Heat Treatment and Related Processes

Depending upon t h e composition of t h e parent material,

welding process employed and the associated welding conditions
involved various heat treatment and related processes may take
place or may be made to take place for achieving the desired end
product. Some of t h e well known processes and treatments
amongst them include the following.

1. Annealing,
2. Sub-critical Annealing,
3. Spherodization,
4. Normalising,
5. Quench hardening,
6. Tempering,
7. Secondary hardness,
8. Austempering,
9. Martempering,
10. Stress relieving,
11. Solution treatment,
12. Precipitation hardening or Age hardening,
13. Strain age embrittlement,
14. Temper embrittlement,
15.
16. Carbide precipitation and sensitization.

Brief description of these processes follows.

3.6.1. Annealing
Welding may seriously affect the size and the conditions of the
grains of which the material is composed. Depending upon the
welding process used, the grains of the material may grow to large
size or they may be distorted due to the stresses set up during
welding and subsequent cooling. Such stresses are corrected by
annealing and the grains refined, so that the material becomes
softer and more ductile, and free from residual stresses.
 C
400 -
300 -
200 -
100- , 0.83'~
0 I I I l l l l l
0 '0.2
O/o *c
l a 1 Temperature rang& f o r f u l l and
-
0.4 0.6 0.8 1.0 1.2 1.4 1.6

isothermal annealing.

Furnace cooling ( f u l l annealing 1 TT

Time -
( b ) Time -temperature cycles f o r f u l l onneabng and isothermal
annealing processes.
Fig. 3.27. Temperature range and heating and cooling cycles for

full and isothermal annealing processes.

For annealing or full annealing a steel weldment is heated to

30 to 50°C above the upper transformation temperature (A3)which
varies with the carbon content of the steel. It is held at that
temperature long enough for the carbon to distribute itself evenly
throughout the austenite. For most practical purposes it is held
1
at the annealing temperature for 2 - minute per mm thickness of I
2
material. The steel is then cooled slowly, preferably in a furnace
or buried in hot ashes or lime so as to cool at a rate of 55"Chr or
below. Microstructure of steel obtained with carbon content of 1
0.83% or less is normally grains of pearlite and ferrite. A variant I
of full annealing called isothermal anneal is sometimes employed.
3.6.1.1. Isothermal Annealing
Full annealing takes considerable time and valuable furnace
capacity. To overcome these drawbacks isothermal annealing may
be employed. In isothermal annealing the weldment is heated to
and held at the full annealing temperature of 30 to 50°C above
A, temperature followed by cooling to and holding in a salt bath 1
at 650°C until the steel attains that temperature and transforms 1
completely to pearlite and then cooled freely in air.
Annealing temperature range for full and isothermal annealing
alongwith thermal cycles involved are shown in Fig. 3.27.
3.6.2. Subcritical Annealing
In this process steel is heated to about 650°C; this temperature
is high enough to produce both recrystallisation and uniformity of
structure. After the heating it is cooled freely in air. If a steel with
prior ferrite-pearlite structure is given this treatment the surface
tension effects around the cementite lamellae are sufficient to
contract the latter into rounded carbide grade. w e n applied to
higher carbon steels this process causes the cementite to assume
a spherical shape that makes it easier to machine, and work it
subsequently. A similar structure is obtained when the steel has
a prior hardened structure e.g. HAZ, but in this case the carbides
are more finely dispersed. Fig. 3.28 shows the heating and cooling
cycle for subcritical annealing'on a time-temperature graph. This
process was formerly called process annealing.
3.6.3. Quench Annealing
It is the treatment used for softening austenitic stainless
steels, including Hadfield manganese steel. In these steels, the
martensite point is below room temperature, but if the steel is
cooled too slowly from high temperatures, carbides may
precipitate and the austenite may transform, at least in part to
ferrite. To soften them, it is theefbre necessary to heat to 1000 to
llOO°C, to ensure all the carbides are taken into solution, and then
to air-cool or even water-quench.
 looor

l a 1 Temperature range for sub-critical

annealing.

Time hours -
I b 1 Time-temperature graph for subcritical annealing.

