Role of Microstructural Degradation in the Heat-Affected Zone

of 2.25Cr-1Mo Steel Weldments on Subscale Features during

Steam Oxidation and Their Role in Weld Failures
R.K. SINGH RAMAN

Microstructural degradations in the base metal adjacent to the weld pool, i.e., the heat-affected zone
(HAZ), caused during welding of 2.25Cr-1Mo steel, were characterized by electron and optical
microscopy of different regions of the weldments. In order to study the influence of the microstruc-
tural degradations on scaling kinetics in steam and the resulting subscale features, samples of the
base metal, the HAZ, and weld metal specimens were extracted from the weldment and oxidized in
an environment of 35 pct steam 1 nitrogen at 873 K for 10 hours. Oxide scales formed in the three
regions and the underlying subscales were characterized using scanning electron microscopy (SEM)
and electron probe microanalysis (EPMA). Influence of the ‘‘free’’ chromium content in the three
weldment regions on protective scale formation and on the subscale features has been investigated.
As the principal achievement, this study has clearly shown the occurrence of oxidation-induced void
formation in the subscale zone and grain boundary cavitation in the neighboring area during steam
oxidation of the HAZ. This article also discusses the possible role of oxidation-induced void for-
mation and grain boundary cavitation in the inferior service life of welds in 2.25Cr-1Mo steel com-
ponents.

I. INTRODUCTION nents.[9] Since weldments are an indispensable part of most

LOW-ALLOY ‘‘Cr-Mo’’ ferritic steels, viz., 2.25Cr-
1Mo and 1Cr-0.5Mo steels, are used extensively in the
steam generating and handling systems of power plants (in
the temperature range of 623 to 873 K) because they satisfy
the required mechanical properties, weldability, formability,
and corrosion resistance.[1,2] Common applications of
2.25Cr-1Mo steel include reactors for refining and process-
ing of petroleum and high-temperature/high-pressure
vessels for thermal reforming, polymerization, alkylation,
and hydrocracking.[3–6] This material is also a strong can-
didate for the fabrication of pressure vessels used for the
gasification and liquefaction of coal.[7]
The microstructures of Cr-Mo ferritic steels are very sus-
ceptible to thermomechanical treatments. This microstruc-
tural susceptibility is often exploited in order to develop
carbide precipitates of a required chemistry, morphology,
and distribution to effect precipitation hardening. However,
due to the metastable nature of the chemical composition
and the morphology of the strengthening precipitates, the
secondary precipitates undergo undesirable transformations
during elevated temperature service and/or thermomechan-
ical treatments experienced during fabrication, viz., weld-
ing, forging, hot rolling, etc.
The strength of the weldments of these steels is generally
reported to be inferior,[7,8] to the extent that the creep rup-
ture of the welds is often the life-limiting factor. In fact,
about 80 pct of the in-service failures are reported to take
place in the weld region of low-Cr ferritic steel compo-
R.K. SINGH RAMAN, Postdoctoral Research Associate, is with the
Department of Communication and Electronic Engineering, Royal
Melbourne Institute of Technology (RMIT), Melbourne-3000, Australia.
Manuscript submitted April 22, 1997.
component fabrication, considerable efforts have been di-
rected, in the past three to four decades, to the correlation
of the in-service failure of these steels with the microstruc-
tural degradation caused during welding.
A. Microstructural Features and Oxidation Resistance of
2.25Cr-1Mo Steel
Microstructural changes due to welding include varia-
tions in the grain size in the area adjoining the weld metal
(i.e., the heat-affected zone (HAZ)) and enrichment of Cr
in the secondary precipitates and/or additional Cr-rich pre-
cipitate formation.[1,2,7,9–11] Trapping of ‘‘free’’ chromium
(in the matrix) through Cr-rich precipitate formation and
variations in grain size is reported to alter the oxidation
resistance of low-Cr alloys.[12,13,14] For example, the heat
treatments which cause depletion of chromium due to Cr-
rich carbide formation impair the oxidation resistance of
2.25Cr-1Mo steel by forming a less protective scale. In a
similar way, the HAZ of Cr-Mo steel weldments, in which
extensive formation of Cr-rich precipitates occurs,[10,11] may
exhibit a greater oxidation rate than other weld regions.
Low-chromium steels are also known to undergo internal
oxidation[12,15] resulting in distinct ‘‘subscale’’ formation
(subscale is the region underneath the external oxide scale).
The surface scaling-rate data are generally of secondary im-
portance to design engineers (primarily because surface
scaling of steels follows parabolic kinetics, and the scaling
rate decreases considerably after the initial period). How-
ever, internal oxidation at alloy grain boundaries and as-
sociated phenomena, which may provide an easy path for
crack propagation,[16,17,18] would clearly be of direct rele-
vance to component design engineers because of its direct
bearing on the creep/fatigue life of welded components of
Cr-Mo steels.

