International Journal of Pressure Vessels and Piping 110 (2013) 17e23

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International Journal of Pressure Vessels and Piping

journal homepage: www.elsevier.com/locate/ijpvp

Effect of temper and hydrogen embrittlement on mechanical

properties of 2,25Cre1Mo steel grades e Application to Minimum
Pressurizing Temperature (MPT) issues. Part I: General considerations
& materials’ properties
Sylvain Pillot a, *, Cédric Chauvy b, Stéphanie Corre a, Lionel Coudreuse b, Andrew Gingell a, b,
Déborah Héritier a, Patrick Toussaint c
a
Industeel France, Site du Creusot, Le Creusot Research Center, ArcelorMittal Group, France
b
Industeel France, Site de Châteauneuf, ArcelorMittal Group, France
c
Industeel Belgium, ArcelorMittal Group, Belgium

a b s t r a c t
Keywords: Standard and Vanadium-alloyed 2,25Cre1Mo steel grades (EN 10028-2 12CrMo9-10/ASTM A387 gr. 22
Hydrogen and 13CrMoV9-10/ASTM A542 tp. D) are commonly used for the fabrication of heavy pressure vessels for
2,25Cre1Mo
applications in petroleum refining plants.
Pressure equipment
Minimum pressurizing temperature
These reactors are made of heavy plates, forged shells, forged nozzles and fittings. They are subjected
Temper embrittlement to thermal cycles (stop and go) and to severe service conditions (high temperatures and high hydrogen
Hydrogen embrittlement partial pressures). A primary concern for end-users is the definition of the Minimum Pressurizing
Charpy toughness Temperature (MPT) of the equipment. This temperature is the lowest temperature at which the vessel
Fracture toughness can be repressurized after shutdown and insures no risk of brittle failure of the containment body. The
MPT is defined by fracture mechanics and/or CVN approaches and calculations.
This first part of the paper presents the impact of thermal aging and exposure to hydrogen on ma-
terials’ mechanical properties and consequently on the value of MPT.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction metal temperature and internal pressure to insure at every time a

One very important concern in both petrochemical and refining
industries is the risk of brittle (i.e. unstable) failure of the pressure
vessels. Thick wall pressure reactors in these industries are
designed to operate at relatively high temperatures (in the range
300e480
C), and at high pressures and hydrogen partial pressures
(in the range 15e200 bars). This particular combination can lead to
numerous and various problems that must be kept under control.
During unit shutdowns, for example for maintenance opera-
tions, pressure and temperature are decreased to much lower levels
than ones corresponding in-service conditions. At the end of the
maintenance procedures, the operation staff restarts the unit,
increasing the inner-vessel pressure and temperature to the oper-
ational conditions, thus starting a new production cycle. During the
early stages of the start-up process, strict attention must be paid to
* Corresponding author.
E-mail address: sylvain.pillot@arcelormittal.com (S. Pillot).
sufficient toughness of the reactor material to resist to increasing
pressure state. This is done by controlling accurately the heating
and pressurization rate of the vessel, avoiding by the way condi-
tions that could cause brittle failure. This dramatic and unaccept-
able situation could occur if the ferritic steel temperature is not
high enough to reach a level of fracture toughness sufficient to
mitigate crack instability and then catastrophic failure of the
confinement wall.
Ensuring sufficient toughness at every temperature deals with
definition of Minimum Pressurizing Temperature (MPT) which
then serves as a guideline for future operation of a given reactor. A
vessel start-up program that is based on MPT concept includes a
system of steps of temperatureepressure couples that must be
strictly abided by when the production cycle is restarting.
In the case of a newly fabricated reactor, the definition of MPT is
quite easy because all needed material properties can be required at
the delivery of the pressure vessel and then the reactor is designed
to avoid the risk of brittle failure. Steelmakers, fabricators, engi-
neerings, and end-users are aware of the potential problems and

