Stainless Steel

Stainless Steels
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Stainless Steels
T. Sourmail and H. K. D. H. Bhadeshia
Introduction
Steels are said to be stainless when they resist corrosion; the is achieved by dissolving sufficient chromium in
the iron to produce a coherent, adherent, insulating and regenerating chromium oxide protective film on the
surface. It is not surprising therefore that they are used in the harsh environments of the chemical, oil
production and power generation industries, and in utility goods such as furniture, automotive trims and
cutlery, where both aesthetic appearance and corrosion resistance are important design criteria.
The stainless character occurs when the concentration of chromium exceeds about 12 wt%. However, even
this is not adequate to resist corrosion in acids such as HCl or H2SO4; higher chromium concentrations and
the judicious use of other solutes such as molybdenum, nickel and nitrogen is then needed to ensure a
robust material.
There are requirements other than corrosion which have to be considered in engineering design. For this
reason, there is a huge variety of alloys available, but they can be classified into four main categories:
z
z
z
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hardenable stainless steels;

ferritic stainless steels;
austenitic stainless steels;
duplex stainless steels.
Specialist grades include the precipitation hardened or oxide dispersion strengthened alloys.
Corrosion Resistance
Iron does not occur in its native state because it combines readily with oxygen and other elements. It is
extracted from its ore and given the opportunity, tends to revert to a compound by reacting with the
environment. Rusting is an example of this reversion process. The process can be retarded by adding
chromium, which at sufficiently large concentrations forms a protective oxide film at the surface. The nature
of this oxide film depends on the chromium concentration, but when the latter exceeds about 12 wt%, the a
passive film of chromium oxide only about 1-2 nm thick covers the steel, which becomes stainless as long as
the chromium is in solid solution in the steel.
Corrosion can nevertheless occur if the passive film breaks down, locally or uniformly:
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Uniform corrosion can occur in acidic or hot alkaline solutions. Loss by this mechanism can be
estimated and allowed for in design. The corrosion rate is very slow when the metal is in the passive
state.
General corrosion resistance is better at larger chromium contents, but other solutes can be
detrimental. In particular, sulphur in solid solution is believed to make passivation more difficult
[Schtze].
Unfortunately, sulphur alters the temperature dependence of the surface tension of liquid and in doing
so increases the penetration during welding; this is very useful in during the welding of stainless steels
{Llewellyn, 1991]. The fluid flow that occurs in the weld pool is such that in the absence of sulphur,
shallow (wide) weld pools are obtained resulting in unacceptable joints when the concentration is less
than about 0.007 wt%.
An even higher sulphur concentration may be used in free-machining stainless steels where
precipitated sulphur helps break up the machining chips.
http://www.msm.cam.ac.uk/phase-trans/2005/Stainless_steels/stainless.html
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Nickel significantly improves the general corrosion resistance of stainless steels, by promoting
passivation. Austenitic stainless steels therefore possess superior corrosion resistance when compared
with martensitic or ferritic stainless steels (with zero or low nickel concentrations), particularly when in
contact with mineral acids.
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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. It can be initiated at a fault
in the passive layer or a surface defect. The steel underneath the break dissolves leading to a build up
of positively charged metal ions, which in turn causes negative 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, thereby
preventing the regeneration of the passive layer.
In the passive condition, the current density is of the order of nA cm-2; in the pit, however, it may
exceed 1A cm-2. The reason why the current density is so large in the pit is that the anodic region is
very small in area when compared with the cathodic part (the unpitted steel). For a given corrosion
current, this greatly exaggerates the corrosion rate at the pits. Similarly, the concentration of chloride
ions in the vicinity of a pit can be thousands of times greater than that in the solution as a whole.
Figure 1: Pitting corrosion.
The above figure illustrates the process: the anodic dissolution of the steel leads to introduction of
positive metal ions (M+) in solution, which causes migration of Cl- ions. In turn, metal chloride reacts
with water:
M+Cl- + H2O -> MOH + H+ClThis causes the pH to decrease. 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 not. Initiation
has long been associated with MnS inclusions which are difficult to avoid in the steel-making process. It
appears that the inclusions are surrounded by a Cr depleted region which is believed to cause the
initiation [Ryan et al., 2002].
Increasing the Cr content, or adding Mo or N enhances the pitting resistance. The potency of a solute in
this respect is expressed empirically in terms of their weight percentages as a pitting index:
pitting index for duplex stainless steels =Cr+3.3Mo+16N
pitting index for austenitic stainless steels =Cr+3.3Mo+30N
One obvious environment where pitting corrosion is of concern is marine applications. Type 316
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austenitic stainless steel (18Cr-12Ni and 2-3 wt% Mo) is often the material of choice in this case. When
the marine requirements are particularly severe, as with offshore platforms, alloys with molybdenum
concentrations up to 5 wt% are used. for example, call for heavily alloyed steels with up to 6 wt% Mo.
Street furniture is another case where pitting resistance might be relevant, particularly in colder regions
where salt de-icing is common.
Stainless steel in boat

