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Advanced Heat

Resistant Steels for


Power Generation
J. W. Nutting 1924-1998

These proceedings are inscribed in honour of Professor J. W. Nutting,


who during a long and distinguished career contributed to major
advances in ferrous and non ferrous materials development and
application technologies.
Advanced Heat
Resistant Steels for
Power Generation
Conference Proceedings
27-29 April 1998
San Sebastian, Spain

Edited by
R. Viswanathan and J. Nutting
Organised by
10M Communications Ltd
assisted by Inasmet, Spain
on behalf of
The Electric Power Research Institute
Palo Alto, California, USA
co-hosted by
Iberdrola, Spain
Book 708
First published in 1999 by
10M Communications Ltd
1 Carlton House Terrace
London SW1Y 5DB

© 10M Communications Ltd

10M Communications Ltd


is a wholly-owned subsidiary of
The Institute of Materials

ISBN 1 86125 079 7

EPRI Report Number TR-111571

Typeset by
Fakenham Photosetting Ltd
Fakenham, UK

Printed and bound in the UK at


The University Press, Cambridge
Contents

Overview of the Power Generation Business in the United States 1


A. F. Armor

The Long Term Structural Stability of Power Generation


Steels - Some Basic Considerations 12
J. Nutting
Section 1: Boilers 31

New Developments in Steels for Power Generation Boilers 33


F. Masuyama

Section 1A: Steel Developments 49

Development of 12% Cr Heat Resistant Steel Plate


(TEMPLOY F-12M) for usc Boiler 51
K. Hayashi, T. Kojima and Y. Minami

The Commercial Development and Evaluation of E911, a Strong


9% CrMoNbVWN Steel for Boiler Tubes and Headers 65
J. Orr, L. N. Buchanan and H. Everson

Alloy Design of Advanced Ferritic Steels for 650°C USC Boilers 84


F. Abe, M. Igarashi, N. Fujitsuna, K. Kimura and S. Muneki

Development and Application of2.25Cr-1.6W (HCM2S) Steel Large


Diameter and Thick Section Pipe 96
N. Komai, F. Masuyama, I. Ishihara, T. Yokoyama, Y. Yamadera,
H. Okada, K. Miyata and Y. Sawaragi

The Development of Steel Grade 92 for Large Thick Section Components for
Advanced Coal Fired Power Plant 109
S. Price and M. A. Walsh

Development of 9Cr-2W Casting Steel for Valves in Elevated Temperature


Fossil Power Plants 119
T. Honda, T. Kusano, T. Osada, K. Hirano and K. Takemoto

v
vi CONTENTS

Section lB: Service Experience 131

New 9-12% Cr Steels for Boiler Tubes and Pipes: Operating Experiences and
Future Developments 133
W. Bendick, F. Deshayes, K. Haarmann and J.-C. Vaillant

Properties After Service Exposure of2.25Cr-l.6W-V,Nb (HCM2S) and


12Cr-0.4Mo-2W-1Cu-V,Nb (HCM12A) Steel Tubes in a Power Boiler 144
Y. Sawaragi, K. Miyata, S. Yamamoto, F. Masuyama, N. Komai and
T. Yokoyama

Use of X 10 CrMoVNb 9-1 Steel in Power Plant Retrofitting Applications-


Experience and Application Potential 157
B. Hahn, V. Baumhoff and M. Zschau

Service Experience with the Application of Advanced Materials in Improved


Coal Fired Power Plants Operating in the Range 593 to 610°C 172
1. Kajigaya, K. Yamamoto, M. Yuuki and G. Nakayama

Effects of Microstructure on Intergranular Corrosion of Weldments of


Co-Based Alloys for Power Plant Valves 184
T. Honda, H. Takaku and T. Sakuma

Section 2: Microstructures 197

Microanalysis of9-12% Chromium Steels P92 and P122 199


M. Hattestrand, M. Schwind and H.-O. Andren

Forecasting Microstructural Change in Austenitic Steels for


Boiler Applications 212
R. G. Faulkner, D. Meade, C. C. Goodwin, M. W. Spindler and R. Hales

Precipitation Reactions in 3Cr1.5Mo Power Plant Steel 223


N. Fujita and H. K. D. H. Bhadeshia

Ageing Embrittlement of Fe-12Cr Steels 234


T. Angeliu, E. L. Hall, M. Larsen, A. Linsebigler and C. Mukira

Microstructure and Creep of a T91 Steel 247


S. Spigarelli, E. Cerri, E. Evangelista and P. Bontempi

Effects of Tungsten on Mechanical Properties and Microstructure in


9Cr-0.5Mo-W Steels 259
H. Naoi, M. Ohgami, Y. Hasegawa, H. Mimura and T. Fujita
CONTENTS vii

Simulation of Carbo-Nitride Coarsening in Multicomponent Cr-Steels for


High Temperature Applications 270
A. Gustafson, L. Hoglund and J. Agren
The Effect of Tungsten on Creep Properties of High Chromium Steels for
Steam Turbines 277
R. Ishii, Y. Tsuda, M. Yamada and M. Miyazaki

Creep Fatigue Crack Behaviour of Two Power Plant Steels 288


C. Berger, J. Granacher, M. Tramer, K. Maile and G. Schellenberg

Creep-Fatigue Characteristics of Advanced High Strength Cr- W Steels for


Power Boiler Applications 298
M. Sato, H. Kimura, M. Abe, M. Yamauchi and M. Fujita

Properties of a 12% CrMo V High Temperature Turbine Steel


Containing FeWTiC 309
P. Bates, M. A. Walsh and S. Price

The Effect of Heat Treatment on the Properties of Forgings from Modified


Chromium Steels 322
A. [akobova, M. Filip, V. Foldyna, V. Vodarek and A. Korcak

Effect of Trace Elements on the Creep Properties of Ferritic Steels for


Steam Turbine Rotors 332
Y. Murata, M. Morinaga, R. Hashizume, T. Azuma, Y. Tanaka and
T.Ishiguro

Section 3A: Turbines 347

European High Temperature Materials Development for


Advanced Steam Turbine 349
D. V. Thornton and K.-H. Meyer

Manufacturing and Properties of 2%Cr Family Steels for a


Large HP-LP Rotor Forging 365
T. Nakada, T. Tsuchiyama, M. Miyakawa, O. Matsumoto,
H. Nakashima, O. Ishiyama and T. Abe

Experience in Manufacturing and Mechanical Properties of Turbine Rotor


Forgings and Discs in Improved 10% CrMoWVNbN Steel 375
K.-H. Schonfeld and H. Wagner
viii CONTENTS

Metallurgical Procedure and Results Melting Boron Alloyed 10wt% Cr ESR


Steel for Power Generation Machinery 386
M. Maurischat, N. Blaes, K. Langner and H. Wagner

High Purity 9CrMo VNiNbN Rotor Forging for Advanced High Pressure-
Low Pressure Steam Turbine 397
Y. Tanaka, T. Azuma, Y. Shudo, S. Ong, Y. Ikeda and T. Ishiguro

Development and Manufacturing of Advanced 12%Cr Rotor Forgings for


Ultra High Temperature Steam Conditions 408
T. Tsuchiyama, O. Matsumoto, O. Ishiyama, Y. Yasumoto and T. Abe

Development of Heat Resistant l2%CrWCoB Steel Rotor for


usc Power Plant 418
K. Hidaka, Y. Fukui, S. Nakamura, R. Kaneko, Y. Tanaka and T. Fujita

Development of High Strength Corrosion Resistant Ferritic Steels for


Large Size Forgings in Gas- and Steam Turbines with High Efficiency 430
A. Goecmen, P. Ernst, P. Holmes and C. Toennes

Section 3B: Oxidation 433

Materials for Advanced Boilers 435


W. T. Bakker

Low Alloy Steel Tll - Autsenitic Stainless Steel 347H Bimetallic Tubes for
Corrosive Environments in Steam Power Plants 445
J. A.Berroeta, J. Valle, E. Ayala, M. A. Roman,]. de Luis, X. Gomez
and J. Echberria

The Effects of Oxidation on the Service Life of 9-12% Chromium Steels 457
P. J. Ennis, Y. Wouters and W. J. Quadakkers
Study of Corrosion Resistance of Newly Developed 9-12%Cr Steels for
Advanced Units 468
K. Nakagawa, 1. Kajigaya, T. Yanahisawa, M. Sato and M. Abe

Development of a New Heat Resistant Austenitic Stainless Steel for


High Temperature Components of Power Generation 482
Y. Nishiyama, Y. Sawaragi, N. Otsuka, H. Hirata, S. Kihara and
I. Kajigaya
CONTENTS ix

Development of the High Temperature Materials for Ultra


Super Critical Boilers 494
A. Tohyama and Y. Minami

Corrosion Testing of Superheater Steels for 600°C Steam in


Biomass/Co-Fired Boilers 507
P. J. Henderson, T. M. Eriksson, J. Tollin and T. Abyhammar

Section 4: Further Developments 517

US Developments in Advanced Turbine Materials 519


B. Seth

Development of Ultra-Super Critical Plant in Japan 543


K. Muramatsu

Production and Properties of Modified 9Cr-1Mo Steel Forging (F91)


for Valve Bodies 560
Y. Yamamoto, S. Sea, J. Matsumoto, Y. Kadoya, T. Nishimura and
R. Magoshi

Advanced Heat Resistant Steels for Steam Turbines 574


M. Miyazaki, M. Yamada, Y. Tsuda and R. Ishii

Development of a High-Strength Martensitic CrNiMo VNb Steel with


lO.5%Cr and O.ll%C (OPTIMAR Type) 586
M. Schirra and K. Ehrlich

Creep Modelling and Strengthening Mechanism of Tungsten Alloyed


9-12%Cr Steels for Power Plant Applications 596
K. S. Park, F. Masuyama and T. Endo

