Consequences of PWHT requirements on service properties for

petrochemical grades
Cdric CHAUVY
1,2
, Lionel COUDREUSE
2
and Philippe BOURGES
1
1
ARCELORMITTAL INDUSTEEL, CRMC, Le Creusot, France
2
ARCELORMITTAL INDUSTEEL, Chateauneuf, France
E-mail: cedric.chauvy@arcelormittal.com


Abstract
During fabrication of Pressure Vessels, materials are
submitted to several heat treatments. Indeed, the initial heat
treatment (Quenching and Tempering for instance) of the
base material, which leads to achieve the target properties, is
often followed by Intermediate Stress Relieving (ISR) and
Post Weld Heat Treatment (PWHT). The aim of such
treatments is to insure a good behaviour of the welded zones
(HAZ and Weld Metal) in terms of residual stresses and
mechanical properties. Generally many (several) simulated
PWHT (up to 4 or more) are required, which can affect the
base material. Two main cases must then be considered. On
the one hand, these PWHT can deteriorate the tensile
properties of the already tempered base material. On the other
hand, weldability and toughness of some materials can be
detrimentally affected by the accumulation of heat treatments.
It is therefore mandatory to consider the effect of the
complete set of heat treatments for the various zones: Base
Material, HAZ and Weld Metal. This work shows typical
examples in order to illustrate those problems. Special
attention is paid on Cr-Mo(-V) steels, which are widely used
in the energy industry. The case of C-Mn steels (A516gr70) is
also addressed with the effect of Ceq requirements on the
final compromise between properties and heat treatments.
Some ways for improvement are proposed, on the basis of the
equivalent tempering parameter concept.
Introduction
Plates and other components of a pressure vessel usually
undergo various heat treatments in order to make them
meeting the requirements, which may be either customer
specifications or international standards. The base metal
before welding can thus be normalized, normalized and
tempered or quenched and tempered.
During vessels fabrication, the manufacturer performs
several thermal cycles: preheating, post heating, DHT (De-
Hydrogenation Treatment), ISR (Intermediate Stress
Relieving), PWHT (Post Weld Heat Treatment). Due to the
temperature range, only ISR and PWHT can be considered as
real heat treatments.
Usually, it is considered that tempering confers the
mechanical properties on the base metal and the following
heat treatments confer the properties on the weld area. But, in
particular in case of repairs, it is not unusual to perform
several cycles of PWHT: up to 3 or 4. Then, all these thermal
cycles can affect more or less the properties of the base metal.
Thus, in order to minimize the effect of PWHT on the base
metal mechanical properties, the steelmakers are frequently
asked to perform the tempering (if required) at higher
temperature than the PWHT, which focus on the weld metal.
Moreover, the mechanical tests have to be carried out after
simulated PWHT (Temperature above 454C according to
ASME or other code) in order to prove that the base metal
can withstand these thermal cycles.
However, in many cases, the PWHT has a real influence on
the base metal properties and the steelmakers have to take it
into account while defining the grade and the manufacturing
route. For instance, in case of thick wall reactors (>100mm)
which require PWHT at high temperature during long
periods, the steel supplier can sometimes be brought to
decline the tempering temperatures required by the customer
specification. Indeed, it is sometimes not possible to
guarantee the required properties if using a too high
tempering treatment for a given grade.
Generally, the most convenient way to quantify the effect
of several thermal cycles on the properties is to use time-
temperature equivalent laws or tempering parameters. For
pressure vessel steels, the parameter commonly used is the
Larson Miller Parameter LMP (also called Hollomon-Jaffee
Parameter).
The goal of this paper, after a brief resume on the
tempering parameter, is to show the limits in term of
tempering and PWHT of different steel grades. Especially in
case of heavy gauges, the final properties are not only given
by the tempering step but by the whole thermal history that
has to be applied to the material.





Safety and Reliability of Welded Components in Energy and Processing Industry
- 339 -
Equivalent Tempering Parameter: LARSON-
MILLER Parameter
The influence of time and temperature on mechanical
properties is well known. Figure 1 gives an illustration of
typical curves that can be drawn from experience (for a
2.25Cr -1Mo steel grade in that case). Nevertheless, it is
difficult to compare the effect of different heat treatments,
made at different temperatures and different durations, and it
is also impossible to determine the cumulative effect of two
or more heat treatments at different temperatures.

