CHAPTER 25

Oxidation of Materials

CONTENTS
25.1 Introduction ......................................................................................411
25.2 Energy of oxidation ..........................................................................412
25.3 Rates of oxidation ............................................................................412
25.4 Data ..................................................................................................415
25.5 Micromechanisms ............................................................................416
Examples ..................................................................................................419
Answers ....................................................................................................420

25.1 INTRODUCTION
In the last chapter we said that one of the requirements of a high-temperature
material—in a turbine blade, or a super-heater tube, for example—was that it
should resist attack by gases at high temperatures and, in particular, that it
should resist oxidation. Turbine blades do oxidize in service, and react with
H2S, SO2, and other combustion products. Excessive attack of this sort is obvi-
ously undesirable in such a highly stressed component. Which materials best
resist oxidation, and how can the resistance to gas attack be improved?
The earth’s atmosphere is oxidizing. We can get some idea of oxidation-
resistance by using the earth as a laboratory, and looking for materials that sur-
vive well in its atmosphere. All around us we see ceramics: the earth’s crust
(Chapter 2) is almost entirely made of oxides, silicates, aluminates, and other
compounds of oxygen; and being oxides already, they are completely stable.
Alkali halides, too, are stable: NaCl, KCl, NaBr—all are widely found in nature.
By contrast, metals are not stable: only gold is found in “native” form under
normal circumstances (it is completely resistant to oxidation at all tempera-
tures); all the others in our data sheets will oxidize in contact with air.

411

Engineering Materials 1: An Introduction to Properties, Applications and Design, Fifth Edition. https://doi.org/10.1016/B978-0-08-102051-7.00024-5
© 2019, David R. H. Jones and Michael F. Ashby. Published by Elsevier Ltd. All rights reserved.
412 CHAPTER 25: Oxidation of Materials

Polymers are not stable either: most will burn if ignited, meaning that they oxi-
dize readily. Coal and oil (the raw materials for polymers), it is true, are found
in nature, but that is only because geological accidents have sealed them off
from all contact with air. A few polymers, among them PTFE (a polymer based
on —CF2—), are so stable that they survive long periods at high temperatures,
but they are the exceptions. And polymer-based composites, of course, are just
the same: wood is not noted for its high-temperature oxidation resistance.

25.2 ENERGY OF OXIDATION

This tendency of many materials to react with oxygen can be quantified by lab-
oratory tests that measure the energy needed for the reaction
Material + Oxygen + Energy ! Oxide of material

If this energy is positive, the material is stable; if negative, it will oxidize. The bar-
chart of Figure 25.1 shows the energies of oxide formation for our four catego-
ries of materials; numerical values are given in Table 25.1.

25.3 RATES OF OXIDATION

When designing with oxidation-prone materials, it is obviously vital to know
how fast the oxidation process is going to be. Intuitively one might expect that,
the larger the energy released in the oxidation process, the faster the rate of oxi-
dation. For example, one might expect aluminum to oxidize 2.5 times faster
than iron from the energy data in Figure 25.1. In fact, aluminum oxidizes much
more slowly than iron. Why should this happen?
If you heat a piece of bright iron in a gas flame, the oxygen in the air reacts with
the iron at the surface of the metal where the oxygen and iron atoms can con-
tact, creating a thin layer of iron oxide on the surface, and making the iron turn
black. The layer grows in thickness, quickly at first, and then more slowly
because iron atoms now have to diffuse through the film before they make con-
tact and react with oxygen. If you plunge the piece of hot iron into a dish of
water the shock of the quenching breaks off the iron oxide layer, and you
can see the pieces of layer in the dish. The iron surface now appears bright
again, showing that the shock of the quenching has completely stripped the
metal of the oxide layer which formed during the heating; if it were reheated,
it would oxidize at the initial rate.
The important thing about the oxide film is that it acts as a barrier which keeps
the oxygen and iron atoms apart and cuts down the rate at which these atoms
react to form more iron oxide. Aluminum, and most other materials, form
oxide barrier layers in just the same sort of way—but the oxide layer on alumi-
num is a much more effective barrier than the oxide film on iron is.
 25.3 Rates of Oxidation 413

–1500
Ceramics Metals Polymers Composites

Beryllium
Aluminum
Zirconium
–1000 Uranium
Titanium

Materials unstable in oxygen

Silicon Tantalum
Ni3Al–Ni3Nb
Niobium
Chromium
Si3N4 Zinc Co–Cr7 C3/
SiC Ni–TaC/
Molybdenum
–500 Co–TaC
Energy (kJ mol–1)

Tungsten
Diamond/ Iron/tin Woods/CFRP
Most WC cermets
Graphite Nickel polymers
Cobalt
Lead GFRP
Copper
MgO/SiO2
Platinum
0 Al2O3/BeO PTFE
Silver
Gold

Materials stable in oxygen

LiCI
500

NaCI

KCI
1000

FIGURE 25.1
Energies of formation of oxides at 273 K in kJ mol-1 of oxygen O2.

