02
Edition 1 - 2002
W O R L D S TA I N L E S S
training notes
stainless steel vs corrosion:
how stainless steel is affected by and
resists corrosion
Steel is the most used construction material.
However, nature attempts to revert steel, an
unnatural form of iron, to its natural oxide.
This process is corrosion.
Stainless steel is an iron-based (ferrous)
material which, due to its primary property
of corrosion resistance, is used in aggressive
conditions which many materials could not
withstand. An understanding of the basic
mechanisms of corrosion will assist in
preventing the use of stainless steel in
situations and conditions which adversely
affect its performance.
THE PROCESS OF CORROSION
Essentially, two forms of corrosion exist:
• wet (aqueous) corrosion
• dry (gaseous) corrosion
This paper covers the more common forms
of wet (aqueous) corrosion of stainless steel:
• general corrosion
• galvanic corrosion
• erosion/abrasion corrosion
• intergranular corrosion
• pitting corrosion
• crevice (shielded) corrosion
• microbiologically-induced
corrosion (MIC)
• stress corrosion cracking (SCC)
These forms of corrosion do not just affect
stainless steel. Carbon steels, low alloy steels
and other metals and alloys also undergo
similar forms of corrosive attack. Some
forms of corrosion are easily visible or
readily identifiable (e.g. general and pitting
corrosion), whereas others are not always
easily detectable nor apparent (e.g. stress
corrosion cracking – SCC).
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U N D E R S TA N D I N G S TA I N L E S S S T E E L A N D I T S P R O P E R T I E S
Wet (aqueous) corrosion
Wet (aqueous) corrosion is an attack on the
metal by aggressive substances, generally
dissolved in water to give a corrosive
solution (electrolyte). A damp film or dust
containing dissolved aggressive substances
also results in a corrosive electrolyte.
The severity and extent of the corrosion
depends on the following:
• the concentration of the aggressive
substances in the corrosive solution;
• the temperature of the corrosive solution;
and
• the presence and nature of contaminants
and trace elements within the solution.
Figure 1: Schematic illustration of
The concentration is generally both known superheated layer occuring at
and controlled. Care should be taken to the metal surface under
conditions of heat transfer
avoid conditions where the concentration can
vary, such as condensation, evaporation and contaminants can affect this balance and
concentration in crevices. This may result in either aggravate or lower the severity of the
unexpected, severe or localised corrosion corrosion.
attack.
The temperature is usually known and
STAINLESS STEEL
uniform. Care must be taken to prevent Stainless steel is a generic term covering the
higher localised temperatures, e.g. during family of chromium-containing (Cr) alloys.
heat transfer in solar heaters or heating coils The chromium (Cr) content is usually
(see Figure 1). A thin film of super-heated between 10.5-30%. Other alloying elements
corrosive solution coats the metal surface which increase the corrosion resistance of
through which the heat is transferred. The stainless steel may also be added, e.g. nickel
temperature of this film must be taken into (Ni), molybdenum (Mo), copper (Cu),
account, as it gives rise to far more titanium (Ti) and niobium (Nb).
aggressive conditions than those related to Stainless steels are, therefore, iron-based
the average bulk temperature. (Fe) alloys with a maximum alloy content of
Because all aqueous corrosion is approximately 50% (the balance being Fe).
electrochemical, there is always an Stainless steels are classified according to
equilibrium between the reactions at the their internal crystal structures which result
metal surface and those within the corrosive from their different chemical compositions
solution. Even trace amounts of (alloy content) (see Figure 2, p2).
I N T E R N AT I O N A L S TA I N L E S S S T E E L F O R U M
The plain Cr stainless steels are martensitic
or ferritic types.
Stainless steels containing generally more
than 8% Ni are austenitic.
An extension of these are the austenitic
stainless alloys which have an alloy content
of more than 50%. Lower Ni levels do not
result in a fully-austenitic crystal structure
and, instead, the duplex stainless steels,
which have a mixed ferritic/austenitic crystal
structure, result.
Note: The common constituent elements of
stainless steels will be referred to in the text
by their chemical symbols:
Fe-iron C-carbon
Cr-chromium Ni-nickel
Mo-molybdenum Ti-titanium
PASSIVITY
Passivity is the built-in natural resistance
which stainless steels possess to combat
corrosion. It is defined as a state in which a
metal or alloy loses its chemical reactivity
and becomes inert.
A Cr content of more than approximately
10.5% gives stainless steel this passivity, due
to the formation of an extremely thin but
uniform, continuous, tenacious and stable Cr-
rich oxide film on the surface (see Figure 3).
Figure 2: The family tree of stainless steel
02 stainless steel vs corrosion: how stainless steel is affected by and resists corrosion
The formation and properties of the passive
film are enhanced by higher Cr content and
additions of other alloying elements, e.g. Ni
and Mo. The improved passivity which
results, extends the use of stainless steel
modified in this way into applications of
higher corrosiveness and concentrations.
The Cr oxide passive film forms
spontaneously in air, but chemical oxidation
(e.g. use of 15% nitric acid for 20-30
minutes at 60˚C followed by a thorough
water wash) improves its integrity and results
in a higher resistance to corrosion.
Therefore, machined stainless steel
components or mechanically-ground areas
should be passivated in nitric acid (after
removing all traces of oils and other
contaminants). This is particularly necessary
if the components are for use as critical
components in aggressive environments.
Care must be taken to maintain and preserve
the integrity of the passive film:
• avoid mechanical damage and
contamination;
• repair any affected areas (e.g. high
temperature scale adjacent to a weld,
mechanically damaged or ground areas,
nated areas) by pickling and passivating
or a plain passivation treatment; and
• ensure a constant and sufficient
Figure 3: Schematic illustration of the
formation of a passive film on
the surface of stainless steel by
oxygen or oxidising
environment
availability of oxygen or oxygen-
containing agent.
GENERAL CORROSION
General corrosion occurs uniformly over the
entire surface of the stainless steel. It is the
least dangerous form of corrosion because
the rate of corrosion is measurable and
predictable and can, therefore, be allowed for
when designing for a required life or safety
factor.
General corrosion rates are measured and
reported in different units:
• loss of mass: grams/square
metre/hour (g/m2/hr)
• loss of thickness: millimetres/year
(mm/yr) or mils/year (mpa)
The approximate interrelationship of these
units is 1g/m2 /hr = l.lmm/yr = 43mpy. The
severity of attack or suitability of material is
indicated in different ways (see Tables 1 and
2 and Figure 4, p3).
General corrosion rates for stainless steels
are often very low. For example, in a
particular solution, grade 316 may corrode at
0.03mm/yr and grade 304 at 0.07mm/yr.
This does not mean that 316 is twice as
corrosion-resistant as 304, but that both are
suitably resistant to corrosion because each
corrodes at less than 0.1mm/year.
However, general corrosion rates are often
determined under laboratory conditions
using chemically pure solutions. More
meaningful results are obtained if plant
solutions are used or if the corrosion rates
are determined under in-service conditions.
Reported general corrosion rates often have
a notation, e.g. OP. This indicates that an
additional corrosion mechanism is likely to
occur (pitting corrosion in this example) and
care must be exercised.
ISSF training notes page 2
Reported general corrosion rates should be
used as guidelines only and full account
should be taken of the following:

