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Institute of Materials Research, Slovak Academy of Sciences, Watsonova 47, 040 01 Kosice, Slovakia
b Slovak Energy Machinery, Tov
arenska 210, 93 528 Tlmace, Slovakia
c Institute of Physics of Materials, Academy of Sciences of Czech Republic, Zi
zkova 22, 616 62 Brno, Czech Republic
Received 2 October 2006; received in revised form 3 July 2007; accepted 16 July 2007
Abstract
Phase evolution in the weld metals of P92 and E911 steels weld joints were studied during ageing at 625 C for up to 9000 h. The phases:
ferrite + M23 C6 + MX + Laves found by means of analytical TEM in the annealed states agree with the results of the thermodynamic calculation of
equilibrium phases. The cross-weld hardness values, HV10, after 1000, 3000, and 9000 h ageing overlap each other and are approximately 15 units
below that of the post-weld heat-treated (PWHT) state. Charpy impact energy with the notch at the centerline of the weld metal was measured. Its
values decrease after ageing from approximately 6080 to 12 J compared to the PWHT state. In 912%Cr steel with W this phenomenon can be
explained by a priori heterogeneity in the weld metal, its large former austenite grain size, the precipitation and growth of M23 C6 and Laves phase
particles on grain and packet boundaries.
2007 Elsevier B.V. All rights reserved.
Keywords: Weld metal; P92; E911; Phase evolution; Thermodynamic calculations; Impact toughness
1. Introduction
Environmental and commercial demands on energy production have led to the development of steels operable at
supercritical conditions. An addition of tungsten and molybdenum (1.82W and 0.5Mo, respectively) and optimization of
other alloying elements in 912Cr advanced steels offer almost
30% higher creep rupture strength at 600 C after 105 h than
classical P91 steel [1,2]. Steels such as E911, P122, and P92
(ASME code) based on the steels developed in Japan are among
the most promising. In addition to the more severe operating
conditions in ultra supercritical plants, the newly developed
steels enable weight reduction of the thick section components
of boilers and turbines. Compared with P91 steel, W-containing
steels have worse ductility. The embrittlement has been ascribed
to higher amount of precipitates of intermetallic Laves phase
because of its inherent brittleness and unfavorable size [3,4].
After normalization and tempering, the advanced steels possess tempered martensite microstructure composed of ferrite and
precipitates. The precipitates are mostly of two types, M23 C6
precipitating mainly on grain and subgrain boundaries, and MX
0921-5093/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2007.07.036
(1)
290
Table 1
Chemical composition of filler metals
Filler metal
Si
Mn
Cr
Mo
Ni
Nb
P92
0.11
0.11
0.37
0.2
0.45
0.6
8.8
8.8
0.4
0.5
0.6
0.7
1.6
1.6
0.2
0.2
0.06
0.05
0.04
0.05
E911
W ZCrMoWVNb9 1 1 wire
E ZCrMoWVNb9 1 1 B 42 H5, electrode
0.11
0.1
0.25
0.38
0.6
0.45
8.8
9.0
1.0
1.0
0.7
0.7
1.0
1.0
0.2
0.2
0.05
0.06
0.05
0.07
Fig. 1. LM micrographs of P92 (left column) and E911 (right column) weld metals: (a and b) after PWHT and (c and d) after ageing at 625 C for 9000 h.
291
lic phases (Laves, sigma) were taken into account in the calculation.
3. Results
3.1. Microstructure
The microstructure of P92 and E911 steels in the PWHT
state and after ageing at 625 C for 9000 h is shown in Fig. 1.
The tempered microstructure of both weld metals is macroscopically heterogeneous. The areas of former columnar grains with
typical martensite structure comprising large packets of laths
alternate with inter-bead heat affected areas with smaller polyhedral grains of finer martensite. No delta ferrite was observed.
Because the welding procedure used weaving, there is a smooth
transition between columnar areas and inter-bead heat affected
zones.
On the microscopic level, an inhomogeneity of particle distribution is characteristic, the localities with more and less
intensive precipitation in the matrix can be found. After 9000 h
ageing the former austenite, packet, and some of the lath boundaries are almost continuously decorated with large particles
compared to the PWHT conditions, as demonstrated in Fig. 2.
Analysis of the observed and calculated phases of the E911
and P92 weld metals is given in Table 2. In both cases the Cr-rich
M23 C6 and (V, Nb)-rich MX particles have been documented for
all investigated conditions. Laves phase was found only after
ageing at 625 C. Figs. 3 and 4 illustrate a typical distribution
and morphology of the above mentioned secondary phases.
Fig. 2. SEM metallography of P92 (left column) and E911 (right column) weld metals: (a and b) after PWHT and (c and d) after ageing at 625 C for 9000 h.
292
Fig. 3. Example of Laves phase in P92 weld metal after ageing at 625 C for 1000 h: (a) TEM micrograph of extraction replica, (b) electron diffraction pattern, and
(c) its solution for B = [2 0 1].