Fig. 3.28. Temperature range and schematic representation of heating and

cooling cycle employed for sub-critical annealing process.
 3.6.4. Spherodization
It is a process by which steels with carbon content more than
0.40% are made softer. The steel is herted to just below the lower

Fig 3.29. Typlcal microstructure of spherodised steel (0 40%C)

transformation temperature A, (723°C) a n d held a t t h a t
temperature for a number of hours. This results in the cementite
collecting into spherical shaped particles leaving ferrite throughout
the remaining structure a s shown in Fig 3.29. Coolin:, is allowed to
take place very slowly throughout the upper part of the cooling range.
-
800
4 2 hrs
r---7
Long hours
A, ( 7 2 3 ' ~)

UI

Time hours -
Fig. 3.30. Time-temperature diagram for two types of spherodizing processes.
 More recently faster method of spherodization has been
adopted by which the steel is first heated to slightly above the
lower critical temperature (A,) and held there for about two hours.
The heat is lowered relatively fast to a temperature of 625 to
705"C, the cooling rate being as rapid as is possible to attain. The
steel is then held a t t h e lower spherodizing temperature,
 I

for 4 to 15 hours, depending upon the degree of

1!
spherodization and softness required. After soaking the steel a t
625 to it is removed from the furnace or furnace cooled, if
softer and stress-free steel is required. Final hardness depends
upon the degree of spherodization and the size of the spheroidal
cementite particles obtained by this process. Fig 3.30 shows the
spherodising temperatures and the time-temperature relationship
in the two types of spherodising processes.
3.6.5. Normalising
I
Normalising is the process of heating steel 30 to 50°C above
the upper transformation temperature for the particular
composition of steel being normalised to modify the grain size, to
make the microstructure more uniform and usually to improve
mechanical properties. I t is held a t t h a t temperature just
sufficient tim'e for steel to transform to austenite; followed by
cooling in still air. In transforming to austenite the pearlite grains
absorb the ferrite, giving rise to many small grains of austenite
which, on fairly rapid cooling, transform back to fine-grained
ferrite-pearlite structure. Fig. 3.31 shows the normalising range
on iron-carbon equilibrium diagram and the thermal cycle
involved in normalising.
Normalising is faster than full annealing and is often used in
the welding industry to refine any coarse grain structure, to
reduce stress after welding or to remove any hard zones in the
HAZ. Because of fine-grained structure, the normalised steel has
good toughness properties.
Normalising treatment is particularly applicable to low carbon
and some low alloy steels. A typical example of this process is
normalising of mild steel pipes. The pipes are heated to between
this temperature being held for a period of two
minutes for pipes up to 100 mm inside diameter, and for five
minutes with over 100 mm diameter followed by slow cooling in
still air.
3.6.6. Quench Hardening
In quench hardening steel is heated to 30-50°C above the
upper transformation temperature a n d held a t t h a t
temperature long enough for the internal structure to transform
to austenite. Overheating and prolonged heating should be
avoided in order to prevent grain growth. Steel is then quenched
by immersing i t in oil, water or some other cooling media.
Successful quenching converts the austenite to martensite while
slower cooling rates may yield pearlitic structure. The properties
produced will depend upon the carbon content of steel, the
temperature to which it is heated, the time for which it is held a t
that temperature, and the cooling rate. If carbon, in steel, is less
than 0.15%, no effect of quenching may be observed. If carbon
content is more than 0.83%, no attempt is made to convert the free
cementite to austenite because this constituent is already hard
and the high temperature required to convert it into austenite
would produce a coarse structure which will make steel more
brittle after quenching without any appreciable increase in
hardness and strength. The hardening capacity of steel increases
with the increase of carbon up to about 0.60%. Fig. 3.32 shows the
hardening range for steel and the thermal cycle used for quench
hardening.
When water is used as the quenching medium it is held a t
25°C or below and is continuously agitated during the quenching
operation to achieve more uniform and faster cooling action. A 5%
sodium chloride brine solution provides a more satisfactory cooling
medium for c'arbon steels; i t gives faster and more uniform
quenching action and is less affected by increase in temperature.
A 3 to 5% sodium hydroxide quenching bath is also recommended
for carbon steels; it provides even faster cooling rates than sodium
chloride bath.
Oil quenching is resorted to for thin sections of carbon steel
and high alloy steels because of less danger of cracking and
reduced distortion and quenching stresses. Oil cools steel much
more slowly during the last cooling stage. This is desirable as it
results in much less danger of severe internal stresses, warping
and cracking.
Air cooling is employed for some high alloy steels of the air
hardening type.
3.6.7. Tempering
A quench hardened steel with a structure of martensite is very
brittle. To reduce this hardness steel is given a tempering
treatment in which it is reheated to a temperature of 180 to 650°C,
depending upon the properties required, followed by air cooling.
This improves toughness and ductility a t the expense of hardness
and strength as shown in Fig. 3.33. Sometimes tempering to
within a temperature range of 260-310°C may show a loss of
toughness; that is why this range of temperature is referred to as
Brittle Tempering Range.
In general longer the time of treatment a t a given tempering
temperature t h e better t h e result from i t . I t i s therefore
recommended that a t least one hour be allowed a t any tempering
temperature for satisfactory results.
Tempering of steel is usually accomplished in liquid bath such
as oil, salt or lead. Tempering is also successfully accomplished in
 ( a ) Tempering range for steels

