Corrosion Engineering

Lecture
on
Types of Corrosion
Prepared by:
Dr. U. Achutha Kini
Mr. Suhas Y. Nayak

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4. TYPES OF CORROSION
Uniform Corrosion:
This is also called general corrosion. The surface effect produced by most direct chemical
attacks (e.g., as by an acid) is a uniform etching of the metal. On a polished surface, this type
of corrosion is first seen as a general dulling of the surface and, if allowed to continue, the
surface becomes rough and possibly frosted in appearance. The discoloration or general
dulling of metal created by its exposure to elevated temperatures is not to be considered as
uniform etch corrosion. The use of chemical-resistant protective coatings or more resistant
materials will control these problems. While this is the most common form of corrosion, it is
generally of little engineering significance, because structures will normally become
unsightly and attract maintenance long before they become structurally affected. This leads
to relatively uniform thinning on sheet and plate materials and general thinning on one side
or the other (or both) for pipe and tubing. It is recognized by a roughening of the surface
and usually by the presence of corrosion products. The mechanism of the attack typically is
an electrochemical process that takes place at the surface of the material. Differences in
composition or orientation between small areas on the metal surface create anodes and
cathodes that facilitate the corrosion process. Most often caused by misapplying materials
in corrosive environments, general corrosion often can be tolerated because the effect of
metal loss is relatively easy to assess and allowances can be made in the initial design.
Protective coatings are particularly effective in controlling uniform corrosion. Uniform
corrosion or general corrosion, as sometimes called, is defined as a type of corrosion attack
(deterioration) that is more or less uniformly distributed over the entire exposed surface of
a metal. Uniform corrosion refers to the corrosion that proceeds at approximately the same
rate over the exposed metal surface. Cast irons and steels corrode uniformly when exposed
to open atmospheres, soils and natural waters, leading to the rusty appearance. In natural
environment, oxygen is the primary cause of uniform corrosion of steels and other metals
and alloys. General attack corrosion accounts for the greatest amount of metal destruction
by corrosion, but is considered as a safe form of corrosion, due to the fact that it is
predictable, manageable and often preventable.

Mechanism
The anodic reaction in the corrosion process is always the oxidation reaction:
= ++ e
In acidic environments, i.e., pH<7, the cathodic process is mainly the reduction of hydrogen
ions:
2 + + 2e = H2
In alkaline or neutral environment, i.e., pH=7 or pH>7, reduction of the dissolved oxygen is
the predominant cathodic process that causes uniform corrosion:
O2+2 2O+4 = 4 −
The cathodes and anodes are located randomly and alternating with time. The end result is
more or less uniform loss of dimension.
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Prevention
 Uniform corrosion can be prevented by using the following methods:
 Selection of a more corrosion resistant alloy
 Use thicker materials for corrosion allowances.
 Replace with corrosion resistant non-metallic material.
 Use paints or metallic coatings such as plating, galvanizing or anodizing.
 Use corrosion inhibitors or modifying the environment.
 Cathodic protection (Sacrificial anode or impressed current method).
 Anodic protection.

Galvanic Corrosion/ Two Metal/ Bimetallic Corrosion

Galvanic corrosion is an electrochemical action of two dissimilar metals in the presence of
an electrolyte and an electron conductive path. It occurs when dissimilar metals are in
contact. It is recognizable by the presence of a buildup of corrosion at the joint between the
dissimilar metals. For example, when aluminum alloys or magnesium alloys are in contact
with steel (carbon steel or stainless steel), galvanic corrosion can occur and accelerate the
corrosion of the aluminum or magnesium. A potential difference usually exists between two
dissimilar metals when they are immersed in a corrosive or conductive solution. If these
metals are placed in contact (or else electrically connected), this potential difference
produces electron flow between them. Corrosion of the less corrosion resistant metal is
usually increased and the attack of the more corrosion resistant metal is decreased, as
compared with the behaviour of these metals when they are not in contact. The less
resistant metal becomes anodic and more resistant metal becomes cathodic. Usually
cathodic metal or cathode corrodes very little or not at all. The driving force for current and
corrosion is the potential developed between the two metals.
In galvanic corrosion polarization of the reduction reaction (Cathodic polarization) usually
predominates. Since the degree of cathodic polarization and its effectiveness varies with
different metals and alloys, it is necessary to know something about their polarization
characteristics before predicting the extent or degree of galvanic corrosion for a given
couple. The nature and aggressiveness of the environment determine to a large extent the
degree of two metal corrosion. Usually the metal with lesser resistance to the given
environment becomes the anodic member of the couple. Sometimes the potential reverses
for a given couple in different environments. Galvanic corrosion also occurs in the
atmosphere. The severity depends largely on the type and amount of moisture present.
Example: Corrosion is greater near the sea shore than in a dry rural atmosphere.
Condensate near the seashore contains salt and therefore is more conductive (and
corrosive) and a better electrolyte than condensate in an inland location, even under equal
humidity and temperature conditions. Galvanic corrosion does not occur when the metals
are completely dry since there is no electrolyte to carry the current between the two
electrode areas. Accelerated corrosion due to galvanic effects is usually greatest near the
junction, with attack decreasing with increasing distance from that point. The distance
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affected depends on the conductivity of the solution. Another important factor in galvanic
corrosion is the area effect, or the ratio of the cathodic to anodic areas. An unfavorable area
ratio consists of a large cathode and a small anode. The greater the current density at the
anodic area greater is the corrosion rate.

Mechanism
Following fundamental requirements are to be met for galvanic corrosion to occur:
 Dissimilar metals (or other conductors, such a graphite).
 Electrical contact between the dissimilar conducting materials (can be direct contact or a
secondary connection such as a common grounding path).
 Electrolyte (the corrosive medium) in contact with the dissimilar conducting materials.
 Different metals and alloys have different electrochemical potentials (or corrosion
potentials) in the same electrolyte.
When the corrosion potentials of the various metals and alloys are measured in a common
electrolyte (eg. Natural sea water) and are listed in an orderly manner (descending or
ascending) in a tabular form, a galvanic series is created. It should be emphasized that the
corrosion potentials must be measured for all metals and alloys in the same electrolyte
under the same environmental conditions (temperature, pH, flow rate etc.), otherwise, the
potentials are not comparable. The potential difference between two dissimilar metals is
the driving force for the destructive attack on the active metal (anode). Current flows
through the electrolyte to the more noble metal (cathode) and the less noble metal (anode)
will corrode. The conductivity of the electrolyte will also affect the degree of attack. The
cathode to anode area ratio is directly proportionate to the acceleration factor.

