Materials Selection for Corrosive Environment

When selecting materials, each component must be considered with respect to design, manufacture
and its effect on the total geometry. However, it is also important that the materials in adjacent
components are compatible. With regard to corrosion, compatibility often means that detrimental
galvanic elements must be avoided. Not only the main structural materials, but also insulation and
other secondary materials must be taken into account to prevent galvanic corrosion.
In many cases it is possible to avoid other forms of corrosion by using a favourable combination
of materials, e.g. to include a material that implies cathodic protection against uniform, selective,
pitting, crevice or erosion. Corrosion and Protection corrosion on critical regions, even against
stress corrosion cracking or corrosion fatigue. Not only do the grades of structural, load-bearing
materials have to be specified, but also surface treatment and coatings.
Properties of materials
The corrosion properties and other functional properties of materials depend on several external
factors such as geometry, manufacture, surface conditions, environmental factors and mechanical
load conditions. For each functional property, these factors have to be evaluated. The final
materials selection is often a result of compromises between various properties and their
dependence on external factors.
How to select a Material?
A proper selection of materials depends on sufficient knowledge on how the actual practical
conditions affect each material candidate. To ensure that important aspects are not forgotten, check
lists should be used, which should include risk of different forms of corrosion for each candidate,
relevant conditions affecting each form of corrosion, possibilities of changing the corrosion
properties of a certain material, possibilities for application of various protection methods,
accessibility for maintenance, environmental conditions, loads and special requirements during
various parts of the lifetime etc. The best tools for weighing the various aspects are quantitative
expressions of properties and performance data valid under various conditions, such as corrosion
rate and distribution, lifetime in corrosion fatigue, mechanical or electrochemical threshold value
compared with corresponding quantified requirements or service conditions, i.e. specified lifetime,
actual stress intensity factors and functions, and corrosion potential.
The simplest way is to choose the material that has been used before for the same or some similar
purpose. If the material selection plays a less important role, or if the risk and consequence of
changing to a new material are uncertain, it may be preferable to stick to the same as before.
As a general guideline for materials selection primarily dictated by corrosion aspects, the reason
for the corrosion resistance of the respective material candidates may be used. If the resistance is
based upon:
1. Passivity, the alloy is suitable for oxidizing environments (only in the absence of species that
promote localized corrosion).
2. Immunity, the alloy is suitable for reducing environment.
This means that reducing environments are compatible with relatively noble metals or alloys
(copper, lead, nickel and alloys based upon these metals). When metallic materials are to be used
in oxidizing environment, on the other hand, their corrosion resistance must be based upon
passivity (e.g. titanium and alloys that contain sufficient amounts of chromium). Irrespective of
the mentioned rule, a metal is usually most corrosion resistant when it contains the smallest
possible amounts of impurities.
Some natural combinations of environment and material
Environment Material
Nitric acid Stainless steels
Caustic solutions Nickel and nickel alloys
Hydrofluoric acid Monel
Hot hydrochloric acid Hastelloys (Chlorimets )
Dilute sulphuric acid Lead
Non-staining atmospheric exposure Aluminium
Distilled water Tin
Hot, strongly oxidizing solutions Titanium
Ultimate resistance Tantalum
Concentrated sulphuric acid Steel

