Corrosion of aerospace metals

Corrosion is simply defined as the chemical attack of metals that results in deterioration and
loss of material. A corrosive fluid is usually involved, with the most common being water
containing reactive chemicals (such as chloride ions).
Corrosion of metal aircraft components can range in severity from superficial discoloration to
severe pitting and cracking that can cause sudden, catastrophic failure. Common examples of
corrosion damage to aircraft include corrosion thinning at fastened joints owing to water
intrusion; pitting of exterior skins; stress-corrosion cracking at drilled holes, cut-outs and
other geometric stress raisers; and corrosion of fuel tanks. Figure 1 shows examples of
corrosion damage to metals used in aircraft.

Fig 1 : Examples of corrosion damage to metal aircraft components:

(a) surface corrosion; (b) corrosion cracking; and (c) exfoliation corrosion.

The type of corrosion and the rate that corrosion takes place is determined by many factors.
Important factors include the:
1. Composition, metallurgical properties and heat treatment of the metal alloy;
2. Type of surface films and protective systems on the metal;
3. Presence of stresses, voids and other defects in the metal;

4. Composition and concentration of the corrosive liquid or gas; and

5. Temperature and humidity of the environment.

Corrosion Process
Corrosion is an electrochemical process involving two dissimilar materials that are placed in
electrical contact with each other in the presence of an electrolyte. The two dissimilar
materials can be two metals (e.g. aluminium and titanium), metal and composite (e.g.
aluminium and carbon fibreepoxy laminate) or, on a smaller scale, the boundary and core of
a metal grain. The electrolyte is usually a corrosive liquid such as water containing charged

atoms called ions, such as negatively charged chloride (Cl ) ions. The most common

electrolyte involved in aircraft corrosion is water that contains Cl and other negatively
charged ions. The water can come from rain, humidity, and potable water used on the aircraft.
Certain aviation fluids, cleaning solvents and paint strippers used on aircraft surfaces contain
corrosive ions and therefore also act as an electrolyte.

Fig.2 : Schematic of the galvanic cell

The electrochemical process of corrosion is generally described as a galvanic cell, which is
shown in Fig.2. The cell is created when two dissimilar materials are placed in contact with
an electrolyte. One metal forms the anode and the other metal the cathode to the cell.
Corrosion occurs to the anode material whereas the cathode material remains unaffected. The
metal that is the anode has a higher negative charge, called the electrode potential, than the
cathode material. Table 1 gives the ranking for the standard electrode potentials of a variety
of metals, including those used in aircraft. The metals are listed in order of increasing
electrode potential to form the electromotive force (emf) series. When two dissimilar metals
form a galvanic cell then the metal higher in the emf series is the cathode and the lower metal
in the series is the anode. For example, aluminium alloy is higher (or more cathodic) than

magnesium and, therefore, when these two metals are in contact in the presence of an
electrolyte then the galvanic cell which is created causes the magnesium to corrode whereas
the aluminium is unaffected. As another example, carbon fibreepoxy composite causes
aluminium to corrode because of its higher position in the emf series. In general, the greater
the difference between the electrode potential of the two materials the faster the anodic metal
corrodes.
Table 1 : Standard electrode potential rankings for selected metals and composites in seawater

Corrosion occurs in a galvanic cell by the movement of electrons from the anode to cathode.
The anode and cathode must be electrically connected, usually by being in contact, to allow
the flow of electrons. The liquid electrolyte, which is also conductive owing to the presence
of ions, must be in contact with both the anode and cathode to complete the electric circuit. In
the corrosion process, the loss of electrons from the anode creates positively charged metal
ions, which leave the anodic metal surface and dissolve in the electrolyte fluid. For example,
3+

when aluminium corrodes it undergoes the anode reaction: Al Al + 3e . The aluminium