A collection of factors affecting galvanic corrosion of metals presented by J. W. Oldfield

includes the following:
Type of joint:
Welded, fasteners, separated but with external connection.
Total geometry:
Area ratio, distances involved, surface shape, surface condition, number of galvanic cells.
Bulk solution properties:
Oxygen content, pH, conductivity, corrosivity, pollutant level.
Bulk solution environment:
Temperature, flow rate, volume, height above surface.
Mass Transport:
Migration, diffusion, convection
Protective film characteristics:
Dependence on electrolyte conditions and potentials
Reaction kinetics:
Metal dissolution, oxygen reduction overvoltage, hydrogen evolution overvoltage

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Prevention
Some of the practices used to prevent galvanic corrosion are given below:
 Select combinations of metals as close together as possible in the galvanic series.
 Avoid the unfavorable area effect on a small anode and large cathode.
 Insulate dissimilar metals wherever practicable. It is important to insulate the metals
completely if possible.
 Apply coatings with caution. Keep the coatings in good repair, particularly the one on the
anodic member.
 Add inhibitors, if possible, to decrease the aggressiveness of the environment.
 Avoid threaded joints for materials far apart in the galvanic series.
 Design for the use of readily replaceable anodic parts or make them thicker for long life.
 Install a third metal that is anodic to both metals in galvanic contact.
Beneficial applications:
Galvanic corrosion has several beneficial or desirable applications
 Cathodic protection – It is simply the protection of the metal structure by making it the
cathode in the galvanic cell.
Example: Galvanized steel The zinc coating is put on steel not because it is corrosion
resistant but because it is not.
The zinc corrodes preferentially and protects the steel. Zinc acts as a sacrificial anode.
 Cleaning silver : Cleaning of silverware in the home.
Most household silver is cleaned by rubbing with an abrasive.
This removes silver and particularly bad for silver plate because the plating is eventually
removed.
A simple electrochemical cleaning method consists of placing the silver in an aluminium
pan containing water and baking soda.
The current generated by the contact between silver and aluminium causes silver sulfide
to be reduced back to silver, no silver is actually removed

Pitting Corrosion
Pitting corrosion is localized corrosion that occurs at microscopic defects on a metal surface.
The pits are often found underneath surface deposits caused by corrosion product
accumulation. However, if corrosion does occur, it forms at random in pits. Pitting is most
likely to occur in the presence of chloride ions, combined with such depolarizers as oxygen
or oxidizing salts. Methods that can be used to control pitting include maintaining clean
surfaces, application of a protective coating, use of inhibitors or cathodic protection for
immersion service. Molybdenum additions to stainless steel are intended to reduce pitting
corrosion. Effect of molybdenum is to block active sites at the surface. This blocking reduces
the amount of aggressive chloride ions at active sites, and thereby increases the resistance
to chloride attack. Pitting results in holes in the metal. These holes may be small or large in
diameter, but in most cases they are relatively small. Pits are sometimes isolated or so close
together that they look like a rough surface. Pit may be described as a cavity or hole with
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the surface diameter about the same as or less than the depth. Pitting causes equipment to
fail because of perforation with only a small percent weight loss of the entire structure.
It is often difficult to detect pits because of their small size and because the pits are often
covered with corrosion products. In addition, it is difficult to measure quantitatively and
compare the extent of pitting because of the varying depths and numbers of pits that may
occur under identical conditions. Pitting is particularly vicious because it is a localized and
intense form of corrosion, and failures often occur with extreme suddenness.
Pitting usually requires an extended initiation period before visible pits appear. This period
ranges from months to years, depending on both the specific metal and the corrosive
medium. Once started, however, a pit penetrates the metal at an ever increasing rate. In
addition pits tends to undermine or undercut the surface as they grow. Pits usually grow in
the direction of gravity. Most pits develop and grow downward from horizontal surfaces.
Lesser number start on vertical surfaces, and only rarely do pits grow from the bottom of
horizontal surfaces.
A corrosion pit is an unique type of anodic reaction. It is an autocatalytic process. That is,
the corrosion processes within a pit produce conditions which are both stimulating and
necessary for the continuing activity of the pit. The gravity effect of pitting mentioned
before is a direct result of the autocatalytic nature of pitting. Since the dense, concentrated
solution within a pit is necessary for its continuing activity, pits are more stable when
growing in the direction of gravity. Also, pits are generally initiated on the upper surfaces of
the specimens before chloride ions are more easily retained under these conditions. Even
though, it appears that pitting quite similar to crevice corrosion, deserves special
consideration since it is a self-initiating form of crevice corrosion. Simply, it does not require
a crevice, but creates its own crevice/hole.
Pitting is usually associated with stagnant conditions such as a liquid in a tank or liquid
trapped in a low part of an inactive pipe system. Velocity or increasing velocity, often
decreases pitting attack. Ordinary steel is more resistant to pitting than stainless steel alloys.
Although the general corrosion of steel is much greater than of stainless steel, rapid
perforation due to pitting does not occur.
Surface finish has a marked effect on pitting resistance. Pitting and localized corrosion are
less likely to occur on a polished surface than on etched or ground surfaces. Materials that
show pitting, or tendencies to pit, during corrosion tests should not be used to build the
plant or equipment under consideration.
Some materials are more resistant to pitting than others. Addition of molybdenum to 304
and 316 SS results in a very large increase in resistance to pitting. Adding inhibitors is
sometimes helpful, but this may be a dangerous procedure unless attack is stopped
completely. If it is not, intensity of the pitting may be increased. Researchers have found
that the environment inside the rust bubbles is almost always higher in chlorides and lower
in pH (more acidic) than the overall external environment. This leads to concentrated attack
inside the pits. Similar changes in environment occur inside crevices, stress corrosion cracks,
and corrosion fatigue cracks. All of these forms of corrosion are sometimes included in the

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term "occluded cell corrosion." Pitting corrosion can lead to unexpected catastrophic system
failure. Sometimes pitting corrosion can be quite small on the surface and very large below
the surface. Uniform or pitting corrosion not directly associated with galvanic corrosion
mechanisms, and is often called “stand-alone corrosion.”

Pitting corrosion is characterized by the following features:

 The attack is spread over small discrete areas. Pits are sometimes isolated and sometimes
close together, giving the area of attack a rough appearance.
 Pits usually initiate on the upper surface of the horizontally placed parts and grow in the
direction of gravity.
 Pitting usually requires an extended initiation period before visible pits appear.
 Conditions prevailing inside the pit make it self-propagating without any external
stimulus. Once initiated, the pit grows at an ever increasing rate.
 Stagnant solution conditions lead to pitting.
 Stainless steels, aluminum, and their alloys are particularly susceptible to pitting.
 Carbon steels are more resistant to pitting than stainless steels.
 Most failures of stainless steels occur in neutral-to-acid chloride solutions.
 Aluminum and carbon steels pit in alkaline chloride solutions.
 Most pitting is associated with halide ions (chlorides, Bromides) and hypochlorites, which
are particularly aggressive.
 Cupric, ferric, and mercuric halides are extremely aggressive because their cations are
cathodically reduced and sustain attack.
Mechanism
In order for pitting to take place, the formation of an anode is a prerequisite. With the
formation of an anode, a local corrosion cell is developed. The anode may be formed as a
result of
(a) lack of homogeneity at the metal corrosive interface, caused by impurities, grain
boundaries, niches, rough surface, etc. The difference in the environments can
cause, the formation of concentration cells on the metal surface.

