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Edition 1 - 2002


training notes U N D E R S TA N D I N G S TA I N L E S S S T E E L A N D I T S P R O P E R T I E S

the metallurgy of stainless steels

This Training Note explains the basic Brearly’s discovery led to the development of Factors such as hot and cold work, the
principles of stainless steel terminology, a ‘family’ of stainless steels. thermal history (heat-treatment, welding)
specifications, mechanical and physical and fabrication processes may also affect
Advancements in welding and steel-making
properties, thermal treatments, fabrication the properties.
technology in the 1940’s and 1960’s gave
requirements and applications, and the
impetus to the development and applications The primary property of stainless steels is
factors which govern the classification,
of stainless steels. The developments resistance to wet (aqueous) corrosion and
properties and behaviour of different
continue to fulfil the growing needs of scaling (oxidation at high temperatures –
stainless steels.
industry sectors such as the building, also called dry corrosion). Stainless steels
The most common constituent elements chemical, petro-chemical, mining, power- also exhibit many secondary properties
of stainless steel are Iron (Fe), Carbon (C), generation, nuclear, and food processing which make them extremely versatile
Nitrogen (N), Chromium (Cr), Nickel (Ni), industries. materials.
Sulphur (S), Molybdenum (Mo) and Cr is not the only alloying element used in
Titanium (Ti). Only the chemical symbol stainless steels. Ni, Mo and copper (Cu) THE CLASSIFICATION OF
will be used throughout the text. enhance the passivity in more aggressive STAINLESS STEELS
conditions. Manganese (Mn), silicon (Si), Metals are crystalline solids. The atoms
HISTORY OF STAINLESS STEEL aluminium (Al), N, S, selenium (Se) and Ti are arranged in regular patterns (crystal
Harry Brearly of Sheffield, England is have a lesser effect on the corrosion and heat structure) which are repeated millions of
generally attributed with the discovery resistance, but modify the mechanical and times within any one grain of solidified
of stainless steel, although there had physical properties, such as fabricability, metal. The direction/orientation of the
been considerable investigation work in weldability and machinability. crystals change at the grain boundary.
France and Germany before this. While
experimenting with steels for gun barrels in
1913, Brearly produced a steel containing
±13-14% Cr with a relatively high C content.
This steel did not rust when
exposed to the atmosphere.

The main effect of alloying Cr in Fe is the

increased resistance to both corrosion and
oxidation (scaling) at high temperatures
(see Figure 1).

Passivity is a state in which a metal or alloy

exhibits very low chemical reactivity and is
inert in many corrosive media. Cr imparts
passivity to stainless steel.

In general terms, stainless steels are iron-

based (ferrous) materials containing more
than 11-12% Cr. This level of Cr makes the
steel passive by forming an extremely thin
(30-50 angstrom, i.e. 3-5x10-7 mm thick),
Figure 1: Effect of chromium (Cr) alloy additions to corrosion and scaling resistance
continuous and stable chromium oxide film of iron (Fe)
on the surface of the stainless steel.

