[Seminar]

Lecture on Fundamental Aspects of High Temperature

Corrosion and Corrosion Protection
Part 1: Basic Theory
Manabu NOGUCHI*, and Hiroshi YAKUWA**

Abstract
Starting from this issue, we will provide “Lecture on fundamental aspects of high temperature corrosion and corrosion
protection” through a series in six parts. The series will describe corrosion protection engineering that we developed using our
actual equipment, starting from basic aspects of high temperature corrosion. In this issue, a basic theory of high temperature
corrosion is described. High temperature corrosion is subject to thermodynamics and diffusion phenomena in solids. The
parabolic rate law can be considered as the most important law. Since corrosion develops while substances move inside the
corrosion product (scale), the corrosion rate is inversely proportional to the thickness of the scale. In other words, because the
corrosion product plays a role in corrosion prevention, forming a scale having a high corrosion protection effect is critical to
successful corrosion protection. Influential factors for the formation of a scale are outlined here.
Keywords: High temperature corrosion, High temperature oxidation, Parabolic rate law, Wagner’s theory, Dissociation pressure,
EIlingham diagram, Diffusion in solids, Oxide scale

1. Introduction 2. Thermodynamics of high temperature

This is the first issue of the“Lecture on Fundamental
Aspects of High Temperature Corrosion and Corrosion
Protection.”In relation to basic theories about high
temperature corrosion, this document introduces the
ba sic physica l phenomena t hat i n f luence h igh
temperature corrosion. In the case of aqueous corrosion,
a chemical reaction occurs in an aqueous solution. On the
other hand, in the case of high temperature corrosion, a
solid-gas reaction occurs between a metal (solid) and an
oxidizing agent (gas). The basic behaviors of high
temperature corrosion are explained by thermodynamics
and transfer (diffusion) in a solid. Since we focus on
explanation concerning formulas, some formulas were
not derived, which may affect your understanding of
some formulas. Accordingly, for further information,
refer to the references. This document describes the
basic theories, taking high temperature oxidation, which
is typical high temperature corrosion, as an example.
* Ebara Environmental Plant Co., Ltd.
** Technologies, R&D Division
oxidation
2.1 Basic thermodynamics
Most metals are generated by reducing ores. In other
words, oxides, etc., are stable under natural conditions.
Therefore, to generate a metal, a charge of energy is
required. Metals tend to return to a more stable state
as an ore by reacting to oxygen, etc. Smelting is done
artificially and corrosion occurs naturally. Without
water, in many cases the corrosion rate at a normal
temperature does not cause a particular problem.
However, as the temperature rises, corrosion progresses
at a rate that is an engineering problem not to be
ignored. Corrosion that occurs unrelated to water is
called high temperature corrosion. The reaction of the
high temperature corrosion in which metallic element
M is transformed into oxide Mα Oβ is represented by
formula (1-1).
2α 2
―M ＋ O2 → ―M α O β………………………………… (1-1)
β β
To calculate the free energy (∆G) in formula (1-1),
formula (1-2) is used.

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 Lecture on Fundamental Aspects of High Temperature Corrosion and Corrosion Protection Part 1: Basic Theory

α 2/ β
MαOβ
∆G ＝ ∆G0 ＋ RT ln―… ……………………… (1-2)
α 2α/
M ・PO2
β

∆G0：Standard free energy of formation
R：Gas constant
T：Absolute temperature
α x：Activity of x
PO2：Oxygen partial pressure
Here, based on the ∆G value, the following can be
estimated:
　∆G ＜ 0 ; T
 he reaction represented by formula (1-1)
is in progress. … Oxidation
　∆G ＝ 0 ; Equilibrium
　∆G ＞ 0 ; A
 reverse reaction inverse of the reaction
represented by formula (1-1) is in Fig. 1-2　Ellingham diagram

progress. … Reduction
When ∆G = 0, PO2 is the oxygen partial pressure at partial pressure is greater than 2.6 × 10-28 atm. At a
which the metal and the oxide are balanced. The temperature of 800 °C, it is 1.2×10-14 atm. Judging from
pressure is called dissociation pressure and represented thermodynamic stability, the lower the temperature,
by the formula below. the easier the oxidation reaction. However, because
mass transfer generally controls the oxidation rate, the
（ ）
∆G0
PO2 ＝ exp ―
RT
… …………………………………… (1-3)
higher the temperature, the faster the oxidation rate.
In short, if the oxygen partial pressure of the The kinetics will be described in the following chapter.
atmosphere is greater than the dissociation pressure, a Fig. 1-1 also shows the dissociation pressure of Cr2O3.
metal is oxidized, and if it is lower than the dissociation The graph shows that the dissociation pressure of Cr
pressure, the oxide is reduced to a metal. Figure 1-1 is much lower than that of Ni, and that Cr is more
shows the dissociation pressure of NiO which is likely to be oxidized than Ni. In the graph, there are
calculated by using Thermodynamic Database MALT2 three areas: A, B, and C in ascending order of oxygen
(sold by Kagaku Gijutsu-Sha). The dissociation pressure partial pressure. In Area A, both Ni and Cr are stable.
increases as the temperature rises. At a temperature of In Area B, only Cr is oxidized. In Area C, the graph
400 °C, the oxidation reaction progresses if the oxygen indicates that both metal oxides are stable. This
thermodynamic stability is summarized in the
0 Ellingham diagram, whose horizontal and vertical axes
Area C show temperature and ∆G0, respectively. Figure 1-2
－20
shows an example 1). In the figure, M indicates the
Oxygen partial pressure　log（PO2）atm

