Frenkel defects that involve vacancies. An atom or ion sitting on a lattice site
can diffuse by jumping to adjacent vacant sites. For metal atoms, this is relatively easy because of the short
jump distances. The jump distances in ionic crystals are much longer, because cation and anion sites are
surrounded by oppositely charged species.
Small, interstitial atoms diffuse readily from one interstitial position to another. In ionic oxides, the cations may
diffuse interstitially, but the anions are usually not small enough to do so. In ionic crystals, an interstitial ion
may crowd into a regular lattice site, displacing an ion, which is forced to move into an interstitial position or to
the next lattice site.
Diffusion can be described by Fick's two laws, as noted in many texts (Ref 6, 14, 15). Fick's first law states that
the rate of mass transfer is proportional to the concentration gradient:

(Eq 14)

The flux, J, is the mass diffusing per second through a unit cross-sectional area due to the concentration
gradient, (∂C/∂t), and D is the diffusion coefficient, expressed in square centimeters per second. The diffusion
coefficient is a function of diffusing atoms, the structure through which the diffusion takes place, and the
temperature.
Under most conditions, the concentration gradient does not remain fixed with time and distance. For instance,
the concentration of carbon diffusing into a metal (for example, a steel) changes with time and depth into the
metal. Fick's second law describes this change under isothermal conditions as:

(Eq 15)

The diffusion coefficient is assumed to be independent of distance, x, to a first approximation, and the
concentration, C, is dependent on the distance x. Equation 14 must be solved for the particular geometry and
boundary conditions involved (flat, round, or spherical specimens, etc.). For carbon atoms diffusing inward
from a flat surface, with constant composition-independent diffusivity, no subsurface phase change in the metal
or movement of the metal surface, and a constant surface concentration, the solution to Eq 14 for the
concentration of carbon at any distance x from the metal surface is:
(Eq 16)

where CM is the carbon concentration at the metal/carburizing environment interface, CX is the concentration at
time t and distance x from the surface, and Co is the initial constant concentration at any distance x when t = 0.
The concentrations here are in moles of carbon per cubic centimeter of metal. The error function of the
argument z, erf(z), is tabulated in many books on probability. As carburization proceeds, CM and Co remain
constant; therefore, for any fixed value of CX, the depth of penetration, x, of the carburization diffusion reaction
is dependent on diffusion time:

The diffusion coefficient D in rather stoichiometric compounds can usually be assumed to be proportional to
the defect concentration. The diffusion coefficient can also vary with crystal orientation in noncubic crystals.
For oxides that are epitaxial or have a preferred orientation, the diffusivity can be several times more or less
than it would be for a random oxide. Temperature has a major effect on D by increasing it exponentially,
according to the Arrhenius equation:
D = Doe(-Q/RT) (Eq 17)
where Do is a temperature-independent constant called the frequency factor that is a function of the diffusing
species and the diffusion medium, and Q is the activation energy for the diffusion (Ref 6).
The activation energy is a measure of the temperature dependence of a diffusion process. A high value of Q
means that diffusion proceeds much more rapidly at high temperatures but very slowly at low temperatures.
Typical values of Do and Q in oxides are listed in Table 2 of the article “Kinetics of Gaseous Corrosion
Processes” in this Volume.
When two metals with a large difference in their diffusion coefficients interact, there is a net transport of
material across a plane that initially separated them. This phenomenon is called the Kirkendall effect.
Multicomponent interdiffusion is a complex process that requires use of multivariable diffusion couples in a
phase field approach (Ref 16) or knowledge of diffusion pathways in multicomponent phase diagrams (Ref 17)
to model the process and provide an understanding of the contributions to interdiffusion. These methods are
based on the formalism of Fick's law, which includes diffusion interactions among the chemical species (Ref
18).
Protective coatings and superalloy substrates generally have widely diverse compositions due to the intended
balancing between mechanical properties and corrosion resistance. Depending on the actual temperature,
chemical gradients between the coating and superalloy substrate may cause interdiffusion phenomena to occur.
Interdiffusion between the coating and the substrate (Ref 19) can modify the oxidation and corrosion resistance
of the coating and the mechanical properties of the coating-substrate system. Interdiffusion slowly changes the
chemical composition of both the coating and the alloy and subsequently may alter the microstructure of the
coating and/or the substrate. In addition, selective oxidation reactions can induce alloy phase transformations
(Ref 20, 21). In a hot corrosion environment, the formation of metal sulfides in the protective coating may
eventually lead to diffusion via grain boundaries or other relatively easy diffusion pathways into the coating,
which may alter the long-term performance of a coating/alloy system versus that observed in an oxidation
environment.
In gaseous reactions with metals and alloys, metal ions are formed at the metal/scale interface, and the gaseous
species, such as oxygen, is reduced at the scale/gas interface. All metal oxides, nitrides, and sulfides conduct
both ions and electrons that are associated with diffusion processes. The electronic conductivities of oxides are
usually several orders of magnitude greater than their corresponding ionic conductivities; thus, the diffusion of
cations or gaseous ions (i.e., oxygen, sulfur, nitrogen, hydrogen, etc.) controls the reaction rate (Ref 12).
Almost without exception, cations and gaseous ions do not diffuse at comparable rates in a given scale, because
lattice defects for one of the component species typically predominate. Thus, growth of the scale for gaseous
reactions with a metal or alloy should result in scale growth at either the metal-scale or the scale-gas interface if
the reactions are controlled by diffusion (Ref 12).
In general, all oxides, sulfides, nitrides, and so on are nonstoichiometric compounds, because their actual,
compositions deviate from their respective ideal molecular formulas. Some scales have an excess and others
have a deficiency of metallic ions or a corresponding deficiency or excess of gaseous ions.
Nickel oxide (NiO) is an example of a metal- deficient oxide. For each nickel cation vacancy, there are two
trivalent nickel cations in the normal lattice positions, as shown in Fig. 2 of the article “Kinetics of Gaseous
Corrosion Processes” in this Volume. The trivalent ions are considered the combination of a divalent nickel
cation and an associated positive-charged electron hole, or absence of an electron (Ref 12); hence, this is
termed a p-type semiconductor. Ionic transport occurs by the diffusion of nickel vacancies from the nickel/gas
interface to the Ni/ NiO interface. Electronic conduction occurs by the predominant diffusion of the electron
holes. Accordingly, electrons migrate from the metal surface, by electron holes, to the adsorbed oxygen atoms,
which then become oxygen anions. In this way, while Ni2+ cations and electrons move outward through the
scale toward the gas, cation vacancies and electron holes move inward toward the metal. Consequently, as the
scale thickens, cation vacancies may tend to accumulate to form voids at the nickel/NiO interface.
A metal-excess oxide carries the excess as either interstitial cations or as oxygen anion vacancies. Interstitial
cations are small enough to fit into interstitial spaces in the oxide lattice and jump from one interstitial position
to another during diffusion. Beryllium oxide (BeO) typifies a cation-excess, n-type semiconductor oxide,
because the beryllium ion (Be2+) is small enough to move interstitially through the BeO scale. Its structure is
shown in Fig. 3 of the article “Kinetics of Gaseous Corrosion Processes” in this Volume.
Oxygen in the gas adsorbs on the BeO surface and picks up free electrons from the BeO to become adsorbed
O2- ions, which then react with excess Be2+ ions that are diffusing interstitially from the beryllium metal. The
free electrons generated at the metal surface from beryllium ionization travel rapidly through vacant high-
energy levels. As with p-type oxides, the cation-excess, n-type oxides grow at the oxide/gas interface as cations
diffuse outwardly through the scale (Ref 6).
For n-type semiconducting oxides where the cations are too large or too highly charged to assume an interstitial
position, anion vacancies are required to form the metal-excess structure. This group of anion-deficient, n-type
semiconducting oxides is exemplified by zirconium dioxide (ZrO2). In this case, although most of the cations
are contributing four electrons to the ionic bonding, a small fraction of the zirconium cations only contributes
two electrons to become zirconium ion, Zr2+. Therefore, to maintain electrical neutrality, an equal number of
anion vacancies must be present in the oxide. This arrangement is shown in Fig. 4 of the article “Kinetics of
Gaseous Corrosion Processes” in this Volume. The oxide grows at the metal/oxide interface by inward
diffusion of O2- through the anion vacancies in the oxides (Ref 6, 22).
A number of compounds that can be nonstoichiometric with either a deficiency of cations or a deficiency of
anions are amphoteric. An example is lead sulfide (PbS), which has a minimum in electrical conductivity at the
stoichiometric composition. Thus, if the composition is Pb1-xS, it is p-type, and if it is PbS1+x, it is n- type.
Similarly, intrinsic semiconductors, such as cupric oxide (CuO), have a few electron holes in their valence band
and an equal number of free electrons in their nearly vacant conduction band. Electronic current is carried both
by migration of electron holes in the low-energy bonding levels and by free electrons in the higher-energy
conduction levels (Ref 6). Examples of p-type, n-type, and amphoteric superconducting sulfides, oxides, and
nitrides are listed in Table 1 of the article “Kinetics of Gaseous Corrosion Processes” in this Volume.
All oxides contain some substitutional impurity cations from the alloy before oxidation or other gaseous high-
temperature reaction. Although the solubility limit for foreign ions is low, they can have a great effect on
diffusivity in the oxide and consequently, on the oxidation rate. By doping alloys with certain elemental
additions, high-temperature gaseous reaction rates can be reduced.
In the very early stages of oxidation and especially at low temperatures, some oxides appear to grow with an
amorphous structure. In general, these oxide glasses contain more oxygen than metal in their formulas, so that
oxygen networks form around each of the metal ions. The random network ring structures that result allow
large anions or molecular oxygen to move through them more readily than the smaller cations do. Amorphous
oxides tend to crystallize as they age. Examples are silicon dioxide (SiO2), Al2O3, tantalum pentoxide (Ta2O5),
and niobium pentoxide (Nb2O5).
As a crystalline oxide grows on a metal surface, the oxide often aligns its crystal structure to be compatible with
the structure of the metal substrate. This epitaxy finds the best fit, but not a perfect fit, between the oxide or
scale and the substrate crystal structures.

Additional Aspects of Scale Growth

Stress develops in an epitaxial scale layer as it grows, due to the slight misfit between the scale and metal
crystals. The stress is likely to produce dislocation arrays in the scale that could be paths of mass transport
through the film via diffusion. A mosaic structure, consisting of small crystallites with orientations very slightly
tilted or twisted with respect to each other, may develop in the scale because of the growth stresses. The
boundaries between the crystallites are dislocation arrays that serve as easy diffusion paths (Ref 6).
Recrystallization of either the scale or the substrate may alter the stress conditions substantially.
Stresses in epitaxial layers increase as the films grow thicker, until, at some point, the bulk scale tends to
become polycrystalline, and epitaxy is gradually lost. Epitaxy may last up to approximately 50 nm in many
cases, but it is seldom strong over 100 nm. As the scale grows thicker, crystals that are favorably oriented for
growth will grow at the expense of their neighboring grains until the scale surface consists of a few large grains
with similar orientation. The variation in growth rate of different scale grains produces the roughening of the
scaled surface that is commonly observed (Ref 6).
A pure metal that can oxidize to more than one valence will form a series of oxides, usually in separate layers.
For example, iron has valences of +2 and +3 at high temperatures and forms wustite (FeO), magnetite (Fe 3O4),
and hematite (Fe2O3) scale layers. The scale layers will be arranged with the most metal-rich oxide species
appearing next to the metal, and progressively less metal content is found in each succeeding layer toward the
outside layer. In addition, a concentration gradient exists with each layer, with higher metal ion concentration
closest to the metal/scale interface.
If the oxygen partial pressure in the gas is so low that it is below the dissociation pressures of the outer oxygen-
rich oxides, then only the thermodynamically stable inner oxides will form. In general, the lowest-valence inner
oxide will usually be p-type because of the ease with which electron holes and cation vacancies can form. The
outermost oxide is often n-type because of its anion vacancies. A scale consisting of an inner layer with cations
diffusing outward and an outer layer with anions diffusing inward will grow at the oxide/oxide interface (Ref
6).
Polycrystalline oxides develop stresses along their grain boundaries because of enhanced growth of oxide
grains in preferred orientations. Short-circuit diffusion along grain boundaries may lead to oxide or high-
temperature scale formation at the boundaries that imparts increased compressive stresses. Second-phase
inclusions may oxidize at a different rate than the parent metal or alloy and lead to high stresses within the
scale. Composition variations within a high- temperature coating or within gaseous-formed scales may also
create stresses within the scale. Alloying constituents may react to a gaseous environment at different rates,
leading to preferential growth of a scale from one or more elemental metal components. If diffusion is too slow
to maintain constant composition within the scale, stress can develop in the alloy (Ref 6).
The activation energies for diffusion along line and surface defects in solids are much less than those for
volume diffusion. Dislocations, grain boundaries, porosity networks, and external surfaces offer rapid diffusion
paths at low temperatures, at which volume diffusion is extremely slow. In metals, diffusion along dislocations
is more important than volume diffusion below approximately one-half of the absolute melting point. At high
temperatures, volume diffusion predominates in both metals and oxides.
At very high temperatures, oxides and high- temperature scales may evaporate entirely or limit the protective
nature of these protective scales. Platinum and refractory metals tend to have volatile oxides (Ref 6). As
evaporation removes material from the scale layer, diffusion through the scale increases until the evaporation
and diffusion rates are equal. The scale thickness remains constant, and the scale or oxide of the metal or alloy
grows paralinearly. If more than one oxide or scale layer protects the substrate, the higher-valent outermost
oxide/scale always has the higher vapor pressure and is thus more volatile.
Sample geometry may influence the stresses within a scale. The stress state (compressive or tensile) depends on
whether the surface profile of the sample is convex or concave and whether the scale grows at the scale/gas
interface or at the metal/scale interface. Figure 9 shows how the stress state may be altered in an oxide scale as
it grows, assuming the original growth stresses were compressive. Other scales formed from gaseous reactions
will behave similarly.
Fig. 9 Stress development on curved surfaces. (a) Oxide grows by cation diffusion on a convex surface.
(b) Oxide grows by anion diffusion on a convex surface. (c) Oxide grows by cation diffusion on a concave
surface. (d) Oxide grows by anion diffusion on a concave surface

In Fig. 9(a), for a convex surface on which oxide grows at the oxide/gas interface by cation diffusion outward
through the scale, the metal surface will gradually recede, increasing the compressive stresses at the
metal/oxide interface. If adhesion is to be maintained, the oxide has to follow the retreating interface,
generating further compressive stresses in the scale. Stress relief can occur by either shear fracture, if the scale
is extremely adherent, or by oxide buckling due to decohesion that could lead to local tensile failure. Figure
9(b) shows oxidation of a convex surface on which the oxide grows at the metal/ oxide interface by anion
diffusion inward. The compressive stresses that develop at the metal/ oxide interface are due only to the volume
change of the reaction oxide (volume generated is greater than the volume of metal consumed). Oxide that is
pushed away from the growth area will gradually reduce its compressive stress until the outer surface may even
be in tension. This may lead to the development of a laminated oxide structure, because new oxide forms under
the older, buckled, decoherent oxide layer (Ref 6, 15).
For concave surfaces,Fig. 9(c) illustrates oxide growth at the oxide/gas interface by outward diffusion of
cations. As the metal surface recedes, the compressive stresses due to oxide growth are reduced. If further
adhesion is weak, further oxidation may lead to spallation of the oxide. If adhesion forces at the oxide/substrate
interface are strong, further scale growth will cause development of tensile stresses in the oxide adjacent to the
substrate. Figure 9(d) shows growth on a concave surface by anion diffusion inward for reaction at the metal-
oxide interface. Very high compressive stresses develop during growth, until they exceed the cohesive strength
of the oxide, and shear cracking results (Ref 6, 15).
A preferential reaction of a gaseous species (oxygen, sulfur, nitrogen, etc.) with one constituent in an alloy or
refractory may alter the chemical composition of the material to the point where crystallographic phase
transformation is experienced. A change in temperature may also cause transformations. Volume changes
associated with these phase transformations can induce significant stresses in both the alloy and scale or high-
temperature coating.
For oxides that grow by cation diffusion outward through cation vacancies (p-type oxides, such as NiO), the
vacancies are created at the oxide/gas interface and diffuse inward through the scale as they exchange places
with an equal number of outward-diffusing cations. The vacancies are annihilated within the oxide, at the
metal/oxide interface, or within the metal, depending on the type of oxide system. In some oxides, the
vacancies collect together within the oxide to form approximately spherical cavities. The preferred sites for
cavity formation are along paths of rapid diffusion, such as grain boundaries and dislocation lines.
Vacancies that are annihilated at the metal/oxide interface may cause detachment of the scale, because voids
that form reduce oxide-to-metal adhesion. If attachment is only partial, the oxidation rate slows down, because
the cross-sectional area available for diffusion decreases (Ref 6).