3+

ions (Al ) created by this reaction pass into the electrolyte, causing the loss of material from
the metal surface. The electrons produced by the anode reaction flow to the cathode where
they combine with ions already dissolved in the electrolyte. The ions present in water are
+

positively charged hydrogen (H ), which react with the electrons to form hydrogen gas:
+

2H + 2e H2. The metal of the cathode does not corrode, but simply conducts the electrons
received from the anode to the positively charged ions in the electrolyte.
Three conditions must exist simultaneously for corrosion to occur:
1. Two dissimilar materials or two regions of different electromotive potential within a
metal in order to form the anode and cathode.
2. A conductor (usually a metal) between the anode and cathode.
3. An electrolyte such as water.
Stopping corrosion of metal aircraft components involves removing one or more of these
conditions.

Types of corrosion
There is no single type of corrosion that occurs in aircraft. Instead, corrosion can take many
forms, including:
1.
2.
3.
4.
5.
6.
7.
8.

general (or uniform) surface corrosion,

galvanic (or two-material) corrosion,
pitting corrosion,
crevice corrosion,
intergranular corrosion,
fretting corrosion,
exfoliation corrosion, and
Stress corrosion.

General surface corrosion

General (also called uniform) surface corrosion is the most common type of corrosion. It
involves an electrochemical reaction that proceeds uniformly over the entire exposed surface
of the metal, as illustrated in Fig.3. General corrosion is responsible for the greatest
destruction of metal on a tonnage basis, although it is not usually a serious corrosion problem
for aircraft owing to the surface protection measures. General corrosion of metals used in the
airframe only occurs when the surface protection is damaged or incorrectly applied. When it
does occur, general corrosion occurs at the surface and is detected during maintenance
inspection by the presence of grey or white powdery deposits. These deposits are the residual
solid by-product of the corrosion process, such as the electrochemical degradation of
aluminium:
3+

Al Al + 3e

3+

to form metal cations (Al ) that react with oxygen in the atmosphere to form aluminium
oxide powder:
3+

4Al + 3O2 2Al2O3

Fig 3 : General Corrosion

Pitting corrosion
Pitting is one of the most destructive and insidious types of corrosion. Without appropriate
protection, metals such as aluminium, steel and magnesium used in aircraft are susceptible to
pitting corrosion, which is a form of extremely localised attack that results in small holes, as
shown in Figure. Pitting can start at precipitates at the surface of certain alloys when the
particle has a different electrochemical potential from the surrounding metal matrix. Pitting
can also occur in surface regions where the corrosion protective layer is absent. When surface
protection is used small gaps in the layer can occur because of incorrect application or inservice damage by abrasion, erosion or some other event. The corrosion forms as a hole at the
gap in the protective layer, which then develops into a wider cavity below the surface
Pitting requires an incubation period before it becomes visible, which can be months or years
depending on the type of metal and electrolytic fluid. Once started, however, the pit tends to
penetrate the metal at an ever increasing rate forming a large cavity beneath the surface. Most
pits grow downwards from horizontal surfaces, such as upper wing and horizontal stabiliser
surfaces. Pits are less likely to develop on vertical surfaces, and only rarely grow upwards
from the bottom of horizontal surfaces. Therefore, the inspection of aircraft components for
damage caused by pitting corrosion should focus on upper horizontal surfaces. However, pits
are difficult to detect by visual inspection because their surface opening is very narrow and is
often covered with corrosion products, even though the underlying metal is severely
corroded. It can take many months or years for pitting corrosion to appear as visible holes, by
which time the component can be damaged beyond repair. Another problem caused by pitting
corrosion is that the cavities are potential starting points for the growth of fatigue cracks.

(a)

(b)
Fig 4 : (a) Metal surface showing pitting corrosion (b) Examples of different shapes of pitting corrosion
cavities.

