Metal Science

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Precipitation sequences in heat-affected zone

of 2-25Cr-1 Mo steel during stress-relief heat
treatment

C. A. Hippsley

To cite this article: C. A. Hippsley (1981) Precipitation sequences in heat-affected zone of

2-25Cr-1 Mo steel during stress-relief heat treatment, Metal Science, 15:4, 137-147, DOI:
10.1179/030634581790426705

To link to this article: http://dx.doi.org/10.1179/030634581790426705

Published online: 18 Jul 2013.

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Precipitation sequences in heat-affected
zone of 2-25Cr-1 Mo steel during
stress-relief heat treatment
c. A. Hippsley
The development of preCIpItation microstructure
during stress-relief heat treatment of the bainitic heat-
affected zone in 2·25Cr-1Mo steel has been studied
using transmission electron microscopy, scanning
transmission electron microscopy, and energy-
dispersive X-ray analysis techniques on carbon
extraction replicas and thin foils. Examinations have
been made of four 2·25Cr-1Mo alloys ('pure', doped
with 540 ppm phosphorous, doped with 500 ppm tin,
and commercial purity) as part of an overall
investigation into stress-relief cracking in 2·25Cr-
1Mo steel. The precipitation behaviour is discussed in
terms of its relevance to fracto graphic observations
and segregation characteristics which are reported in
detail elsewhere. MS/0636
© 1981 The Metals Society. Manuscript received 18 September
1980; in final form 10 December 1980. The author is in the
Department of Metallurgy and Materials Science, University of
Cambridge.
Studies of intergranular fracture in steels1 have shown that
preferential grain-boundary cracking can be affected by
chemical segregation and microstructural development
acting either independently or synergistically. For example,
intergranular failure after overheating in low-alloy steels
occurs by the coalescence of voids nucleated on a grain-
boundary dispersion of sulphide particles2 with no
requirement for grain-boundary segregation. In contrast,
the mechanism of intergranular '350°C embrittlement' (or
'one-step temper embrittlement') in alloy steels is thought to
involve both the nucleation of cracks at grain-boundary
carbides and their propagation along grain boundaries
weakened by impurity segregation.3 Moreover, some
theories of temper embrittlement4 suggest that grain-
boundary microstructural development and impurity
segregation are themselves interdependent. 5 -7 A thorough
understanding of any intergranular fracture mechanism
requires, therefore, the individual characterization of both
factors, and the influences that they may have on the
embrittlement phenomenon in question.
Stress-relief heat treatment (or 'post-weld heat
treatment') entails the steady heating of a weld, its heat-
affected zone (HAZ), and surrounding parent metal (PM) to
a hold temperature which is sufficiently high to enabfe the
relaxation of residual welding stresses. During this heat
10
treatment, intergranular cracking may occur in the coarse-
grained HAZ,8 -to which has been solution treated by the
weld thermal cycle (Fig. 1). This type of intergranular
fracture is known as 'stress-relief cracking' or 'reheat
cracking' and its investigation is complicated by constantly
changing equilibrium levels of segregation and precipitation
towards which a low-alloy system will tend.
The work presented in this paper forms part of an
investigation into stress-relief cracking in the HAZ of 2·25
Cr-1 Mo steel. The overall project comprises a threefold
approach (i.e. mechanical testing and fractography,
segregation studies, and microstructural studies) which is
applied to a series of four 2·25Cr-1Mo steel alloys
containing various levels of residual impurities. The results
of mechanical testing and fractography and segregation
studies on two of the alloys (A and B) containing low
( ::::;70 ppm) and high (~540 ppm) levels of phosphorus
respectively are presented in detail elsewhere.!! Two
distinct modes of stress-relief cracking were observed during
the heating period of stress-relief heat treatment. At lower
temperatures, a low-ductility intergranular fracture mode
was observed and at higher temperatures, an intergranular
microvoid coalescence mode was found (see Fig. 2). Only
the higher temperature intergranular microvoid coalescence
mode was observed in the low-phosphorous alloy A,
whereas both modes were observed in the high-
phosphorous alloy B. Grain-boundary segregation
measurements indicated that the low-ductility
intergranular fracture mode was associated with grain-
boundary phosphorus enrichment. Subsequently, both
modes have also been observed in tin-doped and
commercial alloys,12 C and D respectively.
The following account describes the development of HAZ
microstructure in all four alloys of 2·25Cr-1 Mo steel in
terms of second-phase particle precipitation history and
particle/matrix chemical composition. Significant events
are discussed with respect to stress-relief fracture
mechanisms and segregation characteristics.
EXPERIMENTAL
Materials and heat treatment
Three of the four 2·25Cr-1 Mo alloys examined were
specially prepared melts while the fourth was a commercial
sample. Alloys A, B, and C were prepared by vacuum
melting Japanese electrolytic iron and high-purity alloying
additions. The bulk chemical analyses of alloys A, B, and C,
and the commercial cast D are given in Table 1. A is a 'pure'
standard with a lower residual content than typical
commercial casts of2·25Cr-lMo steel; B is based on A with
an addition of 540 wt-ppm phosphorus; C is based on A
Metal Science April 1981 137
138 Hippsley Precipitation sequences in heat-affected zone of 2'25Cr-1 Mo steel