• service conditions/variations;
• state of the metal surface/ maintenance of
passivity; and
• the corrosive solution’s uniformity in
terms of concentration, temperature and
contaminants.

Stainless steels exhibit very low general

corrosion rates in many highly aggressive,
corrosive environments. They are not totally
immune or impervious, but are versatile
construction materials offering attractive and
viable life-cycle costs.

Under some conditions, the surface may

exhibit signs of staining, i.e. 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 Figure 4: Schematic illustration of an ISO-Corrosion Chart showing corrosion rates over
range of temperature/concentration
staining is evident, as it is an indication that
passivity has broken down. GALVANIC CORROSION For example, passive stainless steel is far
Galvanic corrosion occurs when two more noble than aluminium. Therefore, one
different metals are in electrical contact and would expect aluminium to corrode faster if
immersed in the same electrolyte (corrosive coupled to stainless steel. Stainless steel
solution) (see Figure 5, p4). fasteners are often used for the joining of
Table 1: Severity of attack and
suitability of material for aluminium. This is acceptable and practical
The less noble, less passive, more active
different corrosion rates due to the usually much larger anodic area of
metal of the two becomes the anode and
Corrosion rate Suitability the aluminium compared with the very small
corrodes at a faster rate.
cathodic area of the stainless steel fastener.
<0.1mm/yr Highly The more noble, more passive, less active
resistant(<5mpy)
metal of the two becomes the cathode and is
0.1-1.0mm/yr • Transition from protected, corroding at a slower than normal
(5-50mpy) highly resistant corrosion rate.
to servere
corrosion An electric current will flow between the
• Metastable different metals and through the corrosive
• Consider use solution. This can be detected by a voltmeter
with care in the circuit.