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 29A, FEBRUARY 1998—577

B. Effect of Localized Oxidation on Mechanical
Properties
It is well known that the in-service gaseous environments
encountered by Cr-containing steels can play a significant
role in determining their mechanical properties.[16,17] To that
extent, metal loss due to high-temperature corrosion (scal-
ing) is generally taken into account when designing com-
ponents (especially thin-walled components) composed of
Cr-Mo–based alloys,[8] and a design allowance is given
based on the scaling-rate data of the base alloy. However,
recent studies on 2.25Cr-1Mo steel[13] have suggested that
the microstructural changes incorporated in the base alloy
upon certain heat treatments can change the scaling rate.
The microstructural changes, as indicated in these studies,
can also alter the extent of related localized corrosion phe-
nomena in the alloy matrix underneath the external scale,
viz., internal oxidation in the alloy matrix and at the alloy
grain boundaries. Localized corrosion is reported to influ-
ence the creep and fatigue properties,[16] due to one or more
of the following phenomena:
(1) crack initiation due to grain boundary oxidation;[16]
(2) crack blunting and arrest due to excessive oxidation at
the grain boundary crack tip;[17,18,19]
(3) grain boundary strengthening due to preferential oxide
precipitation;[19,20,21]
(4) selective leaching of alloying elements from the areas
adjacent to grain boundaries, and vacancy and void for-
mation, which can assist crack propagation;[19,20,21] and
(5) grain boundary cavitation resulting from annihilation of
vacancies created due to selective leaching.[18,19,22]
The prevalence of these phenomena will be governed by
the availability of the selectively oxidized alloying element
(e.g., Cr in Cr-Mo steels) and the oxygen pressure under-
neath the external scale, which is dictated by the nature of
the scale. A study on creep of a stainless steel by Rodri-
guez[17] has clearly demonstrated a transition from a weak-
ening to a strengthening effect on creep as the oxygen
content of the environment was increased from 70 to 256
ppm. The weakening was caused due to the prevalence of
grain boundary notch sharpening at low oxygen contents,
whereas the strengthening occurred due to blunting at the
notch tips at high pressures.
In-air oxidation studies of 2.25Cr-1Mo steel[12] have sug-
gested the extensive occurrence of internal oxidation at the
alloy grain boundaries, sometimes to the extent of detach-
ing the alloy grains from the matrix, which can significantly
degrade the mechanical properties. Smith and Marder[23]
have observed very clear and deep notches along the grain
boundaries of a circumferentially cracked water boiler tube
of 2.25Cr-1Mo steel in a sulfur-containing environment,
and have attributed the component failures to such cracks.
As described earlier, the deleterious effects of localized cor-
rosion, viz., grain boundary penetration/cavitation, etc.,
which can impair the mechanical properties of the alloys,
have not been investigated for any types of Cr-Mo steel
weldments. As an essential part of the mechanism of lo-
calized corrosion (viz., internal oxidation) at grain bound-
aries, the grain boundary diffusion of alloying elements
and, hence, the average grain size of the alloy, will be im-
portant factors.
Both grain size variation and Cr-rich carbide precipita-
tion can occur in the HAZ of the weldments of Cr-Mo
578—VOLUME 29A, FEBRUARY 1998
ferritic steels. In the HAZ of Cr-Mo ferritic steels, Cr-rich
carbide formation and Cr enrichment in the existing sec-
ondary precipitates, which can be detrimental for corrosion
properties, are both reported[10,11] to occur. However, the
inferior mechanical properties of the HAZ of these steels
have generally been attributed only to the role of these mi-
crostructural changes in degrading the deformation prop-
erties of the HAZ of the steel.[1,2,7] The role of precipitation
in localized corrosion properties and, in turn, in alteration
of the mechanical properties, has not received attention, ex-
cept for some comments in one article on the mechanical
properties of 2.25Cr-1Mo steel welds, which indicated en-
hanced grain boundary oxidation and localized Cr depletion
as the possible causes of the degradation of mechanical
properties.[24]
C. Oxidation Resistance/Localized Oxidation of Cr-Mo
Steel Welds
The first reported investigation of in-air, high-tempera-
ture corrosion of weldments of Cr-Mo ferritic steel revealed
that the HAZ oxidized at a much higher rate than the weld
metal and the base metal.[25] The disappearance of fine Mo-
based carbide precipitates and an increase in the amount of
coarse, incoherent precipitates (enriched in Cr) are believed
to be responsible for the inferior mechanical properties of
the HAZ. The Cr depletion has been found to be respon-
sible as well for the inferior corrosion resistance of the
HAZ.[25] Further, creep ruptures are reported to occur in the
intercritical region, a subzone within the HAZ. A recent
study[14] has suggested that the intercritical region has a
high susceptibility for localized attack at the grain bound-
aries and within grains having a high density of precipitates.
Considering the diversity of the prior thermomechanical
treatments and service conditions experienced by Cr-Mo
steels, the information generated by the recent in-air corro-
sion studies can be called a very useful preliminary step in
the direction of understanding the role of microstructural
changes in steel weldments on high-temperature corrosion,
and, in turn, on the mechanical properties of welds. Never-
theless, the studies carried out so far on the high-temperature
corrosion of weldments have not addressed localized corro-
sion (internal oxidation) and associated phenomena, which
could cause crack initiation and propagation. Such studies
will be of direct relevance in the context of understanding
and controlling weld failures. The extent of internal oxida-
tion and grain boundary penetration, and, more importantly,
the rate of grain boundary penetration, will be relevant to
component design engineers for its direct bearing on the
creep/fatigue life of welded components of Cr-Mo steels.
Indeed, grain boundary penetration is considered to be one
of the prime criteria for the assessment of Cr-Mo steel for
high-temperature applications in aggressive environments.[26]
Another important aspect is the role of the environment
on the oxidation rate and the type and extent of localized
corrosion (internal oxidation). As discussed earlier, in ad-
dition to the alloy composition/microstructure and the na-
ture of the scale developed on an alloy, the internal
oxidation will also be governed by the nature of the oxidant
and its partial pressure underneath the scale. There are no
reports on the influence of steam environments on the char-
acteristics of internal oxidation and subscaling in micros-
tructurally different regions in steel weldments.
METALLURGICAL AND MATERIALS TRANSACTIONS A
 Table I. Chemical Composition were distinguished on the basis of microstructural dissimi-
larities. The type and extent of secondary precipitation in
Elements (Wt Pct)
the three regions was characterized by transmission electron
Materials C Si S P Cr Mo Fe microscopy (TEM) using carbon extraction replicas of the
Base metal 0.06 0.18 0.008 0.008 2.18 0.93 bal three regions. Details of the weld characterization can be
Weld metal 0.05 0.40 0.020 0.012 2.30 1.10 bal found elsewhere.[14]

