Corrosion and Corrosion Properties of

Stainless Steels: Part One

Abstract:

Stainless steels are stainless because a protective layer spontaneously forms on

their surfaces and reduces the rate of corrosion to almost negligible levels. Under
normal conditions, this layer heals very rapidly if scratched, so that if stainless steels
only suffered from uniform corrosion, they could survive for literally millions of years.
This thin, invisible surface layer is an oxide that protects the steel from attack in an
aggressive environment. As chromium is added to steel, a rapid reduction in
corrosion rate is observed to around 10% because of the formation of this protective
layer or passive film.
Corrosion and Corrosion Properties of Stainless Steels: Part One
Stainless steels represent the most diverse and complex family of all steels. The single most
important property of stainless steels, and the reason for their existence and widespread use, is
their corrosion resistance. Stainless steels are stainless because a protective layer
spontaneously forms on their surfaces and reduces the rate of corrosion to almost negligible
levels. Under normal conditions, this layer heals very rapidly if scratched, so that if stainless
steels only suffered from uniform corrosion, they could survive for literally millions of years.

Passivity
As mentioned above, the reason for the good corrosion resistance of stainless steels is that they
form a very thin, invisible surface film in oxidizing environments. This film is an oxide that
protects the steel from attack in an aggressive environment. As chromium is added to steel, a
rapid reduction in corrosion rate is observed to around 10% because of the formation of this
protective layer or passive film. In order to obtain a compact and continuous passive film, a
chromium content of about 17% is needed. This is the reason why many stainless steels contain
17-18% chromium.

Figure 1: The effect of chromium content on passivity

The most important alloying element is therefore chromium, but a number of other elements such
as molybdenum, nickel and nitrogen also contribute to the corrosion resistance of stainless
steels. Other alloying elements may contribute to corrosion resistance in particular environments,
for example copper in sulfuric acid or silicon, cerium and aluminum in high temperature corrosion
in some gases.
A stainless steel must be oxidized in order to form a passive film; the more aggressive the
environment the more oxidizing agents are required. The maintenance of passivity consumes
oxidizing species at the metal surface, so a continuous supply of oxidizing agent to the surface is
required. Stainless steels have such a strong tendency to passivate that only very small amounts
of oxidizing species are required for passivation. Even such weakly oxidizing environments as air
and water are sufficient to passivate stainless steels. The passive film also has the advantage,
compared to for example a paint layer, that it is self-healing. Chemical or mechanical damage to
the passive film can heal or repassivate in oxidizing environments. It is worth noting that stainless
steels are most suitable for use in oxidizing neutral or weakly reducing environments. They are
not particularly suitable for strongly reducing environments such as hydrochloric acid.
Corrosion can nevertheless occur if the passive film breaks down, locally or uniformly. This can
happen by different mechanisms depending on the conditions of use. The most common types of
corrosion are the following.
Uniform corrosion of stainless steels can occur in acidic or hot alkaline solutions. It results in
uniform loss which can easily be predicted and allowed for.
General corrosion resistance is increased with increasing chromium content, but other elements
can be detrimental. In particular, sulfur in solid solution is believed to make passivation more
difficult and therefore is generally undesirable for good corrosion properties.
Unfortunately, sulfur makes welding considerably easier and also improves machinability. In the
case of welding, sulfur appears to modify the surface tension of the weld pool and therefore
alters its shape significantly. Austenitic grade 316 with sulfur content lower than 0.007 wt% tend
to have a high width-to-depth ratio while higher sulfur contents lead to a narrower, deeper weld
pool (specifying the sulfur content of 316L for welding).

Some of the standard grades contain a quantity of sulfur deliberately greater than the typical
0.003 that can otherwise routinely be achieved with modern steel-making processes (the free
machining grades).
Nickel significantly improves the general corrosion resistance of stainless steels, by promoting
passivation. The austenitic stainless steels series therefore possesses a corrosion resistance
superior to that of martensitic or ferritic stainless steels (no nickel), particularly with mineral acids.
Pitting corrosion is the result of the local destruction of the passive film and subsequent
corrosion of the steel below. It generally occurs in chloride, halide or bromide solutions. If a fault
in the passive layer or a surface defect results in the local destruction of the former, dissolution of
the steel underneath leads to a build-up of positively charged metallic ions, which in turn causes
negatively charges (e.g. chloride ions) to migrate near the defect. Even in a neutral solution, this
can cause the pH to drop locally to 2 or 3, and can prevent regeneration of the passive layer.
In the passive condition, the current density is in the scale of nanoampers/cm 2; in the pit,
however, it may be above 1A/cmp2. Similarly, the concentration in chloride ions can be
thousands of times greater than that in the solution.

