MATERIAL AND ALLOY

SELECTION

Materials Evaluation and Selection

The selection of appropriate materials in a given environment is a key factor for corrosion control
strategy.
The material selected has to meet the criteria for mechanical strength, corrosion and erosion
resistance for specific service conditions.
The following is a list of factors affecting the performance of materials:

(1) Expected performance and functions of the product.

(2) Physical characteristics.
(3) Strength and mechanical characteristics.
(4) Corrosion and wear characteristics.
(5) Fabrication parameters.
(6) Recycling possibilities.
(1) If a seawater storage tank is to be fabricated, fiber glass would be an ideal material because
of its advantage of density and resistance to corrosion over the conventional steels, such as
AISI 304.
For industrial water supply, discharge of used water and irrigation water, PVC (polyvinyl chloride)
would be ideal because of the advantage of increased durability, non-corrosivity, ease of
maintenance and quality-to-price ratio, they offer.

(2) Characteristics, such as electrical conductivity, thermal coefficient of expansion, and thermal
conductivity, are important considerations for selection of materials.
For instance, cupronickel (90-10 CuNi) are excellent materials for heat exchanger tubes in thermal
desalination plants employing raw seawater, because of their excellent conductivity and corrosion
resistance.
(3) Factors, such as yield strength, tensile strength, fatigue strength and creep strength are crucial
to design as they dictate the ability of a product or component to withstand different types of
stresses imposed upon them while in service.
Mechanical properties are also affected by environment. For instance, the yield strength of steels
may be significantly reduced by saline water over a period of time.
Aircraft flying at lower altitudes in sea coastal areas beset with high humidity, salt particles and
temperatures exceeding 50C, suffer loss of performance. The maximum takeoff weight is
considerably reduced when the temperature exceeds 40C
(4) (a) Materials selected should be compatible with the environment. They must possess sufficient
resistance to corrosion for the designed life.
(b) Appropriate preventive maintenance practice must be adopted to maintain the integrity of the
equipment/component.
The selection of materials must be based on an extensive knowledge of the service environment.
It is to be realized that the behavior of a material may dramatically change when exposed to a
corrosive environment. The behavior of materials largely depends upon the following:
(a) Corrosive medium parameter.
(b) Design parameters.
(c) Materials parameters.

Composition of the corrosive medium.

Physical and external factors affecting the medium.
Presence of dissolved gases, such as oxygen, carbon dioxide, hydrogen sulfide in fluids promotes
the corrosivity of the medium.
Presence of organic matter and bacteria promote the corrosivity of the environment.
Physical state of the corrosive medium has a pronounced effect on the corrosivity of the medium.
For instance, a dry soil would be less aggressive to corrosion than a wet soil in which salts are
dissolved. Similarly, a frozen soil with a very high resistivity exceeding 10 000 ohm-cm would not
corrode a pipe, whereas, a wet soil with a low resistivity, such as 500 ohm-cm would cause severe
corrosion to structure buried in the soil.
Design Parameters
Bimetallic contacts, Crevices, Riveted joints, Spacing for maintenance, Drainage and directional
orientation of loop.
Materials Parameters
Impurity segregation on grain boundaries leading to weakening of grain boundaries,
Microstructural constituents. A heterogeneous microstructure forms anodic and cathodic sites,
Surface treatment, such as galvanizing, phosphating and painting, Alloying elements and film
formation.
(5) Weldability. Welding procedures, such as electric arc welding, friction welding, spot welding,
need to be carefully selected to minimize the effect of corrosion.
Machinability. Machining operations, such as drilling, milling, shearing, turning, may lead to
enhancement of corrosion if they are not properly controlled. Drilling fluids are highly corrosive
and need to be handled with care.

