Stainless Europe

Stainless Steel and

Corrosion

What is corrosion?
Metals, with the exception of the precious metals such What are the major factors of corrosion?
as gold and platinum, that are found in their natural state
are always extracted from ores; metals have therefore a Medium
tendency to revert to their stable state, which corresponds
Chemical nature
to their original state, that is to say their oxide form. Concentration
Metal corrosion is essentially an electro-chemical reaction at Oxidising power
pH (acidity)
the interface between metal and surrounding environment . Temperature
Pressure
Viscosity
Solid deposits
Stainless Steel and the passive layer Agitation
Steel is an alloy of iron and carbon. Contrary to carbon steel,
the presence of a minimum of 10.5 % chromium in the Composition
Manufacturing
stainless steel gives it the property of corrosion resistance. Metallurgical state
(thermal or mechanical
treatment)
The Composition of Stainless Steel Additives
It is the chromium which gives the stainless quality to our steels. Impurities
Design
Surface state
Shape
Assembly (welds, rivets)
Mechanical stresses
Proximity to other metals
Contact with a medium
(partial or total immersion)
Methods of protection
Corrosion
factors
Ageing of the structure
Evolution of stresses
Temperature variability
Modification of coatings
Maintenance frequency

Material Time

Chromium What are the 5 principal types of corrosion linked with

>10,5%
the surrounding environment ?
Iron Carbon Fe+C=steel
<1,2% Fe+C+Cr=stainless steel generalised localised

Pitting
Indeed, on contact with oxygen, a chromium oxide layer is
formed on the surface of the material. This passive layer
protects it and has the particular ability to self repair.
neutral
chloride
Crevice
Reaction of steel and stainless steel in contact
environment
with moisture in the air or water.

Steel Stainless Steel

Formation of iron Formation of Under
oxide (rust) chromium oxide stress
O2

Fe + C Fe + C + Cr > 10,5 %

Generalised Inter-
Rust granular

Passive layer
acid medium

However if this protective layer is damaged, the start of

corrosion can appear
Generalised corrosion is noticed when stainless steel is In the document which follows we describe the 5 principal
in contact with an acid medium and localised corrosion is types of corrosion and we rank the majority of Stainless
seen in the majority of cases when stainless steel is placed Europe grades from standard laboratory tests
in a neutral chloride environment However, the phenomena of corrosion in real life are always
specific, the data described does not exclude extra trials to
choose the optimal material.

Pitting Corrosion

To understand the phenomenon If the potential of the stainless steel in the given medium
Pitting corrosion is a local break in the passive layer of the is superior to the pitting potential =>the stainless steel
stainless steel provoked by an electrolyte rich in chloride corrodes
and or sulphides. At the site of the pitting, where the metal Note: the higher the pitting potential, better shall be the
is unprotected, corrosion will develop if the pit does not corrosion resistance of the grade. Outside the pits, the
re-passivate, in other words if the speed of metal dissolution passive layer is always present to protect the stainless steel.
enables to maintain a sufficiently aggressive environment to
Figure 1 shows pitting potentials obtained for different
prevent its re-passivation.
stainless steels in water containing 0.02M NaCl (710mg/l
Passive layer
Cl-) at 23C.
It shows the influence on the resistance to pitting corrosion
Metal
with the content of chromium and molybdenum for
the ferritics, and chromium, molybdenum and nitrogen content
METAL ATTACK
for the austenitics.
Chlorides
mV/SCE
Figure 1
Passive layer
800
Metal K44
Pitting potential in water containing 0.02MNaCI pH=6,6 at 23C (mV/SCE )

2nd case 700

17-11MT
18-11ML
The metal re-passivates Corrosion of the base metal
600 K45
18-9E/L
passive
layer 18-10T K36
17-7A/C/E 18-7L
Metal
K41
500

16-5MnL
17-4Mn
K39 16-4Mn
This dissolution gives rise to metal ions and electrons and
thus the passage of current (of dissolution) which gives rise 400
to an electrical potential difference between the anodic zone K30-K31
K03
(pitting) and the cathodic zone (the rest of the metal). K09
K10
300
Martensitic