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(b) destruction of a passive film. The destruction of a passive film results in the
formation of a small anode. Therefore, a breakthrough of the protective film on the
metal surface results in several anodic sites and the surrounding surface acts as a
cathode. Thus, an unfavorable area ratio results.
(c) deposit of debris or solids on the metal surface. This generally leads to the formation
of anodic and cathodic sites.
(d) formation of an active-passive cell with a large potential difference. The formation of
a small anode on the passive steel surface, for instance, leads to the formation of
the above cell.
Factors affecting Pitting
(1) Surface defects, such as inclusions, second phases and surface heterogeneity, have been
identified with initiation of pits. It has been established that sulfide inclusions are mainly
responsible for pitting of carbon and stainless steels.
(2) Degree of cold work: Severe cold working increases pitting susceptibility as shown by
austenitic steels in ferric chloride solution.
(3) Surface finish: A smooth surface does not allow accumulation of impurities and
stagnancy to be built up on the metallic surface, thus minimizing the risk for the formation
of differential aeration cells and minimizing corrosion and pitting. However, the pits which
are formed on a smooth and shiny surface are deeper and larger compared to a rough
surface.
4) Sensitizing temperature: The temperature zone which promotes intergranular corrosion
of steels also promotes pitting, because of the weakening of grain boundaries.
(5) Velocity: Pits are often associated with stagnant conditions. High velocity may cause
passivation of the steel surface by greater control of the oxygen with the steel surface, thus
enabling the integrity of the passive film to be maintained.
(6) Environmental contamination. An environment contaminated by dust particles would be
more conducive to pitting. Dust particles on metals absorb moisture and lead to the
formation of differential aeration cells. Salt particles in a marine environment when
deposited on a metal surface lead to intensive pitting of equipment and appliances.
Prevention
(1) Use materials with appropriate alloying elements designed to minimize pitting
susceptibility, e.g. molybdenum in stainless steel.
(2) Provide a uniform surface through proper cleaning, heat treating and surface finishing.
(3) Reduce the concentration of aggressive species in the test medium, such as chlorides,
sulfates, etc.
(4) Use inhibitors to minimize the effect of pitting, wherever possible.
(5) Make the surface of the specimen smooth and shiny and do not allow any impurities to
deposit on the surface.
(6) Minimize the effect of external factors on those design features that lead to the localized
attack, such as the presence of crevices, sharp corners, etc.
(7) Apply cathodic protection, wherever possible.

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(8) Coat the metals to avoid the risk of pitting.

(9) Do not allow the potential to reach the critical value.
(10) Add anions, such as OH- or NO3- to chloride environment.
(11) Operate at a lower temperature, if service conditions permit

Crevice Corrosion
Crevice or contact corrosion is the corrosion produced at the region of contact of metals
with metals or metals with nonmetals. It may occur at washers, under barnacles, at sand
grains, under applied protective films, and at pockets formed by threaded joints. Whether
or not stainless steels are free of pit nuclei, they are always susceptible to this kind of
corrosion because a nucleus is not necessary. Cleanliness, the proper use of sealants, and
protective coatings are effective means of controlling this problem. Molybdenum-containing
grades of stainless steel (e.g. 316 and 316L) have increased crevice corrosion resistance.
Intensive localized corrosion frequently occurs within crevices and other shielded areas on
metal surfaces exposed to corrosives.
This type of attack is usually associated with small volumes of stagnant solutions caused by
holes, gasket surfaces, lap joints, surface deposits, and crevices under bolt and rivet heads.
As a result this form of corrosion is called crevice corrosion or, sometimes, deposit or gasket
corrosion. Contact between metal and non-metal surfaces can cause crevice corrosion as in
the case of gasket, wood, plastic, rubber, glass, concrete, wax, asbestos and fabrics.
Examples of deposits that may produce crevice corrosion are sand, dirt, corrosion products
and other solids. The deposit acts as a shield and creates a stagnant condition thereunder.
To function as a corrosion site, the crevice must be wide enough to permit liquid entry but
sufficiently narrow to maintain a stagnant zone. For this reason, crevice corrosion usually
occurs at openings a few thousandth of an inch or less in width. It rarely occurs within wide
grooves or slots.
Causes
(a) Presence of narrow spaces between metal-to-metal or non-metal to metal components.
(b) Presence of cracks, cavities and other defects on metals.
(c) Deposition of barnacles, biofouling organisms and similar deposits.
(d) Deposition of dirt, mud or other deposits on a metal surface.
Factors
Factors affecting crevice corrosion:
(a) Crevice type.
(b) Alloy composition.
(c) Passive film characteristics.
(d) Geometry of crevice.
(e) Bulk composition of media.
(f) Bulk environment.
(g) Mass transfer in and out of crevice.
(h) Oxygen.

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a) Crevice Type
Crevice type means whether the crevice is between metal-to-metal, metal to non-metal or a
marine growth, like barnacles or other marine biofouling organisms, on the metal surface.
It is important to know whether factors affecting crevice are man-made or natural in order
to select appropriate methods for prevention.

b) Alloy Composition
It is important to know whether or not the alloy is resistant to crevice corrosion.
For instance, work on the various grades of steels, such as SS 304, carpenter alloy, Incoloy
(Alloy 825), Hastelloy (Alloy g), and Inconel (625) showed that the later two alloys were
highly resistant to crevice corrosion in ambient and elevated temperature seawater.
The alloying elements in various grade of steel affect both the electrochemical and chemical
processes, such as hydrolysis, passive film formation, passive current density and metal
dissolution. Hence, the effect of major alloying elements, such as Fe, Cr, Ni and Mo and Fe-
Cr-Ni-Mo class of steels on crevice corrosion initiation is important.
It has been shown that iron, chromium, nickel and Mo improve the resistance of steels to
crevice corrosion. It has been shown that iron, chromium, nickel and Mo improve the
resistance of steels to crevice corrosion. Incoloy (825) - nickel-iron-chromium alloy with
additions of molybdenum. Hastelloy (alloy g 30)- high chromium nickel-base alloy which
shows superior corrosion resistance over most other nickel and iron-base alloys. Inconel
(625) - Nickel-Chromium-Molybdenum alloy with excellent corrosion resistance in a wide
range of corrosive media. Carpenter alloy – High performance alloys.

(c) Passive Film Characteristics

The type of passive film formed is important, as the breakdown of a passive film results in
the onset of crevice corrosion. The improved performance of certain steels can be
attributed to enrichment of the surface film by chromium. The quality of surface films
affects the susceptibility of steels to crevice corrosion. The formation of passive films is
dependent on oxygen and hence, its concentration affects the magnitude of crevice
corrosion. It has been reported that as the seawater temperature is raised from ambient to
70° C, the resistance of steel types 304 and 317 is increased. This has been attributed to the
enrichment of the passive film by chromium which increases its stability.

(d) Geometry of Crevice

The magnitude of crevice corrosion also depends on the depth of the crevice, width of the
gap, number of crevices and ratio of exterior to interior crevice. It has been shown for types
316 and 304 stainless steel that smaller the gap, the less is the predicted time for initiation
of crevice corrosion. The reason is that when the ratio of crevice solution volume to creviced
area is small, the acidity is increased and the critical value for initiation of crevice is achieved
rapidly. The ratio of the bold area to the creviced area also affects crevice corrosion.
Generally, the larger is the bold area (cathodic) and smaller the creviced area (anodic), the

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larger is the probability of crevice corrosion. This has been shown by work on types 304 and
316 stainless steel and Incoloy alloy 825. If the depth is increased, acidity is also increased in
the crevice.