How do we measure rates of oxidation in practice? Because oxidation proceeds

by the addition of oxygen atoms to the surface of the material, the weight of the
material usually goes up in proportion to the amount of material that has
become oxidized. This weight increase, Δm, can be monitored continuously
with time t in the way illustrated in Figure 25.2. Two types of behavior are usu-
ally observed at high temperature. The first is linear oxidation, with
Δm ¼ kL t (25.1)

where kL is a kinetic constant. Naturally, kL is usually positive. (In a few materials,

however, the oxide evaporates away as soon as it has formed; the material then
loses weight and kL is then negative.)
The second type of oxidation behavior is parabolic oxidation, with

ðΔmÞ2 ¼ kp t (25.2)
414 CHAPTER 25: Oxidation of Materials

Table 25.1 Energies of Formation of Oxides at 273 K

Energy (kJ mol-1 of Energy (kJ mol-1 of
Material Oxide Oxygen, O2) Material Oxide Oxygen, O2)

Beryllium BeO 1182 Woods, most  400

Magnesium MgO 1162 polymers, CFRP
Aluminum Al2O3 1045 Diamond, CO2 389
graphite
Zirconium ZrO2 1028 Tungsten WO3+CO2 349
carbide
Uranium U3O8  1000 cermet (mainly
WC)
Titanium TiO 848 Lead Pb3O4 309
Silicon SiO2 836 Copper CuO 254
Tantalum Ta2O5 764 GFRP  200
Niobium Nb2O5 757 Platinum PtO2  160
Chromium Cr2O3 701 Silver Ag2O 5
Zinc ZnO 636 PTFE  zero
Silicon nitride, 3SiO2+2N2  629 Gold Au2O3 +80
Si3N4
Silicon SiO2+CO2  580 Alkali halides  +400 to
carbide, SiC  +1400
Molybdenum MoO2 534
Tungsten WO3 510 Magnesia, MgO Higher Large and positive
Iron Fe3O4 508 Silica, SiO2 oxides
Tin SnO 500 Alumina, Al2O3
Nickel NiO 439 Beryllia, BeO
Cobalt CoO 422

Linear Δm = kLt
(e.g., Ta, Nb)
Platinum
wire
Weight gain, Δm

Parabolic (Δm)2 = kpt

(e.g., Fe, Ni, Cu, Al, Co, Si)
Specimen 0
Furnace windings Time, t

Linear loss, k L – ve
volatile oxides
(e.g., Mo, W)
k L and k P are constants
at any temperature

FIGURE 25.2
Measurement of oxidation rates.
 25.4 Data 415

where kp is another kinetic constant, this time always positive.

Oxidation rates follow Arrhenius’s law (Chapter 22), that is, the kinetic con-
stants kL and kp increase exponentially with temperature:

kL ¼ AL eQL =RT and kP ¼ AP eQP =RT (25.3)

AL and Ap, QL, and Qp are constants. As the temperature is increased, the rate of
oxidation increases exponentially (Figure 25.3).
Finally, oxidation rates obviously increase with increasing partial pressure of
oxygen, although rarely in a simple way. The partial pressure of oxygen in a
gas turbine atmosphere, for example, may well be very different from that in
air, and it is important to conduct oxidation tests on high-temperature compo-
nents under the right conditions.

25.4 DATA
It is important from the design standpoint to know how much material is
replaced by oxide. The mechanical properties of the oxide are usually grossly
inferior to the properties of the material (e.g., oxides are comparatively brittle),
and even if the layer is firmly attached to the material—which is certainly not
always the case—the effective section of the component is reduced. The reduc-
tion in the section of a component can obviously be calculated from data for Δm.
Table 25.2 gives the times for a range of materials required to oxidize them to a
depth of 0.1 mm from the surface when exposed to air at 0.7TM (a typical figure
for the operating temperature of a turbine blade or similar component): these
times vary by many orders of magnitude, and clearly show that there is no cor-
relation between oxidation rate and energy needed for the reaction (see Al, W
for extremes: Al, very slow—energy ¼ 1045 kJ mol1 of O2; W, very fast—
energy ¼ 510 kJ mol1 of O2).

