2.

2 Chemical properties of materials

Chemical properties of materials refer to the reactivity and stability of materials in
the environments of processing and applications.
Oxidation in air and corrosion in aqueous environments (also a type of oxidation)
are the two major chemical processes that are related with the reactivity of materials,
particularly metals.
All metals have a tendency to be oxidised (lose electrons) but their reactivity with oxygen (or
affinity to oxygen) varies significantly from those with a high affinity, e.g. Al, Mg, Ti, to the
noble metals, e.g. Au, Pt, that are inert in air at room temperature.

At room temperature, oxidation of engineering or structural metals in air occurs only on the
surface due the formation of a thin and dense oxide surface layer that separates the metal from
its environment, and hence prevents further oxidation.
At high temperatures, the oxide layer formed on the surface becomes less dense and more
importantly conductive to either or both ions of oxygen and metal, and/or electrons, allowing
metal oxidation to proceed.
When in contact with water, the tendency of metals to lose electrons (e.g. to H+ or dissolved O2)
often leads to the formation of metal cations that enter water, resulting in corrosion of the metal.

Corrosion is enhanced by a number of factors, such as the presence of ions (e.g. those from a
dissolved salt), and hence more significant in seawater than in fresh water.

2.2.1 Oxidation of metals at high temperatures in air

Oxidation of metals in air (or other oxidising gases) at elevated temperatures is largely controlled
by the nature of the oxide film (or scale) on the surface.
Broken and/or porous oxide films: oxygen may access the fresh metal underneath the oxide film,
allowing fast and continuous oxidation.
Coherent and non-porous oxide films: oxidation is retarded but may continue via the diffusion of
oxygen or metal ions or both through the oxide film which may also be conductive to electrons.
(If the temperature is higher than the melting or even boiling point of the oxide, or the pressure is
lower than the vapour pressure of the oxide, no solid oxide film can form on the metal surface and
oxidation takes place catastrophically, e.g. Mo and W.)
The Pilling-Bedworth (P-B) ratio defines the nature of an oxide film on a metal surface and is
expressed as

P B ratio

Mox m
M V
ox ox
nM mox nM mVm

rm and rox, and Vm and Vox : densities and massspecific volumes of metal and oxide; Mm and Mox:
formula masses of metals and oxide; n: number of
metal atoms in the oxide formula.

For P-B ratio < 1, the oxide occupies a smaller volume than the volume of metal from which the
oxide is formed and, in this case, the oxide film is porous and hence non-protective.
For P-B ratio is around 1, the volumes of oxide and metal are nearly equal and the tendency is for
the formation of a continuous, non-porous and protective oxide film.
For P-B ratio >1, the oxide film is protective initially, but as the film thickens, stresses are
developed within the film and these may cause the oxide to flake off from the metal.

2.2.2 Growth of oxide films on metals

For porous films, i.e. P-B ratio < 1
Thickness of the oxide film increases linearly with time at a given temperature, i.e.

y = kt,

y: thickness of film; t: time; k = A exp (- B/T) (Arrhenius Law). (reaction control)

For non-porous films, i.e. P-B ratio 1

Growth of the oxide film can only proceed via (1) electron
transfer reactions at the metal/oxide and/or oxide/air
interfaces, and (2) the diffusion of electrons and either
oxygen or metal ions or both through the oxide film.
At the metal/oxide interface:
At the oxide/air interface:
Overall reaction:

M = M2+ + 2 e
O2 + 2e = O2M + O2 = MO

M2+

O2-

e
metal

oxide

air

oxide film
growth direction

If the diffusion of M2+ is faster than O2-, the combination of the two ions occurs nearby the oxide/air
interface. If the diffusion of O2- is faster than M2+, the combination of the two ions occurs near the
metal/oxide interface. (M2+ is usually smaller than O2- and hence diffuses faster.)
Resistance of the oxide film to electron conduction is usually high, and metal oxidation can therefore
slow down or stop completely when the film thickness becomes sufficiently large.
Defects (e.g. vacancies) in the oxide film help the diffusion of both ions and electrons.
Thickness of the oxide film increases following either a parabolic law or logarithm law.

y2 = kt,

y, t: same as above (diffusion control), or

y = k log (at +1),

a: constant (mixed control)

2.2.3 Protection of metals from high temperature oxidation by alloying

weight gain rate (g cm-2 h-1)

Copper oxidises readily in air at elevated temperatures, but copper-aluminium

alloys are more stable under similar conditions.

Initial oxidation on surface

Experimentally
measured oxidation
rate of Cu-Al
alloys at 800oC.
Note: the weight
gain is due to the
mass addition of
oxygen, but not
that of the oxide.

Understanding the oxidation resistance of alloys

Aluminium has a high affinity to oxygen and forms a very stable and insulating oxide, Al 2O3,
and hence is often added to a parent metal to resist high temperature oxidation.
When a parent metal, e.g. Cu, is oxidised, cuprous oxide, Cu 2O, is formed. This film allows
fast diffusion of the copper ion, Cu+, but not the aluminium ion.
The consequence is that Cu is quickly depleted but Al enriched at the metal/oxide interface.
Further oxidation of the metal proceeds by oxygen ion diffusion through the oxide film.
This leads to the formation of a denser Al2O3 oxide layer which does not allow Cu+ to diffuse
through, and hence stops further oxidation.
rich in Al2O3
Cu+
e
Cu + Al

O2-

Cu2O

O2e
air

oxide film
growth direction

Cu + Al

Cu2O

air

oxide film
growth direction

Addition of Cr or Si into Fe has similar effects on the oxidation of steel. The oxidation of Cr or
Si in Fe leads to the formation of chromic oxide Cr2O3 or iron silicate FeSiO3, both are
impervious to Fe2+ ions. This is why stainless steel is more resistant to oxidation.

