University of kufa / college of engineering

Material engineering department

The oxidation of
metals

Done by (Ali Sarmd Ali)

Supervised by (lect. Marwa)

Biomaterials engineering department

2022-2023

Introduction:
Oxidation is a type of corrosion involving the reaction between a metal
and air or oxygen at high temperatures in the absence of water or an
aqueous phase. It is also called dry corrosion. At normal temperatures,
the oxides of the metals (except gold) are more stable than the metals.
Metals being in the metastable state are bound to form oxides. The rate
of oxidation of a metal at high temperatures depends on the nature of
the oxide layer that forms on the surface of the metal.

In general, the oxides can be categorized in three

groups:

1. The oxide is unstable, i.e., oxide docs not form i.e.,

oxidation does not occur. For example, gold is free of
tarnishing as gold oxide does not form.
2. Some metals form molten or volatile oxides, such as
V2O5 on vanadium and MoO3 on molybdenum: or the
oxygen dissolves in the metal itself, such as in
titanium. The oxidation then occurs catastrophically,
as fast as the oxygen gas is supplied.
3. More commonly a thin film or thick scale of oxide or
oxides form on the surface, which slows down further
oxidation. This aspect is more common and is dealt
here.

Pilling-Bedworth ratio:
Thin surface oxide layers formed up to a thickness of about 3000 A° are called
films, but are called scales if greater than this, and are clearly visible. Very thin
oxide films, such as 20 A° thick produced on aluminium at room temperature,
are invisible, but can be seen when about 100-1000 A° thick from the
interference colours produced by light rays.
The process of tempering of quenched steel is sometimes controlled by
observing the temper colours produced on the clean steel surface. These
colours range from light straw (220°C) to light blue (3I0°C) as the oxide film
increases in thickness as a function of time and temperature.
Thin films invariably decrease the rate of additional oxidation and may, as in
the case of aluminium, be almost completely protective. The oxide film
completely isolates the metal from the air. The tendency for an oxide film (or
scale) to be protective can be approximately evaluated to act as a guide by a
parameter called the Pilling-Bedworth ratio. This is the ratio of oxide volume to
the volume of metal from which the oxide has formed. For the following
oxidation reaction:
A M + (b / 2) O2 → Ma Ob … (14.2)
The Pilling-Bedwortli ratio is-

Where, W is the formula weight of the oxide, w is the atomic weight of the
metal, ρm and ρox are the densities of metal and the oxide, respectively. If this
ratio is less than I, there is insufficient oxide to cover the metal. Tensile
stresses develop in the oxide film, causing the film to become porous, and
unprotective. Oxidation continues rapidly as happens for a metal like
magnesium, Fig. 14.1 (a). If the ratio is equal to, or slightly greater than unity,
an adherent, non-porous, protective oxide film forms such as typical on
aluminium, Fig. 14.1 (b).

If the ratio is greater than two (to three), i.e., volume of the oxide is greater
than that of the metal. Initially, the thin oxide film acts as a protective layer.
However, as the thickness of the scale increases, high compressive stresses
develop in the oxide. The brittle oxide scale cracks and spalls or flakes off the
metal surface and normally a breakaway oxidation occur such as for iron, Fig.
14.1(c).
Table 14.1 illustrates the P-B ratios for some metals. This ratio does not
accurately predict oxidation resistance in all cases. This ratio acts as an
empirical criterion and does not include other properties more important in
determining oxidation resistance, such as good adherence, high melting point,
a low vapor pressure, good high temperature plasticity to resist fracture and
low electrical conductivity, or low diffusion coefficients for metal ions and
oxygen, similar coefficient of expansion as the metal itself for cyclic
temperatures (alternate heating and cooling cycles in service can cause the
oxide layer to crack).
As oxidation proceeds more rapidly with the rise of temperature, even an
adherent oxide film may not afford sufficient protection at elevated
temperatures.