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In pure solid Fe, this atomic arrangement/ atom at each corner of a cube with an Steel: change in crystal structure
crystal structure changes at various additional atom in the centre of the cube, i.e.
Steel is essentially Fe alloyed with small
temperatures and is stable over different body-centred cubic structure (BCC),
amounts of C.
ranges of temperature. Fe is one of the few known as delta (δδ) iron or delta ferrite,
metals which exhibits this change of crystal which is magnetic. Ferrite and austenite crystal structures will
structure. Steel is basically a Fe-C alloy and exist over a range of both temperature and C
stainless steel is basically a Fe-Cr alloy. The On cooling to 1,400˚C, the atomic content. Change from one crystal structure to
same changes in crystal structure occur in arrangement abruptly changes to an atom in another does not take place abruptly (unless
these alloys. The different crystal structures each corner of the cube and an atom in the a specific amount of C is alloyed), but also
are termed ferrite and austenite. middle of each face of the cube, i.e. face occurs over a range of temperature and C
centred cubic structure (FCC), known content, during which a mixture of two
Stainless steels are classified by the inherent as gamma (γγ) iron or gamma austenite, crystal structures exists.
crystal structures resulting from both the which is non-magnetic.
chemical composition and the thermal Metallurgists use an equilibrium diagram
treatment: ferritic, austenitic and martensitic On further cooling to 910˚C, the atoms to show the range over which the different
stainless steels. revert to a BCC structure, which is non- crystal structures exist and as a guide to the
magnetic and which has been known as manipulation of various compositions. To
Other forms of stainless steel include
beta (ββ) iron or beta ferrite. obtain an equilibrium diagram, varying
duplex, precipitation hardening and the
compositions are heated or cooled extremely
utility ferritic stainless steel 3CR12 (3CR12 At the Curie temperature (770˚C), the Fe
slowly to allow the different atomic
is a proprietary alloy, usually specified once again becomes magnetic, but there is
arrangements to attain equilibrium and to
under the designation 1.4003). no change in the atomic arrangement. This
stabilise even at low temperatures when the
α) iron or alpha ferrite.
is termed alpha (α
CHARACTERISTICS OF STEEL atomic movements are relatively sluggish.

Pure iron: change in There is a change in volume with each A section of the Fe-C equilibrium diagram is
crystal structure change of crystal structure (see Figure 2A). shown in Figure 3. This diagram shows the
Figure 2 shows the change in crystal changes in the crystal structure of steel and
These changes in atomic arrangement
structure (atomic arrangement) which occurs the ranges over which they exist.
(crystal structure) of Fe are modified both
in pure Fe when heated or cooled. • Slow cooling of a very low C (0.05% C)
by alloying other elements with Fe and the
Atoms have a high energy in the liquid state thermal treatment of such alloys. Different steel:
and move in a random manner. This random types of steel (including the family of As the metal solidifies, delta ferrite
motion ceases on solidification at 1,539˚C. stainless steels) result with a wide range forms. The Fe atoms take on a BCC
The atoms form a geometric pattern: an of mechanical and physical properties. structure. The smaller C atoms move into
the spaces between the Fe atoms. C is
therefore referred to as an interstitial

On further cooling, the BCC delta ferrite

begins to change to FCC austenite until
a fully FCC crystal structure results. The
Fe atoms take up FCC positions with C
in between. C has a high solubility in
the FCC austenitic structure, which is
shown by the size of the austenitic
area in Figure 3, p3.

Figure 2: Change in the crystal structure (atomic arrangement) of pure iron (Fe) Figure 2A: Volume change in pure iron
on heating or cooling (Fe) as crystal structure alters

