Creep Cracking of 9Cr Steels with Boron OMMI (Vol.

3, Issue 3) December 2004

www.ommi.co.uk

IMPROVEMENT OF TYPE IV CREEP CRACKING RESISTANCE OF 9Cr HEAT

RESISTING STEELS BY BORON ADDITION

Masaaki Tabuchi, Masayuki Kondo, Kiyoshi Kubo and Shaju K. Albert,

National Institute for Materials Science (NIMS), Japan

Abstract

Creep lives of high Cr ferritic heat resisting steel weldments decrease due to Type IV fracture,
which occurs as a result of formation and growth of creep voids and cracks on grain
boundaries in fine-grained heat affected zone (HAZ). Because boron is considered to
suppress the coarsening of grain boundary precipitates and growth of creep voids, the effect of
boron addition on the creep properties of 9Cr steel weldments has been investigated. Four
kinds of 9Cr-3W-3Co-VNb steels with boron content varying from 47 to 180ppm, and with
nitrogen content as low as 20ppm, were prepared. The steel plates were welded by gas
tungsten arc welding and crept at 923K. It was found that the microstructures of the HAZ were
quite different from those of conventional high Cr steels such as P91 and P92, namely the
fine-grained HAZ did not exist in the present steel weldments. Boron addition also has the
effect of suppressing the coarsening of grain boundary carbides in the HAZ during creep. As
a result of these phenomena, the welded joints of the investigated steels showed no Type IV
fractures and much better creep lives than those of conventional steels.

Introduction

In consideration of reduction of CO2 emissions and energy saving for thermal power plants,
high Cr ferritic heat resisting steels have been investigated to increase the steam pressure and
temperature conditions of boiler components. The 9-12% Cr steels strengthened by tungsten
addition, P92 and P122, are now finding applications in boiler components of
ultra-supercritical (USC) power plants operating at around 898K. New ferritic steels, which
can be used at 923K, are being studied worldwide [1-3].

For these advanced high Cr steels with high creep strength, the Type IV creep damages and
cracks formed in the fine-grained HAZ decrease the creep lives of welded joints [4, 5]. Poor
creep strength of fine-grained HAZ structure without lath-martensite is considered as the
primary cause of Type IV fracture [6, 7]. Further, grain boundary precipitates such as M23C6
and Laves phase, which are the nucleation site of creep voids, coarsen faster in fine-grained
HAZ than in base metal during creep [8, 9]. In order to improve the creep strength of
fine-grained HAZ and resistance to Type IV cracking, strengthening of grain boundaries is
considered to be efficient.

A proper addition of boron is generally considered to improve the creep strength of base metal
by strengthening grain boundaries [10]. It is reported that boron distributes within the grain
boundary carbides, M23C6, and retards coarsening of them [11-13]. 9Cr-3W-3Co-VNb steel
with higher boron and low nitrogen content, which has better creep strength in long-term tests,
has been developed at NIMS [13]. In this steel, the boron addition also stabilizes the M23C6
Creep Cracking of 9Cr Steels with Boron OMMI (Vol.3, Issue 3) December 2004 2

precipitates and thus retards their coarsening during high temperature exposure. Therefore, it is
expected that the creep strength of the fine-grained HAZ of welded joints can be improved by
proper boron addition. In the present paper, the creep strength and microstructures of the
welded joints of 9Cr-3W-3Co-VNb steel with boron varying from 47 to 180ppm and lower
nitrogen have been investigated.

Experimental Procedure

Four kinds of 9Cr-3W-3Co-VNb steels, varying only in their boron content from 47 to 180ppm,
were produced in the form of plates with 25mm thickness. The chemical compositions of the
steels are shown in Table 1. Nitrogen content of the present steels was kept below 20ppm in
order to avoid the formation of boron-nitride (BN), which reduces the availability of boron for
grain boundary strengthening. The plates were given normalizing and tempering heat
treatments of 1353K for 1h and 1073K for 1h, respectively.