0308-0161/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijpvp.2013.04.017
18 S. Pillot et al. / International Journal of Pressure Vessels and Piping 110 (2013) 17e23

safety margins are used. Evaluation of alloy embrittlement is also

taken into consideration. Steelmakers provide guarantees to their
customers that the steels they produce have a satisfactory resis-
tance to temper embrittlement. This guarantee stems from confi-
dence gained in testing of the steels that comprise of furnace
heating of coupons and subsequent Charpy V-notch impact testing.
In the furnace, the coupons are exposed to an accelerated aging
simulation program, also called Step Cooling.
The situation becomes more complex when the low-alloy steels
are exposed to hydrogen at elevated temperatures. The complexity
arises because of the lack of data characterizing the effects of
hydrogen on fracture toughness. The mechanical tests required to
assess fracture toughness of low-alloy steels exposed to high
hydrogen pressures at elevated temperatures are not very common,
and moreover are not easy to perform. These tests are important
because of the strong embrittling effect of hydrogen on reactor
steels. Another major problem concerns the definition of MPT in Fig. 1. Effect of tempering on CVN and drop weight transition temperature for
the case of vintage reactors that have been operating for years and 2,25Cre1MoeV grade (base metal).

for which historical operating data may not be fully available.

This paper focuses on the degradation mechanisms that pro-
the overall behavior of the structure. In general, customers ask
mote embrittlement of low-alloy steels. The main actors are temper
steelmakers to assure given properties after minimum PWHT
embrittlement and the embrittlement due to hydrogen. For pres-
(corresponding to delivery state of the pressure vessel to final
sure vessels operating in the creep range, creep embrittlement
customer) and after maximum PWHT (corresponding to pressure
should also be taken into consideration. This paper also presents
vessel state after some weld repairs and corresponding PWHT).
the findings of recent tests performed in hydrogen environments to
Furthermore, tempering of a low-alloy steel can also modify
assess mechanical properties.
mechanical properties. Special attention has to be paid to this
This contribution is a set of two papers:
influential parameter. Initial tempering done by steelmakers as
well as further fabrication heat treatments (Dehydrogenation Heat
- Part I hereafter focusing on the effect of temper embrittlement
Treatment (DHT), Intermediate Stress Relieving Treatments (ISR)
and hydrogen embrittlement on materials’ properties
and final Post Weld Heat Treatment (PWHT)) must be performed
- Part II considering the particular case of vintage reactors
with great care. Final properties of pressure vessels’ constitutive
(already operating for years or decades) and giving a realistic
steels are not only a function of their chemical composition, but
example on how to use this methodology to assess actual MPT
also is a function of all heat treatments performed during fabrica-
of pressure equipments. The evolution of existing embedded
tion. A paper by Chauvy et al. [1] focuses on this point and in
defects is also taken into consideration in the last chapter of
particular on the potential detrimental effect of cumulative
this contribution.
treatments.
Following Figs. 1 and 2 give examples of evolution of Charpy
toughness properties (CVN transition temperature giving 54J
2. As delivered materials’ properties
average impact energy TK54J and Drop Weight Nil Ductility Tran-
sition temperature NDT) in the case of 2,25Cre1MoeV steel.
Initial properties of ferritic steels used for construction of
Similar evolution can be plotted for other ChromiumeMolybde-
pressure vessels for petroleum refining or petrochemical applica-
num steels such as conventional 2,25Cre1Mo. More data can be
tions can be assessed by many parameters. The very first point to
found in reference from Pillot et al. [2].
keep under strict control is the chemical compositions and in
Recommendations and guidelines concerning heat treatments
particular the concentrations of impurities in metal. Achieving the
have been published by API [3] (American Petroleum Institute) to
specified alloy chemical composition is the responsibility of ma-
terial’s supplier (steelmaker or filler material supplier). Mechanical
properties of semi-finished products (e.g. plates, tubes, pipes,
forged components), typically in the “as delivered” condition (and
after thermal simulations corresponding to cycles of ISR and PWHT
to be done by builders), are provided by laboratory tests. Consid-
eration on thermal simulation (Step-Cooling simulation) will be
given in the next section.
Material properties of vessel components in “as-delivered”
condition are stipulated in customer specifications. Hence, these
requirements become the basis for all fabrication code calculations.
The main problem is that these initial mechanical properties are not
those that exist in the finished pressure vessel at the beginning of
its service life.
Mechanical properties as tabulated in manufacturers material
test reports generated by steelmakers are affected by subsequent
fabrication processes. All further thermo-mechanical operations
performed by vessel fabricators (e.g. shell rolling, head forming,
welding of the shell courses, heads, and nozzles) will affect the Fig. 2. Effect of tempering on CVN for 2,25Cre1MoeV grade (SAW and SMAW weld
given initial mechanical properties, and as a consequence modify metal).
