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Stainless steels represent the most diverse and complex family of all steels.
The list of their applications is endless: from the harsh environments of the
chemical, oil production and power generation industries to street furniture or
automotive trims without forgetting most cutlery, they are used either for
decorative purposes and/or for their excellent resistance to corrosion.
12% Cr-steels are resitant to atmospheric corrosion but are useless in acids
such as HCl or H2SO4 where they exhibit a corrosion rate even greater than
plain carbon steels. As will be discussed later, corrosion resistance can be
greatly enhanced above that of a basic 12% Cr steel by further addition of Cr
and/or use of other alloying elements such as Ni, Mo, N etc.
Corrosion resistance is of course not the only design criterion: materials cost
considerations will typically favour basic, cheaper grades (12%Cr-0.1%C) rather
than heavily alloyed steels. Mechanical properties must also be taken into
account, as must fabrication difficulties (machinability, deformability, weldability,
etc.). The number of grades is therefore seemingly infinite, with a large number
of standard compositions to which manufacturers add their proprietary variants.
These are usually divided in four or five classes on the basis of their
microstructures:
to which some add precipitation hardened stainless steels, although they are
themselves divided into martensitic/ferritic/etc. so that they could be included in
the above categorisation.
Corrosion resistance
Iron is not stable in most of the environments in which it is used. Like most non-
noble metals, it does not naturally occur in its elemental form and has to be
extracted from oxides. In service, the tendency is for re-formation of these
oxides. Hence the rust that can be observed on most unprotected steel
components.
Materials scientists and chemists often take recourse to thermodynamics to
quantify and compare the stability of different phases, oxides, etc. In this case
however, thermodynamics alone gives an erroneous representation of the
problem: most stainless steels are used in conditions in which the dissolution of
the metal is energetically favorable.
Instead, they owe their environmental resistance to the formation of a chromium
oxide film which acts as a kinetic barrier: atomic transport through this layer is
so slow, that the steel can be considered inert.
The passive film formed at the surface of stainless steels is extremelly thin (1-2
nm). Its chromium content depends on the bulk content, and in general,
increases with the latter. The overall corrosion resistance is also enhanced as
the chromium content is raised.
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 above figure 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:
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 (for example 254SMO, Avesta Sheffield).
Use of stainless steels in offshore platforms.
Street furniture is another case where pitting resistance might be
relevant, particularly in colder areas where salt de-icing is common.
Grain decohesion due to intergranular corrosion, photo courtesy M. Shimada (Shimada et al,
Acta Mater., 2002:50, p2331).
The time and temperature dependency of sensitisation, after Mayo, Mater. Sci. Eng. A,
1997:232, p129.
When austenitic stainless steels are welded, any metal which has been
melted usually cools fast enough to prevent carbide formation. However,
in the metal adjacent to the fusion zone, the so-called heat-affected zone
(HAZ), the temperature changes might be such that sensitisation occurs.
Remedies
Various solutions can be implemented to avoid sensitisation:
The effect of carbon content on the kinetics of sensitisation. After (Gooch, Weld
decay in austenitic stainless steel, The Welding Institute, 1975)
Mechanism
Phase equilibria
Main phases
Iron and its alloys can exist in two crystallographic forms (body centred or face-
centred cubic). In pure iron, the f.c.c. structure exists between 910 and 1400 C,
the b.c.c. structure below and above this interval (up to the melting temperature
of 1539 C).
The importance of this phase-transformation in the metallurgy of steels cannot
be overestimated. This transformation allow for a wide range of microstructures
to be achieved by controlled heat-treatment. Mechanical properties are
essentially related to microstructure, and can therefore be obtained in an
extraordinarily large range of strength, toughness, etc.. Stainless steels are
routinely produced with strengths from 100 MPa to largely more than 1GPa.
Knowledge of the relative stability of the b.c.c. and f.c.c. structures of iron alloys
is therefore of prime concern. The history of stainless steels started with a
martensitic grade (12%Cr-0.1%C) in Sheffield, UK and the austenitic 18%Cr-
8%Cr in Germany ( more about the history of stainless steels). For this reason,
and also because they are most often the major alloying elements, Cr and Ni
have long been used as reference to quantify the influence of alloying elements
on the b.c.c.<->f.c.c. phase transition: chromium additions tend to stabilise the
b.c.c. phase, while nickel additions stabilise the f.c.c. one.
