Journal of Materials Processing Technology 164165 (2005) 964970

Effect of post weld heat treatment on the oxide scaling

of CrMo steel weldments
A. Al-Mazrouee a,b, , R.K. Singh Raman a , R.N. Ibrahim b
a School of Physics and Materials Engineering, Monash University, Melbourne 3800, Australia
b Department of Mechanical Engineering, Monash University, Melbourne 3800, Australia

Abstract

Welding of chromiummolybdenum ferritic steels often causes steep modifications in the microstructure of the weld heat affected zone
(HAZ). The paper presents results to establish the role of such microstructural variations on inhomogeneous scaling across the weldments
of 2.25Cr1Mo and 9Cr1Mo steels, as well as further degradation in microstructure during oxidation of the weldments. Microstructure of
different regions of the steel weldments was characterized by electron/optical microscopy. Oxidation of different weldment regions in air and
steam environments have clearly suggested variations in scaling rates across the weldment regions, and further microstructural degradation
in the HAZ. The paper also presents a report of the effect of post weld heat treatment on oxide scaling behavior. This paper contributes in the
correlation between welding parameters and oxidation behavior.
2005 Elsevier B.V. All rights reserved.

Keywords: 2.25,9Cr1Mo steel; PWHT; Oxide scaling; Microstructural degradation

1. Introduction steels possess a superior combination of elevated temper-

Low-alloy chromiummolybdenum (CrMo) ferritic
steels (viz., 2.25CrlMo and lCr0.5Mo steels) possess a
good combination of mechanical properties, weldability,
formability and corrosion resistance [14]. Because of the
attractive combination of properties, CrMo steels are used
extensively in moderately high temperature (623823 K) ap-
plications, for example, the steam generators of the fossil-
fuel power plants. For applications in stringent corrosive en-
vironments and/or at temperatures higher than 823 K, steels
with higher chromium contents (512%) have been devel-
oped. 9Cr1Mo steels possess improved mechanical prop-
erties and corrosion resistance to its popular predecessor,
2.25Cr1Mo steel [5,6]. 9Cr1Mo steels were originally de-
veloped for steam generators and superheaters of US fast
breeder nuclear reactors, and were subsequently studied ex-
tensively also for its similar use in European fast breeder
reactors [7]. In comparison to 2.25Cr1Mo steels, 9Cr1Mo
Corresponding author.
E-mail address: abdulla.al-mazrouee@eng.monash.edu.au
(A. Al-Mazrouee).
ature mechanical properties and resistance to stress corro-
sion cracking and other forms of corrosion. The modified
version of 9Cr1M steel, which is commercially known as
T91 for tube application and P91 for piping, may be ide-
ally suited to new supercritical boilers at metal tempera-
tures of 873898 K and steam temperatures of up to 838 K.
9Cr1Mo steels, which are currently in limited use in high
temperature components in Australian power plants, are con-
sidered for wider applications in the local power industry.
This paper presents some of the on-going investigation at
Monash University to develop/adopt a procedure that re-
duces microstructural degradation in the vicinity of the weld-
ment.
2. Microstructure of weldments of CrMo steels
The microstructure of CrMo ferritic steels are very
susceptible to thermomechanical treatments, which are of-
ten exploited to develop carbide precipitates of the re-
quired morphology and distribution to effect precipitation
hardening. However, due to their metastable structure and

