Types of Corrosion
Types of Corrosion
Types of Corrosion
CORROSION
Corrosion and its control are of primary importance to all aircraft operators.
Corrosion weakens primary structural members, which must then be replaced
or reinforced in order to sustain flight loads. Such replacements or
reinforcements are costly, time-consuming, and result in unscheduled delays.
Most metals exist in nature as chemical com-pounds such as oxides or
chlorides. For example, aluminum is never found in nature in its pure state, but
must be refined from an ore such as alumina (A1,03). However, when pure
aluminum is exposed to the elements, it combines with oxygen and eventually
changes back to alumina. Corrosion then, is simply a process wherein metals
return to a natural state.
Corrosion is a natural phenomenon which attacks metal by chemical or
electrochemical action and converts it into a metallic compound, such as an
oxide, hydroxide, or sulfate. Substances that cause corrosion are called
corrosive agents. Water or water vapor containing salt combine with oxygen in
the atmosphere .to produce the most prominent corrosive agents. Additional
corrosive agents include acids, alkalis, and salts.
The appearance of corrosion varies with various metals. For example, on
aluminum alloys and magnesium it appears as surface pitting and etching,
often combined with a grey or white powdery deposit. However, on copper and
copper alloys corrosion forms a greenish film and on steel a reddish rust. When
corrosion deposits are removed, the metal's surface may appear etched and
pitted, depending upon the length and severity of attack. If deep enough, these
pits may become sites for crack development. Some types of corrosion can
travel beneath surface coatings and can spread until the part fails.
There are two general classifications of corrosion. chemical and
electrochemical; however. both types involve two simultaneous changes. The
metal that is attacked or oxidized suffers an anodic change, and the corrosive
agent. is reduced and suffers a cathodic change.
CHEMICAL CORROSION
Pure chemical corrosion results from direct expo-sure of a bare surface to
caustic liquid or gaseous agents. The most common agents causing direct
chemical corrosion include:
1. Spilled battery acid or fumes from batteries.
2 Residual flux deposits resulting from inadequately cleaned, welded, brazed,
or soldered joints.
ELECTROCHEMICAL CORROSION
Electrochemical corrosion is similar to the electrolytic reaction that takes place
in a dry cell battery. To understand how this happens, recall the structure of the
atom from Chapter 2. When the number of electrons matches the number of
protons in an atom, the atom is said to be electrically balanced. However, if
there are more or fewer electrons than protons, the atom is said to be charged
and is called an ion. If there are more electrons than protons, it is a negative
ion, but if there are more protons than electrons, it is a positive ion. An ion is
unstable, always seeking to lose or gain electrons so it can change back into a
balanced, or neutral, atom.
Metals are arranged to show the relative ease with which they ionize in what is
called the electro-chemical series. The earlier a metal appears in the series, the
more easily it gives up electrons. In. other words a metal that gives up
electrons is known as an anodic metal and corrodes easily. On the other hand,
metals that appear later in the series do not
2-------------------------------------------------------------------------------------------give up electrons easily and are called cathodic metals. [Figure 12-2]
Many metals become ionized due to galvanic action when brought into contact
with dilute acids, salts. or alkalis, such as those found in industrially
contaminated air. For example, if an aluminum structure
ELECTROCHEMICAL SERIES FOR METALS
(NOBILITY) MOST ANODIC WILL GIVE UP ELECTRONS MOST EASILY.
MAGNESIUM ZINC CLAD 7075 ALUMINUM ALLOY COMMERCIALLY PURE
ALUMINUM (1100) CLAD 2024 ALUMINUM ALLOY CADMIUM 7075-T6 ALUMINUM
ALLOY 2024-T3 ALUMINUM ALLOY MILD STEEL LEAD TIN COPPER STAINLESS
STEEL SILVER NICKEL CHROMIUM GOLD
Figure 12-2. The metals listed above are arranged in order of electrode
potential. Any metal appearing in this series is anodic to any metal which
follows it and will corrode if subjected to galvanic action.
is in contact with moisture having a trace of hydrochloric acid, a chemical
reaction takes place between the acid and the aluminum to form aluminum
chloride and hydrogen.