Welding of the plates was carried out by gas tungsten arc welding (GTAW) process using
Ni-base filler wire, AWS ER NiCr-3 (Inconel 82). This filler wire was chosen because the
creep strength of weld metal should be larger than that of base metal in order to investigate the
Type IV creep cracking resistance in the HAZ. The parameters chosen for welding are given in
Table 2. After welding, post weld heat treatment (PWHT) was carried out at 1013K for 4h.

The side bend test, tensile test and Charpy impact test of the welded joints were conducted.
Creep tests of base metal and welded joint were conducted at 923K using round bar specimens
having 6mm diameter and 30mm gauge length and smooth plate specimens having 4.3mm x
15mm section and 100mm gauge length shown in Fig.1, respectively. Microstructures of the
welded joint were examined using electron back scattering pattern (EBSP) imaging, field
emission scanning electron microscope (FE-SEM) and field emission auger electron
spectroscopy (FE-AES). Experimental results for the present steels were compared with those
of P92 steel [8] whose chemical composition is also shown in Table 1.

Results and Discussion

Weldability
Welding defects were not detected in the HAZ and fusion line in the side bend test. In the
tensile test at room temperature and at 923K, all of the present welded joints were fractured in
base metal. The 0.2% proof stress was 270-290MPa for the present steels. Charpy impact
value was 20-40J/cm2 in base metal, HAZ and fusion line. Thus it was found that the present
steels could be welded using Ni-base filler wire in spite of its higher boron content. The lower
nitrogen content is considered to be better for weldability of the present steels, because BN
scarcely precipitated.

Creep Properties of Base Metals and Welded Joints

Relation between stress vs. creep rupture time of the base metals of different boron content at
923K are shown in Fig.2. For the steels with 47 and 180ppm boron, the creep rupture time
was comparable to that of P92 steel, while for the steels with 90 and 130ppm boron, the creep
rupture time was longer than that of P92 steel. Boron content in the range of 90-130ppm
appears to be optimum for the best creep resistance for the present steel. All of the present
steel showed higher creep ductility whose reduction of area was higher than 90%.
Creep Cracking of 9Cr Steels with Boron OMMI (Vol.3, Issue 3) December 2004 3

Figure 3 shows the creep rupture times of the welded joints of the present steels at 923K. The
creep rupture lives of all welded joints were better than those of P92 steel welded joints.
Especially, the welded joints containing 90 and 130ppm boron showed significantly better
creep lives. For the P92 steel, the creep rupture lives of welded joints were less than base
metal due to the Type IV fracture in the fine-grained HAZ at 923K. For the present steels,
however, none of the welded joints exhibited Type IV fracture. As shown in Fig.4, for stress
levels above 110MPa, fracture took place in the base metal, while for stress levels below
100MPa, the fracture location shifted to the fusion boundary between the Ni-base weld metal
and the ferritic steel. Further, the present steel welded joints showed better fracture ductility in
contrast with the very low ductility of Type IV fracture. Creep voids were scarcely observed in
the HAZ for the present steel weldments.

Figure 5 shows the relations between creep rupture time and boron content of base metals and
welded joints of the present steels. The differences in creep lives between welded joints and
base metal were small especially for lower stress levels. The large degradation of creep
strength in welded joints were not observed for the present steels independent of boron content,
possibly because Type IV fracture did not occur.

Microstructures of HAZ
Figure 6 shows the distribution of Vickers hardness in the HAZ after PWHT before creep test.
The width of the HAZ was about 2.3mm. The hardness value in the HAZ of the present steels
was not different from that of conventional high Cr ferritic steels. The effect of boron content
on Vickers hardness in HAZ was not observed.