07 the metallurgy of stainless steels ISSF training notes page 2

On further cooling, the FCC austenite Note: Rapid cooling of steel containing C Slow cooling will anneal (soften) the
changes to BCC alpha ferrite. The causes different results. Due to the fast steel, while fast cooling (quenching)
Fe atoms form the normal BCC crystal cooling rate, the C atoms cannot reach their will harden the steel and produce high
structure. Due to the low solubility of equilibrium position. Therefore, the C atoms mechanical properties.
C in alpha ferrite, the small amount of prevent the Fe atoms from changing from
Other alloy elements, such as Cr, Mo, Ni,
excess C (due to very low 0.05% C) FCC austenite to BCC ferrite + cementite.
Mn and tungsten (W), enhance the steels
combines with Fe to form a minute The Fe atoms therefore lock into a distorted,
response to heat treatment by quenching,
amount of iron-carbide compound highly-stressed, tetragonal crystal structure.
and higher properties can be developed.
called cementite (Fe3C). This stressed, hard and strong but brittle
These alloys shift the boundary lines of
structure is termed martensite.
The resultant steel is soft (dead mild) the phase changes shown on the Fe-C
and easily formed. These are the deep This effect of C increases rapidly up to equilibrium diagram, but the changes
drawing grades. concentrations of 0.65% C and then more are typified by the Fe-C system.
slowly at higher C levels. The tendency to
• Slow cooling of a medium to high C • The transformation of high C content and
form martensite rapidly decreases at C levels
(e.g. 0.6%C) steel: alloyed steels to martensite is related to
lower than 0.35% C. Lesser amounts of
the weldability of steel. The thermal cycle
BCC delta ferrite does not form. As the martensite containing less C do not stress the
during welding is equivalent to a heat
liquid solidifies over a temperature range, structure to the same degree, giving a softer
treatment process on a confined small
the Fe atoms assume the FCC austenitic and more ductile steel. At less than 0.25% C,
area. The heat input during welding raises
crystal structure and the C atoms take the hardening effect of C is minimal, even
the temperature into the FCC austenite
up their interstitial positions. with extremely rapid cooling.
range and the heat extraction by the
On further cooling, the austenite begins The Fe-C equilibrium diagram also surrounding cold steel is extremely rapid
to change and some BCC alpha ferrite illustrates other characteristics of plain (similar to water or brine quenching). If
forms. At the end of transition (723˚C), carbon or low alloy steels: martensite is formed during the welding
the relatively large remaining amount of • Because steel changes its crystal thermal cycle, the weld zone will be
high C austenite changes to an equivalent brittle and have unacceptable properties
structure, it can be heat treated to develop
large amount of cementite (Fe3C) in a for most engineering applications.
a vast range of properties. The crystal
lamella-mixed aggregate of ferrite and
structure is first changed by heating to • Sub-critical stress relieving reduces
cementite (called pearlite).
within the FCC austenite range and then, stresses induced by the various
Fe3C is a hard brittle substance and depending on the composition, cooled at fabrication processes, e.g. cold forming
increases the strength and hardness of different pre-determined rates to produce and welding. This process is carried out at
the steel but decreases the ductility. the desired properties. a maximum temperature of about 650˚C.
This is high enough to give the atoms
sufficient mobility to reorganise
themselves into new positions, thus
relieving the stress, but is below the
critical temperature of 723˚C at which
BCC begins to change to FCC. This
process is not appropriate for most
stainless steels.
• For the heat treatment operations of
annealing, quenching (‘hardening’) and
normalising, the temperature is raised to
the lowest level necessary to reach full
transformation to the FCC austenite
phase. A uniform, fine grain size results
from the re-arrangement into the FCC
crystal structure at such low temperatures.
This fine grain size is retained in the
transformation on subsequent cooling,
thereby enhancing the mechanical
properties of the steel.
• If the temperature is raised to higher
levels within the FCC austenite phase,
some of the grain boundaries break down
and larger and coarser grains result. A
good degree of grain growth occurs,
therefore, at the high temperatures
Figure 3: Section of the iron carbon (Fe-C) equilibrium diagram (1,100-1,200˚C) required for hot working