High

Low I I 1 1 I I 1 I
0 100
200 300 400
5.00 600 700

Temper~ng temp., C
( b ) E f f e c t of t e m p e r i n g on tnech,anical
properties of steel
Fig. 3.33. Tempering range and the effect of tempering
on mechanical properties of steel.

air tempering furnaces wherein the hot air is circulated around

parts to be tempered. Fig. 3.34 shows a combined hardening and
tempering thermal cycle as a time-temperature diagram.
 Time , hrs -
Fig. 3.34. Time-temperature diagram representing a combined
thermal cycle for quenching and tempering.

3.6.8. Secondary Hardness

In alloy steels which contain certain carbide forming elements
such as tungsten, molybdenum, vanadium, etc., tempering after
hardening produces precipitated carbides in such finely dispersed
form that the hardness is considerably greater than after the
original hardening. At the same time, the breakdown of the
martensite results in increased toughness. Thus, for example, high
speed steel reaches its maximum hardness only after hardening
and tempering to about 550°C, by what is known as Secondary
Hardening Effect. Steels of this type are also, in consequence,
resistant to softening at quite high temperatures and, therefore,
are suitable for high temperature service applications.
For such steels a double tempering treatment is usually
adopted, the steel being air-cooled between the two operations.
The advantage of double tempering accrues from the fact that,
after hardening, the steels normally contain a certain amount of
retained (i.e. untransformed) austenite, which transforms to
martensite, wholly or in part, after the first tempering treatment.
The second tempering treatment breaks down this newly formed
martensite and brings about additional secondary hardening.
Besides increasing the hardness, this practically eliminates the
presence of untempered martensite.
 Time - I
Fig. 3.35. Schematic diagram of austempering heat treatment cycle superimposed
on isothermal transformation diagram for a medium carbon steel.

3.6.9. Austempering
If steel from hardening temperature is supercooled quickly to
about 290°C,austenite at this temperature transforms to a fine
pearlitic or bainite structure of uniform hardness of about
Rockwell, R,56. It requires the holding of austenite a t 290°C for
about one hour to complete this change. This method of tempering
without the formation of martensite is called austenlpering i.e.,
the direct tempering of austenite. This treatment is also
sometimes referred to as Hot Quenching. Fig. 3.35 shows a
. thermal cycle for this process.
It is accepted that the hardness of R,56 obtained by austem-
pering is much tougher than the same steel treated to the same
hardness by the usual method of quench hardening and tempering.
Also, non formation of martensite eliminates much of the danger
of cracking, and reduces the amount of distortion or warping caused
by rapid quenching to room temperature required for the formation
of martensite in normal quench hardening process.
3.6.10. Martempering
Martempering is carried out by cooling the steel from the
hardening temperature through t h e pearlite range to a
 Fig. 3 cycle