To simulate this type of corrosion under laboratory

200
circumstances, a sample is immersed in a corrosive electrolyte
to which an increasing potential is applied until the passive 10 12 14 16 18 20 22 24 26
PREN (%Cr+3,3%Mo+16%N)
layer is broken.
During this dynamic potential (intensity/potential) scan
Norms Standards
the sudden increase in intensity corresponds to the pitting Commercial
ASTM
potential Epitting designations
Type
EN

Martensitic 420 1.4021

INTENSITy K09 409 1.4512
I =50A/cm2 K03 1.4003
K10 410S 1.4000
K30-K31 430 1.4016 - 1.4017
K39 439 1.4510
K41 441 1.4509
K36 436 1.4526
Epitting POTENTIAL
K45 445 1.4621
Passive eld K44 444 1.4521
16-4Mn 201.2 1.4372
16-5Mn 201LN 1.4371
17-4Mn 201.1 1.4618
17-7A/C/E 301 1.4310
The pitting potential corresponds to the potential 18-7L 301LN 1.4318
necessary to initiate stable pits. 18-9L 304L 1.4307
If the potential of the stainless steel in the given medium is 18-11 ML 316 - 316 L 1.4401 - 1.4404
17-11MT 316Ti 1.4571
inferior to the pitting potential => pitting does not start
 As figures 2 and 3 show, this pitting potential can only be used to rank the grades in a given medium.
It diminishes notedly when the temperature (figure 2) or the concentration of chlorides in the medium increases. (figure 3)
700 500

450
Pitting potential in water containing 0.02M NaCI pH=6,6 at 23C (mV/SCE)

Pitting potential in water containing 0.5M NaCI pH=6,6 at 50C (mV/SCE)

K44 K44
600 18-11ML

400
18-11ML
500 350

18-9E/L 300 18-9E/L

400 K36 K36
K41
250 K41
K39
K39
300
200
K30

200 K03-K09-K10 150

K30
100
100
50
K03-K09-K10
0 0
10 12 14 16 18 20 22 24 26 10 12 14 16 18 20 22 24 26
PREN (%Cr+3,3%Mo+16%N) PREN (%Cr+3,3%Mo+16%N)
Figure 2 Figure 3

In order to map the duplex range, tests in the most severe medium, 0.5M NaCl (17.75g/l Cl-) at 50C, were carried out.
The results obtained are shown below.
Pitting potential in water containing 0.5M NaCl, at 23C and 50C (mV/SCE)

Normes

Appellations ASTM
commerciales
Figure 4

Designation EN
Type UNS
DX2202 2202 UNS 32202 1.4062
DX2304 2304 UNS 32304 1.4362
DX2205 2205 UNS 32205 1.4462

Usually we use the PREN (Pitting Resistance Equivalent Number) of the grades to rank their general piting behaviour. The PREN,
%Cr+3.3%Mo+16%N , demonstrates the major influence of these alloy elements.

Our Recommendation
To avoid pitting corrosion:
We would look to see if it is possible to lower the corrosiveness by lowering the temperature of the medium, limiting
contact time, avoiding stagnant areas and reducing the concentration of halogens and the presence of oxidants.
We would choose a grade high in chromium or containing molybdenum.

Crevice Corrosion
To understand the phenomenon
A/ Initiation of corrosion
In an electrolyte high in chloride, a confined (occluded) zone linked for example to bad design, favours the accumulation of chloride
ions. The progressive acidification of the medium in this zone facilitates the de-stabilisation of the passive layer. When the pH in
this zone reaches a critical value called depassivation pH ,corrosion starts. The depassivation pH or pHd is used to characterize
the resistance to crevice corrosion initiation.

Why? How?
Break in the
passive layer
Confined zone and metal attack
(acidification)
 Some pHd values for our stainless steels are given in figure 5. If on a recording we detect a current peak (activity), crevice
The lower the value pHd the better the resistance to crevice corrosion is starting , in the opposite case repassivation takes
corrosion. place.