Surface modification procedures, such as cladding, galvanizing and metallizing (metallic coatings)
increase the resistance of the materials to corrosion.
Salvage or Recycling
Often it might be cost-effective to use an expensive material if it can be recycled with a high salvage
value on completion of the useful life of the equipment/product. Environmental considerations
also demand the recycling of metallic materials.
There are a vast number of material/operational environment combinations, and each can form the
basis for potential corrosion problems to occur.
Of the 103 plus elements in a Periodic Table, approximately 80 are metals, each possessing different
mechanical, chemical, and physical properties. Although all these metals can corrode, they do it in
many different manners. Furthermore, most of these metals have been alloyed to make tens of
thousands of different alloys.
From a purely technical standpoint, an obvious answer to corrosion problems would be to use more
resistant materials. In many cases, this approach is an economical alternative to other corrosion
control methods.
Unanticipated corrosion problems will always occur, and correcting them may require a reactive
approach.

Lists of questions that should be answered in order to estimate the corrosion behavior of
materials either in service or considered for usage.

A common form of representing the corrosion resistance of materials is what is known as

isocorrosion diagrams. The use of the prefix iso refers to lines (or regions) of constant corrosion
behavior across variations in concentration and temperature.

Case Study: Quills for Sulphuric acid use

The use of concentrated sulfuric acid for pH control in water and wastewater treatment,
agriculture, bio-energy and chemical processes is often the best choice due to the ready
availability, low cost and effectiveness of this acid.
Injection
Concentrated sulfuric acid (93%-98%) is an oily liquid with a density nearly twice that of
water and a viscosity similar to honey. Sulfuric acid typically requires additional
diffusion or mixing techniques to assure reliable diffusion into the process stream
without damage to the process piping.

If at all possible, it is best to predilute the acid down to 0.5%-3% concentration.

Advantages of injecting a weaker acid include:
A weaker acid stream is much more miscible and easier to diffuse into a water stream.
The likelihood of corrosion to the pipeline is lessened.

Greater volume allows for higher velocities and a larger injection plume at the
injector to improve distribution.
Better control over final pH as the larger flow volume is easier to control.
Temperature rise of 0.5%-3% dilute acid due to the heat of reaction of the acid
with water is much lower, and allows for easier handling with common piping
materials.
This can eliminate PTFE lined steel piping which is recommended for
concentrated acid dilution systems.

During system shutdown, the acid that remains will mix with the water, and will
not settle at the bottom of the piping in a corrosive, viscous puddle.

Care must be taken when choosing materials for diffusers or injectors that can
withstand sulfuric acid across during dilution process. Various polymeric materials
can be used.

Metals
Carbon Steel

Carbon Steel is often found in the piping of concentrated sulfuric acid. It is not
recommended as it will quickly degrade in the presence of acid and water.
Stainless Steel
Stainless Steel has some resistance to sulfuric acid. 316L S.S. often is used as piping
material around the quill (never use stainless steel for the quill) with good success.
We will discuss only two alloys, Alloy 20 & Hastelloy C-276.

Alloy 20
Alloy 20 (20Cb-3) is one of the so-called "Super" stainless steels that was designed for
maximum resistance to acid attack. It's nickel, chromium, molybdenum and copper
content contribute to its overall resistance to chloride stress corrosion cracking and
general pitting attack.
The alloy is stabilized with columbium to minimize carbide precipitation during
welding. It has good mechanical properties and can be fabricated with comparative
ease.
Corrosion can occur on a Alloy 20 quill if concentrated sulfuric acid is allowed to react
with the water and reach the high temperatures of approximately 150F, particularly if
the concentration even temporarily reaches the 30-80% region, which can easily
occur.
Due to the metal material, longer quills can be supplied compared to teflon without
bending or breaking.

Hastelloy C-276

Hastelloy C-276 is a good choice for nearly all concentrations of sulfuric acid as long as
temperatures are managed.
At higher temperatures, corrosion rates will likely be unacceptable.
Corrosion can occur on a Hastelloy quill if concentrated sulfuric acid is allowed to react
with the water and reach the high temperatures of approximately 150F, particularly if
the concentration even temporarily reaches the 30-80% region, which can easily
occur.

Hastelloy C-276

Cast irons have carbon content between 2 and 4%, and often significant amounts of carbon and
smaller amounts of other elements. The following factors determine the properties of cast iron:
Chemical composition of cast iron
Rate of cooling of the casting in the mold
The type of graphite formed.

