CHAPTER 26

Case Studies in Dry Oxidation

CONTENTS
26.1 Introduction ......................................................................................421
26.2 Case study 1: Making stainless alloys ............................................421
26.3 Case study 2: Protecting turbine blades .........................................422
26.4 Case study 3: Joining metals by soldering and brazing .................426
Examples ..................................................................................................429
Answers ....................................................................................................430

26.1 INTRODUCTION
In this chapter we look first at an important class of alloys designed to resist
corrosion: the stainless steels. We then examine a more complicated problem:
that of protecting the most advanced gas turbine blades from gas attack. The
basic principle applicable to both cases is to coat the steel or the blade with
a stable ceramic: usually Cr2O3 or Al2O3. But the ways this is done differ widely.
Finally, we look at a process in which oxide films must not form on the
surface—joining metals by soldering and brazing.

26.2 CASE STUDY 1: MAKING STAINLESS ALLOYS

Mild steel is an excellent structural material—cheap, easily formed, and strong.
But at low temperatures it rusts, and at high temperatures, it oxidizes. There is a
large demand, for high-temperature applications ranging from chemical reactors
to superheater tubes, for oxidation-resistant steel. In response to this demand, a
range of stainless irons and steels has been developed. When mild steel is
exposed to hot air, it oxidizes quickly to form FeO (or higher oxides). But if
one of the elements near the top of Table 25.1 with a large energy of oxidation
is dissolved in the steel, then this element oxidizes preferentially (because it is 421

Engineering Materials 1: An Introduction to Properties, Applications and Design, Fifth Edition. https://doi.org/10.1016/B978-0-08-102051-7.00025-7
© 2019, David R. H. Jones and Michael F. Ashby. Published by Elsevier Ltd. All rights reserved.
422 CHAPTER 26: Case Studies in Dry Oxidation

more stable than FeO), forming a layer of its oxide on the surface. And if this
oxide is a protective one, like Cr2O3, Al2O3, SiO2, or BeO, it stifles further growth,
and protects the steel.
A considerable quantity of this foreign element is needed to give adequate pro-
tection. The best is chromium, 18% of which gives a very protective oxide film:
it cuts down the rate of attack at 900°C, for instance, by more than 100 times.
Other elements, when dissolved in steel, cut down the rate of oxidation, too.
Al2O3 and SiO2 both form in preference to FeO (refer to Table 25.1) and form
protective films (refer to Table 25.2). Thus 5% Al dissolved in steel decreases
the oxidation rate by 30 times, and 5% Si by 20 times. The same principle can
be used to impart oxidation resistance to other metals. We shall discuss nickel
and cobalt in the next Case Study—they can be alloyed in this way. So, too,
can copper; although it will not dissolve enough chromium to give a good
Cr2O3 film, it will dissolve enough aluminum, giving a range of stainless alloys
called “aluminum bronzes.” Even silver can be prevented from tarnishing
(reaction with sulfur) by alloying it with aluminum or silicon, giving protective
Al2O3 or SiO2 surface films.
Ceramics themselves are sometimes protected in this way. Silicon carbide, SiC,
and silicon nitride, Si3N4, both have large negative energies of oxidation
(meaning that they oxidize easily). But when they do, the silicon in them turns
to SiO2 which quickly forms a protective skin and prevents further attack.
Protection by alloying has one great advantage over protection by surface coating
(like chromium plating or gold plating): it repairs itself when damaged. If the pro-
tective film is scored or abraded, fresh metal is exposed, and the chromium (or alu-
minum or silicon) it contains immediately oxidizes, healing the break in the film.

26.3 CASE STUDY 2: PROTECTING TURBINE BLADES

As we saw in Chapter 24, the materials at present used for turbine blades consist
chiefly of nickel, with various foreign elements added to get the creep properties
right. With the advent of DS and SX blades, such alloys will normally operate
around 950°C, which is close to 0.7TM for Ni (1208 K, 935°C). If we look at
Table 25.2 we can see that at this temperature, nickel loses 0.1 mm of metal
from its surface by oxidation in 600 h. The thickness of the metal between
the outside of the blade and the integral cooling ports is about 1 mm, so in
600 h a blade would lose about 10% of its cross-section in service.
This represents a serious loss in mechanical integrity and makes no allowance
for statistical variations in oxidation rate—which can be quite large—or for pref-
erential oxidation (at grain boundaries, for example) leading to pitting. Because
of the large cost of replacing a set of blades, they are expected to last for more
 26.3 Case Study 2: Protecting Turbine Blades 423

than 5000 h. Nickel oxidizes with parabolic kinetics (Equation (25.4)) so after a
time t2, the loss in section x2 is given by substituting the data into:
 1=2
x2 t2
¼
x1 t1