 S. Pillot et al. / International Journal of Pressure Vessels and Piping 110 (2013) 17e23
control and master the whole pressure vessel fabrication process
and hence to assure sufficient mechanical properties to reactors
(basically strength and toughness). These properties can be
considered as a basis for design, at the beginning of service life of
pressure vessels or reactors. However these properties will evolve
with time and exposure to operating environment. This change in
material behavior is reported in next chapter.
3. Evolution of materials’ properties due to high-temperature
and high hydrogen pressure service
Low-alloy pressure vessels used in high-pressure refining pro-
cesses are generally thick wall (typically 150e350 mm), and built
from forged rings or rolled and welded plates each forming shell
courses. Inner diameters of these reactors typically range from 4 to
5 m. Total weight of these very large components ranges from 500
to 800 metric tons. Reactor wall is a composite structure made of
two different metallic materials. The primary pressure boundary is
fabricated from low-alloy steel (e.g. ChromiumeMolybdenum or
ChromiumeMolybdenumeVanadium steel), while the other
component is a thin corrosion resistant layer of austenitic stainless
steel. While small components can be fabricated from clad plates,
the liner in large and thicker components is typically made using an
electro-slag weld (ESW) overlay.
The primary function of low-alloy steel is to provide strength
and toughness necessary for a pressure boundary to resist to high
pressures and temperatures. In the following text, this part of the
reactor wall will be referred to as “Base Material”. The vessel’s
mechanical behavior is defined by base material. The function of
the stainless steel weld overlay is to protect the low-alloy steel from
corrosion and environmental degradation and its minor influence
on the overall mechanical behavior of the structure is therefore not
taken into consideration.
3.1. Temper embrittlement of CreMo steels
Temper embrittlement is a solid state reaction with very low
kinetic reaction rates. Unlike hydrogen embrittlement, temper
embrittlement takes a lot of time to appear, and then only old re-
actors that have been running for years are affected by this phe-
nomenon. On the contrary, hydrogen embrittlement can occur after
only few days of service. At the very first cooling of the reactor after
200
Base Material [API] 20000Hrs
Base Material [JSW] 30000Hrs
Base Material [Chevron] 35000Hrs
Base Material [Chevron] 75000Hrs
Base Material [ ] 150000 to 200000Hrs
Weld Metal [API] 20000Hrs
150 Weld Metal [JSW] 30000Hrs
Weld Metal [Chevron] 35000Hrs
Weld Metal [Chevron] 75000Hrs
Weld Metal [ ] 150000 to 200000 Hrs
API579 FATT99%
API579 FATT95%
100 API579 FATT50%
FATT (°C)
50
-50
0 50 100 150
Fig. 3. Effect of impurities (J-Factor) on CVN properties (2,25Cre1Mo steel grades) e historical data.
19
a production cycle, the risk of brittle failure due to hydrogen
embrittlement is real.
The extent of temper embrittlement is measured by the shift of
CVN transition to higher temperatures and was first studied in
NickeleChromiumeMolybdenumeVanadium steels used for
forged rotors devoted to low-pressure turbines in electrical power
plants. It has been proven that temper embrittlement is linked to
the co-segregation of impurities at prior austenitic grain bound-
aries. Impurities, such as Tin (Sn), Antimony (Sb), Arsenic (As),
Phosphorus (P), co-segregate with alloying elements (primarily not
only Silicon (Si) and Manganese (Mn), but also Chromium (Cr) and
Nickel (Ni)). The result leads to grain boundary embrittlement, and
subsequently to a risk of intergranular fracture. Temper embrit-
tlement occurs at temperatures below 600
C, but mainly in the
range 350e550
C (typical C-Curves of iso-embrittlement for a
given temperature and time couple as shown in Fig. 5).
Some metallurgical parameters can influence the extent of CVN
transition in low-alloy steels. Increasing grain size can be very
detrimental. Additionally, microstructures that promote high
hardness values are more sensitive than softer microstructures.
This is why weld heat affected zones (HAZ), and in particular, coarse
grain heat affected zone (CG-HAZ) are locations where problems
are the most likely to occur. As previously stated, high Manganese
and Silicon contents are known to promote temper embrittlement.
The role of Molybdenum is more complex. Low concentrations of
Molybdenum (about 0.5%wt, as in the case of P11) is much better
than no addition, and better than higher concentrations (about 1%
wt, for 2,25%Cr steels, such as P22). Some references on this subject
are given in a paper by Bocquet et al. [4]. It is well known from end-
users that standard 2,25Cre1Mo is much more sensitive to temper
embrittlement than 1,25Cre0,5MoeSi and Vanadium modified
2,25Cre1Mo (2,25Cre1Moe0,25V).
Different parameters based on chemical composition have been
created to evaluate low-alloys (and in particular CreMo steels)
sensitivity to temper embrittlement. These chemistry parameters
have been developed using a statistical analysis approach, based on
evaluation of CVN parameters and Ductile to Brittle Transition
temperature (DBTT), also called Fracture Appearance Transition
Temperature (FATT). This method involved testing heats with mi-
nor differences in chemical composition after long isothermal
treatments, both laboratory samples and actual reactor steels were
used.
99% confidence limit
95% confidence limit
50% confidence limit
200 250 300 350 400 450 500
J-Factor
20 S. Pillot et al. / International Journal of Pressure Vessels and Piping 110 (2013) 17e23

