STAINLESS STEEL

AND CORROSION
HOW STAINLESS STEEL These di ent forms of corrosion THE TEMPERATURE
IS AFFECTED BY, AND are sometimes thought to ect This is usually known and uniform.
RESISTS, CORROSION only stainless steels. This is not the Care must be taken to prevent higher
steel is the most utilized material case. Carbon steels, low alloy steels localised temperatures. A typical
of construction. However, natural and many other metals and alloys example of such a condition is that
forces cause steel, an unnatural form may also undergo similar forms of prevailing under heat transfer, for
of iron, to revert to its natural oxide. corrosive attack, but often in ent example, solar heaters or heating coils.
This is corrosion. environments.
The primary property of stainless Dry, or gaseous corrosion will be super-heated corrosive solution that
steel is corrosion resistance and may covered in an upcoming module exists at the metal surface, through
be considered as the only reason addressing the high temperature use which the heat is transferred. It is the
why we use the material. Some may of stainless steels.
say that they use stainless steel for Some forms of corrosion are taken into account, as it gives rise to far
hygiene properties or for aesthetics, easily visible or readily e more aggressive conditions than those
but it is the resistance to corrosion (e.g. general and pitting corrosion), related to the average bulk temperature.
which allows stainless steels to have whereas others are not always easily
these essential b . detectable nor apparent (e.g. stress HEAT SOURCE
Stainless steels, because of their corrosion cracking, SCC).
resistance to corrosion, are often Steam Hot Oil Sunlight

used in highly aggressive conditions, WET (AQUEOUS)

which will cause most alternative CORROSION
METAL
materials to fail rapidly. This is an attack on the metal by
Therefore, an understanding of the aggressive substances generally
basic mechanisms of corrosion will dissolved in water to give a corrosive Thin layer of super heated
solution (electrolyte). A damp lm or solution at the metal surface
assist in selecting the correct stainless
steel for use in a variety of situations dust containing dissolved aggressive CORROSIVE SOLUTION BEING HEATED
and conditions. substances also results in a corrosive
electrolyte. FIG 1: Schematic illustration of
CORROSION The severity and extent of the superheated layer occuring at the metal
corrosion depends on surface under conditions of heat transfer
Essentially there are two forms of
corrosion. The concentration of such
THE PRESENCE AND NATURE OF
Wet (aqueous) corrosion aggressive substances in the
CONTAMINANTS
Dry (gaseous) corrosion corrosive solution.
Because all aqueous corrosion is
This paper will cover the more The temperature of the corrosive
electrochemical there is always an
common mechanisms of Wet solution.
equilibrium between the reactions at
(aqueous) corrosion of stainless steel The presence and nature of
the metal surface and those within the
which can consist of one, or more, of contaminants and trace elements
corrosive solution. Even trace amounts
the following forms of attack within the solution.
of contaminant ect this balance
General corrosion and therefore either aggravate or
Galvanic corrosion THE CONCENTRATION
counteract and lower the severity of the
Atmospheric corrosion This is generally both known and
corrosion.
Erosion/abrasion corrosion controlled. Care should be taken
Intergranular corrosion to avoid conditions where the S TAINLESS STEEL
Pitting corrosion concentration can vary, e.g. stainless steel is a generic term covering
Crevice (shielded) corrosion Condensation and evaporation a family of chromium (Cr) containing
Microbiologically induced Concentration in crevices as this alloys. The chromium content is
corrosion (MIC) may result in unexpected, severe or usually between 11 and 30%. Other
Stress corrosion cracking (SCC) localised corrosion attack. alloying elements which increase
 the corrosion resistance of stainless
steel may also be added, such as, nickel
(Ni), molybdenum (Mo), copper (Cu),
titanium (Ti) and niobium (Nb).

This has been covered in detail in

Module 1 of the Information Series.

The various different groups of stainless

steel are schematically reflected in the
Stainless Steel Family Tree, alongside.