07 the metallurgy of stainless steels ISSF training notes page 3

(rolling or forging). However, the hot smaller, and promotes the formation of a austenite phase field is limited and the single
working processes refine the coarse ferritic crystal structure, making the ferrite phase ferritic crystal structure is not affected.
grains to a finer uniform size. Any hot phase field larger. Cr is, therefore, termed The C also tends to form complex Fe-Cr
working operation should finish at as low a substitutional ferrite stabiliser carbides, which lock the C, further limiting
a temperature as possible to ensure that (or former). its effect on shifting the gamma loop.
the grain refinement which has taken However, due to the low C content of ferritic
A significant feature of the Fe-Cr
place is not negated by the grain growth stainless steels, the amount of Cr locked in
equilibrium diagram is the boundary
due to a high residual temperature in the these carbides does not have the opposing
between the austenite and ferrite fields,
steel. effect of decreasing the Cr level enough to
known as the gamma loop.
affect its ability to suppress the formation
• Finally, temperatures at which melting
Stainless steels contain more than of austenite. Most ferritic stainless steels
can begin must be avoided when heating
approximately 10.5% Cr and are classified contain a small quantity of finely dispersed
steel for hot work operations. Melting
according to their crystal structure. Fe-Cr carbide precipitates.
initiates at the grain boundaries and,
even if only a minute amount of liquid Referring to Figure 4, it is simple to see that
Ferritic stainless steels are magnetic and
metal is formed, it ‘lubricates’ the grain ferritic stainless steels containing 14.5-27%
non-hardenable by thermal treatment, as the
boundaries. This is termed over-heating or Cr will have a ferritic crystal structure.
transformation from one crystal structure
burning. If any hot working is done
But austenitic stainless steels must have a to another cannot take place.
under these conditions, the steel will
stable austenitic crystal structure at all
disintegrate along these ‘lubricated’ Short-time exposures to high temperatures
temperatures and martensitic stainless steels
grain boundaries. (1,000˚C and higher) cause the normal air-
require fast thermal transformation from
austenite. How is it possible to produce melted ferritic stainless steels to suffer from
austenitic and martensitic stainless steels high temperature embrittlement and loss of
when the austenitic (gamma) phase field is corrosion resistance. These detrimental
Changes in crystal structure limited to Cr levels below 11-12% Cr? effects are related to the grain coarsening
While steels are based on the alloying of within the single phase ferritic crystal
small amounts of C with Fe, stainless steels Ferritic stainless steels structure and to the levels of C and N in the
are based on the alloying of Cr with Fe. The ferritic stainless steels, which have a steel which form Cr carbides and nitrides.
Cr content of 14.5-27.0% Cr, will have a The heat affected zone (HAZ) adjacent to a
The Fe-Cr equilibrium diagram (see Figure
BCC ferritic crystal structure which is weld reaches these temperatures and,
4) is used to indicate the changes in crystal
retained from room temperature to melting therefore, suffers a loss of properties.
structure for stainless steels. BCC ferrite and
point. This composition passes outside the
FCC austenite do exist, but the shapes and
gamma loop (see Figure 5). Ferritic stainless steels exhibit low
extent of the areas are different from those of
temperature brittleness. As the temperature
the Fe-C alloy system, i.e. Carbon steel. Ferritic stainless steels have a low C content
drops below room temperature, they change
which seldom exceeds 0.06% C – well below
The Cr atom takes up a place in the crystal from being tough and ductile to becoming
the specified minimum.
structure normally occupied by an Fe atom. exceedingly brittle at ±0˚C. In the HAZ, this
Cr suppresses the formation of austenite, Therefore, the effect of C in moving the ductile to brittle transition takes place at
making the austenite (gamma) phase field gamma loop and expanding the FCC higher temperatures (40-60˚C and above).

Figure 5: Schematic representation of typical Cr contents

of ferritic stainless steels. Passing outside the
Figure 4: Section of the iron chromium (Fe-Cr) equilibrium diagram gamma loop

