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

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 oxide Formation of chromium Under
(rust) 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 types of corrosion and we rank the majority of Stainless
is seen in the majority of cases when stainless steel is Europe grades from standard laboratory tests
placed 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
La corrosion par piqûre choose the optimal material.
Pitting Corrosion

To understand the phenomenon > If the potential of the stainless steel in the given medium is
Pitting corrosion is a local break in the passive layer of the superior to the pitting potential =>the stainless steel corrodes
stainless steel provoked by an electrolyte rich in chloride Note: the higher the pitting potential, better shall be the
and or sulphides. At the site of the pitting, where the metal corrosion resistance of the grade. Outside the pits, the
is unprotected, corrosion will develop if the pit does not passive layer is always present to protect the stainless steel.
re-passivate, in other words if the speed of metal dissolution
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 Cl-)
at 23°C.
Passive layer
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
K44
Metal
Pitting potential in water containing 0.02MNaCI pH=6,6 at 23°C (mV/SCE )

2 cases
700
17-11MT
18-11ML
The metal re-passivates Corrosion of the base metal K45
600 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
Standards
the sudden increase in intensity corresponds to the pitting Commercial
Designations ASTM
potential Epitting Designation: Type
EN

Martensitic 420 1.4021

IntensitY
K09+ 409 1.4512
I =50µA/cm2 K03 1.4003
K10 410S 1.4000
K30-K31 430 1.4016 - 1.4017
K39 439 1.4510
K41 441 1.4509
Epitting K36 436 1.4526
POTENTIAL
K45 445 1.4621
Passive Field 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 necessary 18-7L 301LN 1.4318
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 0.5M NaCI pH=6,6 at 50°C (mV/SCE)

K44 K44
600
Pitting potential in water containing 0.02M NaCI pH=6,6 at 23°C (mV/SCE)

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 50°C, were carried out.
The results obtained are shown below.

1200
23° 50° 23°
Pitting potential in water containing 0.5M NaCl, at 23°C and 50°C (mV/SCE)

700

23°
600
Standards
No pits
No pits
No pits

Commercial ASTM
500
Figure 4

50° Grades Designation EN

23° 23°
400 Type UNS
23° DX2202 2202 UNS 32202 1.4062
300
50° DX2304 2304 UNS 32304 1.4362
50°
200 DX2205 2205 UNS 32205 1.4462
50° 50°
100

0
DX2202 DX2205 DX2304 304 316 K44

>
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 recommandation
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
speed of crevice corrosion propagation for different grades.
Figure 5: Depassivation pH of various stainless steels in NaCl
2M (71g/l Cl-) de-aerated and acidified with HCl at 23°C 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

aggressiveness and temperature of the medium.
Depassivation pH of various stainless steels in NaCl 2M ( 71g/l Cl-)

3,5
de-aerated and acidified with HCl at 23°C

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 23°C.
2

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

DX2205
1 2000 K30/K31 K41

K39
0,5
10 15 20 25 30 35 1500
+(71g/l de Cl-)

PREN (%Cr+3,3%Mo+16%N)

K45
1000

B/ Propagation of corrosion
Once corrosion is initiated, its propagation occurs by active 164Mn
500 165MnL DX2202
dissolution of the material in the crevice. 174Mn
K44 187L DX2304
In the laboratory, we simulate this type of corrosion by 177A 1810T 1711MT
1810L 1811ML 1812MS 1813MS
recording the potentiodynamic scans in chloride mediums of 0
189E

increasing acidity. 1 3 5 7 9
DX2205
11 13
0,2%Cr+%Mo+0,4%Ni

>
Our recommandation
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 pièce 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.

If ferritics with 20% chromium limit the risk of crevice corrosion initiation, they do not, with the exception of
K44 containing 2% molybdenum, curb its propagation unlike austenitic or duplex more highly nickel and / or
molybdenum alloyed.

Intergranular Corrosion

To understand the phenomenom

Consequently, the zone directly adjacent to the grain
At temperatures greater than 1035°C , the carbon is in solid boundaries is greatly impoverished.
solution in the matrix of the austenitic stainless steels. The sensitisation state takes place in a lot of environments
However, when these materials are cooled slowly from these by privileged initiation and the rapid propagation of corrosion
temperatures or even heated between 425 and 815 °C, on the de-chromed sites.
chromium carbides precipitate at the grain boundaries. These For unstabilized ferritic stainless steels, the sensitisation
carbides have a higher chromium content in comparison to temperature is greater than 900°C.
the matrix.
 >
Our recommandation
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 1050/1100°C or
a tempering of the welded piece can be done.

Stress Corrosion
> Although stress corrosion of ferritics can be provoked by
To understand the phenomenon particularly aggressive tests in the laboratory ,
their body cubic centred structure rarely renders them subject
We mean by « stress corrosion » the formation of cracks to this type of phenomena in practice .
which start after a period of long incubation and which
afterwards can propagate very rapidly and provoke downtime > The face cubic centred structure of austenitic stainless
of the equipment by cracking . 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 50°C
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 .

Chlorides 1000
Temperature effects
Aggressive medium

PASSIVE LAYER cracking

Fissuration

No cracking
contraintes STAINLESS contraintes
100
Time to crack (hours)

PASSIVE LAYER

10
STAINLESS
CRACKs

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

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 154°C
[ From a study by Copson [ref] . Physical Metallurgy of Stress Corrosion Cracking,
Interscience, New York, 247 (1959).]
Our recommandation
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
surface of the material which are attacked by the corrosive
medium. On the micrographic scale,this corresponds to a
regular uniform loss of thickness or loss of weight (uniform or
generalised corrosion as opposed to localised corrosion).
We see this corrosion in acid mediums. Indeed, below a critical
The maximum current reading of the activity peak allows us
to classify the resistance of different grades to this type of
corrosion (see figure 7).
Generally, the higher the current, the faster and greater the
dissolution, thus the less the grade will be resistant.

September 2013, Aperam Stainless Europe. FT-Corrosion.en. While everycare has been taken to ensure that the information contained in this publication is as accurate as possible, Aperam Stainless Europe cannot guarantee that it is complete nor that it is free from error.
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 stainless steel.

In the laboratory, we measure this speed of corrosion in an 100

acid medium by graphing the polarisation curve (see below).
An increasing potential scan is imposed on the metal and the
corresponding intensity is recorded.

10

Polarization curve in an acidic medium

Potential U 1

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
Up B Figure 7: Critical current «icrit» at the peak maximum in H2SO4
2M de-aerated at 23°C
Activity
KARA® is a brand of Aperam Stainless Europe, registered in numerous countries. © Aperam.

Immunity M

>
Current
density (I)

Cathodic Curve
Anodic Curve Our recommandation
UP = Pitting Potential 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
In a low oxidising medium, the cathodic curve (M) cuts the anodic curve reinforce the existing passive film but also the combined
below the pitting potential: metal remains intact. effect of noble alloys (nickel, molybdenum and copper) which
In a strong oxidising medium, the cathodic curve (B) cuts the anodic curve slow down the dissolution of the material when the stability
above the pitting potential: pits appear on the surface of metal. of its passive layer is broken.

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