Pseudo-binary (isopleth) Fe-Cr diagram for 0.1% C. Chromium additions stabilise the b.c.c. form of
iron, beyond about 18%, Fe-Cr steels no longer undergo the α/γ transition (ferritic stainless steels).
Without carbon, the limit beyond which austenite no longer forms is about 13.5
wt%. However, additions of carbon stabilise the austenite and therefore
increase this limit.
Other alloying elements also affect the stability of austenite/ferrite in one
direction or another. This has led to their classification as α-stabilisers or γ-
stabilisers. The concept of Cr-equivalent (for α-stabilisers) and Ni-equivalent (for
γ-stabilisers) is widely used in conjunction with the Schaeffler diagram to
quantify their roles:
Cr equivalent = (Cr) + 2(Si) + 1.5(Mo) + 5(V) + 5.5(Al) + 1.75(Nb) + 1.5(Ti) +
0.75(W)
Ni equivalent = (Ni) + (Co) + 0.5(Mn) + 0.3(Cu) + 25(N) + 30(C)
All in weight percent.
Schematic Schaeffler diagram. Although primarily intended for use in welding, this diagram is
sometimes used in alloy design as it provides an easy way to estimate the microstructure of a
stainless steel.
Modern thermodynamics calculation tools such as Thermocalc or MTDATA
based on the CALPHAD method allow more rigourous determination of
equilibrium phase diagrams in multicomponent systems.
Second phases
Martensite formation
Categories
On the basis of their main microstructural features, grades of stainless steels
are typically divided into four categories:
These steels still undergo the b.c.c./f.c.c. transformation of iron, although the
range of austenite stability is reduced.
As for conventional steels, mechanical properties can be considerably altered
by heat-treatments. Typical heat-treatments consist of austenitisation at a
temperature suitable for dissolution of carbides. Stainless steels have a high
hardenability, that is to say, reconstructive transformations are considerably
slowed by the presence of Cr, so that a fully martensitic structure can be
achieved without a severe quench. Oil or water quenching are nevertheless
used with large sections so as to ensure martensite formation throughout.
The table below shows the composition and typical use of AISI standard
martensitic grades:
AISI
N Comments/Applica
grad C Mn Si Cr Mo P S
i tions
e
The basic
composition. Used
11.5
0. 0.0 0.0 for cutlery, steam
410 0.15 1.0 - - -
5 4 3 and gas turbine
13.0
blades and buckets,
bushings..More.
Addition of sulphur
for machinability,
12.0
1.2 1. 0.0 0.1 used for screws,
416 0.15 - - 0.60
5 0 4 5 gears etc. 416 Se
14.0
replaces suplhur by
selenium. More
0.75 16.0
440 1. 0.0 0.0 As 440A, higher
- 1.0 - - 0.75
B 0 4 3 hardness
0.95 18.0
Ferritic stainless steels: contain typically more chromium and/or less carbon
than the martensitic grades. Both changes act towards stabilisation of ferrite
against austenite so that ferrite is stable at all temperatures. Therefore, ferritic
stainless steels cannot be hardened by heat-treatments as is the case of
martensitic ones. They exhibit lower strength but higher ductility/toughness.
Typical application may include appliances, automotive and architectural trim
(i.e. decorative purposes), as the cheapest stainless steels are found in this
family (aisi 409).
AISI
Comments/Applicatio
grad C Mn Si Cr Mo P S
ns
e
0.0 11.5-
405 1.0 1.0 - 0.04 0.03 0.1-0.3 Al
8 14.5
0.1 14.0-
429 1.0 1.0 - 0.04 0.03
2 16.0
0.1 16.0-
430 1.0 1.0 - 0.04 0.03
2 18.0
0.2 23.0-
446 1.5 1.0 - 0.04 0.03 0.25 N
0 27.0
High chromium ferritic stainless steels such as 446 are sensible to the so-called
'475 C embrittlement', which is caused by the decomposition of the Fe-Cr solid
solution in two phases, Fe and Cr-rich respectively. Around 475 C and below,
and for Cr contents greater than about 25 wt%, this decomposition is spinodal
and typically exhibits wavelength below 10 nm. As the decomposition occurs, a
continuous increase of hardness is observed: for example, the hardness of an
Fe-28Cr steel can increase by more than 300 Hv over an exposure 10,000 at
450 C (Ishikawa et al., Mater. Trans. JIM, 36:1995, p16-22). This results in a
severe drop of impact toughness and ductility.