250
Base Material - J<150
Base Material - J<250
Base Material - J<400
Base Material - J>400
200 Weld Metal - J<150
Weld Metal - J<250
Weld Metal - J<400
Weld Metal - J>400
150 J=500

100
FATT (°C)

J=350

50
J=250

-50
J=150

-100
1000 10000 100000 1000000
Exposing Time (Hrs)

Fig. 4. Effect of impurities (J-Factor) on CVN properties after very long exposing time at service temperatures (2,25Cre1Mo steel grades) e historical data.

The two most widely used parameters are Watanabe’s J-Factor
[5] (standard and simplified) for base materials, and the Bruscato
X-bar Factor [6] for weld metals. A third parameter, called “Equiv-
alent Phosphorus” content [7] can be used for both base and weld
metal but is not widely used. The definition of these parameters is
given hereafter by equations (1)e(4).
 J  Factor is given by : J ¼ ðSi þ MnÞ*ðP þ SnÞ*10; 000
computed with elemental concentrations expressed in weight
percent.
 A “simplified” J  Factor is given by : J 0 ¼ ðP þ SnÞ
computed with elemental concentrations expressed in weight
percent.
Last revisions of API RP 934 generalize the use of Bruscato Factor
for both base materials and weld metals, instead of Bruscato Factor
for welds and J-Factor for bases. This recent evolution of the stan-
dards is due to the general misunderstanding of J-Factor values for
Silicon containing steel grades such as A387 gr. 11 (1,25Cre0,5Moe
Si) or A387 gr. 5 (5Cre0,5MoeSi) that can not be compared to the
values of non Si-containing steels.
(1) API 579-ASME FFS1 [10] (Fitness for service) gives statistical
relationships between FATT and compositional J-Factor values.
They are based on data collection represented in Fig. 4. FATT esti-
mations for 2,25Cre1Mo steel grade (both weld and base) are given
by equations (5)e(7)
(2)
FATTmean ¼ 77:321 þ 0:57570$J  5:5147$104 $J 2 (5)
FATT95% ¼ 48:782 þ 0:77455$J  8:5424$104 $J 2 (6)

 Bruscato Factor is given by : X

FATT99% ¼ 15:416 þ 0:72670$J  8:0043$104 $J 2 (7)
¼ ð10*P þ 5*Sb þ 4*Sn þ AsÞ=100 (3)

computed with elemental concentrations expressed in ppm.

