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from10th to12th April2017


Mr.Rahul Gupta

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ASMInternational PuneChapter.



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Corrosion has been described as destruction of metal by chemical or
Corrosion from electrochemical reaction with its environment. This
section describes the types and chemical processes of corrosion, and
some of the Environments common methods used to prevent it.
Most environments are corrosive, but by no means to the same
Environments that foster corrosion include: air and moisture; fresh,
distilled, or saltwater. , rural, urban, and industrial atmospheres;
steam and other gases such as chlorine, ammonia, hydrogen sulfide,
sulfurdioxide, fuel gases; mineral acids such as hydrochloric, sulfuric,
and nitric; organic acids such as naphthenic, acetic, and formic;
alkalies; soils; solvents such alcohols and dry cleaning fluids;
vegetable and petroleum oils; and a variety of food products. In
general, the inorganic materials are more corrosive.

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For example, corrosion in the petroleum industry is due more to
sodium chloride, sulfur, hydrochloric and sulfuric acids, water than
the oil, naphtha, or gasoline. Corrosion of steel and iron by air and
moisture, referred to as rusting, is very common and results in
tremendous corrosion and loss. The rapid rusting of clean,
unprotected iron and steel is well known to everyone. .
Corrosion rates vary widely for almost any given metal with
geographical location. For instance, a specimen of polished carbon
steel exposed to a rural inland atmosphere will rust at a very slow
rate, due to the low humidity and no contamination from industrial
fumes or saline atmospheres. Such a location would represent about
the most favorable environmental condition for minimizing corrosion.

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A subsequent step in increasing corrosivity might be in a coastal area
where a certain amount of saline atmosphere would be involved.
Under these conditions, corrosion rates will further increase
probably several fold over the rural, lowhumidity conditions.
A coastal location near a chemical plant where humidity is high and
quantities of industrial fumes are present. Under these conditions,
corrosion rates of most common metals (without specific protection)
are extremely high. Probably the nearultimate conditions for
Corrosivity of a specific metal or metal alloy will vary greatly in
conventional atmospheric exposure, depending upon geographical
location and atmospheric conditions. Thus, selection of metals
and/or the means of protecting them is a dynamic problem in the
metals industry. Our examples have illustrated just one of the many
factors that influence atmospheric corrosion.

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There are many other factors adding to the complexity of the
problem of estimating corrosion rates and selecting materials that
will provide acceptable performance. Some of the questions to
consider are:
Will the metal be used to contain or handle corrosive materials,
such as food items or chemicals?
Will the metal be used in an ambient temperature, or at elevated
or cryogenic (low) temperatures?
What types of loads will be applied to the component in service?
Effect of Temperature: Almost without exception, whether the
environment is mild or aggressive, corrosion rate for an otherwise
constant set of conditions will increase as temperature increases.
Further, this is seldom a straightline relationship. The corrosion
rates increase exponentially as temperature increases.

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General Corrosion can be classified as: Wet or Dry; direct
combination or electro chemical; or by corrosive media including
atmospheric (gas corrosion),
Classification liquid (aqueous or nonaqueous), and soil
Wet corrosion occurs when liquids are present and at
temperatures below the dew point.
Dry corrosion occurs in the absence of liquids or above the dew
point. Vapors and gases are usually the corroding environment. Dry
corrosion is generally associated with high temperatures. An
example would be the corrosion of steel by furnace gases. Dry
corrosion at ordinary temperatures is usually very slow.
Sometimes the presence of moisture or water changes the
corrosiveness of the environment completely. For example, dry
chlorine at room temperature is practically non corrosive to
ordinary steel. Wet chlorine, however, is extremely corrosive and
attacks most of the common metals and alloys. The reverse is true
for Titanium, which corrodes in dry chlorine gas.

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Direct Corrosion. Direct combination, or direct corrosion, usually
occurs at high temperature, similar to dry corrosion. It involves a
reaction between a metal and nonmetallic elements or compounds,
such as steam, oxygen, sulfur, and chlorine. Using the example of
iron in an atmosphere containing sulfur dioxide (dry corrosion), the
reactions are:
Fe + SO = FeS + O
2Fe +02= 2FeO

Electrochemical corrosion occurs in liquids or electrolytes (solutions

containing ions). Most liquids, such as plain water, seawater, acids,
and other chemicals, are good conductors of electricity. Most of the
corrosion is caused by liquids.