References cited in this section

2. N. Birks and G.H. Meier, Introduction to High Temperature of Metals, Edward Arnold, London 1983
3. B. Mishra, Extractive Metallurgy, Metals Handbook Desk Edition, 2nd ed., ASM International, 1998, p
718

4. G.Y. Lai, Corrosion by Halogens, High Temperature Corrosion of Engineering Metals, ASM
International, 1990, p 85–115

5. W.J. Moore, Physical Chemistry, 4th ed., Prentice-Hall, 1972, p 99–101

6. S.A. Bradford, Fundamentals of Corrosion in Gases, Corrosion, Vol 13, Metals Handbook, 9th ed.,
ASM International, 1987, p 61–76

7. G.W. Castellan, Physical Chemistry, 2nd ed., Addison-Wesley, 1971, p 257–258

8. L.L. Sheir and G.T. Burstein, Corrosion: Corrosion Control, Vol 2, 3rd ed., L.L. Sheir, J.A. Jarman,
and G.T. Burstein, Ed., Butterworth-Heinemann, 1994, p 20:65–20:66

9. G.D. Smith, High Temperature, Corrosion Tests and Standards—Application and Interpretation, R.
Baboian, Ed., American Society of Testing and Materials, 1995, p 149

10. L.R. Scharfstein and M. Henthrone, Testing at High Temperatures, Handbook on Corrosion Testing and
Evaluation, W.H. Ailor, Ed., John Wiley & Sons, 1971, p 291–366

11. C. Wagner, Types of Reaction in the Oxidation of Alloys, Z. Elektroch., Vol 63, 1959, p 772–782

12. M.G. Fontana, Corrosion Engineering, 3rd ed., McGraw-Hill, 1986, p 505–520

13. I.G. Wright, High Temperature Corrosion, Corrosion, Vol 13, Metals Handbook, 9th ed., ASM
International, 1987, p 97–103

14. R.E. Reed-Hill and R. Abbaschian, Physical Metallurgy Principles, 3rd ed., PWS- Kent Publishing,
1992, p 360–420

15. A.S. Khanna, Introduction to High-Temperature Oxidation and Corrosion, ASM International, 2002, p
40–60, 172–201, 205–214

16. K. Wu, Y. Wang, and J.E. Morral, Predicting Interdiffusion Microstructure Using the Phase Field
Approach, Elevated Temperature Coatings: Science and Technology IV, N.B. Dahotre, J.M. Hampikian,
and J.E. Morral, Ed., The Minerals, Metals and Materials Society, 2001, p 133

17. E. Basuki, A. Crosky, and B. Gleeson, Interdiffusion Behaviour in Aluminide- Coated René 80H at
1150 °C, Mater. Sci. Eng. A, Vol 224, 1997, p 27–32

18. L. Onsager, Reciprocal Relations in Irreversible Processes, Part I, Phys. Rev., Vol 37, 1931, p 405–426;
Reciprocal Relations in Irreversible Processes, Part II, Phys. Rev., Vol 38, 1931, p 2265–2279

19. A. Sanz, L. Llanes, J.P. Bernadou, M. Anglada, and M.B. Rapaccini, Influence of the Stress State on the
Diffusion Phenomena Across the Interface Between a Protective Coating and a Single Crystal
Superalloy, Elevated Temperature Coatings: Science and Technology II, N.B. Dahotre and J.M.
Hampikian, Ed., The Minerals, Metals and Materials Society, 1996, p 373

20. D.J. Young and B. Gleeson, Alloy Phase Transformations Driven by High Temperature Corrosion
Processes, Corros. Sci., Vol 44, 2002, p 345–357
21. J.-G. Duh and J.-W. Lee, Diffusion-Related Kinetics in the Oxidation-Induced Phase Transformation of
Fe-9Al-3Cr- 31Mn Alloys, J. Electrochem. Soc., Vol 136, 1989, p 847–853

22. D.A. Jones, Principles and Prevention of Corrosion, 2nd ed., McGraw-Hill, 1996, p 412–415

D.A. Shifler, High-Temperature Gaseous Corrosion Testing, Corrosion: Fundamentals, Testing, and
Protection, Vol 13A, ASM Handbook, ASM International, 2003, p 650–681

High-Temperature Gaseous Corrosion Testing

David A. Shifler, Naval Surface Warfare Center

Measurement of High-Temperature Degradation

Sample Preparation for Testing

For high-temperature testing, samples need to be prepared and processed in a similar manner as they would for
actual service. The materials should be characterized by chemical composition, fabrication history, and by
morphology or microstructure (Ref 23).
The size and shape of laboratory and field test samples can vary, but samples should be large enough to obtain
meaningful quantitative information on exposure to the test environment. The samples should be large enough
that the corrosion reaction being tested does not fully consume the material exposed. Geometry asperities, such
as corners and edges, should be eliminated, if possible, because they tend to be less corrosion resistant than
planar surfaces. The geometry, on the other hand, should reflect the part, component, or system as much as
possible. Samples need to be identified, but any markings should not influence the test performance of the
sample.
The samples should be prepared for testing in a specified manner so that the sample surfaces are clean, uniform,
and defect-free to minimize conditions that may affect the testing results. Carburized, decarburized, or cold-
worked layers should be removed (Ref 23). The samples should be handled carefully to avoid contamination.
Before testing, each sample must be measured precisely to calculate the surface area and/or accurately weighed
(for small samples, generally to a precision of 0.1 mg). Testing will alter the dimensions or the mass during
exposure. After measuring the samples, they should be either inserted into the test setup or stored in a dessicator
until needed.
Because deviations in test parameters may vary slightly over time and with sample placement within the test
apparatus, replication is necessary. Samples in duplicate or triplicate will often be sufficient, but larger sample
sizes are strongly advised when the test materials are highly variable. The consistency of the test results will be
improved and the test result scatter decreased when the test parameters are tightly controlled and multiple
samples are used (Ref 23).
If a test is often repeated, a pedigreed control sample should be used to calibrate the experimental laboratory or
service test. This will verify whether test parameter abnormalities exist or if breakdown in operational controls
has occurred during a test. Use of the control samples provides this measure of assurance. Control samples
should be thoroughly characterized (chemical composition, fabrication history, microstructure, and physical and
mechanical properties) (Ref 23).

Mass Change

Mass changes, either losses or gains, are determined by calculating the weight change per unit area, usually as a
function of time, temperature, and pressure. Mass change is calculated as follows:
(Eq 18)

where Wf is the final weight in grams, Wo is the initial weight in grams, and A is the original area in centimeters
squared or meters squared. A plus or minus sign indicates a net gain or loss. It is important to record whether
the test sample has been descaled or not and by what method. The scale may be difficult to remove if it is
tightly adhered or part of an oxide substructure. There are standard methods used for descaling.
It is misleading if single data point or single analytical measurements are made over a long time duration,
because corrosion rates and modes usually vary with time. The use of the mass change method to measure
corrosion rate will also be inaccurate if spallation of the surface layer occurs during the test duration. Three
additional limitations of the mass change method are that (a) it lacks the registering of subsurface attack, such
as intergranular attack, which, at times, is quite deep; (b) deep localized corrosion (e.g., pitting) is averaged
over the weight of the entire specimen, and thus, the extent of the attack is minimized; and (c) weight gains due
to oxygen or sulfur absorption would interfere with weight loss measurements.

Structural Changes

Structural changes in a high-temperature test sample can result in depletion of a constituent in the material or
thermal effects on the stability of the material. An example of alloy depletion is the dissolution of carbides near
the substrate surface because of high-temperature exposure. A common thermal effect is the precipitation of
topologically close-packed phases, such as mu, Laves, and sigma, over time within certain temperature ranges.
Analytical methods, discussed later, can be used to confirm these structural changes.

Metallographic Analysis

Analysis can be most easily performed by optical metallography but may be done using scanning electron
microscopy or transmission microscopy. Metal loss is defined as one-half the difference between the original
thickness and the remaining thickness after exposure, as shown in Fig. 10 (Ref 24). Thickness extends to just
beneath the scale/surface surface and excludes the thickness of internal attack:

(Eq 19)

where to is the original thickness or diameter, and tm is the sample thickness or diameter after a term of
exposure.

Fig. 10 Schematic showing thickness measurements to, original thickness; tm, sample thickness after a
term of exposure; and tr is the remaining good metal thickness. Source: Ref 24
Depth of attack describes the formation of voids, internal precipitation, or penetration due to corrosion. This is
termed depth of penetration or, in the case of oxidation, as internal oxidation. This attack may be due to loss of
a material constituent to a high-temperature gaseous environment or internal reaction in the material. Voids are
often associated with grain boundaries, because the boundaries are a major route for fast diffusion of the
alloying element lost. Alloying elements of high vapor pressure or those that form volatile products with the
gaseous environment are prone to cause voids.
It often is more convenient to test round samples, such as rods or pins. Corrosion attack of such test samples
can be measured by metallographic examination at a specified magnification at designated intervals around the
specimen circumference. The readings at each site around the circumference consist of the outer diameter of the
remaining material and the inner reading marking the maximum corrosion penetration at a specific interval site.
The measurements reported for round samples are described subsequently, with differences noted based on
whether or not the samples are coated.
Uncoated alloy pin measurements affected by corrosion include average material loss on a radius and maximum
material penetration.
Average Material Loss on a Radius. This is the combination of the average change of specimen diameter
(original diameter minus the remaining diameter after full test exposure) and the average radius of corrosion
loss due to all forms of oxidation and sulfidation ([outer diameter minus inner diameter]/2), as shown in Fig.
11. This measurement is usually averaged from a total of all measurements; however, because of the occasional
variations in the original pin diameters, the average material loss on a radius is measured at specified intervals
of each test specimen. Because these measurements are performed at discrete sites around the circumference,
the average material loss on a radius is a statistical average:

(Eq 20)

where D is the original diameter, D1 is the diameter of the structurally intact alloy, and N is the number of
measurements on the test sample. Measurements are made to the nearest 0.02 mm (0.001 in.).

Fig. 11 Schematic of measuring high-temperature corrosion of uncoated metals and alloys on round
specimens

Maximum Material Penetration. This measurement includes surface loss plus the depth of all oxides and
sulfides that may be scattered or in local concentrations, such as grain boundaries. Only the greatest depth value
is reported as the maximum penetration, that is:

(Eq 21)

where D is the original diameter, and D2 is the diameter of the alloy pin unaffected by oxides and sulfides or
any other form of corrosion (such as intergranular corrosion or void formation) caused by the high-temperature
exposure. Measurements are made to the nearest 0.02 mm (0.001 in.). This type of measurement is most
relevant to high-stress applications, such as turbine blades or critical incinerator components. Subsurface attack
in local areas may also promote failures through fatigue or thermal cycling.
Coating Measurements Affected by Corrosion. High-temperature components are sometimes coated to provide
improved protection. Depth of attack can be measured for these materials as well. Measurements of interest are
average coating loss on a radius and maximum coating penetration on a radius.
Average Coating Loss on a Radius. This measurement reflects loss in coating thickness due to all forms of
oxidation and sulfidation. An average of all measurements is made per test specimen, as depicted in Fig. 12:

(Eq 22)

where C0 is the original coating thickness, X1 is the coating attack due to all forms of oxidation and corrosion,
and Y1 is the coating-substrate interface.

Fig. 12 Schematic of measuring high-temperature corrosion of coated materials on round specimens. C0,
original coating thickness; D0, original coating plus substrate diameter; X1, coating attack; Y1,
coating/substrate interface; Z1, maximum coating attack

Maximum Coating Penetration on a Radius. This is a measurement of the deepest attack found anywhere along
the test sample (Eq 23). This number yields a measurement of maximum depth-of-coating attack. Maximum
penetration numbers are typically used to rank coating performance in these tests, under the assumption that
once the coating has been completely penetrated, it no longer provides the intended protection to the substrate.
Although average coating loss may be considerably less than the maximum penetration, the greatest degree of
attack is determined to be the most critical measurement for coating assessments.

(Eq 23)

where C0 is the original coating thickness, Z1 is the maximum coating attack due to all forms of oxidation and
corrosion, and Y1 is the coating- substrate interface. Unlike the average coating loss, which is an average of a
number of measurements, the maximum coating loss is a single measurement where the penetration was
greatest.
Round specimens are preferred because they can be measured accurately by metallographic techniques across
any diameter, which is an important consideration, because an uneven attack frequently occurs. Round
specimens also minimize the influence of thermal stresses on the corrosion properties of materials. Sharp
corners on test specimens may initiate spalling and premature oxide/coating failure that may not be
characteristic of the material in actual service. Wedge, airfoil, or other unevenly shaped specimens are generally
more difficult to analyze, except when using the weight-change method for measuring the degree of corrosion.
However, weight change is not always an accurate quantification of the corrosion process.
Statistical Analysis of Corrosion Measurements. For better assurance of uncoated or coated corrosion
measurements, multiple test specimens are recommended. Five multiple samples provide good statistical
averaging (Ref 25). Because of the redundancy of the multiple test specimens, it is possible to perform a
statistical analysis of the measurement data (Ref 26). This is accomplished by using the two-sample t-test,
unequal variance, for examining the existence of real versus random differences between the corrosion data of
any two given coatings or alloys. This statistical method tests the hypothesis (commonly referred to as the null
hypothesis) that the means of the sets of data from two alloys or coating samples are equal against the
alternative hypothesis that the mean on one alloy or coating set of data is greater than that of the second set.
This statistical test is performed at a specified probability level (usually set at 90%) that the differences in the
means are real and are not due to random variations. This statistical analysis does not project which alloy or
coating is better or worse; it only examines the probability that the observed difference is real and not due to
random variations. See also the articles “Statistical Interpretation of Corrosion Test Results” and “Statistics for
the Corrosionist” in this Volume.
Analysis of Corrosion Products. It is usually desirable to analyze corrosion products and degradation
phenomena for both composition and morphology. Such analysis may be performed by in situ methods or ex
situ techniques that may require special handling and sample preparation. Compositional analysis can be done
by wet chemistry, x-ray diffraction, high- and low-energy electron diffraction, x-ray fluorescence, electron
probe microanalysis, inductively coupled atomic emission spectroscopy, atomic absorption spectroscopy,
Fourier transform infrared spectroscopy, mass spectroscopy, and other methods. Structural morphology and
analysis may be done using light microscopy image analysis, microhardness measurements, transmission
electron microscopy, scanning electron microscopy, scanning Auger microscopy, field emission microscopy,
plus other techniques. For details of these analytical methods, see Materials Characterization, Volume 10 of
ASM Handbook, and Ref 10.

References cited in this section

10. L.R. Scharfstein and M. Henthrone, Testing at High Temperatures, Handbook on Corrosion Testing and
Evaluation, W.H. Ailor, Ed., John Wiley & Sons, 1971, p 291–366

23. G.D. Smith, P. Ganesan, C.S. Tassen, and C. Conder, High Temperature Gases, Corrosion Tests and
Standards—Application and Interpretation, R. Baboian, Ed., American Society of Testing and
Materials, 1995, p 359

24. “Practice for Simple Oxidation Testing,” G 54, ASTM International

25. I. Miller and J.E. Freund, Probability and Statistics for Engineers, 3rd ed., Prentice- Hall, 1985, p 188

26. J.R. Nicholls and P. Hancock, The Analysis of Oxidation and Hot Corrosion Data— A Statistical
Approach, High Temperature Corrosion, NACE-6, R.A. Rapp, Ed., NACE International, 1983, p 198–
210

D.A. Shifler, High-Temperature Gaseous Corrosion Testing, Corrosion: Fundamentals, Testing, and
Protection, Vol 13A, ASM Handbook, ASM International, 2003, p 650–681

High-Temperature Gaseous Corrosion Testing

David A. Shifler, Naval Surface Warfare Center

High-Temperature Corrosion and Degradation Processes


Testing of high-temperature corrosion requires a degree of understanding of the major corrosion processes,
based in large part on the material being exposed and the environment to which the material is exposed, along
with the other basic factors discussed earlier. It must be realized that actual service environments and
conditions may be far more complicated than simple laboratory tests may provide. High-temperature corrosion
or degradation of materials may occur through a number of potential processes:

• Oxidation
• Carburization and metal dusting
• Nitridation
• Sulfidation
• Hot corrosion
• Chloridation and other halogenization reactions
• Hydrogen interactions
• Molten metals
• Molten salts
• Aging reactions, such as sensitization
• Creep
• Erosion-corrosion and wear
• Environmental cracking (stress-corrosion cracking and corrosion fatigue)