(e) Effect of Temperature

The rate of crevice corrosion propagation of stainless steel alloys, such as types 304 and
316, is decreased in natural seawater, when the temperature is increased from ambient to
70°C. The tendency for initiation of crevice corrosion is not affected by increase in
temperature. The above trend may be attributed to the decreased solubility of oxygen with
increased temperature and changes in the nature of the passive film which is formed.

(f) Bulk Solution Composition

The breakdown of a passive film on a metal surface largely depends on the aggressiveness
of the electrolyte. All chloride containing solutions are highly aggressive and contribute to
onset of crevice corrosion. Seawater and brackish water are high aggressive and promote
crevice corrosion of steels.

(g) Mass Transfer in and out of Crevice

There are three forms of mass transport: migration, diffusion and convection. Most of the
current is carried by migration and diffusion. The process of bringing chloride ions increases
the concentration of chloride ions in the small crevice, hence, the aggressiveness of the
electrolyte inside the crevice is increased. The solution at a stage becomes highly acidic and
the pH is lowered.

(h) Oxygen
The onset of crevice corrosion is strongly linked with the nature of the passive film on the
metal surface. If the passive film is very stable, crevice corrosion is blocked. Oxygen is
essential for the formation of passive film on the metal surface. Hence, it has an important
influence on the onset of crevice corrosion. As oxygen is consumed within the crevice, a
potential difference is set up between the creviced areas and the boldly exposed areas open
to oxygen. A differential concentration is, therefore, set up which accelerates oxygen.
However, as the temperature is increased, oxygen solubility decreases which retards the
crevice process. The exact relationship between oxygen and temperature is not clearly
understood.

Mechanism
Most of the mechanism is based on certain type of concentration cells. The following is a
summary of some of the concentration cell mechanisms, which have contributed to the
understanding of the mechanism of crevice corrosion.

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Metal ion concentration cells.

According to this old theory, a difference in metal ions exists between the crevice and
outside, hence, a corrosion cell is formed. The area with low metal concentration becomes
the anode and other, the cathode. Anodic dissolution at the anode, therefore, initiates.
Differential Aeration Theory
A high concentration of oxygen on the surface outside the crevice and a low oxygen
concentration inside a crevice creates a differential aeration cell, which initiates crevice
corrosion.

Prevention
Methods and procedures for combating crevice corrosion are as follows:
(1) Use welded joints instead of bolted or riveted joints.
(2) Seal crevices by using non-corrosive materials.
(3) Eliminate or minimize crevice corrosion at the design stage.
(4) Minimize contact between metals and plastic, fabrics and debris.
(5) Avoid contact with hygroscopic materials.
(6) Avoid sharp corners, edges and pockets where dirt or debris could be collected.
(7) In critical areas, use weld overlays with highly corrosion resistant alloy.
(8) Use alloys resistant to crevice corrosion, such as titanium or Inconel. Increased Mo
contents (up to 4.5%) in austenitic stainless steels reduce the susceptibility to crevice
corrosion. Use appropriate alloy after prescribed service tests for a specific application.
(9) Apply cathodic protection to stainless steels by connecting to adjacent mild steel
structure.
(10) For seawater service, maintain a high velocity to keep the solids in suspension.
(11) For better performance of steels in seawater, allow intermittent exposure to air to
allow the removal of protective films.
(12) Use inhibiting paste, wherever possible.
(13) Paint the cathodic surface.
(14) Remove deposits from time to time.
(15) Take precautions against microbial corrosion, which creates crevices and is very
damaging to low Mo stainless steels.

Intergranular Corrosion
It has been defined commonly as a form of localized attack on the grain boundaries of a
metal or alloy in corrosive media, which results in the loss of strength and ductility. The
localized attack may lead to dislodgment of the grain. It works inwards between the grains
and causes more loss of strength than the same total destruction of metal uniformly
distributed over the whole surface. The attack is distributed over all the grain boundaries
cutting the surface. Intergranular corrosion is less dangerous than stress corrosion, which
occurs when stress acts continuously or cyclically, in a corrosive environment, producing

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cracks following mostly intergranular paths. The difference between the two, i.e.
intergranular corrosion and stress corrosion cracking is important.
There are many materials which are susceptible to intergranular corrosion and not to stress
corrosion cracking. The attack is very common on stainless steel, nickel and aluminum
alloys. Metals are crystalline materials. They consist of grains. As corrosion proceeds along
the grain boundaries, the grains become weaker particularly at the grain boundaries and
they eventually disintegrate.
Intergranular corrosion is an attack on or adjacent to the grain boundaries of a metal or
alloy. A highly magnified cross section of most commercial alloys will show its granular
structure. This structure consists of quantities of individual grains, and each of these tiny
grains has a clearly defined boundary that chemically differs from the metal within the grain
center.
Intergranular corrosion can be caused by impurities at the grain boundaries, enrichment of
one of the alloying elements, or depletion of one of these elements in the grain boundary
areas. Small amounts of iron in aluminium, wherein the solubility of iron is low, have been
shown to segregate in the grain boundaries and cause intergranular corrosion. Depletion of
chromium in the grain boundary regions results in intergranular corrosion of stainless steel.
Die cast zinc alloys containing aluminium exhibit intergranular corrosion by steam and
marine atmosphere.
Mechanism
The following three steps illustate the mechanism of intergranular corrosion of austenitic
steels:
(1) Sensitization in the temperature range 550-900° C.
(2) Diffusion of carbon to a grain boundary and formation of carbide. This leads to depletion
of chromium content along the grain boundary.
(3) Weakening of the grain boundary and disintegration of the grains.

The stabilized austenitic stainless steels are attacked intergranularly, under certain
conditions, because of chromium carbide precipitation.
Following three methods are used to control or minimize intergranular corrosion of the
austenitic stainless steels:
 Employing high temperature solution heat treatment, commonly termed as quench
annealing or solution quenching.
 Adding elements that are strong carbide formers (called stabilizers).
 Lowering the carbon content to below 0.03 %.

Stress Corrosion Cracking

Stress corrosion cracking (SCC) is caused by the simultaneous effects of tensile stress and a
specific corrosive environment. Stresses may be due to applied loads, residual stresses from
the manufacturing process, or a combination of both. Cross sections of SCC frequently show
branched cracks. This river branching pattern is unique to SCC and is used in failure analysis