In order to clarify the grain boundary structures of the welded joints, EBSP analysis was
conducted. Results of EBSP analysis, inverse pole figure of [001], for the present welded joint
with 90ppm boron are indicated in Fig.7 in comparison with the results for P92 steel weldment.
Generally, for the conventional high Cr ferritic steel, the area at 1.5mm from the fusion line
corresponds to fine-grained HAZ, which does not have lath-martensite structure, and 0.5mm
from fusion line corresponds to coarse-grained HAZ. For P92 steel, the grain size at 1.5mm
from the fusion line was smaller than 10µm, as shown in Fig.7. For the present steel with
90ppm boron, however, the microstructures of the HAZ were considerably different from
those for conventional high Cr ferritic steels. It should be noted that at 1.5mm from the
fusion line, most of the grains had nearly the same size as those of the base metal, further the
lath-martensite structure was clearly observed. At 0.5mm from the fusion line, the smaller
grains were observed, but the average grain size was larger than 30µm and lath-martensite
structure was also observed. These characteristics of HAZ microstructure were common for
all the present steel welded joints independent of boron content. The fine-grained HAZ
structure was not observed in all the present steel welded joints.

Creep Properties of HAZ

In order to investigate the creep strength of the HAZ for the present steels, creep tests were
conducted on simulated HAZ specimens. The simulated HAZ specimens were produced by
heating up to the peak temperature, which was from 1100K to 1400K, and then cooling down.
The creep tests of simulated HAZ specimens were conducted using round bar specimens
having 6mm diameter and 30mm gauge length at 923K. The creep rupture times of simulated
HAZ specimens heated up to AC3 (1223K) of 90ppm and 47ppm boron steel are shown in Fig.8.
For P92 steel, the creep rupture time of AC3 simulated HAZ, which has fine-grained HAZ
structure, was significantly lower than that of base metal [8]. However, the degradation of
Creep Cracking of 9Cr Steels with Boron OMMI (Vol.3, Issue 3) December 2004 4

creep strength in AC3 simulated HAZ was smaller for the present steels, and consequently the
creep strength of AC3 HAZ for the present steels was much better than that for P92 steel.

Figure 9 shows the creep rupture times of simulated HAZ specimens heated to several peak
temperatures for 90ppm boron steel and P92 steel. From these results, it was clarified that the
degradation of creep strength in the HAZ was small for the present steel. It is considered that
because of the larger grain size and lath-martensite structure of the HAZ, the degradation of
creep strength in the HAZ is smaller for the present steels. Because the difference of creep
strength between base metal and simulated HAZ was small, Type IV fracture was not observed
in the present steel weldments.

Effect of Boron on Precipitates

Creep strength was improved not only for base metal but also for simulated HAZ and welded
joint by appropriate boron addition, as shown in Figs.2, 3 and 8. It is reported that boron is
found inside the M23C6 precipitates after tempering and creep, and thereby promotes the
formation of a fine distribution of M23C6 precipitates [10-13]. Hence, distribution of M23C6
precipitates both in HAZ and base metal were examined using FE-SEM. Figure 10 shows the
back-scattered (BS) images of the base metal and HAZ of welded joints for the present steels
with 47ppm boron and 90ppm boron crept for about 5000h. The white precipitates are Laves
phase and grey ones are M23C6, which are precipitated on prior austenite boundaries. It is
clearly observed that the size of M23C6 in 90ppm boron steel is much smaller than that of
47ppm boron steel in both base metal and HAZ, while the size of Laves phase was not affected
by boron content.

The creep rupture times of both simulated HAZ and base metal were about three times longer
for 90ppm boron steel than that for 47ppm boron steel, as shown in Fig.8. These differences
of creep strength can be attributed to the size of M23C6 precipitates, because the grain size and
lath-martensite structure were similar for these two steels. The boron content in the
precipitates was analyzed using field emission auger electron spectroscopy (FE-AES). An
example for FE-AES analysis of M23C6 carbides in the HAZ of 90ppm boron steel is shown in
Fig.11. Boron was detected from some of M23C6 carbides present along prior austenite
boundaries and lath boundaries, however boron could not be detected from the small carbides
present inside the grains. It is considered that appropriate boron addition suppress the
coarsening of M23C6 on grain boundaries during creep and improve the creep strength not only
for base metal but also for the HAZ.