Δm Increasing T
In k L, In k P

Slope is
–QL/R or
–QP/R

1/T t
FIGURE 25.3
Oxidation rates increase with temperature according to Arrhenius’s law.
416 CHAPTER 25: Oxidation of Materials

Table 25.2 Time in Hours for Material to Be Oxidized to a Depth of 0.1 mm at 0.7 TM in Air
Material Time Melting Point (K) Material Time Melting Point (K)

Au Infinite? 1336 Ni 600 1726

Ag Very long 1234 Cu 25 1356
Al Very long 933 Fe 24 1809
Si3N4 Very long 2173 Co 7 1765
SiC Very long 3110 Ti <6 1943
Sn Very long 505 WC cermet <5 1700
Si 2  106 1683 Ba ≪0.5 983
Be 106 1557 Zr 0.2 2125
Pt 1.8  105 2042 Ta Very short 3250
Mg >105 923 Nb Very short 2740
Zn >104 692 U Very short 1405
Cr 1600 2148 Mo Very short 2880
Na >1000 371 W Very short 3680
K >1000 337
Note: Data subject to considerable variability due to varying degrees of material purity, prior surface treatment, and presence of
atmospheric impurities such as sulfur.

25.5 MICROMECHANISMS
Figure 25.4 illustrates the mechanism of parabolic oxidation. The reaction
M + O ! MO

(M is the oxidizing material and O is oxygen) goes in two steps. First M forms an
ion, releasing electrons, e:
M ! M + + + 2e

These electrons are then absorbed by oxygen to give an oxygen ion:

O + 2e ! O

The process involves the diffusion of ions and the conduction of electrons
through the oxide layer. There are three ways in which this can occur — see
Figure 25.4, Case 1, Case 2 and Case 3.
As we saw in Chapter 22 (Equation (22.2)), diffusion is described by Fick’s first
law


dc
J ¼ D
dx

where J is the flux of atoms (or ions)—the number of atoms/ions diffusing

down the concentration gradient per second per unit area, D is the diffusion
 25.5 Micromechanisms 417

Metal Oxide Air

MO

O– – O– – 2e + O
M M+ +
+2e
x
Case 1. M++
diffuses very slowly in oxide. Oxide grows at metal–oxide interface.
Examples: Ti, Zr, U

Metal Oxide Air

MO
Vacancies
M M++ M++O– – 2e + O
+ 2e
x
– – diffuses
Case 2. O very slowly in oxide. Oxide grows at oxide–air interface.
Vacancies form between metal and oxide.
Examples: Cu, Fe, Cr, Co

Metal Oxide Air

2e

Case 3. Electrons move very slowly. Oxide can grow (slowly) at metal – oxide interface
or oxide–air interface depending on whether M++ diffuses faster than O– – or not.
Example: Al
FIGURE 25.4
How oxide layers grow to give parabolic oxidation behavior.

coefficient (D ¼ D0e–Q/RT), x is distance along the flux lines, and c is the con-
centration of atoms/ions—the number of atoms/ions per unit volume. In
the case of oxidation, the flux consists of ions of either M++ or O , depending
on which of these is the rate-determining ion.
The rate of oxidation is obviously proportional to the flux of ions, so in a time
δt the mass gain δ(Δm) ¼ AJδt, where A ¼ constant. The concentration
gradient of M++ or O  is (c1 – c2)/b, where c1 and c2 are the ion concentrations
on either side of the oxide layer, and b is the thickness of the layer. So, from
Fick’s law,
c  c 
1 2
δðΔmÞ ¼ AD δt
b
418 CHAPTER 25: Oxidation of Materials

Now as oxidation proceeds, the oxide layer grows, from zero thickness initially
to b after time t. So b ¼ B(Δm), where B ¼ constant. Then

BΔmδðΔmÞ ¼ ADðc1  c2 Þδt

We integrate from Δm ¼ 0 to Δm ¼ Δm, and t ¼ 0 to t ¼ t. We assume that c1 and

c2 are both constant. Then

ðΔmÞ2 ¼ CDt (25.4)

where C ¼ constant. This growth law has exactly the same form as
Equation (25.2), with kinetic constant

kP ¼ CD ¼ CD0 eQP =RT (25.5)