0924-0136/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmatprotec.2005.02.222
 A. Al-Mazrouee et al. / Journal of Materials Processing Technology 164165 (2005) 964970
morphology, the strengthening precipitates are known [911]
to undergo extensive changes during thermomechanical treat-
ments such as welding, or during prolonged ageing, ren-
dering deterioration in the mechanical properties of the
weldments.
For example, microstructures of the weld metal, the HAZ
and the base metal of the weldment of 2.25Cr1Mo steel are
different from each other and their detailed description can
be found elsewhere [12,13]. The weld metal of 2.25Cr1Mo
steel has a lath-like arrangement of upper bainite with the lath
boundaries decorated with carbides. The base metal consists
of a mixture of granular bainite and proeutectoid ferrite; the
prior austenite grain boundaries and the bainitic region are
populated with precipitates. Microstructure of HAZ is distin-
guished from both weld metal and base metal, for variations
in grain size and type and extent of secondary precipitation.
Transmission electron microscopy of the HAZ when com-
pared with those of the weld metal and the base metal, have
revealed the differences in the morphology and distribution
of the secondary precipitates. The base metal microstruc-
ture suggests occurrence of bulky precipitates (believed to be
Fe3 C [10]) at and around the prior-austenite grain boundaries
while the interior of the bainitic area is populated largely with
fine precipitates. The fine precipitates, are needle shaped and
in clusters, which are the typical features of the Mo-based
carbides of M2 C type [9,12]. The morphology and distribu-
tion of the precipitates in the weld metal are broadly sim-
ilar to those observed in the base metal whereas those in
the HAZ have distinctly different features. An insignificantly
low population of the needle shaped precipitates (M2 C) dis-
tinguished the microstructure of the HAZ. The precipitates
predominantly present in the HAZ are either parallelepiped
shaped or rod shaped, which are the respective typical
shapes (morphologies) of M7 C3 and M23 C6 types of carbides
[9,12].
As a result of the undesirable transformations in the mi-
crostructure in the HAZ, the creep rupture life of the weld-
ments of CrMo steels is reported to be poor [1416], to
the extent that the creep-rupture of the weldments is often
the life-limiting factor (creep is defined as a time-dependent
deformation at elevated temperatures). Since weldments are
Fig. 1. Oxidation of weldments of 2.25Cr1Mo steel at 773 K for 500 h: (a) surface profile describing the difference in thickness of oxide scales over weld
metal and HAZ, and (b) oxidation kinetics of weld metal, base metal and HAZ [18].
965
an indispensable part of most component fabrications, con-
siderable effort has been directed in the past few decades, to
the correlation of the in-service failure with the microstruc-
tural degradation caused during welding of CrMo steels 1
[2,1014,16,17].
3. Non-homogenous scaling across CrMo steel
weldments
As discussed earlier, microstructural changes due to weld-
ing of 2.25Cr1Mo steel include additional chromium-rich
precipitate formation and/or enrichment of chromium in the
existing secondary precipitates in the HAZ adjoining the weld
metal [2,912]. Trapping of free chromium (in the matrix),
through chromium-rich carbide precipitation in the HAZ of
CrMo steel weldments, and consequent formation of a less
protective scale during subsequent oxidation [10,16] may re-
sult in development of a thicker oxide scale over the HAZ
than the other regions of the weldment, viz., weld metal and
base metal regions.
Air-oxidation of the weldments of CrMo steels has been
reasonably investigated [12,13,1921]. A typical surface pro-
file describing the difference in thickness of the oxide scales
over the weld metal and HAZ of the oxidized weldment of
2.25Cr1Mo steel (shown in Fig. 1a) has unambiguously es-
tablished that a much thicker scale forms (viz., nearly 14 m
thicker) over the HAZ region. The greater scale thickness
over HAZ is also confirmed by the oxidation kinetics of dif-
ferent regions separated out of the weldments, as shown in
Fig. 1b.
Recent investigation of high-temperature oxidation of
weldments of 9Cr1Mo steel have also suggested non-
homogeneous scaling across the weldment regions, as evi-
denced from the surface profile and scaling kinetics (shown
in Fig. 2). However, it is interesting to note that unlike the
weldments of 2.25Cr1Mo steel, where scaling of HAZ was
found to be greater than the neighbouring basemetal and weld
metal regions (Fig. 1), in the case of 9Cr1Mo steel, it is the
weld metal region that oxidized at a higher rate than the HAZ
or base metal regions.
966 A. Al-Mazrouee et al. / Journal of Materials Processing Technology 164165 (2005) 964970

Fig. 2. Oxidation of weldments of 9Cr1Mo steel at 923 K: (a) surface profile describing the difference in thickness of oxide scales developed in 100 h over
weld metal and HAZ, and (b) oxidation kinetics of weld metal, base metal and HAZ, for 500 h [18].

