07

Edition 1 - 2002

W O R L D S TA I N L E S S

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

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.

I N T E R N AT I O N A L S TA I N L E S S S T E E L F O R U M
Rue Col. Bourg 120, B-1140 Brussels, Belgium Telephone: +32 (2) 702 8900 Facsimile: +32 (2) 702 8899 Email: issf@iisi.be Web: www.worldstainless.org
In pure solid Fe, this atomic arrangement/
crystal structure changes at various
temperatures and is stable over different
ranges of temperature. Fe is one of the few
metals which exhibits this change of crystal
structure. Steel is basically a Fe-C alloy and
stainless steel is basically a Fe-Cr alloy. The
same changes in crystal structure occur in
these alloys. The different crystal structures
are termed ferrite and austenite.
Stainless steels are classified by the inherent
crystal structures resulting from both the
chemical composition and the thermal
treatment: ferritic, austenitic and martensitic
stainless steels.
Other forms of stainless steel include
duplex, precipitation hardening and the
utility ferritic stainless steel 3CR12 (3CR12
is a proprietary alloy, usually specified
under the designation 1.4003).
CHARACTERISTICS OF STEEL
Pure iron: change in
crystal structure
Figure 2 shows the change in crystal
structure (atomic arrangement) which occurs
in pure Fe when heated or cooled.
Atoms have a high energy in the liquid state
and move in a random manner. This random
motion ceases on solidification at 1,539˚C.
The atoms form a geometric pattern: an
Figure 2: Change in the crystal structure (atomic arrangement) of pure iron (Fe)
on heating or cooling
07 the metallurgy of stainless steels
atom at each corner of a cube with an
additional atom in the centre of the cube, i.e.
body-centred cubic structure (BCC),
known as delta (δδ) iron or delta ferrite,
which is magnetic.
On cooling to 1,400˚C, the atomic
arrangement abruptly changes to an atom in
each corner of the cube and an atom in the
middle of each face of the cube, i.e. face
centred cubic structure (FCC), known
as gamma (γγ) iron or gamma austenite,
which is non-magnetic.
On further cooling to 910˚C, the atoms
revert to a BCC structure, which is non-
magnetic and which has been known as
beta (ββ) iron or beta ferrite.
At the Curie temperature (770˚C), the Fe
once again becomes magnetic, but there is
no change in the atomic arrangement. This
α) iron or alpha ferrite.
is termed alpha (α
There is a change in volume with each
change of crystal structure (see Figure 2A).
These changes in atomic arrangement
(crystal structure) of Fe are modified both
by alloying other elements with Fe and the
thermal treatment of such alloys. Different
types of steel (including the family of
stainless steels) result with a wide range
of mechanical and physical properties.
Steel: change in crystal structure
Steel is essentially Fe alloyed with small
amounts of C.
Ferrite and austenite crystal structures will
exist over a range of both temperature and C
content. Change from one crystal structure to
another does not take place abruptly (unless
a specific amount of C is alloyed), but also
occurs over a range of temperature and C
content, during which a mixture of two
crystal structures exists.
Metallurgists use an equilibrium diagram
to show the range over which the different
crystal structures exist and as a guide to the
manipulation of various compositions. To
obtain an equilibrium diagram, varying
compositions are heated or cooled extremely
slowly to allow the different atomic
arrangements to attain equilibrium and to
stabilise even at low temperatures when the
atomic movements are relatively sluggish.
A section of the Fe-C equilibrium diagram is
shown in Figure 3. This diagram shows the
changes in the crystal structure of steel and
the ranges over which they exist.
• Slow cooling of a very low C (0.05% C)
steel:
As the metal solidifies, delta ferrite
forms. The Fe atoms take on a BCC
structure. The smaller C atoms move into
the spaces between the Fe atoms. C is
therefore referred to as an interstitial
element.
