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. Corrosion is to be distinguished from erosion, which is primarily destruction by mechanical action. The corrosion occurs because of the tendency for metals to return to their natural state.
Noble metals, such as gold and platinum, do not corrode since they are chemically uncombined in their natural state. Four conditions must exist before corrosion can occur (see Figure 2-1):
(1)
Presence of a metal that will corrode (anode);
(2) Presence of a dissimilar
conductive material (cathode) which has less tendency to corrode;
(3) Presence
of a conductive liquid (electrolyte); and
(4) Electrical contact between the
anode and cathode (usually metal to metal contact, or a fastener.
b.
Elimination of any one of these conditions will stop corrosion. An example
would be a paint film on the metal surface (see Figure 2-2).
Some metals (such as stainless steel and titanium), under the right conditions,
produce corrosion products that are so tightly bound to the corroding metal
that they form an invisible oxide film (called a passive film), which prevents
further corrosion. When the film of corrosion products is loose and porous
(such as those of aluminum and magnesium), an electrolyte can easily penetrate
and continue the corrosion process, producing more extensive damage than
surface appearance would show.
202.
DEVELOPMENT OF CORROSION.
a.
All corrosive attack begins on the surface of the metal. The corrosion process
involves two chemical changes. The metal that is attacked or oxidized undergoes
an anodic change, with the corrosive agent being reduced and undergoing a
cathodic change. The tendency of most metals to corrode creates one of the
major problems in the maintenance of the aircraft, particularly in areas where
adverse environmental or weather conditions exist.
b.
Paint coatings can mask the initial stages of corrosion. Since corrosion
products occupy more volume than the original metal, paint surfaces should be
inspected often for irregularities such as blisters, flakes, chips, and lumps.
203.
FACTORS INFLUENCING CORROSION.
a.
Some factors which influence metal corrosion and the rate of corrosion are the:
(1)
Type of metal;
(2) Heat treatment and grain direction;
(3) Presence of a
dissimilar, less corrodible metal (galvanic corrosion);
(4) Anode and cathode
surface areas (in galvanic corrosion);
(5) Temperature;
(6) Presence of
electrolytes (hard water, salt water, battery fluids, etc.);
(7) Availability
of oxygen;
(8) Presence of different concentrations of the same electrolyte;
(9)
Presence of biological organisms;
(10) Mechanical stress on the corroding
metal; and
(11) Time of exposure to a corrosive environment.
b.
Most pure metals are not suitable for aircraft construction and are used only
in combination with other metals to form alloys. Most alloys are made up
entirely of small crystalline regions, called grains. Corrosion can occur on
surfaces of those regions which are less resistant and also at boundaries
between regions, resulting in the formation of pits and intergranular
corrosion. Metals have a wide range of corrosion resistance. The most active
metals (those which tend to lose electrons easily), such as magnesium and
aluminum, corrode easily. The most noble metals (those which do not lose
electrons easily), such as gold and silver, do not corrode easily.
c.
Corrosion is accelerated by higher temperature environments which accelerate
chemical reactions and allow greater moisture content at saturation in air.
d.
Electrolytes (electrically conducting solutions) form on surfaces when
condensation, salt spray, rain, or rinse water accumulate. Dirt, salt, acidic
gases, and engine exhaust gases can dissolve on wet surfaces, increasing the
electrical conductivity of the electrolyte, thereby increasing the rate of
corrosion.
e.
When some of the electrolyte on a metal surface is partially confined (such as
between faying surfaces or in a deep crevice), metal in this confined area
corrodes more rapidly than other metal surfaces of the same part outside this
area. This type of corrosion is called an oxygen concentration cell. Corrosion
occurs more rapidly than would be expected, because the reduced oxygen content
of the confined electrolyte causes the adjacent metal to become anodic to other
metal surfaces on the same part immersed in electrolyte exposed to the air.
f.
Slimes, molds, fungi, and other living organisms (some microscopic) can grow on
damp surfaces. Once they are established, the area tends to remain damp,
increasing the possibility of corrosion.
g.