 Equivalent Phosphorus content is given by : PE

¼ C þ Mn þ Mo þ Cr=3 þ Si=4 þ 3; 5*ð10*P þ 5*Sb þ 4*Sn þ AsÞ
(4)

computed with elemental concentrations expressed in weight

percent.
Fig. 3 shows FATT scattering as a function of J-Factor. It can be
noticed that FATT increases dramatically with increasing concen-
tration of impurities. It suggests that a low level of impurities must
be specified and obtained in order to get acceptable CVN toughness.
Fig. 4 shows the evolution of FATT at specific exposure times, at
service temperatures for impurities concentrations (in that case
based on J-Factor). It can be seen that CVN properties of the 2,25Cre
1Mo steels with low concentrations of impurities retain acceptable
FATT below or just above room temperature. In the case of high J-
Factor steels that have been exposed to elevated temperatures for
very long time of service conditions, the CVN ductileebrittle tran-
sition temperature can approach 200
C. More results can be seen Fig. 5. Iso-embrittlement curves used to define Step-Cooling heat treatments (taken
in papers by Prescott [8,9]. from Refs. [4,12]).
 S. Pillot et al. / International Journal of Pressure Vessels and Piping 110 (2013) 17e23 21

0
0 1 2 3 4 5 6

-20

-40

TK54J (°C)
-60

-80

-100
Base Material
Base Material SC
-120
Weld Metal
Weld Metal SC
-140
Martensitic HAZ
Martensitic HAZ SC
-160
H2 content (ppm)

Fig. 8. Evolution of TK54J as a function of H2 content (2,25Cre1Mo).

Fig. 6. Profiles of hydrogen concentration in material and overlay before and after
cooling down of a reactor in refining plant.
the differences in temperature between the PWHT steel and the
To evaluate sensitivity to temper embrittlement of low-alloy step cooled coupons at 54J fracture energy (“temperature shift”) is
steel grades used in refining plants, many users have opted to multiplied by a factor of 2,5 or 3. Multiplying the test coupon shift
require a simulation heat treatment test program called “Step temperature by 2,5 provides a useful correlation to reactors that
Cooling” to be included as part of the purchase agreement. The have operated at 400e450
C for periods up to 30 years [11,12].
purpose of this Step-Cooling heat treatment program is to provide a For steelmakers, temper embrittlement mitigation consider-
relatively quick and cost-effective method to simulate the embrit- ations have led to further requirements. In general, steels devoted
tlement behavior that occurs after long-term isothermal exposure. to high-temperature service are typically required to:
It is based on the “iso-embrittlement” curves (C-Curves) shown on
the timeetemperature diagram depicted in Fig. 5.  Have special chemistry: most common rules for base materials
While many different variations exist, a typical step-cooling test are J < 150 in the case of 1,25Cre0,5MoeSi steel grade or
program takes approximately two weeks of total time. In refining J < 100 for 2,25Cre1Mo(eV) grades. Additional requirements
applications, the most traditional step-cooling program makes use for P þ Sn < 0.012%wt, can be added. For weld consumables,
of the following cycle: heat-up to 593
C, soaking for 1 h, cooling at the most common criterion is X-bar <15 or 12.
5.6
C/h with soaking steps at 538
C (15 h), 524
C (24 h), 496
C  Have coupons tested before and after Step-Cooling heat treat-
(60 h) and 468
C (125 h). Coupons exposed to this step cooling are ment to evaluate the embrittlement of the given material.
then machined into Charpy V-notch samples and impact tested at
various temperatures as required by API 934-A (Materials and Nevertheless, usefulness of Step Cooling must be balanced by
Fabrication of 2,25Cre1Mo, 2,25Cre1Moe0,25V, 3Cre1Mo, and noticing that 2,25Cre1Mo steels purity is now very good (J-factor
3Cre1Moe0,25V Steel Heavy Wall Pressure Vessels for High- always below 100 due, to strong improvements in steelworks) and
temperature, High-pressure Hydrogen Service) to determine an then 54J impact energy is achieved in general close 100
C for
appropriate transition curve. base materials. For this very low J-factor steels, shift due to temper
Historically it has been shown that step-cooling test programs embrittlement is not significant anymore and then Step Cooling
do not simulate the full extent of embrittlement that has been becomes not mandatory.
observed in samples removed from retired reactors that have been Discussions between steelmakers and API were ongoing for
in service for many years. Nevertheless, step-cooling testing does years to remove this embrittlement test which is very detrimental
provide a relative measure of an alloy tendency to temper embrit- to delivery schedules. Since May 2008 revision of API RP 934, one
tlement. In order to add a measure of conservatism to the design,
0
0 1 2 3 4 5 6
6
Base Material
2,25Cr-1Mo steady state -20
Base Material SC
2,25Cr-1Mo-V steady state
5 Martensitic HAZ
Local Hydrogen Content (ppm)