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 2A: Volume change in pure iron
(Fe) as crystal structure alters
ISSF training notes page 2
 On further cooling, the FCC austenite
changes to BCC alpha ferrite. The
Fe atoms form the normal BCC crystal
structure. Due to the low solubility of
C in alpha ferrite, the small amount of
excess C (due to very low 0.05% C)
combines with Fe to form a minute
amount of iron-carbide compound
called cementite (Fe3C).
The resultant steel is soft (dead mild)
and easily formed. These are the deep
drawing grades.
• Slow cooling of a medium to high C
(e.g. 0.6%C) steel:
BCC delta ferrite does not form. As the
liquid solidifies over a temperature range,
the Fe atoms assume the FCC austenitic
crystal structure and the C atoms take
up their interstitial positions.
On further cooling, the austenite begins
to change and some BCC alpha ferrite
forms. At the end of transition (723˚C),
the relatively large remaining amount of
high C austenite changes to an equivalent
large amount of cementite (Fe3C) in a
lamella-mixed aggregate of ferrite and
cementite (called pearlite).
Fe3C is a hard brittle substance and
increases the strength and hardness of
the steel but decreases the ductility.
Figure 3: Section of the iron carbon (Fe-C) equilibrium diagram
07 the metallurgy of stainless steels
Note: Rapid cooling of steel containing C
causes different results. Due to the fast
cooling rate, the C atoms cannot reach their
equilibrium position. Therefore, the C atoms
prevent the Fe atoms from changing from
FCC austenite to BCC ferrite + cementite.
The Fe atoms therefore lock into a distorted,
highly-stressed, tetragonal crystal structure.
This stressed, hard and strong but brittle
structure is termed martensite.
This effect of C increases rapidly up to
concentrations of 0.65% C and then more
slowly at higher C levels. The tendency to
form martensite rapidly decreases at C levels
lower than 0.35% C. Lesser amounts of
martensite containing less C do not stress the
structure to the same degree, giving a softer
and more ductile steel. At less than 0.25% C,
the hardening effect of C is minimal, even
with extremely rapid cooling.
The Fe-C equilibrium diagram also
illustrates other characteristics of plain
carbon or low alloy steels:
• Because steel changes its crystal
structure, it can be heat treated to develop
a vast range of properties. The crystal
structure is first changed by heating to
within the FCC austenite range and then,
depending on the composition, cooled at
different pre-determined rates to produce
the desired properties.
Slow cooling will anneal (soften) the
steel, while fast cooling (quenching)
will harden the steel and produce high
mechanical properties.
Other alloy elements, such as Cr, Mo, Ni,
Mn and tungsten (W), enhance the steels
response to heat treatment by quenching,
and higher properties can be developed.
These alloys shift the boundary lines of
the phase changes shown on the Fe-C
equilibrium diagram, but the changes
are typified by the Fe-C system.
• The transformation of high C content and
alloyed steels to martensite is related to
the weldability of steel. The thermal cycle
during welding is equivalent to a heat
treatment process on a confined small
area. The heat input during welding raises
the temperature into the FCC austenite
range and the heat extraction by the
surrounding cold steel is extremely rapid
(similar to water or brine quenching). If
martensite is formed during the welding
thermal cycle, the weld zone will be
brittle and have unacceptable properties
for most engineering applications.
• Sub-critical stress relieving reduces
stresses induced by the various
fabrication processes, e.g. cold forming
and welding. This process is carried out at
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
(1,100-1,200˚C) required for hot working
ISSF training notes page 3
 (rolling or forging). However, the hot
working processes refine the coarse
grains to a finer uniform size. Any hot
working operation should finish at as low
a temperature as possible to ensure that
the grain refinement which has taken
place is not negated by the grain growth
due to a high residual temperature in the
steel.
• Finally, temperatures at which melting
can begin must be avoided when heating
steel for hot work operations. Melting
initiates at the grain boundaries and,
even if only a minute amount of liquid
metal is formed, it ‘lubricates’ the grain
boundaries. This is termed over-heating or
burning. If any hot working is done
under these conditions, the steel will
disintegrate along these ‘lubricated’
grain boundaries.