Such processes will soon reach at equilibrium due to

electric neutrality, and result in a potential difference
between the metal and water across their interface.

M
M
metal water

e
e
e

M+
M+
M+
metal water

The potential difference is characteristic for a given

metal and, when standardised, with reference to
hydrogen gas and ion and the contacting solution
(electrolyte), forms the basis of the activity or
electromotive series of metals.
Under non-standard conditions, e.g. when the
contacting solution is seawater, the order of metal/ion
couples in the activity series can differ from the
standard series, and is termed the Galvanic series.

noble metals

Eo / V

Na/Na+
Mg/Mg2+
Al/Al3+
Zn/Zn2+
Cr/Cr3+
Fe/Fe2+
Cd/Cd2+
Co/Co2+
Ni/Ni2+
Sn/Sn2+
Pb/Pb2+
H2/H+
Cu/Cu2+
Hg/Hg2+
Ag/Ag+
Pt/Pt2+
Au/Au+

-2.71
-2.38
-1.67
-0.76
-0.54
-0.44
-0.40
-0.28
-0.25
-0.14
-0.13
0.00
0.34
0.79
0.80
1.20
1.80

anodic

Zn = Zn2+ + 2e

metal/ion

cathodic

When in contact with water, metals tend to lose part of

their electrons to become ions which then enter the
nearby solution, leaving electrons behind in the metal.
This process is termed the ionisation of metal. e.g.

base metals

2.2.4 Ionisation and electromotive force

standard electrode
potentials of some
metal/metal ion couples

Mg
Mg alloy
Zn
Galvanised Steel
Al
Cd
Mild Steel
Wrought iron
Cast iron
Austenitic stain
less steel
Pb
Sn
Ni
Cu
70/30cupronickel
Ti
Au

Galvanic series
of metals in
seawater

2.2.5 Corrosion of metals in aqueous solutions

Composition corrosion cells

When dissimilar metals are connected by both electronic and
ionic pathways, an electrochemical or corrosion cell is formed in
which currents flow in opposite directions in the two pathways,
carried by electrons and ions respectively, driven by the
difference in electromotive potentials between the two metals.
In a Zn-Cu cell, the ionisation of Zn (anode, more negative electrode
potential) is accelerated due to the electrons leaving Zn and joining
the current flow, leading to dissolution or corrosion of the metal. The
ionisation of Cu (cathode, more positive potential) is suppressed due
to the arrival of electrons from Zn via the external circuit and Cu is
protected from corrosion.

Cu
cathode

Zn
anode

Zn2+

composition corrosion cell

Fe2+

Stress corrosion cells

Metal ionisation is faster in regions of concentrated stress.
(More often in alloys than in pure metals.)

stress corrosion cell

Corrosion electrode reactions

anode: (1) M = M+ + e;
(2) 2M + 2OH = M2O + H2O + 2e
(3) M + OH = MOH + e

(4) M + X MX + e

cathode: (1) M+ + e = M
(2) 2H+ + 2e = H2
(3) O2 + 2H2O + 4e = 4 OH

Fe

O2

Oxygen concentration corrosion cells

Metal ionisation can be affected by solution compositions, and is
usually faster in dilute solutions of the metal ion than in
concentrated ones.

Fe(OH)2

Oxygen gas is soluble in water and its reduction can function as the
cathode reaction in a corrosion cell.
Uneven distribution of oxygen concentration increases metal
ionisation rate by promoting oxygen reduction near the high oxygen
region.

cathode,
high oxygen
concentration

OHe

anode,
low oxygen
concentration

Fe2+

concentration corrosion cell

Fe = Fe2+ + 2e;

anode:

water containing oxygen

Cathode: O2 + H2O + 4e = 4OH

Fe2+ + 2OH Fe(OH)2 (Fe2+ diffuses faster than OH)

cathode
metal

Micro-oxygen concentration corrosion cells

anode

air

O2

Fe2+

H2O

anode areas
O2

Fe2+

cathode

anode

cathode
e

e
steel

water drop on metal surface

Pourbaix diagrams

Pourbaix diagram is helpful in estimating the

corrosion conditions of metals.

1
corrosion

E (V)

Corrosion in water often involves e.g. the OH

ion and hence depends on pH. Plotting the
potential of metal corrosion against the pH in
solution leads to the E ~ pH diagram, or
Pourbaix diagram.

Corrosion protection
Use of protective coatings---Separate metals from
the corrosive environments.

Paints are cheap to use, but not resistant to scratches.

They also age and weather, which make the paint
coating porous and flakes off the substrates.
Metal coatings e.g. Al, Zn, Cr, are more often applied
to cheap steels and, if broken, function as the anode
in a corrosion cell.
Cathodic protection (sacrificing anode)---Use of a
metal of more negative potential to form a corrosion
cell with the metal to be protected so that electrons
are supplied from the ionisation of the sacrificing
metal.

passivity

-1

corrosion

Immunity

14

pH
A simplified Pourbaix diagram for iron

Use of inhibitors and passifying agents

are capable of (1) regulating pH of the
solution, (2) helping to form protective
films on metal surfaces, or (3) other
functions, and are often used in closed
water systems, e.g. the cooling water
system in cars.