CHE 431

Module 1:

Introduction

Module 2:

Principles of Corrosion

Module 3:

Forms of Corrosion

Module 4:

Corrosion Testing

Module 5:

Corrosion Control by Material selection

Module 6:

Corrosion Control by protective coatings and Inhibitors

Module 6:

Corrosion Control by Cathodic and Anodic Protection

Module 8:

Corrosion in Automobile, Chemical and Petroleum Industry

Corrosion is the destructive attack of a metal by chemical or electrochemical reaction with its
environment. Corrosion process produces a new and less desirable material from the original
metal and can result in a loss of function of the component or system. The corrosion product we
see most commonly is the rust which forms on the surface of steel.

Forms of Corrosion
1) Uniform or General Corrosion
2) Pitting Corrosion
3) Crevice Corrosion
4) Galvanic Corrosion
5) Erosion Corrosion
6) Inter-granular Corrosion
7) Stress Corrosion Cracking
8) CO2 corrosion
9) H2S Corrosion
10) Strong acids Corrosion
Why Metals Corrode
Metals corrode because we use them in environments where they are chemically unstable. Only
copper and the precious metals (gold, silver, platinum, etc.) are found in nature in their metallic
state. All other metals, to include iron-the metal most commonly used-are processed from
minerals or ores into metals which are inherently unstable in their environments.

Measurement of Corrosion Rate

The measurement of corrosion is usually done by the following methods:
A. Weight loss method
Weight Loss test is the most commonly used for measurement of corrosion. In this method,
a clean piece of metal or alloy is measured, weighed and exposed to the corrosive
environment for a particular period of time. The piece is then taken out, cleaned to remove
the corrosion products and reweighed to determine the loss of weight.
The rate of corrosion of the metal, , is then calculated using
=

where

K = constant,
D = Density

T = Time of exposure,

W = Weight loss,

A = Area,

Relationship between R and K is given below

Corrosion Rate, R
Constant, K
Millimeters per year (mpy)
3.45 X 106
Inches per year (in/yr)
3.45 X 103
Inches per month (ipm)
2.87 X 102
Micrometer per year (mpy)
8.76 X 107
Picometers per second (pps)
2.78 X 106

B. Microscopic examination
The main objective of this examination on the specimen is to check the nature of the
corroded surface, the number of pits formed and their depth and the presence of intergranular corrosion.
C. Measurement of electrical resistance
If the test sample is in the form of a thin wire or strip, its electrical resistance increases as
corrosion decreases its cross-section. Hence, periodic or continuous measurement of the
resistance between the ends of the specimen can be used to monitor the corrosion.

The process of corrosion (Five facts)

This series of steps tells us a lot about the corrosion process.
(1) Ions are involved and need a medium to move in (usually water)
(2) Oxygen is involved and needs to be supplied
(3) The metal has to be willing to give up electrons to start the process
(4) A new material is formed and this may react again or could be protective of the original metal
(5) A series of simple steps are involved and a driving force is needed to achieve them
The most important fact is that interfering with the steps allows the corrosion reaction to be
stopped or slowed to a manageable rate.
Corrosion problems can be solved in the following ways:
1. Select a material that is resistant to the corrosive environment.
2. Give metal a protective coating.
3. Change the service conditions, such as temperature, pressure, or velocity.
4. Change environment chemistry, such as pH, concentration, aeration, or impurities.
5. Add a corrosion inhibitor.
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6. Shift the electrical potential of the metal by cathodic or anodic protection.

7. Modify the design of the equipment or system.
8. Let it corrode and replace it (often a viable alternative!).
The methods listed above are the accepted ways of dealing with a corrosion problem, but not all
of them apply in a given situation. In particular, the corrosion engineer often cannot change the
service conditions or environment chemistry. These may be as unalterable as the ocean, or nearly
as unalterable: an industrial process that is running fairly smoothly where any change will be
fanatically opposed by the production people. Most corrosion problems originate with either
improper design or improper materials selection. However, a good choice of material can
overcome severe environmental conditions and even some deficiencies in design.
MATERIALS SELECTION
The two major types of materials used are:
I.
II.