300
400
500
600
700
800
1 10 100
Time (h)
MPa
UTS (Temp 635C) UTS (Temp 665C) UTS (Temp 690C) YS (Temp 635C)
YS (Temp 665C) YS (Temp 690C)
635C
635C
665C
665C 690C
690C

Figure 1: Influence of the temperature and time on the tensile
properties (grade A387gr22 cl2).

Therefore, the use of an equivalence parameter, which
involves both time and temperature, is of great interest. The
most used tempering parameter is called the Larson-Miller
Parameter LMP (or the Hollomon-Jaffee parameter).

The Larson-Miller Parameter formula is given hereafter for a
single heat treatment:

( ) ( ) t LMP log 20 + = (1)

with: temperature (K) and t time (hours)

It is also possible to extend this relationship to a multiple
treatment. In that case, the method is to choose one
temperature (usually the one used for the first treatment)
and to calculate for each treatment an equivalent duration t
eq

at temperature , by equalizing the LMP between the set of
conditions (, t
eq
) and (
i
, t
i
).


( )
( )
)
log
20
(
10
i
i i
t
eqi
t

+

=

(2)

These durations have then to be integrated in the formula
(1) and this leads to the following general expression:

(

|
.
|

\
|
+ =

=
n
i
eqi eq
t LMP
1
log 20 (3)

is an arbitrary chosen temperature (K)
t
eqi
is the equivalent duration at for a treatment i made at
i

during t
i
(hours)

The figure 2 below is an example of the relevance of such a
parameter. It shows a lot of data obtained with a single
treatment (blue dots) but also some results from multiple
treatments (red and green dots within red lines).

300
400
500
600
700
800
19000 19500 20000 20500 21000 21500
LMP

M
P
a
UTS one cycle YS one cycle UTS (660C-5h30 + 690C-24h)
YS (660C-5h30 + 690C-24h) UTS (710C-6h + 690C-33h) YS (710C-6h + 690C-33h)
In

Figure 2: Mechanical properties as a function of LMP (grade
A387gr22 cl2)

Once this parameter id defined, it is possible to study the
effect of cumulative heat treatments, which can be either ISR
or PWHT, on the different properties required for the
application (mainly tensile characteristics and toughness).
The next parts of this article aim to give illustration of the
impact of cumulative heat treatments on different steel
grades. Two steel families, widely used in the petrochemical
and refinery industry, will be taken as classical examples.
First, the case of Cr-Mo steels will be addressed since these
grades are typical of this kind of issue. Secondly, C-Mn steels
such as A516gr70 will be discussed with a special focus on
microalloying elements. These examples have been chosen in
order to highlight the increasing gap between requirements
and what can be accepted by steelmakers. Indeed, these
grades often undergo strong PWHT(s) and that can result in a
loss of properties and thus not to match the requirements
anymore.





Safety and Reliability of Welded Components in Energy and Processing Industry
- 340 -
GRADE 1.25Cr 0.5Mo / CromElso11
Figures 3 and 4 illustrate respectively the evolutions of the
tensile and toughness properties as a function of the
tempering parameter LMP for A387gr11. These results have
been achieved from 80 and 143 mm thick plates with
comparable chemical analysis. The tempering parameters
have been calculated for different combinations of
temperatures and holding time. (temperature from 660 to
740C; holding time between 30 min and 38h).

250
300
350
400
450
500
550
600
650
700
19000 19500 20000 20500 21000 21500
LMP
M
P
a
UTS 80mm thick YS 80mm thick UTS 143mm thick YS 143mm thick
Min YS A387gde11 cl2: 310MPa
UTS range A387gde11 cl2: 515/690MPa

Figure 3: Evolution of tensile properties of A387gde11cl2 as
a function of the tempering parameter.

Figure 3 shows that the tensile properties required for the
grade can be obtained for tempering parameters up to 21000.
There is no significant difference between both thicknesses.
For that LMP range, tensile properties are not the limiting
element for that grade.

