Professional Documents
Culture Documents
Dr.SantoshS.Hosmani
DEPT. METALLURGY & MATERIALS SCIENCE,
COLLEGE OF ENGINEERING, PUNE
HeatTreatmentof
Stainless Steels StainlessSteels
Simple austenitic steels usually contain between 18 and 30wt% Cr 8 to
Issue of Sensitisation in Stainless Steels
Simple austenitic steels usually contain between 18 and 30wt% Cr, 8 to
20wt% Ni and between 0.03 and 0.1wt% C.
The solubility limit of carbon is about 0.05wt% at 800 C, rising to 0.5wt% at
1100 C. Therefore, solution treatment between 1050 C and 1150 C will
take all of the carbon into solution and rapid cooling from this temperature
range will give a supersaturated austenite solid solution at room
temperature.
However, slow cooling or reheating within the range 550800 C will lead to
the rejection of carbon from solution, usually as the chromiumrich carbide, the rejection of carbon from solution, usually as the chromium rich carbide,
Cr
23
C
6
, even when the carbon content of the steel is very low (<0.05 wt%).
Carbon tends to diffuse toward grain boundaries in austentic stainless steels
Issue of Sensitisation in Stainless Steels
during material preparation, welding or improper heating in the temperature
range of 425 C to 815 C. This leads to precipitation of (Fe,Cr)
23
C
6
adjacent to
the grain boundaries. The chromium concentration in the grain boundary region
i d d hil h h i i i h i i f h i i is reduced while the chromium concentration in the interior of the grain remains
unchanged. This process is referred to as sensitization.
The chromium depleted grain boundary region is less resistant to corrosion than
the interior of the grain. If the chromium concentration falls below a critical
value, preferential corrosion takes place at the grain boundaries while the
interior of the grains remains passive under certain electrochemical conditions.
This process is known as intergranular corrosion (IGC).
The precipitation of the chromium carbides is process in which diffusion of
carbon plays a critical role; therefore, the ageing conditions, i.e. the p y g g
temperature and time of exposure to heat, play a critical role in determining the
amount of chromium in the grain boundaries after sensitization. The fraction of
chromium in the region adjacent to the grain boundary decreases with the
increase in sensitization time in the temperature range where carbide formation
occurs. A minimum critical Cr content is required in the grain boundaries for the
material to remain resistant to IGC.
Issue of Sensitisation in Stainless Steels
FIGURE: Complete intergranular cracking of the sensitized type 304
stainless steel in 400 hours of exposure to high purity water at
2800C. The figure shows (a) intergranular facets of the fracture
f d (b) d i t l b h ti surface and (b) secondary intergranular branches emanating
from the main intergranular crack.
Ref.: BARC HIGHLIGHTS. Engineering - Material Research
Issue of Sensitisation in Stainless Steels
More grain boundary
martensite is present.
The 1112% Cr-type ferritic stainless steels are susceptibile to sensitization
during continuous cooling after welding at low heat input These steels transform
The ferrite-ferrite grain boundaries are sensitized, whereas the
ferrite-martensite phase boundaries are largely unattacked
during continuous cooling after welding at low heat input. These steels transform
partially to austenite in the high-temperature heat-affected zone (HTHAZ) during
cooling, with the austenite transforming to martensite at lower temperatures. The
ferrite-martensite boundaries were generally observed to be unsensitized. The
results suggest that if enough austenite forms in the HTHAZ during cooling, it acts
as a carbon sink to dissolve excess carbon. This prevents supersaturation of the
ferrite phase and subsequent carbide precipitation that could lead to sensitization
of the ferrite grain boundaries Excessive welding speeds appear to promote of the ferrite grain boundaries. Excessive welding speeds appear to promote
sensitization during low heat input welding.
Ref.:M.L.Greeff andM.duToit:WeldingJournal(Nov.2006)243.
Issue of Sensitisation in Stainless Steels
FIGURE: Sensitized HAZ of 304
FIGURE: Sensitized 304 stainless steel
pipe after service in dilute nitric acid. Note
FIGURE: Sensitized HAZ of 304
stainless steel plate. Chromium
carbides are indicated by chains of
dark particles along austenite grain
b d i
pipe after service in dilute nitric acid. Note
that the weld metal and the HAZ closest
to the weld metal are unaffected, but the
region of the HAZ that reached peak
t t i th f 480 t
boundaries.
temperatures in the range of 480 to
870C is severely attacked.
Ref.:WeldingHandbook,8thEdition,Vol.4,p.273
Issue of Sensitisation in Stainless Steels
Possible Resolution Treatment: after welding, the steel
can be reheated to 9501100 C to allow Cr
23
C
6
to can be reheated to 950 1100 C to allow Cr
23
C
6
to
redissolve, and further precipitation is then prevented by
rapid cooling to avoid the Cshaped curve.