4. PWHT as a welding parameter
Generally, fabrication and repair of CrMo steels requires
a PWHT. The main advantages of PWHT are to relieve
residual stresses and to enhance the HAZ properties. As
a result, many researchers [2226] concentrate on PWHT
treatments and their role in mechanical properties of the
weldment. However, there is no enough work on the ef-
fect of PWHT treatments on the oxidation behavior of the
weldment.
Recent investegation on the effects of different PWHT
treatments on oxidation behviour showed a reduction in the
oxidation resistanece of basemetal of annealed PWHT in
steam for 500 h at 823 K. The data of gain mass (m) per
unit area as a function of time, representing the kinetics of
steam oxidation of the material at each temperature are given
in Fig. 3.
As a result, the basemetal of the annealed PWHT has
thicker oxide scale than conventional PWHT (see Fig. 4).
On the other hand conventional PWHT did not show any
significant reduction in the oxidation resistance and the ox-
ide thickness is similair to the normalised and tempered base
metal.
PWHT is not always preferred because it is sometimes
expensive and in many cases very complicated. The main
opposition to PWHT is that the activity can considerably in-
crease the cost of welding due to the significant time delays
and the equipment required. This can be a particularly se-
vere problem if PWHT is performed under conditions where
control of temperatures is difficult. Sometimes factors such
as geometry of component or the location of the repair may
be an obstacle for PWHT. Also, excessive PWHT tempera-
tures have been found to decrease the creep resistance of the
HAZ in 2.25Cr1Mo steel [27]. PWHT may also affect the
nearby components, which require replacement or machining
to restore tolerance, thereby increasing both downtime and
cost.
Different procedures such as temper bead welding (TBW)
have been developed as a result of the increasing need for
welding repair and to eliminate PWHT. The TBW tech-
nique is an attractive alternative to PWHT, which is other-
wise essential for repair welding. TBW makes use of the

Fig. 3. kinetics of steam oxidation at 823 K for 500 h.