2A1 + 6HC1 2A1C1,, + 31t
If all of the aluminum used in the construction of aircraft were pure aluminum,
corrosion would not
be a problem. However, as discussed in Chapter 7, aluminum must be alloyed
with other metals to increase its strength. The most common alloying agent is
copper. In a structural piece of alloyed aluminum the microscopic: grains of
copper and aluminum serve as the cathode and anode of a galvanic cell.
Aluminum is more negative than copper and acts as the anode in the
electrochemical action. There is no flow of electrons between the two alloying
agents within the metal until an external path is provided to form a complete
circuit. This path is furnished by the electrolyte. which can be a surface film of
moisture containing such pollutants as acids, salts, or other industrial
contaminants. I Figure '12-4]
The electrode potential difference between the aluminum and copper grains
causes positive ions to exist within the aluminum. When the electrolyte film
covers the surface, the aluminum ions attract chlorine ions from the
hydrochloric acid and form aluminum chloride, the salt of corrosion. Hydrogen
ions are attracted to the copper by the electrons from the aluminum. These
hydrogen ions become neutralized and form molecules (H,) which leave the
surface as a free gas. Corrosion forms on the anodic aluminum, but no
corrosion products are evident on the copper cathode.
ELECTRON FLOW
ANODIC AREA CORROSION FORMS HERE
2024 ALUMINUM ALLOY
CATHODIC AREA NO CORROSION
Figure 12-4. Aluminum alloys have both anodic and cathodic areas. Corrosion
appears at the anodic area when chlorine atoms from
the electrolyte join the aluminum chloride.
4----------------------------------------------------------------------------------------------------------------------------This type of electrochemical attack produces pits filled with corrosion salts, and
is usually rather localized. However, if the entire surface is covered with a
strong electrolyte, corrosion can develop uniformly over an extensive area.
This type of corrosion is called a direct chemical attack.
This basic introduction shows the four requirements for the formation of
corrosion:
1 Presence of a metal that will corrode (anode).
Figure 12-7. This photomicrograph of the surface of an alu minuet, sheet shows
pitting that is a result of corrosion.
begins, it is propagated by means of concentration cells or galvanic action.
GALVANIC CORROSION
This common type of corrosion occurs any time two dissimilar metals make
electrical contact in the presence of an electrolyte. For example, galvanic
corrosion can take place where dissimilar metal skins are riveted together, or
where aluminum inspection plates are attached to the structure with steel
screws.
When metals of the same galvanic grouping are joined together, they show
little tendency for galvanic corrosion. But metals of one group corrode when
they are held in contact with those in another group. The further apart the
groups, the more active the corrosion. In addition, corrosion is much more rapid
when the anodic metal is smaller than that of the cathodic metal. The reason
for this is the greater area of the cathode allows a higher rate of electron flow,
accelerating the speed of the reaction. On the other hand, if the corroding
metal (anode) is larger than the less active metal (cathode) corrosion is slow
and superficial. [Figure 12-8]
CONCENTRATION CELL CORROSION
Concentration cell corrosion, or crevice corrosion, is corrosion of metals in a
metal-to-metal joint, corrosion at the edge of a joint even though the metals
are identical, or corrosion of a spot on a metal's surface covered by a foreign
material. Oxygen concenCORROSION PRODUCTS
ELECTROLYTE
(CATHODE)
STEEL FASTENER
(ANODE)
2024 ALUMINUM ALLOY
1
1
Figure 12-8. A potential for galvanic corrosion exists when a steel fastener is
used to hold a 2024 aluminum alloy inspection plate in place. If contaminated
moisture gets between the two metals, the aluminum is corroded rather than
the steel screw. However, if 2024 aluminum alloy and magnesium are riveted
together and covered by an electrolyte, the magnesium corrodes instead of the
aluminum.