z
The ice-breaker in the background

has a stainless steel hull.
The exposed railings are all

stainless steels.
Sensitisation is one of the corrosion mechanisms which causes widespread problems in austenitic
stainless steels, particularly in welded assemblies. This problem can be so severe as to cause grain
decohesion, as shown Fig. 2.
Figure 2: Grain decohesion due to intergranular corrosion, photo courtesy M.
Shimada (2002).
In normal conditions, austenitic stainless steels are given a high-temperature heat-treatment, often
called a solution-treatment, which gives a fully austenitic solid solution. However, at temperatures below
about 800C, there is a tendency to precipitate chromium-rich carbides as the alloy enters the carbide
plus austenite phase field.
The main carbide phase is M23C6, where the 'M' stands for a mixture of metal atoms including iron,
molybdenum, chromium and manganese, depending on the steel composition and heat-treatment.
These carbides require long-range diffusion in order to precipitate and hence can be avoided by rapid
cooling from the solution-treatment temperature.
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The precipitation of M23C6 and M7C3 occurs primarily at the austenite grain surfaces which are
heterogeneous nucleation sites; it can occur in a matter of minutes at temperatures around 750C. The
chemical composition in the vicinity of the grain boundaries can be altered by the precipitationof the
chromium-rich particles. The resulting chromium-depleted zone at the grain boundaries makes them
susceptible to intergranular anodic-attack even under stress--free conditions. Once again, the anodic
regions present a much smaller area (grain boundaries) compared with the rest of the exposed surface
which is cathodic; the localised rate of corrosion at the boundaries is therefore greatly exaggerated.
This is the essence of sensitisation.
Sensitisation in the context of welded samples leads to the phenomenon of weld decay. Regions are
created in the heat-affected zones of the welds which precipitate carbides, become sensitised and fail
by localised corrosion, almost as if the weld is unzipped in the sensitised region.
Remedies to Sensitisation
Figure 3 shows that the steel is safe from sensitisation at low times because precipitation has not yet
occurred with a vengence. Prolonged heat treatment makes the steel safe by permitting diffusion to
eliminate chromium concentration gradients in the austenite.
Figure 3: Time and temperature dependency of sensitisation (Mayo, 1997).
A variety of solutions exist to avoid sensitisation:

{
The first one is to reduce the carbon content of the steel, making it more difficult to precipitate
carbides. Stainless steels with an 'L' associated with their numerical designation (e.g., 304L and
316L) have been manufactured with carbon cocentrations less than about 0.03 wt%, which
compares against the normal grades which typically have some 0.08 wt% of carbon. Figure 4
shows how carbon accelerates sensitisation.
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Figure 4: Effect of carbon on sensitisation (Gooch,