07 the metallurgy of stainless steels ISSF training notes page 4

These factors result in the inferior Martensitic stainless steels have the Austenitic stainless steel
weldability of these steels which, therefore, following properties: The Cr content of austenitic stainless steels
limits their use as welded components to • magnetic; exceeds 16% Cr, which would indicate a
thin gauges. • moderate corrosion resistance: ferritic crystal structure (see Figure 4, p4).
they are alloys of Fe-Cr-C, with
To improve the properties associated with Alloying elements which shift the gamma
significant amounts of C and a relatively
the standard ferritic stainless steels, the super loop must be used, both to expand the
low maximum Cr content, some of which
ferritic stainless steels were developed. austenitic crystal structure into the ferritic
is tied up as Cr carbides and, thus, not
regions of higher Cr content and to retain it
The significant features of the super ferritic contributing to the passivity of the steel;
at the lower temperatures (see Figure 7).
stainless are as follows: and
• an alloy content that, when heated, passes Ni is the most commonly-used alloying
• a high Cr content (typically 18-25% Cr) through the gamma loop to FCC element in the 300 series of stainless steels,
and Mo additions (typically 1-4% Mo), austenite. Subsequent moderate to fast but manganese (Mn) can also be used to
which improve the corrosion resistance; cooling produces the hard martensitic replace some of the Ni in the 200 series
• low levels of both N and C (less than atomic crystal structure. They are of stainless steels.
0.03% each), which prevent the hardenable by heat treatment. These elements are substitutional austenite
detrimental effects resulting from the
Martensite has high strength and hardness stabilisers/formers which take the place of
formation of Cr nitrides and Cr carbides
but is brittle and has low ductility and an Fe atom in the crystal structure. They are
during welding; and
toughness. It must, therefore, be subjected large atoms which diffuse slowly in Fe and,
• additions of small amounts of Ni,
to a further heating cycle (tempering) at therefore, stabilise the austenitic crystal
which improve the resistance to high
temperatures below that at which the structure down to temperatures below that
temperature embrittlement.
austenite transformation occurs. The at which the atoms have sufficient mobility
However, the weldability, even though tempering temperature is varied to obtain the for a crystal structure change to occur.
improved, is still a constraining factor required combinations of strength, hardness, In some grades of austenitic stainless steels,
limiting the general use of super ferritic ductility and toughness. Heat treatment of small amounts of N are added. The result is
stainless steels as welded components to a martensitic stainless steel also maximises an interstitial austenite stabiliser which
maximum thickness of approximately 5mm. their corrosion resistance. helps the Ni increase and stabilise the
Martensite has very poor weldability. The austenitic crystal structure.
Martensitic stainless steels
It would appear impossible for a steel with heat input and subsequent cooling of the The Ni content of the 300 series austenitic
more than 11-12% Cr to be ‘stainless’ yet HAZ is equivalent to heat treatment carried stainless steel is adjusted to cater for the
still be able to attain the necessary thermal out on a confined area. Hard brittle various chemical compositions of the
transformation by rapidly cooling the FCC martensite forms in the HAZ. Special different austenitic stainless steel grades:
austenite to produce the ‘jammed up’, precautions help avoid this and any • 17% Cr needs a minimum of 7% Ni to
distorted and therefore hard martensitic martensite that does form must be tempered. stabilise the austenite, but 26% Cr, as
crystal structure. The properties of welded martensitic in some heat resisting grades, needs
stainless steels are usually unacceptable 20% Ni to ensure a stable austenitic
C, a powerful interstitial austenite for general engineering applications. crystal structure;
stabiliser, is used as the alloying element to
shift the gamma loop to higher Cr contents,
thereby expanding the FCC austenitic phase
field (see Figure 6).

This effect of C is constrained by the strong

ability of Cr to maintain the BCC ferritic
structure and, due to the high affinity of
Cr for C, Cr carbides will form.

Therefore, the C and Cr contents have to be

balanced: this ensures the required thermal
transformation of crystal structure and
avoids a reduction in the passivity resulting
from an excessive amount of Cr being
extracted from the matrix and locked up
as Cr carbides.

The Cr content of martensitic stainless steels

Figure 6: Schematic representation Figure 7: Schematic representation
is limited to relatively low levels of 12-18% illustrating the effect of carbon illustrating the effect of nickel
Cr – the steels with lower Cr content having (C) in shifting the gamma (Ni) in both shifting the gamma
lower C. loop allowing austenite to loop and stabilising austenite
martensite transformations down to low temperatures