2,25Cr-1Mo end of cooling -40

Martensitic HAZ SC
2,25Cr-1Mo-V end of cooling
TK54J (°C)

4 -60

3 -80

-100
2

-120
1

-140

0
0 50 100 150 200 -160
Position in Base Material (mm) H2 content (ppm)

Fig. 7. Profiles of H2 content in base material before and after cooling down. Fig. 9. Evolution of TK54J as a function of H2 content (2,25Cre1MoeV).
22 S. Pillot et al. / International Journal of Pressure Vessels and Piping 110 (2013) 17e23

60

2,25Cr1Mo (690°C - 8Hrs + SC)

50

C-0,5Mo (610°C - 3Hrs20min)

Shift of FATT under hydrogen (°C / ppm)

5Cr0,5MoSi (710°C - 1Hr40min)

2,25Cr1Mo (690°C - 8Hrs + SC)

2,25Cr1Mo (690°C - 8Hrs)

40

2,25Cr1Mo (690°C - 8Hrs + SC)

2,25Cr1MoV (705°C - 8Hrs + SC)

2,25Cr1MoV (705°C - 8Hrs + SC)

30
2,25Cr1Mo (690°C - 8Hrs)

C-Mn (65ksi)

2,25Cr1Mo (690°C - 8Hrs)

2,25Cr1Mo (literature)

2,25Cr1MoV (705°C - 8Hrs)

2,25Cr1MoV (705°C - 8Hrs)

C-Mn (70ksi)
20

10

0
Base metal Martensitic HAZ Weld Metal
Localisation of Charpy V-Notched specimens

Fig. 10. CVN transition curve shift as a function of H content (ppm weight) in CreMo(eV) and CeMn steels.

complementary paragraph has been added concerning relevancy equilibrium between hydrogen partial pressure inside the reactor
of Step Cooling. This paragraph takes into account quality evolu- and hydrogen concentration in the steel is reached. During shut-
tions in steel shops. Simulated aging tests can be now waived in down, the equilibrium solubility of hydrogen is lower, and the
the case of high quality steelmakers provided that Watanabe’s J- hydrogen tries to equilibrate to room temperature conditions,
factor remains below 100 and 54J Impact energy temperature is hence diffusing through low-alloy base and austenitic overlay.
below 60
C. If one on those two conditions is not achieved, step- Fig. 6 depicts steady state concentration gradient of hydrogen
cooling tests have to be performed. through a reactor wall during operation and after cooling. Note that
the concentration in the low-alloy steel is highest at the interface
3.2. Hydrogen embrittlement of CreMo steels with the austenitic stainless steel overlay. One common problem
associated with the diffusion of hydrogen is Hydrogen Induced
Hydrogen embrittlement of CreMo reactor steels has not been Disbonding (HID) phenomenon. This is discussed in detail in a
studied as much as temper embrittlement judging by the lack of paper from Coudreuse et al. [13]. Also discussed in this latter paper
data available in literature. Nevertheless, it is one of the most crit- is a method to compute hydrogen concentrations and gradient
ical problems in refining plants. Atomic hydrogen comes from the through the wall thickness.
dissociation of hydrogen molecules at high pressures and temper- Fig. 7 shows the results of a calculation of hydrogen concen-
atures, and from cracking of hydrocarbon molecules in the reactor. tration in low-alloy steels reactor wall after cooling. Methodology,
Hydrogen is absorbed onto the surface, and then diffuses into the geometry and data used for calculation are ones given in the paper
steel during the production cycle. At steady state conditions, by Pillot et al. [14].