0
50
100
150
200
250
300
350
400
19000 19500 20000 20500 21000 21500
LMP
E
n
e
r
g
y

(
J
)
Kv (-29C) 80mm thick Kv (-29C) 143mm thick
Kv min
80mm thick
Kv min
143mm thick

Figure 4: Evolution of toughness (Kv -29C) of
A387gde11cl2 as a function of the tempering parameter.

On the other hand, figure 4 shows a different behavior for
toughness properties at -29C, which get worse beyond a
given tempering parameter value. Moreover, the thickness
plays a really detrimental role on the results and have thus to
be taken into account. It appears that impact properties and
thickness constitute the limiting elements to the tempering
parameter for 1.25Cr-1Mo steel. As a matter of fact, the more
important the thickness is, the less there will be possibilities
to perform tempering treatments and PWHT at high
temperatures.
Then, for the thickest products, steelmakers are often
conducted to decline customer specification requirements.
When the tempering parameter calculated following the
requirements does not allow guaranteeing impact properties,
there is never a single answer that can be made. Table 1
illustrates an example of a requirement that cannot be
matched (the tempering parameter calculated following the
requirements does not allow guaranteeing impact properties)
and the different proposals that can be done in order to be in
line with what is feasible.

TABLE 1: EXAMPLE OF REQUIREMENTS FOR A387GDE11 CL2
AND POSSIBLE PROPOSALS. PLATE THICKNESS: 125MM.
Tempering PWHT LMP Kv
Max LMP
acceptable
Requirement >=690C 670C -17h 20176 >54J av (-18C) 20100
proposal 1 650C 670C -17h 20055 >54J av (-18C) 20100
proposal 2 690C 660C -17h 20033 >54J av (-18C) 20100
proposal 3 >=690C 670C -17h 20176 >54J av (-12C) 20300


Several alternative proposals can thus be made:

- Proposal 1: it is possible to meet the requirements of the
specification in term of impact properties and PWHT. But
this implies the tempering temperature to be below the
PWHT temperature, which is sometimes difficult to be
accepted whereas it is consistent with the LMP approach.

- Proposal 2: if one wants to keep the tempering temperature
at 690C, maintaining impact properties, then it is necessary
to reduce the PWHT temperature. This can lead to difficulties
for the Vessel manufacturer, who wants to ensure sufficient
toughness in the weld metal and also to reduce significantly
the residual stresses.

- Proposal 3: it is also possible to respect heat treatment
impositions (Tempering and PWHT) but in that case it will be
needful to reduce impact test requirements, otherwise the
steelmaker will not be able to ensure its production.

Therefore, there is a need of discussion between the
different concerned parts in order to define the best adapted
solution in terms of compromise between PWHT, LMP,
tempering and Charpy V-notch requirements. If ever the
requirements are mismatching the material feasibility it is
then necessary to choose another material. For thick vessel,
when low temperature toughness properties are required (-
18C; -29C), the use of A387gde22 cl2 is a safer
alternative).
Safety and Reliability of Welded Components in Energy and Processing Industry
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GRADE 2.25Cr 1Mo / CromElso22
Figure 5 illustrates the influence of the tempering
parameter on tensile strength of 2.25Cr-1Mo steel
(A387gr22), for plates up to 250 mm thick. On this figure, the
lower thresholds of UTS requirements are specified according
to different standards of 2.25Cr-1Mo steels (ASTM and EN).
Chemical compositions for these different standards are the
same; that is only by modifying the heat treatment that it is
possible to have an effect on the mechanical properties.

2.25Cr-1Mo steel softening curve
400
450
500
550
600
650
700
750
18500 19000 19500 20000 20500 21000 21500
Larson Miller Parameter
M
P
a
UTS
UTS mini A 542B Cl4: 585MPa
UTS mini A387gde22 cl2 :515MPa
UTS mini 12CrMo9-10 :540MPa

Figure 5: Influence of tempering parameter on tensile
strength of 2.25Cr-1Mo steel.

In order to guarantee the properties, a maximum value of
the tempering parameter can be determined depending on the
corresponding standard. Table 2 gives the maximum
tempering parameters for satisfying the tensile strength
requirements from the different standards; the maximum
tempering temperatures and PWHT conditions (for 200mm
thick plates) are also reported. It appears that the choice of
the standard will strongly affect the amount of PWHT
allowable on the grade. The lower the minimum UTS, the
higher could be the Larson-Miller Parameter and therefore the
more there will be possibilities for increasing the total amount
of PWHT.


