Revision - Stainless Steels Cambridge

3/4/2019 Stainless Steels
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:
hardenable stainless steels;

ferritic stainless steels;
austenitic stainless steels;
duplex stainless steels;
precipitation-hardened stainless steels;
oxide dispersion-strengthened stainless steels.
Stainless steel aircraft
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:
Uniform corrosioncan 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 [Schütze].
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.
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.
Pitting corrosionis 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 pHto 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 -+ H 2O -> MOH + H +Cl -
http://www.phase-trans.msm.cam.ac.uk/2005/Stainless_steels/stainless.html 1/17
This causes the pHto decrease. The cathodic reaction, on the surface near the pit follows:
O 2+ 2H 2O -> MOH + 4OH -
While 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 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.
The ice-breaker in the background has a

Stainless steel in boat The exposed railings are all stainless steels.
stainless steel hull.
Sensitisationis 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 800°C, there is a tendency to precipitate chromium-rich carbides as the
alloy enters the carbide plus austenite phase field.
The main carbide phase is M 23C 6, 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.
The precipitation of M 23C 6and M 7C 3occurs primarily at the austenite grain surfaces which are heterogeneous nucleation sites; it can occur in
a matter of minutes at temperatures around 750°C. 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.
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
stabilisedstainless 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 900°C for one hour. This is because during lower temperature heat treatments, M 23C 6may 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.
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 M 23C 6(c γM23C6) 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.
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
1100°C, 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).
Niobium in stainless steels
Phase Equilibria
Main Phases
The designation stainless steelimplies 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 body-centred cubic (b.c.c.) and face-centred cubic
(f.c.c.). In pure iron, the f.c.c. structure persists 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 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 stabilisersand 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 γ to α 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).
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 M 23C 6in equilibrium at for example,
600°C. In practice, this carbide is only found after relatively long ageing. because it is preceded by Intermediate phases in the sequence cementite, M
2X and M 7C 3, leading finally to M 23C 6.
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 (M S) and finish temperatures (M F). For martensitic steels,
the range [M S-M F] should be above the room temperature to ensure fully martensitic structure. On the contrary, the [M S-M F] range of austenitic
stainless steels is often well below 0°C, 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 α and ε 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.
Categories
On the basis of their main microstructural features, there exist the following key categories of stainless steels:
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 M
Stemperatures well below 0°C.
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 750°C 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 300°C 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 C Mn Si Cr Ni Mo P S Comments/Applications
11.5- The basic composition. Used for cutlery, steam and gas turbine blades and buckets,
410 0.15 1.0 0.5 - - 0.04 0.03
13.0 bushings...
12.0- Addition of sulphur for machinability, used for screws, gears etc.416 Se replaces
416 0.15 1.25 1.0 - 0.60 0.04 0.15
14.0 suplhur by selenium.
0.15- 12.0-
420 1.0 1.0 - - 0.04 0.03 Dental and surgical instruments, cutlery....
0.40 14.0
15.0- 1.25-
431 0.20 1.0 1.0 - 0.04 0.03 Enhanced corrosion resistance, high strength.
17.0 2.0
0.60- 16.0-
440A 1.0 1.0 - 0.75 0.04 0.03 Ball bearings and races, gauge blocks, molds and dies, cutlery.
0.75 18.0
0.75- 16.0-
440B 1.0 1.0 - 0.75 0.04 0.03 As 440A, higher hardness
0.95 18.0
0.95- 16.0-
440C 1.0 1.0 - 0.75 0.04 0.03 As 440B, higher hardness
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 600°C. Current
research focuses on achieving service temperatures of 630-650°C 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 C Mn Si Cr Mo P S Comments/Applications
405 0.08 1.0 1.0 11.5-14.5 - 0.04 0.03 0.1-0.3 Al
409 0.08 1.0 1.0 10.5-11.75 - 0.045 0.045 (6xC) Ti min
429 0.12 1.0 1.0 14.0-16.0 - 0.04 0.03
430 0.12 1.0 1.0 16.0-18.0 - 0.04 0.03
446 0.20 1.5 1.0 23.0-27.0 - 0.04 0.03 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 '475°C embrittlement', which is caused by this clustering process. At and below
475°C, 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 450°C (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
0°C. However, plastic deformation can induce martensite at temperatures higher than M S(the sample then is attracted by a magnet since the α-
martensite is ferromagnetic whereas austenite in such alloys is not). The M Dtemperature is that at which martensite cannot be induced no matter
how much the austenite is deformed.
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 C max. Si max. Mn max. Cr Ni Mo Ti Nb Al V
301 0.15 1.00 2.00 16-18 6-8
302 0.15 1.00 2.00 17-19 8-10
304 0.08 1.00 2.00 17.5-20 8-10.5
310 0.25 1.50 2.00 24-26 19-22
316 0.08 1.00 2.00 16-18 10-14 2.0-3.0
321 0.08 1.00 2.00 17-19 9-12 5 x %C min.
347 0.08 1.00 2.00 17-19 9-13 10 x %C min.
E 1250 0.1 0.5 6.0 15.0 10.0 0.25
20/25-Nb 0.05 1.0 1.0 20.0 25.0 0.7
A 286 0.05 1.0 1.0 15.0 26.0 1.2 ~1.9 ~0.18 ~0.25
254SMO 0.02 0.8 1.0 18.5-20.5 17.5-18.5 6-6.5 ~1.9 ~0.18 ~0.25
AL-6XN 0.03 1.0 2.0 20-22 23.5-25.5 6-7
Figure 8. Micrographs of austentiic stainless steels
Type 302 austenitic stainless steel, cold-rolled and then annealed at