temperature a t or a little above the temperature

holding a t this temperature until the temperature of steel is
uniform throughout and finally air cooling through the martensite
range. Fig. 3.36 shows a t h e r m a l cycle for martempering
treatment. The aim of martempering is to avoid the risk of
cracking due to the thermal stresses set up during rapid cooling
from high temperatures. This also makes it possible to cool slowly
through the martensite range, thus minimising the additional
s t r e s s e s s e t u p a s a r e s u l t of t h e volume change which
accompanies t h e transformation of austenite to martensite
thereby constituting a risk of cracking.
It is a condition of successful martempering that no trans-
formation shall occur during the initial cooling. Ordinary carbon
steel, for example, is hardly suitable since it undergoes rapid
transformation a t all temperatures between the pearlite and
martensite ranges. High alloy steels on the other can be
held for long periods a t intermediate temperatures without the
risk of transformation as is evident from the TTT diagram of Fig.
2.29.
Martempering treatment is also sometimes referred to as step
hardening
 3.6.11. Stress Relieving .
Stress relieving is carried out after welding to remove or
reduce welding stresses. Total elimination of residual stresses
after welding is possible only by annealing. that leads
to excessive softening a n d reduction i n strength therefore
stress-relieving is adopted in which the welded (steel) component
is uniformly heated to below the recrystallisation temperature

Time -
Fig. 3.37. A schematic thermal cycle for stress-relieving
treatment of low carbon steel components.

(A,)-normally to 550-650°C for mild steel and held there for a

1
period of 2 - minutelmm thickness the component depending
2
upon the thickest section present. This is followed by slow cooling,
preferably i n a furnace, atleast up to a temperature of about
400°C. Fig. 3.37 shows the thermal cycle for stress relieving
treatment.
Examination of s t r e s s relieved components shows t h a t
recrystallisation of the ferrite takes place which contributes to the
relaxation of residual stresses of the welded joint.
Sometimes low temperature stress-relieving is carried out a t
about 450°C for a longer period of time. At this lower temperature
very little, if any, recrystallisation of the ferrite takes place. If the
welded component is held a t 450°C for one hour, and slowly cooled
thereafter, about 40% of the stresses will be relieved, that may be
regarded as adequate for some purposes.
Further, it may be known that any gases trapped in the cooling
weld may be released from the welded component during the
stress relieving treatment.
Stress relieving is frequently adopted, among other things, for
welded pressure vessels. Usually by this treatment residual
stresses are decreased to a tolerable level without any marked
decrease in mechanical strength or change in microstructure.
However, such a treatment rarely makes the structure completely
free from residual stresses.
3.6.12. Solution Treatment
I n some alloys solid solubility is gradually increased by
heating; Fig. 3.38 shows a part of the equilibrium diagram for a
system of this type. The alloy of composition 'X' will, if slowly

-soak
--

Heat \

&& "....
.. .5;
Solution
treatment
.temp*

Alloy x

Equillbrium diagram

Fig. 3.38. Equilibrium diagram for a solid-solution alloy and the

process details for its solution treatment.

cooled from its molten state, consi'st of solid solution of metal B in

metal A, in which are embedded particles of metal B. When this
alloy is reheated to a high enough temperature, the excess metal
B will be taken into the solid solution. Now, if it is quenched there
will be insufficient time for precipitation of metal B to occur, and
the excess B atoms will be trapped in the solid solution and the
alloy will be in a condition of non-equilibrium. At this stage the
excess B atoms will be scattered throughout the structure and the
overall effect will b e to produce improvement i n corrosion
resistance and increase in tensile strength with good ductility.
Heating and quenching to produce this effect is called solution
treatment, and is the first step towards increasing the strength of
the alloy. Cold working may be carried out after solution
treatment, thereby increasing the strength without any effect
upon the corrosion resistance of the solid solution alloy. Such a
treatment is popularly applicable to some aluminium alloys e.g.,
AI-Cu alloys.
3.6.13. Precipitation Hardening or Age Hardening
If a solution treated alloy is reheated but to a lower
temperature than that required for solution treatment, the atoms
of metal B will have enough energy to start their precipitation
from the solid solution so that the e q uilibrium is restored.

* )$j\y.&
I

....., .

Solution
treatment
Precipitation hordenina

Fig. 3.39. Schematic representation of solution treatment

and precipitation hardening processes.