－40
melting point of an element, and M indicates the
Area B
－60 melting point of an oxide. From the figure, the

－80
dissociation pressure of each oxide can be estimated.
For example, at 1 000 °C, the dissociation pressure of
－100
Cr 2O 3 is about 10 -22 atm, which is indicated by the
Area A Ni/NiO　dissociation pressure
－120
Cr/Cr2O3　dissociation pressure broken line in Fig. 1-2. If the value is converted into the
－140 H 2/H 2O ratio, it is around 10 3 to 10 4. The lower an
0 200 400 600 800 1 000

Temperature　℃
element is positioned in Fig. 1-2, the more stable its

Fig. 1-1　Dissociation pressures of NiO and Cr2O3 oxide becomes, and the harder the oxide is reduced to

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 Lecture on Fundamental Aspects of High Temperature Corrosion and Corrosion Protection Part 1: Basic Theory
the element. For example, at 1 000 °C, FeO, NiO, etc.
are positioned higher than CO2, which means that they
are less stable than CO2. In other words, if FeO coexists
with C (carbon), Fe is reduced, and CO2 is generated.
On the other hand, substances such as Al2O3, SiO2, and
Cr2O3 are more stable than CO2. Similarly, if Al coexists
with CO2, Al is oxidized, and CO2 is reduced. As shown
above, the Ellingham diagram is widely used to
examine possibilities of reactions.
Metals such as Al, Si, and Cr are known as elements
with a good high-temperature oxidation resistance.
This means that their oxides are more stable than
those of Fe and Ni. An element (such as Cr) that is
likely to be oxidized (stable oxide) may turn to an
element that is hard to be oxidized (slow oxidation
rate). Therefore, it should be understood that
equilibrium and kinetics are considered separately.
2.2 Thermodynamics of corrosion products
Figure 1-3 is a schematic diagram of a corrosion
product (hereinafter referred to as an oxide scale). On
the interface between the oxide scale and the
atmospheric gas, if the gas flow is sufficient, the oxygen
partial pressure is equal to that of the atmosphere. In
the oxide scale, an oxygen partial pressure gradient
occurs. The deeper the layer in the oxide scale, the
lower the partial pressure. Then, if thermodynamic
equilibrium is established on the interface between a
metal and its oxide, the metal can coexist with the
PO2
M MαOβ
O2 partial pressure
of the atmosphere
PO2
MαOβ PO2'
dissociation
pressure
x
Scale thickness
Fig. 1-3　Schematic diagram of an oxide scale
oxide, and they are considered to be in equilibrium
with each other. Thus, the oxygen partial pressure is
equal to the dissociation pressure. For Ni at 1 000 °C,
the oxygen partial pressure is 4.5 × 10-11 atm. For Cr at
the same temperature, the pressure is 9.1 × 10-23 atm.
Understanding an oxygen partial pressure drop in this
scale is important for understanding high temperature
corrosion phenomena.
3. Kinetics of high temperature oxidation
3.1 Rate formula
The following are the typical processes of high
temperature oxidation. (Actually, there are other
processes such as adsorption and dissociation of
oxygen. However, they are omitted here for simplicity.)
(1) D
 iffusion in the gas: Oxygen moves to the surface of
the oxide scale, from the atmosphere.
(2) D
 iffusion in the scale: Ionic metal or oxygen moves
in the oxide scale.
(3) R
 eaction: The metal reacts with oxygen, and then
the oxide scale grows.
Since diffusion in a gas is generally much faster than
that in a solid, diffusion in the gas does not become the
rate-controlling step except in special circumstances. If
an oxidation rate depends on diffusion or reaction in
the gas, the oxide scale thickness (x) is proportional to
the time (t), which is expressed in formula (1-4).
x ＝ kl・t… ……………………………………………… (1-4)
Formula (1-4) is called the linear law, and kl is called
the linear rate constant. The above formula is satisfied
when the growth of the oxide scale is insufficient in an
early stage of corrosion and diffusion in the solid is not
PO2''
a problem. In this case, the mechanism of controlling
the corrosion reaction does not work, causing corrosion
damage often, which does not fit practical use.
On the other hand, when mass transfer in a scale
becomes the rate-controlling step, the thicker the scale,
the longer the time the mass transfer takes. Therefore,
the growth rate of the oxide scale (dx/dt) is inversely
proportional to the scale thickness (x).
dx k'p
　―＝ ―……………………………………………… (1-5)
dt x
Integrating and arranging the above formula results
in formula (1-6).
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driving force based on Fick’s first law.