07 the metallurgy of stainless steels ISSF training notes page 5

• Mo is added to improve the corrosion operations, e.g. grade 305 for deep drawing, strengths of duplex in comparison with
resistance to chlorides. It is a contain an over-supply of Ni. Grade 302HQ austenitic or ferritic stainless steels).
substitutional ferritic stabiliser and the (S30430) contains 3% copper, another
When duplex stainless steels were initially
Ni content has to be increased in these austenite stabiliser, as a lower cost
developed, their weldability was restrained
grades to counteract this effect; and alternative to the increased nickel in grade
by the formation and retention of ferrite in
• C, an interstitial austenite stabiliser, 305. This grade is common in cold heading
the HAZ. This limited their use as welded
is reduced to low levels in the ‘L’ grade applications. The 200 series stainless steels,
components to sheet and thinner plate
austenitic stainless steels. The Ni content which use Mn to partly replace Ni as the
thickness. Technological developments
must, therefore, be increased to overcome austenite stabiliser, work harden more
have improved their weldability.
the lower tendency to form and stabilise rapidly than the 300 series.
the austenitic crystal structure. The weldability of the majority of duplex
Due to the ‘martensite’ produced during
stainless steels in thick section may now be
Austenitic stainless steels have, therefore, cold work, work-hardened austenitic
classified as good. The alloying element N,
the following properties: stainless steels will exhibit a slight degree
a powerful interstitial austenite stabiliser,
• non-magnetic; of magnetism, depending on the amount of
has contributed most to eliminating the
• extremely stable crystal structure; cold work and the composition of the steel.
detrimental effects of retained ferrite in the
• excellent weldability; and
Solution annealing can remove the work- HAZ. It promotes the formation of a higher
• non-hardenable by heat treatment,
hardened condition. The steel is heated to fraction of austenite within the crystal
but hardenable by cold work.
high temperatures (approximately 1,050˚C). structure and assists the reformation of
Ni diffuses slowly, even at high The ‘martensite’ precipitates dissolve and are austenite within the HAZ. The result within
temperatures. Lengthy exposure to high taken back into an equilibrium solution of the HAZ is good ductility, toughness and
temperatures results in very little grain a fully recrystallised austenitic structure. corrosion resistance equivalent to those of
growth or embrittlement. the parent metal.
Duplex stainless steels
The substitutional austenitic stabilising Duplex stainless steels are relatively new Duplex stainless steels which contain N to
elements prevent a crystal structure change members within the family of stainless achieve the higher balanced austenitic ratio
on cooling. Therefore, hardening by thermal steels. They are sometimes available as within the crystal structure are often called
treatment cannot take place. proprietary alloys. second generation duplex stainless steels.
But the crystal structure ‘wants’ to change Duplex stainless steels have the following
Duplex stainless steels are two-phase, having
and is therefore termed metastable. These properties:
a dispersion of FCC austenite in a matrix of
changes occur during cold working when • magnetic;
BCC ferrite. This is because they contain an
movement occurs along planes (slip planes) • non-hardenable by heat treatment;
insufficient amount of the austenite
within the grains. Constraints are eased and • good mechanical and physical properties
stabilising element (Ni).
there is enough energy for a crystal structure (generally similar or superior to austenitic
change to take place at extremely small These stainless steels have improved and ferritic stainless steels); and
localised areas along the slip planes. corrosion resistance and higher strength than • excellent corrosion resistance (generally
austenitics. Because of this higher strength, equivalent or superior to austenitic
Tiny patches of ‘martensite’ are formed.
the duplex grades require higher forces to stainless steels).
This ‘martensite’ is low in C, tough, and of
form and they cannot be as readily cold
varying crystal structure – either BCC or
fabricated as the austenitic stainless steels. Precipitation-hardening
hexagonal close packed (HCP). It is different
from the martensite formed in martensitic stainless steels
The higher Cr content and, in most alloys,
stainless steels and is, therefore, often an addition of Mo, result in greater Austenitic stainless steels are not heat
referred to as ‘quasi-martensite’. resistance to pitting and crevice corrosion. treatable and have, in the forms used in
fabrication, low strength but excellent
The normal austenite to martensite volume SCC, which may initiate within the austenite corrosion resistance and fabricability.
expansion takes place and these small fraction, is restricted by the ferrite fraction
martensite islands act as ‘keys’ along the slip Martensitic stainless steels can be heat
of the duplex structure. The ferrite:austenite
planes. Further movement is thus inhibited, treated to develop high strength, but this
ratio of duplex stainless steels depends on
making the austenitic stainless steels harder, limits their fabricability (especially their
the composition, i.e. the amounts of ferrite
stronger and resistant to further distortion weldability). Their corrosion resistance
formers, e.g. Cr and Mo, and austenite
by cold work. is only fair to moderate.
formers, e.g. Ni and N. This ferrite:austenite
Work hardening enables extremely high ratio varies from 70:30 to 50:50. The precipitation-hardening stainless steels
strength levels to be developed (over were developed to overcome these
The size and distribution of the ferrite and
2,000MPa in cold drawn wire). limitations and are mostly available as
austenite phases in the duplex structure is
proprietary alloys.
The lean alloy/composition grades of dependent on both the thermo-mechanical
austenitic stainless steels contain a minimum (hot working) cycles and the heat treatment. There are three types of precipitation-
level of austenite stabiliser alloying elements This relationship is also important in hardening stainless steels:
to make them fully austenitic. These grades, developing the mechanical and physical • martensitic;
e.g. grade 301, work harden rapidly. Grades properties of duplex stainless steels • semi-austenitic; and
specifically intended for cold-working (especially the higher tensile and yield • austenitic.

