Corrosion and Degradation of Materials

Photograph showing a bar of steel that has been bent into a horseshoe
shape using a nut-and-bolt assembly. While immersed in seawater, stress
corrosion cracks formed along the bend at those regions where the tensile
stresses are the greatest.
Why Study Corrosion and Degradation of Materials?
With a knowledge of the types of and an understanding of the
mechanisms and causes of corrosion and degradation, it is possible to take
measures to prevent them from occurring. For example, we may change the
nature of the environment, select a material that is relatively nonreactive,
and/or protect the material from appreciable deterioration.
Corrosion is the destructive attack of a material by reaction with its
environment. The serious consequences of the corrosion process have
become a problem of worldwide significance. In addition to our everyday
encounters with this form of degradation, corrosion causes plant shutdowns,
waste of valuable resources, loss or contamination of product, reduction in
efficiency, costly maintenance, and expensive overdesign. It can also
jeopardize safety and inhibit technological progress.
INTRODUCTION
To one degree or another, most materials experience some type of
interaction with a large number of diverse environments. Often, such
interactions impair a materials usefulness as a result of the deterioration of
its mechanical properties (e.g., ductility and strength), other physical
properties, or appearance. Occasionally, to the chagrin of a design engineer,
the degradation behavior of a material for some application is ignored, with
adverse consequences.
Deteriorative mechanisms are different for the three material types. In
metals, there is actual material loss either by dissolution (corrosion) or by
the formation of nonmetallic scale or film (oxidation). Ceramic materials are
relatively resistant to deterioration, which usually occurs at elevated
temperatures or in rather extreme environments; the process is frequently
also called corrosion. For polymers, mechanisms and consequences differ
from those for metals and ceramics, and the term degradation is most
frequently used. Polymers may dissolve when exposed to a liquid solvent, or
they may absorb the solvent and swell; also, electromagnetic radiation
(primarily ultraviolet) and heat may cause alterations in their molecular
structure. The deterioration of each of these material types is discussed in
this chapter, with special regard to mechanism, resistance to attack by
various environments, and measures to prevent or reduce degradation.

CORROSION OF METALS
Corrosion is defined as the destructive and unintentional attack of a metal;
it is electrochemical and ordinarily begins at the surface. The problem of
metallic corrosion is one of significant proportions; in economic terms, it has
been estimated that approximately 5% of an industrialized nations income
is spent on corrosion prevention and the maintenance or replacement of
products lost or contaminated as a result of corrosion reactions. The
consequences of corrosion are all too common. Familiar examples include
the rusting of automotive body panels and radiator and exhaust
components.
Corrosion processes are occasionally used to advantage. For example,
etching procedures, make use of the selective chemical reactivity of grain
boundaries or various microstructural constituents. Also, the current
developed in dry-cell batteries is a result of corrosion processes.
Fundamental Components
Corrosion can be defined as the deterioration of material by reaction to its
environment.
Corrosion occurs because of the natural tendency for most metals to return
to their natural state; e.g., iron in the 4 required components in an
electrochemical corrosion cell: 1) An anode; 2) A cathode; 3) A conducting
environment for ionic movement (electrolyte); 4) An electrical connection
between the anode and cathode for the flow of electron current. If any of
the above components is missing or disabled, the electrochemical corrosion
process will be stopped.
Whats needed for Corrosion
An anode. This is where the damage occurs. Oxidation takes place.
A cathode. Heres where the reduction reaction takes place.
An electrolyte. (Almost any moisture will do.)
A current path between the cathode and anode.
Finishing of Materials
Wood
The environmental factors that affect degradation in wood are;
Biological organisms fungi and insects
Risk of wetting or permanent contact with water
Wood is susceptible to attack when the moisture content exceeds 20%
Degradation of Materials
Physical and Mechanical effects of degradation in wood;
Change in cross-sectional dimensions, swelling and shrinkage
Strength and stiffness decrease as moisture content increases
Durability is affected
Coatings can be compromised
Degradation of Materials
Plastics
--It is widely accepted that plastics do not corrode however microorganisms
which can decompose low density polyethylene do exist.
--Elastomers can cause other plastics to corrode or melt due to prolonged
contact e.g. rubber left on a setsquare.
--UV light will weaken certain plastics and produce a chalky faded
appearance on the exposed surface.
--Heat will weaken or melt certain plastics even at relatively low
temperatures.
--Cold can cause some plastics to become brittle and fracture under
pressure.
Metals
--Most metals corrode because they react with oxygen in the atmosphere,
particularly under moist conditions this is called oxidation.
--Ferrous metals such as steel are particularly susceptible to oxidation and
require on-going maintenance or they will suffer inevitable structural failure
--Choice of metal, environmental location and design features must all be
considered carefully.
--Some non-ferrous metals are particularly resistant to corrosion, e.g.
Copper and zinc.
--They form strong oxides on their surfaces (as do aluminium and lead) and
these protect the metal from further oxidation.
FORMS OF CORROSION
1. Uniform attack 2. Galvanic corrosion
3. Crevice corrosion 4. Pitting corrosion
5. Inter-granular corrosion 6. Selective leaching
7. Erosion corrosion 8. Stress corrosion
Uniform Attack Corrosion
Uniform corrosion is characterized by corrosive attack proceeding evenly
over the entire surface area, or a large fraction of the total area. General
thinning takes place until failure. On the basis of tonnage wasted, this is the
most important form of corrosion.
However, uniform corrosion is relatively easily measured and predicted,
making disastrous failures relatively rare. In many cases, it is objectionable
only from an appearance standpoint.
Cathodic protection (CP) is a technique used to control the corrosion of a
metal surface by making it the cathode of an electrochemical cell.