giving
 
5000 1=2
x2 ¼ 0:1 ¼ 0:29 mm
600

Obviously this sort of loss is not OK, but how do we stop it?
As we saw in Chapter 24, the alloys used for turbine blades contain large
amounts of chromium, dissolved in solid solution in the nickel matrix. If we
look at Table 25.1, which gives the energies released when oxides are formed
from materials, we see that the formation of Cr2O3 releases much more energy
(701 kJ mol–1) than NiO (439 kJ mol–1). This means that Cr2O3 will form in
preference to NiO on the surface of the alloy. Obviously, the more Cr there is in
the alloy, the greater is the preference for Cr2O3. At the 20% level, enough
Cr2O3 forms on the surface of the turbine blade to make the material act a
bit as though it were chromium.
Suppose for a moment that our material is chromium. Table 25.2 shows that
Cr would lose 0.1 mm in 1600 h at 0.7TM. Of course, we have forgotten about
one thing. 0.7TM for Cr is 1504 K (1231°C), whereas for Ni, it is 1208 K
(935°C). We should probably consider how Cr2O3 would act as a barrier to
oxidation at 1208 K rather than at 1504 K (Figure 26.1). The oxidation of Cr
follows parabolic kinetics with an activation energy of 330 kJ mol–1. Then
the ratio of the times required to remove 0.1 mm (from Equation 25.3) is
t2 exp  ðQ=RT1 Þ
¼ ¼ 0:65  103
t1 exp  ðQ=RT2 Þ

Thus the time at 1208 K is

t2 ¼ 0:65  103  1600 h

¼ 1:04  106 h

Of course, there is only at most 20% Cr in the alloy, so the alloy behaves only
partly as if it were protected by Cr2O3. Experimentally, we find that 20% Cr
increases the time for a given metal loss by only about 10 times; that is, the time
taken to lose 0.1 mm at blade working temperature becomes 600  10 h ¼
6000 h rather than 106 hours.
Why this large difference? Whenever you consider an alloy rather than a pure
material, the oxide layer—whatever its nature (NiO, Cr2O3, etc.)—has foreign
elements contained in it, too. Some of these will greatly increase the diffusion
424 CHAPTER 26: Case Studies in Dry Oxidation

Temperature (K)
2000 1500 1200 1000

kP at 1504 K

In kp Slope
−330,000/R

kP at 1208 K

4 6 8 10
1/T (K−1) × 104

FIGURE 26.1
The way in which kp varies with temperature.

coefficients or electrical conductivity of the layer, and make the rate of oxida-
tion much more than it would be in the absence of foreign element
contamination.
One therefore has to be very careful in transferring data on film protectiveness
from a pure material to an alloyed one, but the approach does give us an idea of
what to expect. As in all oxidation work, however, experimental data on actual
alloys are essential for design.
This 0.1 mm loss in 6000 h from a 20% Cr alloy at 935°C, though better than
pure nickel, is still not good enough. What is worse, we saw in Chapter 24 that,
to improve the creep properties, the quantity of Cr has been reduced to 10%,
and the resulting oxide film is even less protective. The obvious way out of this
problem is to coat the blades with a protective layer (Figure 26.2). This is usually
done by spraying molten droplets of aluminum on to the blade surface to form
a layer, some microns thick. The blade is then heated in a furnace to allow the Al
to diffuse into the surface of the Ni. During this process, some of the Al forms
compounds such as AlNi, which are themselves good barriers to oxidation,
while the rest becomes oxidized up to give Al2O3—which, as we can see from
our oxidation-rate data—should be a very good barrier. An incidental benefit of
 26.3 Case Study 2: Protecting Turbine Blades 425

AI
As-sprayed
Ni alloy

Al2O3
After diffusion
annealing Al Ni, etc., compounds

Ni alloy

FIGURE 26.2
Protection of turbine blades by sprayed-on aluminum.

the AlNi layer is its poor thermal conductivity—this helps insulate the metal of
the cooled blade from the hot gases, and allows a slight extra increase in blade
working temperature.
Other coatings, though more difficult to apply, are even more attractive. It is
possible to diffusion-bond a layer of Ni–Cr–Al alloy to the blade surface to give
a ductile coating which forms a very protective film of oxide. And zirconium
oxide (zirconia) is now used as a combined thermal barrier and oxidation pro-
tection coating on many hot end components.

Influence of coatings on mechanical properties

So far, we have been considering the advantage of an oxide layer in reducing the
rate of oxidation. Oxide films, however, have some disadvantages.
Because oxides are usually quite brittle at the temperatures encountered on a
turbine blade surface, they can crack, especially when the temperature of the
blade changes and differential thermal contraction and expansion stresses
are set up between alloy and oxide. These can act as initiation sites for thermal
fatigue cracks, and because oxide layers in nickel alloys are well bonded to the
underlying alloy, the crack can spread into the alloy itself (Figure 26.3).