Activity peak measurement for a pH lower to the depassivation

pH can then be considered to quantitatively compare the
Figure 5: Depassivation pH of various stainless steels in NaCl speed of crevice corrosion propagation for different grades.
2M (71g/l Cl-) de-aerated and acidified with HCl at 23C
This value is sensitive to the alloy elements which improve the
passivity and limit active dissolution, principally molybdenum,
nickel and chromium (see figure 6 ).
4
The speed of propagation is also a function of local
Depassivation pH of various stainless steels in NaCl 2M ( 71g/l Cl-)

3,5 aggressiveness and temperature of the medium.

de-aerated and acidified with HCl at 23C

3
Figure 6: Critical current icrit at the peak of activity for
2,5
various stainless steels in NaCl 2M (71g/l de Cl-) deaerated
and acidified with HCl at 23C.
2

Critical current icrit at the peak of activity for various stainless steels in NaCl 2M
2500 Martensitic
1,5 K03/K09/K10

(71g/l de Cl-) de-aerated and acidified with HCl at 23C.

1 2000 K30/K31 K41

K39
0,5
10 15 20 25 30 35 1500
PREN (%Cr+3.3%Mo+16%N)

K45
1000

B/Propagation of corrosion
164Mn
500 165MnL DX2202
Once corrosion is initiated, its propagation occurs by active 174Mn
K44 187L DX2304
dissolution of the material in the crevice. 177A 1810T 1711MT
1810L 1811L
In the laboratory, we simulate this type of corrosion by 0
1898 1812MS 1813MS

recording the potentiodynamic scans in chloride mediums of 1 3 5 7 9

DX2205
11 13
increasing acidity. 0.2%Cr+%Mo+0.4%Ni

Our Recommendation
Our first recommendation to avoid crevice corrosion is to optimise the design of the piece to avoid all artificial
crevices. An artificial crevice can be created by a badly made joint, a rough or bad weld, deposits, gaps between
two plates etc.,
If the confined zone is unavoidable, it is preferable to enlarge this zone and not to make it smaller.
If the design of the pice is not modifiable or if the fabrication process makes difficult to avoid confined zones,
the risk of crevice corrosion is very high . We recommend, in this case, choosing an appropriate grade, in
particular a stainless steel austenitic or duplex when the product will be in contact with corrosive media or part
of the process equipment.

Intergranular corrosion

To understand the phenomenon

Consequently, the zone directly adjacent to the grain
At temperatures greater than 1035C , the carbon is boundaries is greatly impoverished.
in solid solution in the matrix of the austenitic stainless The sensitisation state takes place in a lot of environments
steels. However, when these materials are cooled slowly by privileged initiation and the rapid propagation of corrosion
from these temperatures or even heated between 425 on the de-chromed sites.
and 815 C, chromium carbides precipitate at the grain For unstabilized ferritic stainless steels, the sensitisation
boundaries. These carbides have a higher chromium content temperature is greater than 900C.
in comparison to the matrix.
 Our recommendation
In practice , this case of corrosion can be encountered in the welded zones . The solution for the austenitic
consists of using a low carbon grade called L (Low C%<0.03%) or a stabilized grade, and the titanium or
niobium stabilized ferritic grades.

The volume of the piece permiting a thermal treatment of the quenching type (rapid cooling) at 1050/1100C
or a tempering of the welded piece can be done.

Stress Corrosion
To understand the phenomenon
We mean by stress corrosion the formation of cracks
which start after a period of long incubation and which
afterwards can propagate very rapidly and provoke
downtime of the equipment by cracking .
Although stress corrosion of ferritics can be provoked by
particularly aggressive tests in the laboratory ,
their body cubic centred structure rarely renders them subject
to this type of phenomena in practice .
The face cubic centred structure of austenitic stainless
steels can present a risk.

This particularly dangerous phenomenon is the result
of the combined effects of 3 parameters:
- temperature, since stress corrosion rarely develops
under 50C
In effect , it favours a mode of planar deformation which can
generate very strong stress concentrations locally. As shows
the graph below, this is particularly true for classic austenitic
stainless steels with 8% nickel; an increase in nickel above
10% is beneficial .