Manufacturing processes such as machining, forming, welding, or heat treatment
can leave stresses in aircraft parts. This residual stress can cause cracking
in a corrosive environment when the threshold for stress corrosion is exceeded.
h.
Corrosion, in some cases, progresses at the same rate no matter how long the
metal has been exposed to the environment. In other cases, corrosion can
decrease with time, due to the barrier formed by corrosion products, or
increase with time if a barrier to corrosion is being broken down.
204.
FORMS OF CORROSION.
There
are many different types of corrosive attack and these will vary with the metal
concerned, corrosive media location, and time exposure. For descriptive
purposes, the types are discussed under what is considered the most commonly
accepted titles.
a.
Uniform Etch Corrosion.
Uniform
etch corrosion results from a direct chemical attack on a metal surface and
involves only the metal surface (see Figure 2-3).
On a polished surface, this type of corrosion is first seen as a general
dulling of the surface, and if the attack is allowed to continue, the surface
becomes rough and possibly frosted in appearance. The discoloration or general
dulling of metal created by exposure to elevated temperatures is not to be
considered as uniform etch corrosion.
b.
Pitting Corrosion.
The
most common effect of corrosion on aluminum and magnesium alloys is called
pitting (see Figure 2-4). It is first noticeable as a white or
gray powdery deposit, similar to dust, which blotches the surface. When the
deposit is cleaned away, tiny pits or holes can be seen in the surface. Pitting
corrosion may also occur in other types of metal alloys. The combination of
small active anodes to large passive cathodes causes severe pitting. The
principle also applies to metals which have been passivated by chemical
treatments, as well as for metals which develop passivation due to
environmental condition.
c.
Galvanic Corrosion.
Galvanic
corrosion occurs when two dissimilar metals make electrical contact in the
presence of an electrolyte (see Figure 2-5).
The rate which corrosion occurs depends on the difference in the activities. The
greater the difference in activity, the faster corrosion occurs. For example,
magnesium would corrode very quickly when coupled with gold in a humid
atmosphere, but aluminum would corrode very slowly in contact with cadmium. The
rate of galvanic corrosion also depends on the size of the parts in contact. If
the surface area of the corroding metal (the anode) is smaller than the surface
area of the less active metal (the cathode), corrosion will be rapid and
severe. When the corroding metal is larger than the less active metal,
corrosion will be slow and superficial. For example, an aluminum fastener in
contact with a relatively inert Monel structure may corrode severely, while a
Monel bracket secured to a large aluminum member would result in a relatively superficial
attack on the aluminum sheet.
d.
Concentration Cell Corrosion.
Concentration
cell corrosion is corrosion of metals in a metal to metal joint, corrosion at
the edge of a joint even though joined metals are identical, or corrosion of a
spot on the metal surface covered by a foreign material (see Figure 2-6).
Another term for this type of corrosion is crevice corrosion. Metal ion
concentration cells, oxygen concentration cells, and active passive cells are
the three general types of concentration cell corrosion.
(1)
Metal ion concentration cells.
The
solution may consist of water and ions of the metal which is in contact with
water. A high concentration of the metal ions will normally exist under faying
surfaces where the solution is stagnant, and a low concentration of metal ions
will exist adjacent to the crevice which is created by the faying surface. An
electrical potential will exist between the two points; the area of the metal in
contact with the low concentration of metal ions will be anodic and corrode,
and the area in contact with the high metal ions concentration will be cathodic
and not show signs of corrosion. Figure 2-6
illustrates metal ion concentration cell corrosion.
(2)
Oxygen concentration cells.
The
solution in contact with the metal surface will normally contain dissolved
oxygen. An oxygen cell can develop at any point where the oxygen in the air is
not allowed to diffuse into the solution, thereby creating a difference in
oxygen concentration between two points. Typical locations of oxygen
concentration cells are under either metallic or nonmetallic deposits on the
metal surface and under faying surfaces such as riveted lap joints. Oxygen
cells can also develop under gaskets, wood, rubber, and other materials in
contact with the metal surface. Corrosion will occur at the area of low oxygen
concentration (anode) as illustrated in Figure 2-6.