Provided the temperature is not too high they will not leave the
solid solution but form regidns within it where the B population
is higher and so locally strengthen the solid solution. The alloy is
then given a long soaking time, followed by free cooling. Such a
heat treatment is known as Precipitation Hardening or Age
Hardening or simply Ageing. Fig 3.39 shows the thermal cycle for
solution treatment cum precipitation hardening.
 Testing temperature -
Fig. 3.40. Effect of ageing treatment on impact values.
.Columnar

~fit is cold
rolled aiuminium
in which the cookscence
of particles produces
Region d grain growth lowest hardness
with gran sire increasing
II)
U)
w~thincreasing temperature
0)
C
~2
0
I
Highest
I unaffected
by heat
i
I

-
-0I
I

0
r
ri Ub
Lowest e ss
id
Fig. 3.41. Effect of overaging on hardness of aluminium alloy weld.
(After Kenyon)
 The overall effect of precipitation hardening treatment is to
produce increased strength and hardness a t the expense of
ductility resulting in lower impact values as shown in Fig. 3.40.
Consequently an ageing-resistant metal, for example steel, should
have a stable transition, even if it is subjected to ageingtreatment.
Hardening of an alloy by ageing is said to be due to strain in
the crystal structure set up by the migration of B atoms (solute)
to form local clusters. Most heat treatment alloys are heat treated
by solution treatment followed by precipitation treatment and a
few among these are of naturally ageing type.
If precipitation treatment is continued for too long, the local
aggregation of atoms results in the formation of separate particles
with a crystal structure differing from the matrix. The local strain
in the crystals is thereby relieved and the hardness of the alloy is
decreased and,it is said to be overaged. For a given alloy, the higher
the precipitation treatment temperature the sooner the optimum
conditions are reached.
Welding of age-hardened aluminium alloys results in a
softened zone alongside the weld due to the overageing effect as
shown in Fig. 3.41.
3.6.14. Natural Ageing .
. In the case of some alloys, precipitation after solution
treatment occurs a t room temperature, starting very soon after
quenching and it takes about 4 days. This process of precipitation
hardening is called natural hardening. Duralumin (A1+4%Cu)is
a typical natural ageing alloy.
E Amongst steels mild steel is the most susceptible to ageing. If
nitrogen is present in steel, iron nitride can be precipitated at
temperatures below A,. Precipitation of iron nitrides (Fe,,N2) at
room temperature is known as Steel Ageing. Ageing can take place
in a zone heated to temperatures around 200-300°C if free
nitrogen is present in steel. .
New metallurgical procedures have helped in lowering the
nitrogen content in steel, or binding it to a stable nitride phase
(e.g. AlN), and consequently present-day steels are generally not
susceptible to ageing.