 A. Al-Mazrouee et al. / Journal of Materials Processing Technology 164165 (2005) 964970
Fig. 4. SEM microgrph showing cross section of the thicker oxide scale
formed over anneald PWHT basemetal.
welding procedure to achieve the optimum microstructure
without PWHT. It uses the heat of each pass in the first
layer to refine the HAZ of the adjacent pass using 50%
overlap. Then with the higher heat input of the second
layer the metallurgical structure of the first layer is tem-
pered. Thus the metallurgical structures aimed for PWHT
are achieved through TBW and accordingly PWHT is elim-
inated. The use of the TBW technique has been proved to
be adequate for the integrity of a repaired component in-
cluding those constructed out of 2.25Cr1Mo steels [28].
TBW might effect the oxidation behavior of the HAZ and the
weld metal, therefore a study is going on to investegate that
effects.
5. Oxide scale thickness in context of failure analysis
Crack growth history of a failed can be determined by
examination of oxide scales that form at the fracture surface of
a cracking high temperature component. This technique, that
has been applied in failure investigations of boiler headers,
steam pipes, steam chests/castings, weldments and turbine
blades [29], involves measurement of the thickness of oxide
scales at locations between which the crack velocity is to be
determined [30]. Such measurements of oxide scale thickness
over the entire fracture surface will provide the crack growth
history.
In relation to assessment of crack growth from scale
thickness measurement, the non-homogeneous scaling across
the welments of CrMo steels and the PWHT (as de-
scribed/established in Sections 3 and 4 above), could lead
to an erroneous estimations. A greater scaling rate of HAZ,
base metal of annealed PWHT of 2.25Cr1Mo steel and weld
metal of 9Cr1Mo steel, can overestimate the exposure time
(and, hence, underestimate the crack velocity). Therefore,
while determining the crack growth history of welded com-
ponents, it will be necessary to take into account the different
scaling rates of the steel weldments.
967
6. Oxidation-assisted microstructural degradation
Intergranular cavitation and rupture life of metallic materi-
als are reported to be influenced by both the environment and
secondary precipitation1 [8,32] as well as the internal pre-
cipitation caused by the residual oxygen in the alloy matrix
[33]. This section discusses an investigation on the oxidation-
assisted microstructural degradation in a 2.25Cr1Mo steel
weldment.
In a critical investigation [19], specimen coupons includ-
ing the weld metal, heat affected zone (HAZ) and base metal
regions were oxidised at 873 K in steam. A cross-section
through the oxidised specimen of HAZ (seen in Fig. 3) ex-
clusively suggested features of cavitation at the alloy grain
boundaries. No grain boundary cavitation was observed in
the region adjacent to the sub-scale regions in the oxidised
specimens of weld metal and base metal.
It takes a specific combination of oxygen partial pressure
beneath the external scale, alloy microstructure, temperature
and the nature of resulting external scale to establish and sus-
tain internal oxidation. The more-protective inner scales (i.e.,
those scales with high Cr contents), which formed on both the
weld metal and the base metal, resulted in a limited inward
diffusion of oxygen ions, and hence a less extensive internal
oxidation. A less-protective inner scale formed in the case of
the HAZ, presumably permitted a greater inward diffusion
of oxygen ions, thus facilitating a greater concentration of
oxygen available for reaction with the chromium of the al-
loy matrix. More rapid diffusion of oxygen ions through the
HAZ scale caused extensive internal oxidation and formation
of a subscale zone densely populated with internal precipi-
tates. Depletion of Cr, due to extensive internal precipitation
in the subscale zone of oxidised HAZ, may necessitate dif-
fusion of Cr from adjacent areas in the alloy matrix, which
will potentially lead to the generation of excess vacancies.
These vacancies, preferentially annihilating at grain bound-
aries, could lead to the grain boundary void formation, seen
in Fig. 5.
Grain boundary cavitation resulting from extensive inter-
nal oxidation can provide an easy path for crack propagation
[31,34], and hence needs to be taken into account for high
temperature component design because it has a direct bear-
ing on the creep/fatigue life. In this context, the oxidation-
assisted grain boundary formation in the alloy matrix neigh-
bouring the subscale zone in the oxidised HAZ specimen
is particularly important since in-service failures are com-
monly found to occur in the HAZ of the welded components
of 2.25Cr1Mo steel1 [4,16].
Samples of 2.25Cr1Mo steel tubes in service of 150,000 h
at 813 K were received from a power plant. The base metal
showed no evidence of creep cavitation damage. On the other
hand, severe oxidation is evident in the vicinity of the flash
welding area. The HAZ suffered excessive corrosion than the
base metal and some oxide notches can be seen in Fig. 6.
Also, internal oxidation is observed to be more evident in
the vicinity of HAZ. Depletion of Cr, due to extensive internal
968 A. Al-Mazrouee et al. / Journal of Materials Processing Technology 164165 (2005) 964970

Fig. 5. Magnified features in the sub-scale and adjacent zones in the HAZ
of 2.25Cr1Mo steel weldment. The arrows indicate regions of extensive
precipitation and void formation in the sub-scale (B), and grain boundary
cavitation in the adjoining area (C) [19].
Fig. 7. Extensive precipitation and void formation in the sub-scale and grain
boundary cavitations.
effect, an experimental program is underway at Monash Uni-
versity to adopt a suitable temper bead welding process or
PWHT for welding 2.25Cr1Mo and 9Cr1Mo steels. The
salient features of this program are described below.
Temper-bead technique (see Fig. 9) is an approved proce-
dure to escape from post weld heat treatment (PWHT), which
can be in some cases difficult or impossible to undertake. It is
used successfully for repair in power industry using shielded
metal arc welding process [35] which is in some ways a low
productivity process.
An alternative and high productivity process, namely, flux
cored arc welding (FCAW) is nominated to be a cost effec-
tive choice for repair. Although the FCAW process is rela-
tively old, it represented less than 5% of the total amount of