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to identify when this form of corrosion has occurred. Cracking generally proceeds
perpendicular to the applied stress. The cracks appear to be randomly oriented. Depending
upon the metal structure and the environmental composition, crack morphology can vary
from a single crack to extreme branching. In some cases, the cracks are virtually without
branches and in other cases they exhibit multi-branched “river delta” patterns. SCC of an
insulated stainless-steel condensate line is quite common. Water wetted the insulation and
caused chlorides to leach from the insulation onto the hot metal surface. This is a common
problem on steam and condensate lines. Control is by maintaining the jackets around the
lines so that moisture doesn't enter the insulation or is quickly drained off.
Cross sections of SCC frequently show branched cracks. This river branching pattern is
unique to SCC and is used in failure analysis to identify when this form of corrosion has
occurred.
Several years ago, wide spread use of plastic tubing was started in new house construction
and for repair of old systems. Flexible tubing was used to connect faucets to the fixed metal
piping. Flexible plastic piping is now used less often in this service-especially for hot water
service as it is found to be susceptible to SCC.
Characteristics
(1) Stress, either residual or applied, is required. There is a simultaneous action of stress and
corrosion.
(2) Generally all alloys are susceptible to SCC, however, there are a few pure metals which
have been observed to undergo SCC, such as 99.999% Cu and high purity iron.
(3) SCC of a specific alloy is caused by only a few chemical species in the environment.
(4) There is a period called “induction period” which is necessary to produce crack initiation,
similar to the induction period required for producing pitting.
(5) Conditions of cracking are specific to alloy and environment. An alloy maybe corroded in
one corrosive medium while it may not under SCC. All the specific environments for a
particular alloy are not known.
(6) The mode of cracking may be intergranular or transgranular. The transition from
intergranular to transgranular depends upon factors, such as heat treatment, corrosive
medium, stress level and temperature.
(7) The rate of attack is very rapid at the crack tip and very low at sides of the crack.
(8) There is a particular corrosion reaction critical for SCC to occur.
Requirements for SCC:
The following conditions are necessary for SCC to occur:
(1) A susceptible metal/alloy.
(2) A specific environment.
(3) A tensile or residual stress.

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Figure 1: SCC Triangle

Types of SCC:
(a) Chloride stress corrosion cracking. It occurs in austenitic steels under tensile stress in
the presence of oxygen, chloride ion and high temperature.
(b) Caustic stress corrosion cracking. Cracking of steels in caustic environments where the
hydrogen concentration is high, for instance, cracking of Inconel tubes in alkaline solutions.
(c) Sulfide stress corrosion cracking. Cracking of steels in hydrogen sulfide environment as
encountered in oil drilling industry.
(d) Seasonal cracking. The term is now obsolete. It had a historical significance only. It refers
only to SCC of brass in ammoniacal environment, but still occasionally occurs in refrigeration
plant using ammonia refrigerant.

Two classic cases of SCC are: Season cracking of brass and Caustic embrittlement of steel.
1. Season cracking refers to the SCC failures of the brass cartridge cases.
During periods of heavy rainfall, cracks were observed in the brass cartridge cases at the
point where the case was crimped to the bullet. It was later found that the important
environmental component in season cracking was ammonia, resulting from the
decomposition of organic matter.
2. Many explosions of riveted boilers occurred in early steam driven locomotives.
Examination of these failures showed cracks or brittle failures at the rivet holes. These areas
were cold worked during riveting operations, and the analysis of whitish deposits found in
these areas showed caustic or sodium hydroxide, to be the major component. Hence, brittle
fracture Caustic embrittlement.
Not all metal- environment combinations are susceptible to cracking.
For example:
 Stainless steels crack in chloride environments but not in ammonia containing
environments, whereas brasses crack in ammonia containing environments but not in
chloride environments.
 Stainless steels do not crack in sulfuric acid, nitric acid, acetic acid, or pure water, but they
do crack in chloride and caustics.
 The important variables affecting SCC are temperature, solution composition, metal
composition, stress, and metal structure.

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Cracking generally proceeds perpendicular to the applied stress.

The cracks appear to be randomly oriented. Cracks vary in the degree of branching. In some
cases, the cracks are virtually without branches and in other cases they exhibit multi-
branched “river delta” patterns. Depending upon the metal structure and the environmental
composition, crack morphology can vary from a single crack to extreme branching.
Increasing the stress decreases the time before cracking occurs.
For each alloy environment combination there is probably an effective minimum, or
threshold, stress. This threshold value must be used with considerable caution since
environmental conditions may change during operation. The minimum stress depends on
temperature, alloy composition, and the environmental composition. The criteria for the
stresses are simply that they be tensile and of sufficient magnitude. These stresses may be
due to any source: applied, residual, thermal, or welding. In fact there are numerous cases
of SCC observed in which there is no externally applied stress. As stress corrosion cracks
penetrates the material, the cross sectional area is reduced and the final cracking failure
results entirely from mechanical action. At present there appears to be no general pattern
to the environment that cause SCC of various alloys. SCC is well known in various aqueous
mediums, but it also occurs in certain liquid metals, fused salts, and non-aqueous inorganic
liquids.
The presence of oxidizers often has a pronounced influence on cracking tendencies.
In fact, the presence of dissolved oxygen or other oxidizing species is critical to the cracking
of austenitic stainless steels in chloride solutions, and if the oxygen is removed, cracking will
not occur. As is the case of most chemical reactions, SCC is accelerated by increasing
temperature. The susceptibility of stress corrosion cracking is affected by the average
chemical composition, preferential orientation of grains, composition and distribution of
precipitates, dislocation interactions, and progress of the phase transformation. These
factors further interact with the environmental composition and stress to affect time to
cracking, but these are secondary considerations. Corrosion plays an important role in the
initiation of cracks. A pit, trench or other discontinuity on the surface of the metal acts as a
stress raiser. SCC’s are observed to start at the base of the pit.

Methods of prevention of SCC

1. Lowering the stress below the threshold value if one exists. Done by annealing, thickening
the section or reducing the load.
2. Eliminating the critical environmental species by, for example, degasification,
demineralization, distillation etc.
3. Changing the alloy is one possible recourse if neither the environment nor the stress can
be changed.
4. Applying the cathodic protection to the structure with an external power supply or
consumable anodes.
5. Adding inhibitors to the system if feasible.

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6. Coatings are sometimes used, and they depend on keeping the environment away from
the metal. For example, coating vessels and pipes that are covered with insulation
7. Shot peening (or shot blasting) produces residual compressive stresses in the surface of
the metal. Peening of cracked surfaces is not recommended.

Corrosion Fatigue
Corrosion fatigue is a special case of stress corrosion caused by the combined effects of
cyclic stress and corrosion. No metal is immune from some reduction of 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. Control of
corrosion fatigue can be accomplished by either lowering the cyclic stresses or by corrosion
control. The "beach marks" on the propeller shown below mark the progression of fatigue
on this surface. The high magnification scanning electron microscope image shows striations
(individual crack progression marks). Fatigue is defined as the tendency of the metal to
fracture under repeated cyclic stressing. Usually, fatigue failures occur at stress levels below
the yield point after many cyclic applications of this stress. Studies have shown that during
the propagation of a fatigue crack through a metal, the frequent cyclic stressing tends to
hammer or pound the fractured surface smooth. A crack propagates until the cross sectional
area of the metal is reduced to the point where the ultimate strength is exceeded and rapid
brittle failure occurs. The surface of the brittle fracture usually has a roughened appearance.
Corrosion fatigue is defined as the reduction of fatigue resistance due to the presence of a
corrosive medium. Thus the corrosion fatigue is not defined in terms of the appearance of
the failure, but in terms of mechanical properties. There is usually a large area covered with
corrosion products and a smaller roughened area resulting from the final brittle fracture. It
is important to note that the presence of corrosion products at a fatigue fracture point does
not necessarily indicate corrosion fatigue. Superficial rusting can occur during ordinary
fatigue fracture, and the presence of rust and other corrosion products does not necessarily
mean that fatigue life has been affected. Corrosion fatigue is probably a special case of SCC.
However, the mode of fracture and the preventive measures differ and is justifiable to
consider it separately. Renewed attention has been given to corrosion fatigue because of
potential catastrophic failures in aerospace, nuclear, and marine structures. Extensive
testing and detailed theoretical studies have been conducted. Corrosion fatigue resistance is
markedly affected by the stress cycle frequency. Corrosion fatigue is most pronounced at
low stress frequencies. Low stress frequency cycles result in greater contact between metal
and corrosive. Corrosion fatigue is also influenced by the corrosive to which the metal is
exposed. Oxygen content, temperature, pH, and solution composition influence corrosion
fatigue.
Corrosion fatigue is a process in which a metal fractures by fatigue prematurely under
conditions of simultaneous corrosion and repeated cyclic loading at lower stress levels than
would be otherwise required in the absence of a corrosive environment. Metals and alloys
will crack in the absence of corrosion if they are subject to high cyclic stress for a number of