Oxidation. Most metals and alloys oxidize on exposure to temperatures above 300 °C (570 °F) in environments
containing greater than 1 vol% O2. Alloys are protected to varying degrees by the oxide layer. The thickness of
the protective oxide often follows parabolic rate kinetics. Gas composition influences the rate of oxidation. The
effects of oxygen concentration and temperature are specific to each alloy. Scale growth rates increase with a
rise in temperature. Oxidation environments may be classified on the basis of the oxygen activity. Oxidizing
environments contain an excess of free oxygen, while reducing environments contain no free oxygen at
equilibrium in the gas mixture. Mixed-oxidant environments that are reducing tend to be more corrosive than
oxidizing conditions.
Preferential grain-boundary oxidation, thermal cycling, the presence of moisture, and chloride- or sulfur-
containing gases cause service lives much shorter than those predicted from isothermal oxidation. Small
additions of rare earths, such as lanthanum, cerium, and yttrium, or the presence of dispersed oxides, such as
yttria, ceria, zirconia, and lanthania, improve the scale adhesion and scale resilience of chromia-forming alloys
to cyclic oxidation of Cr2O3-forming alloys, such as austenitic stainless steels and chromium-nickel alloys (Ref
27). These effects may include (a) more rapid formation of a continuous Cr2O3 scale, (b) reduction in the
oxidation rate, (c) improved scale adherence, and (d) a change in the scale-forming reaction location from the
scale-gas interface to the scale-alloy interface. Reactive elements are known to improve the oxidation resistance
of many high-temperature alloys, particularly if the resistance is dependent on Cr2O3 formation.
Loss of oxide adhesion and integrity may be caused by mechanical damage via spallation or cracking of the
oxide film from cyclic oxidation of chromia and alumina oxides formed on nickel-base alloys due to the
mismatch of thermal expansion coefficients between the oxide and the base alloy (Ref 28).
Carburization of metals and alloys is a form of internal attack where the formation of carbide corrosion
products occurs on exposure to temperatures above approximately 760 °C (1400 °F) in gases containing
methane, carbon monoxide, hydrocarbons, carbon, or other carbonaceous compounds. Carburization alone
usually does not result in corrosion or alloy wastage, but adsorption and diffusion of carbon into the base alloy
can lead to significant changes in the alloy mechanical properties, leading to possible alloy embrittlement.
Variables that affect the carburization rate are the temperature, exposure time, alloy composition, and the partial
pressures of H2, CH4, and H2S. The H2S tends to slow alloy carburization rates.
Carburization is usually controlled by both carbon and oxygen activities. Carbon activity is a function of both
the environment and of the metal or alloy. The carbon activity of a metal or alloy can be determined by
thermodynamics. Generally, the lower the oxygen activity, the greater the tendency for carburization to occur.
Carburization is a diffusion-controlled reaction where the maximum carbon gradient occurs at the reaction
surface. Grain-boundary diffusion of carbon tends to be significantly faster than intragranular diffusion (Ref
23). It is often observed that there is a change of the carbide species from the surface to the interior.
Carbon dioxide produced in an oxidizing environment is less corrosive than carbon monoxide, CO, which is the
prevalent carbonaceous gaseous species in a reducing environment. Reducing or oxidizing environments will
usually be dependent on the stability of the oxide formed; the relative oxidizing or reducing atmosphere can be
determined, to a first approximation, by use of the Ellingham diagrams discussed earlier.
Under simultaneous oxidizing and carburizing conditions where hydrocarbons are present in the gas stream
and/or with the introduction of oily components, stainless steels and nickel-base alloys are susceptible to severe
carburization called green rot (Ref 29). Green rot occurs when internal chromium carbides are formed during
carburization; subsequent oxidizing of the carbides at the grain boundaries may result in embrittlement.
Corrosion products in the pits consist of metal carbides, metal oxides, and graphite. The attack is localized, and
carburization is confined to the pit.
Carburization may be tested in several gaseous environments, such as CH4-H2 (reducing) or CO2-H2-H2O
mixtures, or under pack carburization, where active charcoal is packed around the sample in a steel box and
tested to the desired testing temperature. The carbon reacts with open pockets of air to generate carbon
monoxide, which, in turn, disproportionates via the Boudouard reaction—C (s) + CO2 (g) = 2CO (g), where “s”
and “g” represent solid and gas, respectively—into an oxidizing mixture of carbon dioxide and carbon.
Carburization testing in the laboratory offers the convenience of access to the necessary equipment for precise
control of conditions along with the ability to control measurement schedules. However, the laboratory test may
not mimic all environmental and mechanical conditions, such as stress, design effects (corners, crevices, dead
zones, etc.), thermal fluctuations in service abrasive damage, flow stream effects, and metal-to-metal contact
reactions. Thus, the investigator may not be able to reproduce the complete atmosphere that is being simulated
in the laboratory and thereby runs the risk of missing a key element in determining the rate of carburization
degradation. Reference 30 reviews the phenomenon of carburization and procedures for testing and evaluating
carburization.
Metal dusting can be described as a catastrophic form of carburization occurring under conditions where the
carbon activity (aC) in the gaseous atmosphere is much greater than that in the metal. The degradation takes
place in strongly carburizing atmospheres (aC » l). Although metal dusting has taken place at temperatures as
high as 1095 °C (2000 °F) in strongly reducing gaseous environments, it generally occurs at temperatures from
480 to 815 °C (900 to 1500 °F). Deterioration and material wastage by metal dusting in carburizing gases at
425 to 815 °C (800 to 1500 °F) result in pitting and overall wastage of stainless steels with or without an
oxidizing environment (Ref 31, 32, 33, 34, 35).
Slight modifications in the process conditions may significantly affect the occurrence and extent of metal
dusting attack. The phenomenon can produce rapid metal wastage, producing pits and grooves as the affected
metal disintegrates into a mixture of powdery carbon and metal particles. Metal dusting corrosion occurs in
processes from numerous industries that include petrochemical processing (processes involving steam
reforming of methane or natural gas, such as ammonia and methanol production), direct iron-ore reduction, coal
degasification, and heat treating.
Nitridation of alloys in ammonia environments is well known in ammonia and heat treating industries (Ref 36).
Nitridation characteristics are similar to carburization but are not as commercially common in occurrence. As
with carburization environments, increasing oxygen activity decreases nitridation at a given temperature. It has
been shown that the kinetics of nitridation in N2 are much higher than that found in contact with NH3 at high
temperatures (980 to 1090 °C, or 1800 to 2000 °F) (Ref 37). Heat treating furnaces and accessories for heat
treating powder metal products are typically exposed to N2 or N2-H2 atmospheres at elevated temperatures
(≈1090 °C, or 2000 °F). Alloys can be susceptible to nitridation attack in combustion environments even when
such environments are oxidizing.
The internal precipitation of nitrides in heat- resisting alloys containing chromium or aluminum has been
known to follow parabolic kinetics, indicating the diffusion of nitrogen is the rate-controlling step. Thermal
cycling, which leads to cracking of the oxide scale and/or spallation, destroys the effectiveness of the barrier
oxide, leading to internal nitridation.
Sulfidation is most often a reaction of a metal or alloy with gaseous species, although reaction with molten
sulfur-containing species is possible. Sulfidation produces a metal-sulfur compound that forms on or beneath
the surface of the material. The extent of corrosion depends on the partial pressure of sulfur relative to oxygen
at a given temperature and the relative stability of the oxides and the sulfides at the same temperature.
Sulfidation may involve the formation of oxides plus sulfides in reducing gases, such as hydrogen/hydrogen
sulfide mixtures, or in oxidizing gases, such as air-sulfur dioxide or air-sulfur dioxide water. In most
environments, Al2O3 or Cr2O3 form preferentially to the sulfides, but destructive sulfidation attack may occur at
oxide crack sites (Ref 38). The reduced species, H2S, is more corrosive than the oxidized species, SO2 Gaseous
reactions or molten phases, such as low-melting-point metal-sulfide eutectics, cause sulfidation. Sulfidation of
nickel results in the formation of eutectic Ni3S2 that has a melting point of 635 °C (1175 °F) with a sulfur
solubility of 0.005% (Ref 39). The eutectic formation causes the initiation and propagation of intergranular
corrosion. The sulfidation rate of metals and alloys is usually many times higher than the corresponding
oxidation rate. Metal sulfides generally are more complex and have lower melting temperatures than the
corresponding oxides (Ref 40).
Adding chromium improves resistance to sulfide attack and increases the operating temperature limit of an
alloy in a sulfidizing environment. Chromium sulfide formed below the surface of the protective oxide layer
may lead to depletion of chromium and breakaway corrosion of the alloy. Once sulfur has entered into the
alloy, sulfur tends to react preferentially with chromium or aluminum to form additional sulfides; this may
cause redistribution of the scale-forming elements or interfere with the formation of protective oxide scales.
Nickel-chromium alloys have been successfully used at service temperatures of 750 to 1200 °C (1400 to 2200
°F). Manganese, silicon, and aluminum additions improve the resistance of nickel alloys to sulfur attack (Ref
41).
Scaling rates of high-temperature stainless steels are higher in dry sulfur dioxide environments than in air, due
to the formation of chromium sulfides below the protective chromia scale. The introduction of water vapor into
air- sulfur dioxide environments accelerates sulfidation attack (Ref 13).
Sulfur can be transported through the Al2O3 and Cr2O3 protective scales under certain conditions, resulting in
discrete sulfide precipitates observed at the scale/alloy interface. Sulfide concentrations above approximately
10 to 20 ppm have been shown to modify the adhesion strength and cyclic oxidation resistance of the protective
oxide scales. Generally, cobalt-chromium binary alloys have resistance to sulfidation superior to nickel-
chromium binary alloys because of the slower outward diffusion of cobalt ions through the scale during
sulfidation and the relatively high melting point of the cobalt-Co4S3 eutectic (Ref 42).
Hot corrosion is a complex process involving both sulfidation and oxidation (Ref 43). Hot corrosion is a form
of accelerated oxidation that affects alloys and coatings exposed to high-temperature gases contaminated with
sulfur and alkali metal salts (Ref 44). These contaminants combine in the gas phase to form alkali metal
sulfates; if the temperature of the alloy is below the dewpoint of the alkali sulfate vapors and above the sulfate
melting points, molten sulfate deposits are formed (Ref 44). Molten sodium sulfate is the principal agent in
causing hot corrosion (Ref 45, 46). Sulfide formation results from the interaction of the metallic substrate with
a thin film of fused salt of sodium sulfate (Ref 47, 48, 49). Sulfur compounds come from two sources in a
marine gas turbine engine: sulfur from the combustion fuel, which often ranges from 0.1 to 1 wt% (or more),
depending on the grade of fuel, and sulfate salts contained in marine air that are ingested into the hot section of
the turbine engine.
Chloride salts can act as a fluxing agent and dissolve protective oxide films or cause alloy oxides to fracture
and spall. Air in a marine environment ingested into the combustion zone of any marine gas turbine engine will
be laden with chlorides unless properly filtered. Sodium chloride (NaCl) has been viewed as an aggressive
constituent in the hot corrosion of gas turbine components in the marine environment (Ref 50, 51).
Two general forms of sulfate hot corrosion exist. Type I, high-temperature hot corrosion (HTHC), occurs
through multiple mechanisms. It is generally thought to transpire by basic fluxing and subsequent dissolution of
the normally protective oxide scales by molten sulfate deposits that accumulate on the surfaces of high-
temperature components, such as hot section turbine blades and vanes. The HTHC usually occurs at metal
temperatures ranging from 850 to 950 °C (1560 to 1740 °F). Type I hot corrosion involves general broad attack
caused by internal sulfidation above 800 °C (1470 °F); alloy depletion is generally associated with the
corrosion front. This basic fluxing attack involves raising the Na2O activity in the molten sulfate by formation
of metal sulfides (Ref 52). Very small amounts of sulfur and sodium or potassium can produce sufficient
Na2SO4 or K2SO4. In gas turbine environments, a sodium threshold level below 0.008 ppm by weight precluded
type I hot corrosion (Ref 13).
Type II, low-temperature hot corrosion (LTHC), occurs in the temperature range of 650 to 750 °C (1200 to
1380 °F) where is relatively high or melts are deficient in the oxide ion concentration, leading to acidic
fluxing of metal oxides, which results in pitting attack (Ref 53). Sulfides are found in the pitted area (Ref 54).
The LTHC may involve a gaseous reaction of SO3 or SO2 with CoO and NiO, which results in pitting from the
formation of low-melting mixtures of Na2SO4 and NiSO4 or Na2SO4 and CoSO4 in nickel-chromium, cobalt-
chromium, cobalt-chromium-aluminum, and nickel-chromium-aluminum alloys (Ref 13, 55). The interaction of
these oxidation products with salt deposits forms a complex mixture of salts with a lower melting temperature
(Ref 15). When the salt mixture melts, the corrosion rate increases rapidly. If other reactants are added, melting
temperatures of the resultant salts can be further lowered. High chromium content (>25 to 30 wt% Cr) is
required, generally, for good corrosion resistance to hot corrosion. Nickel-base alloys with both chromium and
aluminum show further improvement in hot corrosion resistance.
Acid-base oxide reactions with molten sulfate through the measurement of oxide solubilities as a function of
Na2O activity in fused Na2SO4 were examined (Ref 56). Oxide solubility is dependent on Na2O activity, which
also serves to rank the acid-base character of individual oxides.
Other impurities, such as vanadium (≥0.4 ppm), phosphorus, lead, chlorides, and unburned carbon, can be
involved in lowering salt melting temperatures, altering the sulfate activity, or changing the solution chemistry
and acidity/basicity that leads to accelerating hot corrosion. Vanadic hot corrosion appears to be potentially
more complex, because five compounds exist in the sodium, vanadium, oxygen system (Ref 57). The high-
temperature reaction of sulfate and vanadium with ceramic oxides involved a Na 2O- V2O5 system that could be
explained by Lewis acid-base chemistry (Ref 58). Basic zirconia (ZrO2)-stabilizing oxides, such as Y2O3, do
not react with Na3VO4 (or 3Na2O-V2O5) but do react with the V2O5 component of NaVO3 (Na2O- V2O5) and
V2O5 itself to form YVO4 (Ref 59). Acidic oxides, such as Ta2O5, react with the Na2O component of Na2VO4
and NaVO3 to form sodium tantalates and yield α-TaVO5 with V2O5. The vanadate that is most corrosive in the
initiation of vanadic attack will depend on the acidity/basicity of the coating or alloy oxide. No reaction occurs
when the acid-base properties of a stabilizing oxide are equal (Ref 60). The thermochemistry of vanadate and
sulfate melts and reaction with different stabilizing oxides with SO3-NaVO3 was studied (Ref 61).
High chromium content (>25 to 30% Cr) is required for good resistance to hot corrosion. Nickel alloys with
both chromium and aluminum show improved hot corrosion resistance. However, inspection of phase stability
diagrams for the systems M-Na-O-S, where M can be nickel, cobalt, iron, aluminum, or chromium, indicates
that there are no combinations of melt basicity and oxygen activity where these metals, absent of a protective
oxide film, are stable in contact with fused sodium sulfate (Ref 62). The relative hot corrosion resistance of a
number of alloys has been evaluated in incinerator environments where hot corrosion can occur (Ref 38, 63,
64).
Yttria-stabilized zirconia (YSZ) is attacked at high temperatures and destabilized by phosphorus impurities in
fuel (Ref 65). The acid P2O5 reacts with basic Y2O3 to form the salt YPO4. Zirconia also synergistically reacts
with sodium and P2O5 to form NaZr2(PO4)3. The YSZ thermal barrier coatings (TBCs) have been exposed to
PbSO4-Na2SO4 molten salts without observable destabilization or reaction with this ceramic (Ref 66). However,
lead, as PbO, appears to cause TBC failures by reacting with chromium in the NiCrAlY bond coat to form
PbCrO4.
Chloridation. Chlorides often accumulate rapidly on metallic surfaces of test samples. In one study, typical
deposits contained 21 to 27% Cl when the flue gas contained 40 to 140 ppm HCl (Ref 67). Municipal wastes
were characterized as having a 0.5% halide dry content, of which 60 wt% was derived from organic polymer
sources (Ref 68). Chloride salts have melting temperatures as low as 175 °C (347 °F), which can act as fluxing
agents that dissolve protective oxide films. High-temperature components exposed to air from a marine
environment will be laden with chlorides. The following compounds may cause rapid corrosion of carbon steel,
if present:
Compound Melting point
°C °F
Molten SnCl2 246 474
SnCl2 + NaCl 199 390
ZnCl2 283 541
Eutectic PbCl2/FeCl3 175 347
Eutectic ZnCl2/NaCl 262 504
Attack by halogens at elevated temperatures occurs through the volatility of the reaction products. Oxides that
form in combustion gases will be porous and prone to fracture. Stainless steels are generally passive, but
surface pitting may occur in chloride-containing environments. Nickel- base alloys can be expected to have
superior corrosion resistance, as compared to stainless steel alloys (Ref 69). Clay containing aluminum silicate
may inhibit chloride-related corrosion by raising the melting points of chloride salts through the formation of
sodium aluminum silicates, which expel HCl and SO3 (Ref 70). Problems with chlorides can be mitigated if
plastics and other sources of halogens are removed or minimized from the waste stream. Increasing the oxygen
content and adding water vapor has also reduced the corrosion rate of various alloys by chlorides in a simulated
waste incinerator environment (Ref 67). Hydrogen chloride can be formed from the combustion from chlorine-
containing polymers and can dissociate into hydrogen and chlorine gases. Low pCl2 will generate a reducing
environment. However, HCl can react with oxygen (generally, catalyzed by surface oxides) to generate water
and possibly very high Cl2 pressures. The corrosion products of chloridation tend to be volatile and have low
melting points. Other halogens may also affect metals and alloys in a manner similar to chlorides.
Laboratory halogenization testing environments are divided into two groups: those possessing no measurable
oxygen and those containing measurable oxygen. In the oxygen-free environments, liquid phases and volatile
reaction products may lead to erratic corrosion attack. Halogen-plus-oxygen environments often exhibit
paralinear behavior as oxide scale and volatile halide reactions occur simultaneously.
Corrosion-resistance testing of materials is properly conducted in electrically heated furnaces using ceramic
tubes with end caps containing pusher rods to manipulate the corrosion specimens under atmosphere. The end
caps should be coated with a castable material to protect them from corrosion. Gas composition may be either
purchased or synthesized from the components, using halogen-resistant electronic flow controllers or mixers.
The specimens may be in the form of pins with dimensions similar to those mentioned for sulfidation testing.
Gas flow streams of a total flow rate of 500 cm3/min (30.5 in.3/min) are considered adequate to ensure a
consistent environment for all specimens. The effluent stream should be reacted with a caustic solution before
venting to remove the reacted and unreacted halogens. At the completion of testing, the specimens should be
examined metallographically for evidence of voiding or liquid-phase corrosion. Scale identification by x- ray
diffraction or electron-dispersive spectrometry can be helpful in clarifying reaction mechanisms.
Hydrogen Interactions. In selected high- temperature reactions, steam may decompose on metal surfaces to
form hydrogen and oxygen. The resulting chemisorbed hydrogen may diffuse into the metal to an appreciable
level. Loss in tensile ductility of steels and nickel-base alloys has been observed in gaseous environments with
a total hydrogen content of 0.1 to 10 ppm at -100 to 700 °C (-150 to 1300 °F). Hydrogen attack occurs when
hydrogen diffuses into the metal (typically steel) and reacts with the carbides to form methane, 4H + Fe3C →
CH4 + 3Fe; the methane causes subsequent internal microcracks that lead to brittle rupture. The larger methane
gas molecules also tend to concentrate at the grain boundaries. When methane gas pressures exceed the
cohesive strength of the grains, a network of discontinuous, intergranular microcracks is produced. The reaction
rate depends on the amount of carbon in the alloy, the hydrogen concentration, diffusion, total gaseous pressure,
and temperatures in the range of 200 to 600 °C (400 to 1110 °F). Hydrogen damage has been observed in utility
boilers at temperatures as low as 316 °C (600 °F) (Ref 71). Hydrogen damage can occur in high-strength alloys,
resulting in loss of tensile ductility. Nickel-base alloys are much less susceptible to hydrogen damage than
ferrous-base alloys.
Nickel and nickel-base alloys are susceptible to attack in gaseous hydrogen environments. The same factors that
affect hydrogen interactions in ferrous alloys are also operative for nickel-base alloys, although to a slightly
lesser degree, because face-centered cubic metals have a greater number of slip planes and have lower
solubilities for hydrogen than body-centered cubic metals (Ref 72). Hydrogen in nickel-base alloys may lead to
intergranular, transgranular, or quasi- cleavage cracking. The Fe-Ni-Cr (Incoloy) and Inconel alloys show
ductility reductions when exposed to hydrogen, particularly age-hardenable alloys (Ref 72).
Molten Metals. Corrosion may cause dissolution of an alloy surface directly, by intergranular attack, or by
leaching. Liquid metal attack may also initiate alloying, compound reduction, or interstitial or impurity
reactions. Carbon and low-alloy steels are susceptible to various molten metals or alloys, such as brass,
aluminum, bronze, copper, zinc, lead-tin solders, indium, and lithium, at temperatures from 260 to 815 °C (500
to 1500 °F). Plain carbon steels are not satisfactory for long-term use with molten aluminum. Stainless steels
are generally attacked by molten aluminum, zinc, antimony, bismuth, cadmium, and tin (Ref 73). Nickel,
nickel-chromium, and nickel-copper alloys generally have poor resistance to molten metals, such as lead,
mercury, and cadmium. In general, nickel-chromium alloys also are not suitable for use in molten aluminum
(Ref 74). There are no metals or alloys known to be totally immune to attack by liquid aluminum (Ref 75).
Liquid metal embrittlement (LME) is a special case of brittle fracture that occurs in the absence of an inert
environment and at low temperatures (Ref 76). Decreased stresses can reduce the possibility of failure in certain
embrittling molten alloys. Stainless steels suffer from LME by molten zinc. Small amounts of lead will
embrittle nickel alloys, but molybdenum additions appear to improve lead LME resistance. The selection of
fabricating processes must be chosen carefully for nickel- base superalloys. Liquid metal embrittlement can
occur when brazing precipitation-strengthened alloys, such as Unified Numbering System (UNS) N07041 (Ref
77). Many nickel superalloys crack when subjected to tensile stresses in the presence of molten (B-Ag) brazing
filler alloys.
Molten salts are often involved in sulfidation, chloridation, hot corrosion, or high-temperature coatings, as
discussed previously. The corrosiveness of the environment depends on the surface temperature and the
condition of and/or the corrosive ingredients in the medium. Molten salts are employed in a number of
applications, including metal heat treating; nuclear, fossil, and solar energy systems; reactive-metal extraction;
high-temperature batteries; and fuel cells.
Molten salts tend to flux the inherent scale that forms on heat-resistant alloys. In the presence of molten ash
products, the oxide, even in oxidizing environments, becomes unstable and dissolves. Oxygen and water vapor
tend to accelerate molten salt corrosion. Molten salt corrosion can take the macroscopic form of uniform
thinning, pitting, or internal or intergranular attack.
Alkali sulfates deposited on the fireside surfaces of boilers may react with SO3 or SO2 to form mixtures of
alkali pyrosulfates (melting point: 400 to 480 °C, or 750 to 900 °F) or alkali- iron trisulfates (melting point: 550
°C, or 1020 °F) that cause fireside corrosion of reheater and superheater tubes (Ref 78). Molten sodium
pyrosulfates (Na2S2O7) (melting point: 400 °C, or 750 °F) or potassium pyrosulfates (K2S2O7) (melting point:
<300 °C, or 570 °F) react with carbon steels by dissolving the protective oxide film and then reacting with iron
to cause accelerated wastage. A few parts per million of vanadium accelerate this reaction. The melting point of
these deposits on waterwall tubes ranges from 300 to 410 °C (570 to 770 °F).
Testing is often done in quartz or platinum crucibles, either in air or in a controlled atmosphere. Molten salts
can induce significant mass transport due to thermal gradients within the crucible. Molten salt corrosion
generally involves dissolution of an alloying element in the higher- temperature regions and subsequent
deposition of the element in the cooler parts of the system.
Aging Reactions. Long-term aging effects in service can cause metallurgical changes that alter the mechanical
and corrosion properties of materials. Testing should reflect long-term aging effects on materials properties.
Graphitization is a microstructural change that can occur in carbon and low-alloy steels. Pearlite (alternating
ferrite and Fe3C platelet structure) normally found in such steels will transform in time to graphite and ferrite at
temperatures above 425 °C (800 °F), which causes loss of ductility and promotes embrittlement. Alloying
additions of at least 0.7% Cr and 0.5% Mo markedly improve resistance of carbon steels to graphitization. Weld
sites are particularly susceptible to graphitization. Treatments or operating conditions that heat ferritic and
austenitic stainless steels to 500 to 900 °C (930 to 1650 °F) can cause segregation at the grain boundaries by the
precipitation of complex chromium carbides (if carbon content is less than approximately 0.03 wt%), the
formation of sigma phase, or the precipitation of other deleterious phases. Nickel-base superalloys are also
susceptible to grain-boundary segregation. Nickel-base superalloys can be embrittled by less than 20 ppm sulfur
segregation to alloy grain boundaries.
Grain-boundary segregation may result in localized corrosion if the grain boundaries are not as resistant as the
alloy matrix, which may be a consequence of segregation causing depletion of corrosion-resistant elements.
Pitting is another form of localized corrosion. Both dissolved oxygen and carbon dioxide can promote pitting of
carbon steels. An alkaline pH can diminish corrosion, with the evolved gases likely to be neutral to acidic. Ash
deposition, thermally induced stress, and particulate erosion may cause conditions that accelerate localized
corrosion by cracking the protective oxide layer.
Iron, nickel, and cobalt superalloys owe their unique strength, up to a fairly high threshold temperature, to the
presence of strengthening particles, such as inert oxide dispersoids, carbides, coherent ordered precipitates, and
solid- solution-strengthening agents, in a face-centered cubic (with appropriate nickel additions) structure.
Introduction of precipitates into the alloy through solid-solution reactions requires specific alloy chemistries
and heat treatments to achieve the desired mechanical properties. However, at prolonged exposures to high
temperatures (760 to 1000 °C, or 1400 to 1830 °F), the phase rule alone suggests that a large number of new
phases could nucleate within multicomponent superalloys to form a number of microstructural instabilities (Ref
79). These instabilities can include transformation of a metastable phase to a more stable but incoherent phase,
as in carbide transformation, stress-induced differential diffusion of solute atoms (coarsening of M23C6 at grain
boundaries), or dissolution of strengthening precipitates in critical areas of the microstructure. Structural
instabilities of austenitic high-temperature alloys at elevated temperatures can also include the formation of new
topologically close-packed (tcp) phases, such as sigma, mu, and Laves phases, which are brittle and possess
cracklike morphologies that can adversely affect alloy tensile and stress-rupture ductility and impair resistance
of the alloy to crack growth (Ref 79).
Intergranular corrosion occurs at or adjacent to grain boundaries, with little corresponding corrosion of the
grains. Intergranular corrosion can be caused by impurities at the grain boundaries or enrichment or depletion
of one of the alloying elements in the grain-boundary area. Austenitic stainless steels, such as type 304 (UNS
S30400), become sensitized or susceptible to intergranular corrosion when heated in the range of 510 to 790 °C
(950 to 1450 °F). In this temperature range, Cr23C6 precipitates, thus depleting chromium from an area along
the grain boundaries below the level required to maintain stainless mechanical and corrosion-resistant
properties. The depleted area is a region of relatively poor corrosion resistance. Controlling intergranular
corrosion of austenitic stainless steels occurs through: (a) employing high-temperature solution heat treatment;
(b) adding elements (stabilizers) such as titanium, niobium, or tantalum that are stronger carbide formers than
chromium; and (c) lowering the carbon content below 0.03%.
Creep. Dislocations form in the oxide as it grows epitaxially on the metal because of the crystallographic lattice
mismatch between oxide and metal. As the growth continues, these glissile slip dislocations move out into the
oxide by the process of glide. Once out in the oxide, they become sessile growth dislocations. Creep may also
develop in the alloy. Creep can affect the alloy, the protective films formed on the alloy, or the coating
performance.
Although dislocations are present in the oxide, slip is not an important process in relieving growth stress (Ref
79). Plastic deformation of the oxide occurs only at high temperatures, at which creep mechanisms become
operative. The three important creep mechanisms in oxides are grain-boundary sliding, Herring-Nabarro creep,
and climb (Ref 80). Grain-boundary sliding allows relative motion along the inherently weak boundaries.
Herring-Nabarro creep allows grain elongation by diffusion of ions away from grain- boundary areas in
compression over to boundaries in tension (Ref 81). Within the grains, dislocation climb is controlled by
diffusion of the slower-moving ions. The creep rate increases with the amount of porosity in the oxide.
The strength of a component within the creep range decreases rapidly when the material temperature increases.
Creep entails a time-dependent deformation involving grain sliding and atom movement. When sufficient strain
has developed at the grain boundaries, voids and microcracks develop. With continued operation at high
temperatures, these voids and microcracks will grow and coalesce to form larger and larger cracks, until failure
occurs. The creep rate will increase and the projected time to rupture will decrease when the stress and/or the
metal temperature are increased. In gas turbines, the use of directionally solidified or single-crystal alloys with
chemistries that promote high-temperature strength minimize degradation by creep.
Creep may be affected by gaseous reactions. Metal components in steam turbines and jet engines must
withstand high stresses for long times at high temperatures. Specimens undergoing creep testing should be
representative of a service component. A creep test is generally run under constant load and constant
temperature for periods of 1000 to 10,000 h or more. Because the creep rate is a function of stress, a rise in
stress will normally cause a corresponding increase in the creep rate. The temperature should be maintained
within close tolerances, such as specified by the ASTM E 139, “Standard Test Methods for Conducting Creep,
Creep Rupture and Stress-Rupture Tests of Metallic Materials.”
A stepped isothermal method has been developed to predict long-term creep performance in much less time
than the traditional constant-load test. This test avoids stress variations by using single specimens and performs
the tests within days. It forecasts long-term creep performance by increasing the temperature in steps; the creep
curve is mapped out in sections, and change in creep rate between each temperature step determines the level of
acceleration. This creep test method also provides a rapid method of studying creep behavior, residual strength,
and the effects of other forms of degradation.
Erosion-corrosion and wear accelerate or increase the deterioration of a metal because of the relative movement
between a corrosive fluid and the metal surface. Erosion may accelerate corrosion of high-temperature
components discussed previously. Generally, mechanical wear, abrasion, or abrupt changes in flow direction
are involved. Metal or alloy loss results when the protective, passive surface films are damaged or worn, and
rapid attack comes about. Metals or alloys that are soft and readily damaged or mechanically worn, such as
copper or lead, are susceptible to erosion. Impingement by solid particles may contribute to erosion-corrosion,
which accelerates several forms of corrosion in the various gaseous or molten environments. Other factors
controlling the rate of metal loss are related to the quantity, impact angle, speed, and density of the eroding
medium.
The appearance of erosion-corrosion is characterized by grooves, gullies, waves, and rounded holes, which
usually exhibit a directional pattern. Increases in velocity may cause no increase in attack until a critical
velocity is reached. Erosion-corrosion can occur on metals and alloys that are completely resistant to a
particular environment at low velocities. Greater velocity may either increase or decrease attack, depending on
the nature of the corrosion or passivating mechanisms. Increasing the oxygen, carbon dioxide, or hydrogen
sulfide concentration in contact with the metal surface may accelerate the attack of steel. Reduced attack may
occur from increased velocity either by raising the diffusion or transfer of ions that diminish the stagnant
surface film or by preventing deposition of salt or dirt that could cause crevice corrosion. Coal-fired generation
systems are subject to erosion-corrosion conditions. Several laboratory techniques and methodologies have
been established to study erosion-corrosion (erosion-oxidation and erosion-sulfidation) at high temperatures.
How these laboratory methods simulate plant conditions and the limitations of each method are reviewed in Ref
82.
Wear is defined as damage to a solid surface that generally involves progressive loss of material and is due to
relative motion between that surface and a contacting substance or substances. Tribocontacts cause damage to
surfaces at high temperature, usually by many consecutive steps by several different mechanisms. Material loss
from the surface can cause wear marks. Fundamental causes of material removal can be shear fracture,
extrusion, fracture, chip formation, tearing, brittle fracture, fatigue fracture, chemical dissolution, and diffusion
(Ref 83). The rate at which surfaces wear depends on the characteristics of each surface, the presence of
abrasives, the speed and angle of contact, and other environmental conditions. There are several modes of wear
(abrasive, polishing, solid-particle erosion, cavitation erosion, liquid impingement, slurry erosion, sliding and
adhesive wear, fretting, corrosive and oxidative wear, and others) that are discussed in more detail in Friction,
Lubrication, and Wear Technology, Volume 18 of ASM Handbook. Wear tests designed to closely simulate the
condition of specific processes are discussed in Ref 84. There are no standardized tests for wear at high
temperatures at this time.
Environmental cracking can occur with a wide variety of metals and alloys in specific environments.
Environmental cracking is defined as the spontaneous brittle fracture of a susceptible material (usually quite
ductile itself) under tensile stress in a specific environment over a period of time. Stress-corrosion cracking
(SCC) and corrosion fatigue are two forms of environmental cracking that can lead to failure.
Stress-corrosion cracking results from the conjoint, synergistic interaction of residual or applied tensile stress
and a specific corrodent for an otherwise ductile alloy. The tensile stress may be either applied (such as caused
by internal pressure) or residual (such as induced during forming processes, assembly, or welding). Stress-
corrosion cracking involves the concentration of stress and/or the concentration of the specific corrodent at the
fracture site. Stress-corrosion cracking fractures may be oriented either longitudinally or circumferentially, but
the fractures are always perpendicular to the stresses. Stress-corrosion cracking may be reduced either by
removing applied or residual stresses or by avoiding concentrated corrodents.
Alloy composition, heat treatment, the exposure time, temperature, and solution media affect SCC. Fluctuating
temperatures can accelerate SCC of austenitic stainless steels in the presence of chlorides, particularly at high-
stress points from design, operation, or fabrication. Nickel alloys exhibit improved resistance to environmental
cracking, as compared to carbon and stainless steels, although nickel alloys are not immune to SCC. Stress-
corrosion cracking of certain nickel alloys has occurred in high-temperature halogen ion environments, high-
temperature waters, and high-temperature alkaline systems and environments containing acids and H 2S. Stress-
corrosion cracking of nickel-base alloys is dependent on the stress level, chloride concentration, alloy
composition, and temperature. Susceptible temperature ranges vary from 175 to 330 °C (345 to 625 °F). Higher
temperatures tend to lower the chloride threshold concentration and stress levels required for cracking. Ferritic
stainless steels are usually not considered susceptible to SCC, but stressed martensitic stainless steel grades can
crack in chloride environments.
Fatigue involves cyclic stresses applied to the component or system during service. Cyclic stresses below the
yield stress of a material can reduce its expected life through the initiation and propagation of transgranular
cracks. The number of cycles required to produce cracking depends on the level of strain and the environment.
Vibration and thermal cycling can lead to initiation and propagation of fatigue degradation. Vibration fatigue
cracks originate and propagate as a result of flow-induced vibration. Circumferential orientations are common
to vibration fatigue cracks.
Corrosion fatigue failures are caused by the combined effects of a corrosive environment and cyclic stresses of
sufficient magnitude. A corrosive environment accentuates this form of degradation by initiating stress raisers
for corrosion fatigue to start and/or lowering the stress necessary to continue the propagation of this cracking
process. Corrosion usually lowers the minimum stress level and/or the number of cycles that will cause failure,
compared to an inert environment. Corrosion fatigue cracks may develop at stress-concentration sites (stress
raisers) such as pits, notches, or other surface irregularities. Corrosion fatigue is commonly associated with
rigid restraints or attachments.
Thermal fatigue cracks develop from excessive strains induced by rapid cycling and sudden fluid temperature
changes in contact with the tube metal across the tube wall thickness. This can be caused by rapid thermal
fluctuations above proper process operational parameter limits. Water quenching by spraying also can induce
thermal fatigue cracks by suddenly cooling component surfaces. This causes high tensile stresses between the
component surface and the bulk metal or alloy; the cooled surface metal tends to contract, while this metal
surface becomes restricted by the hotter metal below the surface.
Stress Rupture. Although not strictly a corrosion-related phenomenon, stress rupture is often involved when the
component is subjected to high temperatures where changes in the microstructure or corrosion of the substrate
reduce the effective thickness of the component to the point where failure occurs. Stress and temperature
influence the useful life of materials in a given gaseous environment.
Most metals and alloys in an oxidizing environment are protected to varying degrees by an oxide layer. Alloy
oxidation from air or steam forms an oxide scale along the metal surface that grows and thickens with time. The
degree of protection of these formed surface scales and resistance of the alloy in a given environment will
depend on factors such as chemical composition, thermodynamic stability, cation or anion transport through the
scale, ionic defect structure, and morphological features of the scale.