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OXYGEN CONCENTRATION CELL CORROSION
When water covers the surface of an aluminum air-craft skin and seeps into the
cracks between lap joints, oxygen concentration cell corrosion can form. Since
water in an open area readily absorbs oxygen from the air, it attracts electrons
from the metal to form negative hydroxide ions:
2H,0 + O + 4 Electrons > 4(OH)
The electrons required to form these negative ions come from the metal itself.
The area between the skins does not give up electrons to the water on its
surface because there is not enough oxygen there to form hydroxide ions.
Instead, its electrons flow to the cathodic surface the open. area. The area
between the skins, having lost electrons. Now contains positive aluminum ions.
and this area becomes the anode.
Electrons flow within the metal from the anode to the cathode, leaving positive
metal ions in the area between the sheets. These positive aluminum ions
attract negative hydroxide ions from the open water and the aluminum
corrodes, forming aluminum hydroxide. The unusual characteristic of this type
of corrosion is that it forms in the areas where there is a deficiency of oxygen.
[Figure 12-91
Oxygen concentration cell corrosion can occur on aluminum, magnesium, or on
ferrous metals. It forms under marking tape of ferrules on aluminum
tubing, beneath sealer that has loosened, and under bolt or screw heads.
Figure 1 2-1 0)
When dirt or other oxygen-excluding contamination forms on an anodized
surface and the oxide film is scratched, oxygen concentration cell corrosion can
prevent the protective film from re-forming.
METAL ION CONCENTRATION CELL CORROSION
The electrode potential within a metal is dependent on the different metals that
make up the alloy.. However, a potential difference can occur if an electrolyte
having a nonuniform concentration of metal ions covers the surface. For
example, some metal-to-metal joints rub against each other. creating a high
concentration of metal ions adjacent to a low concentration of metal ions.
Figure 12-10. Oxygen concentration cell corrosion has formed under the ferrule
on this tube.
CATHODIC AREA
t ELECTRON FLOW
AL + + + (OH) (OH) (OH) (OH) (OH) (OH) AL + + +
ANODIC AREA
Figure 12-9. Oxygen concentration cell corrosion forms in the areas where there
is a deficiency of oxygen
7_____________________________________________________________________________
corrosive attack. An electrical potential develops between the large area of the
cathode (passive film) and the small area of the anode (active metal).
FILIFORM CORROSION
Filiform corrosion is a special form of oxygen concentration cell corrosion or
crevice corrosion which occurs on metal surfaces having an organic coating
system. It is recognized by its fine threadlike lines under a polyurethane
enamel finish. Filiform corrosion often results when the wash primer used on a
metal has not been properly cured. A wash primer is a two-part metal
preparation material in which phosphoric acid converts the surface of the metal
into a phosphate film that protects the metal from
Figure 12-11. Metallic ion concentration cell corrosion forms in the open at the
edge of the lap joint.
8_________________________________________________________________________
12-12
Cleaning and Corrosion
corrosion. provides an excellent hand for paint. This conversion process relies
on moisture in the air and, if there is not enough moisture to convert all of the
acid. some acid remains on the metal. If a dense polyurethane finish is then
applied. the acid becomes tripped and reacts with the aluminum alloy form
corrosion. 'Figure 12-121
Filiform corrosion shows itself as a puffiness under the paint film and is first
noticed around rivet heads and along the lap joints of skins. When the paint
film is broken . you will notice that the puffiness was caused by- the growth Of
the powdery salts of corrosion there is no cure for filiform corrosion short of
stripping ,all of the paint, removing the corrosion. treating the metal's surface.
and refinishing the aircraft. Fililorm corrosion does not usually form under
acrylic lacquer. because it is porous enough to allow moisture from the air to
penetrate the film and complete the conversion of any excess acid. Filiform
corrosion can be prevented by storing aircraft environment with a relative
humidity below 70 percent. using coating systems having a low rate of diffusion
for oxygen and water vapors. and by washing aircraft to remove acidic
contaminants from the surface, such as those created by pollutants in the air.