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cycles. The number of cycles for failure decreases as the stress is increased. Below a certain
stress the metal will last indefinitely. This level is termed as 'Endurance Limit' of the
material. If, however, the material under cyclic stress is subject to a corrosive environment,
the endurance limit of the material is sharply reduced. The premature failure of a material
from the exposure to the combined action of corrosion and cyclic stress is called 'Corrosion
Fatigue’.
Some major examples where corrosion fatigue is encountered are given below:
(1) Ships
(2) Offshore platforms
(3) Drilling rigs
(4) Navigation tuners
(5) Aircrafts
(6) Submarine pipelines
(7) Communication equipments
(8) Heat exchanger tubes
(9) Pump shafts
(10) Alternate dry and wet zones.

Characteristics
(a) The main distinguishing feature of corrosion fatigue cracks is the presence of several
cracks near the fracture. In a normal fatigue failure, usually one crack is present.
(b) The corrosion fatigue cracks run parallel to each other and are aligned perpendicular to
the direction of principal stress.
(c) Corrosion fatigue cracks in carbon steels often propagate generally from the base of
corrosion pits.
(d) Generally, the fatigue corrosion cracks in certain steels are transgranular in nature.
(e) The striations formed in corrosion fatigue failure are less pronounced than in normal
fatigue failure, as shown by electron microscopy.
(f) The cracks generally initiate at the surface where the stress is maximum.
(g) The fractured surface is dull in appearance and may contain corrosion products.

Prevention
The aim of the protective measures is to prevent corrosion fatigue cracks from initiating
rather than stopping them from propagation once they have been initiated.
(1) The fatigue life in corrosive environments can be increased by introducing compressive
stresses. The compressive stresses can be introduced by shot-peening, shot-blasting,
nitriding and carburizing.
(2) Cathodic protection has been used to prevent fatigue crack initiation. It can be achieved
by attacking a more active metal than that being protected or by the impressed current
technique. The use of electrodeposited coatings, such as zinc coating or cadmium coating,

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have been found to offer a better protection than the hot dipped zinc and cadmium
coatings, because of the compressive stresses introduced during electrodeposition.
(3) Application of nickel coating has been found to be effective in preventing corrosion
fatigue. Use has been made of non-metallic coatings, like epoxy, rubber and enamel, to
increase fatigue life. Once the coating is mechanically damaged, the fatigue resistance is
adversely affected due to acceleration of underneath the coating.
(4) The fatigue life of carbon steels and stainless steels is known to be improved by the
formation of a passive layer on the surface. The passive layers can be formed by a technique
known as “anodic protection”. In anodic protection, the steel is polarized by raising its
potential to the passive region. The fatigue life of carbon steels and stainless steels maybe
improved by this technique in oxidizing environment. This technique is generally used to
improve the fatigue life of steels in an oxidizing environment.
(5) The composition of an alloy can be modified to increase its resistance to corrosion
fatigue. The resistance of stainless steels can be improved by increasing the Ni content. The
resistance of mild steel can be improved by addition of 1-2% titanium. Such modifications in
compositions are not the ideal solutions as the cost factor may sometimes be prohibitive for
making such modifications.
(6) The corrosion fatigue life can also be improved by environmental modification, such as
adding inhibitors to the environment. The fatigue resistance of steel in a chloride-sulfate
solution is increased by adding sodium dichromate.
Such inhibitors act by forming protective films on the surface of the metal being subjected
to corrosion fatigue. The selection of a right inhibitor and its effective concentration is
important for prevention of corrosion fatigue.

Fretting Corrosion
The rapid corrosion that occurs at the interface between contacting, highly loaded metal
surfaces when subjected to slight vibratory motions is known as fretting corrosion.
The photo in the next slide shows fretting corrosion of a fence post and wires which swing in
the wind and wear against the post. Both the fence post and the connecting wires are
experiencing fretting corrosion. Fretting corrosion is greatly retarded when the contacting
surfaces can be well lubricated as in machinery-bearing surfaces so as to exclude direct
contact with air.

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Examples
(1) Fretting of the blade roots of tube blades.
(2) Loosening of the wheels from axles. For example, the coming out of railroad car wheel
from the axle due to vibrations.
(3) Fretting of electrical contacts.
(4) Fretting damage of riveted joints.
(5) Surgical implantations.

This type of corrosion is most common in bearing surfaces in machinery, such as connecting
rods, splined shafts, and bearing supports, and often causes a fatigue failure.
It can occur in structural members such as trusses where highly loaded bolts are used and
some relative motion occurs between the bolted members. Fretting describes corrosion
occurring at contact area between materials under load subjected to vibration and slip. It
appears as pits or grooves in the metal surrounded by corrosion products. Fretting is also
called as friction oxidation, wear oxidation, chafing, or false brinelling. It has been observed
in engine components, automotive parts, bolted parts, and other machinery. Essentially
fretting is a special case of erosion corrosion that occurs in the atmosphere rather than
under aqueous conditions. Fretting corrosion is very detrimental because of the destruction
of metallic components and the production of oxide debris.

Factors affecting fretting corrosion

1. Contact load - Wear is a linear function of load and fretting would, therefore, increase
with increased load as long as the amplitude is not reduced.
2. Amplitude - No measurable threshold amplitude exists below which fretting does not
occur. An upper threshold limit, however, exists above which a rapid increase in the rate of
wear exists. Amplitude oscillations as low as 3 or 4 nm are sufficient.
3. Number of cycles - The degree of fretting increases with the number of cycles. The
appearance of surface changes with the number of cycles. An incubation period is reported
to exist during which the damage is negligible. This period is accompanied by a steady-state
period, during which the fretting rate is generally constant. In the final stage, the rate of
fretting wear is increased.
4. Temperature - The effect of temperature depends on the type of oxide that is produced.
If a protective, adherent, compact oxide is formed which prevents the metal-to-metal
contact, fretting wear is decreased. For example, a thick layer of oxide is formed at 650°C on
titanium surface. The damage by fretting is, therefore, reduced at this temperature. The
crucial factor is not the temperature by itself, but the effect of temperature on the
formation of oxide on a metal surface. The nature and type of the oxide is the deciding
factor.
5. Relative humidity - The effect of humidity on fretting is opposite to the effect of general
corrosion where an increase in humidity causes an increase in the rate of corrosion, and an

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increase in dryness causes a decrease in corrosion. Fretting corrosion is increased in dry air
rather than decreased for metals which form rust in air.
Mechanism
Fretting corrosion is usually a combination of corrosion and abrasive wear. The motion
between the surfaces removes protective films and results in accelerated attack. Also, most
corrosion products are abrasive and their presence increases the removal of protective films
and in direct abrasion of the metal.