Non metallic materials

Metallic materials

Non metallic materials

Plastics
Ceramics
Concrete
Wood

Metallic materials

Carbon steels
Stainless steels
Aluminium
Copper alloys
Titanium

Iron is second most abundant metal element in the earths crust and is primarily used to produce steel, one
of the most important structural materials in the world.
Steel is an alloy of iron and various other metals, which are used to enhance the properties (strength,
resistance to corrosion, tolerance to heat etc) of iron. Changing the type and amount of the elements
alloyed with iron can produce different types of steel. The most common steels are:

1. Carbon steels, which contain between 0.5-1.5% carbon. These are the most common steels and
are used for auto bodies, ship hulls, knives, machinery and all types of structural supports.
2. Low alloy steels, which contain between 1-5% other metals (often nickel or tungsten). Nickel
steel is able to withstand high level of tension and is, thus, often used in the construction of
bridges and for making bicycle chains. Tungsten steels keep their shape and strength in high
temperature environments and are used in impact, rotary applications, such as drill bits.
3. High alloy steels, which contain 12-18% of other metals are only used in specialty applications
due to their high cost. One example of a high alloy steel is stainless steel, which often contains
chromium and nickel, but can be alloyed with various other metals as well. Stainless steel is very
strong and highly resistant to corrosion.
Carbon Steel
Most large metal structures are made from carbon steel-the world's most useful structural
material. Carbon steel is inexpensive, readily available in a variety of forms, and can be
machined, welded, and formed into many shapes. Unprotected carbon steel rusts readily when
exposed to air and moisture. This iron oxide film (the rust) is active and accelerates corrosion by
forming more iron oxide; and, because of the greater volume of the iron oxide, this tends to flake
and fall away.

Stainless Steel
A stainless steel is defined as a ferrous alloy containing enough chromium to passivate in some
environment, such as air and water. At least 10% Cr (but usually ~12%), is required to form a
passive film (mainly Cr2O3). The carbon content is typically quite low in stainless steels, so the
terms carbon steels and steels refer to nonstainless steels, since stainless steels have nothing
in common with ordinary steels in terms of corrodibility.
Stainless steel differs from carbon steel by the amount of chromium present. Stainless steels
contain sufficient chromium to form a passive film of chromium oxide, which prevents further
surface corrosion by blocking oxygen diffusion to the steel surface and blocks corrosion from
spreading into the metal's internal structure. Passivation occurs only if the proportion of
chromium is high enough and oxygen is present.
Stainless steels are usually the first choice for a probably corrosive environment with unknown
properties, because these alloys are resistant to a wide range of oxidizers, but they cannot
withstand strong reducing solutions, such as hydrochloric acid. Stainless steels can be corroded,
despite their name.

Stainless steel does not readily corrode, rust or stain with water as ordinary steel does. However,
it is not fully stain-proof in low-oxygen, high-salinity, or poor air-circulation environments.
There are different grades and surface finishes of stainless steel to suit the environment the alloy
must endure. Stainless steel is used where both the properties of steel and corrosion resistance
are required.
Stainless steel is 100% recyclable. There is a
many stainless steel markets. The product is
purchased at a less-than-prime price and sold
houses. The material may have scratches,
specifications.

secondary market that recycles usable scrap for

mostly coil, sheet, and blanks. This material is
to commercial quality stampers and sheet metal
pits, and dents but is made to the current