Oxide

Alloy
Fatigue or
thermal fatigue
crack

FIGURE 26.3
Fatigue cracks can spread from coatings into the material itself.
426 CHAPTER 26: Case Studies in Dry Oxidation

The properties of the oxide film are therefore important in affecting the fatigue
properties of the whole component.

Protecting future blade materials

You may wonder why we did not mention the “refractory” metals Nb, Ta, Mo, and
W in the chapter on turbine-blade materials. These metals have very high melting
temperatures (see below) and should therefore have very good creep properties.
Nb 2740K
Ta 3250K
Mo 2880K
W 3680K

But they all oxidize very rapidly indeed (refer to Table 25.2), and are useless
without coatings. The problem with coated refractory metals is that if a break
occurs in the coating (e.g., by thermal fatigue, erosion by dust particles, etc.),
catastrophic oxidation of the underlying metal will take place, leading to rapid
failure. The “unsafeness” of this situation is a major problem that has to be
solved before we can use these otherwise excellent materials.
The ceramics SiC and Si3N4 do not share this problem. They oxidize readily
(refer to Table 25.1); but in doing so, a surface film of SiO2 forms which gives
adequate protection up to 1300°C. And because the film forms by oxidation of
the material itself, it is self-healing.

26.4 CASE STUDY 3: JOINING METALS BY SOLDERING

AND BRAZING
We might think it is always a good thing to have a protective oxide film on the
surface of a metal. But not always—if you want to join metals together by sol-
dering, the protective film is a problem.
For example, we often need to “soft” solder copper together—copper wires to
copper tracks in PCBs, copper tubes and fittings together in plumbing installa-
tions. Traditional soft solder is an alloy of lead and tin, with a melting point
between 184 and 327°C, depending on the percentages of Pb and Sn (there
is pressure to replace the Pb in soft solders because of possible health risks).
Even at room temperature, a copper surface has a very thin layer of oxide, and
when the copper is heated to the melting temperature of the solder, the oxide
grows. In order to solder copper parts together successfully, it is essential to
have metal-to-metal contact between the solidified solder and the copper.
The test is whether the solder—when molten—“wets” the copper surface.
The solder will not wet the copper if there is oxide on the surface of the copper.
 26.4 Case study 3: Joining Metals by Soldering and Brazing 427

Molten
Copper
solder
oxide
Copper
metal

FIGURE 26.4
Molten solder will not “wet” a film of copper oxide

Figure 26.4 shows a piece of copper, which was heated to the melting point of
soft solder, and then had soft solder melted on top of it. You can see that the
solder has “balled-up” on the copper surface. It has not spread out over the sur-
face, because the solder has not “wetted” the copper. After cooling the copper
back down to room temperature, you will find that it is possible to lever the ball
of solder off the copper—there has not been metal-to-metal contact for the sol-
der to stick to the copper.
So the problem reduces to: “how do we get rid of the oxide layer on the copper
before we apply the molten solder, and how do we make sure that the oxide
cannot regrow while we are doing the soldering?”.
Figure 26.5 shows the same test done on a copper component which was
cleaned with abrasive paper, and then coated with flux. The flux is a soft paste
of natural resin extracted from pine trees, which melts when the copper is
heated up, and spreads out over the surface. The flux contains resin acids, which
“dissolve” the oxide film at the soldering temperature, and it also acts as a bar-
rier to oxygen, preventing the oxide from regrowing. You can see that the solder

Copper metal

Molten
solder Copper metal

FIGURE 26.5
Molten solder “wets” an oxide-free copper surface.
428 CHAPTER 26: Case Studies in Dry Oxidation