07 the metallurgy of stainless steels ISSF training notes page 6

These terms should not be confused with • 13-8 It has a Cr content of 11-12% Cr and is,
the same terms used to designate the • PH13-8 Mo therefore, classified as a ferritic stainless
standard classifications of stainless steels. • stainless W steel. However, because of its minimum
• custom 450 & 455 Cr content, it is sometimes referred to as
An exact balance of the chemical
a corrosion-resisting steel.
composition is critical to ensure the Typical properties which can be attained
development of the phases and precipitates are as follows: The Cr content of 3CR12 places it at the
required to achieve the desired properties. • 0.2% proof stress 1,200-1,600MPa; critical boundary of the gamma loop,
Several elements, e.g. aluminium (Al), • tensile strength 1,300-1,600MPa; & i.e. small variations within its chemical
copper (Cu), Ti and Mo, are used, either • hardness 42-49 HRC. composition which are either austenite or
alone or in combination, to obtain the ferrite stabilisers (formers) could render the
These are the most used of the precipitation-
precipitation-hardening reactions. crystal structure either austenitic or ferritic
hardening stainless steels, used as bar, rod,
at high temperatures (see Figure 4, p4).
Precipitation-hardening stainless steels have wire, heavy forgings, sheet and thinner plate.
similar or superior mechanical properties to The composition is, therefore, controlled
the martensitic stainless steels and have a Semi-austenitic types during manufacture to ensure a critical
corrosion resistance approaching that of These are essentially austenitic in the balance between austenite and ferrite exists
grade 304 austenitic stainless steel. solution annealed condition and then at the high temperatures employed for hot
converted to a martensitic structure by working.
The thermo-mechanical (hot working) and various heat treatments.
complex heat treatments and welding Both C and N are strong austenite formers
procedures which are necessary to develop Typical alloys include the following: and are both limited to low levels in 3CR12.
and retain the properties of these stainless • 17-7PH (‘grade 631’) If the levels of these elements approach the
steels must be allowed for in any application • PH 14-8Mo specified maximum (0.03% each), they need
of these steels. • PH15-7Mo to be constrained by a further alloy addition
• AM 350 & 355 of the stabilising element of Ti. Stable Ti
The precipitation-hardening heat treatment
Typical properties which can be attained carbides and nitrides are formed, which
is a time-temperature relationship dependent
are as follows: minimise the effect of C and N. Since Ti is
on the type of alloy.
• 0.2% proof stress 1,250-1,793MPa; a ferrite former, it has to be counterbalanced
In the martensitic and semi-austenitic types, • tensile strength 1,500-1,825MPa; & by the addition of Ni, which is an austenite
the atoms of the precipitating phase collect in • hardness 45-50 HRC. former.
clusters which are continuous and coherent
These are the next most used of the C and N are kept at levels well below
with the matrix phase. They are not visible by
precipitation-hardening stainless steels, the maximum specified, so it is no longer
ordinary optical means as no actual
used mostly as sheet and strip. necessary to use Ti to constrain these
precipitation has yet occurred. This is termed
elements and Ni to balance the crystal
pre-precipitation – maximum strengthening
Austenitic types structure, but it is still an option that
occurs at this stage. If the precipitation
These steels have a stable austenitic crystal may be used.
process is continued, the clusters of atoms
grow and precipitate out as intermetallic The final crystal structure is dependent
compounds, which form a grain boundary Typical alloys include the following: on the thermal history.
between the precipitate and the matrix phase. • 17-10P
With the improvements noted above, and
This reduces the strain and coherence is lost. • A286
by using a controlled, slow cooling rate
Therefore, the strength decreases and the • HNM
from the final hot rolling temperature, the
material becomes over aged.
Typical properties which can be attained austenitic fraction transforms at elevated
In the austenitic types, the precipitates are are as follows: temperatures and a predominantly fine
allowed to form second phase intermetallic • 0.2% proof stress 675MPa; grained ferritic structure develops.
compounds. This increases the strength in • tensile strength 975-1,025MPa; and
Fast cooling rates would transform the
the austenite matrix, but not to the same • hardness 32-34 HRC.
austenite fraction to ‘martensite’, with the
extent as in the martensitic and semi-
These are the least used of the precipitation- ferrite remaining. The ferrite/’martensite’
austenitic types of precipitation- hardening
hardening stainless steels. However, they balance is directly related to the
stainless steels.
can be used at both higher and lower ferrite/austenite which exists at the high
Martensitic types temperatures than the other types. temperatures.
The chemical composition is balanced so UNS S41003 corrosion-resisting The ‘martensite’ formed in 3CR12 is not the
that a martensitic crystal structure results steel same as that in martensitic stainless steels.
when cooled to ambient temperature after It has a very low C content and is, therefore,
This is a proprietary alloy which was
solution treatment. These are also called not highly stressed. The atoms are arranged
developed by Middleburg Steel and Alloys
maraging steels. imperfectly with vacant atomic sites (i.e.
and commercially launched in 1980. As
Typical alloys include the following: other proprietary designations are available, highly dislocated or of high dislocation
• 17-4PH (‘grade 630’) it is usually specified under the designation density). This lath martensite is relatively
• 15-5PH of 1.4003. tough and ductile.