>1.0mm/yr Severe corrosion Metals and alloys may be ranked according to

(>50mpy) Not suitable how active (anodic) or noble (cathodic) they
are in any specific electrolyte. This is known Galvanic corrosion of an
aluminium window frame adjacent
as galvanic series. The most common is the to stainless steel bolts. Stainless
Table 2: Methods of reporting
galvanic series in sea water (see Figure 6, p4). steel bolts are not normally a
general corrosion rates
problem in aluminium because of
0 or A <0.1mm/yr The rate at which the anodic member the ‘area affect’. In this case this
corrodes depends on the following: does not apply because the
1 or B 0.1-1.0mm/yr
window was in a building with
2 or C >1.0mm/yr • the difference in the corrosion potentials,
stainless steel cladding on the walls.
or in greater detail i.e. how far apart they are in the galvanic
E <0.05mm/yr series;
• the ratio of the surface areas of anodic The converse, i.e. aluminium fasteners used
G 0.05-0.25mm/yr
(active) metal to cathodic (noble) metal; for joining stainless steel, should never occur
S 0.25-0.5mm/yr
and because the small anodic aluminium fastener
B 0.5-1.25mm/yr
• to a lesser degree, the physical distances would corrode at a vastly increased rate.
U >1.25mm/yr between the metals.

02 stainless steel vs corrosion: how stainless steel is affected by and resists corrosion ISSF training notes page 3