Section 5: Welding 609

Behaviour of Advanced 9-12Cr Steels and its Weldments in Short and


Long Term Tests 611
H. Cerjak and E. Letofsky

High Alloy Ferritic Steel: Mechanical and Creep Properties and its
Microstructural Evolution 622
A. Di Gianfrancesco, O. Tassa, S. Matera and G. Cumino
x CONTENTS

Delta Ferrite Formation in 9-12% Chromium Steel Weldments 633


E. Ayala, M. A. Roman, J. Vega, X. G6mez, T. G6mez-Acebo and
J. Echberria
Optimisation of Dissimilar Metal Weld Procedures for High
Temperature Design 644
M. A. Roman, V. Bicego, G. Fedeli, B. Brown, H. van Wortel,
N. Taylor and E. Ayala

Creep Properties of Heat Affected Zone of Weld in W Containing 9-12%


Chromium Creep Resistant Martensitic Steels at Elevated Temperatures 655
Y. Hasegawa, M. Ohgami and Y. Okamura

The Effect of Submerged-ARC Welding and PWHT on Creep Damage


Occurrence in Long-Seam Welded Cr-Mo High Energy Piping 668
C. D. Lundin and G. Zhou -

Summary of Papers 681


J. Nutting
Author Index 685

Subject Index 689


Preface

The Electric Power Research Institute has been organIsIng international


conferences on advanced materials development for fossil power plants
approximately once every three years. The previous conference entitled
'Clean Steel: Superclean Steel' was held on 6-7 March 1995 in London. Since
that time, major advancements with respect to heat resistant 9-12%Cr
martensitic steels have been made and the conference organising committee
therefore chose to focus on this subject during this conference.
Increasingly stringent environmental regulations and the need for reduced
fuel costs have made it necessary to develop power generation systems with
greater efficiency than those available in the past. One way to increase the
efficiency of pulverised coal-fired stations is to increase the steam tem-
perature and pressure. To do this without decreasing the reliability and
service life of the boiler and turbine components, alloys with higher creep
strength have been required. Ferritic steels have been preferred until now,
due to their lower cost, and greater resistance to thermal fatigue resulting
from a combination of lower coefficient of thermal expansion and higher
thermal conductivity. Alloy development has therefore centred around
improvement of the 9-12%CrMoVNb steels by optimising the amount of Mo,
V and C, substitution of part of the Mo by Wand additions of Co, Cu and B.
For boiler tube and piping applications, these efforts have resulted in
weldable grade steels such as NF 616 (P92), HCM12a (P122) and E 911 capable
of operating up to 620°C (1150 P) at 30 MPa (4500 psi). With some design
0

modifications and by using further improved alloys currently being evalu-


ated, the operating temperatures can be pushed up to 650°C (1200 P). Parallel
0

developments with respect to rotors have occurred in forging grade alloys


which can be operated in the turbine environments up to 650°C (1200°F).
Thus, it is now possible to construct plants with 650°C steam conditions using
martensitic steels for boiler and turbine components with minimal technical
risk and at reasonable costs. It now appears, however, that the optimisation of
9-120/0Cr steels has been pushed to its limits and increases in temperature
beyond 650°C will require the use of austenitic stainless steels and nickel
alloys.
The exciting developments described above were captured in nearly 60
papers presented at this conference. Participation in the conference was truly
international, with an attendance of 135 delegates from 17 countries. The
proceedings of this symposium is a state-of-the-art document, summarising
the latest developments in the heat resistant 9-120/0steels and is expected to
have enduring value for many years to come. Fittingly, it is dedicated to the
memory of Professor J. W. Nutting, who during a long and distinguished

xi
xii PREFACE

career, contributed substantially to the development of power plant steels and


to the understanding of the evolution of microstructures in these steels. As
chairman of the organising committee for this series of conferences, and as a
consultant, his assistance to EPRI has been invaluable. As a friend and
distinguished colleague, it is a pleasure to inscribe this proceedings in his
honour. I am also extremely thankful to the other members of the organising
committee Dr T. Abe, Ms L. Davies, Dr G. Honeyman, Dr F. Masuyama, Dr
G. J. Neate, Dr K. Schonfield, Dr J. Tagle, Dr Y. Tanaka and Dr D. V. Thornton
for their unstinting help and to Ms L. Davies and Miss T. Aubin of The
Institute of Materials for their assistance as general organisers of the con-
ference.
I hope that the present volume will be looked upon as a fitting tribute to the
memory of the late Jack Nutting.

R. Viswanathan
Organising Committee

J. W. Nutting (Chairman) EPRI Consultant, UK


R. Viswanathan (Co-Chairman) EPRI, USA
J. A. Tagle Iberdrola, Spain
T.Abe Kobe Steel Ltd, Japan
G. A. Honeyman Forged Rolls (UK) Ltd, UK
F. Masuyama Mitsubishi Heavy Industries, Japan
G. J. Neate PowerGen, UK
K. Schonfeld Saarschmiede GmbH, Germany
Y. Tanaka The Japan Steel Works Ltd, Japan
D. V. Thornton ALSTOM, UK
L. Davies 10M Communications Ltd, UK

xiii
Overview of the Power Generation
Business in the United States
A.F.ARMOR
Energy Conversion, EPRI, 3412 Hillview Avenue, P.O. Box 10412, Palo Alto,
CA 84303-0813, USA

INTRODUCTION

The United States is the world's largest power market, a $250 billion industry
and one that is rapidly opening up to competition and deregulation. Fossil
plants are being bought and sold; more than 20 000 MW have changed hands
to date. There are more than 100 active buyers in this market that include
domestic and international utilities, independent power producers, energy
companies, power marketers, and financial houses. Also emerging in the US
are scores of power marketers seeking to connect buyers of electricity with
sellers. Often such marketers own generation. The regulated utilities too can
be both sellers and buyers of electricity, and frequently have independent
arms that own generating plants outside of their regulated territory. These
plants may have been bought from others or constructed as merchant plants
with the intent of supplying low cost energy to the spot market.
In charge of ensuring the requisite flows of power across the grid system
are independent system operators (150s). An ISO provides open access to the
transmission system, uniform transmission pricing, and system security. One
important role of the ISO is to procure ancillary services for customers, such
as spinning reserve, VAR support, and black start capability, a business
estimated at $19 billion in the USA.

The Impact on Existing Plants


So today, in this burgeoning competitive market for electricity, generating
companies are reviewing the value of their fossil plants seeking opportunities
and making decisions to improve corporate value. Such decisions must be
made in a business climate where revenues, fuel costs, environmental needs,
competitive challenges, and equipment life are not entirely predictable,
indeed could be changing on time scales ranging from hours to weeks or
months. Reasoned judgments need to be made about the retention or
purchase of power plants, strategic re-alignment of the fleet, and tactical
deployment of capital and O&M resources. And pervasive in this environ-

1
2 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

ment is the drive to improve plant asset value, so that the generating units
provide a steady and reliable cash flow for the owner.

New Plant Markets


And for new plants, based on the expected mix of coal, oil, gas, nuclear, and
renewables through the year 2010, Table 1 suggests two scenarios for the

Table 1 USA generation mix through the year 2010 evolving (e) and advanced (a)
technology scenarios (billions kWh) (Source: EPRI 1995)

1990 1995 2000 2005 2010


Generation Mix ----
Nominal Efficiency E A E A E A

Rankine Coa135% 1570 1647 1800 1200* 1663 800* 1462 400*
Cycles, Coal 40% 10 10 20 20 30 30
Brayton Oil 35% 131 131 131 131 131 131 131 131
Cycles Gas 330/0 262 514 541 541 546 546 374 374
Repower, 45% 10 100 100 300 300 300 300
Gas 45% 10 50 450* 50 300* 50 300*
Gas 50% 20 20 50 300* 100 550*
Combined
Coal 50% 10 210* 100 463* 600 962*
Cycles
Fuel Cell 60% 10 10 50 50
Nuclear 523 468 495 495 550 550 619 619
Renewables Hydro 262 393 611 611 681 681 716 716
TOTAL (BkWh)
(1 BkWh = 3.65GJ) 2748 3173 3768 3768 4101 4101 4432 4432

* Retirement of existing coal units begins after 1995. These are replaced by new gas and
coal combined cycles. Rate of retirement increases from 'Evolving' to Advanced'
I

scenarios.

introduction of new technology into the generation mix in the USA.l The first
may be termed an 'evolving technology scenario' based on the most-likely
timing of commercialised advanced coal and gas-fired power plants. The
second is a more optimistic 'accelerated technology scenario' where the
replacement of old coal-fired power plants by new combined cycles, based on
both natural gas and coal, is greatly accelerated. It is not yet known which of
these scenarios is most likely.
The central station generation options for fossil fuels may be described as
follows:
1. Coal, oil, and gas-fired plants of conventional design with typical plant
efficiencies of 35% (coal and oil) and 33% (gas). Mostly Rankine cycles.
2. Repowered plants, based on gas-firing and combined cycle operation,
with efficiencies of around 45%.
THE POWER GENERATION BUSINESS IN THE UNITED STATES 3

3. New combined cycles based on gas-firing (about 45% efficiency with


today's gas turbines, and 50% with advanced gas turbines), and on coal-
firing with gasification, utilising advanced gas and steam turbine
technology (50% efficiency).
4. Coal-fired Rankine cycles with advanced steam conditions and about
40% plant efficiency.
5. Integrated coal gasification fuel cells perhaps combined with gas tur-
bines with efficiencies of 60% or more.
All efficiencies are based on high heating value (HHV) of the fuel.