1700
weld-simulation stress-relief
1500 heat treatment heat treatment
~
"'1300
w
a:::
~ 1100
<( hold
a:::
w
a..
~ heating
.-
w

500
intcirpass

300
o 2 4 6 8 2 4 6 8 10
TIME) min TIME,h
Weld-simulation and stress-relief thermal cycles a

with an addition of 500 wt-ppm tin; and D is a commercial

cast with residual content within specification.
Four bars (2 x 1 x 5 cm) of each alloy were austenitized
for 1 h at 1225 K, quenched in oil, and tempered for 1 h at
925 K to produce a parent metal (PM) microstructure. They
were then given a weld-simulation heat treatment consisting
of a thermal cycle similar to that measured by Myers13 for
the HAZ of a multipass MMA butt weld in 0·5Cr-Q·5Mo-
0·25V steel (Fig. 1) and employed in the stress-relief
cracking mechanical test,11 Stress-relief heat treatment was
simulated by heating the bars in a programmable vacuum
furnace at 100 K h -1. The heating cycle was interrupted at
various stages to produce a series of specimens of each alloy
with microstructures corresponding to those of stress-relief b
testpieces at the following temperatures in the stress-relief a low-ductility intergranular fracture; b intergranular microvoid
heat treatment: 300, 725, 840, and 975 K, which represent coalescence
the initial state (as-weld-simulation heat treated), a low 2 Scanning electron micrographs showing two distinct
temperature in the low-ductility intergranular fracture stress-relief fracture morphologies
regime, a low temperature in the intergranular microvoid
coalescence regime, and the stress-relief 'hold' temperature
respectively. replication. Discs (3 mm dia.) were ground to 5-10 Jlm
thickness and twin-jet electropolished in a solution of 5%
Electron microscopy and X-ray perchloric acid in ethanol at 230-240 K and 25 V potential.
microanalysis A JEM 200A transmission electron microscope (TEM)
Carbon extraction replicas were taken from sections of each was used for morphological studies at accelerating voltages
alloy in each of the four heat-treated conditions after of 100 kV for replicas and 200 kV for foils. Energy-
polishing to 0·25 Jlm (diamond paste) and etching for 70 s in dispersive X-ray microanalysis was performed in TEM
2% nital. A selection of thin foils covering the range of heat mode on replicas in a Philips EM400 with EDAX detector
treatments was also produced to check the authenticity of and Link Systems signal processing. Count rates of

Table 1 Bulk chemical analyses of alloys A-D, wt-%

Alloy Cr Mo Mn Si Ni Cu V W 'Nb As Sb

A, 'pure' 2·25 0·97 0·55 0·025 0·02 0·015 <0·01 <0·01 <0·01 <0·01 <0·01
B, P doped 2'25 1·02 0·57 0·02 0·03 0·015 <0·01 <0·01 <0·01 <0·01 <0·01
C, Sn doped 2·23 1·03 0·57 0·06 0·01 <0·01 <0·01 <0·01 <0·01 <0·02 <0·01
0, commercial 2·12 0·93 0·53 0·19 0·20 0·15 <0·01 <0·02 <0·01 <0·02 <0·01

Alloy Sn P S Ti Zr Bi Co Al C N 0

A, 'pure' <0·01 0·007 0·006 <0·01 0·09

B, P doped <0·01 0·054 0·006 <0·01 0·12
C, Sn doped 0·05 0'005 0·005 0·10 0·001 0·015
0, commercial 0·01 <0·02 0·03 <0·01 <0·01 <0·01 <0·01 <0·01 0·13