PASSIVITY discolouration needs to be removed Care must be taken to maintain and

Passivity is the built-in mechanism before passivation can take place. preserve the integrity of the passive
which stainless steels possess to combat Passivation is the chemical treatment film.
corrosion. It is defined as a state in of a stainless steel with a mild oxidant, Avoid mechanical damage and
which a metal or alloy loses its chemical such as a nitric acid solution, for the contamination.
reactivity and becomes inert. purpose of enhancing the spontaneous Repair any affected areas, for
A chromium content of more than formation of the protective passive film. example;
approximately 11% gives stainless steel Such chemical treatment is generally high temperature scale adjacent to a
this passivity, due to the formation of an not necessary for the formation of the weld, by pickling
extremely thin but uniform, continuous, passive film, but will generate a more mechanically damaged or ground
tenacious and stable chromium-rich rapid and complete passivity. areas, by optional passivation
oxide film on the surface. Thermal contamination can be contaminated areas by passivation.
The formation and properties of removed mechanically (by grinding/ Ensure a constant and sufficient
the passive film are enhanced by polishing) or chemically by pickling. availability of oxygen or oxygen
increasing the chromium content and Pickling is an acid treatment to remove containing agent.
also by adding certain other elements, high temperature oxide films resulting
particularly molybdenum and nitrogen. from welding, heat treatment, hot FORMS OF
The improved passivity which results working or other high temperature CORROSION
extends the use of stainless steels into operations. Mixed acids solutions, such A number of different mechanism
more corrosive applications. as nitric+hydroflouric acid solutions, of corrosion of stainless steel
The key to the corrosion resistance are most widely used by fabricators of are recognised. The underlying
of stainless steels is this passive layer stainless steel equipment and removes mechanism of all aqueous corrosion
and care must be taken to ensure that, both metallic contamination and high is electrochemical in nature, but the
if damaged in any way, it should be temperature scales. These scales are not initiation of corrosion, often due to a
allowed to repair itself. only undesirable for aesthetic reasons, breakdown of the passive layer, may be
The passive layer can be damaged they also result in a reduced corrosion caused in different ways, depending on
or removed mechanically (scratching, resistance of the underlying stainless particular conditions.
machining or polishing), thermally steel surface layer. Passivation alone
(by welding or heat treatment) or will not remove the scale. Chemical GENERAL CORROSION
chemically (by contamination with passivation alone is, however, able to In general corrosion, the attack is
iron particles or salt). If this happens, remove ferrous contamination and uniform over the entire surface and is
the corrosion resistance of the steel may re-form the passive layer. Note that similar to that generally seen on mild
become compromised. chemical passivation is not necessarily steel. General corrosion of stainless
The passive film will re-form required as a separate step after steels is normally observed in highly
spontaneously in an oxygen containing pickling. All that is required is that the corrosive reducing acid environments,
environment (provided that the stainless steel equipment is properly often associated with the chemical and
surface has been thoroughly cleaned rinsed with clean water and dried. mining industries.
or descaled) to restore the corrosion In the case of the passive layer being It is the least dangerous form of
resistance of the stainless steel, but this destroyed by mechanical damage, the corrosion because the rate of corrosion
does not happen instantaneously. In passivity can be restored by passivation, is measurable and predictable and
addition, any contamination or thermal as detailed above. can therefore be allowed for when

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 designing for a required life or safety solutions. More meaningful results are
factor. obtained if plant solutions are used, or
General corrosion rates are measured if the corrosion rates are determined
and reported in different units as; under in- service conditions.
a corrosion current in milliamp per The most common indicator, and
square centimetre (mA/cm2) that used in a number of different
a penetration of thickness in “corrosion manuals”, is that of a band
millimetre per year (mm/year) of corrosion rates, as indicated in
a loss of thickness in milliinches Table 1 below: These bands are used
(mils) per year (mpy) in drawing up iso-corrosion graphs,
a loss of mass in grams per square used by corrosion engineers to predict
metre per day (g/m2  day) safe operating conditions in various
Conversion between the units for the chemical environments, as illustrated in Table 3: Isocorrosion graph showing
corrosion of iron (Fe) is as follows: Tables 2 and 3 below. Typically a band suitability of different stainless steel grades
The severity of attack or suitability of “0” is considered to be safe, that of in sulphuric acid
of material is indicated in different “2” is unacceptably high, while “1” is
ways. General corrosion rates are an intermediate area and should be
have a notation of “Op”. This indicates
often determined under laboratory treated with caution.
that an additional corrosion mechanism
conditions using chemically pure Reported general corrosion rates often
is likely to occur (pitting corrosion
in this example) and care must be
exercised.
mA/cm2 mm/year mpy g/m2 day
Reported general corrosion rates,
mA/cm2 1 11.6 456 249 as indicated above, should be used as
guidelines only and full account should
mm/year 0.063 1 39.4 21.6
be taken of:
mpy 0.00219 0.0254 1 0.547 Service conditions/variations.
g/m2 day 0.00401 0.0463 1.83 1 State of the metal surface/
maintenance of passivity.
TABLE 1: SEVERITY OF ATTACK AND SUITABILITY OF MATERIAL FOR The corrosive solution in respect
DIFFERENT CORROSION RATES of uniformity/variation in terms
of concentration, temperature and
contaminants.
CORROSION RATE CORROSION RATE
Stainless steels exhibit very low
Band 0 Highly resistant general corrosion rates in many highly
<0,1mm/yr (<5mpy) aggressive, corrosive environments.
Band 1 • Transition from highly resistant They are not totally immune or
0,1-1,0mm/yr (5-50 mpy) to severe corrosion. impervious, but are versatile materials
• Metastable. of construction offering attractive and
• Consider use with care. viable life cycle costs.
Under some conditions the surface
Band 2 Severe corrosion
may exhibit signs of staining i.e.
>1,0mm/yr (>50mpy) Not suitable
visible rusting. It is very seldom that
such staining indicates corrosion rates
equivalent to those of plain carbon
(mild) steel and, even if left untreated,
minimal metal loss will occur. A simple
cleaning process will usually remove
the staining and restore the surface
appearance. However the cause should
be investigated, especially if severe dark
staining is evident, as it is an indication
that passivity has broken down.