THE IMPACT OF A CARBON-CONSTRAINED FUTURE

Primary energy consumption in the USA is dominated by oil (39 %


), natural
gas (24%
), and coal (22%). Coal provides fuel for about 570/0 of the electricity
utilised in the USA and globally coal utilisation is certain to expand. In fact
coal and lignite represent three-quarters of ultimately recoverable fossil fuel
resources. In the near-term (the next ten years) though, natural gas use will
grow significantly in the USA. Gas consumption, at 20 Trillion Cubic Feet
(TCF) in 1993, will increase through this decade, based on estimated resources
of 1200 TCF in the lower 48 states alone.
USA greenhouse gas emissions (largely CH4 and CO2) totaled 1.4 billion
metric tons of carbon in 1994 and are growing at an annual rate of 1 %

Worldwide, annual carbon emissions from fossil fuel combustion total over
6.0 billion metric tons.
Figure 1 shows the calculated impact of the two generation scenarios
mentioned above. In the evolving scenario, CO2 emissions are reduced
significantly from a 'frozen technology' baseline, but still rise to levels 34%
higher than 1990 levels by the year 2010. An aggressive scenario postulating
rapid introduction of coal and gas-based combined cycles, and the retirement
of three quarters of existing coal-fired plants by the year 2010, results in a 16%
increase of CO2 emissions over 1990 levels. The conclusion is that the
application of high efficiency fossil generation technology has a significant
impact on CO2 emissions, and by the year 2010 will potentially save 620
million tons of CO2 emissions per year. However, fossil technology advances
alone will be insufficient to cap CO2 emissions at 1990 levels without
additional supportive actions.

WHAT IS A FOSSIL PLANT WORTH?

Events of the last year have clearly shown that a new era in the power
industry has begun, that of buying and selling old fossil-fired power
4 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Total Generation Emissions


Billions kWh Billion Metric Tons of CO2
5000 3

EFFECT OF ADVANCED GENERATION TECHNOLOGY


ON CO2 EMISSIONS IN THE UNITED STATES

4000 2.5

3000 2

1990 1995 2000 2005 2010


(1 BkWh = 3.6 GJ)

Fig.l Possible scenarios for CO2 Emissions Based on Advanced Generation


Technologies

plants, and it could become the hottest new market since 502 emissions
allowances emerged in 1994. Divestiture of fossil assets are stimulated by the
deadlines - set by state regulatory bodies - when the markets for wholesale
and retail power will be opened for broad competition. Likely participants
in this new market: local utilities, independent power producers (IPPs),
power brokers, and cogenerators. Generation assets that will prosper in this
market are those with low net cost of generation, and with plenty of years
of reliable service left. The divestiture by utilities of plants in New England
and California have been followed by similar proposed initiatives in other
states.
A legacy of high fixed costs will almost certainly not be a stumbling block to
plant profitability. A typical fossil plant is twenty years old and cost perhaps
$400/kW to build in the mid-1970s. Fixed charges on this plant may be about
O.45¢/kWh, compared with a production (O&M) expense of perhaps
2.40¢/kWh. Such plants are definitely not stranded capital investments, at
least not in the same sense as newer nuclear units. But to make these plants
competitive may take substantial upgrade/repowering investment, renego-
tiated fuel contracts, a streamlined operating staff, and a guaranteed market
THE POWER GENERATION BUSINESS IN THE UNITED STATES 5

for the electricity. All of these can be arranged by an astute buyer if the plant
asset is judged to be competitively positioned.
The fact of the matter is that some of the more than 2000 fossil-fired units in
the United States are better equipped than others to make it in a deregulated
free market. The 290 GW of coal-fired plants, for example, have much higher
capacity factors - 60% on average - than the 140 GW of oil I gas-fired plants
that operate on average at 30% capacity factor. This implies more usage of
coal-fired units, and thus more profits to the owner. The main reason for this
is the base cost of generation. The ten lowest-production cost fossil plants in
the USA are all coal-fired, with O&M costs for these ten averaging 1.15<t I kWh.
And coal costs are falling due to the surge towards buying cheaper coals from
the Powder River Basin in Wyoming and Montana. However, gas and oil
units can be regionally very competitive.

MARKS OF EXCELLENCE FOR FOSSIL POWER PLANTS

In assessing what it takes to be successful in today's generation business, it is


useful to look at some marks of excellence for fossil power plants. Availability
is certainly one of these. Quite surprisingly, at a time when fossil plants now
average 30 years in age, where capacity factors average only 50%, and where
O&M budgets are being reduced and plant staffing levels cut, the average
equivalent availability factor of USA fossil plants is at a ten-year high of
nearly 83%, as reported by the North American Reliability CounciL And since
roughly 77% of the industry's entire fossil fleet was built before the year 1975,
these older units are increasingly burdened with emission control equipment,
and have baseload heat rates typically 20-300/0 higher than plants of more
modern vintage.
In looking at availability it is hard to ignore the impact of the most
pervasive of all fossil plant problems - boiler tube failures. In the last five
years, the number of tube failures per unit has dropped 6.5% for furnace walls
and 19% for superheaters and reheaters. These improvements are the result of
increased knowledge of tube failure mechanisms and increased management
attention to tube failure reduction programs. Even so, the industry as a whole
still suffers losses of more than $1.5 billion a year from boiler tube failures.
The prime causes of failures remain the same: corrosion fatigue, fly ash
erosion, hydrogen damage, and overheating. But ways to detect, monitor,
repair, and ultimately avoid the problem are definitely known and could be
followed by all utilities. Guidelines on these and more than 30 other tube
failure mechanisms are now available.?

Modernising for Availability Improvement


During the late 1970s and early 1980s increased power outages were fore-
casted. A severe reduction in new power plant construction below historic
6 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

levels was caused by scaled-back nuclear plant programs and (as interest
rates and environmental control costs soared) by lagging fossil plant addi-
tions. Though the premise of looming power shortages was flawed, the
resultant surge of interest in life assessment technologies and diagnostic
monitoring of equipment was exactly right for a rapidly changing industry.
The real issue then, as now, was one of economic life optimisation and of
prudent investment in fossil plant assets. And as with all business decisions,
questions of risk became important. More precisely, utilities sought to
understand the consequences of operating ageing turbine generators and
boilers under new operating scenarios. The good news is that the latest life
estimation technology can ensure safe, reliable operation for older plants,
relying on systematic approaches to component inspections and analyses, and
deeper understanding of the behaviour of power plant materials under
operating pressures, temperatures, and load cycles.'

The Need for Improved Materials


A common theme for new generation, and for upgrades of existing plant, is
that improved materials will be needed as we move into the next century.
Advanced fossil steam and gas-fired plants will require corrosion resistant
materials able to operate at high steam temperatures and pressures and
higher firing temperatures for gas turbine plants. Further the application of
IGCC or PFBC in the future will lead to increased emphasis on corrosion
resistant blades, tubes, coatings etc. Therefore we need a broad advance in
this area to support new generation options.

Repowering of Units
Repowering appears, at first sight, to be a viable option for ensuring success
in the competitive marketplace. The data on the few plants repowered thus
far are impressive: heat rate improvements up to 50 /0,NOx levels reduced by
0

more than half, new capacity added at $600/kW or less, capacity factors
elevated from 15% to 60%, old plant assets revitalised, possible competitive
generation forestalled, and key customers retained. The landmark conver-
sions at Florida Power & Light Company's Lauderdale plant, Southern
California Edison Company's Terminal Island, Glendale Public Service
Department's Grayson, and at Public Service Electric & Gas Company's
Burlington and Bergen plants, add combustion turbines and heat recovery
steam generators to existing older plants. In so doing, they turn uneconomic,
low-utilisation plants into high-value assets. At an even lower invested cost of
about $150/kW, a simpler hot windbox repowering scheme has been shown
to save 15-200/0 in fuel, increase capacity 20-30%, and reduce NOx levels by
80%.
But the opportunity to repower, it seems, is not being embraced on a wide
THE POWER GENERATION BUSINESS IN THE UNITED STATES 7

scale. An EPRI conference+ suggested that the issue is the uncertain future all
utilities face. As one conference speaker put it, 'Where would this project fit in
the world of retail wheeling? Is this where we want to put $400 million? Will
repowering soon be displaced by more advanced technology?'
Nevertheless it is believed that the repowering of older units will accelerate
in the next 10 years as new owners of generation assets seek ways to advance
their plants in the eyes of power marketers.
A second mark of excellence is plant operating cost. Figure 2 is a list of lowest

Operating Costs, 1994


14 - (Source: UDI figures from FERC data)

12 -
III Production Expense, $/MWh I I
I ~ II
~.:k.'.~.:.;~.; -,~.~.·.:1.·.