From the experimental results mentioned above, it can be concluded that the appropriate
addition of boron and low nitrogen significantly improves the creep strength of the HAZ and
the resistance to Type IV cracking of welded joints because of the larger grain size with
lath-martensite structure of the HAZ and suppression of coarsening of M23C6 precipitates. The
reason why fine-grained HAZ was not observed in the present steel weldments is not clear at
present. Azuma et al studied the transformation of ferrite to austenite for high Cr turbine rotor
steel containing 90ppm boron [14]. The reported grain structures heated to 1173-1273K were
very similar to the HAZ microstructure observed in this study. They described that at first
γ phase was formed after α/γ transformation, and then granular grains were formed by
recrystallization process. It seems that the γ phases formed after α/γ transformation
correspond to the large grains observed at 1.5mm from the fusion line and granular grains
formed by recrystallization process correspond to smaller grains observed at 0.5mm from the
fusion line in Fig.7. The mechanisms of transformation of high boron low nitrogen steel would
be different from those of the conventional ferritic steels.
Creep Cracking of 9Cr Steels with Boron OMMI (Vol.3, Issue 3) December 2004 5

Although there were some research subjects that should be further investigated such as
transformation mechanism during welding, filler wire with matching composition and much
longer-term creep properties, the present results show the possibility to improve the creep lives
of high Cr ferritic steel weldments.

Conclusions

In order to investigate the possibility to improve the Type IV cracking resistance of high Cr
ferritic steel weldments using the grain boundary strengthening effect of boron, creep tests of
the welded joints of 9Cr-3W-3Co-VNb steel with boron content varying from 47 to 180ppm
and low nitrogen content were carried out. The major conclusions from the present study are
summarized as follows:
1. Significant improvement in the creep lives of welded joints of high Cr ferritic steel can be
achieved by controlled addition of boron. From the creep test results available so far, it
appears that Type IV cracking is suppressed in the present steel weldments.
2. Boron content from 90 to 130ppm is the optimum range for achieving good creep
resistance for the base metal and welded joints.
3. Fine-grained microstructures were not observed in the HAZ of welded joints for the
present steels, which is significantly different from conventional high Cr ferritic steels.
4. In addition to the absence of fine-grained structure in the HAZ, suppression of coarsening
of the M23C6 precipitates also contributes to improved creep resistance of the welded
joints.

References

1. T. -U. Kern, M. Staubli and B. Scarlin, ISIJ International, 42 (2002) 1515.

2. R. Agamennone, C. Berger, W. Blum, J. Ehlers, P. J. Ennis, J. Granacher, G. Inden, V.
Knezevic, J. W. Quadakkers, G. Sauthoff, A. Scolz, L. Singheiser, J. Vilk and Y. Wang,
Proc. of 7th Liege Conference on Materials for Advanced Power Engineering, Part III,
(2002) 1279.
3. F. Abe, H. Okada, S. Wanikawa, M. Tabuchi, T. Itagaki, K. Kimura, K. Yamaguchi and M.
Igarashi, ibid, (2002) 1397.
4. K. Bell, Elevated Temperature Midlife Weldment Cracking (Type IV) - A Review, TWI
Report 597, Abington, U.K., (1997).
5. F. Masuyama, M. Matsui and N. Komai, Key Engineering Materials, 171-174 (2000) 99.
6. Y. Hasegawa, M. Ohgami and Y. Okamoto, Proc. of Advanced Heat Resisting Steels for
Power Generation, (1998) 655.
7. M. Tabuchi, T. Watanabe, K. Kubo, M. Matsui, J. Kinugawa and F. Abe, J. of the Society of
Materials Science, Japan, 50 (2001) 116 (in Japanese).
8. M. Matsui, M. Tabuchi, T. Watanabe, K. Kubo, J. Kinugawa and F. Abe, ISIJ International,
41 (2001) S126.
9. K. Shinozaki, D. J. Li, H. Kuroki, H. Harada and K. Ohishi, ISIJ International, 42 (2002)
1578.
10. N. Takahashi, T. Fujita and T. Yamada, Tetsu-to-Hagane, 61 (1975) 2263 (in Japanese).
11. L. Lundin, S. Fallman and H.-O. Andren, Materials Science and Technology, 13 (1997)
233.
12. P. Hofer, M. K. Miller, S. S. Babu, S. A. David and H. Cerjak, Metallurgical and Materials
Creep Cracking of 9Cr Steels with Boron OMMI (Vol.3, Issue 3) December 2004 6

Transactions A, 31A (2000) 975.