INTERGRANULAR CORROSION
intergranular corrosion is an attack along the grain boundaries of a material.
Micro-pho-tographs of aluminum alloys show that they are comprised of
extremely tiny grains held together by chemical bonds. Each grain has a clearly
defined boundary which, from a chemical point of view. differs from the metal
within the grain center. The grain boundary and grain center can react with
each other as anode and cathode when in contact with an electrolyte.
Figure 12-12. Filiform corrosion forms under the dense film of a polyurethane
finish, where it first appears as a puffiness under the finish.
Recall from Chapter 7 that heat treatment diffuses an alloying agent into the
parent metal. Also recall that after the heat treatment process, the alloy must
lie quenched promptly after it is removed from the heat bath. If quenching is
delayed for even a few seconds, particles of the alloying agent precipitate out
of the metal matrix and can become quite large. If quenching is delayed too
long, these metal grains can reach a size that produces areas of dissimilar
metals large enough to form effective cathodes and (nodes so that
intergranular corrosion can form. IFigure 12-13]
ELECTROLYTE ENTERS THROUGH CRACKS IN PAINT-FILM
PAINT FILM
illuroro,""4.1012 11111=1111
(CATHODE)
STEEL FASTENER
INTERGRANULAR CORROSION
(ANODE)
7075-T6\ ALUMINUM
CLADDING
Figure 12-13. Intergranular corrosion of 7075-T6 aluminum adjacent to a steel
fastener. The electrolyte needed for this action is supplied from the surface
through corrosion deposits, and the attack continues along the grain
boundaries.
Spot or seam welding. through localized heating, can also cause grain
enlargement that leaves the metal susceptible to intergranular corrosion.
With some forms of intergranular, corrosion small blisters can occur beneath
the surface. The surface metal over these blisters is quite thin and, when
pricked with a knife point, opens a cavity filled with corrosion. Since
intergranular corrosion occurs within the metal itself, rather than on the
surface, it is quite difficult to detect without ultrasonic or eddy-current
equipment. Once found, about the only practical remedy for intergranular
corrosion is replacement of the part. IFigure 12-14]
EXFOLIATION CORROSION
Exfoliation corrosion is an extreme case of inter-granular corrosion. It occurs
chiefly in extruded
9______________________________________________________________________
Cleaning and Corrosion
12-13
Figure 12-14. The water marks on this hardened steel bearing race are
indications of intergranular corrosion in the hardened metal.
materials, such as channels or angles. where the grain structure is more
laminar (layer-like) than in rolled _sheets or castings. This type of corrosion
occurs along the grain boundaries and causes the material to separate, or
delaminate. As with other types of intergranular corrosion, by the time it is
evident on the surface, the metal has been damaged beyond salvage. [Figure
12-151
STRESS CORROSION
Stress corrosion occurs when metal is subjected to a tensile stress in the
presence of a corrosive environment. The stresses in the metal can come from
improper quenching after heat treatment, or from an interference fit of a
fastener. Stress corrosion can be transgranular or intergranular in nature.
Cracks caused by stress corrosion grow rapidly as the corrosive attack
concentrates at the end of the crack rather than along its sides. [Figure 12-161
Figure 12-15. Exfoliation corrosion is an example of extreme intergranular
corrosion in an extruded material.
Figure 12-16. Stress corrosion forms at the end of a crack and rapidly enlarges
the crack until the material fails.
Since stress corrosion can occur only in the presence of tensile stresses, one
method for preventing this type of corrosion in some heat-treated aluminum
alloy parts is to shot-peen the surface to provide a uniform compressive stress
on the surface. By doing this. the compressive stresses must be overcome by
tensile forces before stress corrosion can form.