Figure 2: Schematic illustration of pitting corrosion

The Figure 2 illustrates the process: the anodic dissolution of the steel leads to introduction of
M+ in solution, which causes migration of Cl- ions. In turn, metal chloride reacts with water
following:
M + Cl- + H2O MOH + H + ClThis causes the drop of pH. The cathodic reaction, on the surface near the pit follows:
O2 + 2H2O MOH + 4OHWhile the propagation phenomenon is well understood, the mechanism of pit initiation is still
debated. The initiation of pitting has long been associated with the presence of MnS inclusions
which are difficult to avoid in the steel making process. It has recently been shown that these
inclusions are surrounded by a Cr depleted region which is believed to cause the initiation.
The pitting resistance of a stainless steel is affected by its composition. Increasing the Cr content
or adding both the molybdenum and/or the nitrogen enhances the pitting resistance, though they
are not equally potent in this respect. For comparison purposes, an index is often used to
represent the combined effect of these elements:
Pitting index = Cr + 3.3Mo + 16N
where Cr, Mo and N are given in weight percent.
One obvious environment where pitting corrosion is of concern is marine applications. AISI type
316 (an 18Cr-12Ni austenitic stainless steel with 2-3% Mo) is often the material of choice. In this
case, although the severe conditions met in offshore platforms, for example, call for heavily
alloyed steels with up to 6% Mo.

Street furniture is another case where pitting resistance might be relevant, particularly in colder
areas where salt de-icing is common.
Date Published: Sep-2008

Corrosion and Corrosion Properties of

Stainless Steels: Part Two
Abstract:

Like all metals and alloys that relay on a passive film for corrosion resistance,
stainless steels are susceptible to localized corrosion, i.e. pitting or crevice corrosion.
Both these types of corrosion usually occur in chloride-containing aqueous solutions
such as sea water, but can also take place in environments containing other
halogenides.

Pitting and crevice corrosion

Like all metals and alloys that relay on a passive film for corrosion resistance, stainless steels are
susceptible to localized corrosion. The protective passive film is never completely perfect but
always contains microscopic defects, which usually do not affect the corrosion resistance.
However, if there are halogenides such as chlorides present in the environment, these can break
down the passive film locally and prevent the reformation of a new film. This leads to localized
corrosion, i.e. pitting or crevice corrosion. Both these types of corrosion usually occur in chloridecontaining aqueous solutions such as sea water, but can also take place in environments
containing other halogenides.
Pitting is a form of (extremely) localized attack that results in holes in the metal. These holes
may be small or large in diameters, but in most cases they are relatively small. A pit may be
described as a hole with the surface diameter about the same or even much less than the depth.
Pitting is a rather insidious form of corrosion. Pitting usually requires an extended initiation period
before visible pits appear. This period ranges from months to years, depending on both the
specific metal and the corrosive environment. In very aggressive environment like acid media
containing ferric chloride serious pitting of stainless steels like e.g. X2CrNi19-11 (304L) can
occur even in a couple of days.
Once started, a pit penetrates the metal at an ever-increasing rate. In addition, pits tend to
undermine or undercut the surface as they grow. Sometimes the diameter of the pit can grow in
diameter extensively below the surface. Pits usually grow in the direction of gravity. Most pits
develop and grow downward from horizontal surfaces. Lesser numbers start in vertical surfaces,
and only rarely do pits grow upward from the bottom of horizontal surfaces.
Pitting is characterized by more or less local points of attack with considerable depth and
normally occurs on free surfaces (See Figure 1).

Crevice corrosion occurs in narrow, solution-containing crevices in which the passive film is
more readily weakened and destroyed. This may be under washers, flanges, deposits or fouling
on the steel surface.
Crevice corrosion can be a result of differences in oxygen or metal ion concentration between the
crevice and its surroundings. Local differences in composition of a solution cause potential
differences on an immersed metal and thus accelerate corrosion. Of particular importance in this
respect are differences in oxygen content, commonly known as differential aeration.
Crevice corrosion is usually attributed to one or more of the following aspects:

Lack of oxygen in the crevice

Build-up of detrimental ions in the crevice

Changes in acidity (decrease of Ph) in the crevice

Depletion of an inhibitor in the crevice.

To avoid crevice corrosion the following preventive measures can be applied:

Application of more resistant construction materials, like high nickel Mo alloys.

Make full penetration welds to avoid crevices

Design vessels for complete drainage

Weld (internal bore weld) instead of rolling in tubes in tube sheets

Inspects vessels and remove deposits frequently

Remove wet packing materials during long shutdowns

Use solid non absorbent gaskets, such as PTFE.

Figure 1: Pitting occurrence depending on Mo content in AISI 304.

