Corrosion of Stainless Steel

Types of Corrosion, Alloying Elements and Environmental Conditions

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 Corrosion of Stainless Steel
Types of Corrosion, Alloying Elements and Environmental Conditions

With regard to corrosion, stainless steel is a very smart group of metals. The excellent corrosion resis-
tance combined with a (still!) affordable price has made stainless steel the most frequently used group
of metals within critical sectors such as the food and pharmaceutical industries as well as the chemi-
cal industry.

The excellent corrosion resistance of stainless steel is caused by a very thin layer of oxides in particu-
lar chromium and iron oxides, and despite a thickness of only a few nanometers, this oxide layer is so
strong that it effectively isolates the steel from the environment. Should the oxide layer suffer from a
breakdown, it is quickly regenerated, and the corrosion protection is re-established.

Unfortunately, this ideal scenario does not always take place; the oxide layer may be damaged with-
out repassivating, and the sad result may be serious corrosion. Once the corrosion has started, rapid
penetration may occur causing the stainless steel to be a very short-lived construction material. The
difference in between the two extremes is sometimes very small: If repassivation takes place, corro-
sion is prevented and, theoretically, the steel may last forever. If not, severe corrosion may take place,
and the life-span of the equipment may be very, very short.

Generel
Generalkorrosion
Corrosion Interkrystallinsk
Intergranular Corrosion

Pitting Corrosion
Grubetring Crevice Corrosion
Spaltekorrosion

Stress .
Corrosion Cracking
Spndingskorr

The most commonly seen types of corrosion attacking stainless steel. General corrosion and intergranular corrosion
are rarely seen, whereas the three others are all too common. Pitting corrosion and crevice corrosion are often dealt
with under the common name of localized corrosion. For further information: See Stainless Steel and Corrosion,
Chapter 6

Corrosion of stainless steel is discussed in detail in Stainless Steel and Corrosion (Claus Qvist Jessen,
Damstahl a/s, October 2011), Chapter 6.

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 Corrosion of
Stainless Steel

Corrosion of Stainless Steel

Types of Corrosion, Alloying Elements and Environmental Conditions

General Corrosion (Stainless Steel and Corrosion, Chapter 6.1)

Also named acid corrosion (abtragenden Korrosion, generel korrosion), general corrosion is a type of
corrosion frequently occurring in very strong acids; however, corrosion may occur in strong alkalines as
well. Unlike any other type of corrosion, general corrosion is recognized by the fact that the whole sur-
face suffers from corrosion. The corrosion is almost uniform and expressed as a number of grams per
square meter, the loss of material may be very high whereas penetration is rather slow.

As mentioned above, general corrosion takes place at extreme pH values, i.e. in very strong acids or,
less common, in strong alkalines. Typical media are sulphuric acid, phosphoric acid and so on, and
apart from the type of media and the strength, corrosion velocity is highly dependant upon the tem-
perature and the presence of impurities, in particular chloride. As a rule, the corrosion increases with
increasing temperature and increasing chloride concentration.

4301 stainless steel bolt suffering from severe general corrosion after having spent
a number of months in a nitric acid-hydrouoric acid pickle bath. Please note that
the loss of metal is quite uniform and quite large, while no penetration has occurred
yet.

The most useful elements in the steel are nickel and molybdenum. In addition, copper (Cu) has a
certain benecial effect when the stainless steel is exposed to reducing acids, such as sulphuric and
phosphoric acids. This is utilized in the austenitic 904L (4539), which contains 1.2-2.0 % Cu.

In the other side of the spectrum, low-alloyed ferritic and, in particular, martensitic steels should not
be used in strong acids and alkalines. Much more detailed information regarding general corrosion of
stainless steel is found in Stainless Steel and Corrosion, Chapter 6.1.

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 Corrosion of Stainless Steel
Types of Corrosion, Alloying Elements and Environmental Conditions

Pitting Corrosion (Stainless Steel and Corrosion, Chapter 6.2)

Pitting corrosion (Lochfra-Korrosion, punktfrtning, grubetring) is a type of corrosion caused by a

local break-down of the protective oxide layer. Unlike the ideal situation, repassivation does not occur,
and severe corrosion will take place locally, while the rest of the steel remains passive. Pitting corro-
sion is the perfect example of the edge-like nature of stainless steel. Either repassivation occurs and
the steel lasts forever, or corrosion takes place, and penetration may occur rapidly.