Gray Cast Iron

Consider cooling of iron containing between 2.0 and 4.3% carbon from the liquid state.
If the cooling is slow, graphite flakes are formed and at room temperature, a structure comprising
of pearlite and graphite (flakes) is formed.
Because of the gray appearance, this type of cast iron is called gray cast iron. It is the most
commonly used cast iron and easiest to machine.
The chemical composition of gray iron ranges from 2 to 4% of total carbon with at least 1% silicon.

White Cast Iron

At fast cooling rate more iron carbide (Fe3C) is formed instead of graphite upon solidification.
The white cast iron fracture to produce a white surface, hence they are called white cast iron.
They serve as raw materials for malleable irons.

Malleable Cast Irons

Cold white iron castings are heated in a malleabilizing furnace to decompose the iron carbide of
white cast iron to graphite and iron.
The graphite is in the form of irregular nodular aggregates, called temper carbon.

Spheroidal Graphite (S.G.) or ductile cast iron

It is produced by treating a high carbon equivalent liquid iron with manganese or cerium to
prevent the formation of graphite flakes.
The structure at room temperature comprises a graphite spheres in a matrix of ferrite.

Duriron contains 14.5% Si and 0.95% C.

3% Mo is added to increase the resistance to HCl, chlorides and pitting Durichlor. In addition to
this Cr is also added to improve the corrosion resistance Durichlor 51.
These alloys are available only in cast form for drain lines, pumps etc.
Used extensively as anodes for impressed current cathodic protection.

Pitting and Crevice Corrosion

Cast irons behave similarly to carbon steels. They show susceptibility to pitting and crevice
corrosion in seawater and similar environments.
Addition of nickelchromium and molybdenum increase their resistance to pitting.

Stress Corrosion Cracking

The following environments cause stress corrosion cracking of cast irons:
(1) Acid chloride
(2) Ammonium nitrate
(3) Hydrogen sulfide
(4) Sodium hydroxide

(5) Seawater
(6) Calcium nitrate
(7) Sodium hydroxide
(8) Sodium nitrate

Graphite Corrosion
Cast iron is prone to selective leaching in soft water, acidic water, brackish water and water
containing low levels of hydrogen sulfide. Observed in gray cast iron.

Flow Induced Corrosion

Addition of chromium, nickel and copper in small concentrations are known to reduce the rate of
corrosion in natural, potable, brackish and seawaters.
The rate of corrosion is strongly affected by the tendency of cast iron to form scales. Carbon dioxide
accelerates the formation of scales in fresh water.
The rate of corrosion of cast iron is directly linked to oxygen content. Cast iron is sensitive to attack
by hydrogen sulfide even in the absence of oxygen.
Corrosion rates of cast iron accelerate with velocity, if the water is not treated with inhibitors.

Corrosion of Cast Iron in Seawater

Cast iron may suffer from graphitic corrosion in seawater.
Cast iron with 13% Ni are used for pump houses, water boxes and other component for service.
Gray cast iron has a greater susceptibility to pitting than malleable cast iron.
The pitting factor, represented as: Deepest pit depth/Average corrosion rate varies with the form
of cast iron.
Gray cast iron and malleable iron are resistant to atmospheric corrosion. They show a higher
resistance than low alloy high strength steels. They are, however, sensitive to attack by H2S
released by sulfate-reducing bacteria.

Carbon steels are a series of alloys of carbon and iron containing up to about 1% carbon and up
to 1.65% Mn, with elements added in specific quantities for deoxidization and residual quantities
of other elements.
In these steels carbon is the major strengthening element.

Low, Medium and High Carbon Steels

Mild steels. Steels containing <0.25% carbon are general purpose steels, commonly used for
food and beverage cans. They have a tensile strength of about 430 N/m2 and yield strength of
230 N/m2.
Medium steels. They contain carbon in the range of 0.250.50% carbon. They are used where
strength and toughness is the demanding factors.
(d) High carbon steels. They contain more than 0.5% carbon. They are used for hammers,
punches, drills, razors, etc.

High Strength Low Alloy Steels

These steels have strength in the range of 2948 MPa, and tensile strength in the range of 4162
MPa. They are mainly used as structural steels. Mn, Nb, V, Ni, Ti in small amount are added.
They are weldable. The strength depends on the alloying elements and their content.