1975).
An alternative is use solutes (such as Nb, Ti, V or Ta) which have a greater affinity for carbon than
chromium. These are called stabilised stainless steels, for example, types 321 (Ti stabilised) and
347 (Nb stabilised) austenitic stainless steels. Titanium cannot in general be used to make alloys
deposited by arc welding because it readily oxidises; type 347 is used instead as a filler metal. In
welding applications, grade 321 is not used as a filler metal because titanium does not transfer
well across a high temperature arc. Niobium stabilised 347 is used instead as a filler metal.
Stabilisation involves more than just an addition of Nb or Ti. A heat-treatment must be performed
to stimulate the formation of TiC or NbC, for example by hoding at 900C for one hour. This is
because during lower temperature heat treatments, M23C6 may form faster than TiC or NbC.
In some cases, a solution-treatment can be given after fabrication to dissolve carbides which may
have formed on grain boundaries.
A variety of other factors impact on the problem, such as the austenite grain size and the
crystallographic character of the grain boundaries. Sensitisation can be avoided by grain
boundary engineering (Shimada et al., 2002), by creating a crystallographic textures which
favours low-energy boundaries which are less effective as heterogeneous nucleation sites. A
reduction in the austenite grain size can also help by increasing the number density of any
carbides and hence reducing the extent of associated Cr diffusion fields.
Mechanism
As explained earlier, sensitisation is caused by the formation of chromium carbides on grain
boundaries. The precipitates absorb chromium from the adjacent austenite causing a localised
breakdown in passivity.
Fig. 5: Mechanism of sensitisation.
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This short description of the problem hides most of its interesting complexity. The minimum chromium
concentration reached in the austenite ajacent to the carbide is in principle determined by the
appropriate part of the phase diagram, which predicts that the chromium content of the austenite in
equilibrium with M23C6 (cM23C6) is slightly lower than the bulk composition. However, the minimum
concentration reached in the austenite is smaller than indicated by the phase diagram because of
multicomponent diffusion effects, the dynamics of the solute fluxes towards the precipitates.
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Environmentally assisted cracking (EAC) is a generic term used to describe the consequences of a
three--fold interaction between stress, environment and microstructure, an interaction which leads to
unexpected failure with no ductility, usually involving a period of slow crack growth prior to final failure.
Failure occurs at applied stresses well below the macroscopic yield strength. The stress can be due to
factors other than the intended design stress, for example, residual stress induced during fabrication.
An aqueous environment is required in the form of immersion or via a thin film on the surface when the
component is exposed to humid atmospheres. Dissolved oxygen and anionic species such as chlorides
and fluorides accelerate EAC.
Some forms of this kind of cracking can be particularly dangerous because it may take thousands of
hours for a crack to nucleate, but considerably less for it to propagate. Dramatic examples of
catastrophic failure include the collapse of swimming pool ceilings becuase of the stress corrosion
cracking o Type 304 or 316 austenitic stainless steels. For this reason, it has been suggested that 6
wt% Mo austenitic stainless steels should be used in these environments.
Recent work has shown that it is also possible to sensitise titanium--containing stainless steels by the
grain boundary precipitation of Ti(C,N) at 1100C, by a microgalvanic mechanism (Joe and Kim, 1999).
A sensitised steel becomes more sensitive to EAC when impurities such as sulphur and phosphorus
segregate to the austenite grain boundaries (McIntyre et al., 1996).
Phase Equilibria
Main Phases
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The designation stainless steel implies little more than a 12% Cr content. Most of the stainless steels are
based on the Fe-Cr-C and Fe-Cr-Ni-C systems, but other alloying elements are also important.
Iron and its alloys can exist in several crystallographic forms, of which the most common are the bodycentred cubic (b.c.c.) and face-centred cubic (f.c.c.). In pure iron, the f.c.c. structure persists between 910
and 1400C, the b.c.c. structure below and above this interval (up to the melting temperature of 1539C).
The importance of this phase-transformation in the metallurgy of steels cannot be overestimated. This
transformation allows 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 more than 1 GPa.
Knowledge of the relative stabilities 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 steel (12Cr-0.1C wt%) in Sheffield, UK and
the austenitic 18Cr-8Ni wt% in Germany. For this reason, and also because they are most important alloying
elements in stainless steels, Cr and Ni form the reference relative to which the influence of other solutes is
classified: have long been used as reference to quantify the influence of alloying elements on the b.c.c.<>f.c.c. phase transition: those elements which like Cr promote ferrite are called ferrite stabilisers and those
which like Ni promote austenite are called austenite stabilisers. The equations below give a rough guide of
the potency of individual elements to act as ferrite or austenite stabilisers when compared with the
corresponding effects of Cr and Ni respectively (concentrations in wt%):
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)
Figure 4 shows that an excessive amount of chromium can eliminate austenite at all temperatures, making it
impossible to achive a to transition. This is the domain of the ferritic stainless steels discussed below.
Figure 6: Vertical section of Fe-Cr-C diagram for 0.1C
wt%.
Without carbon, the limit beyond which austenite no longer forms is about 13.5 wt% chromium. However,
additions of carbon help stabilise the austenite and therefore increase this limit (Fig. 6).
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Chromium and nickel equivalents are also used in the welding industry to plot the microstructures obtained
when a weld solidifies and cools to ambient temperature (Fig. 7). Although these diagrams are popular, it
should be understood that they are not phase diagrams but rather represent the microstructures obtained
under specific cooling conditions.
Figure 7: Schaeffler diagram for weld metals.
Precipitate Phases
These include carbides, nitrides or intermetallic compounds. Since most stainless steels serve at ambient
temperature, the intermetallic compounts are of little relevance as they are extremely slow to precipitate
because even though they may be thermodynamically stable phases, they are difficult to nucleate.
It is evident from Figure 6 (Fe-Cr-C phase diagram) that typical martensitic steels should exhibit ferrite and
M23C6 in equilibrium at for example, 600C. In practice, this carbide is only found after relatively long ageing.
because it is preceded by Intermediate phases in the sequence cementite, M2X and M7C3, leading finally to
M23C6.
These precipitation sequences become more complex in heavily alloyed ferritic or austenitic stainless steels,
such as those destined for the power generation industry. Considerable effort is being devoted to
understanding and estimating the precipitation sequences in such alloys because the are intended to serve
safely for 30 or more years, i.e., for time periods far in excess of what can be reasonably achieved in the
alloy development exercise (Robson and Bhadeshia, 1997; Fujita and Bhadeshia, 2002; Sourmail, 2001;
Sourmail and Bhadeshia, 2003).
Martensite formation
Most stainless steels have a high hardenability, meaning that the reconstructive transformation of austenite to
(ferrite + carbides) is unlikely to happen unless the steel is cooled particularly slowly.
The most important features of these martensitic alloys are therefore the martensite start (MS) and finish
temperatures (MF). For martensitic steels, the range [MS-MF] should be above the room temperature to
ensure fully martensitic structure. On the contrary, the [MS-MF] range of austenitic stainless steels is often
well below 0C, which is why they can be used in cryogenic applications; austenite does not have the
classical ductile-brittle transition associated with body-centred cubic iron (martensite, ferrite). Cold
deformation can induce martensitic transformation to and martensite, the extent depending on the strain
and on the chemical composition. Heavily alloyed austenitic steels with up to 20Cr and 25Ni wt% are fully
stable.
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Categories
On the basis of their main microstructural features, there exist the following key categories of stainless steels:
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z
z
Martensitic stainless steels, typified by types 410/420/440, containing about 12Cr and 0.1C wt% as the
basic composition, leading to a fully martensitic microstructure at room temperature.
Ferritic stainless steels containing larger amounts of Cr which stabilises the ferritic phase.
Austenitic stainless steels, such as type 304 typically contain 18Cr and 8Ni wt%; the nickel balances
the effect of chromium stabilise the austenitic phase; the nickel also makes the alloy more expensive
than the martensitic variants. The large susbtitutional content depresses the MS temperatures well
below 0C.
Duplex stainless steels, whose microstructure is approximately made up of 50/50 ferrite/austenite and
in many applications are less expensive and stronger than the fully austenitic variants.
Martensitic Stainless Steels