GALVANIC CORROSION
Galvanic corrosion can occur when two
different metals are in electrical contact
and are immersed in the same corrosive
solution.
The galvanic series (or electro
potential series) determines the nobility
of metals and semi-metals. When two
metals are submerged in an electrolyte,
Table 2: Generic isocorrosion graph while electrically connected, the less

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 noble (base) will experience galvanic
corrosion. The rate of corrosion is
determined by the electrolyte and the
difference in nobility. The difference
can be measured as a difference in
voltage.
The adjacent image illustrates
the galvanic series for seawater (in
decreasing order of electrical activity).
Metals nearer the bottom of the table are
less noble and have a greater tendency
to lose electrons than the more noble
metals found higher on the list.
Note that stainless steel appears twice
in this galvanic series. This represents
the stainless steel in the active state,
with no passive film and in the passive
state, with the passive film intact.
The relative surface area of two
metals is an important factor when
evaluating galvanic corrosion. If the
surface area of the more noble metal is
small compared with the surface area
of the less noble metal, the more noble
metal will not significantly accelerate
the corrosion of the larger area of the
less noble metal.
In the first example below, the
large area of stainless steel sheet will
dramatically increase the corrosion rate
of the carbon steel fasteners resulting in
a rapid failure.
In the second example below,
the stainless steel fasteners will not
accelerate the corrosion of the steel
plate because the area of the anode
(carbon steel) is large compared to the
cathode (stainless steel fasteners).

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 PITTING CORROSION
Pitting corrosion, or pitting, is a form
of extremely localised corrosion that
leads to the creation of small holes in
the metal. The driving power for pitting
corrosion is the depassivation of a small
area, which becomes anodic while the
balance of the product (a much larger
area) becomes cathodic, leading to
very localised galvanic corrosion. The
corrosion penetrates the mass of the
metal, with limited diffusion of ions.
In stainless steels, pitting corrosion
is generally caused by halide ions
(which are usually chlorine ions, as
these are found in sea water, soils and
many raw materials). These halide
ions:
Attack localised weak points in the
passive film,
Destroys passivity in a very small
area, forming
Micro-anodes,
Extremely unfavourable ‘galvanic
effect’.
There are several preventive
approaches to avoid pitting. Examples
are listed below:
Proper material selection e.g.
using 316, or duplex stainless steels
containing Mo or N and having a
higher pitting resistance compare to
304. In other words, use higher alloyed
stainless steels for increased resistance PREmn = CR + 3.3Mo + 22N - Mn
to pitting corrosion. The chart above shows the relative
Control pH, chloride concentration pitting corrosion resistance of some
and temperature. of the most common stainless steels.
Agitation of stagnant fluid. Ferritics are shown in red, austenitics
in blue and duplex stainless steels in
PITTING green.
RESISTANCE The graph can be used as a tool
EQUIVALENT (PRE) – for material selection and material
RELATIVE PITTING substitution. For example, it can be the access of the corrosive to the
RESISTANCE seen that 304, 441 (S43940) and 2001 stainless steel surface is limited. These
The pitting resistance equivalent have similar pitting resistances and can spaces are generally called crevices.
number (PRE or PREN) is a measure of thus be used in similar environments. The corrosion resistance of a stainless
the relative pitting corrosion resistance Similarly, 316, 444 and 2304 are similar, steel is dependent on the presence of
of stainless steel in a chloride-containing have better pitting resistance and the passive film, but it is possible under
environment. The pitting resistance of for example are suitable in marine certain conditions for this passive film
stainless steel is primarily determined atmospheres. to break down, for example in halide
by its composition. The elements which Originally the PRE was used as an solutions or reducing acids. However,
have a significant impact are chromium, indication of resistance to pitting in sea areas where the passive film can break
molybdenum and nitrogen. water: down can also be the result of the way
The formula, which quantifies their If > 36, then resistant to pitting components are designed, for example
respective contribution, is: in marine environments including under gaskets, in sharp re-entrant
splashing. corners or associated with incomplete
PREN = CR + 3.3MO + 16N PRE > 40 is required for sea water weld penetration or overlapping
immersion. surfaces. These can all form crevices
This is the most common PRE formula
which can promote corrosion.
that is used. A more accurate PRE
CREVICE To function as a corrosion site, a
formula that is becoming more
commonly used is PREmn, which
CORROSION crevice has to be of sufficient width
Crevice corrosion refers to corrosion to permit entry of the corrodent, but
takes into account the negative effect of
occurring in confined spaces in which narrow enough to ensure that
manganese.