Table II. Welding Conditions B. Specimen Separation and Steam Oxidation

Process MMA On the basis of their microstructural dissimilarities, spec-
Electrode diameter 3.15 mm imen coupons of the weld metal, HAZ, and base metal were
Preheat 473 K separated using a precision wafering blade and employing
Arc voltage 22 V repetitive metallographic examination. The HAZ, being a
Arc current 110 A narrow region, was ascertained by several cycles of polish-
Welding speed 3.75 mm s21 ing, etching, and microscopic examination, so that the HAZ
specimens consisted only of the corresponding microstruc-
tures (i.e., the HAZ specimen did not consist of the neigh-
boring base metal or weld metal microstructures).
Sample coupons of the base metal, HAZ, and weld metal
(separated from the weldment, as shown in Figure 1) were
oxidized in an environment containing a mixture of 35 pct
steam and nitrogen (oxygen pressure : ;1025 atm) at 873
K for 10 hours in a thermobalance.

C. Characterization of Scales and Subscale Regions

Fig. 1—Schematic diagram showing locations of weld metal, HAZ, and
base metal in weldment and cuts for separating the weld metal, HAZ and
base metal specimens.
The present study has been carried out to investigate the
steam oxidation of weldments of 2.25Cr-1Mo steel, and it
aims to develop an understanding of the following: (1) the
nature and kinetics of scale formation over the weld metal,
the HAZ, and the base metal regions of the weldments; (2)
the internal oxidation, alloy grain boundary oxidation, and
grain boundary cavitation in different weldment regions,
and how these phenomena are influenced by the nature of
scale and alloy microstructure; and (3) the possible role of
these phenomena in weld failures. The purpose of the pres-
ent study is, mainly, to investigate the role of microstruc-
tural variations in the as-welded material.
II. EXPERIMENTAL PROCEDURES
Oxide scales and the underlying subscale regions devel-
oped on the weld metal, HAZ, and base metal specimens
during steam oxidation were characterized by scanning
electron microscopy (SEM), electron probe microanalysis
(EPMA), and X-ray diffraction (XRD). The morphology of
the scales in the three regions was compared by SEM, and
the oxides in the scales were identified by XRD. In order
to reveal the features across the scale, the subscale, and the
adjacent alloy matrix, the oxidized specimens were
mounted on their cross section, polished, and etched. Fea-
tures in the cross sections were observed by SEM, and their
chemical characterization was carried out by EPMA line
profiles for Fe, Cr, and O across the scale and subscale
regions.
III. RESULTS
A. Electron Microscopy and Optical Microscopy of
Different Regions of Weldment

A. Weld Preparation and Characterization
Plates (12-mm thick) of 2.25Cr-1Mo steel base material
(composition as given in Table I) were supplied by Thyssen
Stahl Aktiengsell Schaft (Germany) in the normalized-plus-
tempered condition (austenitized at 1223 K for 17 minutes
followed by air cooling; tempered at 1003 K for 60
minutes). The normalized-and-tempered plates were welded
together by the manual metal arc (MMA) welding tech-
nique using basic-coated 2.25Cr-1Mo electrodes (details of
the welding process are given in Table II). The chemical
compositions of the base metal and the deposited weld
metal are given in Table I. Chromium contents of both the
regions are similar. Transverse sections of the weldment
were polished, etched (2 pct nital/20 seconds) and exam-
ined by optical microscopy. The three regions in the weld-
ment, viz., the weld metal, the HAZ, and the base metal,
The microstructures of the weld metal, the HAZ, and the
base metal of the weldment of 2.25Cr-1Mo steel are dif-
ferent from each other, and their detailed description can
be found elsewhere.[7,14] The weld metal of 2.25Cr-1Mo
steel has a lathlike 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. The microstructure
of the HAZ is distinguished from both the weld metal and
base metal by variations in grain size and type and extent
of secondary precipitation.
The TEM photomicrographs of the carbon replicas of the
HAZ, when compared with those of the weld metal and the
base metal, indicate differences in the morphology and dis-
tribution of the secondary precipitates, as shown in Figures
2(a) through (c). The base metal microstructure suggests