TABLE 2: MAXIMAL LMP IN ORDER TO MATCH THE
STANDARDS REQUIREMENTS.
Standards
LMP
maxi
Tempering PWHT
SA387 gde22 cl2 20850 710C 690C -33h
EN10028-2
12CrMo9-10
20550 660C 680C - 33h
SA542B cl4 20000 650C 655C -33h

The tempering parameters given in the above table have
been calculated for tempering times leading to a
homogeneous temperature through the whole thickness of the
product. In fact, there is often no tempering times
requirements. Therefore, it could be possible to reduce the
tempering parameter by reducing the holding time. However
from a metallurgical point of view, this can produce
heterogeneities of properties though the thickness that can
have consequences during the fabrication of the vessel.
For example, tempering at 720C during 1h leads to a
tempering parameter of 20,000. The same tempering
parameter can be obtained with a tempering at 690C during
5h30. Whereas, for a 50 mm thick plate, there is no problem
to perform a tempering treatment at 720C for 1h, it is not the
case for a 250 mm thick plate, for which it is better to apply a
tempering of 690C for 5h30 in order to homogenize the
thermal effect through the thickness. Therefore, the LMP
approach must not be applied without taking into account the
specificity of thick plates. There must be production rules that
ensure thermal homogeneity of the products and thus give the
boundaries to respect in terms of heating rate and holding
time.

GRADE 2.25Cr 1Mo-0.25V / CromElso22V
2.25Cr-1Mo-V steels (SA 542DCl4a or equivalent) are
more and more used in refining installations for high
hydrogen pressure and high temperature range. Indeed, using
of 2.25Cr-1Mo-0.25V grade instead of 2.25Cr-1Mo allows a
significant reduction of thickness, especially since the new
2007 ASME VIII division 2 issue, which decreased the safety
coefficients. The interest has thus grown with the size of the
newly designed reactors. Another important advantage for the
final users is weld overlay resistance. Indeed, this Vanadium
enhanced grade does not exhibit some hydrogen induced
disbonding problems at the plate-overlay interface.
However, once again, in order to obtain the required
properties in the welds, especially the Charpy toughness, the
vessel fabricator needs to perform PWHT at high
temperatures (> 700C). This leads the grade to be able to
withstand such high temperature PWHT during sometimes
more than 30h. Considering the trend to increase these
PWHT requirements, Industeel has carried out some
optimization studies in order to improve the resistance to
softening. There are two ways to reach that goal. The first one
is to play on the microstructure itself whereas the second one
is to add some chemical elements that will create stable
precipitates resisting to softening.
Figure 6 illustrates the effect of different alloying elements
on the softening curve and shows how it is possible to
guarantee tensile strength properties of A542D cl4a for very
thick products (>150mm), and for high tempering parameters
by using micro-alloying. On one hand, Boron promotes
quenchability and therefore improves the microstructure of
the steel, especially for thick products. This leads to avoid the
Safety and Reliability of Welded Components in Energy and Processing Industry
- 342 -
loss of tensile strength properties at mid-thickness for higher
tempering parameters. On the other hand, an optimization of
Vanadium and Niobium contents reduces the softening during
tempering. This creates stable carbides known to be resistant
to softening. In all cases, the amount of B and Nb is much
reduced however.

550
600
650
700
20000 20200 20400 20600 20800 21000 21200 21400
PR
M
P
a
Min UTS : 585MPa
Max UTS : 690MPa
Effect of boron
Effect of V and Nb
optimisation

Figure 6: Influence of alloying on UTS for 2.25Cr -1Mo-V
(thk > 150mm, properties at thk): Curves representing
minimum values.

In order to illustrate this trend with some industrial data, the
figures 7&8 hereafter provide some results obtained on
A542D at different stages of the thermal history, that is to say
after quenching and tempering (Q&T), after minimum PWHT
and after maximum PWHT as well. Moreover, a large range
of thickness is considered, starting from 127mm up to
230mm.