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 the corrodent remains stagnant.
Accordingly, crevice corrosion usually
occurs in gaps a few micrometres wide
and is not found in grooves or slots
in which circulation of the corrodent
is possible. This problem can often be
overcome by paying attention to the
design of the component, in particular
to avoiding formation of crevices or at
least keeping them as open as possible,
or by using flexible washers or gaskets
which form a perfect seal.
Crevice corrosion is a very similar
mechanism to pitting corrosion; alloys
resistant to one are generally resistant
to both. Crevice corrosion can be
viewed as a less severe form of localised
corrosion when compared with pitting.
The depth of penetration and the rate
of propagation in pitting corrosion are
generally significantly greater than in
crevice corrosion.
Crevices can develop a local
chemistry which is very different from
that of the bulk fluid.

ATMOSPHERIC and consequent failure of steel parts, Exposed surfaces facilitating rain
CORROSION Essential automobile parts failing cleaning.
Atmospheric corrosion is: from corrosion. Surface finish of stainless steel and
The corrosion of metals exposed to Costly repairs include repair and roughness.
air and its pollutants. painting of bridges and towers, Maintenance,
An electrochemical process where a replacing of fencing and maintenance Washing frequency.
film of electrolyte forms on the metal of building exteriors, to name a few. The corrosion rate can be decreased
surface. Generally, atmospheric corrosion is by controlling the above five factors or
When air pollutants such as SO2, defined by geographic location, local by selecting a more corrosion resistant
CO2, NOX and salts dissolve in a film of weather conditions and architectural stainless steel. The corrosion map of
water and increase its conductivity and design. South Africa is shown above.
corrosivity. There are several factors to take into
Atmospheric corrosion is a serious account in determining the degree of INTERGRANULAR
worldwide problem affecting people corrosion to be expected: CORROSION
in all walks of life. It is of concern to Environment, Intergranular corrosion, sometimes
homeowners, architects, engineers, Rural, urban pollution, industrial known as sensitisation, is a form
designers, maintenance personnel and pollution. of corrosion where the boundaries
accountants. All outdoor and indoor Salt, of grains of the material are more
materials exposed to the elements are Coastal/marine exposure and susceptible to corrosion than that the
potentially subjected to degradation distance from sea. rest of the grain.
resulting from atmospheric conditions. De-icing salt exposure (normally This is most frequently caused
Damage caused by atmospheric only in in Europe and North America). during the welding of thick sections of
corrosion can be dangerous as well as Weather, high carbon stainless steel as a result
costly, for example: Temperatures, humidity and rainfall. of chromium carbide precipitation at
Bridges failing as a result of rusting Design, the grain boundaries and chromium