CHARACTERISTICS OF
STAINLESS STEELS
Changes in crystal structure
While steels are based on the alloying of
small amounts of C with Fe, stainless steels
are based on the alloying of Cr with Fe.
The Fe-Cr equilibrium diagram (see Figure
4) is used to indicate the changes in crystal
structure for stainless steels. BCC ferrite and
FCC austenite do exist, but the shapes and
extent of the areas are different from those of
the Fe-C alloy system, i.e. Carbon steel.
The Cr atom takes up a place in the crystal
structure normally occupied by an Fe atom.
Cr suppresses the formation of austenite,
making the austenite (gamma) phase field
Figure 4: Section of the iron chromium (Fe-Cr) equilibrium diagram
07 the metallurgy of stainless steels
smaller, and promotes the formation of a
ferritic crystal structure, making the ferrite
phase field larger. Cr is, therefore, termed
a substitutional ferrite stabiliser
(or former).
A significant feature of the Fe-Cr
equilibrium diagram is the boundary
between the austenite and ferrite fields,
known as the gamma loop.
Stainless steels contain more than
approximately 10.5% Cr and are classified
according to their crystal structure.
Referring to Figure 4, it is simple to see that
ferritic stainless steels containing 14.5-27%
Cr will have a ferritic crystal structure.
But austenitic stainless steels must have a
stable austenitic crystal structure at all
temperatures and martensitic stainless steels
require fast thermal transformation from
austenite. How is it possible to produce
austenitic and martensitic stainless steels
when the austenitic (gamma) phase field is
limited to Cr levels below 11-12% Cr?
Ferritic stainless steels
The ferritic stainless steels, which have a
Cr content of 14.5-27.0% Cr, will have a
BCC ferritic crystal structure which is
retained from room temperature to melting
point. This composition passes outside the
gamma loop (see Figure 5).
Ferritic stainless steels have a low C content
which seldom exceeds 0.06% C – well below
the specified minimum.
Therefore, the effect of C in moving the
gamma loop and expanding the FCC
Figure 5: Schematic representation of typical Cr contents
of ferritic stainless steels. Passing outside the
gamma loop
austenite phase field is limited and the single
phase ferritic crystal structure is not affected.
The C also tends to form complex Fe-Cr
carbides, which lock the C, further limiting
its effect on shifting the gamma loop.
However, due to the low C content of ferritic
stainless steels, the amount of Cr locked in
these carbides does not have the opposing
effect of decreasing the Cr level enough to
affect its ability to suppress the formation
of austenite. Most ferritic stainless steels
contain a small quantity of finely dispersed
Fe-Cr carbide precipitates.
Ferritic stainless steels are magnetic and
non-hardenable by thermal treatment, as the
transformation from one crystal structure
to another cannot take place.
Short-time exposures to high temperatures
(1,000˚C and higher) cause the normal air-
melted ferritic stainless steels to suffer from
high temperature embrittlement and loss of
corrosion resistance. These detrimental
effects are related to the grain coarsening
within the single phase ferritic crystal
structure and to the levels of C and N in the
steel which form Cr carbides and nitrides.
The heat affected zone (HAZ) adjacent to a
weld reaches these temperatures and,
therefore, suffers a loss of properties.
Ferritic stainless steels exhibit low
temperature brittleness. As the temperature
drops below room temperature, they change
from being tough and ductile to becoming
exceedingly brittle at ±0˚C. In the HAZ, this
ductile to brittle transition takes place at
higher temperatures (40-60˚C and above).
ISSF training notes page 4
These factors result in the inferior
weldability of these steels which, therefore,
limits their use as welded components to
thin gauges.
To improve the properties associated with
the standard ferritic stainless steels, the super
ferritic stainless steels were developed.
The significant features of the super ferritic
stainless are as follows:
• a high Cr content (typically 18-25% Cr)
and Mo additions (typically 1-4% Mo),
which improve the corrosion resistance;
• low levels of both N and C (less than
0.03% each), which prevent the
detrimental effects resulting from the
formation of Cr nitrides and Cr carbides
during welding; and
• additions of small amounts of Ni,
which improve the resistance to high
temperature embrittlement.
