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Creep and LCF Behaviors of Newly Developed Steel for A-USC

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Creep and LCF Behaviors of Newly Developed Steel for A-USC
Creep and LCF Behaviors of Newly Developed
Advanced Heat Resistant Austenitic Stainless
Steel for A-USC
Guocai Chai, Magnus Boström, Magnus Olaison and Urban Forsberg
Linköping University Post Print
N.B.: When citing this work, cite the original article.
Original Publication:
Guocai Chai, Magnus Boström, Magnus Olaison and Urban Forsberg, Creep and LCF
Behaviors of Newly Developed Advanced Heat Resistant Austenitic Stainless Steel for A-USC,
2013, Procedia Engineering, (55), 232-239.
http://dx.doi.org/10.1016/j.proeng.2013.03.248
Copyright: Elsevier
http://www.elsevier.com/
Postprint available at: Linköping University Electronic Press
http://urn.kb.se/resolve?urn=urn:nbn:se:liu:diva-91924
Available online at www.sciencedirect.com
Procedia Engineering 55 (2013) 232 – 239
6th International Conference on Creep, Fatigue and Creep-Fatigue Interaction [CF-6]
Creep and LCF Behaviors of Newly Developed Advanced Heat
Resistant Austenitic Stainless Steel for A-USC
Guocai Chaia,b∗, Magnus Boströma, Magnus Olaisona, Urban Forsberga
b
a
Sandvik Materials Technology, SE-811 81 Sandviken, Sweden
Division of Engineering Materials, Linköping University, SE-58183 Linköping, Sweden
Abstract
Austenitic stainless steel grade UNS S31035 (Sandvik Sanicro® 25) has been developed for use in super-heaters and
reheaters in the next generation of A-USC power plants. This new grade shows very good resistances to steam oxidation
and hot corrosion, and higher creep rupture strength than other austenitic stainless steels available today. This makes it an
interesting alternative for super-heaters and reheaters in future high-efficient coal fired boilers. This paper will mainly focus
on the study of the creep and LCF behavior of the material at temperatures from 600°C to 750°C by using TEM and ECCI.
The mechanisms at different temperatures and loading conditions have been identified. The interactions between
dislocations and precipitates and their contribution to the creep rupture strength have been discussed. In this paper, different
models have been used to evaluate the long-term creep behavior of the grade. A creep rupture strength near 100MPa at
700°C for 100 000h has been predicted.
Authors. Published
by Elsevier
Ltd.
© 2013
2013The
Published
by Elsevier
Ltd. Selection
and/or peer-review under responsibility of the Indira Gandhi Centre for
SelectionResearch.
and peer-review under responsibility of the Indira Gandhi Centre for Atomic Research.
Atomic
Keywords: Heat resistant austenitic stainless steel; superheater; A-USC; creep; fatigue
1. Introduction
The demand for electric power is continuously increasing around the world. Meanwhile the consciousness of
the environmental impact from human action is growing. Although combustion processes generate carbon
dioxide, coal-fired thermal power generation is still one of the most important methods in the medium to longterm future to satisfy this demand, as coal is available at a competitive price and often is the single domestic
energy source [1]. However, the biggest challenge facing coal-fired power plants is to improve their energy
efficiency. This can be accomplished by increasing the maximum steam temperature and the steam pressure.
Conventionally, the heat efficiency of coal-fired power plants has stayed at around 41% in the super critical
(SC) condition with a temperature of 550°C and pressure of 24.1MPa. In order to attain a power generating
efficiency of about 43%, ultra super critical (USC) conditions with a steam temperature at about 600°C should
∗
Corresponding author:
E-mail address: [email protected]
1877-7058 © 2013 The Authors. Published by Elsevier Ltd.