The composition is such that the austenite in these steels is able to transform into martensite. This allows a
degree of control on the mechanical properties by exploiting the phase change. Typical heat-treatments
consist of austenitisation at a temperature high enough to dissolve carbides followed by quenching to obtain
martensite. Given the high hardenability inherent in such alloys, the quench rate required to achieve
martensite is not high; oil and water quenching are used only when dealing with thick sections.
Typical compositions cover 12 to 18 Cr and 0.1 to 1.2 C wt%. As with other martensitic steels, a balance
must be sought between hardness and toughness. An untempered martensitic structure typically is strong but
lacks toughness and ductility to an extent which depends on the carbon concentration. As a conseqnece, the
martensite is in many cases tempered between 600 and 750C to optimise the mechanical properties.
In applications such as cutlery, surgical instruments etc., high strength is desirable and toughness/ductility
are of little concern. A lower temperature tempering is then used to retain most of the strength. Type 420
steel (0.15-0.4C, 1.0Mn, 1.0Si, 0.04P, 0.03S, 12-14Cr wt%) is a typical composition for such applications. Its
proof strength in the quenched and tempered condition can be in excess of 1.2 GPa. Type 440C tempered at
300C has a proof strength of about 2 GPa.
Table 1 shows the compositions and typical uses of AISI standard martensitic grades:
Table 1: Martensitic Stainless Steels
Grade
410 0.15
416 0.15
Mn Si
Cr Ni Mo
11.51.0 0.5
- 13.0
1.25 1.0
12.014.0
0.1512.01.0 1.0
0.40
14.0
15.0431 0.20 1.0 1.0
17.0
420
0.6016.01.0 1.0
0.75
18.0
0.7516.01.0 1.0
440B
0.95
18.0
440A
440C 0.95- 1.0 1.0 16.0- -
0.60
-
Comments/Applications
The basic composition. Used for cutlery, steam
0.04 0.03
and gas turbine blades and buckets, bushings...
Addition of sulphur for machinability, used for
0.04 0.15 screws, gears etc. 416 Se replaces suplhur by
selenium.
0.04 0.03 Dental and surgical instruments, cutlery....
1.250.04 0.03 Enhanced corrosion resistance, high strength.