Crevice corrosion
Crevice corrosion (also called concentration cell corrosion) is the most common type of
corrosion damage found on many older aircraft which have not been adequately maintained.
It usually occurs in crevices under fastener heads, under loose paint, within delaminated
bonded joints, or in unsealed joints. It is an aggressive form of corrosion that occurs locally
inside crevices and other shielded areas of metals exposed to corrosive fluid. The process of
crevice corrosion is shown schematically in Fig.5. Crevice corrosion occurs in shielded
regions where a small volume of stagnant corrosive fluid is trapped between two surfaces,
such as under loose paint, within a delaminated bond-line or in an unsealed joint. Oxygen
molecules in the stagnant fluid have low solubility. As a result, the fluid inside the crevice
becomes depleted of oxygen when it remains stagnant and shielded from the atmosphere. The
lower oxygen content in the crevice helps to form an anodic region at the metal surface. The
metal surface in contact with the trapped moisture exposed to air forms a cathode. An excess
of positively charged ions occurs in the crevice causing the stagnant solution to become
acidic. To ions in the fluid migrate into the crevice causing a local and small galvanic cell to
be created. Because crevice corrosion can only occur when the oxygen level in the corrosive
fluid inside the crevice is different from that outside the crevice, it is also known as
differential aeration corrosion. The most effective way to eliminate crevice corrosion is to
keep water out of joints and tight spaces between surfaces.
Crevice corrosion can quickly develop into pitting or exfoliation corrosion when left
untreated, depending on the types of metal and corrosive fluid. It is for this reason that
crevices within aircraft, such as fastener holes and joints, must be sealed with a durable
protective coating that stops the ingress of corrosive fluid.

Fig 5 : Schematic of crevice corrosion within a fastened joint.

Intergranular corrosion
Intergranular corrosion involves the localised attack of the grain boundaries in a metal. The
intergranular corrosion process is shown in Fig. 6. Corrosion damage occurs along the grain
boundaries whereas the core of the grains is unaffected. Intergranular corrosion occurs
because the electrochemical potential of the grain boundary is different from the grain core
and, therefore, the grain boundary and grain core form, respectively, the anode and cathode of
a tiny galvanic cell.

The grain boundary is anodic because its chemical composition is different to the grain core.
The difference can be caused by a higher concentration of impurity elements at the grain
boundaries, depletion of alloying elements in the grain boundary region, or some other
chemical difference between the boundary and core of a grain. For example, in 2000 series
aluminium alloys (AlCu) the precipitation of CuAl2 particles within the grains depletes the
amount of copper at the grain boundaries. The lower copper content makes the grain
boundaries anodic with respect to the grain core. The formation of other types of precipitates,
either along the grain boundaries or inside the grains, can also cause a difference in the
electrochemical potential between the outer and inner regions of grains.

Fig 6 : (a) Schematic of integranular corrosion. (b) Intergranular corrosion below a metal surface.

In the presence of a corrosive fluid, a small-scale galvanic cell is created between the core
and boundary of a grain and this leads to intergranular corrosion. The corrosion process
causes the gradual disintegration of the metal by grains breaking away from the surface after
the boundaries have been corroded. Intergranular corrosion is a potential problem for many
types of heat-treatable aluminium and magnesium alloys used in aircraft, although it may be
avoided by the use of surface protection.

Fig 7 : Exfoliation corrosion(Photograph)

A special type of intergranular corrosion is called exfoliation corrosion, which involves the
lifting of surface grains by the force of corrosion products at the grain boundaries. Exfoliation
corrosion starts at the surface but it mainly involves subsurface attack that proceeds along
narrow paths parallel with the surface. The attack is usually along the grain boundaries
(intergranular corrosion). When the grain boundaries corrode they form corrosion products
that exert pressure on the surface grains which forces them upwards. This causes the grains to
peel back like the pages of a book, as shown in Fig. 7. Exfoliation corrosion is characterised
by leafing of thin layers of uncorroded metal between layers of corrosion product. The grains
are removed from the surface by abrasion or other mechanical action, which allows the
underlying grains to then lift up and the exfoliation process to continue. High-strength
aluminium alloys are susceptible to exfoliation corrosion, and their resistance to this type of
corrosion is improved by over-ageing during heat treatment.