Selection and peer-review under responsibility of the Indira Gandhi Centre for Atomic Research.
doi:10.1016/j.proeng.2013.03.248
233
Guocai Chai et al. / Procedia Engineering 55 (2013) 232 – 239
be reached. By increasing the temperature up to 700°C (A-USC condition) and pressure of above 300 bars, a
power plant efficiency of higher than 50% can be reached and CO2 emission can be reduced by about 45%
comparing with that of SC condition [2]. However, the steam data in practice will be limited by the material
properties of the boiler tubes, especially tensile strength at elevated temperatures and creep strength combined
with corrosion resistance.
A new austenitic stainless steel grade, Sandvik Sanicro 25 (UNS S31035), has recently been developed for
the purpose of A-USC [3] in collaboration with a number of different industrial partners within the Thermieproject in Europe, intended for use in super-heaters and reheaters in advanced ultra-supercritical boilers at
temperatures up to 700°C. They have been test-installed in different boilers in Europe and have run for more
than five years, and are still in very good conditions [4]. This paper will describe the development and
properties, especially creep and low cycle fatigue properties of Sandvik Sanicro 25 material.
2. Sandvik Sanicro 25 heat resistance austenitic stainless steel
Since Sandvik Sanicro 25 was aimed for use in super-heaters and reheaters with metal temperatures up to
700°C, the design principles for this alloy were to achieve a stable microstructure, high strength by
precipitation strengthening with stable nano precipitates and solution hardening, high corrosion resistance with
high Cr content. Ni and N that can suppress the formation of sigma phase were added to reach sufficient
structural stability and good fabricability. The chemical composition is shown in Table 1.
Table 1. Nominal composition of Sandvik Sanicro 25 (wt%).
Cmax
Si
Mn
Cr
Ni
W
Co
Cu
Nb
N
Fe
0.1
0.2
0.5
22.5
25
3.6
1.5
3.0
0.5
0.23
Bal.
(a)
(c)
(b)
(d)
Fig. 1. Fine precipitates that contribute to the creep strength of Sandvik Sanicro 25 austenitic stainless steel, (a) M23C6, 700°C for 1000
hours, (b) Laves phase, 700°C for 30 000 hours, (c) Copper-rich phase, 700°C for 30 000 hours, (d) Nanoparticles, 700°C for 30 000 hours.
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Guocai Chai et al. / Procedia Engineering 55 (2013) 232 – 239
Figure 1 shows some fine precipitates observed in this newly developed Sandvik Sanicro 25 austenitic
stainless steel that can contribute to the improvement of the creep strength. Both intra- and intergranular M23C6
precipitates can be observed (Fig. 1a). In the grain boundaries, they have a <100>Ȗ // <100>M23C6 coherent
relationship to the austenite matrix. Laves phase was observed both randomly within the grains but also ordered
on what appears to be former twin boundaries (Fig. 1b). Both coherent Laves phase precipitates with a
[100]Laves // [100]Ȗ orientation relationship, and incoherent Laves phase precipitates were observed. In the aged
material the Laves phase are needle shaped but rather small. In the creep tested materials, these particles are
fine and isometric. Copper rich nanoparticles can also be observed. They are round with a size up to 50 nm
(Fig. 1c). In this material, a dense distribution of about 10 nm large precipitates was observed (Fig. 1d). Due to
the limitation of the TEM, these particles could not be identified, but they are probably MX carbides or
carbonitrides. Similar particles have been identified in other analyses. These particles were rather stable [4].
Seamless tubes in a variety of dimensions have been manufactured ranging from 25 mm to 114 mm outer
diameter. A matching filler material has also been developed. Code cases as per the American Society of
Mechanical Engineers Boiler and Pressure Vessel Code, Section I and Section VIII, have been filed. Actual
code cases are planned to be available during 2012.
3. Creep behaviors
Up to now (October 2011), the longest time to rupture from the creep test of this alloy is approximately 74
000 h (73902 hours, 195MPa/650°C) and some samples are still running. Fig. 2(a) shows the results of the
creep in rupture plots. With linear least squares regression (Larson-Miller relation) to extrapolate the creep
rupture data, the predicted 105 h creep rupture strength at 700ºC is 104 MPa.