Corrosion Characteristics of Carbon and Low Alloy Steels

Carbon steel is the most universally used material for service in seawater. It is used for various
applications in ships and shipping industry.

Advantages easy availability, low price, a satisfactory rate of corrosion and ease of fabrication.
On exposing to water, iron corrosion products would be formed and may create operational
problems of equipment and plants.

Factor affecting corrosion Dissolved oxygen, pH, Temperature, material factors, Alkalies,
Hydrogen attack, geothermal fluids (deficient in O2 but H2S present), CO2 corrosion in oil and gas
fields.

These are alloys of iron, chromium and other alloying elements that resist corrosion in several
environments.
A steel cannot be called stainless unless it has a minimum of 12% of chromium as chromium is
the major element responsible for corrosion resistance. Cr itself is a reactive element, however, its
alloys passivate and show excellent resistance to corrosion in many environments.
There are several classes of stainless steels categorized by their microstructures:
(1) Ferrite Ironchromium + low carbon (between 12 and 25% chromium and less than 0.1% C).
Non-hardenable steels, consists of iron, has a BCC structure, shows good resistance to stress
corrosion. In a high purity variety total C+N content is below 250 ppm. This improves pitting and
crevice corrosion resistance.
(2) Martensitic. Ironchromium + higher amount of carbon (1218% Cr and between 0.1 and
1.2% carbon). They can be hardened by heat treatment. Heat treatment can result in high tensile
strength. Used in applications requiring moderate corrosion resistance plus high strength and
hardness.

(3) Austenitic. FCC iron (1626% Cr, more than 6% Ni and carbon as low as 0.1% or even less).
They are non-magnetic and cant be hardened by heat treatment. They have better corrosion
resistance than martensitic and ferritic steel in general.
Ferritic and austenitic steel can be hardened only by cold working.
(4) PH (Precipitation hardening) These are ironchromiumnickel alloys containing
precipitating element, such as Al. Strength is achieved by precipitation hardening heat
treatment. One example is (177 PH) steel containing 0.09 C17 Cr7 Ni1.0 Al1.0 Mn.
Hardened and strengthened by solution quenching followed by annealing at 800-1000oF for a
long duration. Used in aircraft and missile industry.

The effect of alloying elements in steel

Chromium (Cr)
This is the most important alloying element in stainless steels. It is this element that gives the
stainless steels their basic corrosion resistance. The corrosion resistance increases with increasing
chromium content. It also increases the resistance to oxidation at high temperatures.

Nickel (Ni)
Ni reduces the corrosion rate and is thus advantageous in acid environments.
Molybdenum (Mo)
Molybdenum substantially increases the resistance to both general and localized corrosion.
Copper (Cu)
Copper enhances the corrosion resistance in certain acids.
Silicon (Si)
Silicon increases the resistance to oxidation, both at high temperatures and in strongly oxidizing
solutions at lower temperatures.
Carbon (C)
Carbon reduces the resistance to intergranular corrosion. In ferritic stainless steels carbon
will strongly reduce both toughness and corrosion resistance.

Nitrogen (N)
Nitrogen increases the resistance to localized corrosion, especially in combination with
molybdenum. In ferritic stainless steels nitrogen will strongly reduce toughness and corrosion
resistance.
Titanium (Ti)
Titanium is a strong carbide former. In austenitic steels it is added to increase the resistance to
intergranular corrosion but it also enhances the mechanical properties at high temperatures. In
ferritic stainless steels titanium is added to improve toughness and corrosion resistance by
lowering the amount of interstitials in solid solution.
Niobium (Nb)
Niobium is a strong carbide former. As titanium it promotes a ferritic structure. In austenitic steels
it is added to improve the resistance to intergranular corrosion but it also enhances mechanical
properties at high temperatures.
Aluminium (Al)
Aluminium improves oxidation resistance, if added in substantial amounts. It is used in certain
heat resistant alloys for this purpose.
Sulphur (S)
Sulphur is added to certain stainless steels, the free-machining grades, in order to increase the
machinability. At the levels present in these grades sulphur will substantially reduce corrosion
resistance, ductility and fabrication properties, such as weldability and formability.