Stainless steel (4301) specimen after a few days of exposure in a saltwater (NaCl) solution doped with hydrogen peroxide (H2O2).
While 99 % of the steel remains unharmed, some of the pits (in the frame) have caused pene-tration. The microscopic photo to
the right shows a magnication of the framed section.

Usually, the risk of pitting corrosion (and also crevice corrosion, see below) increases with
Increasing chloride concentration,
Increasing temperature,
Increasing concentration of oxidants and
Decreasing pH (increasing acidity)

Regarding the alloying elements, the resistance towards pitting corrosion is increasing with increasing
contents of Cr, Mo and N, while the effect of Ni is comparatively small. Non-metallic impurities, such
as S and P, reduce the corrosion resistance signicantly.

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 Corrosion of
Stainless Steel

Corrosion of Stainless Steel

Types of Corrosion, Alloying Elements and Environmental Conditions

Pitting Resistance Equivalent (Stainless Steel and Corrosion, Chapter 6.2.6)

If we stick to the useful alloying elements, Cr, Mo and N, loads of experiments have shown that the
resistance of the steel towards initiation of pitting corrosion can be estimated as a Pitting Resistance
Equivalent, the so-called PREN. PREN is calculated according the formula below, and, as a rule of
the thumb, the higher the PREN, the higher the resistance towards pitting corrosion. Two steel grades
with the same PREN can therefore be expected to perform equally good towards pitting corrosion.

PREN = %Cr + 3,3 %Mo + 16 %N

Please note that molybdenum (Mo) works with a factor 3.3 and is therefore 3.3 times better than a si-
milar amount of chromium (Cr). With a factor 16, nitrogen is even better, however, this only plays a role
in duplex steels (i.e. 4462 and 4410) and high-alloyed austenites, such as 4547 (254 SMO).

Through the PREN, its possible to determine the resistance of a certain stainless steel towards the ini-
tiation of pitting corrosion, and its even possible to make a table listing the different steel grades along
with their PREN. The most common grades are to be found in the Table below. For a more thorough
list (including much more information dealing with the corrosion properties of stainless steel), please
check out Stainless Steel and Corrosion, Chapter 6.2.6, table 6.1.

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 Corrosion of Stainless Steel
Types of Corrosion, Alloying Elements and Environmental Conditions

Co Mo N PREN

2.4819 / Hastelloy C-276 15 16 - 67,8

1.4547 / 254 SMO 20 6,2 0,2 43,7
1.4410 (superduplex) 25 4,5 0,3 43,0
1.4539 / 904L 20 4,5 - 34,5
1.4462 (UNS S32205) 22 3,0 0,15 34,3
1.4435 17,0 2,5 - 25,3
1.4436 / 4432 16,5 2,5 - 24,8
1.4362 (duplex 2304) 23 - 0,10 24,6
1.4162 (lean duplex 2101) 21 0,1 0,20 24,5
1.4401 / 4404 / AISI 316(L) 16,5 2,0 - 23,1
1.4571 / AISI 316Ti 16,5 2,0 - 23,1
1.4521 / AISI 444 17 1,8 - 22,9
1.4301 / 4307 / AISI 304(L) 17,5 - - 17,5
1.4509 / AISI 441 17,5 - - 17,5
1.4016 / AISI 430 16 - - 16,0
1.4034 / AISI 440B (0,43-0,50 C) 14 0,5 - 15,7
1.4057 / AISI 431 (0,12-0,22 C) 15 - - 15,0
2.4816 / Inconel 600 14 - - 14,0
1.4021 (0,16-0,25 C) 12 - - 12,0
1.4003 / AISI 410 11 - - 11,0

PREN table containing some of the most commonly found grades of stainless steel. The higher the PREN, the better resistance
towards pitting corrosion. The colours of the rows refer to the metallurgical structure:

Austenit Ferrit Duplex Martensit

Martensi Nikkelleg.

In a way, the table above can be regarded as a kind of pecking order for the corrosion resistance (pit-
ting and crevice corrosion). The higher in the table, the higher the PREN, and the better is the cor-ro-
sion resistance of the particular stainless steel. Note that the martensitic knife steels (4034, 4057 and
4021) are in the bottom, whereas the high-alloyed super steels (i.e. 4547, 4410) are in the top.