Stainless steels resistance to corrosion and staining, low maintenance, and familiar lustre make
it an ideal material for many applications. The alloy is milled into coils, sheets, plates, bars, wire,
and tubing to be used in cookware, cutlery, household hardware, surgical instruments, bridges,
major appliances, industrial equipment (for example, in sugar refineries) and as an automotive
and aerospace structural alloy and construction material in large buildings. Storage tanks and
tankers used to transport orange juice and other food are often made of stainless steel, because of
its corrosion resistance. This also influences its use in commercial kitchens and food processing
plants, as it can be steam-cleaned and sterilized and does not need paint or other surface finishes.
The stainless steels are classified into five general groups according to their metallurgical
structures, with the choice of which one to use depending not only on corrosion resistance but
also on required strength and cost. In economic terms they can compete with higher cost
engineering metals and alloys based on nickel or titanium, whilst offering a range of corrosion
resisting properties suitable for a wide range of applications. They have better strength than most
polymer products (GRP), are readily repairable and 'recyclable' at the end of their useful life.

Ferritic Stainless Steels

Low carbon and nickel content

Good corrosion resistance
Good weldability and toughness
Magnetic

The standard ferritic grades are alloyed with chromium (11.219%), but with no, or a very small,
addition of nickel. As nickel is one of the most expensive alloying elements, and experiences
high price volatility, the low nickel content of the ferritic grades makes them more price stable
compared to grades with high nickel content.

Molybdenum is added to some grades to improve corrosion resistance, while alloying with
niobium and/or titanium improves weldability. The ferritic grades are magnetic due to their
ferritic microstructure.
There are also ferritic grades with increased resistance to high temperatures (8001,150 C).
These grades are typically alloyed with more carbon than standard ferritic grades to increase
creep strength, and with silicon and aluminium to improve resistance to oxidation.
Austentic Stainless Steels

Good to excellent corrosion resistance

Good weldability and formability
Good creep resistance
Non-magnetic

The austenitic grades are the largest type of stainless steels, and can be divided into five subgroups:

Cr-Mn grades also referred to as 200-series grades have some of the nickel replaced
with manganese and nitrogen
Cr-Ni grades general-purpose grades mainly alloyed with chromium and nickel, but
with no molybdenum
Cr-Ni-Mo grades also general-purpose grades, but with increased corrosion resistance
due to alloying with molybdenum
High-performance grades high alloying content for use in very demanding
environments
High-temperature grades high chromium and nickel content, but no molybdenum, for
use at temperatures exceeding 550 C

The austenitic grades have good to excellent corrosion resistance, as well as good formability
and weldability. Their high impact strength at low temperatures is often exploited in cryogenic
applications. The austenitic grades are non-magnetic in the solution-annealed condition. Cold
working increases their strength and certain grades are therefore supplied in the temper rolled
condition and may then be magnetic due to the presence of some martensitic
Martensitic Stainless Steels

High strength
High wear resistance
Limited corrosion resistance
Magnetic
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The martensitic grades are the smallest group of stainless steels. For improved strength and
hardenability they have a higher carbon content compared to other grades, and nitrogen is
sometimes added to further improve strength.
These grades contain no, or small, amounts of nickel, and molybdenum is seldom added. Adding
some nickel and reducing the carbon content improves the poor weldability of martensitic
grades. Sometimes sulfur is added to improve the machinability.
Duplex Stainless Steels

Very good corrosion resistance

Good weldability
Lightweight
Magnetic

These steels have a microstructure which is approximately 50% ferritic and 50% austenitic. This
gives them a higher strength than either ferritic or austenitic steels. Duplex grades have a ferriticaustenitic microstructure that combines many of the beneficial properties of ferritic and
austenitic stainless steels. The duplex microstructure also contributes to high strength and high
resistance to stress corrosion cracking.
Duplex stainless steels are characterized by high chromium content (20.125.4%) and low nickel
content (1.47%) compared to austenitic grades. The low nickel content makes duplex grades
more price stable. Molybdenum (0.34%) and nitrogen are added to improve corrosion
resistance, while nitrogen also increases strength. The duplex grades LDX 2101 and 2304 are
sometimes referred to as lean duplex grades, while the duplex grades 2507 and 4501 are also
called 25Cr super duplex grades. Due to their ferrite content the duplex grades are magnetic
Precipitation Hardening Stainless Steels