Alloys, such as stainless steel, which owe their corrosion resistance to
surface passivity, are particularly susceptible to this type of crevice
corrosion.
(3)
Active passive cells.
Metals
which depend on a tightly adhering passive film, usually an oxide for corrosion
protection, such as corrosion resistant steel, are prone to rapid corrosive
attack by active passive cells. The corrosive action usually starts as an
oxygen concentration cell. As an example, salt deposits on the metal surface in
the presence of water containing oxygen can create the oxygen cell. The passive
film will be broken beneath the dirt particle. Once the passive film is broken,
the active metal beneath the film will be exposed to corrosive attack. An
electrical potential will develop between the large area of the cathode
(passive film) and the small area of the anode (active metal). Rapid pitting of
the active metal will result as shown in Figure 2-6.
e.
Intergranular Corrosion.
Intergranular
corrosion is an attack along the grain boundaries of a material. 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.
Rapid selective corrosion at the grain boundary can occur with subsequent
delamination (see Figure 2-7). High strength aluminum alloys such as
2014 and 7075 are more susceptible to intergranular corrosion if they have been
improperly heat treated and are then exposed to a corrosive environment.
f.
Exfoliation Corrosion.
Exfoliation
corrosion is an advanced form of intergranular corrosion where the surface
grains of a metal are lifted up by the force of expanding corrosion products
occurring at the grain boundaries just below the surface. The lifting up or
swelling is visible evidence of exfoliation corrosion (see Figures 2-8
and 2-9). Exfoliation is most prone to occur in wrought
products such as extrusions, thick sheet, thin plate and certain die forged
shapes which have a thin, highly elongated platelet type grain structure. This
is in contrast with other wrought products and cast products that tend to have
an equiaxed grain structure.
g.
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 characteristic wormlike trace of corrosion products
beneath the paint film (see Figures 2-10
and 2-11). Filiform occurs when the relative
humidity of the air is between 78 and 90 percent and the surface is slightly
acidic. Corrosion starts at breaks in the coating system and proceeds
underneath the coating due to the diffusion of water vapor and oxygen from the
air through the coating. Filiform corrosion can attack steel and aluminum
surfaces. The traces never cross on steel, but they will cross under one
another on aluminum which makes the damage deeper and more severe for aluminum.
If filiform corrosion is not removed and the area treated and a protective
finish applied, the corrosion can lead to intergranular corrosion, especially
around fasteners and at seams. Filiform corrosion can be removed using glass
bead blasting material with portable abrasive blasting equipment and/or
mechanical means such as buffing or sanding. Filiform corrosion can be
prevented by storing aircraft in an 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.
205.
CORROSION AND MECHANICAL FACTORS.
Corrosive
attack is often aggravated by mechanical factors that are either within the
part (residual) or applied to the part (cyclic service loads). Erosion by sand
and/or rain and mechanical wear will remove surface protective films and
contribute to corrosive attack of underlying metal surfaces. Corrosive attack
that is aided by some mechanical factor usually causes the part to degenerate
at an accelerated rate compared to the rate at which the same part would
deteriorate if it were subjected solely to corrosive attack. Environmental
conditions and the composition of the alloy also influence the extent of
attack. Examples of this kind of alliance are stress corrosion cracking,
corrosion fatigue, and fretting corrosion.
a.
Stress Corrosion Cracking.