2.0
Ball bearings and races, gauge blocks, molds and
dies, cutlery.
0.75
0.04 0.03
0.75
0.04 0.03 As 440A, higher hardness
0.75
0.04 0.03 As 440B, higher hardness
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1.20
18.0
In addition to the standard grades, a large number of alloyed martensitic stainless steels have been
developed for moderately high temperature applications. Most common additions include Mo, V and Nb.
These lead to a complex precipitation sequence. A small amount (up to 2 wt%) of Ni is added to improve the
toughness.
The 12Cr-Mo-V-Nb steels are used in the power generation industry, for steam turbine blades operating at
temperatures around 600C. Current research focuses on achieving service temperatures of 630-650C
under a stress of 30 MPa.
Ferritic stainless steels

Ferritic stainless steels: typically contain more chromium and/or less carbon than the martensitic grades.
Both changes act to stabilise ferrite, so much so that it is the stable phase at all temperatures. Therefore,
unlike the martensitic grades, ferritic stainless steels cannot be hardened by heat-treatment. They exhibit
lower strength but higher ductility/toughness. Typical applications may include appliances, automotive and
architectural trim (i.e., decorative purposes), as the cheapest stainless steels are found in this family (type
409).
Table 2: Ferritic Stainless Steels
Grade
405
409
429
430
446
C
0.08
0.08
0.12
0.12
0.20
Mn
1.0
1.0
1.0
1.0
1.5
Si
1.0
1.0
1.0
1.0
1.0
Cr
11.5-14.5
10.5-11.75
14.0-16.0
16.0-18.0
23.0-27.0
Mo
-
P
0.04
0.045
0.04
0.04
0.04
S
0.03
0.045
0.03
0.03
0.03
Comments/Applications
0.1-0.3 Al
(6xC) Ti min
0.25 N
Iron-chromium body-centred cubic solutions are such that there is a tendency under appropriate conditions
for like atoms to cluster; at temperatures below a critical value, the solution tends to undergo spinodal
decomposition into chromium-rich and iron-rich regions. High chromium ferritic stainless steels such as type
446 thus become susceptible to the so-called '475C embrittlement', which is caused by this clustering
process. At and below 475C, in steels containing more than 25 wt% of chromium, the spinodal typically
exhibits a wavelength of about 10 nm. There is a continuous increase of hardness as the composition wave
develops, for example, the hardness of an Fe-28Cr wt% steel can increase by more than 300 HV over an
exposure 10,000 h at 450C (Ishikawa et al., 1995). This results in a severe drop of impact toughness and
ductility.
The addition of nicikel appears to accelerate the spinodal and raises the maximum temperature at which it is
observed. When post-weld heat-treatment is not possible, the welding of ferritic stainless steels is usually
done with a metal filler containing Ni, and there is therefore the possibility of weld embrittlement on prolonged
exposure at elevated temperatures.
Austenitic stainless steels

These steels are often in a metastable austenitic state at room temperature or below. Most grades have a
martensite-start temperature well below 0C. However, plastic deformation can induce martensite at
temperatures higher than MS (the sample then is attracted by a magnet since the -martensite is
ferromagnetic whereas austenite in such alloys is not). The MD temperature is that at which martensite
cannot be induced no matter how much the austenite is deformed.
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The presence of nickel improves considerably the corrosion resistance when compared to the martensitic
and ferritic grades.
Type 304 is the basic 18Cr8Ni (18/8) austenitic stainless steel, so widely used that it accounts for about 50%
of all stainless steel production. Other standard grades have different preferred applications; for example,
type 316 which contains up to 3 wt% Mo, offers an improved general and pitting corrosion resistance, making
it the material of choice marine applications and coastal environments. In severe conditions however, even
type 316 cannot cope and molybdenum-enriched alloys such as 254SMO are used.
Table 3: Austenitic Stainless Steels
AISI grade
301
302
304
310
316
321
347
E 1250
20/25-Nb
A 286
254SMO
AL-6XN
C max.
0.15
0.15
0.08
0.25
0.08
0.08
0.08
0.1
0.05
0.05
0.02
0.03
Si max.
1.00
1.00
1.00
1.50
1.00
1.00
1.00
0.5
1.0
1.0
0.8
1.0
Mn max.
2.00
2.00
2.00
2.00
2.00
2.00
2.00
6.0
1.0
1.0
1.0
2.0
Cr
16-18
17-19
17.5-20
24-26
16-18
17-19
17-19
15.0
20.0
15.0
18.5-20.5
20-22
Ni
6-8
8-10
8-10.5
19-22
10-14
9-12
9-13
10.0
25.0
26.0
17.5-18.5
23.5-25.5
Mo
Ti
Nb
Al
2.0-3.0
5 x %C min.
10 x %C min.
0.25
1.2
6-6.5
6-7
~1.9
~1.9
0.7
~0.18
~0.18
~0.25
~0.25
Figure 8. Micrographs of austentiic stainless steels
Grain structure of an austenitic stainless steel NF709