Environmental Stress Cracking

Environmental stress cracking is dened as the premature failure of materials under the
combined effects of stresses (static or cyclic; applied or residual), and damaging
environments (corrosive or noncorrosive). Various types of environmental stress cracking
include (i) stress corrosion cracking, (ii) hydrogen damage, (iii) corrosion fatigue, and (iv)
fretting corrosion.

Stress-corrosion cracking
Stress corrosion cracking results from the combined effect of a corrosive environment and a
tensile stress. It is recalled that the surface energy required to extend a crack is considered to
be provided totally by strain energy. The stress acting on the metal may arise from an
external applied stress such as structural or aerodynamic loads or an internal stress that comes
from a variety of sources during metal processing, with the most common being metal
working (such as rolling or bending), nonuniform cooling during heat treatment, and
machining without proper stress relief. Internal residual stresses often provide the driving
force for stress corrosion in many metal components. Another potential source of stress in
aircraft structures is fastener heads which have been overtightened, thus causing stresscorrosion cracking in the material underneath the fastener head. Failure by stress-corrosion
cracking can occur at stress levels well below the yield strength of the metal. Stress-corrosion
cracks often initiate at pits, notches or other stress raiser sites on the metal surface in the
presence of a corrosive fluid. The specific nature of stress corrosion is complex and difficult
to describe via a single mechanism. Stress corrosion cracks can propagate either intergranularly or transgranularly, depending up (i) nature of the material, (ii) the environment, and
(iii) the stress level.
Experiment shows that a correlation exists between the crack propagation mechanism and the
type of dislocation structure developed by materials having FCC structure. If dislocations
cannot cross-slip with relative ease, they tend to form planar arrays. It is recalled that such a
dislocation structure is promoted by short-range order and/or low stacking fault energy.
Under this condition, the cracks tend to propagate intergranularly. Conversely, in the absence

of short-range order or if the material has a high stacking fault energy, dislocations can crossslip with relative ease, forming subgrain boundaries, and the material becomes resistant to
intergranular stress corrosion cracking. However, in this case, the cracking can occur
transgranularly. Sensitization of the material by grain boundary precipitates localizing
corrosion attack alongside grain boundaries promotes intergranular stress corrosion cracking.
Grain size is another material character inuencing stress corrosion cracking. Whether the
cracking occurs intergranularly or transgranularly, the material becomes more resistant to
stress corrosion cracking as its grain size is reduced, which is related to the higher strength
associated with a ner grain size.
For a given material, the crack propagation mechanism can change from transgranular to
intergranular if the environment is altered. Also, the nature of the environment can have a
strong inuence on the stress level at which the cracks can propagate. In a given
environment, the cracks can propagate under an applied stress as low as 10% of the yield
strength of the material. However, in another environment, the stress required to propagate
the cracks in the same material can be as high as 90% of the yield strength.
A distinguishing feature of stress corrosion cracking is that the cracks grow incrementally or
in a stepwise manner, giving rise to branching as shown in Fig. 8. However, exceptions to
this rule do exist. Although various models are proposed to explain the mechanism of stress
corrosion cracking, the sequence of events leading to crack propagation according to a
commonly accepted model are (i) A protective passive lm (Al2O3) at a crack tip is ruptured
under the inuence of the local stress; (ii) once the protective lm is ruptured, anodic
dissolution occurs at the crack tip; (iii) the material redevelops a protective passive lm at the
crack tip; and so on. There is accumulating evidence that transgranular stress corrosion cracks
proceed by a series of cleavage events; i.e., the cracks propagate along certain
crystallographic planes.
An alternative mechanism involves the absorption of corrosive chemicals at the crack tip;
these break the strained metal bonds, thereby forcing crack growth.