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 29A, FEBRUARY 1998—579


Fig. 2—TEM images showing needle-shaped secondary phase (Mo2C)
predominantly in (a) base metal and (b) weld metal and parallelepiped
and rod-shaped phases (M23C6 and M7C3) exclusively in (c) HAZ.
Fig. 3—Weight gain vs time plots of weld metal, base metal, and HAZ
samples separated out of 2.25Cr-1Mo steel weldment and oxidized in 35
pct steam 1 N2 at 873 K.
the occurrence of bulky precipitates (believed to be Fe3C[14])
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
580—VOLUME 29A, FEBRUARY 1998
Fig. 4—SEM micrograph showing general surface morphology of oxide
formed over the weld metal region of 2.25Cr-1Mo steel weldment
oxidized in 35 pct steam 1 N2 at 873 K for 10 h.
and in clusters (Figure 2(a)), which are the typical features
of the Mo-based carbides of an M2C type.[27] The mor-
phology and distribution of the precipitates in the weld
metal (Figure 2(b)) are broadly similar 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 (M2C) distinguished the micro-
structure of the HAZ. The precipitates predominantly pres-
ent in the HAZ are either parallelepiped-shaped or
rod-shaped (Figure 2(c)), which are the respective typical
shapes (morphologies) of the M7C3 and M23C6 types of car-
bides.[27]
B. Scaling Kinetics during Steam Oxidation
As shown in Figure 3, the HAZ oxidized at a consider-
ably higher rate than the base metal and the weld metal.
The oxidation kinetics of the three regions were found to
be close to parabolic. The parabolic rate constants (kp (mg2
cm24 h21)) for the three regions were found to be 7.7 for
the HAZ, 3.9 for the base metal, and 4.3 for the weld metal.
The term kp is related to the weight gain over unit surface
area (DW) by (DW)2 5 kpt, where t is the oxidation time.
C. Characterization of Scale/Subscale Regions
Unlike the featureless oxide morphology observed during
air oxidation of a 2.25Cr-1Mo steel weldment,[14] oxide
scales formed over the base metal, HAZ, and weld metal
regions show faceted oxide grains (Figures 4 through 6).
The faceted oxide grains generally indicate that the oxida-
tion occurred under a low oxygen partial pressure such as
that employed for oxidation tests in the present investiga-
tion. However, the scales formed over the HAZ consisted
of much coarser grains (Figure 5(a)) compared to those
over the weld metal (Figure 4) and the base metal (Figure
6). In addition to the overall coarse grain scale, the HAZ
scale is also distinguished by sporadic areas of excessive
scale growth, as shown through a typical micrograph in
Figure 5(b).
Cross sections of the oxidized samples of the weld metal,
HAZ, and base metal regions are shown in Figure 7 and in
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 5—SEM micrographs showing surface morphology of oxide formed
over the HAZ region of 2.25Cr-1Mo steel weldment oxidized in 35 pct
steam 1 N2 at 873 K for 10 h: (a) general surface morphology and (b)
morphology in the sporadic areas with excessive scale growth (indicated
as A).
Fig. 6—SEM micrograph showing general surface morphology of oxide
formed over the base metal region of 2.25Cr-1Mo steel weldment oxidized
in 35 pct steam 1 N2 at 873 K for 10 h.
the corresponding EPMA profiles for iron, chromium, and
oxygen in Figures 8 and 9. There are at least three distinct
layers in the cross sections of all three regions: a thick
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 7—SEM micrographs showing cross sections of oxide scales and
subscale zones formed over specimens extracted out of different regions
of 2.25Cr-1Mo steel weldment and oxidized in 35 pct steam 1 N2 at 873
K for 10 h: (a) HAZ, (b) weld metal, and (c) base metal.
compact-looking outer layer, a subscale region consisting
of extensive internal oxide precipitates, and a thin layer
between the external layer and the subscale. However, the
cross section of the oxidized HAZ specimen can be distin-
guished from those of the weld metal and base metal spec-
imens by two features, viz., a subscale with extensive void
formation and internal precipitation (the precipitates ap-
pearing blocky), and an additional region in the alloy ma-
trix adjacent to the subscale with features suggesting
cavitation or precipitation at the alloy grain boundaries in
this region. In fact, these grain boundary features were in-
dicated to be cavities, by observations at a higher magni-
fication (Figure 10), which was subsequently confirmed by
X-ray imaging. Hence, it can be concluded that grain
boundary cavitation occurred in the alloy matrix adjacent
to the subscale during oxidation of the HAZ. In this region,
interestingly, there are indications of cavitations even at
those grain boundaries which do not connect with the subs-
cale, as shown in Figure 11. No grain boundary cavitation
was observed in the region adjacent to the subscales in the
oxidized specimens of weld metal and base metal (Figure
VOLUME 29A, FEBRUARY 1998—581