Figure 7: Influence of LMP and thickness on UTS for the
grade 2.25Cr -1Mo-V.

Figure 7 shows that even for usual maximum PWHT
(705C during 33h), the UTS requirement is still met. One
can also underline that the effect of thickness is more present
for low LMP than the highest ones. It is interesting to notice
the decrease as a function of the tempering parameter. In
particular, this implies that the initial target in the Q&T state
must be close to upper limit of UTS requirement.


Figure 8: Influence of the thickness and the tempering
parameter on Yield Strength for grade 2.25Cr-1Mo-V.

Figure 8 above describes the evolution of the yield strength
as a function of the tempering parameter. Even if the trend is
obviously the same as for UTS, it appears that the margin is
larger regarding the minimum requirement to be met.
Anyway these two last figures clearly show the influence of
multiple PWHT on the mechanical properties of the base
metal. The chemical analysis optimization has given some
extra margin but the material is close to its metallurgical
limit.
Figure 9 shows the average values of Charpy-V impact
testing obtained at -18C (for Q&T) and -29C after some
PWHT. Results concern plate thickness between 127 and
230mm with 1/4
th
and 1/2th sampling. It can be noticed that
the impact properties remain completely satisfactory for all
the considered LMP range, whatever the thermal history of
the plate. Thus toughness does not appear to be a limiting
factor for the time being in terms of acceptable PWHT.



Figure 9: Influence of the thickness and the tempering
parameter on impact properties for grade 2.25Cr-1Mo-V.

To summarize, the optimization carried out on 2.25Cr-
1MoV steel has allowed to reach the level of mechanical
LMP
Safety and Reliability of Welded Components in Energy and Processing Industry
- 343 -
properties required for 250 mm thick plates while respecting
a LMP at 21200.
GRADE A516 gde70 / CarElso70
The case of C-Mn steels such as A516gr70 is slightly
different in that sense that there is another requirement to be
taken into account while discussing the specification: the
maximum Carbon Equivalent Ceq. This parameter aims to
ensure a good weldability and is commonly defined by using
the IIW formula given hereafter:

( ) ( )
15 5 6
Cu Ni V Mo Cr Mn
C C
eq
+
+
+ +
+ + =
(4)

There is therefore a lot of elements that are not included in
this concept but according to A516 or A20. We will see later
how some other elements can be used and their limitations.
The target is then to obtain an acceptable microstructure,
matching the requirements, with a given chemical
composition. The cooling rate for higher thickness will be
lower than for the thinnest one. Ensuring the properties will
then imply to adapt the Ceq value.
Figures 10 and 11 illustrate the influence of the tempering
parameter on the tensile properties (UTS) and impact Charpy-
V toughness of A516gr70, for two classical levels of Ceq:
0.43 and 0.45. This grade exhibits some limitations in terms
of acceptable PWHT because of the softening effect that will
finally kill the material.
For instance, figure 10 shows the decrease of the tensile
properties when increasing the tempering parameter. The
highest Ceq gives an extra margin that can be useful to meet
the specification. However, guaranteeing tensile properties in
conformity with the A516gr70 standard implies to limit the
tempering parameter value at approximately 18500 and
18900, for a Ceq of 0.43 and 0.45 respectively.

Influence of tempering parameter on UTS values
450
460
470
480
490
500
510
520
530
540
550
17400 17600 17800 18000 18200 18400 18600 18800 19000 19200
LMP
U
T
S

(
M
P
a
)
485 MPa ( Minimum required UTS)
600C -15h 610C -15h 620C -15h
A 516 gde 70
Thickness range 100/200mm
Ceq =0.43
Ceq =0.45

Figure 10: Influence of tempering parameter on UTS values
for A516gr70.

Figure 11 shows, on one hand, that impact strength at low
temperature decreases when the tempering parameter
increases. This is important to note that in the case of C-Mn
steels, too strong PWHT leads to deteriorate both the
toughness and the tensile properties. On the other hand, the
graph shows that better levels of toughness are obtained with
Ceq of 0.43 instead of 0.45. Finally, there is once again a
compromise to find taking into account the entire
specification which involves heat treatments, Ceq and
Charpy-V toughness values.