However, the weldability, even though
improved, is still a constraining factor
limiting the general use of super ferritic
stainless steels as welded components to a
maximum thickness of approximately 5mm.
Martensitic stainless steels
It would appear impossible for a steel with
more than 11-12% Cr to be ‘stainless’ yet
still be able to attain the necessary thermal
transformation by rapidly cooling the FCC
austenite to produce the ‘jammed up’,
distorted and therefore hard martensitic
crystal structure.
C, a powerful interstitial austenite
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
is limited to relatively low levels of 12-18%
Cr – the steels with lower Cr content having
lower C.
07 the metallurgy of stainless steels
Martensitic stainless steels have the
following properties:
• magnetic;
• moderate corrosion resistance:
they are alloys of Fe-Cr-C, with
significant amounts of C and a relatively
low maximum Cr content, some of which
is tied up as Cr carbides and, thus, not
contributing to the passivity of the steel;
and
• an alloy content that, when heated, passes
through the gamma loop to FCC
austenite. Subsequent moderate to fast
cooling produces the hard martensitic
atomic crystal structure. They are
hardenable by heat treatment.
Martensite has high strength and hardness
but is brittle and has low ductility and
toughness. It must, therefore, be subjected
to a further heating cycle (tempering) at
temperatures below that at which the
austenite transformation occurs. The
tempering temperature is varied to obtain the
required combinations of strength, hardness,
ductility and toughness. Heat treatment of
martensitic stainless steel also maximises
their corrosion resistance.
Martensite has very poor weldability. The
heat input and subsequent cooling of the
HAZ is equivalent to heat treatment carried
out on a confined area. Hard brittle
martensite forms in the HAZ. Special
precautions help avoid this and any
martensite that does form must be tempered.
The properties of welded martensitic
stainless steels are usually unacceptable
for general engineering applications.
Figure 6: Schematic representation
illustrating the effect of carbon
(C) in shifting the gamma
loop allowing austenite to
martensite transformations
Austenitic stainless steel
The Cr content of austenitic stainless steels
exceeds 16% Cr, which would indicate a
ferritic crystal structure (see Figure 4, p4).
Alloying elements which shift the gamma
loop must be used, both to expand the
austenitic crystal structure into the ferritic
regions of higher Cr content and to retain it
at the lower temperatures (see Figure 7).
Ni is the most commonly-used alloying
element in the 300 series of stainless steels,
but manganese (Mn) can also be used to
replace some of the Ni in the 200 series
of stainless steels.
These elements are substitutional austenite
stabilisers/formers which take the place of
an Fe atom in the crystal structure. They are
large atoms which diffuse slowly in Fe and,
therefore, stabilise the austenitic crystal
structure down to temperatures below that
at which the atoms have sufficient mobility
for a crystal structure change to occur.
In some grades of austenitic stainless steels,
small amounts of N are added. The result is
an interstitial austenite stabiliser which
helps the Ni increase and stabilise the
austenitic crystal structure.
The Ni content of the 300 series austenitic
stainless steel is adjusted to cater for the
various chemical compositions of the
different austenitic stainless steel grades:
• 17% Cr needs a minimum of 7% Ni to
stabilise the austenite, but 26% Cr, as
in some heat resisting grades, needs
20% Ni to ensure a stable austenitic
crystal structure;
Figure 7: Schematic representation
illustrating the effect of nickel
(Ni) in both shifting the gamma
loop and stabilising austenite
down to low temperatures
ISSF training notes page 5
• Mo is added to improve the corrosion
resistance to chlorides. It is a
substitutional ferritic stabiliser and the
Ni content has to be increased in these
grades to counteract this effect; and
• C, an interstitial austenite stabiliser,
is reduced to low levels in the ‘L’ grade
austenitic stainless steels. The Ni content
must, therefore, be increased to overcome
the lower tendency to form and stabilise
the austenitic crystal structure.