This is the same as Equation (25.3), with the parabolic constant AP ¼ CD0.
This shows us why some films are more protective than others: protective films
are those with low diffusion coefficients—and thus high melting points. That is
one reason why Al2O3 protects aluminum, Cr2O3 protects chromium, and SiO2
protects silicon so well, whereas Cu2O and even FeO (which have lower melt-
ing points) are less protective. But there is an additional reason: electrons must
also pass through the film and these films are insulators (the electrical resistivity
of Al2O3 is 109 times greater than that of FeO).
Although our simple oxide film model explains most of the experimental obser-
vations we have mentioned, it does not explain the linear laws. How, for exam-
ple, can a material lose weight linearly when it oxidizes as is sometimes observed
(see Figure 25.2)? Well, some oxides (e.g., MoO3, WO3) are very volatile. Dur-
ing oxidation of Mo and W at high temperature, the oxides evaporate as soon as
they are formed, and offer no barrier at all to oxidation. Oxidation, therefore,
proceeds at a rate that is independent of time, and the material loses weight
because the oxide is lost. This behavior explains the catastrophically rapid sec-
tion loss of Mo and W shown in Table 25.2.
The explanation of a linear weight gain is more complex. Basically, as the oxide
film thickens, it develops cracks, or partly lifts away from the material, so the
barrier between material and oxide does not become any more effective as oxi-
dation proceeds. Figure 25.5 shows how this can happen. If the volume of the
oxide is much less than that of the material from which it is formed, it will crack
to relieve the strain (oxide films are usually brittle).
If the volume of the oxide is much greater, on the other hand, the oxide will
tend to release the strain energy by breaking the adhesion between material
and oxide, and springing away. For protection, then, we need an oxide skin that
is neither too small and splits open (like the bark on a fir tree) nor one that is
 Examples 419

Volume oxide
⭐ volume material

Volume oxide
⭓ volume material
Examples: Ta, Nb
FIGURE 25.5
Breakdown of oxide films, leading to linear oxidation behavior.

too big and wrinkles up (like the skin of an elephant), but one which is just
right. Then, and only then, do we get protective parabolic growth.

EXAMPLES
25.1 The oxidation of a particular metal in air is limited by the outward diffusion of
metallic ions through an unbroken surface film of one species of oxide.
Assume that the concentration of metallic ions in the film immediately next to
the metal is c1, and that the concentration of ions in the film immediately next
to the air is c2, where c1 and c2 are constants. Use Fick’s law to show that the
oxidation of the metal should satisfy parabolic kinetics, with weight gain Δm
given by

ðΔmÞ2 ¼ kp t

25.2 The oxidation of another metal is limited by the outward flow of electrons
through a uniform, unbroken oxide film. Assume that the electrical potential in
the film immediately next to the metal is V1, and the potential immediately next
to the free surface is V2, where V1 and V2 are constants. Use Ohm’s law to show
that parabolic kinetics should apply in this case also.
25.3 The kinetics of oxidation of mild steel at high temperature are parabolic, with
( )
2 4 1 138kJ mol1
kp ðkg m s Þ ¼ 37exp 
RT

Find the depth of metal lost from the surface of a mild steel tie bar in a furnace
at 500°C after 1 year. You may assume that the oxide scale is predominantly
FeO. The atomic weight and density of iron are 55.9 kg kmol1 and
7.87 Mg m3; the atomic weight of oxygen is 16 kg kmol1. What would be the
loss at 600°C?
25.4 Of the many metals found in the earth’s crust, why is gold the only one that is
found “native,” that is, as pieces of pure metal?
420 CHAPTER 25: Oxidation of Materials

25.5 The energy released when silver reacts with oxygen at room temperature is
small—only 5 kJ mol1 of O2. At 230°C, the energy is zero, and above 230°C the
energy is positive (i.e., silver is stable and does not oxidize). Use this
information to explain why small electrical contacts are usually plated with a
thin layer of silver. Why is gold not used instead?
25.6 Why does the rate at which a metal oxidizes not necessarily correlate with the
energy released in the oxidation reaction?
25.7 Explain why some metals show either a linear weight gain or a linear weight
loss with time during oxidation.

ANSWERS
25.1 See Section 25.5, and Equations (25.4) and (25.5).
25.2 Ohm’s law is I ¼ V/R. Mass gain is proportional to I, and R is proportional
to oxide layer thickness. Otherwise, the working is identical to that in
Example 25.1.
25.3 kP ¼ 1.74  10–8 kg2 m–4 s–1. Δm ¼ 0.74 kg m–2. Δm is due to addition of oxygen
to the metal. Weight of iron removed as oxide ¼ 2.59 kg m–2. Thickness of metal
lost ¼ 0.33 mm (reworking for 600 °C gives 1.13 mm).
25.4 As shown in Table 25.1, gold is the only metal, which requires energy to make it
react with oxygen (80 kJ mol–1 of O2). It therefore remains as unreacted metal.
25.5 If there is any contact resistance, the contacting surfaces will be heated up by
the current. If the temperature goes above 230 °C, any silver oxide will
decompose, producing pure metal-to-metal contact. Gold is not used because
it is vastly more expensive than silver.
25.6 See Section 25.3 paragraphs 1–3, and Section 25.4.
25.7 See Section 25.3 paragraph 4, Section 25.5 last three paragraphs, Figures 25.2
and 25.5.