High strength
High wear resistance
Limited corrosion resistance
Magnetic

These steels can develop very high strength by adding elements such as Copper, Niobium and
Aluminium to the steel. With a suitable aging heat treatment, very fine particles form in the
matrix of the steel which imparts strength. These steels can be machined to quite intricate shapes
requiring good tolerances before the final aging treatment as there is minimal distortion from the
final treatment. This is in contrast to conventional hardening and tempering in martensitic steels

where distortion is more of a problem. The precipitation hardening grades are hardened by a
special mechanism involving the formation of precipitates within the microstructure.
How do I choose which stainless steel to use?
Most decisions about which steel to use are based on a combination of the following factors:
a. What is the corrosive environment? Atmospheric, water, concentration of particular
chemicals, chloride content, presence of acid.
b. What is the temperature of operation? High temperatures usually accelerate corrosion
rates and therefore indicate a higher grade. Low temperatures will require a tough austenitic
steel.
c. What strength is required? Higher strength can be obtained from the austenitic, duplex,
martensitic and PH steels. Other processes such as welding and forming often influence
which of these is most suitable. For example, high strength austenitic steels produced by
work hardening would not be suitable where welding was necessary as the process would
soften the steel.
d. What welding will be carried out? - Austenitic steels are generally more weldable than the
other types. Ferritic steels are weldable in thin sections. Duplex steels require more care
than austenitic steels but are now regarded as fully weldable. Martensitic and PH grades are
less weldable.
e. What degree of forming is required to make the component? Austenitic steels are the most
formable of all the types being able to undergo a high degree of deep drawing or stretch
forming. Generally, ferritic steels are not as formable but can still be capable of producing
quite intricate shapes. Duplex, martensitic and PH grades are not particularly formable.
f. What product form is required? Not all grades are available in all product forms and sizes,
for example sheet, bar, tube. In general, the austenitic steels are available in all product
forms over a wide range of dimensions. Ferritics are more likely to be in sheet form than
bar. For martensitic steels, the reverse is true.
g. What are the customers expectations of the performance of the material? This is an
important consideration often missed in the selection process. Particularly, what are the
aesthetic requirements as compared to the structural requirements? Design life is sometimes
specified but is very difficult to guarantee.
h. There may also be special requirements such as non-magnetic properties to take into
account.
i. It must also be borne in mind that steel type alone is not the only factor in material
selection. Surface finish is at least as important in many applications, particularly where
there is a strong aesthetic component.
j. Availability. There may be a perfectly correct technical choice of material which cannot be
implemented because it is not available in the time required.

k. Cost. Sometimes the correct technical option is not finally chosen on cost grounds alone.
However, it is important to assess cost on the correct basis. Many stainless steel applications
are shown to be advantageous on a life cycle cost basis rather than initial cost.

Summary of the main advantages of the stainless steel types

Type
Ferritic

Austenitic

Duplex

Martensitics

Precipitation
hardening

Examples Advantages

Disadvantages
Limited
corrosion
resistance,
410S, 430, Low cost, moderate corrosion
formabilty & elevated temperature
446
resistance & good formability
strength compared to austenitics
Widely available, good general Work
hardening
can
limit
corrosion
resistance,
good formability
&
machinability.
304,316
cryogenic toughness. Excellent Limited resistance to stress
formability & weldability
corrosion cracking
Good stress corrosion cracking
Application temperature range
1.4462
resistance,
good
mechanical
more restricted than austenitics
strength in annealed condition
Corrosion resistance compared to
austenitics & formability compared
420, 431 Hardenable by heat treatment
to ferritics limited. Weldability
limited.
Limited availability, corrosion
Hardenable by heat treatment, but
resistance,
formability
&
17/4PH with better corrosion resistance
weldability restricted compared to
than martensitics
austenitics

Other 'Families' of stainless steels

There is a wide range of stainless steel types. Special grades with enhanced compositions have
been developed and are available that minimise the short comings of any particular type.
These include: -