Fig. 2 (a). Creep strength versus rupture time of Sandvik Sanicro 25 austenitic stainless steel and the linear regressions in the creep data,
(b). Modeling by free temperature model (FTM) [9].
As we know, pressure vessel components are normally designed for a long service time such as 200 000 h.
However, such creep data are usually not available for design. The design data are therefore obtained by
extrapolation from the creep data of shorter tests. Different models and approaches have been developed. One
recently proposed procedure for extended extrapolation of creep rupture data is the free temperature model
(FTM) that allows for extrapolation by more than a factor of three in time [5]. The procedure is based on a
time-temperature parameter (TTP), which has the general mathematical form:
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Guocai Chai et al. / Procedia Engineering 55 (2013) 232 – 239
PTTP = v(T ) log(tr ) + w(T )
(1)
where PTTP is the time-temperature parameter, tr is the time to rupture, and v(T) and w(T) are functions of
temperature. The free temperature model is reported to be well suited for austenitic stainless steels [5]. The
master curve is expressed by the creep stress as a function of polynomial in the TTP:
nP
log(σ ) = ¦ a j TTP j
j =0
(2)
The coefficients aj are fitted to the creep rupture data and the stress – rupture time relations are derived. The
reason for using a polynomial in log (tr) rather than log (σ) which is the more common approach, is that it has
been shown that this improves the accuracy in extended extrapolated values [5]. To extrapolate the creep
rupture data, the polynomials in Eq. 1 were both set to order 3 and the master curve, Eq. 2, was set to a second
order polynomial. Fig. 2(b) shows an extrapolation with rupture data up to 40000 h at different temperatures.
The extrapolation was performed three times with rupture data up to 40000 h where the evaluation satisfies the
post evaluation tests (PATs) and other criteria proposed by the European Collaborative Creep Committee
(ECCC) [6]. At 700ºC and 100000 h, the rupture strength from this extrapolation is 99 ± 3 MPa, which is close
to that from the linear least squares regression (104MPa).
250
60
UNS S31035 (VdTÜV 555)
UNS 30432 (VdTÜV 550)
TP310HCbN (VdTÜV 546)
TP310MoNbN (VdTÜV 563-2)
HR6W (Vd TÜV 559/2)
50
Stress (MPa)
Rupture elongation (%)
200
150
100
50
0
550
(a)
600
650
Temperature (°C)
700
40
30
20
COMTES 700,
Scholven
22400h
10
750
0
550
(b)
600
650
700
Temperature (°C)
750
Fig. 3(a). A comparison of creep rupture strength of different austenitic stainless steels at 100 000 hours according to European Vd TÜV
data sheets, (b). Ductility of creep tested and field tested Sandvik Sanicro 25 material.
Fig. 3(a) shows a comparison of the creep rupture strength of Sandvik Sanicro 25 (UNS S31035) with some
commercially available austenitic stainless steels, taken from corresponding TÜV documents [7]. The creep
rupture strength of Sandvik Sanicro 25 was set to 95 MPa at 700°C/100 000 hours in the Vd TÜV approval
555. This is higher than what are stated for the other materials. Sandvik Sanicro 25 has a good ductility. The
tube after the installation in the COMTES trial in the power plant in Scholven at 670°C/256 bar for 22400
hours had still an elongation of 26% (Fig. 3(b)).
In the temperature range up to 700°C, one of the main creep strengthening mechanisms is the interaction
between dislocations and precipitates. Fig. 4 shows two examples how interactions between dislocations and
precipitates in a Sandvik Sanicro 25 creep specimen tested with 210 MPa at 700°C and with a rupture time of
3153 h. Moving dislocations at the nano-sized particles can be seen. Around the intragranular precipitates, the
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Guocai Chai et al. / Procedia Engineering 55 (2013) 232 – 239
dislocation density is high which indicates that they function as obstacles for the dislocation movements. This
increases the creep strength. These nano-sized particles were identified as M23C6 and Laves phases using
electron diffraction. In the dislocation dense area, dislocation walls have formed [4]. In Fig. 5b, it can also be
observed that smaller nanoprecipitates such as copper rich particles and MX particles are more effective as
obstacles for the dislocation movements. Dislocation clouds or clusters near the precipitates can be observed.