- the applied or residual stresses In austenitic stainless steels, the austenitic stainless steels
with manganese perform worse.
- the corrosiveness of the medium : presence of Cl-, H2S
or caustic media NaOH The austeno-ferritic structure of the duplex gives them
an intermediate behaviour, very close to the ferritics in the
chloride medium and even better in the H2S medium .

1000
Chlorides
Temperature effects
Aggressive medium
Cracking
Passive layer
No cracking

Stress Stainless steel 100

STAINLESS
Time to crack (hours)

Passive layer
10
STAINLESS

Cracks

The metallurgical structure of stainless steels influences their behaviour in this type 1
of configuration

0 20 40 60 80
Nickel content, wt.%

Effect of nickel content on the resistance to stress corrosion of

Stainless steel containing from 18-20% chromium in magnesium chloride at 154C
[ From a study by Copson [ref] . Physical Metallurgy of Stress Corrosion Cracking,
Interscience, New York, 247 (1959).]
Our recommendation
To avoid this type of corrosion :
Suppress the stresses or have a better redistribution, by optimising the design or by
a stress relieving treatment after forming and welding of the pieces concerned.
lower the temperature if possible
If not practicable, choose the grade most adapted, favouring as a solution a
ferritic or duplex but bearing in mind the other corrosion problems encountered .
 Uniform corrosion

To understand the phenomenon

This is the dissolution of all the affected points on the The maximum current reading of the activity peak allows us
surface of the material which are attacked by the corrosive to classify the resistance of different grades to this type of
medium. On the micrographic scale,this corresponds to a corrosion (see figure 7).
regular uniform loss of thickness or loss of weight (uniform
or generalised corrosion as opposed to localised corrosion). Generally, the higher the current, the faster and greater the
dissolution, thus the less the grade will be resistant.
We see this corrosion in acid mediums. Indeed, below a
critical pH value, the passive layer protecting the stainless
steel is no longer stable and the material suffers a
generalised active dissolution. The more acid the medium,
the faster the corrosion and the loss of thickness of the

March 2010, ArcelorMittal - Stainless Europe. Fiche Corrosion.eng. While everycare has been taken to ensure that the information contained in this publication is as accurate as possible, ArcelorMittal - Stainless Europe, in common with all ArcelorMittal
stainless steel.
100
In the laboratory, we measure this speed of corrosion in an
acid medium by graphing the polarisation curve (see below).
An increasing potential scan is imposed on the metal and the

Group companies, cannot guarantee that it is complete nor that it is free from error. KARA is a trademark of ArcelorMittal - Stainless Europe, registered in numerous countries. Design and conception: www.agencembcom.com
corresponding intensity is recorded.
10

Polarization curve in an acidic medium

1
Potential U

Transpassivity

0.1

Passivity
0.01
K09 K03 K30 K41 K39 K45 K44 16-4 18-9E 17-4 18-11
Mn Mn ML

Pre-passivity Figure 7: Critical current icrit at the peak maximum in H2SO4

Up
2M de-aerated at 23C

Activity
B

Immunity M
Current
density (I)

Cathodic curve Our recommendation

Anodic curve
UP = Pitting potential
In a low oxidising medium, the cathodic curve (M) cuts the anodic curve
below the pitting potential: metal remains intact.
In a strong oxidising medium, the cathodic curve (B) cuts the anodic curve
above the pitting potential: pits appear on the surface of metal.
To avoid this type of corrosion, choose
the appropriate grade in regard to the acid
medium used.
We note the favourable impact of chromium
and molybdenum which reinforce the
existing passive film but also the combined effect of noble
alloys (nickel, molybdenum and copper) which slow down the
dissolution of the material when the stability of its passive
layer is broken.

Head office Information

ArcelorMittal Paris Tel. :+33 1 71 92 06 52
Stainless Europe Fax : +33 1 71 92 07 97
1-5 rue Luigi Cherubini www.arcelormittal.com/stainlesseurope
FR-93212 La Plaine Saint Denis Cedex