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Electrochemical Theory. This is the accepted theory explaining
corrosion, and it is actually quite simple. For an electrochemical
reaction to take place, there are two basic requirements: (a) anodes
and cathodes must be present to form a cell, and (b) direct current
must flow. The anodes and cathodes may be very close together
(local cells), or they may be far apart. The current may be self
induced, or it may be impressed on the system from an outside
The anode is the area where corrosion occurs and where current
leaves the metal and enters the solution. The cathode is the area
where no corrosion occurs and where current enters the metal from
the solution. Anodes and cathodes can form on a single piece of
metal because of local differences in the metal or in the environment.
The metal at the anode dissolves and becomes an ion. It is oxidized
and loses electrons. . These electrons are accepted at the cathode

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Immersion in an electrolyte or conducting fluid is required to
complete the circuit to carry the current (electrons) from the anode
or anodic area to the cathode or cathodic area. For example, high
(purity) water is used in certain applications to keep corrosion at a
very low rate. However, most waters such as tap water and seawater
are not pure and are good conductors.
Figure 3. Hydrogen ions accept electrons at the cathode and form
hydrogen gas. This is visible & is called polarization of the cathode.
Polarization of a local cathode by a layer of hydrogen minimizes
Fe (metal) + 2H (ions) = Fe (ion) + H (gas)
The quantity of current that passes through this cell is proportional to
the amount of metal that corrodes; that is, one ampere per year
equals approximate 10kg of steel.

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Anything that interferes with these reactions or the cell circuit
could/ reduce corrosion. In pure water, hydrogen bubbles collect on
the cathode, thus providing an insulating blanket that reduces
current flow and practically stops corrosion. This is called
polarization; because it occurs on the cathode, it is termed cathodic
polarization (see Figure 4), In strong acid solutions, the hydrogen is
continuously evolved as bubbles breaking from corroding steel with
the corrosion continuing unabated until either all the metal or acid is
Most waters contain dissolved oxygen. This oxygen combines with
the hydrogen to form water and thus prevents accumulation of
hydrogen (polarization), and corrosion proceeds unhampered.
Oxygen acts as a cathodic depolarizer in this case. This is the reason
why boiler water is de aerated (see Figure 5).

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In neutral or alkaline waters (containing dissolved oxygen) the anode
reaction involving the corrosion of iron is the same, but the cathode
reaction is as follows:
H + 0 + 2e = 20H (hydroxyl ion) leading to the formation of Fe(OH)2
Corrosion of steel by water containing oxygen. When depolarization
occurs (hydrogen and oxygen combine to form water) corrosion again
The anodic and cathodic areas must be separated by a finite distance.
These areas could also be far apart a meter (yard) or more in some
cases. For example, one piece of pipe might act as the anode and the
section next to it as a cathode.

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The reason the same piece of metal acts differently is that
differences exist at the interface on the metal surface itself. The
differences may be chemical or metallurgical in nature, depending
on the character of the metal. Examples are impurities, such as
oxides and other inclusions; grain boundaries; orientation of grains;
differences in composition of the microstructure; localized stresses;
and scratches and nicks or other rough surfaces.
Figure 6 summarizes the points just made and may be considered a
basic diagram illustrating corrosion of metals in electrolytes or
aqueous solutions. Anodes and cathodes must form,, current must
flow through the environment (outside the metal) from the anodes
to cathodes, and through the metal from the cathodic to the anodic
areas. These are the basic requirements as stated above. Preventing
any of the above will prevent corrosion.

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When two dissimilar metals are in contact, for example copper and
steel, one usually behaves as the anode , while the other as cathode.
The metal with less corrosion resistance becomes the anode (or
anodic) and the more corrosionresistant metal becomes the cathode
(or cathodic). For the example given, iron becomes the anode and
copper becomes the cathode. Accordingly, it is said that steel is
anodic to copper. Dissimilar metals in contact form galvanic cells. Any
anode and cathode form a galvanic cell, but to avoid confusion the
term galvanic corrosion shall be reserved for corrosion caused by
dissimilar metals.
When an anode and cathode form a potential difference, or voltage,
exists between the anode and cathode. Accurate determinations of
potentials for various elements resulted in the emf series shown in
Table I.