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Protection, Vol 13A, ASM Handbook, ASM International, 2003, p 650–681

High-Temperature Gaseous Corrosion Testing

David A. Shifler, Naval Surface Warfare Center

High-Temperature Materials

High-temperature coatings provide a barrier from corrosive or highly oxidative environments that may degrade
the substrate alloy. To provide optimal performance, coatings need to have good adherence to the substrate,
ductility to resist thermal cycling, few or no defects that may provide easy pathways to deleterious gases, good
compatibility with the substrate, and maintain corrosion resistance over the design life of the high-temperature
component. There is a wide range of coatings and coating processes for protecting components in a variety of
operating conditions (Ref 85).
Diffusion Coatings. Aluminide coatings on transition metals and alloys based on iron, nickel, and cobalt are β-
FeAl, β-NiAl, and β- CoAl, respectively. Diffusion aluminide coatings are typically processed via pack
cementation, slurry diffusion, or chemical vapor deposition (Ref 86). Subsequent heat treatments help develop
the proper mechanical properties and trigger further diffusion within the coating. The principal protective oxide
generated by the high- temperature oxidation of these aluminide intermetallics is Al 2O3, which causes
subsequent improved oxidation and corrosion resistance of aluminide coatings; however, less-protective oxides
can form if other alloying elements are present in the substrate, either in solution or as precipitated phases (Ref
87).
Modified aluminide coatings designate an aluminide class that is altered by the addition of a secondary element
such as chromium, platinum, a reactive element, or a combination of these elements (Ref 89). These coatings
are generated either by incorporating the secondary element into the coating by pack codeposition or by
deposition of the modifying element prior to an aluminization process by electroplating, electrophoresis
sputtering, chemical vapor deposition, or pack cementation (Ref 86).
Overlay coatings are MCrAlY-type coatings (where M is iron, cobalt, nickel, or a combination of these
elements) applied by either electron beam physical vapor deposition (EB-PVD) or by thermal or plasma
spraying. Typically, these coatings initially contained cobalt or nickel, with 15 wt% Cr, 12 wt% Al, and 0.1 to
0.9 wt% Y. To improve its resistance to low-temperature type II hot corrosion, the cobalt was partially replaced
with nickel, the aluminum content was reduced somewhat, and the chromium content was increased from 15 to
20 wt% to almost 32 wt%. Hafnium was used as a replacement for yttrium in some MCrAlX coatings, where X
(yttrium or hafnium) promoted coating adhesion and oxidation resistance under thermal cycling conditions. The
MCrAlY coatings have been air plasma sprayed (APS) as a cost-savings procedure, but it often produces a
poor-quality coating. There are various procedures and methods by which plasma spraying may be done, many
of which are proprietary or patent protected. Low-pressure plasma spraying (LPPS) and argon-shielded
spraying produce better-quality coatings.
The principal oxide in the outer portion of a MCrAlY overlay coating is Al 2O3. Yttrium is more prevalent in the
outer scale and promotes oxidation resistance. Hafnium also promotes oxidation resistance and prevents sulfur
from segregating to the coating-substrate interface, thus providing one mechanism of improving the overlay
coating adhesion.
Nickel, cobalt, or both and chromium are found in the inner half of the coating nearer to the coating-substrate
interface. Increases in chromium content improve both the hot corrosion resistance and the oxidation resistance
of the overlay coating but tend to make the coating less ductile.
Thermal barrier coatings (TBCs) usually consist of a porous layer of zirconia, ZrO2, that is stabilized in the
metastable tetragonal phase by approximately 8 wt% yttria, Y2O3. The yttria- stabilized zirconia (YSZ) is
applied using either plasma spraying or by EBPVD over a bond coat, which is usually MCrAlY (where M is
cobalt and/or nickel) or a diffusion aluminide. The bond layer is typically 75 to 125 μm (0.003 to 0.005 in.),
and the TBC is 125 to 375 μm (0.005 to 0.015 in.) thick. Application of the TBC system to hot section
components in a gas turbine has been able to decrease metal surface temperature by approximately 150 °C.
(270 °F). The TBCs also smooth out hot spots, thus reducing thermal fatigue stresses. A thermally grown oxide
(TGO) layer is formed between the bond coat and the TBC during fabrication and tends to grow thicker on
high-temperature exposure of the TBC.
The EB-PVD-applied TBCs tend to produce a columnar structure with fine, ribbonlike voids, porosity within
the columns aligned normal to the plane of the coating, and superior compliance to residual stresses. Plasma-
sprayed TBCs have disklike voids aligned parallel to the coating plane and promoting superior insulating
efficiency.
There are a number of degradation modes that can limit the life of a TBC (Ref 54) as a result of oxidation due
to the possible porosity network in the TBC. By understanding the specific thermomechanical failure modes,
TBCs can be designed for greater reliability and durability (Ref 88). The EB-PVD thermal barrier coatings tend
to spall at the TGO/bond coat interface or in the alumina layer (Ref 89). It was observed that intermittent water
vapor degraded the adherence of alumina to the bond coat under a TBC layer more severely than alumina
formed on the same bond coat in the absence of a TBC (Ref 57).
Hot corrosion exposure to vanadium salts and sulfur trioxide promotes corrosion of stabilized zirconia by acid
leaching of yttria. Yttria loss destabilizes the zirconia, and thermal cycling causes rapid coating failures. This is
potentially serious when burning low-grade fuels (Ref 90). For engine use, ZrO2 must be stabilized in its high-
temperature tetragonal structure to avoid a destructive monoclinic-to-tetragonal phase transformation at 1100
°C (2010 °F). Scandia, Sc2O3, improves vanadate hot corrosion resistance of stabilized zirconia (Ref 59).
Refractories. The corrosion resistance of refractories is based on the thermodynamics of the potential corrosion
reactions, the reaction rates and kinetics of these possible reactions, the composition and form of the refractory
material, and the surface chemistry of the refractory with corrosive gaseous, liquid, or solid environments. The
spontaneous direction of the possible corrosion chemical reactions can be calculated, which can indicate the
reactions that are theoretically possible. The reaction kinetics will be dependent on the specific environment
(gaseous, liquid, or solid), surface chemistry, the material microstructure and composition, refractory phase(s),
and the temperature. All ceramics or refractories used in an oxygen-rich environment are oxides or develop a
protective oxide on their surface (such as SiO2 on SiC or Si3N4). Although oxide ceramics are inert and resist
oxidation and reduction, they are not chemically inert. Ceramic corrosion between ceramic oxides and molten
salt deposits generally can be explained as oxide/ acid-base reactions (Ref 57).
To determine if a particular slag is acidic or basic, the ratio of lime to silica in the slag is commonly used. As a
general rule, the slag is basic if the CaO-to-SiO2 ratio (or CaO + MgO to SiO2 + Al2O3 ratio) is greater than 1.
If the ratio is less than 1, the slag is considered acidic (Ref 91). Gases and liquids can penetrate deeply into
highly porous refractories that can exacerbate spalling and accelerated corrosion. Oxidizing gases, such as NOx,
Cl2, O2, CO2, H2O, and SO2, reducing gases (NH3, H2, CxHy, CO, and H2S), and vapors of volatile elements and
compounds may react with different refractories. Hydrodynamic mass transport by either convection or
diffusion can markedly affect the corrosion rate of a refractory in an environment. Nonwetting refractories are
relatively resistant to corrosion with liquids or gases. Molten aluminum, iron, silica, and other constituents
derived from the incinerator waste streams can react with refractories to form new compounds or phases that
can have different melting temperatures, dimensional stabilities, and corrosion resistances. The new phases or
compounds can cause dimensional changes that can cause problems in the chamber. High-purity refractories are
more corrosion resistant, because certain minor impurity components have microstructures, phases, and defect
structures that can introduce significant corrosion. High-purity refractories improve corrosion resistance by
avoiding low-melting eutectics. Alkali impurities should be minimized as much as possible. Solids, either as
fine particulates or dust, can cause degradation of refractories through abrasion or deposition.
Test Standards. Since the 1990s, worldwide work has focused on formulating standard tests for physical and
mechanical property determinations (Ref 92). Oxidation and corrosion standards have received attention more
recently. Oxidation should be relatively straightforward, thus allowing current test methodologies to be used.
Methodologies for hot corrosion resistance of superalloys can be adaptable to ceramics; guidelines for hot
corrosion testing have been published by a technical working group of the Versailles Agreement on Advanced
Materials and Standards (VAMAS) (Ref 93). The Japanese Industrial Standard JIS R 1609, “Testing Methods
for Oxidation Resistance of Nonoxide High-Performance Ceramics,” published in 1990, was the first standard
developed for ceramics.
ASTM International has several standards for measuring corrosion resistance:
ASTM Title
designation
C 621 “Standard Test Method for Isothermal Corrosion Resistance of Refractories to Molten
Glass”
C 863 “Standard Test Method for Evaluation Oxidation Resistance of Silicon Carbide Refractories
at Elevated Temperatures”
C 288 “Standard Test Method for Disintegration of Refractories in an Atmosphere of Carbon
Monoxide”
C 454 “Standard Practice for Disintegration of Carbon Refractories by Alkali”
More information on ceramic corrosion testing can be found in Ref 94.