The
simplest method to apply CP is by connecting the metal to be protected
with a piece of another more easily corroded "sacrificial metal" to act as the
anode of the electrochemical cell. The sacrificial metal then corrodes
instead of the protected metal.
Aluminium sacrificial anode (light colored rectangular bars) mounted on a
steel jacket structure.
Degradation of Materials
Metals
Sacrificial (cathodic) Protection
This is where one metal is deliberately sacrificed to protect another
Sea water attacks bronze propellers. A slab of magnesium, aluminium or
zinc is attached to the wooden hull near the propeller. This becomes the
anode and corrodes while the expensive propeller (cathode) is protected.
The anode must be replaced regularly.
Galvanic corrosion
Galvanic corrosion occurs when two metals or alloys having different
compositions are electrically coupled while exposed to an electrolyte.
The less noble or more reactive metal in the particular environment will
experience corrosion; the more inert metal, the cathode, will be protected
from corrosion.
For example, steel screws corrode when in contact with brass in a marine
environment; or if copper and steel tubing are joined in a domestic water
heater, the steel will corrode in the vicinity of the junction. Depending on
the nature of the solution, one or more of the reduction reactions.
For galvanic corrosion to occur, three conditions must be present:
1. Electrochemically dissimilar metals must be present
2. These metals must be in electrical contact, and
3. The metals must be exposed to an electrolyte
Crevice corrosion
Crevice corrosion , this form of attack is generally associated with the
presence of small volumes of stagnant solution in occluded interstices,
beneath deposits and seals, or in crevices, at nuts and rivet heads. Deposits
of sand, dust, scale and corrosion products can all create zones where the
liquid can only be renewed with great difficulty.
This is also the case for flexible, porous or fibrous seals (wood, plastic,
rubber, cements, asbestos, cloth, etc.).
As a result, this form of corrosion is called crevice corrosion or, sometimes,
deposit or gasket corrosion.

Crevice corrosion is initiated by changes in local chemistry within the
crevice:
1.Depletion of inhibitor in the crevice
2. Depletion of oxygen in the crevice
3. A shift to acid conditions in the crevice
4. Build-up of aggressive ion species in the crevice
Pitting corrosion
Pitting is another form of very localized corrosion attack in which small pits
or holes form. They ordinarily penetrate from the top of a horizontal surface
downward in a nearly vertical direction. It is an extremely insidious type of
corrosion, often going undetected and with very little material loss until
failure occurs.
Pitting is one of the most destructive and insidious forms of corrosion. It
causes equipment to fail because of perforation with only a small percent
weight loss of the entire structure.
This is similar to crevice corrosion. It is based on low oxygen concentration
at the bottom of the pit.
This is very common in materials that protect themselves with a passive
layer, i.e. stainless. Also, aluminum.
--Highly localized. Goes deep into the metal.
--Chloride ions find their way into the pits, exacerbating the situation.
Pitting is perhaps the most dangerous and vicious of all the other types of
corrosion. In pitting small or large and deep or shallow pits and holes are
formed on the surface, completely destroying the metal.
--If pitting occurs in a metal machine the machine completely stops working.
It is caused due to some chemical corrosive reagents.
--Another reason why this form of corrosion is considered the most
dangerous is that this type is difficult to predict and although it may take
place gradually and silently the function of the metal stops suddenly
without a warning.
InterGranular corrosion
The microstructure of metals and alloys is made up of grains, separated by
grain boundaries. Intergranular corrosion is localized attack along the grain
boundaries, or immediately adjacent to grain boundaries, while the bulk of
the grains remain largely unaffected.
This form of corrosion is usually associated with chemical segregation
effects (impurities have a tendency to be enriched at grain boundaries) or
specific phases precipitated on the grain boundaries. This type of corrosion
is especially prevalent in some stainless steels.

Selective Leaching
Selective leaching, also called dealloying, demetalification, parting and
selective corrosion, is a corrosion type in some solid solution alloys, when in
suitable conditions a component of the alloys is preferentially leached from
the material. The less noble metal is removed from the alloy by microscopic-
scale.
--A common example is the dezincification of unstabilized brass, whereby a
weakened, porous copper structure is produced.
--Dezincification selectively removes zinc from the alloy, leaving behind a
porous, copper-rich structure that has little mechanical strength.
--Selective Leaching takes place in metal alloys. In selective leaching one of
the metals on the alloy undergoes corrosion.
--May be done intentionally to remove one metal from the alloy.
--The most common example of selective leaching is the removal of zinc
from brass also known as dezincification.
Plug-type dezincification is localized within surrounding surfaces mostly
unaffected by corrosion. This type of dezincification penetrates deeply into
the sidewalls of valves and fittings.
Uniform-layer dezincification leaches zinc from a broad area of the surface.
This type of dezincification uniformly reduces the wall thickness of the valve
or fitting.
Erosion Corrosion
Erosion corrosion is an acceleration in the rate of corrosion attack in metal
due to the relative motion of a corrosive fluid and a metal surface. The
increased turbulence caused by pitting on the internal surfaces of a tube
can result in rapidly increasing erosion rates and eventually a leak. Erosion
corrosion can also be aggravated by faulty workmanship. Erosion-corrosion
is most prevalent in soft alloys (i.e. copper, aluminum and lead alloys). A
combination of erosion and corrosion can lead to extremely high pitting
rates.
Stress Corrosion Cracking(SCC) is the cracking induced from the combined
influence of tensile stress and a corrosive environment. The impact of SCC
on a material usually falls between dry cracking and the fatigue threshold of
that material.
A similar process occurs in polymers, known as Environmental Stress
Cracking(ESC). While similar in action and appearance, SCC and ESC have
different underlying chemical mechanisms. Environmental Stress Cracking
(ESC) is one of the most common causes of unexpected brittle failure of
thermoplastic (especially amorphous) polymers known at present.