Some Special Aspects of Materials Selection for the Offshore Industry

With the huge and expensive installations in deep seawater, and with production equipment and
pipelines carrying very aggressive mixtures of hydrocarbons and salt water, strict demands are
naturally made on the corrosion technology for this industry. During the last few decades, oil
companies have started using more corrosion-resistant materials in production and seawater
systems. There are several reasons for this:
i) Large inhibitor expenses can be eliminated or reduced strongly.
ii) Demands for inspection, maintenance and replacement is reduced. This is of particular
importance in sub-sea production systems.
iii) More rational localization of separators for removal of corrosive species from oil and gas can
be obtained.
iv) More pollution and higher flow rates may be accepted in seawater systems.
v) Weight may be reduced by reducing thickness (omitting corrosion allowance) or by using lighter
materials.
One of the actual concepts comprises a central production platform that receives hydrocarbons
through pipelines from several production units on the seabed at the respective wells. Under these
conditions, corrosion-resistant and strong materials are useful for the sub-sea systems and strong,
light and possibly corrosion-resistant materials for the installations on the platform. Several
materials properties are more or less important, depending on the purpose: in addition to corrosion
resistance, strength, density, and the ratio between strength and density, these properties may
include erosion resistance, weldability, heat resistance, inflammability and thermal properties such
as heat conductivity and expansion coefficient.
Unalloyed and Low-alloy Steels and Cast Irons
Atmospheric corrosion rates can be reduced considerably by use of special low-alloy steels, i.e.
weathering steels. In other natural environments such as soils and waters the differences between
various unalloyed or low-alloy steels are small as regards the surface corrosion forms not affected
by mechanical forces and conditions. When selecting materials within these groups, some kind of
corrosion protection must be considered as an integrated part (coatings, cathodic protection,
corrosion allowance, inhibitors). Regarding corrosion forms that interact with mechanical effects,
i.e. erosion, abrasion, cavitation, fretting, static tensile stresses or fatigue, we must distinguish
sharply between the different steels, since strength and hardness, and in some cases ductility,
toughness and elasticity, have great significance. In oil production, increasing the strength of steel
in order to reduce weight is of considerable interest, but the risk for hydrogen embrittlement (as a
mechanism in stress corrosion cracking or due to cathodic protection) limits the permissible
strength of material in production tubing, casings, production equipment, and welded structures
affected by fatigue.
The selection of material is closely related to design, not least for welded structures. Higher
material strength may be tolerated when the welds are localized in less critical regions and when
the weld quality is improved. Contrary to corrosion in most natural environments, i.e. under O2
reduction, CO2 corrosion is considerably affected by relatively small amounts of alloying
elements. As shown in Table below, the effect of alloying steel for a gas/condensate well with Ni
and Cr is strong. Alloyed steels have therefore been used sometimes in production tubing instead
of carbon–manganese steel, which was commonly used previously.
Effect of alloying with nickel and chromium on the corrosion of steel in gas/condensate.
Ni (%) Corrosion rate mm/y Cr (%) Corrosion rate, mm/y
0 0.9 0 0.9
3 0.1 2.25 1.25
5 0.075 5 0.525
9 0.05 9 0.04
12 0

Unalloyed steel and cast iron without external protection resist concentrated sulphuric acid (>70%)
fairly well at room temperature under stagnant conditions. Carbon steel is therefore often used in
tanks, pipes, tank vehicles, transport containers and production equipment exposed to this
environment. The corrosion rate is higher at high flow rate. Hot acid (made by dissolving SO3 in
acid) may attack grey cast iron along graphite flakes and cause cracking.
Usually, carbon steels are also resistant in alkaline environments such as NaOH and KOH solutions
without contaminations, but may be subject to stress corrosion cracking (caustic embrittlement) at
certain concentrations and temperatures.

High-alloy Cast Irons

Of these materials we shall briefly consider two groups that possess very good corrosion resistance
in many environments: a) silicon iron and b) cast iron with Ni and/or Cr. Table 1 and 2 shows trade
names and compositions of various grades within these groups.
Table 1.
Material % Alloying elements
Durasid Min. 14.5 Si, with or without Mo

Durichlor 14.5 Di, (3) Mo

Duriclor 51 14.5 Si, Mo, Cr

Duriron 14.5 Si, 0.5 (0.95) C

Thermisilid 18 Si

When the Si content in grey cast iron is increased beyond 14%, the corrosion resistance in many
environments becomes very good because a passive film of SiO2 is formed on the iron surface.
The hardness of Si-irons is also high and they resist erosion and cavitation corrosion relatively
well. On the other hand, the tensile strength is low and their weldability is poor (components with
simple shapes may be welded when thorough precautions are taken).