References cited in this section

54. K.T. Chiang, F.S. Pettit, and G.H. Meier, Low Temperature Corrosion, High Temperature Corrosion,
NACE-6, R.A. Rapp, Ed., NACE International, 1983, p 519

57. R.L. Jones, Low-Quality Fuel Problems with Advanced Engine Materials, High Temp. Technol., Vol 6,
1988, p 187; NRL Memorandum Report 6252, 9 Aug 1988

59. R.L. Jones and R.F. Reidy, Development of Hot Corrosion Resistant Scandia-Stabilized Zirconia
Thermal Barrier Coatings, Proceedings of Elevated Temperature Coatings: Science and Technology I,
N.B. Dahotre, J.M. Hampikian, and J.J. Stiglich, Ed., The Minerals, Metals and Materials Society, 1995,
p 23

85. G.W. Goward, Protective Coatings—Purpose, Role, and Design, Mater. Sci. Technol., Vol 2, 1986, p
194–200

86. R. Streiff, Aluminides: Yesterday's and Tomorrow's Coatings for Materials in Aggressive
Environments, Elevated Temperature Coatings: Science and Technology II, N.B. Dahotre and J.M.
Hampikian, Ed., The Minerals, Metals and Materials Society, 1996, p 407

87. G.W. Goward, Protective Coatings for High Temperature Alloys: State of Technology, Proceedings of
the Symposium on Properties of High Temperature Alloys, Z.A. Foroulis and F.S. Pettit, Ed., PV 77- 1,
The Electrochemical Society, 1976, p 806

88. P.K. Wright and A.G. Evans, Mechanism Governing the Performance of Thermal Barrier Coatings,
Curr. Opin. Solid State Mater. Sci., Vol 4, 1999, p 255–265

89. M.J. Stiger, N.M. Yanar, F.S. Pettit, and G.H. Meier, Mechanism of Failure of EB- PVD Thermal
Barrier Coating Induced by High Temperature Oxidation, Elevated Temperature Coatings: Science and
Technology III, J.M. Hampikian and N.B. Dahotre, Ed., TMS, 1999, p 51

90. S. Bose and J. DeMasi-Marcin, Thermal Barrier Coating Experience in Gas Turbine Engines at Pratt &
Whitney, Thermal Barrier Coating Workshop, NASA CP 3312, National Aeronautics Space
Administration, 1995, p 63

91. Handbook of Refractory Practice, 1st ed., Harbison-Walker/Indresco Inc, 1992, p PR-12

92. D.J. Baxter, Oxidation/Corrosion of Advanced Ceramics: A Review of the Progress Towards Test
Method Standardization, Working Party Report, H.J. Grabke and D.B. Meadowcroft, Ed., European
Federation of Corrosion, 14, The Institute of Materials, 1995, p 136–146
93. S. Schneider, Ed., International Survey on the Classification of Advanced Ceramics, VAMAS Report 5,
ISSN 1016-2186, Versailles Agreement on Advanced Materials and Standards, 1991

94. R.A. McCauley, Corrosion of Ceramics, Marcel Dekker, 1995, p 109–128

D.A. Shifler, High-Temperature Gaseous Corrosion Testing, Corrosion: Fundamentals, Testing, and
Protection, Vol 13A, ASM Handbook, ASM International, 2003, p 650–681

High-Temperature Gaseous Corrosion Testing

David A. Shifler, Naval Surface Warfare Center

Testing Methods Used for Materials at High Temperatures

As mentioned previously, high-temperature corrosion may occur in numerous environments and is affected by
numerous factors, such as temperature, alloy or protective coating composition, time, and gas composition.
There is a great need for materials testing, both for research and development of new materials (alloys, high-
temperature coatings, refractories, etc.) and processes and to simulate industrial and application environments
to understand the interactions that occur with current materials choices. The goals of laboratory and field testing
are to characterize materials performance in specific applications and to evaluate the effects of environmental
changes on candidate materials. The test conditions should simulate, as much as possible, the environment of
the specific application of interest.
In the case of gas turbines, fuel and air quality and the specific engine environment in which it operates
influence the corrosion of turbine components significantly. Aeroengines use relatively pure fuels with low
sulfur contents, and the air quality is generally good, unless there are recurrent low-altitude flights or operations
over marine environments. Industrial and shipboard turbine engines use lower-grade fuels with 0.3 to 1.0 wt%
S content as well as other less-pure fuels. Unfiltered air intake for marine gas turbines may contain up to 2600
ppm Na2SO4, 19,000 ppm NaCl, and possibly, sand-derived deposits. Filtration may reduce the NaCl content in
air to ≤0.01 ppm, but this is still sufficient to generate Na2SO4 (as well as Na2SO4 directly created from sulfur
in the fuel), which can lead to sulfidation and hot corrosion. Fuel quality may vary during the service life of the
engine. The use of less- refined, heavy fuels may contain up to 200 ppm vanadium that, when combined with
Na2SO4, accelerates hot corrosion reactions. Engine temperatures may also vary with operational loads by 400
to 500 °C (720 to 900 °F) on going from idle to full power (Ref 95). The engine may ingest solid particles
(sand, ash, dust, and sea salt) or generate pyrolytic carbon from uncombusted or poor oxidizing conditions that
will contribute to metal wastage by erosion and impact turbine components. Carbon may also accentuate
corrosion by reducing sodium sulfate to sulfides. Thermal cycling or transient conditions may further increase
the corrosivity of salt deposits by cracking protective oxide layers. The complexity of the turbine operating
environment and other high-temperature applications makes it impossible to develop simple tests to simulate all
the pertinent parameters. Figure 13 shows the variation of the chemical species within the combustion flame as
a function of the fuel-to-air ratio at a given turbine pressure and inlet temperature (Ref 96). Changing the fuel
source, the amount of salt in the intake air, the inlet temperature, and/or the turbine pressure will change the
speciation and the relative distribution of the chemical products.
Fig. 13 Variation in equilibrium composition of the combustion flame as a function of the fuel-to-air
ratio when pressure p = 22.1 atm (2.24 MPa) and the inlet temperature T0 = 811 K (1000 °F) (for fuel jet
A + 0.3% S; air, 5 ppm sea salt). (a) The major products formed. (b) Sodium- and chlorine-containing
species. Source: Ref 96, 97, 98

Incinerators are also inherently complex high- temperature environments. The corrosiveness of the incinerator
environment depends on the relative stream of wastes that are generated and the efficiency of removing
potential wastes that have been proven to be severely corrosive, such as chlorine-containing plastics.
However, laboratory tests can be representative of in-service conditions by choosing the appropriate deposit or
gas compositions, the temperature, and other operational aspects that can be controlled with a given test
apparatus. Testing may include furnace testing, crucible tests, thermogravimetry or its derivatives, various
burner rig tests, or autoclave testing with a host of analytical techniques to evaluate corrosion products or
materials chemistries. Because some high-temperature reactions are electrochemical in nature, electrochemical
tests (corrosion-potential monitoring, current measurements, and polarization to determine the acido-basicity of
salts) can be employed in test programs (Ref 56, 99).

Furnace Tests

Both horizontal and vertical furnace geometries are widely used in high-temperature testing. High-temperature
oxidation generally leads to external oxide scale together with the formation of internal oxidation products,
particularly in mixed-oxidant or under salt deposit conditions. Furnace exposure methods may involve
isothermal oxidation in air, oxygen, or reduced conditions; cyclic oxidation exposures; gas-phase
corrosion; hot salt corrosion (crucible, salt coat method, or burner rig testing); or diffusion studies at a
temperature range of 250 to 1500 °C (480 to 2730 °F) or higher, depending on the focus of the parameter,
material, and environment being tested. In conjunction with a thermobalance and other ancillary equipment
(discussed later), furnace tests can generate kinetic data and analyze the corrosion products formed as a result of
high- temperature gaseous reactions.
Furnace testing has been used to evaluate and measure the diffusion of chromium to the alloy- scale interface in
several chromia-forming alloys during extended exposures at elevated temperatures. When the alloys were
placed into a furnace and exposed to air at 1050 °C (1920 °F) for 720 h, the depth of chromium depletion could
be measured due to the chromium interdiffusion to the surface. Other alloying elements can have a marked
effect on chromium interdiffusion rate (Ref 100).
Another furnace test involves spraying an aqueous solution, saturated with salt, on specimens heated to a
moderate temperature (approximately 200 °C, or 392 °F) to form a dry salt layer. Once samples are coated with
this salt layer, testing can occur in a furnace at the prescribed temperature in a controlled atmosphere and a
given length of time to monitor the corrosion on the sample (Ref 99). It is fairly simple to recoat coupons with
Na2SO4 or other salts at various intervals in a furnace test.

Molten Salt Tests

The molten salt test is used to determine the susceptibility of materials (alloys, ceramics, and protective
coatings) to corrosion attack from molten salts (Ref 55, 101). It consists of immersing selected samples in the
molten salt for a given period of time and then examining the samples for evidence of attack. The half-cell
potentials are measured in some molten salt immersion tests to study film integrity as a function of such
parameters as oxide thickness, salt composition, and atmosphere. Test parameters in a crucible test are well
defined and can be closely monitored.
For gas turbine applications, experiments are conducted in a resistance-wound electric furnace containing a
high-purity platinum crucible with approximately 50 g (1.8 oz) of reagent-grade sodium sulfate (Na2SO4), as
shown in Fig. 14. Potential measurements are made using platinum as a reference electrode that monitors the
corrosion activity, because in molten salts, corrosion occurs via electrochemical processes (Ref 99). For
sulfidation of alloys, a sustained rise in potential can be observed (Ref 99). A new batch of sodium sulfate is
prepared prior to each exposure to eliminate any possible contamination from other sample immersions. All
specimens are immersed in the molten Na2SO4 for up to 1000 h. A sample examination can be made after 500
h, and, if desired, the samples can be returned to the molten salt bath for an additional 500 h. The molten
Na2SO4 salt temperature typically is maintained at 899 °C (1650 °F). The melting temperature of Na 2SO4 is 884
°C (1623 °F). Still air or argon are used as atmospheres over the molten salts to achieve two levels of oxidizing
conditions (Ref 101). Adding NaCl to the sodium sulfate can test the effects of slag. The crucible test is the
simplest evaluation method to discern the relative resistances of materials in sulfidation and hot corrosion
environments.

Fig. 14 Schematic of molten salt test apparatus with test specimen. Source: Ref 101

In molten salt tests, if the test sample is not completely immersed, there may be three distinct environments to
which the test specimen is exposed. The first is immersion in the molten salt, the second is at the interface
between the molten salt and its vapor, and the third specimen exposure is to the salt vapor. In the Dean test,
Na2SO4 is heated to above 1100 °C (2012 °F) to establish an appropriate vapor pressure, and the sample is
maintained at a temperature below the dewpoint where condensation occurs, so that the SO2/SO3 in the furnace
atmosphere should be controlled (Ref 102).
Table 2 shows how the crucible and other hot test methods compare to actual gas turbine service environments
in terms of simulation, cost, and time (Ref 103). Stability of samples can be monitored by electrochemical-
potential measurements.

Table 2 Accuracy of simulations of hot corrosion test methods, cost, and test times as compared to
service experience of actual gas turbine engines

Type of test Simulation with respect to:(a) Cost(b) Test


Chemistry Aerodynamics time(b)
Gas Solid or System Gas Deposition rate
liquid pressure velocity (dm/dt) of
species condensable species
Engine 10 10 10 10 10 1 1
High pressure, high 10 9 10 9 8 2 2
velocity
High velocity 5 8 4 9 7 3 7
Burner rigs 5 7 3 2 4 7 8
Thermogravimetric 5 6 3 1 2 7 3
analysis
Crucible 2 5 1 1 1 10 10
(a) Simulation: 10 is best simulation of given factor; 1 is worst simulation of actual service.
(b) Relative cost, test time: 10 is lowest cost, shortest time; 1 is highest cost, longest time. Source: Ref 103
It has been found that certain molten mixtures of NaCl and Na2SO4 are more corrosive to superalloys than
Na2SO4 alone (Ref 55). Sodium chloride (NaCl) also lowers the melting temperature of the NaCl-Na2SO4
mixtures relative to Na2SO4. The possibility exists that turbine components downstream of the power turbine
will be exposed to both NaCl and Na2SO4. The NaCl is usually not deposited in the hot sections of the marine
gas turbine engine, but sodium sulfate does form deposits in the hot sections. Vapors of NaCl react with SO2
and SO3 (formed from sulfur in the fuel) to produce Na2SO4. Thermodynamic equations for the formation of
Na2SO4 are (Ref 104):

(Eq 24)

2NaCl + SO3 + H2O ↔ Na2SO4 + 2HCl(g) (Eq 25)


Sample preoxidation before molten salt testing can prolong the period of time before the oxide is penetrated and
the onset of sulfidation begins (Ref 100). The half-cell potential measurements rise with the initiation of
corrosion and generally correlate well with sulfidation attack. Other salts, such as V2O5, that are found in some
fuels in service can be tested in a molten salt crucible test (Ref 105).
After exposure, samples are cleaned of salt by prolonged boiling in distilled or deionized water, oven dried, and
weighed (samples are initially weighed before the molten salt test). The weight change is recorded. Optical
microscopy or scanning electron microscopy is used, where warranted, to examine the specimen surface. X-ray
energy-dispersive spectroscopy, x-ray diffraction, and/or emission spectroscopy are used to identify the
corrosion products formed on the surface. Figure 15 show the relative resistance of two different nickel-base
alloys after immersion for 150 h in a molten salt bath of 75 wt% Na2SO4-25 wt% NaCl at 899 °C (1650 °F).
Figure 15(a) shows the broad corrosion front and the associated development of porosity and void formation
that is typical of high-temperature type I hot corrosion. Figure 15(b) shows catastrophic corrosion of another
nickel-base alloy.
Fig. 15 Corrosion performance of two different nickel-base alloys after 150 h in molten Na2SO4-NaCl at
899 °C (1650 °F). Alloy (a) shows typical type I hot corrosion attack, while alloy (b) shows catastrophic
corrosion attack.