(25Cr20Ni). Many of the grains contain annealing
twins. NF709 is a creep-resistant austenitic stainless
steel used in the construction of highly sophisticated
power generation units.
Type 302 austenitic stainless steel, cold-rolled and

then annealed at 704C for one hour. Partially
recrystallised microstructure. Recrystallised grains
are clean whereas the deformed regions show a
large concentration of defects. There are annealing
twins in the recrystallised region (Hopkin).
Specialist austenitic stainless steels are made with up to 0.4 wt% nitrogen when prepared at ambient
pressure, and up to 1 wt% nitrogen using high-pressure melting techniques (Simmons, 1996). The prime
reason for adding nitrogen is that it is a very effective solid-solution strengthener. Not only do the misfitting
nitrogen atoms interfere statically with moving dislocations, but there is also a drag due to nitrogen atoms
being carried along with the dislocations as they move through the lattice (Rawers and Grujicic, 1966). The
strength of such alloys makes them suitable for niche applications such as power generator retaining rings,
high-strength bolts and superconducting magnet housings.
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The solubility of nitrogen in austenite is reduced by nickel but increased by chromium and manganese.
Excessive nitrogen concentrations can lead to precipitation, particularly of chromium nitrides.
Nitrogen also increases the resistance to localised corrosion (pitting and crevice) in acid-chloride solutions
(see pitting index equation above).
Duplex stainless steels

Duplex stainless steels typically contain
50% austenite and 50% ferrite (Figure 9ac). The two-phase mixture also leads to a
marked refinement in the grain size of
both the austenite and ferrite. This,
together with the presence of ferrite,
makes the material about twice as strong
as common austenitic steels. They contain
only about half the nickel concentration of
typical austenitic stainless steels; they are
therefore less expensive and less
sensitive to the price of nickel. With their
high chromium concentration, they have
excellent pitting and crevice corrosion
resistance, and to chloride stress
corrosion. The two phase mixture also
reduces the risk of intergranular attack; for
the same reason, they are not prone to
solidifcation cracking during welding.
Figure 9: Optical microstructures of duplex and superduplex stainless steels (courtesy S. Sharafi). The
colour etch is achieved using Beraha's reagent, 10 ml HCl, 100 ml H2O and 0.5-1.0 g K2S2O5 (take
appropriate safety precautions when using chemicals).
(a) Duplex stainless steel, IC378, hot rolled in the

direction indicated. The darker etching phase is
ferrite and the remainder is austenite
(b) Duplex stainless steel IC381 (dark phase is

ferrite).
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(c) Duplex stainless steel IC381 (dark phase is

ferrite).
(d) Superduplex stainless steel A219 after heat

treatment at 1150C for 2.5 h. The austenite is yellow
and ferrite is dark brown, with the sigma phase white.
The archetypal duplex alloys contain 22-23Cr, 4.5-6.5Ni and 3-3.5Mo wt%, representing some 80% of all
duplex stainless steel use. Detailed compositions are given in Table 4. A significant application is in the
production of tubing in corrosive oil and gas wells; such tubes have been installed particularly in the North
Sea industries.
Table 4: Duplex stainless steels (wt%). A219 is a superduplex alloy.
Designation
Cr
Ni
Mn
Si
Other
UTS /
MPa
Elongation /
%
Type 329
28.0 6.0 0.10 2.0
1.0
0.04 0.03 1.5 Mo
724
25
Type 326
26.0 6.5 0.05 1.0
0.6
0.01 0.01 0.25 Ti
689
35
2RE60
18.5 4.5 0.02 1.5
1.6
0.01 0.01 2.5 Mo
717
48
IC378
21.8 5.5 0.03 1.38 0.40 0.03 0.01
3.0 Mo 0.18 Cu 0.07

V 0.14 N
IC381
22.1 5.8 0.02 1.92 0.48 0.03 0.01
3.2 Mo 0.07 Cu 0.13

V 0.14 N
A219
25.6 9.4 0.03 0.70 0.60 0.02 0.01 4.1 Mo 0.27 N
In general, the toughness of stainless steels increases in the order ferritic, duplex and austenitic stainless
steels. Duplex stainless steels, because of their high Cr concentration, are prone to the 475C embrittlement
described earlier so their application is frequently confined to temperatures below about 300C.
The superduplex stainless steels have a higher chromium and molybdenum concentration to enhance pitting
corrosion resistance; these ferrite stabilising elements are balanced using a higher nickel and nitrogen
concentrations (austenite stabilisers) in order to maintain about equal amounts of ferrite and austenite (Table
4, Fig. 8d). One definition is that a superduplex stainless steel must have a pitting index which is greater than
40.
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Stainless Steel Thread

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Photographs: Extremely fine stainless steel thread.
Other Topics
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Stainless steels: past, present and future (reproduced with permission).