Stress
corrosion cracking is an intergranular cracking of the metal which is caused by
a combination of stress and corrosion (see Figures 2-12
through 2-14). Stress may be caused by internal or
external loading. Internal stresses are produced by nonuniform deformation
during cold working, by unequal cooling from high temperatures, and by internal
structural rearrangement involving volume changes. Internal stresses are
induced when a piece of structure is deformed during an assembly operation,
(i.e., during pressing in bushings, shrinking a part for press fit, installing
interference bolts, installing rivets, etc.). Concealed stress is more
important than design stress, because stress corrosion is difficult to
recognize before it has overcome the design safety factor. The level of stress
varies from point to point within the metal. Stresses near the yield strength
are generally necessary to promote stress corrosion cracking, but failures may
occur at lower stresses. Specific environments have been identified which cause
stress corrosion cracking of certain alloys. Salt solutions and seawater may
cause stress corrosion cracking of high strength heat treated steel and
aluminum alloys. Methyl alcohol hydrochloric acid solutions will cause stress
corrosion cracking of some titanium alloys. Magnesium alloys may stress corrode
in moist air. Stress corrosion may be reduced by applying protective coatings,
stress relief heat treatment, using corrosion inhibitors, or controlling the
environment. Shot peening a metal surface increases resistance to stress
corrosion cracking by creating compressive stresses on the surface which should
be overcome by applied tensile stress before the surface sees any tension load.
Therefore, the threshold stress level is increased. {Figure 2-13}
b.
Corrosion Fatigue.
Corrosion
fatigue is caused by the combined effects of cyclic stress and corrosion. No
metal is immune to some reduction in its resistance to cyclic stressing if the
metal is in a corrosive environment. Damage from corrosion fatigue is greater
than the sum of the damage from both cyclic stresses and corrosion. Corrosion
fatigue failure occurs in two stages. During the first stage, the combined
action of corrosion and cyclic stress damages the metal by pitting and crack
formation to such a degree that fracture by cyclic stressing will ultimately
occur, even if the corrosive environment is completely removed. The second
stage is essentially a fatigue stage in which failure proceeds by propagation
of the crack (often from a corrosion pit or pits) and is controlled primarily
by stress concentration effects and the physical properties of the metal.
Fracture of a metal part, due to fatigue corrosion, generally occurs at a
stress level far below the fatigue limit in laboratory air, even though the
amount of corrosion is relatively small. For this reason, protection of all
parts subject to alternating stress is particularly important, even in
environments that are only mildly corrosive.
c.
Fretting Corrosion.
Damage
can occur at the interface of two highly loaded surfaces which are not supposed
to move against each other. However, vibration may cause the surfaces to rub
together resulting in an abrasive wear known as fretting. The protective film
on the metallic surfaces is removed by the rubbing action. The continued
rubbing of the two surfaces prevents formation of protective oxide film and
exposes fresh active metal to the atmosphere. Fretting can cause severe pitting
(see Figure 2-15). Dampening of vibration, tightening of
joints, application of a lubricant, or installation of a fretting resistant
material between the two surfaces can reduce fretting corrosion.
d.
Heat Treatment.
Heat
treatment of airframe materials should be rigidly controlled to maintain their
corrosion resistance as well as to improve their essential mechanical
properties. For example, improper heat treatment of clad aluminum alloy may
cause the cladding to incur excessive diffusion because the solution heat
treatment is too long or at too high a temperature. This degrades the inherent
resistance of the cladding itself, and reduces its ability to provide
protection to the core aluminum alloy. Aluminum alloys which contain
appreciable amounts of copper and zinc are highly vulnerable to intergranular
corrosion attack if not quenched rapidly during heat treatment or other special
treatment. Stainless steel alloys are susceptible to carbide sensitization when
slowly cooled after welding or high temperature heat treatment. Post weld heat
treatments are normally advisable for reduction of residual stress.
e.
Hydrogen Embrittlement.
(1) Environmentally
induced failure processes may often be the result of hydrogen damage rather
than oxidation. Atomic hydrogen is a cathodic product of many electrochemical
reactions, forming during naturally occurring corrosion reactions as well as
during many plating or pickling processes. Whether hydrogen is liberated as a
gas, or atomic hydrogen is absorbed by the metal, depends on the surface
chemistry of the metal.
(2)
Atomic hydrogen, due to its small size and mass, has very high diffusivity in
most metals. It will therefore penetrate most clean metal surfaces easily and
migrate rapidly to favorable sites where it may remain in solution, precipitate
as molecular hydrogen to form small pressurized cavities, cracks or large
blisters, or it may react with the base metal or with alloying elements to form
hydrides.