Crucible tests are also conducive to studying the corrosion resistance of alloys in molten chlorides (NaCl-KCl)
and eutectics of several mixed salts, such as NaCl-KCl-Na2SO4-K2SO4. The actual composition and the ratio of
components in salt mixtures can vary the degree of acidity or basicity. This will determine, in large part, the
stability of oxides when exposed to a corrosive environment such as a waste incinerator. The stability of Cr2O3,
NiO, Co3O4, Fe3O4, and SiO2 has been studied in different molten salt bath combinations with varying basicity
that represent possible waste incinerator environmental interactions, as described in Ref 106.
Sodium sulfate can be described by acid-base chemistry in a similar manner as for pH in aqueous solutions.
Specifically, the dissociation of sodium sulfate can be written as Na2SO4 = Na2O + SO3, for which the log10 of
the condensed Na2O activity is a quantitative measure of melt basicity, and the log10 of the gaseous SO3 activity
defines the melt acidity (Ref 62). In the same way as aqueous corrosion, corrosion in fused sodium sulfate is an
electrochemical process. The soluble oxidant, SO3 or S2 , is reduced in the cathodic step for acidic melts.
The sites where cathodic reduction occurs result in a local increase in basicity, to the extent that a sulfide
corrosion product may result. In salt films containing significant concentrations of multivalent transition-metal
cations, the oxidation reaction can occur at the substrate/salt interface, and the cathodic reaction can occur at
the salt/ gas interface through the interactions of the cations, in deference to SO3, with a counterdiffusion of
these metal ions carrying the current through the salt film (Ref 106). Electrochemical reactions affect the acid-
base chemistry of salt films. Electrochemical reactions in molten Na2SO4 have been monitored by a doped
zirconia-oxygen sensor and Ag/Ag+ mullite-sodium sensor during potentiodynamic polarization and cyclic
voltammetry experiments (Ref 107).
Acid-base oxide reactions with molten sulfate through the measurement of oxide solubilities as a function of
Na2O activity in fused Na2SO4 were examined (Ref 56). Oxide solubility is dependent on Na2O activity, which
also serves to rank the acid-base character of individual oxides. The solubilities of NiO, Co3O4, Fe2O3, CeO2,
Cr2O3, Al2O3, and SiO2 have been determined as a function of melt basicity for fused Na2SO4 at fixed
temperatures (Ref 108, 109, 110, 111, 112, 113, 114, 115). The presence of more than one oxide contained in a
salt film will cause greater dissolution than if only one oxide was present. The more basic oxide would exhibit
acidic dissolution that releases oxide ions as corrosion products. The more acidic oxides would react with the
oxide ions to promote basic dissolution (Ref 62).
The melt acidity can be determined by measuring the potential between a reference electrode and a working
electrode contacting a melt of the same composition (Ref 107). Researchers proposed that a negative solubility
gradient was a general criterion for hot corrosion to continue (Ref 116).
There are two major drawbacks to crucible test results when related to gas turbine engines (Ref 96). First, with
the exception of the Dean test, the procedures involve a one-time application of Na2SO4, whereas in service,
there is continuous or near-continuous deposition of Na2SO4 in turbine engines. Secondly, during service,
material surfaces are exposed to temperatures, pressures, velocities, or gas compositions that vary significantly
and rapidly with time, which cannot be easily reproduced in a furnace or crucible (Ref 96, 99, 117, 118).

Thermogravimetric Analysis

Thermogravimetric analysis (TGA), also known as thermogravimetry (TG), can complement the laboratory
testing of materials in gaseous, high-temperature corrosive environments by determining the kinetics and
mechanisms of high-temperature corrosion by measuring the oxide growth and associated change of sample
mass over time at temperature (Ref 119). In this technique, changes in the mass of a sample are studied while
the sample is subjected to a controlled-temperature program. The temperature program is most often a linear
increase in temperature, but isothermal studies can also be carried out, when the changes in sample mass with
time are followed. Thermogravimetry is inherently quantitative and therefore an extremely powerful thermal
technique, but it gives no direct chemical information. Test temperatures may range up to 1700 °C (3092 °F).
The ability to analyze the volatile products during a weight loss is of great value. Additional information can be
obtained by integrating mass spectroscopy or Fourier transform infrared spectroscopy (FTIR) with the TGA
instrumentation. The main high-temperature processes amenable to TGA study (either by measuring weight
losses or weight gains as a function of time) are listed in Table 3.

Table 3 Processes measurable by thermogravimetric analysis

Process Weight gain Weight loss


Adsorption or absorption X …
Desorption … X
Dehydration/desolvation … X
Sublimation … X
Vaporization … X
Decomposition … X
Solid-solid reactions … X
Solid-gas reactions X X
The essential components of the TGA instrument are an electrobalance, furnace, temperature programmer,
sample holder, an enclosure for establishing the required atmosphere, and a means of recording and displaying
the data (Ref 120). Balance sensitivity is usually approximately 1 μg, with a total capacity of a few hundred
milligrams. In oxidation or high-temperature corrosion tests, depending on the capacity of the balance (500 mg
to 100 g), the sample size, and other experimental factors, the actual sensitivity may be a few micrograms to
100 to 200 μm. A typical operating range for the furnace is ambient to 1000 °C (1832 °F), with heating rates up
to 100 °C/min (212 °F/min), but materials may be exposed and measured by TGA to 1700 °C (3100 °F). The
control of the furnace atmosphere requires careful attention, particularly the ability to establish an inert
(oxygen-free) atmosphere, and it is useful to be able to quickly change the nature of the atmosphere.
Compatibility between the materials of construction, the sample, its decomposition products, and the gaseous
atmosphere must be considered. Sample holder materials commonly available include aluminum, platinum,
silica, and alumina. Indication of the sample temperature is by a thermocouple close to the sample. Careful
calibration for temperature is important, especially for kinetic studies. Various means are available for
temperature calibration, which is not a trivial matter, although reproducibility is often more important than
absolute accuracy. Weight calibration is readily achieved using standard weights.
Many factors influence the shape of the TG curve, both sample- and instrument-related, some of which are
interactive. The two primary factors are heating rate and sample size, an increase in either of which tends to
increase the temperature at which sample decomposition occurs and to decrease the resolution between
successive mass losses. The particle size of the sample material, the way in which it is packed, the crucible
shape, and the gas flow rate can also affect the progress of the reaction. Careful attention to consistency in
experimental details normally results in good repeatability. On the other hand, studying the effect of deliberate
alterations in such factors as the heating rate can give valuable insights into the nature of the observed
reactions.
Table 4 lists a set of recommended atmospheres and temperatures for testing materials by TGA under
conditions closely related to certain environments or processes (Ref 119). Continuous TG permits the automatic
recording of mass change for a single sample over a period that is generally 1 to 100 h. Discontinuous
thermogravimetry (DTG) is more widely used when there is an attempt to simulate industrial service. This is
particularly true for complex gaseous atmospheres, under salt deposits, or for long term (100 to >10,000 h in
oxidation or corrosion studies) (Ref 122). Discontinuous methods do present mass gain data per specimen and
impose a thermal shock when the specimens are removed from measurement, but they provide a simple
experiment to be exposed to complex environments and to evaluate a wide variety of alloys in a single test.

Table 4 Recommended testing atmospheres and temperatures for testing materials by


thermogravimetric analysis

Environment Gas composition Temperature


°C °F
Air Air, 2.5% H2O 450–1200 850–2200
Flue gas Air, 2.5% H2O, 0.1–1% SO2 400–1000 750–1850
Waste incineration Air, 2.5% H2O, 0.1–1% SO2, 0.05–0.1% HCl 400–850 750–1550
Sulfidizing environment 0.1–1% H2S, balance H2 300–600 570–1100
Carburizing environment 1% CH4, balance H2, dew-point -45 °C (-50 °F) 800–1100 1450–2000
Nitriding environment 90% N2, 10% H2, dewpoint -45 °C (-50 °F) 800–1300 1450–2350
Metal dusting environment 25% CO, 73% H2, 2% H2O 350–750 660–1380
Coal gasification (wet) 0.1–1% H2S, 5% CO, 2.5% H2O, balance H2 400–700 750–1300
Coal gasification (dry) 0.1–1% H2S, 70% CO, 2.5% H2O, 25% H2 400–700 750–1300
Waste gasification (pyrolysis) 90% H2O, 5% H2, 5% CO, 0.1% HCl, 0.05% H2S 400–700 750–1300
Source: Ref 121
The ability of TGA to generate fundamental quantitative data from almost any class of materials has led to its
widespread use in every field of science and technology. Key application areas are:

• Thermal stability: Related materials can be compared at elevated temperatures under the required
atmosphere. The TG curve can help to elucidate decomposition mechanisms.
• Kinetic studies: A variety of methods exist for analyzing the kinetic features of all types of weight loss
or gain, either with a view to predictive studies or to understanding the controlling chemistry.
• Materials characterization: The TG and DTG curves can be used to “fingerprint” materials for
identification or quality control.
• Corrosion studies: Thermogravimetry provides an excellent means of studying oxidation or reaction
with other reactive gases or vapors.
• Simulation of industrial processes: The thermobalance furnace may be thought of as a mini-reactor,
with the ability to mimic the conditions in some types of industrial reactor.
• Compositional analysis: By careful choice of temperature programming and gaseous environment,
many complex materials or mixtures may be analyzed by selectively decomposing or removing their
components. This approach is regularly used to analyze, for example, filler content in polymers, carbon
black in oils, ash and carbon in coals, and the moisture content of many substances.

Differential thermal analysis (DTA) measures the temperature difference between a reactive sample and a
nonreactive reference and is determined as a function of time, providing useful information about the
temperatures, thermodynamics, and kinetics of reactions. The DTA is a dynamic method detecting the heat of
reaction (exothermic or endothermic) of a physical or chemical change of the measured system. A sample to be
analyzed and an inert substance are heated up in a furnace simultaneously under the same conditions. Within
the sample and the inert substance there are mounted thermocouples that are connected against each other, so
that the temperature difference between sample and inert substance is measured.
Differential scanning calorimetry (DSC) measures temperature and heat flows associated with thermal
transitions in a material. It is thus the most generally applicable of all thermal analysis methods, because every
physical or chemical change involves a change in heat flow. Differential scanning calorimetry involves
recording the energy necessary to establish a zero temperature difference between a substance and a reference
material against either time or temperature as each specimen is subjected to an identical temperature regime in
an environment heated or cooled at a controlled rate. The resulting DSC curve represents the amount of heat
applied per unit time as the ordinate value against either time or temperature as the abscissa; this is related to
the kinetics of the process (Ref 123).
Temperature calibration is carried out by running standard materials, usually, very pure metals with accurately
known melting points. Energy calibrations may be carried out by using either known heats of fusion for metals,
commonly indium, or known heat capacities. Synthetic sapphire (corundum or aluminum oxide) is readily
available as a heat capacity standard, and the values for this have been accurately determined over a wide
temperature range. Typical purge gases are air and nitrogen, although helium is useful for efficient heat transfer
and removal of volatiles. Argon is preferred as an inert purge when examining samples that can react with
nitrogen. Experiments can also be carried out under vacuum or under high pressure, using instruments of the
appropriate design.
In the absence of any discrete physical or chemical transformations, the baseline signal in DSC is related to the
heat capacity of the sample. Differential scanning calorimetry allows this parameter to be determined with good
accuracy over a wide temperature range. The conventional approach is to compare the signal obtained for the
sample above that given by an empty pan, with the signal obtained for a standard material, usually sapphire,
under the same conditions. Careful experimental technique is required to obtain accurate results, but heat
capacities can be routinely measured to an accuracy of better than ±1%.
Other techniques are available for heat capacity measurement by DSC. Accurate data can be obtained in narrow
temperature intervals by using a nonequilibrium pulse technique, which is particularly useful when
measurements need to be made in a region constrained by adjacent complicating phase transitions. Less time-
consuming experiments than those described previously can generate data more rapidly but at the expense of
accuracy and precision, which may be adequate for a given purpose. Modulated- temperature differential
scanning calorimetry (MTDSC), a recent enhancement of DSC, routinely generates heat capacity data from a
standard experiment and can, in fact, measure this in a nominally isothermal condition. However, the classical
method is still recommended for the best-quality results.
Use of DSC provides a cost-effective method for obtaining kinetic and thermodynamic data for condensed
phase phenomena. Observable processes include simple phase transitions, characterization of polymorphism,
and the kinetics and thermochemistry for a variety of complex reactions. Thermodynamic data for pure
substances include melting and boiling points, heat capacity, heat of fusion, heat of solution, and heat of
vaporization.
The DSC-DTA curve may show an exothermic or endothermic peak. The enthalpy changes associated with the
events occurring are given by the area under the peaks. In general, the heat capacity will also change over the
region, and problems may arise in the correct assignment of the baseline. In many cases, the change is small,
and techniques have been developed for reproducible measurements in specific systems.
Some possible processes giving enthalpy peaks are listed in Table 5.
Table 5 Type of peaks related to different processes detected by differential thermal analysis and
differential scanning calorimetry

Process Exothermic Endothermic


Solid-solid transition X X
Crystallization X …
Melting … X
Vaporization … X
Sublimation … X
Adsorption X …
Desorption … X
Desolvation (drying) … X
Decomposition X X
Solid-solid reaction X X
Solid-liquid reaction X X
Solid-gas reaction X X
Curing X …
Polymerization X …
Catalytic reactions X …

Burner Rig Testing

Experiences in the 1960s and 1970s led to the discoveries of severe high-temperature corrosion in shipboard
gas turbine engines that usually did not occur in aircraft turbine engines. Early observations noted severe
corrosion attack on the first-stage blade and vane components of a shipboard marine gas turbine engine was
sufficiently rapid to cause engine failure in several hundred hours (Ref 124). The ingestion of sea salt and the
combustion of fuels containing some measure of sulfur by gas turbine engines operating in marine
environments can lead to corrosion of hot section components, particularly turbine vanes (nozzles) and blades
(buckets). This attack was documented in the early open literature as hot corrosion, as discussed earlier (Ref
124, 125, 126). Accelerated high-temperature corrosion was later observed in shipboard waste incinerators (Ref
41, 63).
The laboratory technique that was found to most nearly approximate the operating conditions of a gas turbine
engine was the burner rig (Ref 117). Burner rig tests provide a compromise between simple laboratory and field
tests (Ref 96). Burner rigs are versatile: they may be used with very-low-sulfur fuel to simulate oxidation
conditions at high temperatures; they may be used with 1 to 6 wt% S, vanadium, and/or high- carbon-residue
fuels to simulate sulfidation and hot corrosion conditions; and they may be used with injection of NaCl to
simulate hot corrosion conditions in a marine environment. Laboratory evaluations are employed as a sorting
test for materials (alloys and coatings) resistant to hot corrosion, sulfidation, and other high-temperature
gaseous corrosion reactions. The basic definition of a burner rig is a device that burns fuel to produce the high-
temperature corrosive environment. There are several variations of burner rigs, each compromising certain
aspects of a gas turbine environment while minimizing costs for testing (Ref 117). There are basically three
types of burner rigs: low-velocity atmospheric pressure rigs, high-velocity atmospheric pressure rigs, and high-
velocity, high-pressure rigs. Table 6 compares the test parameters of low-velocity atmospheric pressure, high-
velocity atmospheric pressure, and high-velocity, high-pressure burner rigs in use (Ref 117).
Table 6 Typical operating parameters for burner rigs (low-velocity atmospheric pressure; high-velocity atmospheric pressure; high velocity, high pressure) simulating gas turbine
environments

Users Type Sea salt Fuel Fuel Metal Air/fuel Pressure, Gas Thermal Test Specimens
concentration, sulphur temperature ratio atm velocity, cycle time,
ppm content, °C °F m/s h Type Number/test Exposure
wt%
Low-velocity atmospheric pressure
DTNSRDC, INCO Ducted 10 Marine 0.4–2 700 1290 30/1 1 5 1/24 h 300– Fin 42 Rotating
and General diesel or and and 1000 carousel
Electric Co. JP-5 doped 900 1650
with
tertiary
butyl
disulfide
Johnson Matthey Ducted 24 Natural gas … … … 30/1 1 … 1/1 h 500 Rod … Rotating
& Co. Ltd. (U.K.) (SO4 added carousel
-1.56 l h-1)
National Physical Ducted 20 continuous, BS 2869 1.0 Varies Varies 28/1 1 0.1 1/22 h 300– 6.35 mm 24 Rotating
Laboratory (U.K.) 9000 1000 (0.25 in.) carousel
intermittent pin
Naval Air Ducted 10 JP-5 … 900– 1650– 30/1 1 8 Yes— 600 Fin 20 Rotating
Propulsion Center 925 1700 variable carousel
Pratt & Whitney Ducted 20 Jet A (SO, 1.3 700 1290 30/1 1 100 at 1/20 h 100– Aerofoil 7 Rotating
Aircraft Group, gas added and and nozzle, 300 carousel
United with 900 1650 much
Technologies primary air) lower at
Corp. specimen
Rolls Royce Ducted Measured as Aviation- 0.3 900– 1650– … 1 … None 100– Pin blade … Rotating
Leavesdon (U.K.) salt flux grade 1100 2010 500 carousel
kerosene
Societé Nationale … 1.9 (Na) … … 850 1560 … 1 10 … … … … …
d'Etude et de
Construction de
Moteurs
d'Aviation
(SNECMA)
(France)
Users Type Sea salt Fuel Fuel Metal Air/fuel Pressure, Gas Thermal Test Specimens
concentration, sulphur temperature ratio atm velocity, cycle time,
ppm content, °C °F m/s h Type Number/test Exposure
wt%
High-velocity atmospheric pressure
Admirality Ducted 0.1 NATO-F 1.0 650– 1200– 50/1 0.76 165 1/25 h 2.5– 6.35 mm 33 Rotating
Research 16 naval 900 1650 1200 (0.25 in.) carousel
Establishment distillate rod
(U.K.)
Avco/Lycoming Ducted 6 JP-4R 0.2 785– 1445– 28/1 to 1 215 Yes— Varies Paddle 12 Rotating
Division 955 1750 33/1 complex carousel
Brown Bovari and … 15 (Na) … 0.3–0.4 … … … 1 90 … 300 … … …
CIE (Germany)
Cranfield Institute Ducted 0.06 Diesel fuel 0.3–1.0 750– 1380– 65/1 1 120–130 12/100 h 100 6.35 mm 33 Rotating
of Technology 850 1560 (0.25 in.) carousel
(U.K.) rod
DTNSROC Ducted … JP4, JP5, or 1.0 700 1290 50/1 1 65–265 1/24 h 500 6.35 mm 18 Rotating
marine and and (0.25 in.) carousel
diesel 900 1650 pin
Howmet Turbine Unducted 5 or 50 JP-5R 0.3 785– 1445– 36/1 to 1 215 Yes— Varies Paddle 12 Rotating
Components (doped with 955 1750 44/1 complex carousel
Corp. tertiary
butyl
disulfide)
NASA, Lewis Unducted 0.5 Na as Jet A 0.03– 700– 1290– 20/1 to 1 100 and 3 min 1–500 Cylinder or 1–8 Single
Research Center NaCl (generally 0.07 1260 2300 50/1 330 forced air wedge stationary,
without cooling/1 rotating, or
additives) h carousel
National Unducted 0–20 JP4 and jet <0.05 <1100 <2010 40/1 1 230 1040—30 150 Turbine 2–26 Cascade
Aerospace Lab A1 °C (85 blade
(The Netherlands) °F) hold 6
s
Rolls Royce, Unducted 0.5–4 Standard 0.2 870– 1600– 45/1 1 200 None 120– Rod 12 Rotating
Derby (U.K.) aviation 1100 2010 600 carousel
kerosene D
Eng RD
2494
Solar Turbine Ducted 3 and 35 JP-5 and 0.04– 900– 1650– … 1 280 1/1 h 150 Paddle … Rotating
Users Type Sea salt Fuel Fuel Metal Air/fuel Pressure, Gas Thermal Test Specimens
concentration, sulphur temperature ratio atm velocity, cycle time,
ppm content, °C °F m/s h Type Number/test Exposure
wt%
International diesel 0.25 980 1800 carousel
Sulzer … 15 (Na) … 0.3–0.4 … … … 1 90 … 300 … … …
(Switzerland)
High velocity, high pressure
Admiralty Ducted 0.1–0.5 NATO-F 1.0 650– 1200– 60/1 1–10 (25 230 1/5 h 100 6.35 mm 20 Rotating or
Research 76 naval 1000 1830 max) (0.25 in.) stationary
Establishment distillate rod blade
(U.K.)
Central Electricity Ducted 1.3 (Na) Low- 0.3–0.8 850– 1560– … Up to 21 20–135 … 300+ … … …
Research sodium gas 900 1650
Laboratories oil
(U.K.)
NASA, Lewis Ducted 0.5 Na or Jet A 0.03– 700– 1290– 20/1 to 4 and 50 100 3 min 1–500 Cylinder or 1–8 Single
Research Center NaCl (generally 0.07 1260 2300 50/1 forced air wedge stationary,
without cooling/1 rotating, or
additives) h carousel
Rolls Royce, Ducted None Avtur … Up to Up to 40/1 17 305 Yes Varies Aerofoil 9 Rotating
Bristol (U.K.) 1260 2300 carousel
Westinghouse Ducted … GT-2 diesel 0.35 1100 2010 … 3 155 13/250 h 250 Rectangular … …
bars
Note: 1 atm = 101.3 kPa. Source: Ref 117
The flow and heat-transfer characteristics around a cylindrical specimen are well documented and can be
readily reproduced from one laboratory to another (Ref 96). Therefore, cylindrical test pins are normally used
for burner rig testing. Specimens are usually rotated to keep all specimens at the same temperature and to
ensure uniform exposure of contaminants from the combustion stream. In general, the specimens are removed
from the test chamber periodically and cooled to achieve thermal cycling. Test cycles may range from every 10
min to once every 24 h, depending on the laboratory and the service application that is being simulated during
the burner rig test. There is no accepted specification for burner rig testing. A recommended test practice was
issued by the working group on hot salt corrosion testing of the Versailles Agreement on Advanced Materials
and Standards (VAMAS) (Ref 127).
Likely, the most important factor as to how well a burner rig simulates gas turbine conditions is the
contaminant flux rate deposited on the test specimens (Ref 102, 128, 129). The corrosion rate dependence on
salt deposition rate is nonlinear and depends on the composition of the salt and the substrate alloy or coating
(Ref 130).
There appears to be no unique salt level at which burner rigs are conducted in different laboratories, and there
are wide variations of salt concentration used. In simulation tests, 1 ppm salt is considered realistic, but 10 ppm
is often used. The corrosion rate typically increases with an increase in salt levels from 0 to 10 ppm. However,
according to one report, varying the salt concentration from 10 to 50 ppm in air has little effect on low-
temperature type II hot corrosion (Ref 131).
Due to the complexity of the turbine service environment and the impossibility for any burner rig test to fully
simulate the service conditions, the results from burner rig testing should be used to rank the relative corrosion
performance of alloys and of high-temperature coatings and should not be used to predict the actual corrosion
rates or service life of these materials in an operating turbine.
Low-velocity atmospheric pressure burner rigs (LVBR) operate at low velocity (0.1 to 10 m/s, or 0.33 to 33
ff/s) (Ref 101). In ducted rigs, specimens are directly exposed to the hot gases from the combustion flame in an
unrestricted manner. Under such conditions, it is impossible to maintain the critical partial pressure of SO3/ SO2
for hot corrosion to proceed (Ref 96).
Ducted LVBR rigs are used to gain better control of the test environment. The dimensions of a ducted
combustion environment influence the aerodynamic flow and the heat-transfer characteristics around the test
specimens (Ref 131). The combination of duct configuration, specimen design, and flow characteristics can
alter the boundary layer at the specimen surface sufficiently to give variations in deposition rates (Ref 96). The
Lynn ducted burner rig is shown in Fig. 16.