The high-alloy silicon irons are used in draining pipelines, pumps, valves, other process
equipment, and anodes for cathodic protection with impressed current.
The most common high-alloy cast irons with Ni and Cr are the socalled Ni-Resist alloys. These
alloys have an austenitic structure, and therefore they are much tougher than the Si-irons and other
cast irons. They are also produced as ductile irons; in this form they may have an ultimate tensile
strength of 500 MPa and fracture elongation of 40%. Ni-Hard is an alloy with extra high hardness
and good resistance against erosion (and abrasion) corrosion, and it is therefore used in flow
systems carrying mixtures of corrosive liquids and solid particles. Ni and Cr-alloyed cast irons
show superior heat resistance to other cast irons.
Table 2. High-alloy cast irons with Ni and/or Cr.
Material % Alloying elements

Ni-Resist 1 15 Ni, 6 Cu, 2 Cr, 2.8 C

Ni-Resist 2 20 Ni, 2.3 Cr, max. 2.0 C
Ni-Resist 3 30 Ni, 3 Cr, max. 2.6 C
Ni-Hard 4 Ni, 2 Cr, white cast iron
Guronit G52 25–30 Cr
Wegucit 30 Cr
U.S. type 446 L(AISI) 23–27 Cr, max. 0.35 C, max. 0.25 N

10.1.5 Stainless Steels

The corrosion resistance of stainless steel is due to passivation by a surface film of chromium
oxide. The chromium content is higher than about 11%, and the low-temperature corrosion
resistance as well as the resistance to oxidation and mill scale formation at high temperature
increase with increasing content of chromium. Pure chromium steels are either ferritic (low
Content, non-hardenable by heat treatment) or martensitic (traditionally higher Content
for most grades, hardenable by heat treatment). With sufficient content of Ni the structure becomes
austenitic, which gives increased formability, weldability, toughness and heat resistance. Contrary
to the steels with ferritic, martensitic or ferritic–austenitic structure, the austenitic steels are non-
magnetic.
Mo gives improved corrosion resistance to certain acids, although no universal resistance exists
versus acids. Nitrogen (N) increases the strength of austenitic steels and affects the structure in the
same direction as Ni, i.e. it is an austenite former. N-content of 0.2% gives markedly better
corrosion resistance of austenitic steels to seawater than does 0.02–0.08%. Cu improves the
resistance versus certain acids. Ti stabilize the structure by preventing precipitation of chromium
carbide and subsequent corrosion at the grain boundaries, i.e. intergranular corrosion. The
stabilization can also be obtained by reducing the content of carbon to below 0.03%.
The martensitic steels are less corrosion resistant than other stainless steels. Since they can be
hardened and tempered, they are used where it is suitable to combine high strength and hardness
with moderate corrosion resistance and/or relatively good resistance to cavitation, erosion or other
wear mechanisms. Examples of applications are ball bearings, turbine blades, valve guides, tools,
cutlery, and surgical instruments.
Grades with 18–27% Cr resist oxygen and sulphur at high temperature. The ferritic steels have
good resistance to atmospheric corrosion, and 16–18% Cr-steel are used in unpainted automobile
parts. These steels resist nitric acid and have been used in tanks for transport and storage of HNO3.
It is very important that the oxide film is dense. On clean and smooth surfaces the oxide is formed
rapidly. Conversely, if the surface is rough or contaminated, with deposits, mill scale, welding slag
etc. the passivation is hindered, and pitting or deposit corrosion may occur. Depending on the
conditions, stainless steels may be attacked by uniform corrosion (in reducing acids, in extremely
oxidizing strong acids and in strong alkalies), pitting, crevice corrosion, intergranular corrosion or
stress corrosion cracking.
The weldability varies much from one type of stainless steel to another and must be checked when
steels for specific applications are selected. In older types of ferritic steels, embrittlement and
intergranular corrosion could occur in the heat affected zone (HAZ). These problems can be
avoided with newer ferritic steels with low contents of C and N. Some of these new steels may be
subject to grain growth in the HAZ. Ferritic–austenitic steels show usually somewhat better weld
properties than do the ferritic steels. The weldability of austenitic steels is generally good, but
there is some tendency to high-temperature cracks in those with highest content of alloying
elements. Change of Environment
The environment may be changed in the following ways in order to reduce corrosion
rates:
a) Decreasing (or increasing) the temperature
b) Decreasing (or increasing) the flow velocity
c) Decreasing (or increasing) the content of oxygen or aggressive species
d) Adding inhibitors connections

Assignment Topic;
Selection of a Material for Corrosive Environment
Submitted To;
Dr. Naveed Anjum
Submitted By;
5401, 5427, 5429, 5430, 5443.
Class;
M.phil (Evening)
Semester;
1st
Department;
Applied Chemistry

Government College University, Faisalabad.