Figure 5: Schematic illustration of Galvanic Corrosion and the conditions which are
required and result
The danger of an increased corrosion rate of
a more active metal coupled to stainless steel
should always be considered.
Stainless steels seldom suffer increased
corrosion rates as a result of galvanic
corrosion due to its high nobility ranking.
One scenario where such an adverse effect
may occur is in stainless steel shafts/spindles
used in contact with a gland packing
material which contains graphite.
Different conditions on the surface of the
same sheet/plate within a fabrication can
also result in a galvanic effect, such as in the
following circumstances:
• mechanically-damaged areas (scratches,
grind marks, weld spatter) impair the
passivity and render these areas anodic to
the surrounding passive (cathodic)
surface; and
• weld deposits of inferior corrosion
resistance (anodic) to that of the parent
plate material (cathodic).
The unfavourable small anode/large cathode
situation, which is usual in such cases,
adversely promotes and accelerates
corrosion.
The principles of galvanic corrosion are
applicable to other forms of corrosion, as
detailed in some of the following sections.
02 stainless steel vs corrosion: how stainless steel is affected by and resists corrosion
EROSION/ABRASION
CORROSION
Erosion/abrasion corrosion is a mechanical
process. Abrasive particles in suspension or
high flow velocities remove the normally
friable products of corrosion from the
surface, thus exposing fresh metal surface to
the corrosive attack. Both aspects act in
synergy and lead to an accelerated metal
loss.
All stainless steels offer a high resistance to
this form of corrosion due to the stable and
tenacious passive film on the surface of the
material and the ability to repassivate. High
Figure 6: Galvanic series of commercial
metals and alloys in sea water
(reduced)
velocities are often beneficial, as this
increases the aeration which assists in
maintaining or restoring the passivity.
If the conditions render the stainless steel
metastable (i.e. the passive film is, for some
reason, destroyed), corrosion will occur at a
rate similar to general corrosion. If the
abrasivity is high, the harder martensitic
stainless steels may be more suitable,
provided their inherent corrosion resistance
to the aqueous corrosive media is
sufficiently high.
INTERGRANULAR CORROSION
C has a high affinity for Cr. Under the right
circumstances, C will combine with Cr to
form a complex Cr Carbide (Cr23C6).
High temperatures, in the range of 450°C -
850°C, result in the formation of the Cr
carbide:
• at lower temperatures the C atom lacks
the mobility to move to combine with the
Cr; and
• at higher temperatures the Cr23C6 does
not form or, if present, begins to
redissolve, albeit slowly, until higher
temperatures of approx. 1,050°C are
reached.
The formation of this Cr23C6 takes place
preferentially at the grain boundaries. A
small amount of C locks up a relatively large
amount of Cr, thus depleting the grain
boundary area in Cr. The steel is then said to
be sensitised.
Corrosion associated with
chromium depletion in the heat
affected zone of a weld in 316
material used as capping on timber
beams in a marine area.
The grain boundaries, depleted in Cr, have
both a lower corrosion resistance and
passivating capacity. These areas, therefore,
suffer a preferential attack which is
accelerated by the galvanic effect – small
corroding anodes via the grain boundaries
and larger non-corroding cathodes via the
body of the grain. The corrosion proceeds
along the grain boundaries and the grains are
literally dissolved out of the metal (see
Figure 7, p5).
ISSF training notes page 4
This form of corrosion is usually related to
welded plate fabrications. Within the heat
affected zone (HAZ), adjacent to a weld,
there is an area which has been heated to
within the sensitising temperature range.
Intergranular corrosion (weld decay) may
therefore occur. Indiscriminate heating, e.g.
for bending operations, can also result in
sensitisation and intergranular corrosion.
The cure
Solution annealing de-sensitises the steel
because it dissolves the Cr23C6 at the high
temperatures used, i.e. the Cr23C6 is taken
back into solution within the metal. The
metal is uniformly heated to 1,050°C-