Cerium (Ce)
Cerium is one of the rare earth metals and is added in small amounts to certain heat resistant
steels and alloys in order to increase the resistance to oxidation and high temperature corrosion.

Corrosion of Stainless Steels in Acids

Stainless steels are subjected to serious corrosion problems in oil refineries as they may
encounter very corrosive fluids, such as hydrochloric acid and naphthenic acids in the process
streams.
Hydrofluoric acid, hydrogen fluoride and fluorine are less corrosive to many metals and
alloys than their own halide counterpart. The nickelcopper alloys, typified by Monel alloy
400 have excellent resistance to hydrofluoric acid corrosion.
Stainless steels, such as 316, suffered severe transgranular corrosion.

Corrosion of nickel alloys and SS in

anhydrous hydrogen fluoride

Corrosion resistance of SS 304 in aqueous HF

Corrosion rate of 304 and 316 steels in flowing seawater

Effect of seawater condition on the corrosion rate of

selected stainless steels

Stainless steels, such as AISI 304 and AISI 316,

perform well in flowing seawater up to 2.0 ms1.

Depth of Immersion
Materials partially immersed undergo a
heavier corrosion attack than materials
fully immersed.
Metal samples are most severely attacked
in tidal zone.

Aluminium and Aluminium Alloys

Aluminium and the aluminium alloys find use in many engineering applications because of their
combination of lightness with strength, their high corrosion resistance their thermal and electrical
conductivity and heat and light reflectivity, and their hygienic and non-toxic qualities.
Aluminum is considered as an extremely corrosion-resistant material due to a thin, protective,
highly adherent oxide film which it forms on the surface.
Pure aluminium is soft and weak, but can be alloyed and heat treated to have a broad range of
mechanical properties. Al-Cu alloy has a precipitated CuAl2, which hardens and strengthens the
material but reduces its corrosion resistance.
Composites of aluminium alloy with a thin cladding on one or both surfaces of a more anodic
aluminium alloy or pure aluminium, enable sheet, plate and tube to be produced with special
combinations of strength and corrosion resistance appropriate to service conditions.
Although originally applied to high strength aircraft alloys, this principle of cladding is now
utilized in several important industrial applications.
Al alloy loses its strength when exposed to temperatures of 350oF and higher. However, they show
excellent properties at cryogenic temperature because it has a FCC structure.

Corrosion Behaviour in Aqueous Environments

The corrosion resistance of aluminium and its alloys is largely due to the protective oxide film
which within seconds attains a thickness of about 10 A on freshly exposed metal; continuation of
growth is markedly influenced by the environment, being accelerated by increasing temperature
and humidity.
In most environments, therefore, the rate of corrosion of aluminium decreases rapidly with time.
In only a few cases, e.g. in caustic soda, does the corrosion rate approximate to the linear.
A corrosion rate increasing with time is rarely encountered with aluminium, except in aqueous
solutions at high temperatures and pressures.

Characteristic Features of Corrosion Behaviour

General dissolution occurs in strongly acid or strongly alkaline solutions, but there are specific
exceptions. In concentrated nitric acid the metal is passive. inhibitors such as silicates permit the
use of some alkaline solutions up to pH 11.5 to be used with aluminium.
Pitting is the most commonly encountered form of aluminium corrosion. Once a pit is formed it
grows because the solution inside the pit become acidic and the protective film cannot grow.
In alkaline media pitting may occur at mechanical defects in the oxide.
In the aluminium copper type alloys, precipitation of CuAI, particles at the grain boundaries
leaves the adjacent solid solution anodic and prone to corrosion.
With aluminium-magnesium alloys the opposite situation occurs, since the precipitated phase
Mg,Al, is less noble than the solid solution. possibility of grain boundary corrosion but not
serious.

Corrosion Resistance of Al 1100 Series (Pure Al)

This series represents commercially pure aluminum ranging from 99 to 99.5% purity.
The ability of aluminum to resist corrosion depends on the inherent ability to form protective
oxide film.
Aluminum dissolves both in acids and alkaline solutions due to instability of aluminum oxide
and hydroxide films. The rate of corrosion is low between pH 5.5 and 8.5. It shows a good
resistance to urban and marine atmospheres unless contaminated with copper.