Grain structure of an austenitic stainless steel NF709 (25Cr20Ni) . Many 704°C for one hour. Partially recrystallised microstructure. Recrystallised
of the grains contain annealing twins. NF709 is a creep-resistant grains are clean whereas the deformed regions show a large
austenitic stainless steel used in the construction of highly sophisticated concentration of defects. There are annealing twins in the recrystallised
power generation units. 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.
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).
Stainless steel, thermally insulated, cups and saucers Austenitic stainless steel
Duplex stainless steels
Duplex stainless steels typically contain 50% austenite and 50% ferrite (Figure 9a-
c). 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 H 2O and 0.5-1.0 g K 2S 2O 5(take appropriate safety precautions when using chemicals).
(a) Duplex stainless steel, IC378, hot rolled in the direction indicated. The (b) Duplex stainless steel IC381 (dark phase is ferrite).
darker etching phase is ferrite and the remainder is austenite
(d) Superduplex stainless steel A219 after heat treatment at 1150°C for
2.5 h. The austenite is yellow and ferrite is dark brown, with the sigma
(c) Duplex stainless steel IC381 (dark phase is ferrite). 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 C Mn Si P S 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 475°C embrittlement described earlier so their application is frequently confined to temperatures below
about 300°C.
The superduplex stainless steelshave 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.
Stainless Steel Seamless Tube and Wire Rod
Manufacturing process illustrated.
Stainless Steel Thread

Extensive article on the subject.
Photographs: Extremely fine stainless steel thread.
Powder Metallurgically Produced Stainless Steel

Sintered, and laser deposited samples
Transformation Texture in Stainless Steel

Crystallographic Texture and Intervening Transformations
Transformation Texture, Stainless Steel
301 Stainless steel
Other Topics
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 δ-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.
M 6C 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.
Stainless steel in Millenium Park, Chicago.
Theses on Stainless Steels

Transformations in Supermartensitic 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)
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

PDF file of entire thesis (12 Mbytes)
Postscript file of entire thesis (28 Mbytes)
Simultaneous Precipitation Reactions in Creep-Resistant Austenitic Stainless Steels

PDF file of entire thesis (40 Mbytes)
Postscript (compressed) file of entire thesis (25 Mbytes)
Chapter 1 (PDF, 0.5 Mbytes)
Chapter 8 (PDF, 34 Mbytes)
Microstructure of Super-Duplex Stainless Steels

Part 1
Part 2
REX734
Z phase, chromium carbides, nitrides, chi, sigma, phi...
References
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.
Schütze, 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 (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, The stainless steel island (a cafe) in the river
The stainless steel island in the river Mur.
Austria. Mur.
The stainless steel island in the river Mur. The stainless steel island in the river Mur.
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 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
Stainless steel in action. Stainless steel in action.
Stainless steel in action.
Stainless steel in action. Stainless steel in action.
Stainless steel in action.
Art
Stainless steel aircraft Stainless steel aircraft
Art
Stainless Steel in Switzerland
Stainless steel bin. Stainless steel bin.
Rust on a stainless steel bin?
Stainless steel at Lucern railway station.
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
Glass bridge supported by steel wires, Science Museum, London Glass and steel bridge, Science Museum, London
Glass bridge supported by stainless steel ropes At the Science Museum, London
Still Pictures
Stainless steel island, Mur, Graz
Movies
5-axis cutting of medical devices using 300 W pulsed Nd:YAG, stainless steel medical equipment. Nitrogen is injected via the cutting nozzle to
minimise discolouration due to oxidation.
Endoscope welding of medical equipment with pulsed YAG. Stainless steel.
Platinum, gold, silver, titanium, stainless steel jewellery, using pulsed YAG. Video shows ring sizing by fine wire addition, resetting of stones and
build-up of jewel setting. Other processes such as jewellery assembly, filling of casting porosity and tacking prior to silver solder are also
commonplace in jewellery manufacture and repair.
Stents: fine tube cutting using pulsed YAG or fibre lasers. Stainless steel and nitinol, typically 0.3 - 5 mm diameter. Stents and other tubular
medical devices such as guidewires require very fine detail cutting from blank tube. He video shows designs being cut from approximately 1 mm
diameter tubes using a pulsed Nd:YAG. Kerf widths down to about 12 μm are feasible.
Hot-extrusion of stainless steel. Photograph