1,060°C and rapidly cooled to prevent the
reformation of any Cr23C6 during the
cooling cycle. This process is easy to apply
to individual sheets, plates or small
components, but is difficult to apply to a
completed fabrication because of the
following reasons:
• distortion can occur at high temperatures;
• uneven heating and cooling can induce
thermal stresses; and
• the surface will be scaled (oxidised) at
these high temperatures, necessitating the
repickling and repassivation of the entire
surface.
Preventing intergranular
corrosion
To help prevent intergranular corrosion, the
following precautions should be taken:
• Always begin fabrication with the
material in the fully annealed state.
• Use the stabilised grades of stainless
steel. These stabilised grades contain the
alloying elements of Ti or niobium (Nb).
These elements have a higher affinity
than Cr for C. Therefore, they lock up the
C as Ti or Nb carbides, leaving
Figure 7: Schematic illustration of sensitization within the NAZ; with associated chrome
carbide precipitation and chromium depletion at the grain boundaries.
02 stainless steel vs corrosion: how stainless steel is affected by and resists corrosion
insufficient free C to combine with and
deplete the Cr.
• Use the ‘L’ grade stainless steels.
The lower C content of ‘L’ grades
significantly increases the time necessary for
sensitisation to occur, therefore providing
adequate protection against sensitisation
during welding (see Figure 8, p6).
Two issues to be aware of are that the ‘L’
grade stainless steels are not easier to weld
than the normal grades and the strength of
the ‘L’ grades decreases at elevated
temperatures, lowering their allowable design
stress at such elevated temperatures. The
following guidelines should then be
followed:
• use ordinary grades if there is no danger
of aqueous corrosion (e.g. condensates
during periodic temperature cycling or
shut down);
• use stabilised grades if conditions
for aqueous corrosion exist; and
• if section thicknesses are low the time to
weld is short enough that ‘L’ grades are
not necessary, so thin sheet and coil and
tube are often only available in standard
(non ‘L’) grades.
Due and proper care during fabrication will
help prevent this type of corrosive attack:
• use correct welding consumables to
prevent the formation of Cr carbides;
• prevent contamination of the weld area
and welding consumables from any
carbon-containing substances, e.g. paint,
oil, grease and shop soil; and
• avoid heating the steel for bending or
forming operations which may cause
sensitisation.
With correct choice of materials and care
during fabrication, intergranular corrosion
should not occur.
PITTING CORROSION
Pitting corrosion on a section of a
table knife used in a hospital
environment where the
dishwashing chemicals proved to
be high in hypochlorite
disinfectant.
This is a dangerous, very localised form of
corrosion which results in small holes or
perforations. There is little measurable
general metal loss.
The chloride ion (Cl-) is the usual cause of
pitting corrosion. It is very aggressive,
mobile and, unfortunately, very common.
Under suitable conditions, a pit may form,
say through the dissolution of a surface
inclusion, perhaps accelerated by a layer of
dirt that limits oxygen entry. Once formed,
the pit will have a lower oxygen
concentration at the base compared with the
surface and corrosion will continue at an
increasing rate. This corrosion is accelerated
by the migration of chloride ions into the pit
due to their electrostatic attraction to the
dissolving metal ions. The M+Cl- formed
will hydrolyse, generating free hydrochloric
acid that helps continue the corrosion:
M+Cl- + H O MOH + H+Cl-
2
The large surrounding cathodic area will also
assist in maintaining a high corrosion rate at
the base of the pit (see Figure 9, p6).
Pitting corrosion occurs in both acidic and
basic aqueous solutions. It is more severe in
acid solution (pH<7) and is less likely to
occur at high pH (solutions of high basicity).
Elevated temperatures increase the danger of
and accelerate the attack. Pitting corrosion is
also more severe in stagnant (de-oxygenated)
solutions.
Pitting corrosion in a free
machining stainless steel plug from
a line containing a high chloride
food pulp.
ISSF training notes page 5