Metal Science April 1981


~ 100 Hz were obtained from replica carbides with
120 kV accelerating voltage, 45° tilt, and a microprobe size
suited to the type of carbide analysed. The EM400
analytical system was also used in STEM mode to monitor
changes in matrix alloying element content (Cr, Mo) in the
vicinity of grain boundaries. This type of analysis was
performed on thin foils of alloy A heated to 975 K. A STEM
probe size of 100 A produced low count rates of 30-40 Hz
requiring a count time of "" 400 s.
Using the above techniques, the following analyses were
executed:
(i) observation of carbide morphological development
during stress-relief heat treatment, i.e. (a)
morphological definition of the HAZ microstructure
before stress-relief heat treatment and (b)
measurement of changes in grain-boundary carbide
number density during stress-relief heat treatment
(ii) observation of chemical development during stress-
relief heat treatment, i.e. (a) measurement of changes
in metalloid composition of the main M 3C type
carbides, (b) identification by energy-dispersive X-ray
microanalysis of 'higher' types of carbide
precipitating during stress-relief heat treatment and
measurement of their relative abundances, and (c)
observation of the chemical composition of matrix
material close to grain boundaries.
The technique of carbide identification by energy-dispersive
X-ray spectra developed by Titchmarsh14 has been
employed to enable rapid particle classification and hence
the accumulation of statistically significant information.
Titchmarsh has shown that, for a given type of carbide in
2'25Cr-1Mo steel identified by microdifTraction, the count
ratios of major X-ray peaks emitted from the alloying
elements chromium (Ka:) and molybdenum (L) to that of
iron (Ka:) vary between well defined limits. This is consistent
with observations from bulk extraction techniques which
indicate that each carbide has a limited range of iron,
chromium, and molybdenum metalloid content. 14
Consequently, it has been possible to identify carbides in
2'25Cr-1Mo alloys A-D* by obtaining their energy-
dispersive X-ray spectra, and comparing these with a set of
standard spectra and associated structure types, i.e. M3 C,
M2C, M7C3, M23C6, and M6C.
For comparison between alloys and observation of
chemical changes during stress-relief heat treatment, it is
sufficient to consider variations in X-ray peak intensity
ratios. However, an estimate of absolute composition (wt-%)
may be obtained from relative peak intensities in the
following manner.
Ci _ [AiQjWjaj exp (- Ujdt)]!!-
Cj AjQiwiai exp (-Uidt) Ij
[.
= kij ~ (adapted from Ref. 15)
Ij .
where
Ai,j = atomic weight of element i,j
Qi,j = ionization cross-section of K or L
shell relevant to i,j
Wi, j = fluorescence yield of K or L shell
relevant to i,j
* The 2'25Cr-IMo alloy used by Titchmarsh for
structure calibration was in fact alloy C (Table 1).
Hippsley Precipitation sequences in heat-affected zone of 2·25Cr-1 Mo steel 139
ai,j = ratio of Ka: or La: intensity to
total K or L intensity respectively
relevant to i,j
Ui,j = mass absorption coefficient of
element i,j in Be
d = density of Be
t = Be-detector window thickness.
kij is thus a constant factor relating the relative concentra-
tions of two elements Ci, Cj to the ratio of their respective Ka:
or La peak intensities Ii' ii'
Correction for absorption of characteristic X-rays in the
particle analysed has been ignored in this treatment, being
close to unity for the average size of carbide present
, ( < 100 nm). Characteristic X-ray fluorescence is of second-
order magnitude to absorption and therefore is also
ignored.
A table of correction factors (kij) calculated from equation
(1), with the data of Green and Cosslett 16 and Powell, 17 is
given with respect to iron (Ka) in Table 2.
RESULTS
Morphological observation
No significant interalloy differences in carbide morphology
were detected at any interruption temperature. The initial
weld-simulated HAZ microstructure was mainly 'lower
bainite', Le. a WidmansHitten dispersion of M3C platelets
within ferrite laths.18,19 However, some areas of 'upper
bainite' were also present, Le. discontinuous films of M3C
carbide lying at ferrite lath boundariesl8,19 (Fig. 3).
The development of grain-boundary carbide number
density during stress-relief heat treatment is illustrated by
the sequence of micrographs in Fig. 4. Micrograph 4d
indicates that spheroidization of grain-boundary carbides
has initiated by 975 K. Extraction of carbides from alloys
interrupted at 300 K (as-weld-simulation heat treated) was
imperfect, but thin-foil TEM indicated that the areas of
replica in which extraction had occurred were representative
of the true grain-boundary carbide number density.
The fraction of grain-boundary 'length' occupied by a
carbide in extraction replicas was estimated from 20 grain-
boundary areas at each temperature (i.e. five per alloy) and
is presented as the parameter exin Fig. 5. Once again, no
significant variation was found between alloys. During
weld-simulation heat treatment, specimens were held at _an
interpass temperature of 575 K before a final cool to room
temperature (Fig. 1). It is therefore assumed that stress-
relief heat treatment did not induce a significant change in
grain-boundary carbide number density before the interpass
temperature was reached,20 i.e. ex(300K) = ex(575K) in
Fig. 5.
(1)
Table 2 EDS X-ray analysis quantification k-factors
normalized to Fe(kcx) *
Element Peak k-factor
Fe 1'000
Cr 0·913
Mo 1'703
spectrum- * The Mo (La' Lp) peaks are considered together because of their
energetic proximity (see Table 3).
Metal Science April 1981
 140 Hippsley Precipitation sequences in heat-affected zone of 2·25Cr-1 Mo steel

Table 3 _EDS X-ray peak energies*

Energy, keY Element Peak

2·293 Mo
2·307 S
2·322 S
2·394 Mo
2-465 S
5·411 Cr
5·894 Mn
5·946 Cr
6·398 Fe
6·489 Mn
7·057 Fe
8·040 Cu
8·904 Cu
17·441 Mo
19·599 Mo