Issue of Sensitisation in Stainless Steels
As shown in the timetemperature sensitisation curves below, the precipitation
of carbides occurs over time at temperatures in the range of about 450850 C.
The time for precipitation to occur is highly dependant upon the amount of
carbon present in the steel, so low carbon content increases resistance to this
bl problem.
Reduction of the carbon Reduction of the carbon
content below 0.03wt% is
possible by modern steel-
making methods involving
l i F oxygen lancing. For
complete immunity from
intergranular corrosion in
18/8 steels, a carbon level ,
of 0.02wt% should not be
exceeded.
Recall yourself from the earlier lectures that:
Addition of metallic alloying elements (except Co) shifts TTT curves Addition of metallic alloying elements (except Co) shifts TTT curves
towards right. But, we made little comment about effect of carbon.
However, I believe that, for a constant concentrations of partitioning (or
carbide forming) metallic alloying elements, if we increase the carbon
content, TTT curves for carbide formation will shift towards left (in the
similar way as mentioned on earlier slide). See also the next slide (this is
same slide which we discussed in the past) in support of this argument.
In the case of alloy steels containing carbide-forming elements such as Cr, Mo,
W d V th i it ti di h t l l t d f W, and V, the precipitation diagrams have two clearly separated ranges of
pearlite and intermediate transformations. Each of the ranges is characterized
by its own C-shaped curves.
When the carbon content of structural steels is up to 0 4 0 5% the stage I When the carbon content of structural steels is up to 0.40.5%, the stage I
transformation is shifted to the right relative to the stage II transformation; if the
carbon content is higher, stage I is found to the left of stage II.
49
0.8%C steel
1.13%C steel
0.8%C steel
0.38%C alloy steel
But, for En 8 (0.4%C) steel, time indicated by dashed line
is smaller than 0.8%C steel why??
0.8%C steel
0.4%C steel (En 8)
The possible reasons could be as follows (this is as per my thought /
opinion):
It is known that the position of TTT diagram can be affected by prior
austenitic grain-size (i.e. grain-boundary-area per unit volume). In
case of 0.4% C steel, there is a formation of ferrite grains in the case of 0.4% C steel, there is a formation of ferrite grains in the
austenite grains prior to the carbide formation (here, carbide is
cementite, Fe
3
C). Due to the formation of ferrite, total grain-boundary-
area per unit volume increases. Therefore, available sites for the
formation of carbide (here, Fe
3
C) increase, i.e. kinetics of the carbide
formation accelerates.
However in 0 38%C alloy steel shift of TTT diagram towards right However, in 0.38%C alloy steel, shift of TTT diagram towards right
side (compared to eutectoid steel) is possibly due to the other metallic
alloying elements in the steel (and may be not due to the decrease in
carbon content) carbon content).
I strongly think that: for the alloy steel with increase in carbon content
(without disturbing other alloying elements concentrations), if there is
no other phase formation (like, above mentioned ferrite formation prior
to carbide formation), TTT curve should move towards left
Issue of Sensitisation in Stainless Steels
Use of strong carbideforming Use of strong carbideforming
elements, Nb, Ti niobium and
titanium form carbides which are
much more stable than Cr
23
C
6
, so much more stable than Cr
23
C
6
, so
they preferentially combine with the
available carbon and thus lessen the
opportunity for Cr
23
C
6
to nucleate.
3 6
TiC and NbC are much less soluble in
austenite than is chromium carbide,
so they will form at much higher so they will form at much higher
temperatures as relatively stable
particles. These should remain
relatively inert during commercial y g
heat treatments involving solution
temperatures no higher than 1050
C, and thus minimize the possible
nucleation of Cr
23
C
6
.
HT of Austenitic Stainless Steels
HT of Austenitic Stainless Steels
Before going into the different heat treatments for austenitic stainless
steels, it is important to remember two particularly important
properties of these steels: (i) low thermal conductivity and (ii) high
thermal expansion coefficient.
The thermal conductivity of the austenitic stainless steels is low; about
fifth f th l f i d thi d f th d ti it f one fifth of the value for pure iron and one third of the conductivity of an
AISI 1025 carbon steel.
The thermal expansion coefficient of the stainless steels is about 50% The thermal expansion coefficient of the stainless steels is about 50%
higher than for pure iron or of an AISI 1025 carbon steel.
While the low thermal conductivity limits the heating up and cooling While the low thermal conductivity limits the heating up and cooling
speeds, the high thermal expansion coefficient requires special care
concerning the spacing between pieces to be treated.
FIGURE: Main thermal
t t t d treatments and
transformations that
occur in austenitic
stainless steels stainless steels
between room
temperature and the
liquid state liquid state.
(Ref.: A.F. Padilha, R.L. Plaut,
and P.R. Rios: ISIJ
International (Japan) 43 135 International (Japan), 43, 135
143, 2003.)