Figure 8: Schematic illustration of the major effect of C content on the time taken for
sensitization of a typical austenitic stainless steel
Preventing pitting corrosion
Pitting can be prevented by raising the
Pitting Resistance Equivalent (PRE) in the
following ways:
• Increase flow rates:
- improve oxygenation of the corrosive
solution;
- remove Cl from incipient pits; and
- prevent stagnant areas, sedimentation
and possible local areas of higher
temperature or concentration.
• Good design to prevent stagnant areas
and crevices where the Cl can concentrate
• A chemically-produced passive film
• Non-impairment, damage or
contamination of the passive film
• Use of cathodic protection, i.e.
intentionally connecting an active,
sacrificial anode (e.g. zinc anode) to the
stainless steel, thereby chemically
protecting (instead of accelerating) the
corroding areas (the pits)
• Using stainless steels of higher alloy
content (see passivity) to raise the
corrosion resistance/passivity.
The PRE = %Cr + (3.3 x %Mo) + (16 x
%N). An alloy with a PRE less than 32 may
Figure 9: Schematic illustration of the factors involved in pitting corrosion
02 stainless steel vs corrosion: how stainless steel is affected by and resists corrosion
be susceptible to pitting (and/or crevice
corrosion), whereas a PRE greater than 32
indicates the alloy is resistant to these forms
of corrosion.
Pitting corrosion in an agitator
shaft and housing made from 316
material left in contact with
stagnant saturated calcium
chloride. Corrosion was accelerated
in the mini-crevices formed from
deposits that settled on the surface
from the stagnant liquid.
CREVICE (SHIELDED)
CORROSION
This type of corrosion attacks the metal
surface where it is shielded or occluded, e.g.
under washers or bolt heads, in the threads
of bolts or pipe fittings, in contact with loose
or absorbent gaskets, under sediments or
Corrosion associated with grinding
marks on the surface of a 316
retaining wall for a water feature
in a shopping centre.
settled solids, under marine growth. Such
areas promote localised concentration effects
and stagnant solutions and, particularly, the
lack of free access/availability of oxygen.
Many aqueous solutions cause crevice
corrosion. Those containing Cl are the more
common because the very mobile Cl enters
the crevice and builds up in concentration.
Crevice corrosion is similar to pitting
corrosion in that limited areas are attacked,
which gives rise to the unfavourable galvanic
effects of small anodes and large cathodes.
Preventing crevice corrosion
The following precautions will help prevent
crevice corrosion:
• avoid flat bottomed tanks where solids
can settle out (sediments);
• have tanks on legs (skirt), rather than
resting on the floor;
• in the design avoid stagnant areas where
sedimentation can occur;
• outlets should be able to drain the tank
completely;
• rounded corners are better than square
corners;
• avoid porosity and undercuts in welds;
• use butt welds rather than lap welds;
• use continuous rather than spaced welds;
• use impervious gasket material tightened
to ensure no ingress of corrosive solution;
• seal threads and other occluded areas
with sealing compounds;
• use materials of higher alloy content to
increase passivity; and
• clean the surface of settled dust and
spillage.
MICROBIOLOGICALLY
INDUCED CORROSION (MIC)
This form of corrosion results from the
microbiological activity of bacteria. It has
many similarities to both crevice and pitting
corrosion. Many aqueous solutions,
especially untreated natural dam, river or
ISSF training notes page 6
mine water, contain an abundance of
bacteria.
The bacteria are of two types (see Figure 10):
• aerobic, i.e. requiring an environment
containing oxygen (O2), where the
bacteria are active in the aqueous
solution; and
• anaerobic, i.e. requiring an environment
free of oxygen, where the bacteria are
dormant in the aqueous solution.
Should any area on the metal surface attract
and anchor the active aerobic bacteria, slime
will build up. This can become thick enough
to lower the oxygen level under the slime,
resulting in a situation equivalent to a
crevice.
The oxygen-deficient area under the slime
then leads to the anaerobic bacteria
collecting and multiplying in this area. These
anaerobic bacteria have the property of
producing aggressive metabolic products
which attack the passive film on stainless
steel. Due to the lack of oxygen,
repassivation is inhibited and pitting attack
results.
The corrosion attack is typified by a shallow
corroded depression which contains a few
deep pits.
STRESS CORROSION
CRACKING (SCC)
Stainless steels are unjustifiably often not
considered for applications due to fear of
stress corrosion cracking. Three co-existing
and inter-relating factors are necessary for
SCC to occur:
1. Tensile stress (either applied or residual
SCC will not occur under compressive
stress conditions) – the higher the stress
the more dangerous the condition.
2. Temperature – the higher the temperature
Stress corrosion in a 316 filter
the higher the risk (SCC seldom occurs made from punched sheet. The
under 60°C). filter was in a hot chloride line in a
food processing plant.
3. The presence of an insidious ion (usually
a halide ion - the chloride ion (Cl) being
the most common). Hydroxides, e.g.
laboratory tests in all stainless steels, but the
caustic soda (NaOH) and hydrogen
common austenitic grades (304 and 316) are
sulphide (H2S), can cause SCC under
particularly prone to this form of corrosion.
conditions of high temperatures and
Duplex steels and the super austenitic
concentrations.
grades are usually specified when chloride
Despite past and current research, there are SCC is probable. Ferritic stainless steel can
still no absolute determinable values below also suffer from SCC but, in this case, the
which chloride-induced SCC can be offending chemical is more usually H2S.
guaranteed not to occur. SCC (see Figure 11) This can be a particular problem with sour
can be induced by highly aggressive gas oil wells.