Austenitic stainless steels have, therefore,
the following properties:
• non-magnetic;
• extremely stable crystal structure;
• excellent weldability; and
• non-hardenable by heat treatment,
but hardenable by cold work.
Ni diffuses slowly, even at high
temperatures. Lengthy exposure to high
temperatures results in very little grain
growth or embrittlement.
The substitutional austenitic stabilising
elements prevent a crystal structure change
on cooling. Therefore, hardening by thermal
treatment cannot take place.
But the crystal structure ‘wants’ to change
and is therefore termed metastable. These
changes occur during cold working when
movement occurs along planes (slip planes)
within the grains. Constraints are eased and
there is enough energy for a crystal structure
change to take place at extremely small
localised areas along the slip planes.
Tiny patches of ‘martensite’ are formed.
This ‘martensite’ is low in C, tough, and of
varying crystal structure – either BCC or
hexagonal close packed (HCP). It is different
from the martensite formed in martensitic
stainless steels and is, therefore, often
referred to as ‘quasi-martensite’.
The normal austenite to martensite volume
expansion takes place and these small
martensite islands act as ‘keys’ along the slip
planes. Further movement is thus inhibited,
making the austenitic stainless steels harder,
stronger and resistant to further distortion
by cold work.
Work hardening enables extremely high
strength levels to be developed (over
2,000MPa in cold drawn wire).
The lean alloy/composition grades of
austenitic stainless steels contain a minimum
level of austenite stabiliser alloying elements
to make them fully austenitic. These grades,
e.g. grade 301, work harden rapidly. Grades
specifically intended for cold-working
07 the metallurgy of stainless steels
operations, e.g. grade 305 for deep drawing,
contain an over-supply of Ni. Grade 302HQ
(S30430) contains 3% copper, another
austenite stabiliser, as a lower cost
alternative to the increased nickel in grade
305. This grade is common in cold heading
applications. The 200 series stainless steels,
which use Mn to partly replace Ni as the
austenite stabiliser, work harden more
rapidly than the 300 series.
Due to the ‘martensite’ produced during
cold work, work-hardened austenitic
stainless steels will exhibit a slight degree
of magnetism, depending on the amount of
cold work and the composition of the steel.
Solution annealing can remove the work-
hardened condition. The steel is heated to
high temperatures (approximately 1,050˚C).
The ‘martensite’ precipitates dissolve and are
taken back into an equilibrium solution of
a fully recrystallised austenitic structure.
Duplex stainless steels
Duplex stainless steels are relatively new
members within the family of stainless
steels. They are sometimes available as
proprietary alloys.
Duplex stainless steels are two-phase, having
a dispersion of FCC austenite in a matrix of
BCC ferrite. This is because they contain an
insufficient amount of the austenite
stabilising element (Ni).
These stainless steels have improved
corrosion resistance and higher strength than
austenitics. Because of this higher strength,
the duplex grades require higher forces to
form and they cannot be as readily cold
fabricated as the austenitic stainless steels.
The higher Cr content and, in most alloys,
an addition of Mo, result in greater
resistance to pitting and crevice corrosion.
SCC, which may initiate within the austenite
fraction, is restricted by the ferrite fraction
of the duplex structure. The ferrite:austenite
ratio of duplex stainless steels depends on
the composition, i.e. the amounts of ferrite
formers, e.g. Cr and Mo, and austenite
formers, e.g. Ni and N. This ferrite:austenite
ratio varies from 70:30 to 50:50.
The size and distribution of the ferrite and
austenite phases in the duplex structure is
dependent on both the thermo-mechanical
(hot working) cycles and the heat treatment.
This relationship is also important in
developing the mechanical and physical
properties of duplex stainless steels
(especially the higher tensile and yield
strengths of duplex in comparison with
austenitic or ferritic stainless steels).
When duplex stainless steels were initially
developed, their weldability was restrained
by the formation and retention of ferrite in
the HAZ. This limited their use as welded
components to sheet and thinner plate
thickness. Technological developments
have improved their weldability.