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In this instance, hydrogen electrode is the reference electrode. The
potential of hydrogen is listed as zero, If platinum were used as a
reference electrode, the voltage for platinum would be listed as zero.
This table is determined under a standard set of conditions including
temperature and concentration of ions in the solutions.
This series ranks the elements according to their relative tendency to
Metals high in the series are reactive and less corrosion resistant.
Metals lower in the series are more noble or more corrosion
For example, metals above copper corrode or oxidize readily.

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This is one reason why gold and silver are often found in their native
state, whereas iron and aluminum are always found in the combined
state and usually mined as oxides.
A metal will replace another metal in solution if the latter metal is
lower in the series. For example, iron will replace copper when
placed in a copper sulfate solution (copper plates out). In other
Words, copper sulphate will corrode iron.
A metal higher in the series will act as the anode, and one lower will
act as a cathode when these two metals are coupled or are in contact
with each other.
When two metals are in contact, corrosion of the anodic member of
the couple is accelerated. This is called galvanic corrosion, or two
metal corrosion.

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Passivity in a metal refers to a relatively inactive state in which the
metal displays a more noble behavior than thermodynamic
considerations predict. Passivity can be more simply defined as the
reason why a metal does not corrode when it should. According to
the emf series, chromium is above iron, and, therefore, chromium is
more reactive or less corrosion resistant than iron (or plain carbon
steel, which is usually over 99% iron). If chromium is added to iron
to make a high chromium (over 12%) steel, this alloy should be less
corrosion resistant than plain carbon steel. On the contrary, these
alloys are the stainless steels .Chromium and the stainless steels
become passive, or exhibit passivity, because of the formation of a
protective film on the surface of the metal.

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An oxide or an absorbed oxygen film acts as a barrier, thus protecting
the metal from the environment.
Aluminum is an active metal and is high in the emf series, but it
possessesgood corrosion resistance. This metal quickly forms a surface
coating of aluminum oxide, which stops further corrosion by many
environments. Titanium also forms .a protective film of Ti0 and high
silicon cast iron forms a protective silica coating.
Lead is above hydrogen in the emf series, yet it shows excellent
resistance to sulfuric acid at concentrations below 90%. Lead sulfate
quickly forms when lead is exposed to sulfuric acid and corrosion stops.
Passivity is a relative term. Steel dipped in nitric acid is passive to copper
sulfate, but it would not resist 10% sulfuric acid. A stainless steel may
exhibit passive behavior in nitric acid and in water, but it would be
attacked by strong hydrochloric acid. Any metal or alloy is passive or
active only in relation to some particular environments.

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Some of the corrosion classifications are unique and distinct, but in
most instances they are, in some way, interrelated. The listing that
follows is some what arbitrary, it covers most forms of corrosion and
failures caused by corrosion.
Nine common forms are listed as follows:
1. Uniform attack or general overall corrosion
2. Galvanic or twometal corrosion
3. Concentrationcell corrosion
4. Pitting corrosion
5. Selective leaching
6. Inter granular corrosion
7. Stresscorrosion cracking
8. Erosioncorrosion
9. Crevice corrosion

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Uniform Corrosion Corrosion of metals by uniform chemical attack is
the simplest and most common form of corrosion and occurs in the
atmosphere, in liquids, and in soil, frequently under normal service
conditions. The rate of attack can be rapid or slow, and the metal
surface can either be clean or be covered with corrosion products.
Selection of a metal that has a suitable resistance to the environment
which the specific part is used and the application of paints and other
types of coatings are two common methods used to control uniform
Uniform corrosion commonly occurs on metal surfaces having a
homogenity of chemical composition and of microstructure .All metals
are affected by this form of attack in some environments: the rusting
of steel and the tarnishing of silver are typical examples of uniform
corrosion. In some metals, such as steel, uniform corrosion produces a
somewhat rough surface by removing a substantial amount of metal,
which either dissolves in the environment or reacts with it to produce
a loosely adherent, porous coating of corrosion products. In reactions
such as the tarnishing of silver in air or the attack on lead in sulfate
containing environments, thin, tightly adherent protective films are
produced, and the metal surface remains smooth.