has wetted the copper surface. The solder is firmly attached to the copper, and
the joint has considerable strength.
The same issues arise when you try to soft solder other metals. Some, like cop-
per alloys, mild steel, zinc-coated steel, and tin-coated steel, solder well—
although different fluxes may be used to get the best results (for example zinc
chloride solution—traditionally referred to as “tinner’s fluid”). But many other
metals—such as aluminum, chromium, stainless steel (chromium again), mag-
nesium, titanium, and beryllium—are difficult (or impossible) to soft solder
in air, because their oxide films are so stable (mechanically and chemically).
Techniques include using aggressive fluxes, and disrupting the oxide film
mechanically while soldering, using a high-frequency transducer.
For high-strength and/or high-temperature applications, metals are soldered
with hard solders (often referred to as brazing). These typically melt in the range
610–950°C, depending on the alloy composition. Some are based on silver,
and can contain exotic elements like palladium, in which case they are very
expensive. At such high temperatures, oxidation is much faster. However cop-
per, copper alloys, and carbon steel are easy to hard solder if aggressive fluxes,
such as borax (sodium borate), are used.
Of course, a great way to stop oxides forming is not to have any oxygen present
at all. This principle is used in vacuum brazing. The parts to be brazed are cleaned
mechanically and assembled, and then preformed rings or foils of hard solder
are put in place. The assembly is placed in the vacuum furnace, the pressure
is reduced to zero, and the furnace is heated up to the temperature needed
to melt the brazing alloy. When the alloy melts, it wets the surfaces of the
parent metal, and is sucked into the joints by capillary action. This produces
a very fine and strong joint line, with none of the defects (such as trapped
air or flux) that can be present in air-brazed joints. For “difficult” metals, hydro-
gen gas can be fed into the vacuum chamber to actively reduce any oxide
(MO + H2 ¼ M + H2O).
Figure 26.6 shows an example of a component fabricated by vacuum brazing—
the lid of a small pot containing an electronic device. This was press formed
from thin Kovar sheet (a controlled expansion alloy with composition
54Fe29Ni17Co and melting point 1450°C). Kovar pins were brazed into holes
in the lid as shown, using Pallabraze 950—an alloy with composition
54Ag25Pd21Cu and melting range 901–950°C. The furnace temperature was
set at 1000°C. Figure 26.6(a) shows the assembly before heating, with the
pin in position and a tiny preformed ring of Pallabraze around the pin. There
is a small clearance between the pin and the hole (typically a few thou) so the
brazing alloy can flow through the joint. When the furnace comes up to tem-
perature, the ring melts, wets the oxide-free Kovar surfaces, and is sucked into
the joint (Figure 26.6(b)).
 Examples 429

Brazing
alloy
ring Glass bead
Lid

(A) Pin

Glass-to-metal
Brazed
seal
joint

(B)
FIGURE 26.6
Making a brazed joint and a glass-to-metal seal.

The diagrams also show the fabrication of a glass-to-metal seal between the lid
and some of the other pins (designed to electrically insulate the lid from the
pins). Small beads of low-expansion borosilicate glass were placed between
the pins and the lid, and when the furnace came up to temperature the glass
flowed and wetted the oxide-free metal surfaces. The brazing alloy was chosen
so that both the brazing and the glass sealing could be done in one single
operation.

EXAMPLES
26.1 Diffusion of aluminum into the surface of a nickel super-alloy turbine blade
reduced the rate of high-temperature oxidation. Explain.
26.2 Explain why many high-temperature components, e.g., furnace flues and heat
exchanger shells, are made from stainless steel rather than mild steel.
26.3 Give examples of the use of alloying elements to reduce the rate at which
metals oxidize.
26.4 Why are the refractory metals (Nb, Ta, Mo, W) of very limited use at high
temperature? What special steps are taken to ensure that tungsten electric
light filaments can operate for long times at white heat?
26.5 Why is oxidation a problem when soldering or brazing metal parts? Why are the
connection tabs on small electrical components usually supplied pre-tinned
with electrical solder?
430 CHAPTER 26: Case Studies in Dry Oxidation

26.6 Why is nichrome wire (Ni + 30Fe + 20Cr), rather than mild steel, used for
heating elements in electric fires?
26.7 Explain, giving examples, why ceramics are good at resisting high-
temperature oxidation.

ANSWERS
26.1 See Figure 26.2 and accompanying text in Section 26.3.
26.2 See Section 26.2 paragraphs 1 and 2. The protective oxide film is Cr2O3,
produced by the chromium content of the stainless steel.
26.3 See Sections 26.2 and 26.3. Examples are Cr in stainless steel (Cr2O3 film), Cr
in Ni alloys (Cr2O3 film), Al in aluminum bronzes (Al2O3 film).
26.4 See Table 25.2. They oxidize very rapidly in air at high temperature. Lamp
filaments are encased in a glass bulb, which is either evacuated or filled with
an inert gas, to keep the oxygen out.
26.5 The oxide layer prevents the molten solder or brazing alloy from wetting the
surfaces to be joined. When the copper connection tabs are soldered to
pretinned copper wire, the pretinning solder melts and this protects the
copper surfaces from oxidation.
26.6 The Cr and Ni form a protective oxide layer on the wire, which resists oxidation
of the alloy at the high running temperature. Mild steel would oxidize far too
rapidly at the running temperature, and would burn out in a matter of days (see
Table 25.2).
26.7 Many are oxides already, e.g., MgO, SiO2, Al2O3, BeO (see Table 25.1). Others,
e.g., SiC and Si3N4, form protective layers of SiO2 when exposed to oxygen at
high temperature (see Section 26.3, last paragraph).