-" ~.I.~.!.!,~,~.
10 -

8 -

6 -
ItI
4 -
r,II ~~
I
.~,I:.r.:.;.:

!i I~.~
2
I
-f-
1.::'.':.'~I~ . II":
o
= ....
: '
~l W~

Fig. 2 Operating costs, largely fuel, are lowest in coal-fired plants, mainly across the
midwest. Generally, these are valuable assets for the utilities, but they compete in
regions of low cost fuel

cost operating units in 1994 in terms of production expenses (including fuel)


per unit of electricity generated. Of the top twenty units in this category in
1994, most were coal-fired, and many were mine-mouth plants in the upper
midwest. Clearly, a message from this is 'do all you can to lower the cost of
fuel and the cost of fuel transportation.' In the southwest where gas-fired
plants are common, we find the plants with lowest non-fuel O&M costs, less
than 0.2~/kWll, a figure that few, if al1y, coal-fired plants are likely to match.
Third, plant capacity factor (Fig. 3) is another indicator of success - a measure
of how valuable a plant is compared to other competing plants in the existing
market for electricity. In the USA, the average CF is 500/0 although, as noted
earlier, coal-fired plants average 60%, and oil/gas fired plants average 30%.
8 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Capacity Factors for the Twenty Largest Fossil Steam


eF, Percent
u.S. Utilities (1994)
100
(Source: UDI figures from FERC data)
90 MW
30000
80 III Capacity Factor 80%

DMW
70

22500
58% 59%
60
55%
52%
0% 50%
50 46% 47%

r
41% 15000
40
34% 34%

30 J
20 7500

10

Fig. 3 Capacity factor is an important parameter indicating the value of a utility's


fossil assets. They range from 27% to 80% for the twenty largest fossil utilities.
Overall, CPs of USA plants average 50%

Increased utilisation of plants minimises wear and tear due to cycling and
improves heat rate. Capacity factor is an important parameter to maximise if a
utility is to earn a return on its investment and stay profitable. The twenty
largest fossil steam utilities shown here have capacity factors ranging from
80% to 27%.

GENERATION ASSETS MANAGEMENT

Assets management practices are now active in the electric industry. They
have been initiated by the EPR! research programs, and by fundamental
changes brought about by competition, which call into question traditional
business practices.
Asset management is essentially the practice of using resources to create
maximum value, which is the essence of a business manager's job. Each
business manager must make decisions on how to use company resources.'
These decisions should be guided by the goals of the business and of the key
THE POWER GENERATION BUSINESS IN THE UNITED STATES 9
Reasonable Rate Socially Responsible
Reliable Service of Return Operations

I Customer Society
• Starting with stakeholders
helps focus attention on
creating corporate value.

Availability Earnings!
Emissions " Translating corporate
Readiness Contribution objectives into meaningful
value measures at the plant
level aligns plant-level
decisions with corporate
goals
GENCO

®
Availability Profitability Environmental
Benefit
.: • Using value-based decision-
~ making clarifies tradeoffs
Value of Plant Products Effect of Rolellnvestmentl and ensures fair allocation of
& Services Strategy Decisions resources.
/

• Using advanced analysis


methods provides a
defensible and repeatable
analysis for specific
Decisions: decisions.

Plant Role Investment Fuel-Blending and


Analysis Analysis O&M Strategies

Fig. 4 The framework for making asset management decisions: A review of stake-
holders helps focus attention on customer needs. Value measurers are established
to measure effectiveness of decision at meeting customer needs. Investments, plant
roles and strategy decisions are analysed for incremental benefit

stakeholders. Figure 4 illustrates how plant assets feed into overall company
goals.

THE IMPORTANCE OF MATERIALS ADVANCES

Advances in fossil plants, particularly pulverised coal-fired plants but


increasingly gasification and pressurised fluid bed plants, have always relied
on stronger materials able to withstand higher steam and gas temperatures
and pressures. This will not change in the future. An early EPR! paper"
described how materials development had evolved (Fig. 5) and discussed, in
the context of the advanced supercritical plant, materials such as co-extruded
tubing resistant to coal ash corrosion, improved creep-resistant 12-chrome
forgings for turbine rotors, superclean steels, and super 9-chrome (P91) steel
for piping, valves, headers, and casings. Now the next generation of strong
10 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

A HISTORY OF POWER PLANT MATERIALS DEVELOPMENT


Boiler tubes SH/RH tubes
•• 1I.~.[11;T2 2
St,amlm ••• val,e.

12 chrome

Development for
power planta Generatorrotor coils
First atUlty
use to full
commercialization

1930 1940 1950 1960

Fig. 5 Taken from Ref. 6, this showed that better materials are now available for
cycling fossil plants including super 9 Chrome steel (P91), which permits thinner
sections and lower thermal stresses in headers, steam lines, valve bodies and
turbine casings. P91 is now fully commercialised and even stronger ferritic steels
are under development

steels7,8 is making possible plants with even higher efficiency, which in turn
permits the generation of power with reduced emissions. This is a driving
force as the world seeks to find a sustainable future for a rapidly growing
world population, hungry for increased economic growth and physical wel1
being.

CONCLUSIONS

Technology advances do sometimes go into hibernation. When business


conditions are slow, as during the oil embargo of the mid-1970s or the
1990-91 recession, it is common for companies to hunker down, defer
investments, and ride out the bad times. But today all economic indicators
signal continued growth. In fact, across the USA, leading indexes point tc
further gains in industrial productivity, jobs, and consumer confidence. A
strong indicator of world growth is that 1190 GW of new generating capacity
is projected worldwide over the next fifteen years, requiring an estimated $1.4
trillion in capital investment. Technology frequently flourishes under such
bullish conditions, and will likely do so over the next decade.
In the USA electric power generation will be dominated increasingly by
environmental control needs, putting an emphasis on the base efficiency oj
THE POWER GENERATION BUSINESS IN THE UNITED STATES 11

new generation, and on heat rate recovery for existing units. The pulverised
coal-fired power plant with flue gas desulfphurisation will be the focus of
most near-term activity related to upgrades and retrofits, particularly for
compliance with the recent Clean Air Act Amendment. But new technology,
based on combined cycles and perhaps coal gasification, is under develop-
ment and being tested in a growing number of demonstration plants.
For many developing nations the future is based on exploiting the oppor-
tunities offered by clean and efficient use of coal. This implies access to the
range of new technologies now being tested at large scale in the USA and
other developed nations. This strategy is both timely and prudent on a global
basis, and relies on continued advances in power plant equipment technol-
ogy, particularly those related to stronger materials with increased life.
Advances in material science, as in the past, enable designers to confidently
put in place the power plants of the next millenium.

REFERENCES

1. A. F. Armor and G. T. Preston: 'The Impact of Fossil Generation Advances


on the Emissions of CO2 in the United States,' Proceedings of the lEA
Greenhouse Gases: Mitigation Options Conference, London, 22-25 August,
1995. Energy Conversion and Management, June-August 1996, 37 (6-8),
671-677.
2. Condition Assessment Guidelines for Fossil Fuel Power Plant Components, EPR!
Report GS-6724, March 1990.
3. Life Optimization for Fossil Fuel Power Plants, EPR! Report GS-7064, Novem-
ber 1990.
4. Proceedings: EPRI/GRI Repowering Workshop, EPR! Report TR-I03968,
October 1993.
5. Five Essays on Modern Asset Management Practices, EPR! Report TR-I08818,
August 1997.
6. A. F. Armor, W. T. Bakker, R. I. Jaffe and G. L. Touchton: 'Improved
Materials for Life Extension of Coal-Fired Power Plants,' Proceedings,
International Conference on Life Extension and Assessment, Nederlands
Instituut Voor Lastechniek, The Hague, Holland, 13-15 June, 1988.
7. W. T. Bakker: 'Materials for Advanced Boilers,' this volume 435-444.
8. Proceedings: New Steels for Advanced Power Plants, EPRI TR-I04952, March
1996.
The Structural Stability of Low Alloy
Steels for Power Generation
Applications
J. NUTTING
Consultant to: EPRI, P.o. Box 10412, Palo Alto, CA 94303, USA

ABSTRACT
The structural changes occurring during the tempering of carbon steels in relation to
Oswald ripening and ferrite grain growth are reviewed, providing a basis for
understanding the behaviour of heat treated low alloy steels used for power
generation equipment. The roles of Cr, Mo and V in Cr-Mo-V and Ni-Cr-Mo-V
steels are discussed and the difficulties associated with the additions of Nb and Ti
and Ware outlined. The carbide precipitation sequences as a function of time and
temperature are described in relation to the in-service structural changes in rotor
steels. The influence of these structural changes on the in-service creep behaviour is
discussed and the roles of sulphides and carbides in reducing creep ductility are
mentioned.
It is concluded that the critical structural change leading to the decrease of creep
resistance as the in-service time increases is the formation of the generic carbide
M6C.Some suggestions as to how this reaction may be hindered are given, together
with an entirely new approach to rotor steel development. It is now possible to make
direct additions of thermally stable alloy carbides to molten steel which, together
with the inherent. carbides, could give both short and long term creep resistance.

1. INTRODUCTION

In developing alloys for service at elevated temperatures, the aim is to


produce a material which can not only withstand the initial service condi-
tions, but is capable of withstanding the service conditions throughout the
whole of the expected design life. The critical issue is the expected design life
which can vary from minutes for rocket motors to 20-25 years for steam
turbines for power generation requirements.
To meet long service life requirements, the usual approach is to heat treat
the alloys used at temperatures sufficiently above the service temperature to
give a microstructure which it is hoped will be stable at the actual working
temperature and throughout the working life. This is relatively easy to
achieve if the working life is up to 1000 hours, but for working lives of 200 000
hours the task is more difficult.
Some of the microstructural factors which have to be considered are
described below for the quenched and tempered low alloy steels widely used
for the construction of fossil fuel fired power generation equipment. Empha-

12
THE STRUCTURAL STABILITY OF Low ALLOY STEELS 13

sis will be placed on the 2.250/0Cr-Mo-V steels used for HP rotors and 3.5 Ni-
Cr-Mo-V steels used for LP rotors.
The approach adopted will be to consider the structural changes occuring
during the tempering of plain carbon steels and then to consider the further
changes introduced as a result of adding first nickel as a non carbide forming
element and then the carbide forming elements Cr, Mo and V.
The structural changes induced as a result of long exposure to elevated
temperatures in service will be described, together with their influence
on creep behaviour and possible methods of modifying the structural
changes.