07 the metallurgy of stainless steels ISSF training notes page 7

Annealing material is necessary to develop CONCLUSION
strength, toughness and ductility, which are This paper has looked at the main factors
required for general engineering materials. which govern the internal crystal (micro)
The annealing temperature is below that at structures and determine the different
which the ‘martensite’ would transform to classifications of stainless steel. The
austenite. This annealing is, essentially, crystal structure also governs the various
more correctly a tempering operation. mechanical, physical and fabricational
Hot forming operations must be carried out properties of stainless steels. These
at a sub-critical temperature range (600- properties make stainless steels an extremely
700˚C) to prevent any inversion to an versatile group of materials.
austenitic crystal structure. It should be noted that some aspects have
Indiscriminate heating of 3CR12, either been greatly simplified to illustrate the basic
for fabrication purposes or in operation, principles. Figures 5, 6 and 7, p4-5 are not
can seriously affect the properties of the exact, but merely depict the changes which
material. take place in the crystal structure.

The weldability of 3CR12 is far greater than

the standard plain Cr ferritic stainless steels.
This is due to the superior properties of the
HAZ which result from the following:
• the very low levels of both C and N
prevent the detrimental effects caused
by the formation of Cr carbides and Cr
• the two-phase crystal structure, which
develops at high temperatures, inhibits
grain growth in the HAZ, thus limiting
the embrittling effects; and
• the ‘martensite’, which results on cooling
from the austenite fraction formed at high
temperatures, is a low C ‘martensite’
which is relatively tough and ductile.

Edition 1
© 2002 Australian Stainless Steel
Development Association

Acknowledgment: The contribution of

the Australian Stainless Steel Development
Association’s Technical and Education
Committees in preparing this course is
acknowledged with thanks. Some material
in this course originated from the Southern
Africa Stainless Steel Development Association.
Disclaimer: The technical data and views
expressed in this publication are for the
general information of interested persons
and should not be relied upon in specific
applications without first securing competent
advice. Whilst all care is taken to ensure that
the information contained herein is accurate
and up-to-date, the ISSF does not warrant its
accuracy or completeness and does not
accept liability for errors or omissions.

07 the metallurgy of stainless steels ISSF training notes page 8