* Neither the Mo (Lal, Lpd nor the S (Kal,2' Ka4, Kp) groups are
3 Transmission electron micrograph of extraction separately resolved in the published spectra and appear as single
replica taken from material as-weld-simulated
peaks.
showi'ng areas of upper bainite (UB) and lower
bainite (LB)

a b

c d
a 300K; b 725 K; c 840 K; d 975 K

4 Transmission electron micrographs of extraction replicas illustrating increase in grain-boundary

carbide density with temperature during stress-relief heat treatment

Metal Science April 1981

 Hippsley Precipitation sequences in heat-affected zone of 2·25Cr-1 Mo steel 141

1·0 M3C type carbides dominated the HAZ microstructure

throughout stress-relief heating and their chromium content
rose with increasing temperature from 3-7 metal wt-% (300-
~-
>-B
<t:>-
OJ--
zU5
840 K) to 15-20 metal wt-% (840-975 K). A comparison of
grain and grain-boundary carbide chromium content in
alloys A-D is presented in Fig. 9. The means and standard
::JZ
Ow 0·5 deviations of > 10 analyses at each temperaturejlocation
mo are given for special melt C and commercial alloy D,
·w
~O together with the means of 5 analyses at each
~ro temperaturejlocation in special melts A and B.
(9~
u The precipitation sequence during stress-relief heat
treatment was found to be similar in all four alloys. M3 C
carbides alone were detected in grain and grain-boundary
o regions at the interruption temperatures of 300, 725, and
300 400 500 600 700 800 900 1000
TEMPERATURE, K 840 K. At 975 K, M2C, M7C3, and M23C6 carbides were
also detected in grain regions, while M2C, M7C3, M23C6,
5 Grain-boundary carbide density IX v. temperature and possibly M6 C carbides were also detected at grain
during stress-relief heat treatment boundaries. An estimation of the relative frequencies of the
various carbide types present at 975 K is presented in
Table 4. The speed of identification possible using the EDS
X-ray microanalysis
Extraction replicas
A set of typical spectra taken from the range of carbides (a) (b)
observed is shown in Fig. 6. The significant peaks are
molybdenum (L), chromium (Kex), iron (Kex), and
molybdenum (Kex) at energies given in Table 3. Strong
copper (Kex,p) peaks, present in all spectra, originated from
copper grids on which the replicas were supported during
analysis. The M3C, M2C, M7C3, and M23C6 carbide
spectra (Fig. 6a-d) generally fell unambiguously within the
molybdenum (L)jchromium (Kex) and iron (Kex)jchromium
(Kex) peak intensity ratios specified by Titchmarsh.14
However, M6C carbide spectra (Fig.6e) indicated a
somewhat higher chromium content than the standard. This
may have been the result of incomplete transformation o 20
(standards being taken after > 1 h at 973 K isothermal
tempering) or the overlap of two different types of carbide (c) (d)
causing false identification.
M 3 C and M 2 C type carbides possessed a distinct
morphology in grain and grain boundary, as illustrated in
Fig. 7:
(i) intralath M3 C platelets, arrowed (a), Fig. 7a
(ii) 'feathery' grain-boundary M3C, arrowed (a),
Fig.7b
(iii) acicular matrix M2C, Fig. 7c
(iv) spherical grain-boundary M2C, arrowed (b), Fig. 7d
The other types of carbide (M7C3, M23C6, and M6C)
A I~IA •

showed no distinguishable morphological characteristics 20 0 20

(Fig.7e).
(<2)
A further type of particle was detected by energy-
dispersive X-ray analysis in replicas taken from all four
alloys at all interruption temperatures. A typical energy-
dispersive X-ray spectrum (Fig. 8a) containing manganese
and sulphur* major peaks with chromium and iron minor
peaks suggests that small manganese sulphide inclusions
were extracted. These inclusions were detected throughout
the HAZ microstructure but tended to be concentrated in
grain-boundary regions. Although they were seldom found
to lie actually on a grain boundary, they were usually
located within a few micrometres of one (see Fig. 8b).
o 10 20
MeC
* The S(Ka) peak lies very close to the Mo(L) peak (see Table 3) but 6 Typical energy-dispersive X-ray spectra taken from
the presence of S rather than Mo in the spectrum of Fig. 8 is five different types of carbide detected; spectra
confirmed by the absence of a high energy Mo(Ka) peak (cf ordinates are X-ray counts while abscissae denote-X-
Figs. 6 and 8). ray energy ranging from 0-20 keV in ~teps of 1 keV

Metal Science April1981

142 Hippsley Precipitation sequences in heat-affected zone of 2'25Cr-1 Mo steel

~~ ...•......•.

..•.....

": .
........ , .···.·.,?:.I·

.
....•.....
/
.. ~
...........•

•••....•......·<>i·····
.••
·.· .....•.•
(>-

...•.....•.•.•.•>
."
i
I
....