2. STRUCTURAL CHANGES DURING TEMPERING OF PLAIN


CARBON STEELS

When plain carbon steels are quenched to room temperature from the
austenitic range, martensite is produced. With carbon contents up to about
0.25%, the martensite has the structure of bundles of laths with each bundle
having a common crystallographic orientation for the lath axis. With carbon
contents greater than 0.6%, the martensite consists of plates with a specific
habit plane, and across the plates there are fine twins. With carbon contents
between 0.25% and 0.6 %
, the martensite consists of mixtures of the two
structural types. In relation to low alloy power generation steels, the predomi-
nant martensite structural type is that of laths. Thus attention will be focused
on structural changes associated with the tempering of laths.
Ideally, after quenching, the structure should consist of a supersaturated
solid solution of carbon in a-iron in which the carbon atoms are present
preferentially in (OO~) type sites, giving rise to a tetragonal distortion. In
reality, this ideal is seldom achieved, particularly with larger section sizes,
and the carbon precipitates from the distorted a structure in the form of fine
carbides having a Widmanstatten distribution with the martensite laths. The
carbide has a hexagonal crystal structure which is believed to have a chemical
composition between Fe2.4-2.8C.This auto-tempered structure then undergoes
further structural changes as the steel is tempered within the range
200-400°C. Cementite (Pe3C) is nucleated at the lath boundaries and grows in
a plate like form. At this stage the tempered structure is almost identical to
that of upper bainite.
A further structural feature of lath martensite is a very high dislocation
density and during tempering, polygonisation of the dislocations occurs and
cementite forms as spherical particles on the sub-grain boundaries.
With tempering temperatures above 450°C an entirely different type of
structure develops.Theoriginal martensite laths re-crystalise and the cemen-
tite particles grow as spheres which are usually located at the ferrite grain
boundary triple points. The newly formed grains have a diameter of about
14 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

O.51-!mand the carbide particles diameter about 0.05-1.0 urn. This structural
type is maintained as the tempering temperature is raised to the ACl value,
say 700°C. However the carbide particles grow by Ostwald ripening and as
they grow this allows the ferrite grains to grow. Detailed studies have shown
that the room temperature yield strength and hardness of the steel are
controlled by the ferrite grain size through the Hall-Petch relationship.

(1)

where ay = yeild strength


ao = friction stress
k = constant
D = ferrite grain diameter
However, after long tempering times when the grain size has become large,
the volume fraction of the carbide begins to exert influence on the hardness
achieved. The above results are summarised in the graph given in Fig. 1.

800

700

600
Z
> 500
~
en
en
Q)
400
c
"E
ctS 300
:c
200

100

Temperature (OC)
Fig. 1 The Vickers hardness of iron-carbon martensites tempered for 1 hour at
temperatures up to 700°C

2.1 Ostwald Ripening of Carbides


The growth of carbides during tempering and during subsequent high
temperature service is controlled by the process of Ostwald ripening.
The concentration of a solute in a solvent at the interface with a second phase
THE STRUCTURAL STABILITY OF Low ALLOY STEELS 15

particle varies with the radius of curvature, of a particle, as given by the


equation:

ln~ = 2Vy (2)


Coo rRT

where C, the solute concentration in the solvent when the particle has a radius
of curvature r.
Coo is the solute concentration in the solvent when the particle has an
infinite radius of curvature, i.e., a planar interface.
V is the volume/Mol of the dispersed phase.
y is the interfacial energy between the particle and the matrix.
R is the gas content.
T is the temperature in'K,

The value of Coo is the solid solubility of the components of the dispersed phase
in the solvent and as the value of r ~ i.e., a planar interface, the value of
00,

2Vy~ 0
rRT

The value of

when r is small tends to be high when considering carbide dispersions in


steel, because the interfacial energy associated with the carbide-ferrite
interface is high as a result of incoherent interfaces being formed at relatively
low tempering temperatures. Schematically the process of growth is shown in
Fig. 2.
It could be concluded from eqn (2) that the higher the temperature the
lower will be the value of

Fig. 2 Schematic process of Ostwald ripening. In the case of plain carbon steels the
diffusing species are carbon and vacancies
16 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

hence the lower will be the driving force for Ostwald ripening, but the
increase in temperature increases rates of diffusion. Thus it is necessary to
consider the kinetics of the growth process.

2.2 Kinetics for Ostwald ripening


Ostwald ripening involves the growth of large particles at the expense of the
smaller particles which are taken into solution. The solute from the small
particle is then transferred by diffusion through the solvent, where it re-
deposits on the large particle.
In the case of plain carbon steels, it might be expected, therefore, that the
rate controlling process for carbide growth would be the diffusion of carbon
through a-iron, a relatively rapid process, (activation energy 80 Klmol ").
This is not the situation. As a small cementite particle goes into solution, the
cementite lattice collapses and the carbon takes up an interstitial site in the
a-iron matrix and vacancies are created at the carbide interface. When a
carbon atom arrives at a growing cementite interface, in order for cementite to
form a local increase in volume is required, since cementite has greater molar
volume than does a-iron. This volume increase can be accommodated if
vacancies migrate to the interface. As vacancies are being generated at the
dissolving particle interface, there is an available supply, but it is the transfer
of vacancies through the a-iron, a relatively slow process which controls the
kinetics of Ostwald ripening, (activation energy 240 Kjmol=l).
An increase in temperature brings about an increase in the diffusion rate, so
Ostwald ripening occurs more rapidly the higher the temperature.
However, once the mean size of the dispersed carbide particles becomes
large, the driving force for further change decreases and the whole coarsening
process slows down.
By further mathematical manipulation of eqn (2) it is possible to show that
for a particular system
3 _ 3 _ K.VmCoot
r, fa - RT (3)

where r1 is the mean particle size after time t. fa is the mean particle size at the
start of the observations, i.e. to. K is a constant related to the diffusivity of the
rate controlling diffusing species.
Starting with a given size distribution of particles and measuring the change
in the particle size distribution with increasing tempering time at constant
temperature, it is possible to determine the growth time dependent on carbide
particles in steel. The results obtained are shown in Fig. 3 and indicate the
validity of the analysis given in eqn (3). The important issue in relation to
THE STRUCTURAL STABILITY OF Low ALLOY STEELS 17

0.3% C 650°C
15

&
.s
Q;
Q) 10
E
cc
(5
Q)
(3
:e
cc
a. 5

o ~--------~------~~------~--------~
-1.0 0.0 1.0 2.0 3.0
Log10 Tempering Time (Hrs)

Fig. 3 The growth of individual carbide particles of different sizes with increase in
the tempering time at 650°C for a 0.30/0 carbon steel initially in the as quenched
condition

micro structural stability is that once the mean particle size has become large
and the small particles have been taken back into solution, further Ostwald
ripening virtually stops.
Thus, in order to obtain long term micro structural stability in a tempered
steel, a high tempering temperature and long tempering time should be
used.

2.3 Some other microstructural aspects of Ostwald ripening


As described above, the structural type established after tempering plain
carbon steels above 450°C consists of ferrite grains with almost spherical
carbides at the grain boundaries. It is possible to argue that the transfer of
vacancies from the dissolving to the growing particles could occur more
readily along the grain boundaries than by diffusion through the grains.
However, the measured activation energies for the softening during temper-
ing at elevated temperatures gives values which are only slightly lower than
those determined for self diffusion in a-iron.

2.4 Further structural changes in grain growth


It is well established that second phase particles present at grain boundaries
hinder boundary migration, hence control grain growth. It is usual to
consider the quantitative effects of particle size and grain size through the
Smith-Zener relationship:
18 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

R 4
-;: = 3f (4)

where R is the radius of curvature of the grains. r is the radius of curvature of


the particles at the grain boundaries.fis the volume fraction of the particles at
the grain boundaries.
Although more sophisticated relationships have been developed, the Smith-
Zener relationship has been found to give reasonable agreement with the
results when applied to plain carbon steels.
Even with prolonged tempering the ferrite grain size achieved is always
less than the austenite grain size established during the initial heat treatment
prior to quenching. Thus some of the ferrite grain boundaries are coincident
with the prior austenite grain boundaries.
If the tempering process is interrupted and the steel plastically deformed,
further re-crystallisation of the ferrite occurs - see Fig. 4. The ferrite grains
'break away' from the original carbides and then much larger grains form.
This can be explained in terms of the Smith-Zener relationship as a decrease
in the volume fraction of the carbides at the grain boundaries which then
allows R to increase (see eqn 4). Many carbide particles are now present
within the ferrite grains and further softening occurs by Ostwald ripening as

270
En8 tempered at 650°C
260 cold work, 0/0

250 • 0
A 20
240 • 30
0 o 40
M 230 o 60
>
I
en
en
220
Q)
c 210
"0
'-
ctl
I 200

190

180

170

160
0 1 2 3 4 5 6 7 8 9 10
Tempering Time (Hrs)
Fig. 4 Variation of hardness with tempering time for 0-34%C steel which has been
cold worked to differing amounts after an initial temper at 650°C and then re-
tempered at the same temperature. The rapid softening with large strains is a result
of 'break away' ferrite grain growth
THE STRUCTURAL STABILITY OF Low ALLOY STEELS 19

before, but the flow stress is now controlled by a combination of the Ashby-
Orowan and Hall-Petch relationships of the form.
1 d lYz
(Jy = (Jo + KsSln2b + KYD (5)

where K; is a constant. S is the inter-particle spacing within the grain. d is the


particle diameter. b is the Burgers vector of the operative dislocations.
When this type of structure develops, the ferrite grain diameter may become
larger than the original austenite grain diameter and the pre-existing auste-
nite grain boundaries are no longer coincidental with the ferrite grain
boundaries. Structures of this type develop in low alloy steels.