Microbial corrosion associated with

a weld. The streaking is a common
feature of this type of corrosion.

Preventing MIC
MIC can be prevented if the following
precautions are taken:

• drain and flush the equipment

immediately after stoppages or plant shut
down;
• employ higher flow rates to prevent
sedimentation and slime build up where
anaerobes can collect and multiply; and
• treat (sterilise) the water to kill the
bacteria.

Figure 10: Schematic illustration of initial aerobic bacteria slime build-up, and subsequent
effects of anaerobic bacteria in the resultant oxygen deficient area

02 stainless steel vs corrosion: how stainless steel is affected by and resists corrosion ISSF training notes page 7

Figure 11: Schematic illustration of SCC in austenitic stainless steel
The initiation of SCC is equivalent to that of
pitting corrosion. Once a pit is formed, the
tensile strength is concentrated at the base of
the pit. The finer the pit, the higher the stress
concentration factor. This leads to mechanical
rupture of the metal at the base of the pit,
exposing fresh, unpassivated (active) metal.
The result is accelerated corrosive attack at
the pit base, re-concentration of stress, and
further mechanical failure.
SCC may take considerable time to initiate
but, once it has begun, there is usually rapid
transcrystalline crack propagation which
results in final failure.
Stress corrosion cracking from a plate
type 316 stainless steel heat
exchanger in a chloride environment.
Cracking originated from the process
fluid side and some metal around the
opening has fallen away. Other
cracks can be seen associated with
the stressed areas formed during the
cold pressing of the ridges.
Preventing SCC
Design is critical to the prevention of SCC.
The design should avoid the following:
• highly-stressed components;
• areas of stress concentration;
• fabrication requirements which result in
residual stress; and
• factors which may contribute to the
initiation of pitting.
Avoid conditions which may introduce Cl:
• Cl-contaminated insulation;
• leakage into the insulation jacket
02 stainless steel vs corrosion: how stainless steel is affected by and resists corrosion
(evaporation of such leakage concentrates
any Cl which it contains within the
insulation); and
• spillage containing Cl which will
concentrate the Cl on evaporation.
Use ferritic stainless steels which are not
usually susceptible to SCC. The passivity of
the ferritic grades is enhanced by higher Cr
content and the addition of Mo. These so-
called super ferritic stainless steels also have
better fabrication properties than the
standard ferritic stainless steels.
Use duplex stainless steels which have a Ni
content which gives them a mixed
ferritic/austenitic crystal structure.
Any SCC which initiates in the austenite is
arrested as the transcrystalline crack
propagation meets up with a ferritic crystal
structure at the grain boundary. The passivity
of these steels is further enhanced by the
higher Cr content and the addition of Mo to
most of the alloys. Duplex stainless steels
have excellent fabrication properties.
Austenitic stainless alloys are used for their
higher passivity and, therefore, their
increased resistance to pitting corrosion and
the subsequent development of SCC. The
inter-related and reinforcing effects of Cr, Ni
and Mo are used in these alloys. A high Ni
content renders alloys resistant to Cl-induced
SCC. Alloys with 28 - 48% Ni seldom suffer
SCC, and a Ni content of >48% may be
considered immune to SCC. SCC is
electrochemical and cathodic or anodic
impressed potential techniques can be used
to prevent the initiation of SCC.
SELECTION FOR CORROSION
RESISTANCE
Consideration of the corrosion mechanisms
that have been described leads to the
conclusion that there is no single steel that
can give cost effective corrosion resistance
for all types of corrosion. The following are
general guidelines that illustrate the
resistance of the various grades to each
major type of corrosion.
Selection for galvanic
corrosion resistance
This has been largely covered earlier in this
Training Note. The majority of stainless
steels have two galvanic states - one in the
normal passive condition, the other is when
the steel is in the ‘active’ state. This active
state is obtained when the steel is in an
environment that removes the passive layer,
e.g a higher level of chloride than the grade
(or surface finish) can resist. Under these
circumstances, it is only slightly better than
carbon steel. By selecting a combination of
metals where there is only a small difference
in the galvanic potential or there is a large
area of the less noble metal compared to the
more noble one then galvanic corrosion can
be minimised. Because of the two potentials
with stainless steel care must be exercised to
ensure the steel is in the passive condition.
Selection for pitting resistance
Pitting corrosion can be evaluated from a
‘Pitting Resistance Equivalent’ (PRE) , as
mentioned above. A tabulation of PRE
values is given in Table 3, p9.
An alternative process sometimes used for
laboratory testing is the evaluation of the
‘Critical Pitting Temperature’ (CPT). This is
the temperature at which pitting will
commence in a particular corrosive solution.
There is an ASTM Standard test for
determining CPT values. (ASTM G61). A
graph of some critical pitting temperatures
for several common steels in varying
concentration neutral chloride solutions is
1
shown in Figure 12 , p9. It can be seen that
at a given temperature or in a given
corroding solution, the alloys follow the
same pattern as predicted from the Pitting
Resistance Equivalent value.
Selection for crevice
corrosion resistance
Crevice corrosion is, in effect, a form of
pitting corrosion and the same methods of
steel selection can be applied. The additional
problem is the effect crevice thickness can
have.
Experimental observation has shown that the
smallest gap between two surfaces in contact
in a normal engineering application is likely
to be about 0.2 micron (i.e. 0.0002 mm).
When the crevice corrosion of steels in a
particular solution are compared with
ISSF training notes page 8
varying crevice gaps then the corrosion Table 3: Values of the Pitting Resistance Equivalent values for the more
resistance follows the same general pattern common stainless steels listed in Training Note 1.
as that for pitting corrosion. A diagram
UNS Name Common/Trade Name Cr Mo N PRE
evaluating the the approximate gap spacing
where crevice corrosion will commence for S43000 430 17 17.0
alloys immersed in ambient temperature
S44400 444 18 2 24.6
seawater (~20,000 ppm chloride ion)2 is
shown in Figure 13, p10. Although not S40900 409 11.5 11.5
stainless steels, the two nickel alloys N06007 S30100 301 17 17.0
and N06625 are included to further illustrate
the point. N06007 (Alloy G) has a PRE of S30400 304 18.5 18.5
42.6 and N06625 (625) has a PRE of 51.2. S31000 310 25 25.0
There is also a parallel of Critical Crevice S31600 316 17 2.1 23.9
Temperature, ie Critical Crevice Temperature
that is sometimes used as a measure of the S31700 317 19 3.25 29.7
steel’s resistance. N08904 904L 20 4.5 34.9