(3)
The accumulation of hydrogen in high strength alloys often leads to cracking,
and this often occurs in statically loaded components several hours or even
days after the initial application of the load or exposure to the source of
hydrogen. Cracking of this type is often referred to as hydrogen stress
cracking, hydrogen delayed cracking, or hydrogen induced cracking. Similar
fracture processes can occur in new and unused parts when heat treatments or
machining have left residual stresses in the parts, and have then been exposed
to a source of hydrogen. For this reason, all processes such as pickling or
electroplating must be carried out under well controlled conditions to minimize
the amount of hydrogen generated.
206.
COMMON CORROSIVE AGENTS.
Substances
that cause corrosion of metals are called corrosive agents. The most common
corrosive agents are acids, alkalies, and salts. The atmosphere and water, the
two most common media for these agents, may act as corrosive agents too.
a.
Acids.
In
general, moderately strong acids will severely corrode most of the alloys used
in airframes. The most destructive are sulfuric acid (battery acid), halogen
acids (i.e., hydrochloric, hydrofluoric, and hydrobromic), nitrous oxide
compounds, and organic acids found in the wastes of humans and animals.
b.
Alkalies.
Although
alkalies, as a group, are generally not as corrosive as acids, aluminum and
magnesium alloys are exceedingly prone to corrosive attack by many alkaline
solutions unless the solutions contain a corrosion inhibitor. Particularly
corrosive to aluminum are washing soda, potash (wood ashes), and lime (cement
dust). Ammonia, an alkali, is an exception because aluminum alloys are highly
resistant to it.
c.
Salts.
Most
salt solutions are good electrolytes and can promote corrosive attack. Some
stainless steel alloys are resistant to attack by salt solutions but aluminum
alloys, magnesium alloys, and other steels are extremely vulnerable. Exposure
of airframe materials to salts or their solutions is extremely undesirable.
d.
The Atmosphere.
The
major atmospheric corrosive agents are oxygen and airborne moisture, both of
which are in abundant supply. Corrosion often results from the direct action of
atmospheric oxygen and moisture on metal, and the presence of additional
moisture often accelerates corrosive attack, particularly on ferrous alloys.
However, the atmosphere may also contain other corrosive gases and
contaminants, particularly industrial and marine environments, which are
unusually corrosive.
(1)
Industrial atmospheres contain many contaminants, the most common of which are
partially oxidized sulfur compounds. When these sulfur compounds combine with
moisture, they form sulfur based acids that are highly corrosive to most
metals. In areas where there are chemical industrial plants, other corrosive
atmospheric contaminants may be present in large quantities, but such
conditions are usually confined to a specific locality.
(2)
Marine atmospheres contain chlorides in the form of salt particles or droplets
of salt saturated water. Since salt solutions are electrolytes, they corrosively
attack aluminum and magnesium alloys which are vulnerable to this type of
environment.
e.
Water.
The
corrosivity of water will depend on the type and quantity of dissolved mineral
and organic impurities and dissolved gasses (particularly oxygen) in the water.
One characteristic of water which determines its corrosivity is the
conductivity or its ability to act as an electrolyte and conduct a current.
Physical factors, such as water temperature and velocity, also have a direct
bearing on the corrosivity.
(1)
The most corrosive of natural waters (sea and fresh waters) are those that
contain salts. Water in the open sea is extremely corrosive due to the presence
of chloride ions, but waters in harbors are often even more so because they are
contaminated by industrial waste.
(2)
The corrosive effects of fresh water varies from locality to locality due to
the wide variety of dissolved impurities that may be present in any particular
area. Some municipal waters (potable water) to which chlorine and fluorides have
been added can be quite corrosive. Commercially softened water and industrially
polluted rain water are usually considered to be very corrosive.
207.
MICRO-ORGANISMS.
a.