Fig. 6. Oxide notch confined within HAZ.

precipitation in the subscale zone of oxidized HAZ is clear

in Figs. 5, 7 and 8.
The grain boundary cavitation is evident in the weldment
area which requires more attention during the life assessment
of these components.

7. Industrial relevance and future work

Creep strength of the weldments of CrMo steels is re-

ported to be poor [14,15], to the extent that about 80% of the
failures are reported [16] to take place in the welds and HAZs.
As discussed in the preceding sections, the microstructural
degradation caused during welding as well as during oxida-
tion are the critical factors contributing to inferior creep prop-
erties of the weldments. It is important therefore to try and de- Fig. 8. Magnified features in the sub-scale and adjacent zones in the HAZ of
velop/adopt such welding procedures that produce relatively ex-serviced 2.25Cr1Mo steel weldment. Arrows indicate grain boundary
less deterioration in microstructure of the weldments. To this cavitations.
 A. Al-Mazrouee et al. / Journal of Materials Processing Technology 164165 (2005) 964970
Fig. 9. Temper bead welding. Second Layer boundary depth (F) + average
height of the first weld layer (H); second layer refining depth (R) [38].
welding done in 1965, then in 1980 it passed the 20% mark
and has been rising since then [37]. This process is becom-
ing an acceptable welding code, as it produces high quality
weldments [36]. The scope of the current studies is to adopt
the optimum parameters for temper-bead welding (TBW) in
conjunction with FCAW. The primary purpose of TBW is
to introduce the stress relieving during the controlled weld-
ing process itself, and thus avoids the need for PWHT and
deleterious microstructural changes. On the other hand, when
PWHT is the only option a new proposed PWHT [28] may be
beneficial in reducing the corrosion-assisted microstructural
degradation encountered in the weldment of 2.25Cr1Mo
steels.
New PWHT procedure showed a good result in laboratory
creep tests [22] and oxidation behavior should to be investi-
gated.
The proposed work will also investigate the oxide scaling
characteristics of weldments produced by TBW Technique,
conventional PWHT and annealed PWHT.
8. Conclusions
The inhomogeneous scaling across the weldments of
2.25Cr1Mo and 9Cr1Mo steels presented in this paper
identifies the possibility of over- or under-estimation of creep
life of welded components if the current practice of assess-
ment failures and remnant creep assessment is applied to
the weldments. For an accurate assessment using oxide scale
thickness, the paper establishes a case for further investiga-
tions by correlating kinetics of the scale thickness growth
across the broadly different (microstructural) zones (viz.,
weld metal, heat affected zone (HAZ) and base metal) of the
steel weldments, in the environments of steam and air. Also,
it shows the role of PWHT in affecting oxidation behavior of
the base metal of the weldment of 2.25Cr1Mo.
For an improved understanding of the deterioration in the
mechanical properties due to deleterious alloy microstruc-
ture, it will be necessary to carry out further investigations as
listed below:
969
Characterising corrosion-assisted microstructural degra-
dation in the alloy matrix across the broadly different
(microstructural) zones (viz., weld metal, HAZ and base
metal) of the steel weldments, in the environments of air
and steam, and thus investigating the role of the environ-
ment in facilitating microstructural degradation,
investigation of the application of temper bead welding
(TBW) and annealed PWHT in improving in-service per-
formance welded structures, and the influence of TBW and
Annealed PWHT in oxide scaling behaviour.
Acknowledgements
The authors appreciate the help of Professor John Price
and Alan Beveridge for their cooperation and interest in the
work.
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