3. THE TEMPERING OF FERRITIC ALLOY STEELS

3.1 The role of non-carbide forming elements


The structural changes occuring during the tempering of low to medium
carbon steels containing non-carbide forming elements, e.g., Ni, Mn and Si,
are almost identical to those described above for plain carbon steels.
The non carbide forming elements generally slow down the softening
reactions. In the case of Si and Mn containing steels, it appears that these
elements stabilise the e-iron carbide, thus a higher tempering temperature has
to be attained before the transformation to cementite occurs.

3.2 The role of carbide forming elements


The carbide forming elements normally added to low alloy steels are Cr,Mo
and V. Other possible carbide formers are Ti,Nb and W. For reasons discussed
below, Ti and Nb are seldom added to low alloy ferritic steels, but W can be a
useful addition.

3.3 The effect of chromium


With low alloy steels under consideration, the Cr contents seldom exceed 3%.
In the absence of other strong carbide formers Cr generally slows down the
softening reactions during tempering. The transformation of e-iron carbide is
hindered, as is the Ostwald ripening of the cementite. At low tempering
temperatures (below 400°C), cementite forms and has a low chromium
content corresponding to the average Cr content of the steel. At higher
tempering temperatures Cr begins to replace Fe in cementite to give (FeCr)3C,
This reduces the Cr content of the ferrite matrix and, whilst this process is
occurring, Ostwald ripening is slowed down. In simple terms, the Cr mops up
20 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

the vacancies as it is being transferred to the carbide. There is, therefore, a


shortage of vacancies to allow the carbide to grow.
Although the chromium carbide Cr7C3 is more stable than Fe3C or (FrCr)3C,
the Cr7C3cannot form directly in the ferrite grains, because the degree of super
saturation with respect both to carbon and chromium is so low that separate
nucleation is difficult. However, with long tempering times Cr7C3is nucleated
at the interface between the a-iron and (FeCr)3C where there is a ready supply
of both Cr and C. Once the (FeCr)3C has been transformed into Cr~3 Ostwald
ripening of this carbide can occur, but it is a slow process, since it requires the
transfer of Cr from the dissolving to the growing particles, and the concentra-
tion gradients which allow the diffusion to occur are very shallow. The
process is different from that in plain carbon steels where there is always a
ready supply of iron atoms at the interface between Fe3C and a-iron.

3.4 The Secondary Hardening of Cr,Mo and V containing Steels


As described above, low alloy steels containing up to 3-4% Cr show only
delayed softening as the tempering temperature is increased after quenching
from the austenitic region. If the Cr content is increased to 7-8% or up to 1%
Mo or V are added, then a new phenomenon occurs. After an initial softening
on tempering at temperatures up to 400°C, a further increase in the tempering
temperature gives rise to an increase in hardness.
The maximum hardness attained may be above that of the as quenched
hardness. The actual values are dependent upon the time and temperature of
tempering, but as a rough guide a temperature of about 550°C is required. At
higher temperatures and with long tempering times the hardness decreases;
the overall behaviour is that of a classical precipitation hardening system -
the rate of hardening increases with the ageing temperature and the peak
hardness decreases with an increase in ageing temperature. The results
obtained with a simple 0.2%-0.7%V steel are given in Fig. 5.
The initial softening reactions are associated with the formation of e-iron
carbide and then cementite as in plain carbon steels. But at temperatures
above 450°C diffusion of the carbide forming alloying elements through the
a-iron can occur. However, with strong carbide forming elements, e.g., V or
Mo, the carbon solubility in the a-iron after it has come into equilibrium with
Fe3C is still sufficiently high for V4C3 or Mo2C to be directly nucleated within
the ferrite and thus give rise to precipitation hardening. Softening then occurs
by Ostwald ripening with the Widmanstatten carbides formed within the
ferrite grains going back into solution as the alloy carbides grow preferen-
tially at the ferrite grain boundaries.
The unusual behaviour of Cr in giving delayed softening at Cr contents up
to 4% and secondary hardening with Cr contents in excess of 7% can readily be
explained by the decreasing carbon solubility in n-iron as the Cr content is
increased, as shown in Fig. 6. With low Cr contents the degree of super
THE STRUCTURAL STABILITY OF Low ALLOY STEELS 21
500~--------~----------------------~----------~

600 e
D

...~--ir .•
,'~ 650 e /0..,
0

, 0 /..'0.•.

CJ)
400

.. e
CJ)
Q) 400D

..
c
"'C
(ij
J:
~
Q)
.::.::: 300
s
0
o .•.
~v AV A
A
V AV
AV
200~--------~-----------------------+------~V~V~

I I I I I I I

1.3 1.4 1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2
T (20 + logt) X 10- 4

Fig. 5 The variation of Vickers hardness after differing tempering treatments of


O.2%C-O.7%V steel, plotted in relation to Hollomon tempering parameter

o
o

~
:::J
C6
CD
0-
E
Q)
I-

Fe 0/0 Carbon
Fig. 6 Schematic equilibrium diagram to illustrate the change of solubility of carbon
in ferrite containing differing amounts of chromium

saturation is insufficient to give separate nucleation of the alloy carbide; with


high Cr contents the degree of super-saturation increases so allowing Cr7C3 to
be separately nucleated within the ferrite.
When secondary hardening occurs Ostwald ripening is slowed down. The
Widmanstatten carbides formed within the ferrite grains, e.g., needles of Mo2C
or plates of V4C3have a low interfacial energy with respect to a-iron; thus with
low values of yin eqn (1) the driving force for particle coarsening is low.
22 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

4. THE CARBIDE PRECIPITATION SEQUENCE

4.1 The addition ofTi, Nb and W


Although Ti and Nb are strong carbide forming elements, they cannot easily
be added to low alloy ferritic steels because they lower the solubility of carbon
in austenite to such an extent that it becomes difficult to heat treat the steels.
As shown schematically in Fig. 7, the austenitising temperature has to be
increased, beyond what is practically feasible, to ensure sufficient carbon is in
solution to obtain an austenite which after transformation gives a martensite,
which will then secondary harden on tempering.
The addition of W to low alloy ferritic steels is a feasible proposition and it
will induce secondary hardening due to the precipitation of WC. However,
the diffusion of W in a-iron is a slow process and in the presence of Mo and V.
M02C and V4C3 are precipitated rather than the WC. The W, therefore,
remains in solid solution where it can bring about solid solution hardening.
With prolonged tempering of low alloy steels the initially formed carbides
(Cr7C3,Mo2C and V4C3)become unstable and are replaced by the more stable
generic carbides of the type M23C6 and M6C where M can represent any
metallic element. An unusual example of this type of carbide is C03W3C,
where cobalt, a non carbide forming element, can replace W, a strong carbide
forming element, to give a more stable form of M6C.
The sequence of carbide structural changes as a function of tempering
temperature and time was first established for 2.25 Cr-1% Mo steel in 1959
using carbon extraction replicas and transmission election microscopy and
the results obtained are presented in Fig. 8. With improvements in micro-

1 % Nb 1% V

o
o

.a~
0)"

~0)
a.
E
0)
I-

950 ~------------------------
Fe % Carbon

Fig. 7 Schematic equilibrium diagram to illustrate the effect of strong carbide


forming alloying elements on the solubility of carbon in austenite
THE STRUCTURAL STABILITY OF Low ALLOY STEELS 23

750
0
0

(l)~ 725
~
Cii 700
Q;
0-
E
(l) 675
l-

c 650
.~
0-
E
(l)
625
I-
600

575
0.5 5 10 50 100 500 1000
Tempering Time (Hrs)

Fig. 8 The carbide phases present after differing tempering treatments of a 2.25 Cr-
l%Mo steel. This diagram was first published in 1959

analytical methods it was thought worthwhile to re-assess the carbide


precipitation sequence and the results obtained are given in Fig. 9.
Similar work has now been carried out on 3.5 Ni-Cr-Mo-V steels and the
results obtained are given in Fig. 10. With the two main types of low alloy
steels used for power generation, the results are remarkably similar. How-

750 M23 c, + Me C
0 + M7 C3 + M2 C
0
725
.a
a)

700
~
(l)
c..
E 675
(l)
I-
0>
c 650
.~
c..
625
E
(l)
I-
600

575
0.5 5 10 50 100 500 1000
Tempering Time (Hrs)

Fig. 9 An updated version (1984)of the diagram given in Fig. 8. More modern
analytical techniques have been used to identify the carbides present after the
different tempering treatments
24 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

700

o
o
600
~
:::J
ca
CD
c..
E
Q)
r- 500
0)
c
.~
c..
E
Q)
r- 400

5 10 50100 5001000 5000


Tempering Time (Hrs)
Fig. 10 The carbide phases present after differing tempering treatments of 3.5% Ni-
Cr- Mo- V rotor steel produced to a super clean specification. The same analytical
techniques have been used as for Fig. 9

ever, the formation of the generic M6C type carbide seems to be hindered by
the presence of nickel, although this carbide forms with long service periods
in LP rotors to a 3.5 Ni-Cr-Mo-V specification. Schematically the precipita-
tion sequence can be represented as follows:

Increasing temperature

The initial tempering temperatures used for the heat treatment of low alloy
power generation steels are too low to give the precipitation of M23C6 or M6C.
However the in-service temperatures which can be looked upon as further
low temperature tempering tends to favour the formation of M6C, rather than
M23C6•
The results obtained also indicate that HP rotors based on Cr-Mo-V steels
are likely to follow the M23C6 route to M6C, since their service temperatures
THE STRUCTURAL STABILITY OF Low ALLOY STEELS 25

are higher than those of LP rotors. It could be argued that LP rotor materials
which follow M2C ~ M6C route are inherently less thermally stable than HP
rotor materials.