0
20
40
60
80
100
120
140
160
180
200
17400 17600 17800 18000 18200 18400 18600 18800 19000 19200
PR
K
v
(
-
4
6

C
)
600C -15h 610C -15h 620C -15h
A 516 gde 70
Thickness range 100/200mm
Ceq =0.43
Ceq =0.45

Figure 11: Influence of tempering parameter on Charpy V
toughness

For special applications, it is frequently asked for
A516gr70 to limit Ceq to 0.43 for weldability reasons, or
even to fulfill the requirements of hardness in HAZ (for
example NACE recommendation is maximum 248Hv /
22HRC) for use in H
2
S environments.
In order to satisfy these requirements an alternative would
be to add a small amount of Nb, in order to delay the
softening effect due to PWHT, without effect on Ceq. The
curves of figures 12 and 13 allow comparing the softening
occurring in the Heat Affected Zone of grade A516gr70 and
of another steel corresponding to the standard BS1501-225
(which contents 0.035%Nb).
The curves of figure 12 show that, for grade A516gr70,
one can guarantee hardness in HAZ lower than 248Hv with a
stress-relieving heat treatment at low temperatures (600C). It
is to note that the recommendation of NACE, which indicate
that the PWHT should be performed above 620C, is not
justified for C-Mn steels. In other words, the minimum
temperature to be applied is the one allowing to respect the
248Hv maximum Heat Affected Zone Hardness while
respecting the minimum stress relieving temperature as per
the construction code, which is 595C (1100F) according to
ASME VIII div1 and div2.
Safety and Reliability of Welded Components in Energy and Processing Industry
- 344 -


Figure 12: Influence of PWHT on hardness values for
A516gr70 without micro-alloying elements.

To the contrary, for micro-alloyed steel with Nb it is
necessary to use strong tempering parameters to satisfy the
requirements of hardness in HAZ (figure 13). This evolution
requires PWHT at high temperature, which afterwards
justifies the addition of Nb. This example illustrates the
"perverse" effect of some requirements. In order to respect
Ceq limitations and tensile properties at the same time, it is
possible to adjust the chemical composition. Nevertheless,
this kind of practices has a cost and the heat treatments have
then to be adjusted.



Figure 13: Influence of PWHT on hardness depending on
micro-alloying elements.




In fact it would be possible to obtain the same result with
non micro-alloyed steel with a lower PWHT temperature. For
instance, it would be possible, according to figures 10 and 11,
to meet the required properties of A516grade70, with a Ceq
of 0.43 and a PWHT limited to 600C.
Even if the specifications are different, the philosophy
remains the same. More and more, stringent requirements
show up. Increasing the PWHT is not the only way to
improve the whole behaviour of the assembly because
adjustments to be made for the base metal can make the
material more difficult to use, in particular for special
application such as sour service. Discussions are once again
needed between everyone in order to best define the good
compromise for such C-Mn steels.


CONCLUSION
These few examples show how the PWHT, and more
generally cumulative heat treatments, can have an influence
on the properties of parent materials. As PWHT requirements
(temperature and holding time) are constantly increasing, it
becomes difficult for the steel producer to meet the
requirements in terms of tensile or Charpy-V toughness
properties. Indeed, the evolution of these properties as a
function of an equivalent tempering parameter (Larson Miller
Parameter) shows that there are some limits for a given grade.
This is a general consideration that applies for both Cr-Mo
and C-Mn steels.
Therefore, it can be sometimes necessary to limit the
PWHT temperature and holding time, or even the tempering
temperature in case of Cr-Mo grades. In that case, In order to
achieve the required mechanical properties, more particularly
for thick products, it can be necessary to have the tempering
temperature below the PWHT temperature. By using this
method, this can ensure that the parent metal will remain at
the required level when strong PWHT are required.
The situation is slightly different for C-Mn steels, where
one cannot play on the tempering step. The limitations for
PWHT are well known by steelmakers and too strong
PWHTs are very detrimental for all the usual properties.
Finally, discussions between the different involved parts
(End Users, Engineering, Manufacturers and Steel Makers)
are primordial in order to find a compromise and conditions
ensuring the best level of properties to the vessel at the end of
the fabrication chain.
Safety and Reliability of Welded Components in Energy and Processing Industry
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