Appearance
Fretting corrosion usually results in scuffed surfaces in joints or at other wear sites. If
inspected soon after the relative motion ceases, the surfaces will often be bright and have
corrosion products attached to the surfaces.

Results in loss of tolerances and loosening of mating parts. Further fretting causes fatigue
fracture since the loosening of the components permits excessive strain, and the pits
formed by fretting act as stress raisers. A classic example of fretting occurs at bolted tie
plates on railroad rails. Frequent tightening of these plates is required because the parts are
not lubricated and fretting corrosion proceeds rapidly.
The basic requirements for the occurrence of fretting corrosion are:
 The interface must be under load.
 Vibration or repeated relative motion between the two surfaces must occur.
 The load and the relative motion of the interface must be sufficient to produce slip or
deformation on the surfaces.
Prevention
Fretting corrosion can be minimized or practically eliminated in many cases by using one or
more of the following preventive measures:
 Increase the magnitude of load at the mating surfaces to minimize the occurrence of slip.
 Keep the amplitude below the level at which fretting occurs, if known for a particular
system. There is lower threshold limit below which fretting does not occur.
 Decrease the load at the bearing surfaces; however, it may not always work.
 Use materials which develop a highly resistant oxide film, at high temperature to
minimize the adverse effect of temperature on fretting.
 Use gaskets to absorb vibration.

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 Increase the hardness of the two contacting metals, if possible, by shot-peening.

Compressing stresses are developed during shot-peening, which resist and increase
fretting resistance.
 Use low viscosity lubricating oils.
 Use materials to resist fretting corrosion.
 Use thick resin bonded coatings.
 Separate the surfaces, for instance, by intermediate sheets of wrapping paper between
stacked sheets.

Dealloying/ Selective Leaching

Dealloying is a rare form of corrosion found in copper alloys, gray cast iron, and some other
alloys. Dealloying occurs when the alloy loses the active component of the metal and retains
the more corrosion resistant component in a porous "sponge" on the metal surface. Control
is by the use of more resistant alloys-inhibited brasses and malleable or nodular cast iron. It
is the removal of one element from the solid alloy by corrosion processes. The most
common example is the selective removal of zinc in brass alloys (dezincification).
Similar processes occur in other alloys systems in which aluminium, iron, cobalt, chromium
and other elements are removed. Selective leaching is the general term that describes these
processes, and its use precludes the creation of terms such as dealuminiumification,
graphitization, decobaltification etc. Common yellow brass consists of appox. 30 % zinc and
70 % copper. Dezincification is readily observed with the naked eye because the alloy
assumes a red or copper colour that contrasts with the original yellow.
There are two types of dezincification: one is uniform, or layer type and the other is
localized, or plug type dezincification.
Overall dimensions do not change appreciably when dezincification occurs. If a piece of
equipment is covered with dirt or deposits, or not inspected closely sudden unexpected
failure may occur because of the poor strength of dezincified material. Uniform or layer type
dezincification seems to favour the high brasses (high zinc content) and definitely acid
environments. The plug type seem to occur more often in the low brasses (low zinc content)
and neutral, alkaline or slightly acidic conditions. Stagnant conditions usually favour
dezincification because of scale formation or foreign deposits settling on the metal surface.
Metal structure and composition are important. Some brasses contain over 35 % zinc. In
these cases a zinc rich phase forms and localized corrosion may occur. Dezincification can be
minimized by reducing the aggressiveness of the environment, or by cathodic protection,
but in most cases these methods are not economical. Usually a less susceptible alloy is used.
For severely corrosive environments where dezincification occurs, or for critical parts,
cupronickels (70-90% Cu, 30-10% Ni) are utilized.
Gray cast iron sometimes shows the effect of selective leaching particularly in relatively mild
environments. The cast iron appears to become graphitized in that the surface layer has the
appearance of graphite and can be easily cut with a penknife. Based on this appearance and
behaviour, this phenomenon was named graphitization/graphitic corrosion. Graphitization
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is usually a slow process. Graphitization does not occur in nodular or malleable cast iron.,
because the graphite network is not present to hold together the residue. White cast iron
has essentially no free carbon and is not subject to graphitization. Graphitization of grey cast
iron is very common leading to the failures of underground pipelines, particularly those
handling hazardous materials.
Selective leaching by aqueous environments occurs in other alloys systems under
appropriate conditions, especially in acids. Selective leaching has been observed in
connection with removal of silicon from silicon bronzes (Cu-Si) and also removal of cobolt
from a Cu-W-Cr alloy. The term dealloying is used and is preferred by some corrosionists.
Dealloying is defined as a corrosion process whereby one constituent of an alloy is
preferentially removed from the alloy leaving an altered residual structure (like
dezincification).

Hydrogen Damage
Hydrogen embrittlement is a problem with high-strength steels, titanium, and some other
metals. Control is by eliminating hydrogen from the environment or by the use of resistant
alloys. Hydrogen blistering can occur when hydrogen enters steel as a result of the
reduction reaction on a metal cathode. Single-atom nascent hydrogen atoms then diffuse
through the metal until they meet with another atom, usually at inclusions or defects in the
metal. The resultant diatomic hydrogen molecules are then too big to migrate and become
trapped. Eventually a gas blister builds up and may split the metal.

Figure 2: Illustration of Hydrogen Diffusion

Hydrogen damage is a general term which refers to mechanical damage of a metal caused
by the presence of, or interaction with, hydrogen.
Hydrogen damage may be classified into four distinct types:
 Hydrogen blistering
 Hydrogen embrittlement
 Decarburization
 Hydrogen attack

Hydrogen blistering results from the penetration of hydrogen into a metal. The results are
local deformation and, in some cases, complete destruction of the vessel wall.

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Hydrogen embrittlement also is caused by penetration of hydrogen into the metal, which
results in a loss of ductility and tensile strength.
Decarburization lowers the tensile strength of steel.
Hydrogen attack refers to the interaction between hydrogen and a component of an alloy at
high temperatures. A typical example of hydrogen attack is the disintegration of oxygen
containing copper in the presence of hydrogen. Both decarburization and hydrogen attack
are high temperature processes.
Hydrogen blistering and hydrogen embrittlement may occur during exposure to petroleum
in chemical process streams, during pickling and welding operations, or as a result of
corrosion. Since both of these effects produce mechanical damage, catastrophic failure may
result if they are not prevented.
High Temperature Hydrogen Attack:
This type of attack requires the presence of atomic hydrogen because of the inability of the
molecular hydrogen to permeate steel at atmospheric temperatures. At temperatures
above 230°C and hydrogen partial pressure above 100psi (7kg/cm 2), atomic hydrogen reacts
with the carbon component in the steel to form methane.
Fe3C + 4H  3Fe + CH4
The removal of carbon as shown by above equation causes a loss of strength. Accumulation
of methane inside builds up high internal pressure inside the steels and creates fissures
preferentially at the grain boundary or non-metallic inclusions. Since neither molecular
hydrogen nor methane is capable of diffusion through the steel, so these gases accumulate.
Therefore, hydrogen attack at high temperature results mainly from the formation of
fissures by methane and by decarburization of steel. The steel after hydrogen attack may
also be found to contain blisters in addition to the fissures.
These blisters, however, differ from the low temperature blisters in that they contain
methane (CH4) instead of hydrogen. Use of stabilized grades of steel is one preventive
method. Prevention of blisters is difficult to avoid by coatings or linings because of the high
permeability of hydrogen. Atomic hydrogen (H) is the only species capable of diffusing
through steel and other metals. The molecular form of hydrogen (H 2) does not diffuse
through metals. Thus hydrogen damage is produced only by the atomic form of hydrogen.
There are various sources of nascent or atomic hydrogen:
 High temperature moist atmospheres,
 Corrosion processes,
 Electrolytes.