Fig. 8—EPMA line profiles for iron, chromium, and oxygen in the scale,
subscale, and alloy matrix regions of (a) HAZ, (b) weld metal, and (c)
base metal regions (profiles starting from the points, A, as indicated in
Fig. 7, and finishing in the alloy matrix neighboring the subscale region).
12) or in the interior of the alloy matrix (i.e., farther away
from the subscale) of any specimen. Subscale regions in
the weld metal and base metal specimens were much less
populated with internal precipitates than the subscale in the
HAZ. However, as shown in Figure 12, in the subscales of
the weld metal and base metal specimens, internal precip-
itation was much more intensive at the grain boundaries
than within the grains. Also, unlike the HAZ specimen,
where voids formed indiscriminately and extensively within
the subscale region, void formation within the subscale of
the weld metal and base metal was restricted to the area
neighboring the grain boundary oxide precipitates (Figure
12).
The EPMA profiles for iron, chromium, and oxygen
(Figure 8) suggest that the thick outer layers of oxide scale
(in Figure 7) consist mainly of iron oxides, and that the
582—VOLUME 29A, FEBRUARY 1998
Fig. 9—EPMA line profiles for chromium contents (on an expanded scale)
in the scale, subscale, and alloy matrix regions of HAZ, base metal, and
weld metal regions (profiles starting from the points, A, as indicated in
Fig. 7, and finishing in the alloy matrix neighboring the subscale region).
Fig. 10—Magnified features in subscale and adjacent zones in HAZ shown
in Fig. 7(a), showing extensive precipitation and void formation in the
subscale (indicated as B) and grain boundary cavitation (indicated as C)
in the adjoining area.
inner layers are oxides of iron and chromium. The XRD
analysis identified the oxide scale to be comprised predom-
inantly of magnetite (Fe3O4); however, the diffraction pat-
terns also consist of peaks corresponding to wustite (FeO),
hematite (Fe2O3), iron-chromium spinel oxide (FeCr2O4),
chromium oxide (Cr2O3), and elemental iron. The wustite
formation can be attributed to the oxidation temperature of
873 K (wustite is stable at temperatures above 843 K). The
XRD patterns, suggesting the presence of Cr-containing ox-
ides, are attributed to the inner layer and the internal pre-
cipitates shown in Figure 7. The predominance of Fe3O4 in
the outer scales and the formation of Cr-rich inner scales
are also corroborated by the EPMA line profiles (Figure 8).
The oxidation resistance of iron-chromium alloys is
known to be effected due to a protective inner layer of
either chromium oxide (in high-Cr alloys) or iron-chro-
mium spinel oxide (in low-chromium steels).[15] However,
the chromium content of the inner layer of Fe/Cr oxides in
low-Cr steels governs the extent of protectiveness.[13,25] A
comparison of Cr profiles on expanded scales (Figure 9)
METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 11—Typical SEM micrograph showing cavitation (indicated as B)
even at those alloy grain boundaries not connecting with the subscale in
the oxidized specimen of HAZ, and void formation in the subscale and
grain boundary cavitation in the adjoining area.
Fig. 12—Representative magnified features in subscale and adjacent zones
in weld metal and base metal regions shown in Fig. 7.
suggests that the relative Cr content in the inner layer of
the scale developed over the HAZ is considerably lower
(;4.25 at. pct) than those in similar scale layers over the
base metal (;13 at. pct) and the weld metal (;11 at. pct).
The chromium profiles in Figure 9 also suggest the pres-
ence of Cr-rich phases in the subscales and the neighboring
area. This high chromium concentration in the subscale ar-
eas is due to Cr-rich internal oxide particles. This was con-
cluded since the Cr peaks in this area are found to occur
in association with oxygen peaks, suggesting a higher-than-
average oxygen concentration and a lower iron concentra-
tion (Figures 8 and 9). The chromium profiles suggest a
higher local concentration of chromium in the area adjoin-
ing the subscale exclusively in the case of the HAZ spec-
imen. However, unlike the Cr profiles for the subscale area,
no oxygen peaks were found to coexist with the Cr peaks.
Hence, the Cr peaks in the area adjoining the subscales are
believed to occur due to Cr-rich carbides rather than oxides.
This conclusion is based on the extensive formation of Cr-
rich secondary carbides exclusively in the HAZ matrix,
METALLURGICAL AND MATERIALS TRANSACTIONS A
as previously reported[10,14] and as observed in the present
study (refer to the TEM results described in Section III–
A).
IV. DISCUSSION
In order to address the goal of this investigation of
2.25Cr-1Mo steel, the following aspects are discussed.
(1) The influence of secondary precipitation in the three
weldment regions (viz., the weld metal, HAZ, and base
metal) on the chemical characteristics of the protective
inner layer of oxide scale.
(2) The influence of the inner scale on the transport char-
acteristics of the species involved in the oxidation by
steam.
(3) The influence of the nature of scale on the character-
istics of the subscale region and the neighboring matrix.
(4) The role of the features of the subscales and the neigh-
boring alloy matrix in weld failures.
The prevalent occurrence of Mo2C and Fe3C precipitates
in the weld metal and base metal regions and that of Cr-
rich precipitates (viz., M7C3 and M23C6) exclusively in the
HAZ, as suggested from the TEM examinations, are in
agreement with the reported literature on the microstruc-
tural variations in the weldments of 2.25Cr-1Mo steel.[10,14]
The precipitation of Cr-based carbides, as observed in the
HAZ of a 2.25Cr-1Mo steel weldment, depletes the effec-
tive (free) chromium in the alloy matrix.[13,14,28,29] Hence, the
inner oxide scale layer developed over the HAZ (where
precipitation of Cr-rich carbides caused extensive Cr deple-
tion in the alloy matrix) contained considerably lower con-
centrations of Cr than the inner layers over the weld metal
and base metal regions, as shown in Figure 9. The Chro-
mium content of the inner oxide layer governs the protec-
tiveness of the scale and, hence, controls the diffusion of
iron and oxidant species through the scale of the iron-chro-
mium alloys, including 2.25Cr-1Mo steel.[30–33] A less pro-
tective inner scale formed over the HAZ, therefore, explains
the higher oxidation rate of the HAZ specimen than that of
the weld metal and base metal specimens (Figure 3).
The formation of a double oxide layer, shown in Figure
7, is consistent with other reports on steam oxidation of
low-alloy ferritic steels.[34–37] Oxidation mechanisms have
taken into consideration three possible types of diffusion:
outward solid-state diffusion of Fe ions, inward lattice or
gas phase diffusion of oxidant species (O22, H2O, and O2),
and outward vapor phase diffusion of volatile Fe(OH)2.[35]
However, while the mechanism involving Fe(OH)2 diffu-
sion has been discounted,[36] there is general agreement on
the counter-diffusion of Fe ions and oxidant species, re-
sulting in an oxidation reaction at both the gas/oxide and
metal/oxide interfaces.[34] Migration of iron ions occurs both
via lattice and grain boundary diffusion; however, the latter
path predominates.[38] There has been a general lack of
agreement[34–38] on the type of migrating oxidant species, as
well as its diffusion path. Mayer and Manolescu[37] have
suggested molecular steam (H2O) and oxygen (O2) to be
the inward-diffusing species, and that pores at the grain
boundary triple points are the diffusion path. Tomlinson
and Cory[34] also observed similar pores, which enable gas
phase diffusion of steam to the metal/scale interface. Ef-
fertz[38] has argued in favor of solid-state diffusion (both
VOLUME 29A, FEBRUARY 1998—583