Scale thickness (amount of corrosion)

Continuous scale destruction

dc
　J ＝− D― … ………………………………………… (1-7)
dx
By combining Wagner’s theory with the parabola

kp=2c
rate law based on Fick’s first law, etc., k p can be
expressed in formulas (1-8) and (1-9) 2), 3).
1 μ'M
kp=c

　kp ＝―∫ DM dμM ……………………………… (1-8)
RT μ''M

1 μ''O
Time

　kp ＝―∫ DO dμO ……………………………… (1-9)
Fig. 1-4　Schematic diagram of the time dependence of RT μ'O
the amount of corrosion
DM and DO respectively represent diffusion
coefficients of the metal (M) and the oxygen in the
x ＝ kp・√t… …………………………………………… (1-6) scale. μM and μO respectively represent the chemical
Formula (1-6) is the parabolic rate law which is potentials of the metal (M) and oxygen. Suffix [ ' ]
important for engineering. kp is called a parabolic rate and [ " ] respectively represent the values on the
c o n s t a n t a nd i s u s ed f o r e va l ua t i ng t h e h ig h interfaces between the metal and the oxide scale and
temperature corrosion resistance of materials. Where x between the oxide scale and the atmosphere. Both the
is scle thickness, the scale thickness = the amount of metal and oxygen move in the scale. However, since
corrosion. Therefore, the unit of k p is [mm·s −½
]. there is usually a large difference in diffusion capability
Generally, the mass change or reduced thickness is between them, the movement of one of them can be
used to evaluate the amount of corrosion in a ignored. Formula (1-8) represents the movement of a
laboratory or in inspection using actual equipment. In metal. Formula (1-9) represents the movement of
this case, by selecting the unit of kp, it is possible to use oxygen. These formulas contain μM and μO that are
“x” (the mass or reduced thickness) according to the difficult to measure. If the deviation of M αO β from the
actual measurement system. On the contrary, when kp stoichiometric composition is small, kp can be expressed
is used for evaluation, be careful about unit systems. with PO2 using formulas (1-10) and (1-11).
Figure 1-4 shows the correlation of oxide scale α・μM ＋β・μO ＝μM α O β ≈ const.………………… (1-10)
thickness (= amount of corrosion) and time associated 1
　μO ＝― ( μ°O2 ＋ RT lnPO2 )… ……………………… (1-11)
with formula (1-6). (The continuous scale destruction 2
shown in the figure is described in section 4.2.) It is In the above formula, μ°O2 represents the standard
found that the growth rate (= corrosion rate) of the chemical potential of O2.
oxide scale becomes slow as time goes by, indicating By plugging the above formulas into formulas (1-8)
that the progress of corrosion is slowed. When the and (1-9), formulas (1-12) and (1-13) are obtained.
scale becomes a barrier against mass transfer, it works β P'O2
　kp ＝―∫ DM dlnPO2 …………………………… (1-12)
as a protective scale and suppresses corrosion. In other 2α P''O2
words, the key to suppressing high temperature 1 P''O2
　kp ＝―∫ DO dlnPO2 …………………………… (1-13)
corrosion is how well to form a protective scale which 2 P'O2
can maintain the parabolic rate law. kp can be expressed as the product of the driving
3.2 Factors affecting the parabolic rate law force and the mobility. The driving force is the oxygen
3.2.1 Diffusion coefficient partial pressure gradient on the interfaces between the
When the oxide scale grows in accordance with the metal and the oxide scale and between the oxide scale
parabolic rate law, diffusion in the oxide scale becomes and the atmosphere. The mobility is expressed by DM
the rate-controlling step. The diffusion equation is or DO which is the self-diffusion coefficient of the metal
expressed by the product of the mobility and the or oxygen in the scale. In other words, these formulas

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show that in order to suppress a corrosion rate, the Ni2＋ O2－ Ni2＋ O2－ Ni2＋ O2－ Ni2＋ O2－
oxygen partial pressure gradient or the diffusion O2－ Ni2＋ O2－ Ni2＋ O2－ Ni2＋ O2－ Ni2＋

coefficient must be small. Cr2O3, Al2O3, and SiO2 are Ni 2＋

O 2－
□ O 2－
Ni 2＋
O 2－
Ni 3＋
O2－

typical oxides with a small diffusion coefficient. Heat- O2－ Ni3＋ O2－ Ni2＋ O2－ Ni2＋ O2－ Ni2＋