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Corrosion rate and expected service life can be calculated from
measurements of the general thinning produced by uniform corrosion.
However, since the rate of attack can change over a period of time,
periodic inspection at suitable intervals is ordinarily done to avoid
unexpected failures.
Modification of the environment by changing its composition,
concentration, pH and temperature, or by adding an inhibitor, are also
effective and appropriate methods of controlling uniform corrosion in
some situations.
Effect of Concentration. The effect on corrosion rate of increasing or
decreasing the concentration of corrodent in the environment to which
a metal is exposed does not follow a uniform patternfirst, because of
ionization effects in aqueous solutions and the effects of even trace
amounts of water in nonaqueous environments, and second, because
of changes that occurr in characteristics of any film of corrosion
products that may be present on the surface of the metal.

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Figure 9. Effect of acid concentration on the corrosion rate of iron
completely immersed in aqueous solutions of three inorganicacids at
room temperature; (a)hydrochloric acid (b) sulfuric acid, and(c) nitric
acid. It should be noted that the scales for corrosion rate are not the
same for all three charts. The corrosion rate of iron (and steel) in nitric
acid in concentrations of 70% or higher, although low compared to the
maximum rate, is still sufficient to make it unsafe to ship or store nitric
acid in these metals.
The rate of corrosion of a given metal usually increases as the
concentra tion of the corrodent increases, as shown in Figure 9(a) for
the corrosion of iron in hydrochloric acid. However, corrosion rate does
not always increase with concentration of the corrodent; the effect
often depends on the range of corrodent concentration as shown in
Figure 9(b) and (c) for iron in sulfuric acid and in nitric acid, respectively.
Nitric acid in bulk is usually stored and shipped in type 304 stainless
steel, aluminum alloy 3003, or commercially pure titanium (grade 2).

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Figure 9.

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Metals that have passivity effects corrode at an extremely low rate at
low acid concentration at room temperature, but lose their passivity at a
certain limiting acid concentration above which the corrosion rate
increases rapidly with increasing acid concentration.
Effect of Temperature. In investigating the effect of temperature on the
corrosion rate of a metal in a liquid or gaseous environment, the
temperature that must be considered is that existing at the
metal/corrodent interface, which often differs substantially from the
temperature of the main body of the corrodent.
This is especially important for heattransfer applications wherehot
wall effect causes a much higher corrosion rate . A rise of 10C (
temperature of the solution can increase the Corrosion rate by a factor
of 2 or more. Hotwall failures are fairly common in heat exchanger
In some metalcorrodent systems. there an exponential rise in corrosion
rate with an increase in temperature

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The steel water system is an exception. As the temperature is raised, the
oxygen content of the water reduces, especially as the boiling point of
the water is approached.
Other exceptions arise where a morderate increase in tempriture
results in the formation of a thin protective film on the surface of the
metal or in passivation of the metal surface.This is important in
tempered steel for temperatures upto 450oC. The Fe3O4 formed
actually protects the steel.
If thick deposits are formed on a heattransfer surface, they have a two
fold effect by (a) changing the metal surface temperature and (b) making
crevice corrosion possible.
When dissimilar metals are in electrical contact in an electrolyte, the less
Galvanic Corrosion metal (anode) is attacked to a greater degree than if
it were exposed alone, and the more noble metal (cathode) is attacked
to a lesser degree than if it were exposed alone.

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This behavior which is known as galvanic corrosion, can often be
recognized by the fact that the corrosion is more severe near the
junction of the two metals than elsewhere on the metal surfaces.
Galvanic corrosion is usually the result of poor design and selection of
materials or the platingout of amore noble metal from solution on a
less noble metal.
The greater the difference in potential between the two metals, the
more rapid will be the galvanic attack. The electromotive force series
ranks the metals according to their chemical reactivity, but applies only
to the laboratory conditions under which the reactivity was determined.
In practice, the solution potential of metals is affected by the presence
of passive or other protective films on some metals, polarization effects,
degree of aeration, and temperatures.Refer to the galvanic corrosion
series for commonly used engineering materials. Materials in the same
category can be safely paired.