>

(~~ .•.•.••...
. .....•

~,
i'

i"~~;
..........
........
I
,....•
'~4'

a M3C grain; b M3C grain boundary; c M2C grain; d M2C grain

boundary; e general
7 Transmission electron micrographs of extraction
replicas taken from alloy 0 at an interruption
temperature of 975 K showing distinct M3C and M2C
carbide morphologies

Metal Science April 1981

 Hippsley Precipitation sequences in heat-affected zone of 21 25Cr-1 Mo steel 143

and 0·90%Mo. Thus, the quantified X-ray analyses are

reasonably consistent with the bulk chemical analyses given
in Table 1, i.e. 96'0%Fe, 2'25%Cr, and 0·97%Mo.

DISCUSSION
A comparison of the four 2'25Cr-1Mo alloys examined in
the course of this microstructural study has shown that their
precipitation behaviour during stress-relief heat treatment
of the heat-affected zone is practically identical. Thus,
microstructural variations cannot be responsible for the
differences in stress-relief cracking behaviour observed
between the doped/commercial and· undoped alloys. 11, 12
The major features of HAZ precipitation history are
summarized in Fig. 11 and will be discussed with respect to
(a) previous work on similar alloys and (b) their relevance to
stress relaxation, micromechanisms of stress-relief cracking,
and grain-boundary impurity segregation.

Comparison with previous work

o 10
b MnS
8 a Transmission electron micrograph of extraction
replica showing a small
inclusion (arrowed "a") with b accompanying energy-
dispersive X-ray spectrum
Several studies of precipitation behaviour have been made
on alloys similar to those examined in this report. Baker and
Nutting21 have observed carbide precipitation in a
commercial 2'25Cr-1Mo alloy in both quenched and
normalized states during isothermal tempering in the range
673-1023 K. Andrews et a/.22 have constructed a set of
diagrams describing the 'equilibrium' carbide structures
present after long aging times (up to 1000 h) at 923 and
973 K in quenched steels with compositions ranging from 0-
6%Cr, 0-2%Mo, and o-l%V. Finally, Titchmarsh14 has
monitored the development of carbide type in a quenched
2'25Cr-1Mo alloy (alloy C, Table 1) during isothermal
tempering at 973 K up to 200 h to demonstrate the energy-
dispersive X-ray spectrum carbide identification technique.
Stress-relief heat treatment involves relatively short
'tempering' times and therefore information on the near-
equilibrium state is of limited application. Andrews et al.22
indicated that, at both 923 and 973 K, the equilibrium
carbide structures present in ferrite were M7C3 and M6C
(in a steel containing 2'25%Cr, l%Mo, O%V, and 0·12%C).
However, Baker and N utting21 proposed that M 6C and
M23C6 were the stable phases at 975 K in a tempered
bainite microstructure (2'25Cr-1Mo steel). The work of
Titchmarsh14 tends to support Baker and Nutting's view in
that, between 100 and 200 h tempering at 973 K, M7C3
20 carbides were observed to decrease in frequency, while M6C
and M23C6 carbides rose in frequency (see Fig. 14).
Figure 11 shows that the transformation of M 3 C to
manganese sulphide 'higher' carbides had begun by 975 K in the stress-relief
thermal cycle, but that the HAZ microstructure was far

technique enabled a statistically significant sample of over

200 carbides to be taken at four grain-boundary regions o grain
from alloys C and D. A similar analysis was executed in ~A ~c .D grain boundary
grain areas for M7C3 and M23C6 type carbides, while
morphological identification was used to estimate the M 2 C
M3 C carbidC25
and M 3 C carbide densities.

STEM of thin foils

The variation of chromium (KaJ and molybdenum (L)
peak intensity ratios (to iron (K(l)) with distance normal to a
grain boundary in alloy A interrupted at 975 K is presented 400 700 800 900 1000
in Fig. 10. No significant inhomogeneity in alloying-element TEMPERATURE, K
content was observed. If the quantification constants of 9 Percentage chromium, present in metallic com-
Table 2 are used to convert mean peak intensity ratios to ponent "M' of M3C carbides, v. temperature during
wt-%, the following values are obtained: 96'0%Fe, 2'36%Cr, stress-relief heat treatment

Metal Science April 1981

144 Hippsley Precipitation sequences in heat-affected zone of 2'25Cr-1 Mo steel

Table 4' Relative frequencies of carbide types present

at 975 K in stress-relief thermal cycle

Grain density
(no. per
unit area), Grain-boundary density,
Carbide type J.lm-2 % frequency