4.2 The formation of M23C6 and M6C


The factors governing nucleation of M23C6 and M6C have not been fully
investigated, but evidence suggests that MZ3C6 is nucleated at the ferrite grain
boundaries. The alloy carbides V4C3 and Mo2C do not seem readily to
dissolve Cr. Thus, there is usually sufficient Cr in the ferrite for Cr23C6to be
nucleated to Cr7C3 particles present at the ferrite grain boundaries. The
specific carbide Cr23C6can readily dissolve iron and the other carbide forming
elements Mo and V to give the generic carbide M23C6.The carbide has a FCC
crystal structure and changes in lattice parameter occur as other elements are
taken in solid solution in the carbide, but as the M23C6carbide develops it
maintains its cubic morphology, that is to say there is lattice matching
between a-iron and the carbide. This implies a low value for the interfacial
energy and, therefore, as V4C3and Mo2C Ostwald ripening does not readily
occur.
It should be noted that as the carbide transition from V4C3,M02C, Cr7C3 to
M23C6occurs there is an increase in the metal/carbon atom ratio from 1.3 to
3.8. Thus there is an increase in volume fraction ofcarbide present in a steel
with a given carbon content.
The transition to M6C is more difficult to account for than the formation of
M23C6.The results given in Figs 8, 9 and 10 indicate thatMgf, forms at lower
temperatures and persists for longer times than does M23C6. The crystal
structure of M6C is hexagonal, but this does not seem to influence the
morphological characteristics of the carbides as they grow in ferritic steels.
The carbide shape is very irregular and with time the particle sizes become
much larger than those of the earlier formed carbides. The previously formed
carbides appear to go back into solution and the carbon and the carbide
forming alloying elements are transferred to the M6C by diffusion.
The M6C appears to be nucleated at the ferrite grain boundaries and does
not form by 'in situ' transformation from previously existing carbides. As the
previously formed carbides dissolve, their influence in keeping the ferrite
grain size small diminishes. This as M6C forms the ferrite grain grows and the
grains may become so large that it becomes difficult to detect the pre-existing
austenite grains.

4.3 Trace Element Effects


The precipitation sequences which occur when supersaturated solid solutions
of various solutions in aluminium decompose thermally are known to be
greatly influenced by trace elements which segregate to the precipitate matrix
26 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

interface.' The segregating species may then lower the interfacial energy and
hence influence Ostwald ripening. An alternative view is that the segregating
element may trap vacancies at the interface and if the vacancy flux is
decreased Ostwald ripening can be slowed down.
Whilst there is little evidence to suggest that trace elements have a
significant influence on Ostwald ripening of Mo2C, V4C3 or Cr~3 there is
some evidence that phosphorus segregates to M6C/a-iron interface and can
slow down solute transfer from the ferrite to complex carbide. Although not
specifically relevant to heat resistant steels, there seems to be clear evidence
that phosphorus can segregate to the Fe3C/a-iron interface where it reduces
the interfacial strength and gives rise to low temperature temper embrittle-
ment (blue brittleness).

5. THE RELATIONSHIP BETWEEN MICROSTRUCTURE AND CREEP


PROPERTIES

It is generally accepted that in order to obtain good creep properties in a


multiphase alloy, the primary requirement is to obtain a suitable dispersion of
particles within the grains of the matrix. The particles act as barriers to the
movement of dislocations generated when a load is applied to the system at
an elevated temperature. But a further requirement is that the particles
themselves should be hard, that is to say they do not shear as dislocations pile
up against them.
It is also accepted that creep can occur by grain boundary sliding. A
consequence of this is the fact that in general the creep resistance is increased
as the grain size increases. With an increase in grain size, the grain boundary
area per unit volume decreases and, therefore, there is a smaller specific area
around which creep can occur. A similar argument applies to the case of sub-
grains. Precipitate particles at grain boundaries and sub-boundaries hinder
boundary sliding and, therefore, tend to improve the creep resistance.
However, when grain boundary sliding occurs, voids may be produced at the
boundary and cracks can develop from triple points. It is possible to argue
that particles at boundaries help to initiate void formation and under these
circumstances it is to be expected that grain boundary particles will lead to
inferior creep properties. It must be remembered, however, that void nuclea-
tion and triple point cracking are characteristics of tertiary creep and,
therefore, the greatest effect of boundary precipitates could be in the final
stages of creep fracture.
It is also well established that the presence of alloying elements in solid
solution can improve the creep resistance. The underlying argument is that
the solute elements increase the frictional forces on the dislocations as they
pass through the matrix. The greater the lattice distortion produced by the
solute the greater is the frictional stress. There are limits to applying this
THE STRUCTURAL STABILITY OF Low ALLOY STEELS 27

argument for improving the creep resistance, because the greater the lattice
distortion produced by the solute the lower will be its solubility in the
solvent. In the case of ferritic steels, tungsten is believed to exert a strong
effect on solid solution creep strengthening.
In face centred cubic alloys a further factor has to be taken into account -
the stacking fault energy. Alloying elements which lower the stacking fault
energy make it difficult for cross slip to occur and hence improve the creep
resistance. In body centred cubic alloys the concept of stacking fault energy is
not so clearly defined, but metallographic evidence suggests that elements
such as silicon in solid solution have the equivalent effect of lowering the
stacking fault energy and it is probable that other strong carbide forming
elements present in steels behave in a similar way. However, the non-carbide
forming elements such as manganese and nickel have the equivalent effect of
raising the stacking fault energy and making cross slip accur more readily,
hence facilitating creep.
A further type of structural change can be induced by the actual creep
process. In ferritic steels with strong carbide forming elements, the disloca-
tions generated during creep can provide sites on which carbide precipitation
can occur and hence provide a further hinderance to dislocation movement,
that is to say the creep resistance. The phenomenon has much in common
with strain age hardening as found in sheet steels and in plain carbon steels
used for high temperature service within the 300°C-450°C temperature
range. With the 2.25% Cr-Mo-V and the 3.5 Ni-Cr-Mo-V steels used for
power generation applications, the high tempering temperatures used to
stabilise the initial microstructure tend to reduce the residual carbon content
of the ferrite to such an extent that dislocation nucleation of alloy carbides
does not occur readily. However, carbide nucleation on dislocation arrays
forming sub-grain boundaries is a common feature of the structure of steels
which have experienced long term exposure to high temperatures.
In pure metals and single phase alloys creep deformation gives rise to the
formation of ledges along the grain boundaries. In multiphase alloys the
boundary ledges provide sites at which precipitates can form. Thus in ferritic
steels subjected to creep deformation grain boundary precipitation of carbides
occurs more readily than in the equivalent steel subjected to a straight
tempering operation where no creep is present.
A further unusual phenomenon which can occur in ferritic steels is the
precipitation of sulphides at the ferrite or pre-existing austenite grain
boundaries.
The precipitation of MnS at austenite grain boundaries whilst cooling
conventional power generatio11 type steels during and after forging has been
extensively studied, since it gives rise to the phenomenon of overheating. It is
possible for further sulphide precipitation to occur in the ferritic state whilst
the steel is in service. The solubility of sulphur in ferrite is greater than the
austenite at equivalent temperatures, thus during high temperature temper-
28 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

ing of a rotor steel sulphur is taken into solution and retained in super-
saturated solid solution during subsequent cooling. At the service tem-
perature the excess sulphur precipitates at grain boundaries as MnS, but this
is a relatively slow process, since the degree of supersaturation is very low.
The interfacial adhesion between MnS and a-iron is very low, hence under
creep conditions void nucleation occurs, which in turn lowers the creep
ductility.
Super clean steels with their low Sand Mn contents show a freedom from
overheating and it seems likely that they will not suffer from in service creep
embrittlement due to sulphide precipitation.
In view of this form of microstructural instability it is surprising that the
superclean philosophy which has been so successfully applied to rotor steels
has not found a similar application to super heater tube materials and to
bolting materials.

6. STRUCTURAL STABILITY AND CREEP

From the arguments used above it can readily be seen that Ostwald ripening
of carbides linked with thermally induced phase changes all lead to a
deterioration in the creep resistance of rotor steels with time at service
temperatures. Some creep induced structural changes may lead initially to an
improvement in the inherent creep resistance, but with time, these structural
changes will be modified and the beneficial influence removed.
It would appear that the critical structural change which leads to long term
reduction in creep resistance can be linked to the formation of the generic
carbide M6C. In Cr-Mo-V type steels the upper compositional limit for the
atomic % of strong carbide forming elements is 2-3.5%, whilst for 3.5% Ni-
Cr-Mo-V and single shaft rotor steels the corresponding value is about
2-2.5%.
All of these steels contain about 1 atomic % of carbon. Thus the atomic ratio
of carbide formers/carbon will be within the range 2-3.50/0.
When the generic carbide M6C forms with its metal/carbon ratio of 6, all
the strong carbide forming elements present in the steel can eventually be
incorporated into this carbide and, apart from losing the carbides V4C3,M02C
and possibly M23C6 which confer creep resistance, the Cr and other carbide
formers which may still be dissolved in the ferrite are mopped up - a change
which will also lower the creep resistance.
It is not too surprising, therefore, that uncertainties arise when attempts are
made to extrapolate the results obtained from short term creep tests to predict
the long term (20-25 year) creep-rupture data. Complex microstructural
changes are. occurring, solid solution strengthening is being lost and such
changes are unlikely to be fully represented by the extrapolation of relation-
ship of the form:
THE STRUCTURAL STABILITY OF Low ALLOY STEELS 29

y = a-k IOglOX (6)


A formula which is the mathematical basis of most predictive methods for
assessing long term creep behaviour.