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If it is impossible to avoid the use of dissimilar metals in cementing
materials, the following precautions should be observed.
The electrical conductivity of the cementing material should be kept to
a minimum.
The use of other ionic compounds should be forbidden.
Contamination of the cementing material, by use of sea water , should
be avoided.
Abnormally delayed drying and subsequent exposure to moisture
should also be prevented as far as possible.

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Dissimilar metals should be spaced as far apart as practicable.
Coating the anode should be avoided, unless the coating is continuous
or unless the intense localized corrosion that may occur at a few
uncoated points can be tolerated. If one of the two dissimilar metals is
to be coated, coat the cathode.
Concentrationcell corrosion occurs on buried metals as a result of their
being in contact with soils that have different chemical compositions,
water contents, or degrees of aeration.
Pitting of materials is extremely localized corrosion that generally
produces Pitting Corrosion sharply defined holes. Every enginecring
metal or alloy is susceptible to pitting. Pitting occurs when one area of a
metal surface becomes anodic in respect to the rest of the surface, or
when highly localized changes in the corrodent in contact with the
metal, as in crevices, cause accelerated localized attack.
Severe pitting corrosion at the water line of ships can be observed. This
is due to salt concentration variatons due to level changes.

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Pitting on clean surfaces ordinarily represents the start of breakdown of
passivity or local breakdown of inhibitor produced protection.
When pits are few and widely separated, and the metal surface
undergoes little or no general corrosion, there is a high ratio of cathode
toanode area and penetration progresses more rapidly than when pits
are numerous and close together.
Difficulty of Detection. Pitting is one of the most difficult to detect forms
corrosion; it can cause failure by perforation while producing only a
small weight loss on the metal.

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Some causes of pitting are local inhomogeneity on the metal surface,
local loss of passivity. mechanical or chemical rupture of a protective
oxide , galvanic corrosion from a relatively distant cathode, and the
formation of a metal iron or oxygen concentration cell under a solid
deposit (crevice corrosion)..
The most common causes of pitting in steels are surface deposits that
set up local concentration cells and dissolved halides that produce
local anodes by rupture of the protective oxide film. Anodic corrosion
inhibitors, such as chromates, can cause rapid pitting if present in
concentrations below a minimum value that depends on the metal
environment combination, temperature, and other factors.
Pitting occurs at mechanical ruptures in protective organic coatings if
the external environment is aggressive, or if a galvanic cell is active.
In corrosionresistant alloys, such as stainless steels, the most common
cause of pitting corrosion is highly localized destruction of passivity by
contact with moisture that contains halide ions and in particular,

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Pitting of Specific Metals. Despite their good resistance to general
corrosion, stainless steels are most susceptible to pitting than many
other metals. The stainless steels higher in chromium, nickel, and
molybdenum are also higher in resistance to pitting, but are not
immune under all service conditions.
Pitting failures of corrosionresistant alloys are relatively uncommon in
solutions that do not contain halides
Pitting of aluminum and magnesium and their alloys in aqueous
solutions is often accelerated by galvanic effects, which occur because
these metals are anodic to most other metals, and by the effects of
dissolved metallic ions and suspended particles in the solution.

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Selective Leaching Selective leaching is the removal of an element from
an alloy by corrosion. The most common example is dezincification.
that is, the selective removal of zinc in brasses. Many alloys are
susceptible to selective leaching under certain condition. The elements
that are more resistant to the environment remain behind, provided
that they have a sufficiently continuous structure to prevent them from
breaking away in small particles.
Dezincification occurs in brasses containing less than 85% copper. Zinc
corrodes preferentially, leaving a porous residue of copper and
corrosion products. Alpha brass containing 70% copper and 30% zinc is
particularly susceptible to dezincification when exposed in an aqueous
electrolyte at elevated temperatures.