Fig 8 : Stress-Corrosion cracking

Stress-corrosion cracking only occurs when the applied or residual stress is above a certain
threshold, as shown in graph. Below this threshold, the driving force for crack growth is too
low. Ideally, all aircraft metal components should operate in this low stress regime. The
threshold may be increased by annealing the metal component to relieve the residual stresses
thickening the section. When the stress is above the threshold, the time-to failure drops
rapidly with increasing stress owing to faster crack growth. Cracking often occurs move
quickly when the metal is subjected to alternating stresses rather than constant stress. This is
a special case of stress-corrosion cracking called corrosion fatigue, which occurs under the
combined actions of cyclic stressing and corrosion. The crack growth rate in corrosion fatigue
is faster and, in some cases, many times faster than the sum of the rates of corrosion and
fatigue when each acts alone. The damage process is faster because cyclic stressing tends to
remove or dislodge corrosion products at the crack tip. Corrosion products often slow the
cracking process by acting as a barrier between the corrosion fluid and crack tip. When the
products are removed by fatigue the crack growth rate is increased.

Graph : Effect of Stress on the time-to-failure of metal caused by stress-corrosion cracking

Stress-corrosion cracking causes a loss in failure strength, and is a potential cause of

component failures in aircraft. The susceptibility of metals to stress-corrosion cracking or
corrosion fatigue is determined by several factors, including alloy composition of the metal;
types and distribution of precipitate particles; amount of strain hardening; and orientation and
size of grains.
High-strength aluminium alloys are susceptible to stress-corrosion cracking when exposed to
water and many other corrosive fluids. Aluminium alloys that contain solute elements such as
copper, magnesium, zinc and lithium are prone to stress-corrosion cracking. These alloying
elements are present in the 2000, 7000 and 8000 alloys used in aircraft components. The
susceptibility of aluminium to stress-corrosion cracking generally increases with the solute
content. The resistance of heat-treatable aluminium alloys to stress-corrosion cracking is also
affected by the age-hardening treatment used to promote precipitation hardening. The
resistance to stress-corrosion cracking is lowest for the heat-treatment condition needed to

achieve maximum strength. This occurs because the formation of CuAl2 and other precipitate
particles during age-hardening reduces the corrosion resistance of aluminium. Therefore, any
improvement in strength gained by the age-hardening of aluminium alloys comes at the
expense of lower resistance against stress-corrosion cracking. The T7 heat treatment
process, which involves thermally ageing aluminium beyond the point of maximum strength,
is often used to improve resistance against stress corrosion cracking. In addition, it is
essential that aluminium structures are treated to resist stress corrosion by corrosion
protective methods, such as Alclad, which are described in the next section. High-strength
steel components are also susceptible to stress-corrosion cracking, and must be protected
using a surface coating such as cadmium or chromium plating.

Fretting corrosion
Fretting corrosion, which is also called friction oxidation or wear oxidation, involves the
deterioration of contacting metals subjected to vibration or slip. The fretting (or rubbing)
action results in fine particle fragments being abraded from one or both materials. These
fragments oxidise into hard, abrasive particles which wear and destroy the metal surface. For
example, the fretting of aluminium produces aluminium oxide (Al2O3) particles that are many
times harder than the metal surface. The process is considered corrosive because the metal
particles must oxidise, which is a form of dry corrosion.
Scratching and abrasion of the metal by the hard oxide particles causes a loss in dimensional
tolerance between contacting surfaces such as structural joints. In extreme cases, it can cause
seizing and galling of moving parts. Fretting corrosion is not usually a common problem with
aircraft, although it has contributed to several aircraft accidents. The most notable case
involved fretting corrosion between electrical contacts in the fuel control system of the F-16
Flying Falcon. Fretting damage between the contacts caused the control system to
automatically shut off the valves to the main fuel supply without warning, resulting in at least
six F-16 crashes before the problem was identified and fixed.