Fig. 13—(a) Morphology and (b) cross section of a 2.25Cr-1Mo steel
sample oxidized at 873 K in an environment of higher oxygen pressure
(steam 1 air) showing features of porous outer scale.
lattice and grain boundary diffusion) of O22 ions (O22 ions
are formed by decomposition of steam at the oxide/gas in-
terface, and the hydrogen formed by this reaction is directly
released, unreacted, back to the gas phase). However, a
careful examination of the reported literature[34,37] indicates
that scales with the grain boundary pores in the surface
were generally developed under high oxygen pressure. This
is confirmed in another report by Cory and Herrington,[39]
where cross sections of low-alloy steels oxidized in high-
pressure steam are found to consist of columnar grains in
the outer scale with pores and cracks at the grain bounda-
ries. Possibly, for this reason, the morphological features
of outer scales developed under the comparatively low ox-
ygen pressures employed in the present studies are consid-
erably different from those observed by Tomlinson and
Cory;[34] the oxide grains in the present study are faceted
and the scale morphologies do not contain grain boundary
pores (Figures 4 through 6). Also, unlike the porous outer
layers observed in the scale cross sections by Cory and
Herrington,[39] the outer scales in the present study are com-
pact (Figure 7) and without any features resembling a po-
rous scale. In order to confirm the dependence of scale
porosity on the oxygen partial pressure, a few samples of
584—VOLUME 29A, FEBRUARY 1998
2.25Cr-1Mo steel were oxidized in steam 1 air (i.e., at an
oxygen pressure higher than experienced during steam ox-
idation in the present study). Both the surface morphology
(Figure 13(a)) and cross section (Figure 13(b)) of the re-
sulting oxide scale indicated a porous nature of the outer
scale, which is similar to the outer scale features observed
in the studies by Tomlinson and Cory[34] and Cory and Her-
rington.[39] The comparison of outer scale morphology in
the present study to those in the studies by Tomlinson and
Cory[34] and Cory and Herrington[39] confirms that the grain
boundary pore formation and the gas phase diffusion of
steam and oxygen molecules through the pores can occur
only at high oxygen pressures. The inability of steam mol-
ecules to reach the metal/oxide interface also rules out the
generation of hydrogen at this interface. In fact, the trans-
port mechanism in the present study appears similar to the
one proposed by Effertz,[38] who suggested that the oxida-
tion reaction took place entirely by solid-state diffusion of
O22 and iron ions together with electron transport from
metal to the gas/oxide interface, and that all hydrogen
formed by the reaction at this interface was released directly
into the gas phase.
The inward diffusion of oxygen ions is particularly im-
portant in the context of internal oxidation and the subscale
features of the different regions considered (Figures 7, 10,
and 12). A less-protective inner scale formed in the case of
the HAZ than in the weld metal and the base metal (as
described earlier), which presumably allowed a greater in-
ward diffusion of oxygen ions and, thus, facilitated the
presence of a greater amount of oxygen available for re-
action with the chromium of the alloy matrix (Cr will se-
lectively oxidize at the low oxygen activity experienced in
the alloy matrix under the scale). Greater diffusion of ox-
ygen ions through the HAZ scale caused extensive internal
oxidation and the formation of a subscale zone thickly pop-
ulated with internal precipitates (this zone consists of
blocky internal precipitates and voids underneath the inner
protecting layer, as shown in Figures 7(a) and 10). The
depletion of Cr due to extensive internal precipitation in the
subscale zone may necessitate the diffusion of Cr from the
adjacent area in the alloy matrix, which obviously causes
the generation of vacancies. These vacancies would anni-
hilate at grain boundaries to cause grain boundary cavita-
tion, as seen in Figures 10 and 11. The fact that a
considerable amount of Cr from the alloy matrix is tied up
as secondary carbide precipitates (M7C3 and M23C6) in the
HAZ (as discussed earlier) may further necessitate the dif-
fusion of Cr from the bulk, under the chemical potential
created by greater inward diffusion of oxygen ions under-
neath the scale developed on the HAZ. The oxidation-as-
sisted vacancy injection and subsequent annihilation of
vacancies, which subsequently form voids, is reported for