Also note that the acid resistant 4401 has a PREN of 23.1, while the common stainless 4301 has only
17.5. This difference is the main reason why the 4401 class is better than the 4301 class in almost all
media even though these media are far from acidic. Its a common misconception that acid resis-
tant steel grades are only better in acid media. In practice, the positive effect against pitting corrosion
is far more important.

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 Corrosion of
Stainless Steel

Corrosion of Stainless Steel

Types of Corrosion, Alloying Elements and Environmental Conditions

Finally, its worth noting that nickel (Ni) doesnt play any role at all for the initiation of pitting corrosion.
A very ne example is Inconel 600, a high-temperature alloy containing only 14 % Cr, but 72 % Ni, but
with regards to pitting corrosion, it performs rather poorly. On the other hand, the comparatively Ni is
great for slowing down a propagating attack, so once the corrosion has started, Ni is quite useful. In
general, though, ghting pitting corrosion is most often a question of preventing the corrosion from
starting, rather than slowing down a running attack.

Crevice Corrosion (Stainless Steel and Corrosion, Chapter 6.3)

Crevice corrosion (CC, Spaltkorrosion, spaltekorrosion) reminds a lot about pitting corrosion; how-ever,
CC takes place in crevices, pores and narrow geometries where there is a poor exchange of media or
none at all. Such places, all transport is controlled entirely by diffusion, and, through a pe-riod of time,
the medium in the crevice becomes both more acidic and contains more chloride than the bulk media.
Therefore, the risk of corrosion in a crevice is always higher than the risk of pitting cor-rosion on the
free surfaces outside the crevice.

An old rule of the thumb states says that the risk of CC is substantial at a temperature 20-25 C be-
low that of pitting corrosion (i.e. the critical pitting temperature, CPT). If the steel is close to its corro-
sion limit, the equipment should be designed so that no crevices are present. If this is not possible, a
more corrosion resistant steel must be chosen. An upgrade should be made.

Also with regards to the importance of the PREN, crevice corrosion correlates with pitting corrosion,
and the values of the table above are also valid for CC. However, CC is a bit more tricky. While the
comparatively noble Ni doesnt play a role in the initiation of pitting (and thus in the PREN equation),
its quite useful regarding repassivation, in particular in the acid, anaerobic environments which may
occur in a crevice.

Due to the effect of Ni, the Ni-free ferritic grades must be expected to perform slightly worse than the
parallel austenites. With regards to pitting, the PREN table is usually quite valid.

Stress Corrosion Cracking (Stainless Steel and Corrosion, Chapter 6.4)

Stress corrosion cracking (SCC, Spannungsrikorrosion, spndingskorrosion) is a type of corrosion gi-

ving rise to cracks. SCC is the most severe type of corrosion, and penetration may occur as a mat-ter of
days rather than months or years, even in thick steel plates. The name itself indicates that the corro-
sion takes place in regions of the steel, where tensile stress is present. Such tensile stress is common
and may occur as a result of any kind of mechanical process including welding and grinding.

The risk of SCC increases with

Increasing chloride content,
Increasing temperature,
Low pH (acid conditions), and
Evaporation

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 Corrosion of Stainless Steel
Types of Corrosion, Alloying Elements and Environmental Conditions

Of these, the temperature is, by far, the most important single factor, ans SCC is more dependent
upon the temperature than any other type of corrosion. In addition, its the only type of corrosion which
tends to be worse above water than below the water line. See Stainless Steel and Corrosion, Chapter
7.4.

Left: SCC in a hot-water tank made of 4301. The tank has been used for the storage of 90
C water; note the ne side-cracks.
Right: Micro-section through one of the cracks from the hot-water tank to the left. Note
the ne appearance of the cracks, combined with the tiny side-cracks, all very typi
cal of chloride-induced SCC.

SCC is a type of corrosion which almost selectively attacks the lowest-alloyed austenites, such as the
4301 class, and normally the 4301 grades are in danger at temperatures above 60-70 C. In practice, ca-
ses are known in which 4301 has been attacked by SCC at much lower temperatures, even below room
temperature.