The weldability of the majority of duplex
stainless steels in thick section may now be
classified as good. The alloying element N,
a powerful interstitial austenite stabiliser,
has contributed most to eliminating the
detrimental effects of retained ferrite in the
HAZ. It promotes the formation of a higher
fraction of austenite within the crystal
structure and assists the reformation of
austenite within the HAZ. The result within
the HAZ is good ductility, toughness and
corrosion resistance equivalent to those of
the parent metal.
Duplex stainless steels which contain N to
achieve the higher balanced austenitic ratio
within the crystal structure are often called
second generation duplex stainless steels.
Duplex stainless steels have the following
properties:
• magnetic;
• non-hardenable by heat treatment;
• good mechanical and physical properties
(generally similar or superior to austenitic
and ferritic stainless steels); and
• excellent corrosion resistance (generally
equivalent or superior to austenitic
stainless steels).
Precipitation-hardening
stainless steels
Austenitic stainless steels are not heat
treatable and have, in the forms used in
fabrication, low strength but excellent
corrosion resistance and fabricability.
Martensitic stainless steels can be heat
treated to develop high strength, but this
limits their fabricability (especially their
weldability). Their corrosion resistance
is only fair to moderate.
The precipitation-hardening stainless steels
were developed to overcome these
limitations and are mostly available as
proprietary alloys.
There are three types of precipitation-
hardening stainless steels:
• martensitic;
• semi-austenitic; and
• austenitic.
ISSF training notes page 6
These terms should not be confused with
the same terms used to designate the
standard classifications of stainless steels.
An exact balance of the chemical
composition is critical to ensure the
development of the phases and precipitates
required to achieve the desired properties.
Several elements, e.g. aluminium (Al),
copper (Cu), Ti and Mo, are used, either
alone or in combination, to obtain the
precipitation-hardening reactions.
Precipitation-hardening stainless steels have
similar or superior mechanical properties to
the martensitic stainless steels and have a
corrosion resistance approaching that of
grade 304 austenitic stainless steel.
The thermo-mechanical (hot working) and
complex heat treatments and welding
procedures which are necessary to develop
and retain the properties of these stainless
steels must be allowed for in any application
of these steels.
The precipitation-hardening heat treatment
is a time-temperature relationship dependent
on the type of alloy.
In the martensitic and semi-austenitic types,
the atoms of the precipitating phase collect in
clusters which are continuous and coherent
with the matrix phase. They are not visible by
ordinary optical means as no actual
precipitation has yet occurred. This is termed
pre-precipitation – maximum strengthening
occurs at this stage. If the precipitation
process is continued, the clusters of atoms
grow and precipitate out as intermetallic
compounds, which form a grain boundary
between the precipitate and the matrix phase.
This reduces the strain and coherence is lost.
Therefore, the strength decreases and the
material becomes over aged.
In the austenitic types, the precipitates are
allowed to form second phase intermetallic
compounds. This increases the strength in
the austenite matrix, but not to the same
extent as in the martensitic and semi-
austenitic types of precipitation- hardening
stainless steels.
Martensitic types
The chemical composition is balanced so
that a martensitic crystal structure results
when cooled to ambient temperature after
solution treatment. These are also called
maraging steels.
Typical alloys include the following:
• 17-4PH (‘grade 630’)
• 15-5PH
07 the metallurgy of stainless steels
• 13-8
• PH13-8 Mo
• stainless W
• custom 450 & 455
Typical properties which can be attained
are as follows:
• 0.2% proof stress 1,200-1,600MPa;
• tensile strength 1,300-1,600MPa; &
• hardness 42-49 HRC.
These are the most used of the precipitation-
hardening stainless steels, used as bar, rod,
wire, heavy forgings, sheet and thinner plate.
Semi-austenitic types
These are essentially austenitic in the
solution annealed condition and then
converted to a martensitic structure by
various heat treatments.