Mechanism of Oxidation:
When a fresh surface of metal like gold comes in contact with oxygen, the
latter forms a loosely bound layer on the surface of gold due to secondary van
der Waals attractive forces arising between the atoms of the metal surface and
the oxygen molecules. This layer is said to be adsorbed oxygen layer, and no
further chemical bonding occurs. This layer is easily removed by applying
ultrahigh vacuum.
In most other metals, the first oxygen molecules coming in contact with the
clean surface of metal, dissociate into oxygen atoms and then, these oxygen
atoms bond chemically with the atoms of the metal surface.
This monolayer of oxygen atoms which forms rapidly over the whole surface of
the clean metal is said to be chemisorbed. This process, involving dissociation
and ionisation of oxygen molecules is known as chemisorption. Additional
oxygen may be physically adsorbed on such a layer.
In the chemisorbed layer, oxide is nucleated at favourable sites on the surface
such as ends of dislocations, steps in surface, impurity atoms, etc. This
nucleation occurs slowly at low temperatures, but soon the whole surface is
covered with a thin film of oxide, which continues to thicken, particularly at
high temperatures.
The initial oxidation represents direct chemical reaction between the metal
and the oxygen. If the initial oxide layer on the surface has pores, or fissures in
it (P-B ratio is less than 1), it is non-protective oxide. Here, molecular oxygen
diffuses through the pores and reacts with the metal to form more oxide at the
metal oxide interface as illustrated in Fig. 14.2. The alkali and alkaline earth
metals such as calcium, magnesium Fig. 14.1 shows such behaviour. These
metals follow linear oxidation rate law. Even metal like molybdenum forming
volatile MoO3 follows the linear relationship.

When the initial oxide film on the exposed metallic surface is protective in
nature, further oxidation is electrochemical in nature.

The reactions are:

Metal ions (M+2) form at metal oxide interlace-
M → M2+ + 2e̅ …(14.4)
Electrons produced (reaction 14.4) are conducted through the oxide layer to
meet the oxygen atoms at oxygen oxide interlace to result in-
½ O2 + 2 e̅ → O-2 …(14.5)
Once, these ions have formed, these react to produce metal oxide by the
reaction-
M2+ + O-2→ MO …(14.6)
When a very thin film of oxide (monolayer, or so) has formed on the surface,
the oxygen atoms on the outer surface extract electrons from the metal
underneath this thin film to become negative ions by the reaction (14.5). These
negative ions exert an electrostatic attraction on the positive metal ions in the
metal.
Initial film being very thin and the force of electrostatic attraction being very
strong, the metal ions (normally smaller than anions) are pulled through the
film to produce metal oxide by reaction (14.6). As the oxide film thickens, the
force becomes weaker since the distance between the metal cation and anion-
oxygen increases.
Further oxidation requires the normal diffusion of ions and the conduction of
electrons through the oxide layer. The electronic conductivities of oxides are
usually several orders of magnitude greater than their ionic conductivities. The
rate of diffusion of ions through the oxide layer is a slow process, and hence
the oxidation drastically slows down.

The oxidation now has a logarithmic type of growth. The rate of diffusion of
ions becomes the controlling step for oxidation.
The oxidation reaction M+2 + O-2→ MO takes place either at the oxygen oxide
interface by the diffusion of metal ions and conduction of electrons through
the oxide layer to this interlace, or at the oxide metal interface by conduction
of electrons to oxide oxygen interface, and by the diffusion of oxygen ions
through the oxide layer to oxide metal interface. The place of oxide formation
depends on the type of defect structure of the oxide lattice formed on the
metal surface.

Kinetics of Oxidation:
An engineer is interested in knowing the rate of (oxidation) reaction. As in
most cases, the oxide formed remains on the surface of metal, the rate of
oxidation can be expressed as weight gain per unit area, or how the thickness
of the oxide film increases with time. Oxidation usually develops with time ‘t’
according to one of the curves illustrated in Fig. 14.8 at a constant
temperature, or more curves in different temperature ranges. These oxidation
for various metals under various conditions.

Linear Rate Law:

This law states that oxidation takes place at a more or less constant rate, i.e.,
thickness, or weight gain of the oxide layer increases with time uniformly.
W = K3(t) …(14.8)
Where, W is weight gain per unit area, t is time, and K3 are constants
dependent on temperature. The linear law applies to the initial stages of most
oxidation before the film is thick enough to be protective, and also wherever
the protection no longer increases as oxidation continues such as, Mo at
temperatures where MoO3 is volatile. Linear relationship is characteristic of
metals which form a porous or cracked scale. Sodium, potassium, magnesium
(with P-B ratio less than 1) also oxidise with linear law, and tantalum,
columbium too with P.B. ratio of about 2.5.