Super ferritics
Super austenitics
Super duplexes
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 Low carbon weldable martensitics

Austenitic precipitation hardening types

Aluminum
Aluminum alloys are widely used in aerospace applications where their favorable strength-toweight ratios make them the structural metal of choice. They can have excellent atmospheric
corrosion capabilities. Unfortunately, the protective properties of the aluminum oxide films that
form on these alloys can break down locally and allow extensive corrosion. This is discussed
further in the section on intergranular corrosion.
The highway guardrail shown on the right is located near the ocean in Florida. The aluminum
alloy maintains a silvery shine except in locations where the passive film has suffered
mechanical damage. The wear caused by the rail touching the wooden post at this location
destroyed the passive film on the edges of the rail and allowed intergranular corrosion to proceed
and cause the exfoliation corrosion shown above. While the corrosion above is very interesting
and makes for an interesting web site, it is important to note that the railing is decades old and
would have never lasted as long in this location if it were made of carbon steel.
Intergranular corrosion is a major problem on airplanes and other structures made from
aluminum alloys. It frequently occurs at bolt and rivet holes or at cutouts where the small grain
boundaries perpendicular to the metal surface are exposed.
Copper Alloys
Brasses and bronzes are commonly used piping materials, and they are also used for valves and
fittings. They are subject to stress corrosion cracking in the presence of ammonia compounds.
They also suffer from dealloying and can cause galvanic corrosion when coupled with steel and
other structural metals. Most copper alloys are relatively soft and subject to erosion corrosion
Titanium
Titanium is one of the more common metals in nature, but its limited use means that small-scale
production operations result in a relatively expensive metal. In the United States it finds
extensive use in the aerospace industry. The Japanese make extensive use of titanium in the
chemical process industries.

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There are two general types of titanium alloys-aerospace alloys and corrosion resistant alloys.
The crevice corrosion of an aerospace alloy flange in a saltwater application is a classic example
of how titanium gets misused.

Plastics
The three general classes of plastics are:
1. Thermoplastics: The thermoplastics consist of long hydrocarbon chains with molecular
weights in the thousands. These plastics are relatively weak and soften further as temperature
increases. Cross-linking, adding bulky side groups to the chains, or partial crystallization
strengthens the polymers.
2. Elastomers: Elastomers are thermoplastics with coiled or kinked chains. High-temperature
strength is greatly improved by occasional cross-links (e.g., by vulcanization with sulfur). These
thermoplastics can be deformed elastically several hundred percent. In corrosion service,
elastomers are mainly used as gaskets and as coatings.
3. Thermosets: Thermosets have been polymerized into three dimensional, noncrystalline
structures that make them strong and rigid. These plastics do not soften when heated and are
relatively expensive. Thermosets are all reinforced for industrial applications.
Concrete
Concrete is used for large tanks, for large-diameter pipe, and as a lining for vessels and steel
pipes. It is commonly reinforced with steel in all types of construction work where tensile
stresses might occur. Being alkaline, concrete is readily attacked by all acids. Calcium ions
in the concrete will leach out in corrosives containing sulfates or they exchange with magnesium
ion solutions, turning the concrete into a soft, porous mass. Carbon dioxide, ammonium ions,
strong alkalies, and some organic compounds also degrade concrete. Special cement
formulations are available that resist sulfates but the aggregate (gravel and sand that make up
roughly 3 of the volume) must also resist the environment. Concrete tanks and pipes must be
lined if strong corrosives are involved.
Concrete containing 30% fly ash has only 1 the permeability of ordinary concrete and so can
protect reinforcing steel much better. Fluoride surface treatment or sodium silicate washes
densify and harden the concrete surface to make it more corrosion resistant. Polymer concretes,
using resins of epoxies, polyesters, vinyl esters, or urethanes, are now being widely used. Their
strengths are comparable with portland cement concretes but they have higher bond strength and
much lower permeability. Applications include bridge overlays, floor drains, and acid-resistant
sewer pipe.

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