Addition of Ni appear to accelerate the spinodal decomposition and raise the
maximum temperature at which it is observed. When post-weld heat-treatment
is not possible, welding of ferritic stainless steels is usually done with a metal
filler containing Ni, and there is therefore the possibility of weld embrittlement.
Austenitic stainless steels: these stainless steels owe their name to their f.c.c.
crystallographic structure. Typical compositions in the early 20th century were
18Cr-8Ni. The austenite in these alloys was only stable because of the relatively
large carbon content, and modern equivalent usually contain up to 10.5 Ni.
These steels are often in metastable conditions at room temperature or below,
and while the reconstructive formation of ferrite is not of concern, the formation
of martensite can be. Most grades have a martensite start temperature (Ms)
well below 0 C. However, cold work can result in formation of martensite at
temperatures higher than Ms (this result in the sample becoming magnetic,
while a fully austenitic structure is not). The impact of deformation on the
stability of the material is conveniently quantified by the M d,30 temperature, the
temperature at which the structure is 50% martensitic for 30% deformation.
The AISI 300 series and other examples of heat resistant austenitic stainless steels; E1250 is
Esshete 1250 (Corus), 254SMO is trademark Avesta Sheffield.
C Si Mn
AISI
ma ma ma Cr Ni Mo Ti Nb Al V
grade
x. x. x.
16-
301 0.15 1.00 2.00 6-8
18
17- 8-
302 0.15 1.00 2.00
19 10
17.5 8-
304 0.08 1.00 2.00
-20 10.5
24- 19-
310 0.25 1.50 2.00
26 22
2.0
16- 10-
316 0.08 1.00 2.00 -
18 14
3.0
5 x
17- 9- %C
321 0.08 1.00 2.00
19 12 min
.
10 x
17- 9-
347 0.08 1.00 2.00 %C
19 13
min.
0.2
E 1250 0.1 0.5 6.0 15.0 10.0
5
20/25-
0.05 1.0 1.0 20.0 25.0 0.7
Nb
18.5 17.5
254SM 6- ~1. ~0.1 ~0.2
0.02 0.8 1.0 - -
O 6.5 9 8 5
20.5 18.5
Duplex stainless steels: duplex stainless steel typically contain 50% austenite
and 50% ferrite. This confers them properties intermediate between the two
types of steels:
a typical strength about twice that of austenitic grades, but lower than
martensitic grades,
a better toughness than ferritic stainless steels, but lower than
austenitics,
Only one duplex steel has an AISI designation (329) so that ASTM numbers are
more currently used to reffer to different grades. The archetypal stainless steel,
type 2205, contains 22-23Cr, 4.5-6.5Ni and 3-3.5Mo. This grade represents
80% of all duplex stainless steel use.
Duplex stainless steels suffer from the 475 C embrittlement described earlier for
ferritic stainless steels and are therefore mostly confined to applications below
300 C.
References
D. N. Wasnik et al., Resistance to sensitization and intergranular
corrosion through extreme randomization of grain boundaries, Acta
Materialia, 2002:50, p4587-4601.
M. Shimada et al., Optimization of grain boundary character distribution
for intergranular corrosion resistant 304 stainless steel by twin-induced
grain boundary enngineering, Acta Materialia, 2002:50, p2331-2341.
T. Sourmail et al., Sensitisation and Evolution of Chromium-depleted
Zones in Fe-Cr-Ni-C systems, ISIJ International, 2003:43, p1814-1820 .
C. Too, MPhil thesis, University of Cambridge, 2002 .
T. Sourmail, Review: Precipitation in Creep-Resistant Austenitic Stainless
Steels, Mater. Sci. Techn. 2001:17, p1-14.
T.Sourmail and H. K. D. H. Bhadeshia, Simultaneous precipitation
reactions in austenitic stainless steels
W. E. Mayo, Predicting IGSCC/IGA susceptibility of Ni-Cr-Fe alloys by
modeling of grain boundary chromium depletion, Mater. Sci. Eng. A,
1997:232, p129-139
T. G. Gooch et al., Weld decay in austenitic stainless steel, The Welding
Insitute, Cambridge, 1975
STAINLESS STEELS IN ARCHITECTURE, BUILDING AND
CONSTRUCTION: GUIDELINES FOR CORROSION PREVENTION
(2001)