Fig. 16 Lynn ducted low-velocity atmospheric pressure burner rig used for hot corrosion testing

As shown in the LVBR schematic diagram (Fig. 17), the air, fuel, and sea salt are injected into the burner rig.
The spray is injected into the forward combustion zone to duplicate high-temperature reactions occurring in gas
turbines. The LVBR has been used for testing with 0.5, 5.0, 10, 100, and 200 ppm sea salt. The lower salt tests
are run for 500 and 1000 h, the 100 ppm salt level for 100 to 500 h (Ref 132), and the 200 ppm salt tests for 100
h. The higher sea salt tests, especially at 200 ppm, are heavily oriented toward sulfidation effects; oxidation
does not appear to play a dominant role. On the other hand, the 0.5 ppm sea salt test yields more of an
oxidation-oriented reaction, as evidenced in past efforts to more oxides and smaller (and fewer) sulfides.

Fig. 17 Schematic of a low-velocity atmospheric pressure burner rig. TC, thermocouple

The important factors that influence hot corrosion in gas turbines are composition of the gas, condensate
composition and deposition rate, and temperature. In order to simulate gas turbine conditions in a LVBR, it is
desirable to duplicate all the variables. However, it is not possible to duplicate exactly, due to the pressure
differentials between the gas turbine (5 to 15 atm, or 500 to 1500 kPa) and the 1 atm (101 kPa) LVBR (Ref
131). Table 7 shows a comparison of the partial pressures of gaseous species in the gas turbine and the LVBR.
The corrosion rate depends on the salt deposition rate, which is nonlinear, and the corrosion depends on the
composition of the salt and the substrate alloy or coating (Ref 130). It is desirable to represent an accelerated
test of the turbine conditions with LVBR testing. This is accomplished by using impurity concentrations of the
gas composition and the salt condensate that are similar between the rig and the turbine and by having a salt
deposition rate that is higher in the rig, usually by a factor of 10, than occurs under turbine operating conditions.

Table 7 Typical operating conditions for gas turbines and low-velocity atmospheric pressure burner
rigs (LVBR)

Gas turbine conditions LVBR conditions


Fuel CH1.7 CH1.7
Air-to-fuel ratio (by weight) 60 30
Pressure, atm (MPa) 12 (1.2) 1(0.1)
, atm (MPa) 1.89 (0.192) 0.10 (0.01)
, atm (MPa) 9.34 (0.946) 0.76 (0.077)
, atm (MPa) 0.42 (0.043) 0.068 (0.0069)
, atm (MPa) 0.35 (0.035) 0.058 (0.0059)
Source: Ref 130
The SO2/SO3 equilibrium is a function of the partial pressure of oxygen. Because of the pressure differential
between the gas turbine and the LVBR, the SO2/SO3 partial-pressure ratio in a LVBR cannot be equivalent to
that in the turbine, and it is not possible to simulate the partial pressures of both SO2 and SO3. To simulate the
turbine conditions as nearly as possible in an LVBR environment, the choices are to use (SO 3 + SO2)
summation of partial pressures or the partial pressure of only SO3 or SO2 (Ref 130). The sulfur levels must be
much higher than in the turbine because of the pressure difference. For an equivalent air/fuel ratio, the sulfur
level in the 1 atm (101 kPa) LVBR test should be p times higher than in the turbine if the use of (SO3 + SO2)
partial pressures are simulated, where p is the pressure in the turbine (Ref 130).
In actual operation, metered fuel is atomized and injected into the combustion chamber. Sea salt or other
soluble contaminants are atomized and injected into the forward combustion area, as shown in Fig. 17. The
gases, sea salt, or other solutions added to the fuel stream are thoroughly mixed by the swirl action of air
entering through tangential slots in the combustion tube. This design precludes stagnation or stratification of the
combustion gases. Downstream, the test specimens are exposed to the products of combustion and sea salt (or
other contaminants, such as artificial urea).
Diesel and high-distillate fuels (NATO F76, JP4, and JP5) (Ref 129), as well as other commercial-grade liquid
fuels, have been used for burner rig testing. Di-tertiary butyl disulfide may be added to NATO F76 diesel fuel
to increase the sulfur concentration to 1% by weight, the maximum prescribed sulfur level for this military-
specified fuel. Other contaminants (vanadium, carbon residue, or other species) can be added to study the
individual or synergistic effects on the resistance of alloys (Ref 133) or protective coatings (Ref 134, 135) to
high-temperature corrosion reactions. As discussed earlier, sulfur and sulfur-containing species have been
shown to be a major reactant in hot corrosion. Fuel flow may be in the range of 4 to 6 cm3/min, or
approximately 1.5 to 2.3 gal, during a 24 h period. The fuel is atomized into a fine dispersion by low-pressure
air and introduced into the forward combustion end of the furnace. The combination of a fine spray of fuel,
excess air, and sufficiently high temperatures achieves instantaneous combustion.
Temperature is attained by the combustion of the fuel and is supplemented by heat from heating elements that
surround the test chamber. The heaters reduce temperature gradients and provide stable, controllable
temperatures between 815 and 1150 °C (1500 and 2100 °F). One control thermocouple is used, which is
positioned in the center of the rotating specimen carousel approximately 25 mm (1 in.) above the refractory
surface and is connected to a controller. The thermocouple allows the rig to normally run at its set temperature
±2 °C (±4 °F). Test temperatures for type I hot corrosion are run between 800 and 950 °C (1472 and 1742 °F),
while type II hot corrosion tests are run between 600 and 800 °C (1112 and 1472 °F). Because of small
variations of construction and operating parameters between LVBR test apparatuses and variations in carousel
configurations, each rig should be calibrated prior to testing.
Air/fuel ratios are often set at 30 to 1 but may range from 15 to 1 (approximately stochiometric conditions) to
approximately 60 to 1. Within very specific limits, temperature changes can be made without changing
combustion conditions. Flame impingement on the specimens is always avoided. On the other hand, fuel-rich
conditions or flame impingement can be obtainable as a special test condition.
The LVBR uncoated or coated test specimens (Fig. 18) are electrically and thermally isolated from one another
by insertion into a moldable ceramic that is placed into a metallic carousel. The carousel rotates at a speed (such
as 30 rpm) sufficient to assure equal thermal exposure of all test specimens.
Fig. 18 Untested low-velocity atmospheric pressure burner rig test specimens. (a) Uncoated nickel-base
alloys. (b) Coated superalloys

The LVBR tests are used to simulate gas turbine conditions and, more recently, the high- temperature, hot
corrosion environment that occurs in waste incinerators. For laboratory testing of the waste environment, urine,
if available, or artificial urine is used to duplicate the corrosive conditions on shipboard incinerators. Sea salt
should be added to either urine solution to further simulate this corrosive marine environment. Therefore, all
contaminants (fuel sulfur content, sea salt, urine, and others) should be determined during the design of the
accelerated test to best simulate the environment under consideration.
Figure 19 shows the effects of type I hot corrosion on materials after 1000 h LVBR exposures at 899 °C (1650
°F). Type I high-temperature hot corrosion (HTHC) occurs through basic fluxing and subsequent dissolution of
the normally protective oxide scales by the molten sulfate deposits at metal temperatures ranging from 850 to
950 °C (1562 to 1742 °F); alloy or coating depletion is generally associated with the corrosion front caused by
type I hot corrosion.
Fig. 19 Low-velocity atmospheric pressure burner rig test results at 900 °C (1650 °F). The nickel-base
alloy (a) and the CoCrAlY-type coating (b) were both attacked by type I hot corrosion. Depletion of an
alloy constituent or coating phase was found along a broad front, with an associated generation of small
voids when the constituent/phase is depleted. Depth of penetration in the coating is 115 to 125 μm (4.5 to
5 mils).

As mentioned previously, the use of cheaper, lower-grade fuels may have some undesired consequences. The
use of a LVBR test can determine whether certain fuel contaminants have an adverse effect on the performance
and service life of hot section turbine coatings. Figure 20 shows the effects on a diffusion nickel aluminide
coating after a 1000 h LVBR test conducted at 704 °C (1300 °F). The fuel parameter being tested in this case
was the fuel carbon residue (on 10% bottoms). Increased carbon residue content in the fuel, in this case, led to
enhanced type II low- temperature hot corrosion (LTHC) (Ref 135). Type II corrosion occurs in the temperature
range of 650 to 750 °C (1202 to 1382 °F), where is relatively high or melts are deficient in the oxide ion
concentration, leading to acidic fluxing that results in pitting attack where the sulfides are found in the pitted
area. The carbon may cause erosion, or its presence in the deposit may promote reduction of sodium sulfate to
sodium sulfide. At a threshold fuel carbon-residue content between 0.19 and 0.33 wt%, type II hot corrosion
vastly increases the average coating loss on a radius (from 23 to 30 μm, or 0.9 to 1.2 mils, to approximately 70
μm, or 2.75 mils), as shown in Fig. 21 (Ref 135) by enhancing the effective sulfate activity.

Fig. 20 Low-velocity atmospheric pressure burner rig pins after 1000 h exposure to combustion gases
from fuel containing (a) 0.099 wt% C residue and (b) 0.33 wt% C residue. Increased carbon residue has
a vast effect on aluminide coating performance.
Fig. 21 Effects of fuel carbon residue (10% bottoms) on type II hot corrosion of nickel aluminide high-
temperature coatings. Source: Ref 135

High-velocity atmospheric pressure burner rigs (HVBR) shown as a schematic in Fig. 22, operate at a velocity
of approximately 0.5 Mach (331 m/s or 1086 ft/s). Other HVBR listed earlier in Table 8 operate from 65 to 330
m/s (213 to 1080 ft/s). Test rigs delivering pressures slightly above atmospheric pressure (up to 1.45 bar or 145
kPa) operate between 0.2 to 0.75 Mach (132 to 496 m/s or 433 to 1630 ft/s) (Ref 160). Like LVBR apparatus,
HVBR test setups may be unducted or ducted. A HVBR can evaluate materials of various geometries and
chemical compositions from 371 to 1371 °C (700 to 2500 °F) under oxidation or corrosive environments. The
test temperature at the center of the specimen carousel is maintained to ±15 °C (±27 °F) (Ref 136).
Fig. 22 Schematic of an unducted high-velocity atmospheric pressure burner rig
Table 8 Burner rig deposition rates for high-velocity and low-velocity types

Rig Temperature Velocity Na in combustion Cl in combustion SO2/SO3 in Deposition Sodium mass flux, Chloride mass flux,
type gas, ppm gas, ppm gas, vpm rate, μg/cm · mg/cm2 · h
2
mg/cm2 · h
°C °F m/s ft/s Back- Average Back- Average h Back- Average Back- Average
ground ground ground ground
High-velocity (HV) burner rigs(a)
HVMS 700 1292 220 720 0.019 0.20 0.038 0.40 123 31 0.13 1.38 0.23 2.41
HVM 750 1382 240 790 0.017 0.017 0.035 0.035 134 … 0.12 0.12 0.21 0.21
HVMS … … … … 0.017 0.18 0.035 0.36 … 28 0.12 1.27 0.21 2.18
HVMS … … … … 0.017 0.17 0.033 0.35 … 13 0.12 1.21 0.20 2.07
HVMH … … … … 0.17 0.17 0.33 0.33 … … 1.15 1.15 1.97 1.97
HVMS 899 1650 270 890 0.015 0.16 0.031 0.33 153 5 0.10 1.09 0.19 1.96
Low-velocity (LV) burner rigs(b)
LVM 750 1382 0.1 0.3 20 112 36 200 325 188 0.30 1.67 0.55 3.0
LVM 850 1562 0.1 0.3 20 112 36 200 325 165 0.30 1.67 0.55 3.0
LVA 850 1562 0.1 0.3 13 13 20 20 47 50 0.19 0.19 0.30 0.30
LVA 950 1742 0.1 0.3 13 13 20 20 47 7 0.19 0.19 0.30 0.30
(a) M, marine; MH, high-load marine; MS, marine + salt-shedding simulation of salt from compressor.
(b) A, low-sulfur fuel, jet engine simulation; M, 1% S fuel, marine. Source: Ref 136
Hot corrosion burner rig tests help to evaluate the potential durability of turbine engine materials, which are
expected to breathe sea salt air from aircraft carriers and coastal bases of operation. This test is accomplished
by injecting a controlled amount of sodium chloride solution into the burner flame.
Materials are subject to thermal cycling that duplicates the flight cycles experienced by aircraft making many
takeoffs and landings daily. The test rigs can heat advanced materials and coatings to the extreme temperatures
and hostile environments in which they are expected to operate by only burning several gallons of jet fuel per
hour rather than full-scale engine tests.
Corrosion rates in HVBR and LVBR correlate with the contaminant flux rate and the amount of salt present on
the test sample surfaces (Ref 117). Deposition efficiency changes with temperature from 10 to 12% at 750 °C
(1382 °F) to 8 to 9% at 850 °C (1562 °F) and approximately 4% at 900 to 950 °C (1652 to 1742 °F) (Ref 137).
Under high-velocity conditions at temperatures of 750 °C (1382 °F) and below, injection of salt particulates has
been shown to result in increased corrosion of corrosion-resistant alloys, while no effect was noted for less
resistant alloys. Such behavior is consistent with mechanical damage to the protective scale formed on
corrosion-resistant alloys by particulate impact (Ref 138, 139). At 850 °C (1562 °F), the salt was semi- molten
and therefore would more likely deposit on the surface rather than fracture the oxide.
To generate similar corrosion rates, salt deposition rates in LVBR tests were required to be much higher than
the contaminant flux in HVBR tests. Table 8 compares the burner rig deposition rates, sodium, and chlorine
mass fluxes (Ref 136).
If the contaminant fluxes are similar, material losses will be higher in the HVBR tests than observed in the
LVBR in the type II hot corrosion existing at 750 °C (1382 °F). In the temperature regime where the type I hot
corrosion predominates, the HVBR metal losses are higher than LVBR results exposed to low-salt fluxes, but
the LVBR results are equal to or higher than the HVBR results, as shown in Table 9 (Ref 136).

Table 9 Maximum metal loss as a function of rig and of sodium flux

Alloy Temperature Average sodium flux, mg/cm2 · h Maximum metal loss, μm/1000 h
°C °F LVBR HVBR
IN-738LC 750 1382 0.1–0.2 … 130
750 1382 1–2 6 200
850 1562 0.1–0.2 60 620
850 1562 1–2 84; 142 100
IN-939 750 1382 1–2 1 10
850 1562 0.1–0.2 28 250
850 1562 1–2 79; 177 200
IN-100 750 1382 1–2 2,625 1,000
850 1562 0.1–0.2 7,030; 8,510 3,000
850 1562 1–2 18,245 3,380
LVBR, low-velocity atmospheric pressure burner rig; HVBR, high-velocity atmospheric pressure burner rig.
Source: Ref 136
Due to the impact of salt particulates, discussed previously, the incubation time for hot corrosion to initiate is
generally shorter in the HVBR test environment than noticed in LVBR tests. Although the metal losses from
HVBR tests are lower than those measured after LVBR exposures, the test time was 2 to 15 times shorter in the
HVBR tests compared to the LVBR test runs. The propagation rates for the two alloys illustrated in Table 10
were similar in both burner rigs.
Table 10 Comparison of incubation times and propagation rates exposed to low-velocity atmospheric
pressure burner rig and high-velocity atmospheric pressure burner rig at 850 °C (1560 °F), with sodium
mass flux of 1 to 2 mg/cm2 · h

Alloy Low-velocity burner rig High-velocity burner rig


Metal loss, Propagation Incubation Metal loss, Propagation Incubation
μm rate, μm/1000 h time, h μm rate, μm/1000 h time, h
1100 1500 100 500
h h h h
IN- 93 213 322 790 24 161 345 30
738LC
IN-939 87 266 448 905 20 156 340 41
Source: Ref 136
The HVBR tests are also conducive to other gaseous reaction studies. Nitridation of several nickel-base alloys
used as transition liners in the combustor section of a gas turbine engine was tested in a dynamic oxidation
high-velocity (100 m/s, or 330 ft/s) burner rig operating for 100 h at 980 °C (1796 °F) (Ref 37). In this test, a
fuel oil mixture was burned with an air-to-fuel ratio of approximately 50 to 1. The specimens were removed
from the test chamber every 30 min and rapidly fan cooled for 2 min before returning the specimens to the test
chamber. Due to the high- velocity combustion gas stream with frequent thermal cycling, all test specimens
experienced oxide spallation and relatively uniform metal loss. The internal attack, measured by metallography,
included both internal oxidation and nitridation, as shown in Fig. 23. Bulk carbon and nitrogen for the test
specimens were analyzed. Iron, aluminum, and titanium alloying additions were found to be detrimental to
resisting nitridation attack.