13. T. Horiuchi, M. Igarashi and F. Abe, ISIJ International, 42 (2002) S67.
14. T. Azuma, K. Miki, Y. Tanaka and T. Ishiguro, Testu-to-Hagane, 86 (2000) 667 (in
Japanese).

Table 1: Chemical compositions for the present steels.

Steel C Si Mn Cr Mo W V Nb Co N B
47ppmB 0.079 0.30 0.48 8.77 <0.01 2.93 0.18 0.046 2.91 0.0017 0.0047
90ppmB 0.074 0.30 0.48 8.93 <0.01 3.13 0.18 0.046 2.92 0.0014 0.0090
130ppmB 0.077 0.30 0.49 8.97 <0.01 2.87 0.18 0.046 2.91 0.0015 0.0130
180ppmB 0.078 0.30 0.50 8.91 <0.01 2.85 0.18 0.047 2.90 0.0011 0.0180
P92 0.09 0.16 0.47 8.72 0.45 1.87 0.21 0.060 0.0500 0.0020

Table 2: Welding parameters.

Welding Procedure Gas Tungsten Arc
Welding filler wire AWS ER NiCr-3
Groove V groove (20 degree)
Preheating and Interpass
373 - 423K
Temperature
1 - 6 pass : 70 - 160A
Welding Current
7 - 32 pass: 180 - 200A
Arc Voltage 8 - 16V
Welding Speed 8 cm/min
No. of Pass 32 pass
PWHT 1013Kx4h, Air cooling

Fig.1: Creep test specimen for the welded joint (unit: mm).
Creep Cracking of 9Cr Steels with Boron OMMI (Vol.3, Issue 3) December 2004 7

Fig.2: Creep rupture times of base metal for the present 9Cr-3W-3Co-VNb steels
with high-B and low-N.

Fig.3: Creep rupture times of the welded joints for the present 9Cr-3W-3Co-VNb steels
with high-B and low-N. The plot with round brackets means that the test is continuing.

Fig.4: Creep fractured welded joint specimens of the 90ppm boron steel at 923K.
Creep Cracking of 9Cr Steels with Boron OMMI (Vol.3, Issue 3) December 2004 8

Fig.5: Effect of boron content on creep rupture time for the base metal and welded joints.

Fig.6: Hardness variation in the HAZ of welded joints.

Creep Cracking of 9Cr Steels with Boron OMMI (Vol.3, Issue 3) December 2004 9

EBSP Analysis (Inverse Pole Figure [001]) 111

001 101

Fig.7: EBSP images for the base metal and HAZ of 90ppm boron steel and P92 steel.

Fig.8: Creep rupture times of AC3 simulated HAZ specimens.

Creep Cracking of 9Cr Steels with Boron OMMI (Vol.3, Issue 3) December 2004 10

Fig.9: Creep rupture time vs. peak temperature in simulated HAZ heat treatment.

Laves
Laves

Base metal
M
M23CC
23 6 6

HAZ

47ppmB, 90MPa, tr =5530h 90ppmB, 100MPa, tr =5030h

Fig.10: FE-SEM images of the precipitates observed in base metal and HAZ
of crept welded joints for 47 and 90ppm boron steels.
Creep Cracking of 9Cr Steels with Boron OMMI (Vol.3, Issue 3) December 2004 11

x104
a)
b)
1.0

Count / sec
0
WW
B+W Cr
-1.0 C Fe
Fe Fe
M23C6 Cr
-2.0
Cr
0 1000 2000
Kinetic energy (eV)

Fig.11: FE-AES analysis of M23C6 in HAZ of 90ppm boron steel crept at 923K for 110MPa.
a) Carbide on prior austenite grain boundary chosen for analysis; b) FE-AES spectra.