Recrystallisation of austenitic stainless steels.
Recrystallised grain size.
Modelling anisothermal recrystallisation in austenitic stainless steels.
Microstructural change in high-temperature heat-affected zone of low-carbon weldable 13% Cr
martensitic stainless steels.
Effect of -ferrite on impact properties of supermartensitic stainless steel heat affected zones.
Modelling simultaneous precipitation reactions in austenitic stainless steels.
Multiple precipitation reactions in austenitic stainless steels.
Neural network model of creep strength of austenitic stainless steels.
Solidification sequences in stainless steel dissimilar alloy welds.
Metastable phase solidification in electron beam welding of dissimilar stainless steels.
Application of Bayesian Neural Network for Modeling and Prediction of Ferrite Number in stainless
steels.
M6C Precipitation in Niobium-Alloyed Ferritic Stainless Steel.
Microstructural change in supermartensitic stainless steels.
Martensitic Stainless Steel Welds
Cracking in Stainless Steel Welds
Ferrite number calculations.
Tensile properties of stainless steels.
Simultation of stainless steel solidification.
Theses on Stainless Steels

Transformations in Supermartensitic Stainless Steels
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Sensitisation of Austenitic Stainless Steels

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Tensile Properties of Stainless Steel

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Introduction
Chapters 1-7
Chapter 8
Chapters 9
Chapter 10
Bibliography
Appendix A
Appendix B
Appendix C
Appendix D
Anisothermal Recrystallisation in Austenitic Stainless Steels

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Postscript file of entire thesis (28 Mbytes)
Simultaneous Precipitation Reactions in Creep-Resistant Austenitic Stainless Steels

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Postscript (compressed) file of entire thesis (25 Mbytes)
Chapter 1 (PDF, 0.5 Mbytes)
Chapter 8 (PDF, 34 Mbytes)
References
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Fujita, N. and H. K. D. H. Bhadeshia, Simultaneous alloy carbide sequence in power plant steels, ISIJ
International, 42 (2002) 760--767.
Gooch, T. G., Weld decay in austenitic stainless steel, The Welding Insitute, Cambridge, 1975
Ishikawa et al., Materials Transactions JIM, 36 (1995) 16-22.
Joe, M. Z. and D. R. Kim, British Corrosion Journal, 34 (1999) 210-213.
Llewellyn, D. T., Steels: Metallurgy and Applications, 1992, Butterworth-Heinemann.
Mayo, W. E., Predicting IGSCC/IGA susceptibility of Ni-Cr-Fe alloys by modeling of grain boundary
chromium depletion, Materials Science and Engineering, 232A (1997) 129-139.
McIntyre, P., C. M. Younes and S. W. Chan, British Corrosion Journal, 31 (1996) 133-137.
Rawers, J. and M. Grujicic, Effects of metal composition and temperature on the yield strength of
nitrogen strengthened stainless steels, Materials Science and Engineering, A207 (1996) 188-194.
Robson, J. D. and H. K. D. H. Bhadeshia, Modelling precipitation sequences in power plant steels,
Materials Science and Technology, 13 (1997) 631--639.
Ryan et al., Nature, 415 (2002) 770.
Schtze, M. ed., Corrosion and Environmental Degradation, Wiley-Vch, Chap 3.
Shimada, M., H. Kokawa, Z. J. Wang, Y. S. Sato and I. Karibe, Optimization of grain boundary
character distribution for intergranular corrosion resistant 304 stainless steel by twin-induced grain
boundary enngineering, Acta Materialia, 50 (2002) 2331-2341.
Simmons, J. W., High-nitrogen alloying of stainless steels, Materials Science and Engineering, A207
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(1996) 159-169.
Sourmail, T., Review: Precipitation in Creep-Resistant Austenitic Stainless Steels, Materials Science
and Technology, 17 (2001) 1-14.
Sourmail, T. and H. K. D. H. Bhadeshia, Modelling simultaneous precipitation reactions in austenitic
stainless steels, CALPHAD, 27 (2003) 169-175.
Sourmail, T., C. Too and H. K. D. H. Bhadeshia, Sensitisation and Evolution of Chromium-depleted
Zones in Fe-Cr-Ni-C systems, ISIJ International, 43 (2003) 1814-1820.
Stainless steels in architecture, building and construction: guidelines for corrosion prevention (2001)
Too, C., M.Phil. thesis, University of Cambridge, 2002.
Wasnik, D. N., V. Kain, I. Samajdar, B. Verlinden and P. K. De, Resistance to sensitization and
intergranular corrosion through extreme randomization of grain boundaries, Acta Materialia, 50 (2002)
4587-4601.
Island Constructed from Stainless Steel, Graz, Austria
The stainless steel island in the

river Mur, Graz, Austria.
The stainless steel island (a cafe)

in the river Mur.