resistant alloys are designed to form one of these oxide Ni 2＋

O 2－
Ni 2＋
O 2－
Ni 2＋
O 2－
□ O2－
O2－ Ni2＋ O2－ Ni3＋ O2－ Ni2＋ O2－ Ni3＋
scales. Stainless steel is the most common heat-resistant
Ni 2＋
O 2－
Ni 2＋
O 2－
Ni 2＋
O 2－
Ni 2＋
O2－
alloy, to which at least a certain amount of Cr is added
O2－ Ni2＋ O2－ Ni2＋ O2－ Ni2＋ O2－ Ni2＋
so that Cr2O3 can be formed by corrosion to provide a
Fig. 1-5　Schematic diagram of a p-type semiconductor
corrosion protection effect.
with positive holes (Ni3+) and vacancies ( □ )
3.2.2 Oxygen partial pressure
Oxide scales contain defects and function as p- or n-type （Step1） （Step2）
semiconductors. An n-type semiconductor has lattice O2－ Ni2＋ O2－ Ni2＋
defects of oxygen, and oxygen ions move in the oxide Ni 2＋
O 2－
Ni 2＋
O2－

scale. In a p-type semiconductor, lattice defects of metal O2－ Ni2＋ +1/2O2 → O2－ Ni2＋ O →

cause metal ions to move in the oxide scale. Figure 1-5 Ni2＋ O2－ Ni2＋ O2－

O2－ Ni2＋ O2－ Ni2＋

is a schematic diagram of defects in NiO that is a typical
p-type oxide. Stoichiometrically, the ratio of Ni to O is 1:1. （Step3） （Step4）

However, there is Ni absence part (indicated by □ in the O2－ Ni2＋ O2－ Ni2＋

figure); therefore the molecular formula is written as Ni 2＋

O 2－
□ O2－ Ni2＋

Ni1 − δ O. In order to maintain electrical neutrality, some O2－ Ni3＋ O－ → O2－ Ni3＋ O2－
Ni 2＋
O 2－
Ni 3＋
O 2－
Ni2 ＋ molecules change to Ni3 ＋ ones. A part where Ni2 ＋
O 2－
Ni 2＋
O 2－
Ni2＋
is lost is called vacancy, and Ni 3 ＋ in which Ni 2 ＋ is
Fig. 1-6　Schematic diagram of forming positive holes (Ni3+)
positively charged is called a positive hole. The former
and vacancies ( □ ) in a p-type semiconductor (NiO)
and latter are represented by “V M'' ” and “h･”
respectively, and the number of charges are represented
by [ '' ] or [ ･ ]. Figure 1-6 shows the processes of Henry’s law, formula (1-15) can be expressed as follows
forming a vacancy and a positive hole. In Step 1, an by using concentration C:
oxygen molecule in the atmosphere reaches NiO. In Step K ＝ CVM''Ch2・PO−2 ½ … ………………………………… (1-16)
2, an oxygen atom is absorbed by NiO. In Step 3, the Due to electrical neutrality, 2 [C V M'' ] = [C h・ ] is
oxygen atom receives an electron from Ni 2 ＋
and is established.
chemically adsorbed by NiO, which forms a positive Therefore, formula (1-15) can be changed as follows:
hole. In Step 4, a reaction couple of O 2-
and Ni 2 ＋
is K
　CVM'' ＝―PO¹⁄₆… ……………………………………… (1-17)
formed, and then it is absorbed by the NiO lattice. On 4 2
the other hand, in the NiO lattice, the Ni2 ＋ site reacted As shown above, the vacancy concentration depends
becomes vacant, simultaneously forming a new positive on the oxygen partial pressure. If metal vacancies are
hole. dominant as defects, and if the diffusion of metal ions in
If a divalent metal vacancy is formed, a series of the oxide scale is caused by a vacancy mechanism
vacancy formation reactions and a reaction equilibrium (diffusion due to position exchanges between vacancies
constant K are expressed in the formula below. and adjacent atoms), the self-diffusion coefficient of the
1 metal is proportional to the vacancy concentration.
　―O2 (g) → O0 ＋ VM'' ＋ 2h·… ……………………… (1-14)

2 DM ∝ CVM'' … ………………………………………… (1-18)

　K ＝αVM'' αh2・PO−2 ½ … …………………………… (1-15) By plugging formulas (1-17) and (1-18) into formula (1-
If V M'' overwhelmingly outnumbers other defect 12), formula (1-19) is obtained.
concentrations and its porosity is low enough to use kp ∝［(PO''2 )¹⁄₆ −(PO' 2 )¹⁄₆］
……………………………… (1-19)