other materials.[40,41]
The more-protective inner scale that was found to form
both on the weld metal and the base metal (as opposed to
on the HAZ) resulted in a limited inward diffusion of ox-
ygen ions and internal oxidation. Hence, the subscale zones
formed on both the specimens (Figures 7(b), 7(c), and 12)
consist of relatively less intensive internal precipitation (of
Cr oxides) within the alloy grains and at the grain bound-
aries (Figure 12) than those regions of the HAZ subscale
(Figure 10). Chromium diffusion from the area adjacent to
METALLURGICAL AND MATERIALS TRANSACTIONS A
grain boundaries caused some void formation in such areas
(Figure 12).
The rupture life of 2.25Cr-1Mo weldments will be af-
fected by some of the microstructural changes caused by
oxidation in the subscale and the adjoining alloy matrix.
Extensive void formation in the subscale region of the HAZ
and grain boundary cavitation in neighboring areas (Figures
7, 9, and 10) act as easy paths for crack propagation. Sur-
face and subsurface cracks are known to initiate/accelerate
fatigue cracks in materials[16] and, thus, can contribute to
the inferior rupture life of the HAZ. Hancock[41] has also
reported oxidation-assisted vacancy injection into the
metal matrix and subsequent void precipitation to be re-
sponsible for the acceleration of creep rupture and the re-
duction of creep ductility. Voids are also observed, though
to a much lesser extent, in areas adjacent to grain bound-
ary oxide precipitates within the subscales of weld metal
and base metal specimens (Figure 12). Subscale void for-
mation is very pronounced in the HAZ subscale (Figure
7). More importantly, the synergistic influence of the ex-
tensive formation of Cr-based internal oxide precipitates
and Cr-rich carbide precipitates in the HAZ results in
grain boundary cavitation in the alloy matrix adjacent to
the subscale region in the HAZ.
Intergranular cavitation and the rupture life of metallic
materials have been reported to be influenced by the com-
bined role of the environment and secondary precipita-
tion,[22,42] as well as by internal precipitation due to residual
oxygen in the alloy matrix (i.e., low oxygen pressures).[43,44]
Hence, oxidation-assisted void formation in the subscale
region and grain boundary cavitation occurring exclusively
in the neighboring alloy matrix of the HAZ, as observed in
this study, are believed to play a significant role in the in-
service mechanical failures that generally take place in the
HAZ of 2.25Cr-1Mo steel weldments. While such void for-
mations will contribute more predominantly to the
creep/fatigue failures of thin-walled components, they will
also be important for fatigue failures of thick-walled com-
ponents.
V. CONCLUSIONS
The results of the steam oxidation of microstructurally
different regions (viz., weld metal, the HAZ, and base
metal) in the weldments of 2.25Cr-1Mo steel lead to the
following conclusions.
1. A less-protective inner scale is developed in the HAZ
region, which causes a higher oxidation rate in the HAZ
than in the weld metal and base metal regions.
2. The formation of a less-protective inner scale is attrib-
uted to the trapping of free Cr, to form Cr-based sec-
ondary precipitates, exclusively in the HAZ.
3. The less-protective scale formation on the HAZ surface
also results in a subscale zone with extensive internal
oxidation, void formation in the subscale, and grain
boundary cavitation in the adjacent alloy matrix.
On the basis of available reports and this work, it is inferred
that the extensive void formation in the subscale region and
the grain boundary cavitation occurring exclusively in the
neighboring alloy matrix of the HAZ can contribute to in-
service mechanical failures in the HAZ of 2.25Cr-1Mo steel
weldments (especially in thin-walled components).
METALLURGICAL AND MATERIALS TRANSACTIONS A
ACKNOWLEDGMENTS
The author is grateful to Professor D.J. Young and Dr.
B. Gleeson, School of Materials Science and Engineering,
The University of New South Wales (MSE/UNSW), Syd-
ney, for their support with experimental facilities, and to
Professor D. Dunne, Head of the Department of Materials
Engineering, University of Wollongong (Australia), Dr. P.
Kruaklis and Mr. M. Yastreboff, MSE/UNSW (Sydney),
and Mr. A. Croker, Australian Nuclear Science and Tech-
nology Organisation (Sydney), for their valuable comments
during preparation of this manuscript. The author is also
grateful to Dr. Baldev Raj, Director, Metallurgy and Ma-