M3C 1--3 74
M2C '" 500 10
M7C3 10
80% }
M23C6 20% 0'1-0·5 3
M6C 0% 3

from equilibrium, containing M3C, M2C, M7C3, M23C6, relief cracking test. 11 Immediately after weld-simulation
and possibly M6C carbides. heat treatment, the HAZ material is much harder than the
The HAZ precipitation sequence is consistent with that parent metal (Le. HAZ as-weld-simulation heat treated,
observed by Baker and Nutting21 for the tempered-bainite 315-360 HV; parent metal, 230-270 HV) and therefore
microstructure in normalized 2'25Cr-lMo steel (con- the parent metal may be expected to relax preferentially.
taining 0·15%C) Le. However, hardness measurements taken at room
temperature from specimens of each alloy, interrupted
I during stress-relief heat treatment, show that HAZ hardness
c;-carbide} M3 C } falls below parent-metal hardness between 840 and 975 K
+ ,cementite
(M3C)
-+ + M
23
C -
6 -+ (from Fig. 12, parent-metal hardness at 975 K 220-
250 HV). This occurs despite the precipitation of a fine
cementite M2 C
dispersion of M2C carbides (see Figs. 7 and 11) indicating
However, some discrepancies are apparent on consideration that the matrix-softening effects of recovery and
of transformation kinetics. Although Baker and Nutting did recrystallization control HAZ hardness in this temperature
not detect M7C3 carbides until >5 h at 975 K, or M23C6 regime.24 Gross plastic deformation will therefore operate
carbides until > 50 h at 975 K, both M7C3 and M23C6 in the HAZ between 840 and 975 K as the HAZ strength
types were positively identified in the HAZ microstructures approaches that of the parent metal, and this may influence
interrupted at '975 K during the stress-relief thermal cycle. the micromechanism of high-temperature stress-relief
Titchmarsh14 also found M7C3 carbides after 1 h at 973 K cracking, as discussed below.
but did not detect M23C6 carbides until> 10 h at 973 K.
Thus, there is general agreement between published work Micromechanisms of stress-relief cracking
on isothermal tempering and the present stress-relief heat SEM fracto graphs illustrating the two types of stress-relief
treatment study with respect to the sequence of carbide
cracking mode observed during heating are presented in
transformation. However, an investigation of the influence Fig. 2. Figure 2a - shows low-ductility intergranular
of microstructure on stress-relief cracking micro- fracture in which grain boundaries have a relatively smooth
mechanisms, which operate in well defined appearance and may also have associated particles on, or
temperature ranges, requires particular kinetic and projecting from, their surfaces. This mode has been detected
thermodynamic information. The above discussion shows in alloys B, C, and D, i.e. those containing appreciable
that this information cannot reliably be derived from
residual impurities, and occurs between 725 and 875 K.12
published data and a specific system (of alloy and tempering
Figure 2b shows intergranular microvoid coalescence
condition) must be examined independently.

Stress relaxation
The volume of HAZ material contributing to stress relief, in
both real and simulated conditions, is small compared with
the volume of parent metal and weld metal which lie within
an appreciable residual-stress field.23 Macroscopic stress
relaxation is dominated by the parent metal in the stress-

tj5 >-
~4 0 Cr(Ka) a:::
~ 0 Mo(L) ~ M3C number densityt
023 __ 0_ JJ_ 0 Q.
>-... 0 0 0 0 5'
o
~2 0 CD
o
Q1 o o z
I- <i:
a:::
~O 0 (9
GB 100 200 300 400 500
DISTANCE FROM GRAIN BOUNDARY,nm 300 1000
10 Energy-dispersive X-ray intensity ratios of Cr(K(l)
and Mo(!) peaks to Fe(K(l) peak v. distance from 11 Summary of carbide development in grain and grain-
grain boundary (GB) in thin foil of alloy A boundary regions during stress-relief heat
interrupted at 975 K in stress-relief thermal cycle treatment

Metal Science April 1981

 Hippsley Precipitation sequences in heat-affected zone of 2·25Cr-1 Mo steel 145

400

.- -
- - - - __ .1
- ~- ----~ -.-
1.-__
-- "-

300
"
t::
f5200
> , A
I
!B
.100 -C
• D
o However, the mode of crack propagation is not yet clear,
300 400 700 800 900
TEMPERATURE, K there being two major possibilities: (a) true 'brittle-
12 Vickers pyramidal hardness of HAZ microstructure
in alloys A-D measured at room temperature v.
temperature during stress-relief heat treatment
consisting of heavily cavitated grain boundaries, whose
cavities are nucleated on small manganese sulphide
inclusions, identified by energy-dispersive X-ray analysis in
SEM studies. This mode occurs in all four alloys in the
temperature range 820-975 K and is the only mode
observed in alloy A ('pure,).11,12 Both modes have also
been detected in other studies of stress-relief cracking.25-3o
Low-ductility intergranular fracture
Energy-dispersive X-ray microanalysis of particles
associated with grain boundaries exposed during low-
ductility intergranular fracture has shown that they contain
no manganese or sulphur and are therefore likely to be
grain-boundary carbides rather than manganese sulphide
inclusions. 11,12 Previous work has also shown that
phosphorus segregates to grain boundaries in alloy B during
stress-relief heat treatment, reaching a maximum at about
725 K (Fig. 13).11 However, although appreciable
phosphorus has been detected at 625 K, low-ductility
intergranular fracture does not appear to initiate below
about 725 K. The microstructural investigation has shown
that grain-boundary carbide number density rises sharply
between 575 and 725 K (Fig. 5) and this would suggest that
a combination of high grain-boundary carbide density and
\
grain-boundary impurity segregation is required before the
low-ductility intergranular fracture mode can occur.
The role of grain-boundary carbides would then be one of
\r \ intergranular crack nucleation by particle fracture or
interface decohesion, enhanced by segregation, in response
to localized dislocation pile-ups which stress the obstructing
precipitates. The nucleation mechanism proposed is
essentially similar to that envisaged for some 350°C
embrittlement phenomena.3
1000
intergranular' cracking involving the decohesion of grain
boundaries weakened by segregated impurities and (b)
crack advance by the linking of very fine, shallow
microvoids nucleated around a high density of grain-
boundary carbides, whose matrix interfaces have been
weakened by segregated impurities. The actual mode of
crack propagation may well involve a combination of both
mechanisms, and at this scale the difference between 'brittle'
and 'ductile' intergranular fracture becomes somewhat
indistinct.
Intergranular microvoid coalescence
The microstructural investigation revealed two points of
relevance to the intergranular micro void coalescence
mechanism:
(i) it has been established that intergranular microvoid
coalescence cavities nucleate on small ("" 0·25 Jlm)
manganese sulphide inclusions 11,28which form during
weld-simulation heat treatment by an 'overheating'
process.2 The manganese sulphide particles, previously
assumed to lie on prior austenite grain boundaries, were
observed in extraction replicas to be displaced from
their associated grain boundaries by up to a few
micrometres (Fig. 8), Le. a cavity diameter (1-5 Jlm;