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 Lecture on Fundamental Aspects of High Temperature Corrosion and Corrosion Protection Part 1: Basic Theory
In general, since P O'' 2, is much greater than P O' 2
formula (1-19) can be simplified as follows:
kp ∝ (PO''2 )¹⁄₆…………………………………………… (1-20)
As shown above, if the substance that moves in the
oxide scale is a metal, and if a divalent metal vacancy
is formed, the corrosion rate is proportional to the 1/6
power of the atmospheric oxygen partial pressure.
If the oxide scale is an n-type semiconductor, the
formula for the formation of a divalent oxygen vacancy
is expressed in the following formula:
1 the temperature. If an examination of the dependence
　OO →― O2 (g) ＋ V¨
O ＋ 2e…………………………… (1-21)
2 on the temperature using the Arrhenius equation does
If the above formula is solved as well as a p-type
semiconductor, the following formulas are obtained.
−¹⁄₆ −¹⁄₆
kp ∝［(PO' 2 ) −(PO''2 ) ］
… ………………………… (1-22)
−¹⁄₆
kp ∝ (PO' 2 ) … ……………………………………… (1-23)
As shown above, when oxygen moves in a scale, it
depends on the oxygen partial pressure on the
interface between the metal and the oxide scale.
If a univalent vacancy is formed, coefficient 6
changes to 4 for both the p- and n-types. Typical
p-types are Cr2O3, FeCr2O4, FeO, Fe3O4, and NiO, and
typical n-types are Fe2O3, Al2O3 and SiO2. Formulas (1-
20) and (1-23) mean that if the oxide scale is a p-type
(e.g. Cr 2O 3 for stainless steel), reducing the oxygen
partial pressure of the atmosphere can reduce the
corrosion rate, depending on the 1/4 to 1/6 power of
the oxygen partial pressure. On the other hand, the
formulas mean that when SiO 2 or Al 2 O 3 is the
protective scale, the corrosion rate does not depend on
the oxygen partial pressure of the atmosphere, except
in a case where the oxygen partial pressure is
extremely low.
3.2.3 Temperature
Generally, a diffusion coefficient is expressed in the
Arrhenius equation.
（ ）
−Q
　D ＝ D0 exp ― … ……………………………… (1-24)
RT
In the above formula, Q indicates activation energy. In
formulas (1-12) and (1-13), k p is considered to be
proportional to the diffusion coefficient and the oxygen
partial pressure gradient, the following formula can be
obtained to express the dependence on the temperature.
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（ ）
−Q
　kp ≈ D0ΔPO2exp ― … ………………………… (1-25)
RT
It is easy to imagine that the corrosion rate rises as
the temperature rises. During high temperature
oxidation, the corrosion rate increases as the diffusion
rate in the oxide scale increases. Because of the
compositions of the scale, reaction mechanism, etc.
change due to a temperature change, formula (1-25) is
often not established. However, the formula is one of
the means to judge how the corrosion rate depends on
not prove the correlation between the corrosion rate
and the temperature, it is highly likely that the reaction
mechanism changed under the temperature conditions.
The Arrhenius equation is very helpful for studying
the corrosion mechanism.
4. High temperature oxidation of practical
alloys
4.1 Composition of the oxide scale
Section 3.2 described that Al 2O 3, SiO 2, Cr 2O 3, etc.
function as protective scales. On the other hand, the
Ellingham diagram in Fig. 1-2 indicates that metals
such as Al, Si, and Cr have high compatibility with
oxygen and are easily oxidized. This section describes
a corrosion protection mechanism of these metals that
are easily oxidized.
Figure 1-7 is a schematic diagram of the oxide scale
of an alloy (Fe-Cr alloy) 4). When a Fe-Cr alloy is exposed
in a high-temperature oxidative atmosphere, corrosion
Fe oxide layer
Cr2O3 internal oxide Cr2O3 continuous layer
B ×
A ×
Fe-Cr
Cr2O3
Fe-Cr Fe-Cr
Alloy Alloy Alloy
Fe oxide
（1） （2） （3）
Fig. 1-7　Schematic diagram of the Fe-Cr alloy oxide scale
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progresses forming an oxide scale. (1) At an early stage
of the corrosion, both Cr2O3 and a Fe oxide are formed.
Each oxygen partial pressure on the interface (point A
in the figure) between the alloy and the Fe oxide and on