Logarithmic Rate Law:

Logarithmic oxidation is generally observed with thin highly protective oxide
films (< 1000 A°) at low temperatures in Cu, Fe, Zn, Ni, Pb, Al, Cr, Mn, Ti, etc.
Fig. 14.8 indicates that W, weight gained per unit area in a logarithmic way
with time, t as:
W = K4 log (K5(t) + K6) …(14.9)
Where, K4, K5 and K6 are constants for a particular temperature, environment
and composition. The oxidation occurs very slowly to become almost constant
after sometime (i.e., oxidation almost does not occur). This law mainly applies
to highly protective thin films such as chromium oxide film, aluminium and
beryllium oxides, iron below 200°C.
Such a rate of oxidation, probably, results from the effect of electrostatic
forces between ions within very thin oxide film in assisting the transport of
ions across the film. At this stage, forces become weaker between ions due to
increased distance between them. Oxidation slows down to give logarithmic
rate.

Parabolic Rate Law:

Wagner showed that when diffusion of ions occurs through the defect
structure oxide layer, the oxidation of pure metals should ideally follow the
parabolic rate law:
W2 = K1(t) + K2 …(14.10)
Where, K1 and K2 are constants. Thus, it is a diffusion controlled mechanism,
and in most cases, the scale is protective (PB is > 1), though not as protective
as logarithmic type. Here, the thickness of oxide increases at a decreasing rate.
The scale grows mainly at oxide-oxygen interface, i.e., diffusion of metal
cations occurs. Oxidation of many metals, Cu (at 800°C), Fe(200°-900°C), Ni. Cr,
Co at elevated temperatures obeys parabolic law.
 =====================
 It is common that some metals oxidize by a combination of rate laws, or
the oxidation occurs by two simultaneous mechanisms. Many times, one
mechanism predominates during initial and other at later stages.
 However, parabolic law does not apply from zero time. Linear oxidation
rate is least desirable, and parabolic as well as logarithmic oxidation
rates are more desirable for alloys used in high temperature
applications. Aluminum has high atmospheric oxidation resistance at
normal temperatures as it oxidizes according to logarithmic rate law.
======================

Control of Oxidation:
High resistance to further oxidation is possible if the initial oxide film has
Pilling-Bedworth ratio slightly greater than one so that it is continuous,
compact and adhering. The film should have high resistance to the conduction
of ions and/or electrons, and be almost stoichiometric i.e., has low diffusivity
to reduce the oxidation rate effectively.
A high free energy of oxidation results in a dense, almost stoichiometric,
chemically stable oxide with excellent protective properties like Cr2O3, AI2O3,
BeO. The film of alumina on aluminium has few lattice defects and thus resists
further oxidation, but above 400°C, concentration of defects in alumina
increases, and growth becomes parabolic. Cr2O3 film on chromium or on
chromium steels has poor ionic conductance and thus, prevents further
oxidation.
The oxide film is protective if it has good adherence, is impervious, non-
volatile, non-reactive with atmosphere, has similar coefficient of expansion as
the metal (if temperature variations are cyclic). The nature of oxide film and its
rate of growth varies with the temperature and environment, and needs actual
expermental testing.
The oxidation resistance of a metal surface thus can also be increased if a
protective oxide film can be provided by some other ways. A suitable alloying
element can be added to the metal which preferentially reacts with oxygen
and forms the protective oxide film. Hauffe’s valency rule, though not
absolutely reliable, is often very useful.
According to this rule, if the oxide film of the base metal is a cation-deficient
structure, then the addition of an alloying element of lower valency, reduces
the cation vacancies in the oxide formed. Addition of nickel to pure chromium,
thus, decreases the oxidation rate but the reverse addition increases the
oxidation rate.
If the base-metal oxide structure has excess cations and electrons in the
interstitial positions, such as in ZnO, the reverse is true. Addition of aluminium
to zinc metal lowers the oxidation rate of zinc, but addition of lithium, of lower
valency increases the oxidation rate. Aluminium addition to Zn decreases
electron concentration, decreases interstitial metal cations, whereas addition
of lithium increases electron concentration and increases interstitial metal
cations.
Selective oxidation can be used to an advantage, where one component or
microstructural constituent of an alloy oxidizes more readily than the others. A
more reactive metal must be chosen to be alloyed with the base metal, which
has more affinity for oxygen then does the base metal.