Microbial attack includes actions of bacteria, fungi, or molds. Micro-organisms
occur nearly everywhere. Those organisms causing the greatest corrosion
problems are bacteria and fungi.
b.
Bacteria may be either aerobic or anaerobic. Aerobic bacteria require oxygen to
live. They accelerate corrosion by oxidizing sulfur to produce sulfuric acid.
Bacteria living adjacent to metals may promote corrosion by depleting the
oxygen supply or by releasing metabolic products. Anaerobic bacteria, on the
other hand, can survive only when free oxygen is not present. The metabolism of
these bacteria requires them to obtain part of their sustenance by oxidizing
inorganic compounds, such as iron, sulfur, hydrogen, and carbon monoxide. The
resultant chemical reactions cause corrosion.
c.
Fungi are the growths of micro-organisms that feed on organic materials. While
low humidity does not kill microbes, it slows their growth and may prevent
corrosion damage. Ideal growth conditions for most micro-organisms are
temperatures between 68 and 104 °F (20 and 40 °C) and relative humidity between
85 and 100 percent. It was formerly thought that fungal attack could be
prevented by applying moisture proofing coatings to nutrient materials or by
drying the interiors of compartments with desiccants. However, some moisture
proofing coatings are attacked by mold, bacteria, or other microbes, especially
if the surfaces on which they are used are contaminated. Microbial growth
occurs at the interface of water and fuel, where the fungus feeds on fuel.
Organic acids, alcohols, and esters are produced by growth of the fungus. These
byproducts provide even better growing conditions for the fungus. The fungus
typically attaches itself to the bottom of the tank and looks like a brown
deposit on the tank coating when the tank is dry. The fungus growth may start
again when water and fuel are present.
d.
The spore form of some micro-organisms can remain dormant for long periods
while dry, and can become active when moisture is available. When desiccants
become saturated and unable to absorb moisture passing into the affected area,
micro-organisms can begin to grow. Dirt, dust, and other airborne contaminants
are the least recognized contributors to microbial attack. Unnoticed, small
amounts of airborne debris may be sufficient to promote fungal growth.
e.
Fungi nutrients have been considered to be only those materials that have been
derived from plants or animals. Thus, wool, cotton, rope, feathers, and leather
were known to provide sustenance for microbes, while metals and minerals were
not considered fungi nutrients. To a large extent this rule of thumb is still
valid, but the increasing complexity of synthetic materials makes it difficult
or impossible to determine from the name alone whether a material will support
fungus. Many otherwise resistant synthetics are rendered susceptible to fungal
attack by the addition of chemicals to change the material's properties.
f.
Damage resulting from microbial growth can occur when any of three basic
mechanisms, or a combination of these, is brought into play. First, fungi are
damp and have a tendency to hold moisture, which contributes to other forms of
corrosion. Second, because fungi are living organisms, they need food to
survive. This food is obtained from the material on which the fungi are
growing. Third, these micro-organisms secrete corrosive fluids that attack many
materials, including some that are not fungi nutrient.
g.
Microbial growth must be removed completely to avoid corrosion. Microbial
growth should be removed by hand with a firm nonmetallic bristle brush and
water. Removal of microbial growth is easier if the growth is kept wet with
water. Microbial growth may also be removed with steam at 100 psi and steam
temperatures not exceeding 150 °F (66 °C). Protective clothing must be used
when using steam for removing microbial growth.
208.
METALLIC MERCURY CORROSION ON ALUMINUM ALLOYS.
Spilled
mercury on aluminum should be cleaned immediately because mercury causes
corrosion attack which is rapid in both pitting and intergranular attack and is
very difficult to control. The most devastating effect of mercury spillage on
aluminum alloys is the formation of an amalgam which proceeds rapidly along
grain boundaries, causing liquid metal embrittlement. If the aluminum alloy
part is under tension stress, this embrittlement will result in splitting with
an appearance similar to severe exfoliation. X-ray inspection may be an effective
method of locating the small particles of spilled mercury because the dense
mercury will show up readily on the X-ray film.
209 -
299 RESERVED.