Fig. 23 Optical micrographs showing internal oxidation and nitridation after the dynamic oxidation
burner rig testing at 980 °C (1800 °F) for 1000 h with 30 min cycling. (a) 230 alloy. Note blocky nitrides
below carbide-depleted zone; fine carbide precipitates were due to aging during the test. (b) Alloy X

High-velocity, high-pressure burner rigs (HPBR), such as the one shown in Fig. 24, are more complex than the
previous two rigs, but this test apparatus most accurately simulates the high-pressure, high-temperature
conditions in a gas turbine engine. Pressure and temperature can be adjusted to duplicate the conditions of a
given engine. A HPBR requires compressors and other ancillary equipment to maintain the desired conditions
in the combustor and the specimen chamber. The combustor and the specimen chamber must be designed to
withstand the imposed pressures at the test temperatures.

Fig. 24 Schematic of high-velocity, high-pressure burner rig

The HPBR is a combustion test rig used for high-temperature environmental durability studies of materials for
advanced aircraft. The facility burns jet fuel and air in controlled ratios to produce combustion gas chemistries
and temperatures that are realistic to those in gas turbine engines. In addition, the test section is also capable of
simulating the pressures and gas velocities representative of today's aircraft. Test samples are easily accessible
for ongoing inspection and documentation of weight change, thickness, cracking, and other metrics. The test
pressures range from 3 to 50 atm (304 to 5066 kPa) and with gas flow velocities of 20 to 305 m/s (65 to 1000
ft/sec) (Ref 117). Conditions of one rig reportedly operated at pressures up to 30 bars (3000 kPa) with gas
velocities of 0.25 to 0.9 Mach (166 to 596 m/s or 544 to 1960 ft/s) and temperatures between 700 to 1100 °C
(1292 to 2012 °F) (Ref 161).

Testing at High Temperature, High Pressure

Test temperature and total system pressure (and the partial pressures of various soluble gaseous species) are two
major factors affecting materials corrosion. There are several commercial and industrial processes that occur at
both high temperatures (HT) and high pressures (HP). Table 11 lists a number of common commercial HT/HP
environments (Ref 140). For simple HT/ HP exposure tests involving aqueous or nonaqueous phases, the total
pressure of the constituents in the test chamber varies with temperature.
Table 11 Typical commercial high-temperature/high-pressure service conditions

Application Environment Temperature Pressure


°C °F MPa bar
Nuclear power High-purity 280–500 536–932 ≤17 ≤170
water/steam/H2
Fluidized bed combustion Air, gas, coal 600–750 1112– 1 10
1382
Oil and gas production Brine, H2S, CO2, S 20–250 68–482 ≤130 ≤1300
Aerospace propulsion Hydrogen -200– -328–1652 0.2–67 1–670
900
Oxygen -200– -328–896 ≤8 ≤80
480
Petroleum refining H2, H2S, hydrocarbons 350–650 662–1202 ≤10 ≤100
Compressed natural gas storage Methane with trace H2S 0–100 32–212 ≤8 ≤80
Thermodynamic power NH3, H2O 100–650 212–1202 ≤1.5– ≤15–
generation 15 150
Geothermal power Brine, steam, H2S ≤370 ≤698 ≤17 ≤170
Steam boiler Water, steam ≤300 ≤572 ≤9 ≤90
Source: Ref 140
The simplest type of HT/HP corrosion test involves a sealed, static, pressurized autoclave vessel, as shown in
Fig. 25. The test vessel contains a solution and vapor space above the solution. The ratio of liquid to gaseous
phases is determined by the amount of each constituent, the vapor pressures of the constituents, and the
temperature. Corrosion samples may be placed in the liquid phase, the gaseous phase(s), or at the phase
interfaces, depending on the type of information required (Ref 140).

Fig. 25 Simple static high-temperature, high-pressure autoclave test vessel configuration. Source: Ref
140

In cases where susceptibility to hydrogen embrittlement cracking (HEC), Stress-corrosion cracking (SCC),
liquid metal embrittlement (LME), or other environmentally assisted cracking (EAC) mechanisms may be
suspected, it is common to evaluate the actual mechanical behavior of the alloys under consideration in the
corrosive environment of interest. Slow strain rate testing (SSRT) or constant extension rate testing (CERT)
may be used in a HT/HP environment. The important aspect of such techniques is the requirement for these
tests to be conducted in a range of strain rate or cross-head extension rate in which the material under
evaluation is going to experience cracking, if it is susceptible (Ref 140).
In general, it is necessary to conduct such tests slowly enough so that the environment has adequate time to
affect the material and produce cracking. These strain rates are typically in the range of 10 -4 to 10-7/s for SCC in
many common metal-environment systems. For HEC, the critical strain rate is somewhat higher (i.e., 10 -2 to 10-
4
/s) in most susceptible iron, nickel, and titanium alloys. The SSRT is particularly adapted to HT/HP in
simulated environments (Ref 140). Because the test is accelerated mechanically by the application of the
dynamic straining, it is possible to use simulated test environments rather than the overly aggressive chemical
environments commonly used in conventional standardized tests.
Figure 26 shows a vessel that can be used to conduct SSRT under HT/HP conditions. In aqueous environments,
the heating is accomplished from the outside of the vessel to uniformly heat the entire test solution surrounding
the specimen. For high-temperature gaseous environments, it may be possible to heat the specimen within the
pressurized test vessel.

Fig. 26 High-temperature, high-pressure test vessel for slow strain rate testing. Source: Ref 140

In some cases, it may be possible to use the similarly designed HT/HP test vessel to conduct fracture or fatigue
loading or both (Ref 140). For such tests, accommodations must be made to be able to handle the generally
larger specimen configuration of fracture mechanics specimens. Additionally, there is the need to closely
monitor crack opening displacement or crack growth or both directly, using various methods that include (a)
pressure and environmentally compatible clip gages, (b) mechanical fixtures that exit the pressure vessel, or (c)
potential drop across the specimen. In the case of potential-drop techniques, as the specimen cross section is
reduced due to crack growth, the electrical resistance measured across the cracked region increases and can be
monitored as a measure of crack growth. Alternately, in some cases, direct measurements of crack opening
displacement can be conducted, using special mechanical feedthroughs in the test vessel. This technique, while
cumbersome, is preferred where the test environment is particularly corrosive and may attack clip gages and
interfere with electrical penetrations for the use with potential-drop techniques.
ASTM G 111, “Guide for Corrosion Tests in High-Temperature or High-Pressure Environment, or Both,”
establishes basic considerations that are necessary for conducting corrosion tests on metallic materials under
conditions of high pressure or a combination of high temperature and pressure, and that will promote
consistency in laboratory results.

Thermal Cycling

Many applications of high-temperature materials require repeated heating and cooling cycles that demand that
materials be resistant to the mechanical stresses and subsequent damage during cycling. As noted in earlier
sections, stresses are generated in the oxide or other gaseous-derived scale formed on metals and alloys in
isothermal exposures. Alloys operating in high-temperature applications can exist if protective oxide films are
formed or protective coatings are applied. For alloys with oxides, operation conditions usually apply large
compressive stresses in the oxide scales due to the thermal expansion coefficients between substrates and
oxides differing by 30 to 50%. A third source of stress in the oxide scale can be from scale growth itself,
because of geometric effects or intrinsic oxide growth from counterdiffusion of oxide-forming species (Ref 28,
141). Table 12 gives the expansion coefficients of some metal-oxide systems. Figure 27 illustrates the strains
that are generated by differential thermal expansion.

Table 12 Linear expansion coefficients of metals and oxides

System Oxide coefficient Temperature range Metal coefficient Temperature Ratio


-6 -6
(×10 αo) (×10 αm) range (αm/αo)
°C °F °C °F
Fe/FeO 12.1 100– 212– 15.3 0–900 32– 1.25
1000 1832 1652
Fe/Fe2O3 14.9 20–900 68– 15.3 0–900 32– 1.03
1652 1652
Ni/NiO 17.1 20– 68– 17.6 0– 32– 1.03
1000 1832 1000 1832
Co/CoO 15.0 20– 68– 14.0 25– 77–662 0.93
1000 1832 350
Cr/Cr2O3 7.3 100– 212– 9.5 0– 32– 1.30
1000 1832 1000 1832
Cu/Cu2O 4.3 20–750 68– 18.6 0–800 32– 4.32
1382 1473
Cu/CuO 9.3 20–600 68– 18.6 0–800 32– 2.0
1112 1473
Source: Ref 15
Fig. 27 Strains generated at the interface between various oxides and substrates by differential thermal
expansion. Source: Ref 15

However, when metals and alloys are exposed in an oxidizing environment subjected to thermal changes,
additional stresses impact on the high- temperature scale, which may alter its service life. If the sum of all these
stresses reaches a critical value, the scales crack, detach, or spall, depending on the stress state (Ref 141) and
the fracture toughness of the interface. The greater the disparity of coefficients of thermal expansion between
the alloy and the oxide, the less adherent the oxide becomes during cooling, although other factors, such as
fracture toughness of the interface, also can contribute to loss of adherence.
It is desirable that product scales, such as metal oxides or high-temperature coatings covering alloys that are
subjected to stresses during thermal cycles, are resistant and adherent during these thermal cycles. It has been
shown that degradation of an aluminized MAR-M-200 subjected to small, 2.8 °C (5 °F) rms wave, temperature
variations at 1150 °C (2102 °F) suffered severe weight loss in 150 h (Ref 142). There have been several
reviews on the effects of thermal cycling on high-temperature materials (Ref 143, 144, 145, 146, 147).
Discussion of the mechanisms and testing methods for evaluating thermal cycling effects occurred during a
recent workshop (Ref 143).
Thermal cycling of the test samples is preferred to simulate operations that exist in many high-temperature
applications. The imposition of thermal cycling during oxidation or other gaseous reaction leads to enhanced
metal-gas reaction rates due to scale failure from either decohesion or cracking and subsequent exposure of the
newly bared alloy to the gaseous environment. Stresses related to thermal cycling increase the spallation of
surface oxides, thereby increasing the propensity toward high-temperature corrosion. Thermal cycling can also
lead to the growth and volume changes of the thermally grown oxide, leading to spallation of thermal barrier
coatings (Ref 148). The effect of cycle frequency is highly dependent on the scale adherence to the substrate,
the type of defect controlling spallation, the total test time, and probably, the test temperature. Water vapor and
humidity may also alter the performance of alloy protective scale during prolonged cooling cycles away from
the furnace; cold spalling may occur. Cycle frequency also affects how the cycling test is performed (Ref 149,
150, 151). A rapid temperature cycling (over 100 cycles/day) was developed to evaluate coated parts from 600
to 1000 °C (1112 to 1832 °F) in air, depending on the alloy substrate. This procedure was able to predict
performance of these coated parts (Ref 152).
Computer programs have been developed to predict cyclic oxidation behavior of superalloys (weight change,
amounts of retained and spalled oxide, total oxygen and metal consumed, and terminal rates of weight loss and
metal consumption), based on models of oxidation-growth laws and input on spalling geometry, oxide phase,
growth rate, spall constant, and cycle-duration parameters. This has provided success in some alloy systems,
but such programs may not predict behavior in all systems (Ref 153, 154).
Table 13 lists the performance of several nickel-base and cobalt-base alloys in different corrosive environments
(Ref 155). Exposure to dynamic oxidation generally causes accelerated corrosion or metal loss, as compared to
static, isothermal oxidation tests. Depending on the composition of the alloy, the corrosion resistance may be
superior in some environments but suffer severely in other high-temperature corrosive atmospheres.
Table 13 Corrosion of selected alloys in various high-temperature environments

Test Temperature Results for indicated UNS alloy


°C °F S31008 N06601 N06625 N06690 N07214 N08120 R30556 N06230 R30188
(a)
Static oxidation in air , average metal 980 1800 1.1 1.3 0.7 … 0.2 3.7 1.1 0.7 0.6
affected, mils 1090 2000 … 2.6 … … … 7.7 … … …
1204 2200 10.3 7.5(b) >47.6 … 0.7 … >150 7.9 >21.7
Dynamic oxidation in air(c), average 980 1800 16.5 20.0 7.6 … 1.2 … 6.2 3.5 4.2
metal affected, mils
Reducing sulfidation(d), maximum depth 871 1600 14 >21.7 … … … … 35.6 … 23.6
of attack, mils perforated
Reducing sulfidation(e), maximum depth 593 1100 … … … … … … 121 … 151
of attack, mils
Hot corrosion(f), maximum metal 675 1250 12 … 5 … … … 2.5 … …
affected, mils
Hot corrosion(g), average corrosion rate, 760 1400 13.0 … … 2.8 (nil) … … … … 46.6 (9)
mils (maximum penetration, mils) (35)
Chloridation(h), average metal affected, 900 1650 … 9.0 10.5 … 6.0 … 6.0 … …
mils 1000 1830 … … … … … … 11.8 … …
(i) 2
Carburization , mg/cm (depth in mils) 980 1800 7.7 … … … … 0 (0) 1.0 0.4 0.5
(84.2) (18.0)
Note: UNS, Unified Numbering System.
(a) Static oxidation in air; lab test for 1008 h, with specimens cycled to room temperature once every 168 h.
(b) Large internal voids not included for N06601 reading.
(c) Dynamic oxidation in air; lab test for 1000 h, with specimens cycled to room temperature once every 30 min.
(d) Ar, 5% H2, 5% CO, 1% CO2, 0.15% H2S; pO2 = 3 × 10-19 atm; duration 500 h, except for 310 stainless steel, which was for 215 h.
(e) H2, 46% CO, 0.8% CO2, 1.7% H2S at designated temperatures.
(f) Recuperator of aluminum remelting furnace flue gases. Mode of corrosion: combined attack by alkali sulfates, chlorides, with oxidation for 1150 h.
(g) Burner rig test with combustion products of No. 2 fuel oil (1.0% S); thermal shock frequency h; corrodent urine.
(h) Ar + 20% O2, 0.25% Cl2 for 400 h at 1000 °C (1830 °F).
(i) Carburization resistance for 500 h in packed graphite. Source: Ref 155
Service Testing

Simulating the environment of an industrial process or application is a compromise in most situations. Most
atmospheres consist of mixed oxidants of varying partial pressures (activities), temperature gradient profiles,
and, in some cases, velocity and erosion parameters as well. Key application variables should be identified and
care should be taken to see that these variables are suitably simulated in the service test. Characterization of gas
composition is as essential as the control of temperature and gas flow rate. Atmosphere synthesis may require a
stream of apparatuses consisting of such units as an inlet saturator, exhaust condensers, gas preheater beds,
catalyst beds, heat shields, bubblers, mass flow meters, and analytical instrumentation. Corrosive gases, such as
sulfur trioxide, will require corrosion-resistant materials of construction (Ref 9).
One standard wire-heater test is described by ASTM B 76, “Accelerated Life of Nickel-Chromium and Nickel-
Chromium-Iron Alloys for Electrical Heating.” The useful life of a material is determined by electrically
heating a section of wire in air to a given temperature, where it is held for 2 min, followed by 2 min of cooling.
This cycle is repeated until a 10% increase in electrical resistance is noted and reported as the useful life of the
material. This testing can take approximately 1 week.
ASTM G 79, “Standard Practice for Evaluation of Metals Exposed to Carburization Environments,” covers
procedures for the identification and measurement of the extent of carburization in a metal sample and for the
interpretation and evaluation of the effects of carburization. It applies mainly to iron- and nickel- base alloys for
high-temperature applications. Four methods are described: method A, total mass gain; method B,
metallographic evaluation; method C, carbon diffusion profile; and method D, change in mechanical properties.
Carburization testing in the field usually requires dedicating all or a portion of a particular piece of equipment
for evaluating alloy performance or for evaluating the effect of process variables on the materials of
construction (Ref 23). Such testing is performed to confirm laboratory data because of a lack of access to
laboratory equipment or professional material expertise, or because of difficulty in duplicating certain
carburization conditions in the laboratory. Atmospheres of low oxygen potential have proven difficult to
duplicate in the laboratory. Direct simulation of ethylene furnaces is difficult in the laboratory because of the
simultaneous interaction of long-term creep and high-temperature corrosion by carbonaceous atmospheres on
the inner diameter and by oxidizing combustion gases on the outer diameter of the furnace tubes (Ref 23). A
new carburization standard test method has been developed to generate carburization data for different
materials under the same test parameters and procedures (Ref 156). This test method is conducted at 982 °C
(1800 °F) for 96 h in H2 containing 2% CH4.
An excellent example of field testing in conjunction with laboratory testing to solve a heat- exchanger corrosion
problem in an industrial chlorinated solvent incinerator is described in Ref 157. A corrosion rack containing
three stainless steels, two high-nickel austenitic alloys, and three nickel-base alloys was placed within the gas
hot stream of a heat exchanger containing HCl and chlorine. The in-situ test results were correlated with
laboratory tests of the same alloys for this application.
Waste incinerator effluent streams contain halogen compounds arising principally from the burning of plastics
and organic matter. A 10 year study of candidate alloy boiler tubes in several field test sites is described in Ref
158. Again, these field tests were confirmed by simulated laboratory test. Metallography and scanning electron
microscopy were used to define the corrosion modes of this mixed-oxidant environment. Ultrasonic thickness-
measuring equipment was used to follow the tube corrosion/ erosion rates at the field site. Tubes were
periodically removed from service for laboratory evaluation. Test tracks have proven to be a valuable source of
performance information on candidate materials in waste incinerator environments (Ref 3, 159).

References cited in this section

3. B. Mishra, Extractive Metallurgy, Metals Handbook Desk Edition, 2nd ed., ASM International, 1998, p
718

9. G.D. Smith, High Temperature, Corrosion Tests and Standards—Application and Interpretation, R.
Baboian, Ed., American Society of Testing and Materials, 1995, p 149

15. A.S. Khanna, Introduction to High-Temperature Oxidation and Corrosion, ASM International, 2002, p
40–60, 172–201, 205–214