Figure 2: Crevice corrosion under a rubber washer in a flat heat exchanger used in brackish
water.
Both forms of corrosion occur in neutral environments, although the risk for attack increases in
acidic solutions.
Chromium, molybdenum and nitrogen are the alloying elements that increase the resistance of
stainless steels to both pitting and crevice corrosion. Resistance to localized corrosion in sea
water requires 6% molybdenum or more.
One way of combining the effect of alloying elements is via the so-called Pitting Resistance
Equivalent (PRE) which takes into account the different effects of chromium, molybdenum and
nitrogen. There are several equations for the Pitting Resistance Equivalent, all with slightly
different coefficients for molybdenum and nitrogen. One of the most commonly used formulas is
the following:
PRE = %Cr + 3.3 x %Mo + 16 x %N
This formula is almost always used for the duplex steels but it is also sometimes applied to
austenitic steels. However, for the latter category the value of the coefficient for nitrogen is also
often set to 30, while the other coefficients are unchanged. This gives the following formula:
PRE = %Cr + 3.3 x %Mo + 30 x %N
The difference between the formulas is generally small but the higher coefficient for nitrogen will
give a difference in the PRE-value for the nitrogen alloyed grades.
Table 1: Typical PRE-values for various stainless steels

Grade304L316L'SAF 2304'317L'2205''904L''SAF 2507''254 SMO''654 SMO'

PRE16xN 19 26
PRE30xN 20 26

26

30
30

35

36
37

43

43

56

46

63

The effect of composition can be illustrated by plotting the critical pitting temperature (CPT) in a
specific environment against the PRE-values for a number of steel grades. The Figure 3 shows
the critical pitting temperature (CPT) in 1M NaCl as a function of PRE-values. The CPT values
are the lowest temperatures at which pitting corrosion attack occurred during testing.

Figure 3: pitting temperature (CPT) in 1M NaCl as a function of PRE-values.

Since the basic corrosion mechanism is the same for both pitting and for crevice corrosion, the
same elements are beneficial in combating both types of corrosion attack. Due to this, there is
often a direct correlation between the CPT- and CCT-values for a certain steel grade.
Crevice corrosion is more severe of the two types of corrosion attack and the CCT-values are
lower than the CPT-values for any stainless steel grade. This is illustrated in Figure 4 where the
critical pitting temperature (CPT) and the critical crevice corrosion temperature (CCT) in 6%
FeCl3 have been plotted against the PRE-values for a number of stainless steels. Again the CPT
and CCT values are the lowest temperatures at which corrosion attack occurred.

Figure 4: Critical pitting temperature (CPT) and critical crevice corrosion temperature (CCT) in
ferric chloride for various stainless steels.
As can be seen from the diagrams in Figures 3 and 4 there is a relatively good correlation
between the PRE-values and the CPT and CCT. Consequently the PRE-value can be used to
group steel grades and alloys into rough groups of materials with similar resistance to localized
corrosion attack, in steps of 10 units in PRE-value or so. However, it cannot be used to compare
or separate steel grades or alloys with almost similar PRE values.
Finally, it must be emphasized that all diagrams of this type show comparisons between steel
grades and are only valid for a given test environment. Note that the steel grades have different
CPTs in NaCl (Figure 3) and FeCl3 (Figure 4). The temperatures in the diagrams cannot
therefore be applied to other environments, unless there is a practical experience that shows the
relation between the actual service conditions and the testing conditions.
The relative ranking of localized corrosion resistance is, however, often the same even in other
environments. The closer the test environment is to the natural environment, i.e. the closer the
test environment simulates the principal factors of the service environment, the more can the
data generated in it be relied on when judging the suitability of a certain steel grade for a specific
service environment. A test in sodium chloride is consequently better than a test in ferric chloride
for judging whether or not a certain grade is suitable for one of the neutral pH, chloride containing
water solutions which are common in many industries.
In order to obtain a good resistance to both pitting and crevice corrosion, it is necessary to
choose a highly alloyed stainless steel with a sufficiently high molybdenum content. However,
choosing the right grades is not the only way to minimize the risk for localized corrosion attack.

The risk for these types of corrosion attack can be reduced at the design stage by avoiding
stagnant conditions and narrow crevices. The designer can thus minimize the risk for pitting and
crevice corrosion both by choosing the correct steel grade and by appropriate design of the
equipment.
Date Published: Oct-2008

Corrosion and Corrosion Properties of

Stainless Steels: Part Three
Abstract:

Intergranular corrosion, also called intercrystalline corrosion, occurs on or adjacent

to the grain boundaries of a metal. It is caused by microsegregation of impurities and
alloying elements on the grain boundaries.
The driving force of intergranular corrosion is the difference between the electrode
potentials of the grain boundary and the grain itself, which form a galvanic cell in
presence of an electrolyte.