Fig. 6 by solid circles (weld metal P92 in Fig. 6a, weld metal
E911 in Fig. 6b). Calculated volume amounts of the equilibrium
phases in dependence on temperature are shown in Fig. 7 for
temperature range 527927 C.
3.2. Mechanical properties
Hardness HV10 of the weld metals after ageing decreased
by approximately 15 units compared to the PWHT state and the
values of all aged states overlap, as illustrated in Fig. 8.
A significant drop in impact energy was seen following
ageing (Table 3). The values of impact energy at ambient tem-
293
Fig. 4. TEM micrograph of (a) secondary phases in P92 weld metal after ageing at 625 C for 3000 h and (b) example of M23 C6 particle and its electron diffraction
pattern for B = [1 1 1] as inlay.
Fig. 5. Evolution of chemical composition of phases in P92 and E911 weld metals with ageing time.
294
Table 2
Phase composition of experimental steels
Phase composition
M23 C6
MX
Laves
P92
PWHT
625 C/10 h
625 C/20 h
625 C/1000 h
625 C/3000 h
625 C/9000 h
Calculated
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
PWHT
625 C/1000 h
625 C/3000 h
625 C/9000 h
Calculated
x
x
x
x
x
x
x
x
x
x
x
x
x
x
E911
Table 3
Impact energy values at room temperature
State
P92 (J)
E911 (J)
PWHT
625 C/1000 h
625 C/3000 h
625 C/9000 h
87, 62, 66
18, 24, 23
12, 12, 10
13, 20, 20
4. Discussion
4.1. Microstructure and phase analysis
The microstructure of the weld metals after PWHT comprised
of tempered martensite with clearly visible acicular structure
initially. This feature slowly disappears with the time of ageing,
resulting in the ferrite-carbide mixture after 9000 h.
According to the thermodynamic calculations, ferrite,
M23 C6 , MX, and Laves phase are the equilibrium phases
for the experimental materials and temperature conditions
(Figs. 6 and 7). These results are in accordance with experimentally found phases except for the states after PWHT, in
which the equilibrium conditions have not been achieved yet.
The volume fraction of M23 C6 phase is about three-times
higher than that of intermetallic Laves phase for the investigated
temperature 625 C, their amounts decrease with increasing
temperature. The amount of MX phase is stable in the calculated temperature range 527927 C for both weld metals
(Fig. 7).
EDX analysis of particles shows that the fine particles of up
to 80 nm in size (after PWHT only up to 20 nm) contain V and
Nb. The wt.% ratio V:Nb is approximately 4.8:1.3 and 4.3:1 for
E911 and P92 WMs, respectively. According to the thermodynamic calculation the particles are of MX type, with a similar
ratio of the above-mentioned elements, and contain nitrogen and
a small amount of carbon, in ratios 19:0.3 and 18:1. The measured particles can be defined as (V, Nb)-rich carbonitrides with
minor contents of Cr and Mo. In high Cr steels particles like these
can be found on all kinds of boundaries as well as in the matrix
[6,8]. After normalizing + tempering, MX carbonitrides precipitate coherently in lath interior. The increased Cr content reduces
Fig. 7. Calculated volume amounts of equilibrium phases MX, M23 C6 and Laves
phase as a function of temperature: (a) for P92 weld metal and (b) for E911 weld
metal.
295
Fig. 8. Cross-weld hardness HV10 after ageing at 625 C: (a) P92 and (b) E911.
296
Fig. 9. SEM micrographs of fracture surfaces of P92 (left column) and E911 (right column) weld metals after (a and b) 1000 h and (c and d) 3000 h ageing.
297
Fig. 10. Fracture surface and SEM metallography of weld metals after 9000 h ageing: (a and b) P92 and (c and d) E911.
298
P92 weld metal contains more tungsten and less molybdenum (53W:7Mo) than that precipitating in E911 weld metal
(41W:16Mo).
Major metallic elements in M23 C6 carbide are Cr, Fe, W, and
Mo. The content of these elements is similar for both weld
metals, and during ageing the amount of Cr increases at the
expense of Fe.
The chemical composition and volume fraction of MX particles is nearly constant for the calculated temperature range
527927 C in both weld metals.
Hardness of the weld metals does not change substantially
after ageing for 10009000 h and is only approximately
15 units lower than the hardness after PWHT.
Ageing led to a decisive reduction of impact energy at
room temperature. This has been ascribed to an unfavorable microstructure containing large austenite grain size after
welding and very coarse Laves phase and M23 C6 particles
precipitated on interfaces.
Acknowledgements
The present work was supported by Slovak Grant Agency
(VEGA) under Grant No. 2/7197/27, COST Action 536, and
by Slovak Research and development agency under the contract
No. COST-0022-06. Our thanks belong also to Dr. Graham Holloway of Metrode Products Limited, Chertsey, for reading the
manuscript and valuable comments.
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