the interface (point B in the figure) between the alloy
and the Cr 2O 3 is the same as its own dissociation
pressure. (2) Fe ions diffuse faster than Cr ions and then
cover Cr 2O 3 particles. Meanwhile, the dissociation
pressure of the Cr2O3 is lower than that of the Fe oxide.
In other words, even in the inside of the Fe oxide where
the Fe metal is stable, the Cr oxide has a stable phase.
Near the alloy surface, dissolved oxygen oxidize Cr
inside the alloy. (3) When this internal oxide layer grows
to a continuous layer, the oxygen partial pressure on the
interface between the alloy and the Cr2O3 decreases to
the dissociation pressure of the Cr 2O 3, suppressing
subsequent internal oxidation. It is known that when
pure iron is oxidized at around 1 000 °C, the scale has a
three layer structure of FeO, Fe3O4, and Fe2O3 viewed
from the metal side. Adding Cr to the scale reduces the
scale thickness and changes the scale composition. Then,
complex oxides such as FeCr 2O 4 are formed, the
increased Cr thickens the FeCr2O4 layer, and the FeO
layer gradually disappears. When the ratio of Cr
increases and exceeds 18%, a layered scale containing
Cr2O3 is formed. And if the ratio exceeds 23%, a mono-
layer of Cr2O3 is formed, suppressing the corrosion rate
Cr-majority oxide layer Fe, Ni, Cr oxide layer Fe oxide layer
Crack
Type304
（Fe-18Cr-8Ni）
Cr2O3 layer
Type310
（Fe-25Cr-20Ni）
Fig. 1-8　SEM photos of and results of EPMA analysis on the
sections of the test specimens which were corroded
in high temperature (in the atmosphere whose
temperature is 1 000 °C, for 200 hours)
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7
drastically5). Figure 1-8 shows the results of an EPMA
(electron probe microanalyzer) analysis on the cross
sections of the test specimens (austenitic stainless steels
[Fe-Cr-Ni]) which were corroded in an atmosphere at
1 000 °C for 200 hours. In the Type304 (18Cr-8Ni), an Fe
oxide layer is formed in the outermost layer (gas side).
Under the layer, there is another oxide layer consisting
of Fe, Ni, and Cr. Under the second layer, there are
cracks made during cooling. Furthermore, as the
innermost layer, the oxide layer that is mainly comprised
of Cr containing Fe and Ni is formed. In the entire
specimen, the corrosion scale grew with a thickness of
100 μm. On the other hand, in the Type310 (25Cr-20Ni),
a Cr2O3 layer consists mostly of the corrosion scale and
the thickness of the scale is around 20 μm, which
indicates that the amount of corrosion was greatly
decreased. The results show that the corrosion scale and
corrosion resistance greatly vary depending on the Cr
content.
Thus, when the oxide of a metal having affinity with
oxygen is formed on the alloy surface, the subsequent
oxidation is inhibited. Then, the slow diffusion of
oxidation of the formed oxide scale inhibits corrosion.
Accordingly, in order to make the oxide scale work as a
protective scale, the metal oxide must have a stronger
affinity with oxygen than that of the base metal. In
addition, the diffusion coefficient in the oxide must be
small. Typical metals having the above properties are
Al, Si, and Cr. In terms of high-temperature strength,
workability, etc., Fe, Ni, Co, etc. are used as a base metal
for heat resistant alloys. To maintain their heat
resistance, protective oxide scale forming elements such
as Cr, Si, and Al are added to the base metal.
Additionally, Mo and W, typical elements to enhance
high-temperature strength are added, and rare earth
elements are added to inhibit the detachment of
corrosion scales. Thus, designs for heat-resisting alloys
include high-temperature strength and corrosion
resistance.
4.2 Stability of oxide scales
As stated in chapter 3, when a protective oxide scale is
formed on an alloy, the corrosion rate decreases
according to the parabolic rate law. Conversely, for
corrosion prevention, it is necessary to select the
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materials that form protective oxide scales in the Table 1-1　Thermal expansion coefficients of metals and oxides