terials Group, and Mr. J.B. Gnanamoorthy, Former Head,
Metallurgy Division, Indira Gandhi Centre for Atomic Re-
search (Kalpakkam, India) for their support and encourage-
ment.
REFERENCES
1. Ferritic Steels for High Temperature Applications: ASM Int. Conf.,
Warren, PA, 1981, A.K. Khare, ed, American Soc. of Metals, OH.
2. Proc. BNES Int. Conf. Ferritic Steels for Fast Reactor Steam
Generators, S.F. Pugh and E.A. Little, eds., BNES, London, 1978.
3. Ferrinc Steels for High Temperature Applications: ASM Int. Conf.,
Warren, PA, 1981, T. Wada, G.T. Eldis, and A.K. Khare, eds.,
American Soc. of Metals, OH, p. 8S.
4. J. Bland: Weld. J.-Res. Suppl., 1956, vol. 35, p. 181s.
5. L.S. Mandich, E.L. Fogelmen, and J.A. Gulya: Symp. Heat Treated
Steel for Elevated Temperature Services ASME, New Orleans, LA,
1956.
6. E.W. Colebeck and J.R. Rait: ‘‘High Temperature Steel and Alloys
for Gas Turbines,’’ 1st Special Report No. 43, 1952, p. 107.
7. K. Laha, K.B.S. Rao, and S.L. Mannan: Mater. Sci. Eng., 1990, A129,
pp. 183-95.
8. ‘‘ASME Boiler and Pressure Vessel Code,’’ Code Case N-47, ASME,
Fairfield, NJ. 1986.
9. B. Chew and P. Harris: Met. Construction, 1979, May, p. 11.
10. P. Roy and T. Lauritzen: Weld. J.-Res. Suppl., 1986, vol. 65, p. 45s.
11. S.D. Mann and B.C. Muddle: Proc. Microstructure and Mechanical
Properties of Aging Material, TMS, Warrendale, PA, 1993, pp. 301-
08.
12. R.K. Singh Raman, A.S. Khanna, R.K. Tiwari, and J.B.
Gnanamoorthy: Oxid. Met., 1992, vol. 37, pp. 1-12.
13. R.K. Singh Raman and J.B. Gnanamoorthy: J. Mater. Sci., 1992, vol.
27, pp. 3435-41.
14. R.K. Singh Raman: Metall. Mater. Trans. A, 1995, vol. 26, pp. 1847-
58.
15. N. Birks and G.M. Meyer: Introduction to High Temperature
Oxidation of Metals, Edward Arnold, London, 1982.
16. C. Phaniraj, M. Valson, S.L. Mannan, and P. Rodriguez: Proc.
Workshop on Oxidation of Metals and Alloys, Indian Institute of
Metals, Kalpakkam Branch, India, 1984, p. 171.
17. P. Rodriguez: Trans. Ind. Inst. Met., 1967, vol. 20, p. 213.
18. P. Shahinian: Trans. ASM, 1957, vol. 49, p. 862.
19. R. Widmer and N.J. Grant: Trans. ASME, 1960, vol. D82, p. 882.
20. H.E. McCoy, W.R. Martin, and J.R. Weir: Proc. Institute of
Environmental Science, 1961, p. 163.
21. I.R. Kramer and N. Balasubramanian: Metall Trans., 1973, vol. 2, pp.
431-36.
22. W.R. Johnson, C.R. Barrett, and W.D. Nix: Metall. Trans., 1972, vol.
3, pp. 695-98.
23. B.J. Smith and A.R. Marder: Corrosion, 1992, vol. 48, p. 29.
24. R.L. Klueh and J.F. King: Weld. J.-Res. Suppl., 1982, vol. 61, p. 302s.
25. R.K. Singh Raman and J.B. Gnanamoorthy: Corr. Sci., 1993, vol. 43,
pp. 1275-88.
26. H. Howarth: Corrosion, L.L. Shrier, ed., Newnes-Butterworths,
London, 1976, vol. I, pp. 7:13-7:44.
27. J. Pilling and N. Ridley: Metall. Trans. A, 1982, vol. 13A, pp. 557-
63.
28. M.E. El-Dahshan, J. Stringer, and D.P. Whittle: Cobalt, 1974, vol. 4,
p. 86.
VOLUME 29A, FEBRUARY 1998—585
29. R.N. Durham, B. Gleeson, and D.J. Young: Proc. 13th Int. Corrosion
Conf., Melbourne, Australian Corrosion Association, Melbourne,
1996, pp. 1-10.
30. R.K. Singh Raman, A.S. Khanna, B.K. Choudhary, and J.B.
Gnanamoorthy: Mater. Sci. Eng. A, 1991, vol. 148, pp. 299-306.
31. S. Leistikow, I. Wolf, and H.J. Grabke: Werkst. Korros., 1987, vol.
38, p. 556.
32. Y. Shida, N. Ohtsunaka, J. Murayama, N. Fujino, and H. Fujikawa:
Proc. JIMS-3: High Temperature Corrosion; appeared in Trans. Jpn.
Inst. Met., 1983, vol. 63.
33. R.K. Singh Raman, A.S. Khanna, and J.B. Gnanamoorthy: Proc. 1st
Int. Conf. on Microscopy of Oxidation, M.J. Bennett and G.W.
Lorimer, eds., The Inst. of Materials, London, Cambridge, United
Kingdom, 1990, pp. 54-58.
34. L. Tomlinson and N.J. Cory: Corros. Sci., 1989, vol. 29, p. 939.
586—VOLUME 29A, FEBRUARY 1998
35. P.L. Surman and J.E. Castle: Corros. Sci., 1969, vol. 9, p. 771.
36. I.E. Klein, J. Sharaon, and A.E. Yaniv: Scripta Metall., 1981, vol. 15,
p. 141.
37. P. Mayer and A.V. Manolescu: High Temperature Corrosion, NACE,
Tokyo, 1981, p. 368.
38. P.H. Effertz: Proc. 5th Int. Congr. Metallic Corrosion, NACE, Tokyo,
1972, p. 920.
39. N.J. Cory and T.H. Herrington: Oxid. Met., 1987, vol. 28, p. 237.
40. R. Rolls and J.H. Cleland: Phil. Mag. A, 1981, vol. 44, p. 943.
41. P. Hancock: Vancancies 76, R.E. Smallmen and J.E. Harris, eds., The
Metals Society, London, 1977, p. 215.
42. E.C. Scaife and P.L. James: Met. Sci. J., 1968, vol. 2, p. 217.
43. H.H. Bleakney: Can. J. Technol., 1952, vol. 30, p. 340.
44. C.E. Price: Acta Metall., 1966, vol. 14, p. 1787.
METALLURGICAL AND MATERIALS TRANSACTIONS A