SOLUTION ANNEALING
Solution annealing is the heat treatment most Solution annealing is the heat treatment most
frequently specified for austenitic stainless steels,
before their actual usage. The main objective of this
treatment, as the name implies, is to dissolve the
phases that ha e precipitated d ring the
FIGURE: Grain boundary M
23
C
6
precipitates in an austenitic
phases that have precipitated during the
thermomechanical processing of the material,
especially the chromium-rich carbides of the
M
23
C
6
-type, where M = Cr, Fe, Mo.
precipitates in an austenitic
stainless steel observed using
transmission electron microscopy.
23 6
yp
As the precipitation of M
23
C
6
occurs in the 450 to
900 C temperature range, the lower temperature
limit for solution annealing should be over 900 C. g
Carbides should be completely dissolved but they
dissolve slowly. Grain growth limits the maximum
solution-annealing temperature. In particular,
abnormal grain growth also known as secondary abnormal grain growth, also known as secondary
recrystallization, must be avoided.
FIGURE: Optical micrograph showing secondary
recrystallization start in a titanium-stabilized austenitic
stainless steel after solution annealing
SOLUTION ANNEALING
Typically, recommended solution-annealing temperatures are around
1010 to 1120 C.
Cooling from heat treatment temperatures should be sufficiently fast to Cooling from heat treatment temperatures should be sufficiently fast to
avoid chromium-carbide precipitation. On the other hand, too fast
cooling rates cause component distortions.
In the case of non-stabilized grades such as AISI 201, 202, 301, 302,
303, 304, 305, 308, 309, 316, and 317, if distortion considerations
permit, water quenching may be utilized. In the case of the AISI 309
and 310 types that contain maximum allowed carbon content and are
susceptible to carbide precipitation, water cooling is mandatory. In the
case of stabilized AISI 321, 347, and 348 types, water cooling is not
needed and air cooling is sufficient to avoid sensitization needed and air cooling is sufficient to avoid sensitization.
STABILIZE ANNEALING
Stabilize annealing is used for stabilized austenitic stainless steels in order Stabilize annealing is used for stabilized austenitic stainless steels in order
to assure maximum intergranular corrosion resistance.
After the solution-annealing treatment, only part of the carbon is bound in
th f f i h h bid MC b it id M(C N) the form of primary phases, such as carbides, MC, carbonitrides, M(C,N),
nitrides MN, or carbosulfides M
4
C
2
S
2
, where M = Ti, Nb, or V. The
remaining carbon stays in solid solution and may precipitate as secondary
carbides like M C at lower temperatures since the carbon solubility in carbides, like M
23
C
6
, at lower temperatures, since the carbon solubility in
austenite under 900 C is very low. Formation of such secondary carbides
can lead to intergranular corrosion.
Careful observation of the earlier shown TTT diagram reveals that the
precipitation start temperature of the thermodynamically more stable MC
carbides is displaced to higher temperatures if compared to the
precipitation start temperature of the less stable Cr rich carbides of the precipitation start temperature of the less stable Cr-rich carbides of the
M
23
C
6
type.
Therefore, exposing the steel, after solution annealing, to temperatures in
the 845 to 955 C temperature range for up to 5 h (depending on
component size), favors MC precipitation in detriment to M
23
C
6
.
STRESS-RELIEF ANNEALING
The most effective way to relieve stresses is to cool the component slowly The most effective way to relieve stresses is to cool the component slowly
from the solution annealing temperature. During slow cooling, some M
23
C
6
precipitation may occur with consequent sensitization. On the other hand,
fast cooling may reintroduce residual stresses and make the component g y p
susceptible to stress-corrosion cracking (SCC). In general, a small amount
of intergranular corrosion is preferable to a failure in few weeks due to
SCC.
Moreover, the selection of a low carbon or of a stabilized steel would be a
more appropriate solution.
Another alternative would be to stress relieve at a lower temperature
range, between 425 and 550 C, where M
23
C
6
precipitation is very slow,
allowing the material to be exposed for some hours without sensitization g
occurrence.
MARTENSITE FORMATION Transformation during Cooling
Strain-Induced Transformation Strain-Induced Transformation
Austenite in stainless steels in general and the austenite in the 300
steels series in particular is not a stable phase: steels series in particular is not a stable phase:
In the solution-annealed condition, the M
s
temperature is normally
below room temperature.
For the majority of these steels, the M
d
temperature (the
temperature below which martensite will form under deformation) is
above room temperature above room temperature.
Two kinds of martensite can occur in stainless steels:
(bcc ferromagnetic) => a
= 0 2872 nm (note that in austenitic SS (bcc, ferromagnetic) > a
= 0.2532 nm; c
= 0.4114 nm
0 3 8 Assuming a