operating environment. In the case of stainless steel Thermal expansion Temperature range
Item
coefficient (10-6K-1) (°C)
and the like, a steel largely containing Cr is selected Fe 14.6 800
according to the severity of the operating environment. Ni 16.3 900
However, forming a protective scale is not sufficient, Cr 9.4 700
Al 26.5 400
and what is important is that the scale is not only not
Si 7.6 0 − 100
destroyed but is also firmly maintained. Fig. 1-4
Type304 18.8 0 − 648
schematically shows changes in the amount of Type410 11.7 0 − 648
corrosion caused by the scale destruction. When the Type430 11.9 0 − 648
scale is destroyed, the corrosion rate drastically FeO 12.2 100 − 1 000

increases at an early stage of the parabolic rate law. Fe3O4 16.6 25 − 1 000
Fe2O3 12.5 25 − 1 000
If scale detachment regularly occurs, the corrosion
NiO 17.1 25 − 1 000
may progress linearly as time passes, as if it followed
Cr2O3 8.7 25 − 1 200
the linear law. Figure 1-9 shows the results of the Al2O3 8.1 25 − 1 200
measurement of the thickness reduction of the SiO2 3 300 − 1 100

superheater tubes in incinerators, as examples of

changes over time in the thickness reduction of actual
machines6). In the long-term tendency, the thickness
reduction increases linearly with time. In the actual
environments, the corrosion caused by this scale
destruction is often a problem.
One of the main causes of scale destruction is
thermal stress. Table 1-1 7), 8) shows the thermal
expansion coefficients of typical metals and oxides.
Since there is a difference in the thermal expansion
coefficient between oxides and metals, temperature
fluctuations cause oxide scales to be destroyed. A
typical cause of temperature fluctuation is start and
stop of equipment. Repeating these operations increases
the risk of scale destruction. The larger the difference
in the thermal expansion coefficient between the base
material and the oxide, the more chances of scale
destruction. Therefore, in the environment in which
1.0
Cr2O3 or Fe2O3 is generated, austenitic stainless steels
whose thermal expansion coefficient is larger than that
of ferritic stainless steels are more likely to have scale
destruction due to thermal stress. Other factors such
as temperature fluctuation during operation9) and soot
blow10) are the thermal stress sources which promote
corrosion. Erosion is also an important factor that
causes scale destruction 11) . The continuous scale
destruction caused by a physical factor such as the
particles contained in combustion gases or the heat
transfer tube in the fluidized bed also increases
thickness reduction. Regarding the time dependence of
the thickness reduction shown in Fig. 1-9, destruction
and reproduction of scales were repeated by a physical
factor such as start and stop or soot blow for removing
attached ashes. It is considered that the linear increase
of thickness reduction was shown as a result.
Because the volume of an oxide is different from that

Unit1
of the base metal, stress is generated in an oxide scale
0.8
as the scale grows, resulting in conditions for scale
Reduced thickness　mm

Unit2

0.6 detachment. The difference in volume is called the

Pilling-Bedworth ratio (PBR) and expressed in the
0.4
following formula:
0.2
Volume of the oxide per metal ion
PBR ＝ … … (1-26)
Volume of the metal per metal atom
0.0
0 5 000 10 000 15 000 20 000
Table 1-212), 13) shows the PRBs of typical metals. If the
Operating time　hr
PBR is 1 or smaller, tensile stress is applied to the
Fig. 1-9　Results of the measurement of the thickness reduction
of the superheater tubes in incinerators oxide scale. Therefore, the scale is easily destroyed,

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 Lecture on Fundamental Aspects of High Temperature Corrosion and Corrosion Protection Part 1: Basic Theory

Table 1-2　Pilling-Bedworth ratios temperature changes and easing the erosion conditions.
Item PBR In short, it is also important to pay attention to the
K-K2O 0.45
operating conditions, for example, for easing scale
Li-LiO2 0.58
destruction factors.
Mg-MgO 0.81
Na-Na2O 0.97
5. Corrosion in a real environment
Cd-CdO 1.21
Al-Al2O3 1.28 5.1 Corrosion in the system which contains
Zn-ZnO 1.55
volatile components
Cu-Cu2O 1.64
It is known that Cr2O3 which is protective oxide partly
Ni-NiO 1.65
Fe-FeO 1.68 changes to CrO3 and volatilizes at a high temperature
Ti-TiO2 1.73 of over 1 000 °C. The following formula, which is a
Co-CoO 1.86 modified formula based on formula (1-5), is proposed as
Cr-Cr2O3 2.07
a general formula for calculating the corrosion rate in
αFe-Fe3O4 2.1
the system containing such volatile components15).
αFe-Fe2O3 2.14
Ta-Ta2O5 2.5 dx k' p
　―＝―− ks……………………………………… (1-27)
Nb-Nb2O5 2.68 dt x
V-V2O5 3.19 ks is the constant that expresses the volatilization
rate. The following is how to interpret this formula. If
resulting in poor protection. However, since most the growth rate of the scale is large enough at an early
metals increase their volumes by combining with stage of the corrosion (k'p>>ks), the scale growth almost
oxygen, their PBRs exceed 1 and compressive stress is complies with the parabolic rate law. However, as time
generated. PBRs are guidelines of the occurrence of passes, the growth rate of the scale decreases, and the
stress in oxide scales, and are particularly important if influence of volatilization cannot be ignored. Finally, the
oxygen moves in the oxide scale and causes a reaction growth rate of the scale caused by corrosion is equal to
on the interface between the metal and the oxide scale. the disappearance rate caused by volatilization, which
On the other hand, if a reaction occurs on the interface causes the scale growth to stop (dx/dt = 0) and
between the oxide scale and the atmospheric gas, the maintains the constant thickness of the scale (scale
reaction progresses on free surfaces. Therefore, stress thickness limit ; x0).
due to the volume difference is unlikely to be k' p
　x0 ＝―……………………………………………… (1-28)
generated. However, actually, in the case of Cr2O3 in k s
which a reaction occurs on the interface between the Plug formula (1-28) into formula (1-5) to calculate the
oxide scale and the atmospheric gas, stress is applied kinetics of the scale growth in the condition where the
to the scale. One of the probable causes is that some scale thickness is x0. The result is ks. This means that
oxygen existing in grain boundaries, etc. enters into after the scale thickness reaches the limit, the corrosion
the scale, resulting in a growth of oxides . In addition
14)
progresses at constant speed ks.
to this cause, various factors come into play. Here, 5.2 Corrosion in compound gas
important factors are that (as PBRs indicate) stress is Actual environments may contain not a single gas
potentially generated in a metal and an oxide scale, and atmosphere but a compound gas one. For example,
that an application of a physical factor to the metal and fossil fuel furnaces contain not only oxygen, but also
oxide scale easily causes scale detachment. Since most su l f ur gases such as H 2 S a nd S Ox , a nd waste
of the past high temperature corrosion studies are incinerators contain a minute amount of chloride gas
about scle destruction, it is a very critical problem. To components such as HCl. In some cases, sulfur and
prevent high temperature corrosion in actual chlorine concentrate on the alloy surface, promoting
environments, take measures such as avoiding corrosion. A corrosion behavior in such a compound gas