However, they have different mechanisms for dislocation crossing. For the copper rich nanoparticles,
dislocations cross the particles mainly by climb / bypass of unit dislocations. For the MX nanoparticles,
deformation might occur by shearing of partial dislocations [4].
(a)
(b)
Fig. 4. Dislocation structures, (a). Interaction between dislocations and precipitates, (b). dislocation cloud or cluster near nona Cu-rich
particles and MX particles
4. Low cycle fatigue properties
Low cycle fatigue properties in this investigation were obtained using cylinder samples with a diameter of
10 mm and measure length of 12.5 mm with a push-pull mode and a frequency of 0.05Hz. They were then
compared with the results from the EU Thermie project. Fig. 5 shows the results of total strain amplitude versus
fatigue life. Generally, Sandvik Sanicro 25 shows a longer LCF life with total strain amplitude comparing with
NF709 material. The results from this test are comparable to that of the Thermie project. Fig. 6b shows the
cyclic stress-strain responses of Sandvik Sanicro 25 with a total strain amplitude of 0.6% at RT, 600°C, 650°C
and 700°C. At RT, the alloy shows a normal cyclic hardening and softening response. At temperature between
600°C and 700°C, only monotonic cyclic hardening can be observed. However, they are not parallel each other.
As expected, the start stress was higher if the temperature is lower. It is interesting to mention however that
cyclic hardening rate increases with increasing temperature. Finally, the stress reached the highest at 700°C.
Another interesting phenomenon is that the stress increases rapidly near the failure period at lower temperature,
especially at 600°C, than higher temperature. When the stress versus strain hysteresis curve was evaluated,
serrated curves were observed, and the amplitude of serration increases with increasing temperature. This
indicates that dynamic strain ageing could have already occurred during the cyclic loading at these
temperatures. The monotonic increase of stress can be attributed to dynamic strain ageing.
In order to investigate some possible damage mechanisms for low cycle fatigue of Sandvik Sanicro 25
material, the electron channel contrast image (ECCI) technique was used to evaluate the damage in the fatigue
tested specimens. In the specimen tested at RT, dense dislocations and deformation bands can be observed.
However, the damage or crack initiation is mainly caused by the formation of defects such as slip bands or
PSB, twin bands and stacking faults. Fig. 6 a and b show two phenomena for the damage during LCF at RT:
damage at the grain boundary caused by the formation of slip bands or stacking faults (Fig. 6(a)) and damage at
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Guocai Chai et al. / Procedia Engineering 55 (2013) 232 – 239
the grain boundary caused by the interaction of the slip bands at different grains (Fig. 6(b)). At high
temperature, twin and stacking fault type of defects are less observed. Dislocation or slip bands and planer
dislocations can be observed. They form a type of elongated sub dislocation structure or cells. Interaction
between the above mentioned defects or dislocation often occurs. With high strain amplitude, damage at grain
boundaries caused by the formation of slip bands can also be observed (Fig. 6(c)). With lower strain amplitude,
localized deformation can be observed in a low magnification. Planer dislocation structure is a typical one. In
this case, the damage occurred both at grain boundary and in grains (Fig. 6(d0). Zig-zag form of grain
boundaries can also be observed. The width of zig-zag is similar to the width of planer dislocations. This may
be attributed to intrusion and extrusion or dislocation slipping process. The above discussion shows that the
damage of Sandvik Sanicro 25 material during LCF depends on temperature and also strain amplitudes.