Base Materials
MC
1%
99%
3 ppm H2
4 ppm H2
Aged - no hydrogen
Aged - 1,5 to 4ppm
KIC ( MPa.Vm)

KI

T-To (To=FATT-80°C) (°C)

Fig. 11. Review of KIC data for 2,25Cre1Mo steel (as delivered, aged, hydrogen charged and aged þ hydrogen charged conditions).
 S. Pillot et al. / International Journal of Pressure Vessels and Piping 110 (2013) 17e23
The embrittling effect of hydrogen in CreMo steel is very close
to that attributed to temper embrittlement. Considering either CVN
transition curves (with and without hydrogen) or fracture me-
chanics toughness transition curves, the effect of hydrogen results
in an upward shift of transition temperature.
Recent CVN transition curves have been published by Sakai et al.
[15] for 2,25Cre1Mo steel grade and Pillot et al. [16] for 2,25Cre
1Mo, 2,25Cre1MoeV and CeMn steels. Figs. 8 and 9 show the shift
in TK54J (temperature for which average impact energy equals 54J)
values in the case of 2,25Cre1Mo and 2,25Cre1Mo-V steel
respectively. Values are shown for base metal, HAZ, and weld metal,
in “as-delivered” and after Step-Cooling conditions as a function of
hydrogen concentration in the bulk.
Fig. 10 shows the shift in CVN transition temperature due to
hydrogen concentration after various heat treatments. This corre-
sponds to the slope of curves given in Figs. 8 and 9. These slopes
indicate the loss of toughness as a function of ppm of hydrogen in steels.
Fig. 11 shows the decrease in fracture toughness with increasing
hydrogen content. It can be seen that the higher the hydrogen
content, the higher the transition temperature. Another way to
evaluate the effects of hydrogen is to consider the toughness at a
given temperature and then, the higher the hydrogen content, the
lower the toughness.
The main database concerns KIC values of base materials in as
delivered conditions. Some data relative to aged material and
hydrogen charged material are also plotted in this figure. In this
plot, KIC is represented as a function of T  T0, where T0 is the
temperature for which static toughness is equal to 100 MPaOm. In
this case, T0 is indexed on FATT temperature obtained with CVN
specimens.
The case of vintage reactors as well as an application of the MPT
determination rules to a virtual pressure vessel will be developed in
Part II of this contribution.
4. Conclusions
The synergistic effect of in-service aging and embrittlement of
steel material under high-temperature and hydrogen atmosphere
conditions have been presented in this paper, emphasizing the
importance of taking into account effect of hydrogen even in low
quantities in the metal. It has been demonstrated that a knowl-
edgeable steel supplier is able to deliver a material that will be
much more resistant to embrittling effects thanks to rigid control of
the delivered metallurgy.
23
Some assumptions on effects of hydrogen on fracture or CVN
toughness have also to be taken into considerations and well vali-
dated. Hydrogen embrittlement is a very complex phenomenon
and very few data are available. Then, particular attention must be
paid to this matter.
References
[1] Chauvy C, Coudreuse L, Bourges P. Consequences of PWHT requirements on
service properties for petrochemical grades. Graz: IIW; 2008.
[2] Pillot S, Balladon P, Bourges P, Bertoni A, Clergé M, Boucher C. Optimisation of
ISR and PWHT of CrMoV steels. In: ESOPE 2004, European symposium on
pressure equipment; 2004.
[3] API.934.A. Materials and fabrication of 2,25Cr-1Mo, 2,25Cr-1Mo-0,25V,
3Cr-1Mo, and 3Cr-1Mo-0,25V steel heavy wall pressure vessels for high-
temperature, high-pressure hydrogen service. API 934-A. American Petro-
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