Due to the content of Mo and Ni, the acid resistant 4401 class is somewhat better, and the typical tem-
perature limit lies somewhere around 100 to 110 C. As above, this limit is not absolute, and cases are
known in which SCC has occurred in 4401 at temperatures of only 30-40 C, particularly in swimming
pool environments. Here, whole light equipment has fallen to the ground due to SCC in the cables.
SCC and its dependence of the environment and the alloying elements are in detail discussed in Stain-
less Steel and Corrosion, Chapter 6.4.2 and 6.4.3.

Ferritic and duplex stainless steels are much less prone to SCC than the parallel austenites, so if SCC
is the primary type of corrosion to be fought, its not a bad idea to think in the direction of 4509 or 4521
instead of 4301 or 4404.

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 Corrosion of
Stainless Steel

Corrosion of Stainless Steel

Types of Corrosion, Alloying Elements and Environmental Conditions

Intergranular Corrosion (Stainless Steel and Corrosion, Chapter 6.5)

Intergranular corrosion (IGC, interkristalline Korrosion, interkrystallinsk korrosion) is a type of corro-sion

which is caused by the formation of chromium carbides in the grain boundaries of the steel. Heat-ing
the steel to a temperature in the range of 500-850 C, carbon is binding the useful chromium (= sen-
sitization) causing a weakening of the zones adjacent to the grain boundaries. In popular, this corre-
sponds to dissolving the cement in between the bricks of a house.

Left: IGC in an Asian made 4301 bend containing 0.055 % C. After an unlucky heat treat
ment causing sensitization, the bend was exposed to an acid media revealing the
problem as IGC.
Right: Micro-section through the same species at to the left. Note the thickened grain
boundaries and the dropped-out grains, both typical for IGC.

The risk of IGC increases rapidly with the carbon content of the steel, and this risk is the main reason
why one should always chose low-carbon steel (i.e. 1.4306, 4307, 4404 or 4435) or titanium stabilized
types (4541, 4571), as compared to normal types (4301, 4401). The thicker the steel (= increased heating
time), the more important it is to use low-carbon steel. Due to the increased effort of the steel works in
order to remove the carbon, IGC is a rare bird these days.

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 Corrosion of Stainless Steel
Types of Corrosion, Alloying Elements and Environmental Conditions

Time (Stainless Steel and Corrosion, Chapter 6.6 + Chapter 7)

For all types of corrosion, the TIME is a very important factor. Long-time exposure is always more
critical than short-term exposure in a similar environment, and frequently its possible to get away with
exposing the steel to a, in theory, too corrosive environment, as long as the contact time is kept su-
ciently low. This is often seen during disinfection of stainless steel tanks. As long as the disinfection
process is kept within a time frame of a few minutes, nothing happens. In contrast, long-term expo-
sure due to left-over disinfectant may give rise to severe corrosion.

The contact time is the main reason why the risk of corrosion is the worst when the steel is immersed
completely into the media. Hereby, we have the large bulk electrolyte and a subsequent risk of in-
ternal galvanic coupling, a problem particularly critical to crevice corrosion. Also in the case of pitting
corrosion, general corrosion and IGC, conditions are worst under water. In contrast, SCC frequently gets
worse above water due to the risk of evaporation and an increase in the chloride concentration.

Above water, contact time is essential, and for constructions above water its important to minimize
the possible contact time. In the case of buildings and tank and pipe equipment alike, it must be en-
sured that all water can be drained off as quickly as possible. If not, corrosion may occur, spanning
from cosmetically annoying supercial pitting corrosion at low temperature to the destructive SCC at
elevated temperature.

In general, anything but SCC tends to be of a cosmetic character, however, such attacks may be quite
annoying anyway regardless if the equipment in question is an architect-made post box or the faade
of an opera house.

Supercial pitting corrosion above water in an aquarium tank (4301). The cor-
rosion is due to variations in the water level causing a short-time contact period
but the risk of evaporation and increasing chloride level.

Almost all available corrosion data are based upon long-term exposure. If the contact time can be
minimized, chances are that the steel may last far better than the information in the corrosion tables.
See Stainless Steel and Corrosion, Chapter 7, and, for a shorter summary, the Damstahl publication
dealing with Atmos-pheric Corrosion.

All references are with regards to Stainless Steel and Corrosion (Claus Qvist Jessen, Damstahl a/s,
October 2011). The book can be ordered through www.damstahl.dk.

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