Selection for resistance to S31254 254SMO 20 6 39.8

microbially induced corrosion S31803 2205 22 3 0.14 34.1
Microbial effects are largely related to their
effect on providing conditions suitable for S32750 S2750 25 4 0.3 43.0
pitting or crevice corrosion. Selection for S32304 2304 23 0.1 24.6
these conditions will therefore help minimise
corrosion resulting from microbial action. A
better arrangement would be to minimise the
possibility of conditions that promote the chromium steels with varying nickel
microbial effects, eg stagnant water in contents is shown in Figure 143, p10.
crevice conditions together with welding It is possible to obtain similar curves to
heat tint. those given for Critical Pitting Temperature
to illustrate the effect of chloride content and
Selection for stress
temperature on stress corrosion, Figure 14.
corrosion resistance
These curves indicate the temperatures and
It has previously been explained that stress
chloride levels that can initiate stress
corrosion is related to alloy, corroding
corrosion cracking in components stressed
environment and stress. In general the level
close to their 0.2% proof stress level. These
of nickel can be taken as a rough indication
curves can only be taken as indicative in
of the resistance to stress corrosion cracking
design since it is very difficult to determine
with the low nickel ferritic and duplex steels
actual stress under service conditions
as well as the high nickel alloys providing
because of the effect of internal stress in the
the best resistance. A curve showing the
component can have on the applied stress.
resistance to stress corrosion of 19%

Figure 13: Approximate corrosion resistance limits for various gap

Figure 12: Critical Pitting Temperature for stainless steels related (ie. crevice) thicknesses in ambient temperature sea
to the chloride content of the corroding solution water for some common corrosion resistant materials

02 stainless steel vs corrosion: how stainless steel is affected by and resists corrosion ISSF training notes page 9
 CONCLUSION
Corrosion is natural and is here to stay.
Natural conditions are, however, greatly and
continuously reinforced by human actions.
Industry is always looking for better
efficiency and yield which go hand in hand
with process conditions of increased severity.

Materials within the family of stainless steels

are excellent at resisting corrosion. They are
used in the construction of critical
components used to meet the needs of many
high-tech industries. They are inexpensive to
maintain and offer excellent
energyefficiencies and overall life-cycle cost
benefits.

The interface of process/design conditions vs

Figure 14: Temperature-chloride content relationship for stress corrosion initiation in some construction materials should always be
stainless steels. The stress was applied for 1,000 hours at a level equal to the
0.2% proof stress considered together when using stainless
steels. Minor modifications to the process
can often result in major effects on the
material used for construction.
END NOTES Stainless steels are most effective at resisting
1. Data assembled from Sandvik Data corrosion when the following issues are
Sheets. properly addressed:
2. Oldfield J W and Sutton W H, Brit • selection;
Corrosion J, Vol 13(2). • fabrication;
3. Data assembled from Sandvik Data • operation; and
Sheets. • maintenance.

Edition 1
© 2002 Australian Stainless Steel Development Association

Acknowledgment: The contribution of the Australian Stainless Steel Development Association’s Technical and Education Committees in preparing this
course is acknowledged with thanks. Some material in this course originated from the Southern Africa Stainless Steel Development Association.
Disclaimer: The technical data and views expressed in this publication are for the general information of interested persons and should not be relied
upon in specific applications without first securing competent advice. Whilst all care is taken to ensure that the information contained herein is accurate
and up-to-date, the ISSF does not warrant its accuracy or completeness and does not accept liability for errors or omissions.

02 stainless steel vs corrosion: how stainless steel is affected by and resists corrosion ISSF training notes page 10