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 Lecture on Fundamental Aspects of High Temperature Corrosion and Corrosion Protection Part 1: Basic Theory
P
（O2）=1%
10
5 Fe（SO ）
FeS2
FeSO4 2 4 3
0 Fe2O3
（SO2）　atm
－5 P
（SO2）=1 ppm
－10 FeS
log P
－15
－20
Fe Fe3O4 Fe2O3
－25
－35 －30 －25 －20 －15 －10 －5
（O2）
log P 　atm
Fig. 1-10　Equilibrium diagram of the Fe-O-S system,
and schematic diagram of an oxide scale
atmosphere can be explained with the thermodynamic
equilibrium diagram. Figure 1-10 is the equilibrium
diagram of the Fe-O-S system at 500 °C, in which
thermodynamic database MALT2 was used for the
calculation. The figure shows that the stable phase
changes depending on the O2 and SO2 partial pressures.
For exa mple , Fe 2 O 3 ha s a st able pha se i n t he
atmosphere in which the O2 and SO2 partial pressures
are 1% and 1 ppm, respectively. When the oxygen
partial pressure decreases, the stable phase is changed
to Fe3O4. When the pressure decreases further, the FeS
st able a rea appea rs . I f Fe is cor roded in t h is
atmosphere, Fe2O3 is formed in the outermost layer, but
the partial pressure decreases in the scale. Therefore, it
is presumed that Fe3O4 is formed in the scale, and the
innermost layer is an area containing both FeS and
Fe3O4. As for corrosion in such mixed gases, note that
even if the amount of the contained gases are very
small and they are in an oxide stable area in the
atmosphere, a tiny amount of gas compounds may be
formed in the scale, resulting in a large influence on the
corrosion. In particular, compounds such as sulfide and
chloride are less dense and adhesive than oxides and
thus cannot be satisfactory protective scales. The
formation of an oxide layer through such a compound
layer may inhibit the formation of a protective oxide
layer or promote scale detachment.
Especially, in the case of chloride corrosion, it was
reported that chloride is formed in the innermost layer
of corrosion and the following recycle reactions
promote corrosion .
16), 17)
Chloride stable area (innermost layer of the scale) ;
Me＋Cl2 →MeCl2
Oxide stable area (gas side of the scale) ;
MeCl2 ＋1/2O2 →MeO＋Cl2
Although the atmosphere is an oxide stable area,
Fe3O4
chlorides are formed in the scale. Part of the formed
FeS/Fe3O4 chloride is oxidized in the oxide stable area, which
Fe
generates Cl 2. When the generated Cl 2 affects the
corrosion again, the corrosion is accelerated. On the
Schematic diagram
0
of an oxide scale other hand, it is known that the use of a volatilization
phenomenon inhibits corrosion in mixed gases. The
following case is reported: When Al is added to an alloy
in the environment which contains a tiny amount of
chloride gas, even if a chloride enters the alloy, AlCl3
with high vapor pressure is formed, preventing the
accumulation of chlorides in the alloy, and inhibiting
corrosion18). As shown above, complicated corrosion
behaviors can be seen particularly in mixed gases.
Accordingly, the corrosion prevention based on fully
understanding of a corrosion mechanism is required.
6. Conclusion
For corrosion study, corrosion protection is a more
important issue than corrosion itself. However, for
corrosion protection, it is a must to understand corrosion.
For this reason, as the first issue of the lecture on high
temperature corrosion, the basics of corrosion are
described, taking high temperature oxidation as an
example. What is important is to understand that high
temperature corrosion is influenced by thermodynamics
and diffusion. Thermodynamics gives directivity for
reaction, diffusion controls the corrosion rate, and the
corrosion rate complies with the parabolic rate law.
However, problems in actual environments often do not
comply with the parabolic rate law. In other words,
what is not compliant with the parabolic rate law is a
problem. The important keys to solving these problems
are performing thermodynamic verif ication and
studying why the parabolic rate law is not established.
The next issue will describe the basics of corrosion
protection methods, including material substrate factors,
corrosion protection engineering by coating, and
environmental factors. In the following issues, concrete
examples will be described.
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 Lecture on Fundamental Aspects of High Temperature Corrosion and Corrosion Protection Part 1: Basic Theory
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