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Austenitic stainless steels become sensitized or susceptible to inter
granular corrosion when heated in the temperature range of about 550
to 850 C(1020 to 1560F).These temperatures are encountered during
manufacturing processess such as welding.
In the sensitizing range, chromium carbides and carbon precipitate out
of solution if the carbon content is about 0.02% or higher. The
chromium carbide in the grain boundary is not attacked, but in many
corrosive environments the chromiumdepleted zone that is
immediately adjacent to the grain boundair is attacked.
One method of reducing the susceptibility of austenitic stainless steels
to inter granular corrosion is to use solution heat treatment, usually by
heating to 1066 to 1121C (1950th 2050F) and immediately water
quenching. By this procedure, chromium carbide is dissolved and
retained in solid solution,.
Solution heat treatment poses problems on many welded assemblies
and is generally impractical on large equipment

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Using stainless steels that contain less than 0.03% carbon (extralow
carbon grades) reduces susceptibility to inter granular corrosion
sufficiently for serviceability in many applications. Somewhat better
performance can be obtained from types 347 or 321 stainless steel,
which contain sufficient titanium and niobium (or niobium plus
tantalum), respectively, to combine with all of the carbon in the steel.
The latter approach is used to correct the condition illustrated and
described in Figure 16.

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Stresscorrosion cracking is a mechanicalenviromnental failure process
In combine to initiate and cracking a metal part. Stresscorrosion
cracking is produced by the synergistic action of sustained tensile
stress and a specific corrosive environment, causing failure in less time
than would the separate effects of the stress and the corrosive
environment if applied together.
Failure by stresscorrosion cracking frequently is caused by
simultaneous exposure to a seemingly mild chemical environment and
to a tensile stress well below the yield strength of the metal. Under
such conditions, fine cracks can penetrate deeply into the pail while
the surface exhibits only faint signs of corrosion. Hence, there may be
no macroscopic indications of an impending failure.
In addition to stresscorrosion cracking, them are several other
processes that cause failure of metal parts by the conjoint action of
mechanical stress and corrosion. These include hydrogen damage
(hydrogen embrittlement), corrosion fatigue, liquid metal
embrittlement, and fretting.
StressCorrosion sustained tensile stress and chemical attack

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Sources of Stresses in Fabrication. The principal sources of high local
stresses in manufacture include (a) thermal processing, (b) stress
raisers, (c) surface finishing. and (d) fabrication.
Thermal Processing. One of the most frequently encountered sources
of thermalprocessing stresses is welding. Shrinkage of weld metal
during cooling, and fixtures, can produce residual tensile stresses as
high as 207 to 276 MPa (30 to 40 ks,) Other thermalprocessing effects
that often produce stresses during manufacture include solidification
of castings (especially those having large differences in section
thickness and those made with castin inserts) and improper heat
treating practices (failure to preheat, when required; overheating
during solution treating; failure to provide required temperature
uniformity in furnaces; use of quenching practices too severe for a
specific alloy or part shape; and undue delay in transferring work
pieces from the quenchant to the tempering furnace).

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Surface Finishing. Residual tensile stresses that are damaging or
potentially damaging in conjunction with environmental attack are
produced in many different types of surfacefinishing treatments.
These treatments . include electroplating, electrical discharge
machining, and (under some conditions) conventional grinding and
machining. When hydrogen is produced in the finishing process and
diffuses into the metal, internal stresses can be produced.
Shot peening and surface rolling often are used to produce
compressive stresses in metal surfaces, but the magnitude of stress
imposed by peening is sometimes not great enough to overcome the
effects of extremely high local tensile stresses.
Fabrication. High residual tensile stresses sometimes result from
bending, stamping, deep drawing, and other coldforming operations.
Residual tensile stresses of 207 to 414 MPa (30 to 60 ksi) have been
measured on the surfaces of cold bent steel tubes.

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Under some circumstances, severe, uniform cold working improves the
resistance of a metal to stresscorrosion cracking. For example, cold
drawn steel wire is more resistant to stresscorrosion cracking than is
oiltempered wire having equal mechanical properties. Also, cold
reduction of lowcarbon steel to 50% or less of its original thickness
makes it relatively immune to cracking in boiling nitrate solutions at
100 to 200C (212 to 392 F) for thousands of hours.
Assembly. Fitup and assembly operations often are sources of tensile
stresses. Press fitting, shrink fitting, and assembly by welding are
among the major operations in this category.
Forming operations used in assembly to retain components can
produce residual tensile stresses that can induce stresscorrosion
cracking, particularly when the parts are used or stored in a corrosive
When movement of a corrodent over a metal surface increases the
rate of ErosionCorrosion attack due to mechanical wear and
corrosion, the attack is called erosion corrosion. All flowing or
turbulent corrosive media can cause erosioncorrosion.