The reduction of hydrogen ions involves the production of hydrogen atoms and the
subsequent formation of hydrogen molecules. Hence both corrosion and the application of
cathodic protection, electroplating, and other processes are major sources of hydrogen in
metals. Certain substance such as sulfide ions, phosphorus and arsenic compounds reduce
the rate of hydrogen ion reduction. Apparently most of these function by decreasing the

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rate at which hydrogen combines to form molecules. In the presence of such substances
there is a greater concentration of atomic hydrogen on the metal surface.

Hydrogen Blistering/Hydrogen Induced Cracking (HIC):

Let us consider tank containing acid electrolyte. And the exterior of the tank is exposed to
atmosphere. Hydrogen evolution occurs on the inner surface as a result of a corrosion
reaction on cathodic protection. At any time there is a fixed concentration of hydrogen
atoms on the metal surface, and some of these diffuse into the metal rather than combining
into molecules. Much of hydrogen diffuses through the steel and combines to form
hydrogen molecules on the exterior surface. If hydrogen atoms diffuse into a void, a
common defect in rimmed steels, they combine into molecular hydrogen. Since molecular
hydrogen cannot diffuse, the concentration and pressure of hydrogen gas within the void
increases. The equilibrium pressure of molecular hydrogen in contact with atomic hydrogen
is several hundred thousand atmospheres, which is sufficient to rupture any known
engineering material.
Hydrogen blistering is most prevalent in the petroleum industry. It occurs in storage tanks,
and in refining processes. One method to control is to add an inhibitor, such as the
polysulfide ion.
For the HIC to occur, the following conditions must occur:
(a) The presence of water phase.
(b) The presence of atomic hydrogen.
(c) An agent that retards the formation of molecular hydrogen at the surface.
(d) Presence of grain boundaries or inclusions.
(e) Maintenance of an active surface.
(f) Discontinuity in metal, such as slag, inclusion and/or void

Sources of Hydrogen:
In order to protect the high strength non-stainless steels against corrosion, a good surface
treatment must be provided. Incidentally, surface treatment like pickling or electroplating,
are likely to introduce hydrogen in the steel. In high strength steels, a small amount of
hydrogen may cause serious cracking. Hydrogen absorption may also take place during
manufacture, fabrication, welding and heat treatment.

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Hydrogen Embrittlement
The initial cause is the same for this corrosion. That is penetration of atomic hydrogen into
metal surface. For titanium and other strong hydride forming metals, dissolved hydrogen
reacts to form brittle hydride compounds. In other materials, such as iron and steel, the
interaction between dissolved hydrogen atoms and the metal is not completely known.
Most of the mechanisms that have been proposed for hydrogen embrittlement are based
on slip interference by dissolved hydrogen. This slip interference may be due to the
accumulation of hydrogen near dislocation sites or micro-voids. Hydrogen embrittlement is
a phenomenon whereby hydrogen is absorbed in the metal (diffuses), exerts local stresses,
and leads to embrittlement of material, such as high strength steels.
Examples of Hydrogen Embrittlement
(1) In plating operations.
(2) In pickling operations.
(3) In cleaning of high strength steels in chloride or fluoride solution.
(4) Manufacturing and fabrication processes.
Materials most susceptible to Hydrogen Embrittlement are:
 Iron,
 titanium,
 zirconium,
 martensitic steels,
 high strength aluminum alloys.
Hydrogen Embrittlement - Mechanism
No definite mechanism of hydrogen embrittlement has been suggested. It has been
considered sufficient to identify hydrogen as a cause for cracking.
It is a general opinion that impurity segregations at the grain boundary act as poisons, and
increase the adsorption of cathodic hydrogen at these sites. It is widely believed that in BCC
materials hydrogen embrittlement is caused by the interaction of hydrogen with defects in

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the structure. Such defects are vacancies, dislocations, grain boundaries, interface, voids,
etc. Hydrogen is trapped in these defects and growth of a crack is facilitated. A large number
of such defects interact with hydrogen and the combined trapping results in a significant
loss of ductility.
Prevention of hydrogen blistering:
 Using “clean steel” - Rimmed steel tends to have numerous voids.
 Using coatings - Metallic, inorganic and organic coatings and liners are often used to
prevent the hydrogen blistering of steel containers. Also, rubber and plastic coatings and
brick linings are frequently employed.
 Using inhibitors - Inhibitors can prevent blistering since they reduce corrosion rate and
the rate of hydrogen ion reduction. Inhibitors however are primarily used in closed
systems and have limited use in once-through systems.
 Removing poisons - Blistering usually occurs in corrosive mediums containing hydrogen
evolution poisons such as sulfides, arsenic compounds, cyanides, and phosphorous
containing ions and rarely occurs in pure acid corrosives.
 Substituting alloys - Nickel containing steels and nickel based alloys have very low
hydrogen diffusion rates and are often used to prevent hydrogen blistering.
Prevention of hydrogen embrittlement:
 Reducing corrosion rate - Hydrogen embrittlement occurs frequently during pickling
operations where corrosion of the base metal produces vigorous hydrogen evolution. By
careful inhibitor additions, base metal corrosion can be largely be eliminated during
pickling with a subsequent decrease in hydrogen pickup.
 Altering plating conditions - Hydrogen pickup during plating can be controlled by the
proper choice of plating baths and careful control of plating current.
 Baking - Hydrogen embrittlement is an almost reversible process, especially in steels.
That is, if the hydrogen is removed, the mechanical properties of the treated material are
only slightly different from those of hydrogen free steel. A common way of removing
hydrogen in steels is by baking at relatively low temperatures (200-300 ⁰F).
 Substituting alloys - Nickel containing steels and nickel based alloys have very low
hydrogen diffusion rates and are often used to prevent hydrogen blistering.
 Practicing proper welding - Low hydrogen welding rods should be specified for welding if
hydrogen embrittlement is a problem. Also it is important to maintain dry conditions
during welding since water and water vapour are major sources of hydrogen.
 Use of inhibitors - Inhibitors may be added to pickling baths to minimize corrosion.
 Heat treatment - Temper at a higher temperature for a long period of time. This would
lower the strength.
 Surface preparation technique - Use techniques which introduce compressive stresses on
the surface.

Department of Mechanical & Manufacturing Engineering, MIT, Manipal 27