Precipitates arising in the

austenkc zone slow down growth
of y-grains and thus make steel fine-grained. In microalloyed steels
nitrides and carbonitrides of alloying elements (Ti, Nb, V, Al, etc.)
chemically bind nitrogen, thereby making the weld more resistant
to ageing.
 Precipitation hardening in austenitic stainless steels. occurs
through formation of an intermetallic phase with Al, Ti and P.
These steels have corrosion resistance comparable to that of other
stainless steels. Precipitation-hardened austenitic stainless steels
become brittle after being exposed for several thousand hours to
temperatures above 290°C. Their usability is therefore limited to
a temperature below about 320°C in long term operations. In
short-term service, however, these steels possess adequate
strength at temperatures up to 500°C and corrosion resistance up
to about 820°C.
Body centred metals are affected similarly by bombardment
with massive fast particles. The bombaradment produces atomic
displacement in the lattice, causing important changes in physical
properties. One of these changes in physical properties is marked
rise in transition temperature. This effect is termed irridiation
damage or irradiation ageing. An important resemblance to the
normal ageing is the annealing of the damage so that physical
properties revert to their former values.
3.6.15. Strain Age Embrittlement
The normal precipitation hardening or Ageing process may also
take the form of strain ageing in the first stage of which nitrogen
atoms segregate at dislocation lines, thereby slowing down the
dislocation mobility. In the second stage .nitrides are precipitated
at dislocation lines, and in the third stage precipitation occurs
throughout the entire volume. This results in reduced charpy
energy and thus lower fracture toughness. That is why this process
is also referred to as strain-age embrittlement.
Strain ageing is a possibility where the metal has been
strained and heated within the temperature range of 100-300°C.
This phenomenon is associated with a fine precipitation or
clustering located at dislocation within the ferrite grains which
are observable under favourable conditions by transmission
electron microscopy (TEM). .
Nitrogen in a carbon or C-Mn steel may be responsible for
strain-age embrittlement. If a nitrogen-bearing steel is subjected
to plastic strain and simultaneously or subsequently heated at a
temperature of about 200°C, notch ductility is reduced. Steel
produced by Bessemer process normally contains high amount of
N, that is why many bridges made with such steels, prior to
Second World War, failed by brittle fracture, and these failures
were attributed to strain-age embrittlement.
The known association of strain-age embrittlement with
nitrogen suggests that the particles are nitrides or carbonitrides.
 Their effect is to shift the impact transition temperature
upwards by about 50°C.
Also, it has been proved that if a small crack forms adjacent
to the weld boundary and is then strained and reheated by
successive weld passes, the tip of the crack can be sufficiently
embrittled to initiate a brittle fracture. The root passes of a
multi-pass weld are similarly strained and reheated and this may
also lead to embrittlement.
Austenitic steels may embrittle a t elevated temperature
due to a strain ageing mechanism during post weld heat treatment
(PWHT) or in service.
Strain-age embrittlement may be prevented by the addition of
strong nitride forming elements such as A1 or Ti but this remedy
is normally not possible for arc welding electrodes because A1 and
Ti burn out in the arc. However, in self-shielded welding, large
amounts uf aluminium and magnesium are often added to the flux
core to provide a vapour shield, and the amount of aluminium i n t '
the weld deposit may be sufficient to prevent embrittlement of the
root passes.
3.6.16. Temper Embrittlement
Ferritic alloy steels may be embrittled by the formation of
unfavourable transformation products, through grain boundary
segregation, called temper embrittlement. If an alloy steel is held
for a period of time within the temperature range 375575°C or,
in the case of more susceptible compositions, is cooled slowly
through this range, it may lead to unwanted increase in the impact
transition temperature. The susceptibility of a steel to temper
embrittlement is normally measured by the temperature shift of
either the 55 J impact energy or the 50% fracture appearance
transition temperature (FATT).
Plain chromium steels are highly susceptible to temper embrit-
tlement, but the addition of 0.5% Mo greatly reduces this tendency.
Elements that markedly increase the degree of embrittlement are
Sb, Sn, P, and As, while Mn, V, B, and Si increase susceptibility
slightly. Weld metal of the same composition as the alloy plate is
also subject to temper e brittlement. The effect is reversible, and
steel may be de-embritqd by heating at temperatures of 600°C
and above. It is caused by segregation of tramp elements to the
prior austenite grain boundaries, and fractures are typically inter-
granular.
Embrittling and alloying elements all act together, for example
Mn and Si increase the 'effects of P and Sn, For Q & T, 2.25 Cr-1
..
 Fig. 3.42. Correlation between the embrittlement susceptibility factor J and the
fracture appearance transition temperature for long-term isothermal heating.

Mo, steel with Arsenic below 0.02% and Sb 0.004%, the

susceptibility to embrittlement may be measured by what is
known as J factor, where J is given by the following equation.
d = ( ~ n + S i ) ( ~ + ~lo4
n)x ...(3.7)

Fig. 3.42 shows the correlation between the J factor and the
fracture appearance transition temperatwre for long term isother-
mal heating. The J factor can be redwed by lowering the Si-con-
tent and controlling P, As, ~ n and , Sb. The Mn level, however,
cannot be reduced without sacrificing tensile strength.
Temper embrittlement is of concern in the operation of heavy-
walled pressure vessels for nuclear power and petro-chemical
plants. In case cracking is found during an inspection of the shell,
then in order to assess the integrity of the vessel it is imperative
to know the fracture toughness. From the initial properties and
the service life and using a correlation such as that shown in Fig.
3.42, it may be possible to calculate the fracture risk. Vessels used
for hydrogenation such as hydrocrackers are especially vulnerable
because on cooling from operating temperature they contain
supersaturated hydrogen, which is a further embrittling factor.
3.6.17. Graphitisation
Under non-corrosive conditions C and C-Mn steel welds may
lose strength due to the phenomenon called graphitisation. This
happens if steel is held at temperatures above 450°C for long
periods of time, resulting in the decomposition of the cementite,
eventually forming nodules of graphite in a low carbon iron
matrix. The breakdown of cementite appears to be promoted by
1
the addition of aluminium to the steel. Carbon and C- -Mo steels
2
are both susceptible to this defect; however, in carbon steel the
graphite nodules tend to be scattered and do 'not form localised
areas of weakness. In C-'MO steel, on the other hand, the
2
graphite forms eyebrows in the HAZ, and there have been isolated
failures in steam lines from this cause. Cr-Mo steels do not suffer
graphitisation since the carbides in it are more stable. For this
reason, Cr-Mo material is often specified for service at elevated
temperature, particularly for piping, where in other respects
1
C- -Mo steel would be ,adeqhate.
2