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 depletion of the surrounding areas. The
chromium depleted areas around the
grain boundaries can be preferentially
dissolved in certain corrosive
environments. This is known as
sensitisation and is summarised below.
Intergranular corrosion occurs where
carbon content in the stainless steel is
high, or where cooling rates in welding
or heat treatment are slow. In most
cases, modern steelmaking practice has
reduced the carbon content to levels
at which we seldom see sensitisation,
except in extremely heavy fabrications.
However, carbon contamination during
fabrication or in service is now a more
serious cause of this problem.
Intergranular corrosion can be
prevented through:
Using a low carbon (e.g. 304L, 316L)
grade of stainless steels. bacteria that can obtain energy by
Using stabilised grades alloyed oxidising organic compounds or
with titanium, for example type 316Ti, molecular hydrogen (H2) while
niobium stabilised grades, for example reducing sulphate (SO4²¯) to hydrogen
347, can also be used. sulphide (H2S). In a sense, these
Titanium and niobium are strong organisms “breathe” sulphate rather
carbide-formers. They react with the than oxygen, in a form of anaerobic
carbon to form the corresponding respiration.
carbides, thus tying up the carbon, Microbiologically influenced
thereby preventing chromium carbide corrosion is a common problem in
formation and resultant chromium industrial processes due to the presence
depletion at the grain boundaries. of microbes, adequate nutrients and
Using post-weld heat treatment to corrosive by-products. Frequently MIC
dissolve the carbides and put chromium results in corrosion failures in waters of
back into solution. extremely low corrosivity and so it is
Ensuring that the welding processes often unexpected.
used have sufficiently low heat inputs MIC is most frequently found
to increase the cooling rate. in water cooling systems and heat
Ensuring that the stainless steel is exchangers and can result in extremely
not contaminated with carbonaceous rapid perforation of tubes and vessels. It
materials, especially prior to welding is also common in the mining industry
or heat treatment. due to the presence of these bacteria in
underground mine waters.
Microbiologically influenced Fig 30: Microbiologically Influenced
MICROBIO- corrosion (also known as MIC) can Corrosion
LOGICALLY be prevented through a number of
INFLUENCED methods such as: Complete drainage and dry-storage.
CORROSION Regular mechanical cleaning if Use of higher alloyed stainless
Microbiologically Influenced corrosion possible. steels, although this may be the most
(MIC) results from the microbiological Chemical treatment of the water with expensive route.
activity of certain bacteria, often found biocides to control the population of
in untreated water. It has the following bacteria. STRESS CORROSION
consequences: CRACKING (SCC)
It can cause very aggressive corrosive Stress corrosion cracking is a localised
Fig 29: Sulphate
attack. Reducing mechanism of corrosion that requires a
It affects many different materials, Bacteria tensile stress, a susceptible material and
not just stainless steel. a specific environment.
There are two types of bacteria: Many metals can suffer SCC, but
Aerobic: Requires environment there has to be a tensile stress, a specific
containing oxygen. environment and a susceptible material.
Anaerobic: Requires environment In the case of stainless steels, the key
free of (or low in) oxygen. issue is the austenitic microstructure.
Sulphate Reducing Bacteria (SRB). This means that austenitic stainless
Sulphate-reducing bacteria are those steels, with nickel between 5% and

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 25%, can be susceptible to SCC. In
stainless steels the specific environment
is halide ions (chlorides, bromides and
fluorides). SCC in austenitic stainless
steels normally only occurs above
about 50oC Because super austenitics
like 254SMO have very high nickel
contents, they are resistant to stress
corrosion cracking.
Duplex stainless steels can also
suffer from SCC in extreme conditions,
such as very high chloride levels or
temperatures in excess of 100°C.
Ferritic stainless steels do not suffer
from chloride induced SCC.
Stress corrosion cracking can be
prevented through:
Avoiding the chemical environment
that causes SCC.
Control of hardness and stress level
(residual or load).
Introducing compressive stress for
example by shot-peening.
Use of materials known not to crack
in the specified environment.
Control operating temperature
Anti SCC lacquer – i.e. eliminate
contact with the environment.
Failure in stainless steels is due to fine
branching transgranular cracks.

ABRASION
& EROSION
CORROSION
Erosion and abrasion corrosion are
two mechanisms which involve
a combination of mechanical and
corrosive attack. Abrasive particles in
suspension, travelling at high velocities,
expose fresh metal surfaces which then
suffer high rates of corrosion. stainless
steels offer a high resistance due to the
synergistic effect of wear plus corrosion
(i.e. wear increases the corrosion rate and
corrosion increases the wear rate).
Abrasion corrosion is characterised by
low stress and low angle particle wear,
for example coal sliding over a wear
plate or slurry in a pipe line.
Erosion corrosion is characterised
by high stress and high angle wear.
For example slurry at a pipe bend or
cavitation in a pump impeller, caused
by collapse or implosion of air or gas
bubbles at the metal surface.
This form of corrosion is best addressed
by:
Suitable selection of materials,
Appropriate design,
Change of environment,
Application of corrosion-resistant
coatings, and
Cathodic protection.

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