Corrosion of Aluminum and its Alloys

Alloys of 5xxx series show a resistance to pitting. Alloys containing copper increase the
tendency to pit. Alloy Al 5052 has been successfully used in seawater with a minimum risk of
pitting. Aluminum alloys of 2xxx series, such as 2024 are not resistant to pitting and the same is
true for alloys of 7xxx series, such as alloy 7050. Alloys 6061 and 6013 show a fairly good
resistance to pitting in marine environment because of smaller copper contents. High strength
alloys containing copper, such as Al 2024, used in aerospace applications are protected against
pitting by coating.

Pitting resistance of heat exchanger tube materials made of aluminium alloys in

desalination service.

Effect of pH and oxygen content on seawater pitting of aluminum alloy tubes based on 30day tests

Intergranular Corrosion
Observed in Al alloys when the acid environment in the pits lead to attack on grain boundaries.
In AlMg alloys (5xxx), phases such as Mg2Cl3, may precipitate at the grain boundaries. AlMg
alloys (5xxx) containing less than 3% Mg, are resistant to intergranular corrosion.
In the 2xxx series, a more noble precipitate, such as CuAl2 may be formed leaving the areas
adjacent to the grain boundaries more reactive promoting their dissolution in the acid pit.

The 6xxx series show susceptibility to intergranular corrosion because of the formation of Mg2Si
precipitate if excessive silicon is present.
Alloys of 7xxx series are prone to intergranular attack because of the formation of a CuAl phase.

By eliminating the sites of pitting or crevice corrosion and minimizing the potential difference
between the grain boundaries and matrix by appropriate heat treatment, intergranular attack can
be minimized or eliminated.

Flow Induced Corrosion

The resistance of aluminum alloys to flow induced corrosion depends on the
stability of the protective oxide films on the surface. Dissolution of these films leads
to accelerated corrosion.
Aluminum alloys of series 5xxx are not adversely affected by velocities up to 3 m/s
in the absence of abrasives in water. The removal of a film adjacent to a film surface
sets up local corrosion cell which accelerates the corrosion process. Alloys of 5xxx
series (such as 5454) show a good resistance to corrosion at velocities up to 3 ms1
at temperatures up to 140C.
The corrosion rate increases with increased velocities in the presence of abrasive
particles, which need to be controlled. The water velocity and pH needs to be
controlled to minimize the effect of flow on localized corrosion. Maintaining pH
below 9 would not allow aluminum to dissolve as AlO2 .
The preventive measures include the minimizing of turbulent flow or changing
water chemistry.

Stress Corrosion Cracking and Corrosion Fatigue

The risk can be minimized by using high strength alloys and or alloys with lower
stress levels. High strength to weight ratio alloys are used in aerospace industry to
lower the risk of SCC.
Alloys of 5xxx and 6xxx series show good fatigue resistance.
Ranking of stress corrosion cracking of major commercial aluminum alloys

Anodizing and Al Cladding

These two corrosion prevention methods are exclusive to aluminum alloys.
Anodizing is used to produce a layer of oxide by applying a specified voltage to aluminum which is
made an anode in an electrolyte of sulfuric acid, oxalic acid or chromic acid. Anodizing provides
longer life and aesthetic values to equipment or articles.
In cladding, one of the alloys acts as a sacrificial material/ protective layer for the other alloy which
is to be protected. High strength aluminum alloys containing copper are sensitive to corrosion,
whereas Al 1100 is highly resistant to corrosion. Thin aluminum sheets (Al 1100) are hot rolled on
the top and bottom of Al 2024-T3 sheet to produce the alclad version of Al 2024-T3.
The pure aluminum (Al 1100) protects due to formations of oxide layer and if need arise acts as a
sacrificial coating to Al 2024 and corrodes in preference to Al 2024.
Because of the limitation of alcladding to sheet metals, new electroplating processes have been
developed to produce pure aluminum coatings on a variety of products, such as screws, fasteners,
forgings, etc.