Common locations for stress corrosion to form are between rivets in a stressed
skin, around pressed-in bushings, and tapered pipe fittings. If stress corrosion is
severe enough, it may be visible through careful visual inspection. However,
dye penetrant inspection is required to find the actual extent of the crack
FRETTING CORROSION
When two surfaces fit tightly together but can mover relative to one another,
corrosion occurs. This type of corrosion is the result of the abrasive wear
caused
by the two surfaces rubbing against each other. This rubbing, known as
fretting, prevents the formation of a protective oxide film, exposing active
metal to the atmosphere. By the time this type of corrosion makes its
appearance on the surface, the damage is usually done and the parts must be
replaced. If the contact areas are small and sharp, deep, grooves resembling
brinell markings or pressure indentations can be worn in the rubbing surface.
AIN. a result, this type of corrosion has also been called false brinelling.
Fretting corrosion occurs around rivets in a skin arrar is indicated by dark
deposits around the rivet heads
10____________________________________________________________________________
12-14
streaming out behind, giving the appearance of rivet smoking. Rivets showing
this sign of fretting must be drilled out and replaced. (Figure 12-17]
CORROSIVE AGENTS
Corrosive agents are substances that are capable of causing a corrosive
reaction. Most corrosive agents fall into one of two categories, acids and alkalis.
However, care must be taken not to overlook other less obvious corrosive
agents such as the atmosphere which contains moisture, salts, or corrosive
industrial agents.
ACIDS AND ALKALIS
Almost all acids and alkalis form effective electrolytes as they react with metals
to form metallic salts, but some electrolytes are more active than others. For
example, the sulfuric acid found in aircraft batteries is especially active in
corroding aluminum. However, a weak solution of chromic or phosphoric acid is
often used as a surface treatment to prepare metal for painting.
Ferrous metals are subject to damage from both acids and alkalis, but
aluminum is more vulnerable to strong alkaline solutions than it is to acids. For
example, an aluminum structure can be severely corroded if it is allowed to
remain in contact with a concrete floor. Water draws out enough lime from the
cement to form an alkaline solution that corrodes the aluminum.
SALTS
12-15
this abrasion tends to damage the natural protective oxide film, seaplanes
must be carefully inspected to detect any damage which would allow water to
get to the base metal of the structure.
AIR
It is obviously impossible to isolate a structure from the air in which it exists,
but the very presence of air is a factor in the deterioration of metal. Marine
atmosphere and air above industrial areas hold large concentrations of salts.
The chemicals precipitate out of the air and collect on the surface of an aircraft
where they attract moisture from the air.
ORGANIC GROWTHS
For years, water which condensed in fuel tanks produced relatively minor
corrosion problems. Small perforated metal containers of potassium dichromate
crystals protected the fuel tanks by changing any water into a mild chromic
acid solution, which inhibited corrosion.
Jet aircraft, however, use a high viscosity fuel which holds more water in
suspension than other aviation fuels. Jet aircraft also fly higher than
reciprocating engine aircraft and the low-temperature flight conditions
associated with these altitudes cause water
that is. entrained in the fuel to condense out and collect the bottom of the
tanks. This water contains' microscopic animal and plant life called microbes.
These organic bodies live in the water and feed on the hydrocarbon fuel.
Furthermore, the dark insides of the fuel tank promote their growth, and in very
short periods of time these tiny creatures multiply and form a scum inside the
tank. This scum can grow to cover the entire bottom of a tank and hold water in
contact with the tank structure. This pro-vides a place for concentration cell
corrosion to form. If the scum forms along the edge of the sealant -in an
integral fuel tank, the sealant can pull away from the structure, causing a leak
and au expensive resealing operation. [Figure 12-18]
It is virtually impossible to prevent the formation of this scum as long as
microbes are allowed to live in fuel. The most successful solution to the
problem has been to use an additive in fuel which kills these organic growths
and prevents the formation of the corrosion-forming scum.
In addition to preventing corrosion by its biocidal action, this same fuel additive
also serves as an antifreeze to prevent entrained water from freezing. Should
entrained water freeze, the resulting slush could plug the fuel screens and
cause-fuel starvation.
SCUM FORMS IN TANK HOLDING WATER IN CONTACT WITH THE METAL
Figure 12-18. Microbial growth within a turbine aircraft fuel tank forms a scum
that holds water against the metal and causes corrosion to form.