Bulk Cr I I
level

Cr level
around
----
carbides I I
I

Distance -
Fig. 3.43. Schematic illustration of the effect of
sensitisation on local chromium level.
 3.6.18. Carbide Precipitation and Sensitization
If an unstabilised Cr-Ni austenitic stainless steel is welded or
brazed it experiences chromium carbide (Cr2,C,) precipitation a t
the grain boundaries, Fig. 3.43, resulting in loss of corrosion
resistance, due to depletion of chromium, in the affected zone. This
tendency towards intercrystalline carbide precipitation is also
known a s Sensitization a n d is affected by different factors
including material composition and thickness, heating time, pwht
(post weld heat treatment), type of microstructure, and t h e
influence of stabilizing elements. The ill effect caused by the
carbide precipitation is referred to as weld decay.

900 Carbon content (O/O)

I

Fig. 3.44. Time-temperature relationships !C-curves) for formation of harmful

amounts of Cr-carbides in stainless steel with various carbon contents.

The major factor causing carbide precipitation is the carbon

content of steel. Steels containing 0.08% or less carbon may suffer
carbide precipitation in thick sections, but not when the thickness
is 3 mm or less. Steels containing 0.03% or less carbon and those
stabilised by the addition of TIor Nb are immune to weld decay
in all thicknesses. The time-temperature-sensitisation (TTS) or
C-curves for various grades of Cr-Ni steels are shown in Fig. 3.44.
For effective control of carbide precipitation in fully austenitic
stainless steel with around 10% Ni, to avoid grain boundary
corrosion, the relationship between maximum Cr and C contents
is given by,
Cr 2 80C + 16.8 ...(3.8)
indicating that standard 18% Cr steel should contain no more t h a n
0.015% c .
The microstructure of t h e steel can affect t h e degree of
sensitization. For example, the presence of &ferrite lowers t h e
sensitization temperature for austenitic stainless steel. While
fully austenitic stainless steel containing 0.05% C has a maximum
sensitization temperature of 750°C , it falls to around 500°C for
steel with 25% delta ferrite. This is because the Cr- content of the
ferrite is markedly higher than that of the austenite in equilibrium
with it. Thus the Cr-rich &ferrite has a higher resistance to grain
boundary attack.
The microstructure of stainless steel becomes sensitive to in-
tercrystalline corrosion in certain media, when the weld or the HAZ
remains longer in the critical temperature range of 425 to 815°C.
Within these limits of temperature chromium carbide, Cr23C6,can
precipitate a t the grain boundaries. For 1818 Cr-Ni steel with a
carbon content of about 0.07%, a dwell time of 6 minutes a t 700°C
is sufficient to induce sensitization (susceptibility to intercrystal-
line corrosion). Therefore, if such steels of higher thickness are to
be welded, they must contain lower carbon contents, with longer
sensitization time. Given in Table 3.1 are maximum plate thick-
nesses with permissible' carbon contents, for steel of type 1818
Cr-Ni, which are not prone to sensitization by welding.
Table 3.1. Permissible Carbon Contents for Different

Thicknesses of 1818 Cr-Ni Steels

S. No. Plate Thickness Permissible Carbon content

(mm) (%/
0.18

0.08

0.06

0.05

0.04

0.03

The problem of sensitization of weld metal or t h e HAZ may be

overcome by PWHT, by annealing a t 1050-1100°C followed by
cooling in water, or air. This results i n dissolving the chromium
carbides. The so-called stabilization anneal a t a temperature of
900 to 950°C does not solve the problem a s it leads to shifting the
sensitization zone; even with low carbon content.