courtesy of Jan-Olof Nilsson.
Rolling of stainless steel into thin sheet. Hot-extrusion. Photograph courtesy of Jan-Olof
Photograph courtesy of Jan-Olof Nilsson. Nilsson.
The extruded, seamless stainless steel tubes. Stepwise reduction of diameter. Photograph
Photograph courtesy of Jan-Olof Nilsson. courtesy of Jan-Olof Nilsson.
Stainless Steel in Dusseldorf, Germany
Stainless steel plant frame
Stainless Steel in Baosteel, China
Stainless steel barriers in Shanghai Large stainless steel rings
409L Ferritic stainless steel: low cost, low thermal expansion and high
corrosion resistance
Movie inside an elevator faced with stainless steel, in Mumbai, India
Sheffield steel made in China
Five axis cutting of medical devices using a laser Phase Field Modelling: Stainless Steel Solidi ca…
ca…
Laser welding of medical devices Solidification of stainless steel
Niobium in Stainless Steels – 2015 Edition Welding of jewellery using laser
Niobium in stainless steel
Stainless steel jewellery
Acknowledgment
The creation of this document was supported in part by the Higher Education Funding Council for England, via the U.K. Centre for Materials
Education.
Links: Stainless Steels

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3/4/2019 Stainless Steels

hardenable stainless steels;

Stainless steel aircraft

Figure 1: Pitting corrosion.

M +Cl -+ H 2O -> MOH + H +Cl -

O 2+ 2H 2O -> MOH + 4OH -

pitting index for duplex stainless steels =Cr+3.3Mo+16N

pitting index for austenitic stainless steels =Cr+3.3Mo+30N

The ice-breaker in the background has a

Figure 2: Grain decohesion due to intergranular corrosion, photo courtesy M.

Figure 3: Time and temperature dependency of sensitisation (Mayo, 1997).

A variety of solutions exist to avoid sensitisation:

Figure 4: Effect of carbon on sensitisation (Gooch,

Fig. 5: Mechanism of sensitisation.

Niobium in stainless steels

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 6: Vertical section of Fe-Cr-C diagram for 0.1C

Figure 7: Schaeffler diagram for weld metals.

Martensitic Stainless Steels

Table 1: Martensitic Stainless Steels

Ferritic stainless steels

Table 2: Ferritic Stainless Steels

Austenitic stainless steels

Table 3: Austenitic Stainless Steels

Figure 8. Micrographs of austentiic stainless steels

Type 302 austenitic stainless steel, cold-rolled and then annealed at

Duplex stainless steels

Table 4: Duplex stainless steels (wt%). A219 is a superduplex alloy.

Stainless Steel Thread

Powder Metallurgically Produced Stainless Steel

Transformation Texture in Stainless Steel

Theses on Stainless Steels

Sensitisation of Austenitic Stainless Steels

Tensile Properties of Stainless Steel

Anisothermal Recrystallisation in Austenitic Stainless Steels

Simultaneous Precipitation Reactions in Creep-Resistant Austenitic Stainless Steels

Microstructure of Super-Duplex Stainless Steels

Island Constructed from Stainless Steel, Graz, Austria

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 supervised the

The memorial is signed by the son of Chiang,

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.

Stainless steel in action.

Stainless steel aircraft Stainless steel aircraft

Stainless Steel in Switzerland

Stainless steel bin. Stainless steel bin.

Rust on a stainless steel bin?

Stainless steel at Lucern railway station.

Stainless steel display

Stainless steel bins at Zurich airport.

Stainless steel bin at Zurich airport.

Science Museum, London

Stainless steel island, Mur, Graz

Hot-extrusion of stainless steel. Photograph

Stainless Steel in Dusseldorf, Germany

Stainless steel plant frame

Stainless Steel in Baosteel, China

Stainless steel barriers in Shanghai Large stainless steel rings