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Impingement corrosion is a severe form of erosioncorrosion.
Steam erosion is another form of impingement corrosion. It occurs
when highvelocity wet steam contacts a metal surface.
Crevice Corrosion A crevice in a metal surface, at a joint between two
metallic surfaces or between a metallic and a nonmetallic surface, or
beneath a particle of solid matter on a metallic surface, provides
conditions conducive to the development of the type of concentration
cell corrosion called crevice corrosion.
In a metalion concentration cell, the accelerated corrosion occurs at
the edge of or slightly outside of a crevice. .

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Effect of Solid Deposits. In powergeneration equipment, crevice
corrosion failures have occurred in mainstation condenser tubes
cooled with seawater, as a result of the formation of solid deposits and
the attachment of marine organisms to the tube wall; these failures
have occurred particularly in condensers tubed with stainless steel.
Riveted and bolted Joints must be considered as possible sites for
crevice corrosion, and thus they require careful attention in design and
assembly to avoid crevices, as well as provisions to ensure uniform
aeration and moderate but not excessive flow rates at the joints. .

Where a corrosion failure has occurred, economical and practical

measures for prevention of future failures of the same type are

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Extreme temperatures and high operating stresses favor the use of
specialpurpose cast alloys. For example, the tubes in gas reformers are
usually, made of cast heatresisting alloys to obtain maximum life at
operating temperatures of 871 to 1010C . Similarly, the use of highalloy
castings enables turbine engines to operate at higher temperatures (and,
therefore, at higher efficiencies) than weldments would permit.
Solution annealing of austenitic stainless steels minimizes the risk of
intergranular attack and stresscorrosion cracking. For stainless steel
weldments that cannot be annealed and that are to be used in
applications where either intergranular corrosion or intergranular stress
corrosion cracking is of concern ,a quenching procedure can be used. In
this procedure, the weld is rapidly quenched to prevent the precipitation
of the chromium carbides. if the quenching procedure proves ineffective,
either a lowcarbon or a stabilized stainless steel may be substituted,
depending on the tensile requirements.
Acrylics, epoxies, phenolics, furanes, and urethanes are used extensively
for Resinous and Inorganic corrosion protection in the form of paints,
potting compounds, adhesives, Base Coatings coatings, and linings. Their
chemical resistance makes them suitable for many applications.

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However, especially for fairly corrosive immersion service,
consideration must always be given to the possible presence of pinhole
porosity in painttype coatings, which may result in pitting and crevice
corrosion, and to the possibility of accelerated galvanic attack where
dissimilar metals are present.
Sealant materials, if properly applied, are highly effective in preventing
crevice corrosion; if not properly applied. they can make it more likely
to occur.
ZincRich Coatings. Organic and inorganic coatings containing zinc dust
give excellent protection to steel and galvanized structures. They
provide sacrificial protection because the zinc particles are in intimate
contact with one another, so that the coating fihu is electrically
Inert Lubricants Certain chemically inert resins (such as silicones,
esters, and fluorocarbons) can serve both as effective lubricants and as
corrosionresistant coatingsand linings. In seacoast environments,
lubricants frequently must perform this dual role of lubrication and
corrosion protection. The role of corrosion protection is often
overlooked when selecting a lubricant for a specific function, as for
wire rope on exposed sliding surfaces.

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The major types of eletrolytic and chemical coatings and surface
treatments ,include electroplating,anodizing, chemical conversion
coatings, and passivation treat Chemical Coatings and rnents. These
processes vary widely in their effectiveness . Anodic and chemical
conversion coatings also serve as excellent bases for organic coatings.
Anodizing of aluminum and aluminum alloys provides effective
protection in natural environments, but not against aggressive
environments, especially acidic and alkaline environments.
Chemical Conversion Coating. Chromate conversion coatings are
extensively used on steel products that have been electroplated with
cadmium or zinc, and they substantially improve the corrosion
resistance. Similar coatings are also produced by electrolytic
processing, with the parts being made the anode in the electrolytic
chrornisting bath. Chromate coatings however, are very thin and can
readily be removed by abrasion or impact. Local bare areas then may
corrode preferentially.
Chromate, phosphate, and other conversion coatings are also used on
aluminum, magnesium, steel, and other metals, but primarily as a base
to improve the adhesion and protective value of organic coatings to be
applied over them.