Intergranular corrosion of stainless steels

The microstructure of metals and alloys consists of a granular composition. Grains are small
crystals whose surfaces join the surfaces of other grains to form grain boundaries. Grain
boundaries separate the grains. Intergranular corrosion, also called intercrystalline corrosion,
occurs on or adjacent to the grain boundaries of a metal. Some causes of intergranular corrosion
are welding, stress annealing, improper heat treating or overheating in service. Inspectors have
difficulty in detecting the early stages of intergranular corrosion. This form of corrosion results in
a loss of strength in metal parts where the grains have fallen out.
Intergranular corrosion is caused by microsegregation of impurities and alloying elements on the
grain boundaries. The driving force of intergranular corrosion is the difference between the
electrode potentials of the grain boundary and the grain itself, which form a galvanic cell in
presence of an electrolyte.
If the phases segregated at the grain boundaries have lower value of electrode potential they will
oxidize (anodic reaction) and the grain metal having higher value of electrode potential will
provide cathodic reaction (reduction). Dissolution of anodic grain boundaries starts from the
surface and advances along the grains interfaces. The process results in deterioration of the
bonding between the grains and drop of mechanical properties.
If the precipitates at the grain boundaries have higher electrode potential the grains will dissolve
(anodic reaction). In this case the grain boundaries will not be attacked. Figure 1 shows the
intergranular corrosion.

Figure 1: Intergranular corrosion.

Stainless steel has a very thin and stable oxide film rich in chrome. This film reforms rapidly by
reaction with the atmosphere if damaged. If stainless steel is not adequately protected from the
atmosphere during welding or is subject to very heavy grinding operations, a very thick oxide
layer will form. This thick oxide layer, distinguished by its blue tint, will have a chrome-depleted
layer under it, which will impair corrosion resistance. Both the oxide film and depleted layer must
be removed, either mechanically (grinding with a fine grit is recommended, wire brushing and
shot blasting will have less effect), or chemically (acid pickle with a mixture of nitric and
hydrofluoric acid). Once cleaned, the surface can be chemically passivated to enhance corrosion
resistance, (passivation reduces the anodic reaction involved in the corrosion process).
Carbon steel tools, also supports or even sparks from grinding carbon steel, can embed
fragments into the surface of the stainless steel. These fragments can then rust if moistened.
Therefore it is recommended that stainless steel fabrication be carried out in a separate
designated area and special stainless steel tools used where possible.
If any part of stainless-steel is heated in the range 900-1400F (482-760C) for any reasonable
time there is a risk that the chrome will form chrome carbides Cr23C6 with any carbon present in
the steel along the austenite grains. This causes depletion of chromium from the austenitic grains
resulting in decreasing the corrosion protective passive film.
This effect is called sensitization. It is also called weld decay since it usually happens during
welding process when the zone around the weld is heated.
Figure 2 shows migration of chromium during heating of stainless steels.

Figure 2: Migration of chromium during heating of stainless steels.

To ensure good corrosion resistance of the weld root, it must be protected from the atmosphere
by an inert gas shield during welding and subsequent cooling. The gas shield should be
contained around the root of the weld by a suitable dam, which must permit a continuous gas
flow through the area.
Welding should not commence until sufficient time has elapsed to allow the volume of purging
gas flowing through the dam to equal at least the 6 times the volume contained in the dam. Once
purging is complete, the purge flow rate should be reduced so that it only exerts a small positive
pressure, sufficient to exclude air. If good corrosion resistance of the root is required, the oxygen
level in the dam should not exceed 0.1% (1000 ppm); for extreme corrosion resistance this
should be reduced to 0.015% (150 ppm).
Backing gasses are typically argon or helium; nitrogen is often used as an economic alternative
where corrosion resistance is not critical, nitrogen + 10% helium is better. A wide variety of
proprietary pastes and backing materials are available than can be use to protect the root instead
of a gas shield. In some applications where corrosion and oxide coking of the weld root is not
important, such as large stainless steel ducting, no gas backing is used.
Figure 3 shows two microstructures of type 304 stainless steel. The figure on the left is the
normalized microstructure and the one on the right is the "sensitized" structure and is susceptible
to intergranular corrosion or intergranular stress corrosion cracking.

Figure 3: Microstructure of stainless steel type 304.

Means of preventing sensitization:

Solution heat treatment: heating to a temperature above 1900F (1040C) followed by quenching (rapid cooling)
in water or quenching oils. During the heating stage the carbides dissolve and their formation is suppressed by
fast cooling.

Lowering concentration of carbon. Sensitization is depressed in low carbon (max. 0.03%) stainless steels,
designated with the suffix L (304L, 316L).

Stabilization by carbide forming elements. Formation of chromium carbides is avoided in stabilized austenitic
stainless steels (321, 347) containing carbide forming elements like titanium, niobium, tantalum, zirconium.
Stabilization heat treatment of such steels results in preferred formation of carbides of the stabilizing elements
instead of chromium carbides.
Date Published: Dec-2008