500
1
NF 709-700C [Thermie]
Sanicro 25 700C [Thermie]
Sanicro 25 RT
Sanicro 25 650C
Sanicro 25 600C
Sanicro 25 700C
450
400
Maximum stress (MPa)
Tatal strain range (%)
0,9
0,8
0,7
0,6
0,5
350
300
250
200
150
100
0,4
50
(a)
0,3
100
700C
600C
650C
RT
(b)
0
1000
10000
Number of cycles
100000
1
10
100
1000
10000
100000
Number of cycles
Fig. 5. (a) Total strain amplitude versus fatigue life for Sandvik Sanicro 25 and NF709 material; (b) Cyclic stress response of Sandvik
Sanicro 25 with a total strain amplitude of 0.6% under strain controlled fatigue test.
(a)
(c)
(b)
(d)
Fig. 6. Electron channel contrast image; (a) and (b). At RT, 0.8% and 5948 cycles, (c). At 650°C, 1.2% and 1571 cycles, (d). At 650°C,
(c)
(d)
0.6% and 4654 cycles.
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Guocai Chai et al. / Procedia Engineering 55 (2013) 232 – 239
5. Other properties
Since Sandvik Sanicro 25 has a high Cr content, it has a good corrosion resistance. The results from a hot
corrosion test with an ash composition: 5% Na2SO4, 5% K2SO4, 30% Fe2O3, 30% Al2O3 and 30% SiO2; and a
gas composition: 0.25% SO2, 3.5% O2, 15% CO2 and balance N2 at 700°C, which was renewed every 100h for
the first 500h and then every 500h up to 3000h, show that Sandvik Sanicro 25 can develop a more protective
oxide layer than the commercially available grade NF709 and thus has much lower corrosion rate (Fig. 7(a)).
The characteristics of the corrosion on Sandvik Sanicro 25 is localized corrosion with some pits especially after
long exposure times whereas the reference grade shows a more uniform corrosion front with a great loss of
thickness. The oxidation tests in steam with a flow of 10 mm/s at 700°C for 1000h also show a lower oxidation
rate for Sandvik Sanicro 25 (Fig. 7(b)). The average weight change for the Sandvik Sanicro 25 samples
exposed for 1000 h at 700°C is only 0.028mg/cm2. The visual examination show a very thin oxide layer formed
on the surfaces, which is approximately 0.8 ȝm.
This alloy has also a very good fabricability. Recent results show that Sandvik Sanicro 25 can be cold bent
up to 30%, equivalent to a R/D ratio of 1.7 without need for post bend heat treatment [8]. The earlier
recommendation in the Vd TÜV approval 555 was 20% or a R/D ratio of 2.5.
600
0,25
Mass change (mg/cm2)
0,20
2
Weight loss (mg/cm )
500
400
300
NF 709
200
100
(a)
S31035
0,15
0,10
0,05
(b)
0
0
500
1000
1500
2000
2500
3000
Time (hours)
0,00
NUS S31035
UNS 30432
NF 709
TP310HCbN
TP347H
Fig. 7. High temperature corrosion properties of heat resistant stainless steels, (a) Hot corrosion tests at 700°C up to 3000 hours. (b)
Oxidation in steam at 700°C for 1000 hours.
6. Conclusions
A new austenitic stainless steel grade, Sandvik Sanicro 25 (UNS S31035), has been developed intended for
superheater and reheaters for A-USC. Extrapolation from creep data with two methods gives a creep strength of
99 ± 3 MPa at 700°C for 100 000 h, which is higher than that of other austenitic stainless steels available today.
The alloy has good low cycle fatigue properties and excellent elevated temperatures oxidation resistance and
hot corrosion resistance.
Acknowledgements
This paper is published by permission of Sandvik Materials Technology. Assistance of the ECCI work by
Mr Jerry Lindqvist is appreciated.
References
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Guocai Chai et al. / Procedia Engineering 55 (2013) 232 – 239
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[5] R.Sandström, Journal of Testing and Evaluation, 31(2003)58-66.
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