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Passivation is common practice in the manufacture of stainless steel
components and assemblies. .
Electro deposition of zinc or cadmium is widely used to protect steel
from Metallic Coatings corrosion. Zinc provides better performance in
industrial areas; cadmium is preferred for marine environments. These
coatings offer sacrificial protection to the steel substrate
Nickel, chromium, and copper are other metals that are readily
applied by electroplating but coatings of these metals are much less
effective than sacrificial coatings in providing corrosion resistance.
Sprayed Metal Coatings. Metal spraying can provide thick protective
coatings. Multiple coatings minimize, but do not completely eliminate,
the occurrence of voids and weak spots in the coatings. Zinc and
aluminum coatings are commonly used.
Cladding can provide thick coatings that arc free of even fine porosity
and, with suitable selection of the cladding metal, give more effective
protection against corrosion of the base metal. Cladding is costly,
however, and cannot be applied to parts of all configurations.

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Galvanic Protection Galvanic protection can be either cathodic
protection (in which the object to be protected is made cathodic) or
anodic protection (in which the object to be protected is made anodic).
The method most commonly used is
Cathodic protection.
Cathodic protection may be of two different types: impressed direct
current or sacrificial anode.
In the impressed direct current type, the structure to be protected is
made the cathode in a directcurrent electrical circuit. The anode in
the circuit is an auxiliary electrode, usually of iron or graphite, located
some distance away from the structure to be protected. The positive
terminal of the source of direct current is connected to the auxiliaiy
electrode, and the negative terminal to the structure to be protected.
Current then flows from the electrode through the electrolyte to the
stmcture, and the structure does not corrode. The applied voltage
need only be high enough to supply an adequate current density to all
parts of the structure to be protected.

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In the sacrificial anode system, the structure to be protected is made
the cathode in a galvaniccorrosion cell, and current is supplied by the
corrosion of anodes that are commonly made of zinc or magnesium.
Voltage and current are limited by the corrosion of the sacrificial
anodes; the number and location of anodes are much more critical in
this method
Anodic Protection. By imposing an external potential to make them
anodic, some metals can be prevented from corroding in an electrolyte
in which they would otherwise be attacked. This technique, which is
called anodic protection, is applicable only to metals and alloys that
show activepassive behavior. It has been applied to iron, titanium,
aluminum, and chromium, but mostly to steel and stainless steel.
Anodic protection is not applicable to zinc, magnesium, cadmium,
silver, copper, and copperbase alloys.

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Anodic versus Cathodic Protection. Anodic and cathodic protection
tend to complement one another; each method has its advantages
and disadvantages. Anodic protection can be used in corrosives
ranging from weak to very aggressive; cathodic protection is restricted
to moderately corrosive conditions because of its high current
requirement, which increases as the corrosivity of the environment
Inhibitors Anodic inhibitors stifle the anodic reaction, usually forming
sparingly soluble substances as adherent protective films. Salts such as
hydroxides, silicates, borates. phosphates, carbonates, andbenzoates
are effective on steel only in the presence of dissolved oxygen.
Cathodic inhibitors stifle the cathodic reaction, either by restricting the
access of oxygen or by poisoning sites favorable for cathodic
hydrogen evolution. Cathodic inhibitors that decrease the corrosive
action of aqueous solutions on steel include salts of magnesium,
manganese, zinc, and nickel. l

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Changes in pH and Applied Potential
Pourbaix diagrams indicate the
conditions for which diffusion bather
films may form on an electrode
surface, but they provide no measure
of how effective r films may be in the
presence of specific anions .
A Pourbaix diagram for iron in water
and dilute aqueous solutions is shown
in Figure 20. Note that there are zones
of corrosion, immunity from
corrosion, and passivity.

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Continuous monitoring of critical variables in both batch operations
and Continuous Monitoring process streams is a valuable tool .
Some of the variables monitored and their applications are noted
and described below.
Electrical Resistance (ER).
Linear Polarization Resistance (LPR).
Electrical Conductivity. The corrosion rate of many metals in organic
systems increases significantly if a corrodenc is present and the
electrical conductivity increases above IO mho.
Continuous Chemical Analysis.

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