10

o
500 600 700 800
TEMPERATURE, K
13 Auger electron peak height ratios of P120 and Cr529
as'% of Fe703' measured at grain-boundary areas of 14 Development of carbide-type frequency with time
specimens fractured in AES system after during isothermal tempering at 973 K, in grain
interruption at various temperatures in stress-relief (dashed curves) and grain-boundary regions (after
thermal cycle 11 Titchmarsh 14)

Metal Science April 1981

146 Hippsley Precipitation sequences in heat-affected
see Fig. 2b). This observation is consistent with the
absence of manganese sulphide particles from low-
ductility intergranular fracture surfaces, which would
run along grain boundaries as delineated by carbide
precipitation ..
(ii) cavity nucleation at second-phase partIcles dunng
creep is often associated with localized grain-
boundary plastic deformation, i.e. sliding or zone
shear. 31 A locally weak grain-boundary region may
form during tempering through (a) precipitation
strengthening of the matrix alone or (b) localized
precipitate-forming-solute depletion by pr~ferential
grain-boundary precipitation. producIng .a
precipitate-free zone (PFZ) adjacent to graIn
boundaries.
32
Cane has demonstrated a relationship between cavity
nucleation and PFZ width in a tempered bainitic 2'25Cr-
1Mo steel. However, the PFZs were formed on
transformation of matrix M 2C carbides to grain-boundary
M 23C6 carbides after 4 h at 973 K. Intergranular microvoid
coalescence in alloys A-D occurs between 820 and 975 K
during the heating period of stress-relief heat treatment, i.e.
at a much earlier stage of tempering than Cane's
microstructure. Chemical and morphological analyses
(Figs. 4 and 10) gave no indication of s?lute depletion or
PFZ formation at this stage of stress-relIef heat treatment.
The fine M 2C carbide dispersion, which precipitates
between 840 and 975 K, is continuous to the grain
boundaries (Fig. 7).
Hardness measurements of parent metal and HAZ
material as discussed above, suggest that gross plastic
deformation of the HAZ may be restricted to this
temperature regime. Nucleation of cavities at. the
manganese sulphide inclusions, which are slIghtly
displaced from the grain boundaries, ma~ not the~efore
require localized grain-boundary deformatIon, b~t SImply
the attainment of a critical strain within the matnx dunng
stress relaxation. This would be consistent with
observations of damage accumulation during creep in
bainitic 2'25Cr-IMo steeP 3 which suggested that the
cavity-nucleation process was controlled by slip dislocations
and hence matrix strain.
Impurity segregation to grain boundaries
Grain-boundary segregation of residual impurities during
stress-relief heat treatment has been observed· in the
phosphorus-doped alloy Bll (Fig. 13) and subsequentl.y in
the commercial alloy D.12 The results so far obtaIned
indicate that the grain-boundary segregation of embrittling
impurities, e.g. phosphorus, tin, antimony, plays a vital role
in the low-ductility intergranular fracture mode of stress-
relief cracking.
Several authors have reported that such impurities also
have an influence on the rates of cavity nucleation and
growth during the operation of the intergranular ini~rovoid
coalescence mechanism in creep tests, or hot-tensIle tests
used to simulate stress relaxation in various low-alloy
steels.34-37 Seah38 has been able to rationalize the
observations of King35 and Miller and Batte39 in terms of
impurity segregation to intergranular cavities at 975 K.
Thus, the segregation of residual impurities during post-
weld heat treatment makes a significant contribution to the
severity of stress-relief cracking by either mechanism. The
microstructural investigation has produced information of
importance to the following aspects of impurity segregati~n :
the mechanisms of segregation and the roles of allOYIng
elements.
Metal Science April 1981
zone of 2'25Cr-1 Mo steel
Mechanisms of segregation
The equilibrium theory of segregation4o,41 has been
successfully employed to account for phosphorus
segregation in alloy B.1l However, an alternative
mechanism has been proposed 5,6which entails the rejection
of impurities (such as P, Sn, Sb, etc.) from growing, ¥~~in-
boundary carbides, in which they have very low solubIlItIes,
into the surrounding matrix. This mechanism has been used
to describe several embrittlement phenomena, e.g. 350°C
embrittlement,3 for which the equilibrium theory appeared
inadequate.
The grain-boundary carbide density behaviour during
stress-relief heat treatment (Figs. 4 and 5) suggest that at
least part of the grain-boundary impurity segregation