river Mur.

river Mur.

river Mur.
Stainless Steel in Subway, Taiwan
In the subway, Taipei
In the subway, Taipei
11/1/2006
Stainless Steels
Page 17 of 22
Stainless Steel in Chinheng Memorial, Tarako National Park, Taiwan
Chinheng, the engineer who

supervised the construction of the
Trans East-West Road. He was
killed by a rock fall following an
earthquake.
Memorial to Chingheng
The memorial is signed by the son

of Chiang, Kai Shek, who was the
President of Taiwan
Elegant use of Stainless Steel in Pusan, Korea
11/1/2006
Stainless Steels
Page 18 of 22
Stainless steel in action.
Stainle
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Stainless Steels
Page 19 of 22
Art
Stainless Steel in Switzerland
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Page 20 of 22
Stainless steel bin.
Stainless steel bin.
Rust on a stainless steel bin?
Stainless steel at Lucern railway station.
11/1/2006
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Page 21 of 22
Stainless steel display
Stainless steel bins at Zurich airport.

Stainless steel bin at Zurich airport.
Science Museum, London

This is an example of a glass and stainless steel bridge, taken from the Science Museum in London. The
toughned-glass slats are structurally supported by stainless steel ropes. The ropes are usually made from
pearlitic steel, but here cost is not a major issue since this is a museum exhibit.
Moving Pictures
Still Pictures
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Acknowledgment
The creation of this document was partly supported by the Higher Education Funding Council for England, via
the U.K. Centre for Materials Education.
Links: Stainless Steels

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hardenable stainless steels;

Stainless steel in boat

The ice-breaker in the background

The exposed railings are all

A variety of solutions exist to avoid sensitisation:

Figure 4: Effect of carbon on sensitisation (Gooch,

Martensitic Stainless Steels

440C 0.95- 1.0 1.0 16.0- -

1.250.04 0.03 Enhanced corrosion resistance, high strength.

0.04 0.03 As 440A, higher hardness

0.04 0.03 As 440B, higher hardness

Ferritic stainless steels

Austenitic stainless steels

Figure 8. Micrographs of austentiic stainless steels

Grain structure of an austenitic stainless steel NF709

Type 302 austenitic stainless steel, cold-rolled and

Duplex stainless steels

(a) Duplex stainless steel, IC378, hot rolled in the

(b) Duplex stainless steel IC381 (dark phase is

(c) Duplex stainless steel IC381 (dark phase is

(d) Superduplex stainless steel A219 after heat

28.0 6.0 0.10 2.0

0.04 0.03 1.5 Mo

26.0 6.5 0.05 1.0

0.01 0.01 0.25 Ti

18.5 4.5 0.02 1.5

0.01 0.01 2.5 Mo

21.8 5.5 0.03 1.38 0.40 0.03 0.01

3.0 Mo 0.18 Cu 0.07

22.1 5.8 0.02 1.92 0.48 0.03 0.01

3.2 Mo 0.07 Cu 0.13

25.6 9.4 0.03 0.70 0.60 0.02 0.01 4.1 Mo 0.27 N

Stainless Steel Thread

Extensive article on the subject.

Stainless steels: past, present and future (reproduced with permission).

Theses on Stainless Steels

Complete thesis (PDF, 18 Mb)

Sensitisation of Austenitic Stainless Steels

Complete thesis (2Mb)

Tensile Properties of Stainless Steel

Complete thesis (zipped folder, 3Mb)

Anisothermal Recrystallisation in Austenitic Stainless Steels

PDF file of entire thesis (12 Mbytes)

Simultaneous Precipitation Reactions in Creep-Resistant Austenitic Stainless Steels

PDF file of entire thesis (40 Mbytes)

Island Constructed from Stainless Steel, Graz, Austria

The stainless steel island in the

The stainless steel island (a cafe)

The stainless steel island in the

The stainless steel island in the

The stainless steel island in the

Stainless Steel in Subway, Taiwan

In the subway, Taipei

In the subway, Taipei

Stainless Steel in Chinheng Memorial, Tarako National Park, Taiwan

Chinheng, the engineer who

The memorial is signed by the son

Elegant use of Stainless Steel in Pusan, Korea

Stainless steel in action.

Stainless steel in action.

Stainless steel in action.

Stainless steel in action.

Stainless steel in action.