Typical alloys include the following:
• 17-7PH (‘grade 631’)
• PH 14-8Mo
• PH15-7Mo
• AM 350 & 355
Typical properties which can be attained
are as follows:
• 0.2% proof stress 1,250-1,793MPa;
• tensile strength 1,500-1,825MPa; &
• hardness 45-50 HRC.
These are the next most used of the
precipitation-hardening stainless steels,
used mostly as sheet and strip.
Austenitic types
These steels have a stable austenitic crystal
structure.
Typical alloys include the following:
• 17-10P
• A286
• HNM
Typical properties which can be attained
are as follows:
• 0.2% proof stress 675MPa;
• tensile strength 975-1,025MPa; and
• hardness 32-34 HRC.
These are the least used of the precipitation-
hardening stainless steels. However, they
can be used at both higher and lower
temperatures than the other types.
UNS S41003 corrosion-resisting
steel
This is a proprietary alloy which was
developed by Middleburg Steel and Alloys
and commercially launched in 1980. As
other proprietary designations are available,
it is usually specified under the designation
of 1.4003.
It has a Cr content of 11-12% Cr and is,
therefore, classified as a ferritic stainless
steel. However, because of its minimum
Cr content, it is sometimes referred to as
a corrosion-resisting steel.
The Cr content of 3CR12 places it at the
critical boundary of the gamma loop,
i.e. small variations within its chemical
composition which are either austenite or
ferrite stabilisers (formers) could render the
crystal structure either austenitic or ferritic
at high temperatures (see Figure 4, p4).
The composition is, therefore, controlled
during manufacture to ensure a critical
balance between austenite and ferrite exists
at the high temperatures employed for hot
working.
Both C and N are strong austenite formers
and are both limited to low levels in 3CR12.
If the levels of these elements approach the
specified maximum (0.03% each), they need
to be constrained by a further alloy addition
of the stabilising element of Ti. Stable Ti
carbides and nitrides are formed, which
minimise the effect of C and N. Since Ti is
a ferrite former, it has to be counterbalanced
by the addition of Ni, which is an austenite
former.
C and N are kept at levels well below
the maximum specified, so it is no longer
necessary to use Ti to constrain these
elements and Ni to balance the crystal
structure, but it is still an option that
may be used.
The final crystal structure is dependent
on the thermal history.
With the improvements noted above, and
by using a controlled, slow cooling rate
from the final hot rolling temperature, the
austenitic fraction transforms at elevated
temperatures and a predominantly fine
grained ferritic structure develops.
Fast cooling rates would transform the
austenite fraction to ‘martensite’, with the
ferrite remaining. The ferrite/’martensite’
balance is directly related to the
ferrite/austenite which exists at the high
temperatures.
The ‘martensite’ formed in 3CR12 is not the
same as that in martensitic stainless steels.
It has a very low C content and is, therefore,
not highly stressed. The atoms are arranged
imperfectly with vacant atomic sites (i.e.
highly dislocated or of high dislocation
density). This lath martensite is relatively
tough and ductile.
ISSF training notes page 7
Annealing material is necessary to develop
strength, toughness and ductility, which are
required for general engineering materials.
The annealing temperature is below that at
which the ‘martensite’ would transform to
austenite. This annealing is, essentially,
more correctly a tempering operation.
Hot forming operations must be carried out
at a sub-critical temperature range (600-
700˚C) to prevent any inversion to an
austenitic crystal structure.
Indiscriminate heating of 3CR12, either
for fabrication purposes or in operation,
can seriously affect the properties of the
material.
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
nitrides;
• 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.
07 the metallurgy of stainless steels
CONCLUSION
This paper has looked at the main factors
which govern the internal crystal (micro)
structures and determine the different
classifications of stainless steel. The
crystal structure also governs the various
mechanical, physical and fabricational
properties of stainless steels. These
properties make stainless steels an extremely
versatile group of materials.
It should be noted that some aspects have
been greatly simplified to illustrate the basic
principles. Figures 5, 6 and 7, p4-5 are not
exact, but merely depict the changes which
take place in the crystal structure.
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.
ISSF training notes page 8