observed may result from carbide rejection, i.e. as l1. rises
rapidly between 600 and 800 K, ph?sphorus and ~ther
impurities may be rejected into the graIn-boundary regIo~s.
Subsequent desegregation follows the decrease In
equilibrium segregation levels with temperature, .after
sufficient impurity-atom mobility has been ~ttaIn~d,
producing a maximum in grain-boundary Impunty
enrichment.
Thus, at present, both theories are consistent with the
observed segregation, and further grain-boundary and
surface segregation studies, including the application ~f a
high-resolution scanning Auger spectroscope, are requIred
to elucidate the situation.
Roles of alloying elements
The two major alloying elements in 2'25Cr-IMo steel play
contrasting roles in impurity segregation. Chromium .is
thought to enhance the segregation of phosphorus to graIn
boundaries in alloy steels.42 This effect can be described
either in terms of single-component segregation
theories,4o,43 through a reduction in phosphorus solid
solubility by chromium in solution,44 or in terms of
Guttmann's multicomponent adsorption theory41 with a
chromium-phosphorus interaction energy and concomitant
cosegregation of chromium with phosphorus.
Figure 9 shows no change in the chromium content of
matrix or grain-boundary M3C carbides below 840 K,
indicating that most of the chromium is present in solution
throughout the temperature range in ~hich p~ospho~us
segregates (Fig. 13). This result is conSIstent WIth graIn-
boundary chromium analysis by Auger electron
spectroscopy which suggests that there is no cosegregation
of chromium with phosphorus during stress-relief heat
treatment (Fig. 13).
Dissolved molybdenum is thought to reduce grain-
boundary segregatIon. 0 f ph osp h orus'45 46 an d t'In46 b y
'scavenging' the impurities as Mo-P, Mo-Sn clusters or
compounds in the matrix. This effect is limited ?y the strong
affinity of molybdenum for carbon and It has been
demonstrated that the formation of M02C during
tempering is coincident with a reduction in the molybdenum
scavenging capacity.45 Figure 11 indicates that Mo-rich
M2C carbides precipitate between 840 and 975 K dur~ng the
heating period of stress-relief heat treatment, whIle. the
work of Titchmarsh14 (Fig. 14) shows that M2C carbIdes
increase in frequency at the expense ofM3C carbides (low in
Mo) during isothermal tempering at 973 K. Thus, during
the later part of stress-relief heating, and over the 'hold'
period (Fig. 1), the level of Mo dissolved in the matrix
decreases, and residual impurities are progressively released
into solution, becoming free to segregate.
Two possible consequences should be noted:
(i) the increase in free residual-impurity levels occurs in
 Hippsley
the intergranular microvoid coalescence cracking
temperature regime and therefore may influence
cavity nucleation and growth rates
(ii) the susceptibility of HAZ material to embrittlement
during service life may be increased by stress-relief
heat treatment.
CONCLUSIONS
1. The development of precIpItation microstructure
during stress-relief heat treatment of the HAZ is similar in
all four 2'25Cr-IMo steel alloys examined. Consequently,
the interalloy variations in stress-relief cracking mechanism
and severity observed 11,12 result from differences in residual
impurity element type and concentration.
2. A relatively high density of grain-boundary carbides is
required, concurrent with grain-boundary impurity
segregation, to induce low-ductility intergranular fracture.
3. There is no association of precipitate-free zone
formation or alloying-element depletion with intergranular
microvoid coalescence, while the small manganese sulphide
inclusions, which are thought to act as cavity nuclei, are
slightly displaced from the prior austenite grain boundaries.
Hence, the nucleation of cavities during intergranular
micro void coalescence fracture may be controlled by matrix
strain.
4. Both carbide rejection and equilibrium segregation
theories are consistent with the observed segregation
behaviour.
5. Stress-relief heat treatment may increase the level of
residual impurities free to segregate, consequently
enhancing (a) impurity effects on the intergranular
microvoid coalescence mode of stress-relief cracking and (b)
subsequent HAZ susceptibility to embrittlement during
service life.
ACKNOWLEDGMENTS
The author would like to thank Dr J. F. Knott and Dr J.
Titchmarsh for useful discussions, and Professor R. W.K.
Honeycombe for the provision of laboratory facilities.
Financial support for this work from AERE Harwell is
gratefully acknowledged.
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