7. SOME POSSIBLE FUTURE DEVELOPMENTS

If the arguments used above are correct, and the experimental evidence
suggests they are, then the requirement to maintain microstructural stability
over long periods in low alloy ferritic rotor steels is to stop or at least hinder
the formation of the generic carbide M6C which is rich in Cr, Mo or V. A
possible solution to this problem would be to add W to the steels, since it is
known that the carbide W6C is more stable than the mixed (Cr,Mo, V)6C. An
even more stable tungsten type carbide is C03W3C. If a carbide of this type
could be introduced to form during long term service it might hinder the
formation of (CrMoV)6 and allow the creep conferring carbides to remain
structurally stable. There would be cost penalties to pay for the Co and W
additions, but metallurgically it would be feasible to produce an alloy steel
with 0.5-1°loCo and 0.5-1010W, together with the normal additions.
A further possibility which is now beginning to look feasible is the direct
addition of carbides to the molten steel. These carbides could confer creep
resistance to reinforce the influence of those produced by the solid state heat
treatment, whilst the new carbides are likely to be very thermally stable.
The initial requirement is to produce 50 urn powder granules having an
iron or nickel matrix in which are dispersed fine carbide particles of, say, (W
Ti)C having a diameter of 1-5 urn. Powders of this type are being produced
commercially by the self propagating high temperature synthesis (S.H.S)
process. If the powders are added to molten steel under non oxidising
conditions, a uniform dispersion of fine carbides is obtained after the steel has
solidified.
Experimental casts of steel containing these powders have been produced
and forged and then heat treated to produce cold rolls which have a similar
outline to rotors.
It is likely that these carbides will have a long term thermal stability, since
they have been formed by precipitation from a complex liquid mixture and
the presence of Ti in the carbide could well hinder the formation of M6C from
the original (Ti W)C. If the added carbides are thermally stable they will help
to maintain the creep resistance of rotor steels, when after long periods in
service the conventional carbides are transforming to M6C.
The new methods of carbide additions to steels hold out exciting possibil-
ities for alloy steel development. Apart from tungsten and titanium, it is
feasible to add other strong carbide formers, e.g. niobium, in this way. As
described above, the conventional metallurgical route of producing carbide
dispersions by heat treatment in the solid state greatly limits what can be
30 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

achieved and effectively bars the use of Ti and Nb in low alloy heat treatable
steels, whilst the likely beneficial effects of forming we cannot be achieved in
the presence of Mo and V.
It would appear that further chapters in the history of the development of
low alloy steels for power generation equipment have yet to be written.

REFERENCES

1. E. D. Hyam and J. Nutting: J.1.S.1., 1956, 184, p. 148.


2. G. R. Speich: Trans A.1.M.E., 1969, 245, p. 2553.
3. A. J. Baker et al.: Electron Microscopy and the Strength of Crystals, Thomas and
Washburn eds, Gordon and Breach, New York, 1963, p. 899.
4. K. Onel and J. Nutting: Metal Science, 1979, 13.1 p. 573.
5. J. W. Martin and R. D. Doherty: Stability of Microstructure in Metallic Systems,
Cambridge University Press, Cambridge, England, 1976.
6. J. Nutting: 1.1.5.1..1 1969, 207, p. 872.
7. R. W. K. Honeycombe: Steels Microstructure and Properties, Edward Arnold,
London, 1981.
8. F. B. Pickering: Physical Metallurgy and the Design of Steels, Applied Science
Publishers, 1978.
9. K. J. Irvine and F. B. Pickering: J.1.S.1., 1960, 195, p. 386.
10. E. Smith and J. Nutting: J.1.S.1., 1994, Special Report, 86.1 1.
11. E. Tekin and P. M. Kelly: 1.1.5.1., 1965, 203, p. 715.
12. F. B. Pickering: 1.1.S.I..1 1959, Special Report, 64, p. 23.
13. R. G. Baker and J. Nutting: J.1.S.1., 1959, 192, p. 257.
14. G. Gage: PhD., Dissertation, Matallurgy Department, Leeds University
1984.
Section 1:
BOILERS
New Developments in Steels for Power
Generation Boilers
F.MASUYAMA
Mitsubishi Heavy Industries, Ltd., 5-717-1, Fukahori-machi, Nagasaki
851-0392, Japan

ABSTRACT

Steam conditions in power plants are gradually being raised with a view to energy
savings and environmental protection. The steam temperature of 600°Cfor modern
power plant has already been realised, and a goal for the future is the 625°C class
with ferritic steels. T 91IP 91 was developed in the early 1980sand was subsequently
widely used for the high-temperature components of power boilers. Its strength,
however, was not sufficient for temperatures of 600°C and above. Since 1980
numerous studies on heat resistant steels have been actively conducted, and, among
the various steels developed for advanced steam cycles, great progress has been seen
in 9-12Cr steels and austenitic steels. In particular, recent ferritic 9-12Cr steels have
become stronger than conventional austenitic stainless steels. The most recent
9-12Cr steels have a creep rupture strength of 140MPa at 600°Cfor 100000 hours.
Such enhancement in creep strength is achieved by the alloying of Wand reduction
of Mo. In the near future a strength of 180MPa is anticipated for ferritic steels
through further studies on the role of alloying elements such as Co. This paper
presents a historical view of developments over the last several decades, as well as a
survey of the current status of steel development for power generation boilers,
mainly with regard to creep strengthening and alloy design.

INTRODUCTION

Energy savings and environmental protection are regarded worldwide as


highly important issues. Operators of thermal power plants are trying to
address these requirements by decreasing fuel costs and C02 emissions
through further improvements in efficiency. Such improvements can be
achieved by elevating steam conditions to even higher ranges of temperature
and pressure.
The development of the modern ultra-supercritical power plant began in
the early 1980s, and the world's first swing-load ultra-supercritical power
plant with conditions of 566°C and 31 MPa started commercial operation in
Japan in 1989. Subsequently, power plants with steam temperatures ranging
from 593 to 610°C have been successively built, and a study is already under
way to implement a temperature of 625°C class using ferritic steels.
For steels used for high temperature components in power plants, good

33
34 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

mechanical properties, corrosion resistance and fabric ability are generally


required, and creep strength in particular is the most important property for
high temperature and high pressure applications. This has led to ongoing
research activities placing emphasis on the improvement of creep strength in
alloy development.

HISTORICAL VIEW OF STEEL DEVELOPMENT FOR POWER BOILERS

Many heat-resistant steels for power boilers have been developed during this
century, and a review of the evolution of strength improvements for the
respective steel groups is given in Fig. 1, which shows 100000 hour creep

l
!.
o
g(0
150

1U
.s::.
m
c
~ 100
e~
a~
a::
Q.

•..I 50
o
.s::.
II)

~
Q

o~~--~~~--~~--~~--~~~
1900 1920 1940 1960 1980 2000
Year

Fig. 1 Historical Improvement of Creep Rupture Strength in Steels for Boiler

rupture strength at 600°C by year of development. Based on 9Cr-lMo steel


(T9) and 12Cr steel (AISI410), which was put into service around 1940,
subsequent development focusing on the 60 MPa class took place from 1960 to
the early 1970s. Continued efforts saw 100 MPa class steels developed in the
early 1980s, with 140MPa class steels appearing in the early 1990s. These
evolutions may be referred to respectively as the first, second, and third
generations. For the next (fourth) generation, 180MPa class steels are expected
to emerge; this level of strength has already been obtained in the laboratory
using new alloy designs employing Co and other elements in addition to W.
The most important contribution of the second generation was the optimi-
NEW DEVELOPMENTS IN STEELS FOR POWER GENERATION BOILERS 35

sation of chemical compositions such as C, V, and Nb, while the third


generation helped to identify alloy designs using Wand martensitic struc-
tures with MX precipitates. These findings in 9-12Cr steels were very useful
in the development of a tungsten strengthened low alloy steel which con-
tained low carbon in order to improve weldability.
In the field of austenitic steels, a new move was initiated from the 1970s to
the early 1980s to improve conventional 18Cr-8Ni series steels originally
developed as corrosion resistant materials for chemical use, mainly with
respect to their creep strength. Another goal pursued from the 1980s to the
early 1990s was to improve the creep strength of conventional 20-2SCr series
steels having superior oxidation and corrosion resistance.

DEVELOPMENTS AND ALLOY DESIGN IN FERRITIC STEELS

Table 1 shows the nominal chemical compositions of ferritic steels for power
boilers. Ferritic steels include 2Cr, 9Cr and 12Cr steels. High-strength 9-12Cr
steels have comparatively good corrosion resistance and can be cost effective
substitutes for 18Cr-8Ni steels. The wall thickness of these steel tubes can also
be reduced, and the oxidation and corrosion resistance improved, in compari-
son with conventional low alloy steels. Recently developed 9-12Cr steels
have strength between those of low alloy steels and 18Cr-8Ni steels, or
strength equal to or higher than that of 18Cr-8Ni steels. Figure 2 compares
allowable stresses for 9-12Cr steels including low alloy steels, and Fig. 3

Temperature CC)

Fig. 2 Comparison of Allowable Stresses of Ferritic Steels for Boiler


36 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

$-(
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NEW DEVELOPMENTS IN STEELS FOR POWER GENERATION BOILERS 37

105 h Creep Rupture Strength at soot


35 MPa 60 MPa 100 MPa 140 MPa 180 MPa
. . -C +W .
l2.25cr-1MO~ 2.25Cr-1MoV I ·Mo +Nb .r--12.-2S-Cr.-1.6-WV-N---'bl
ASME T22 1+Mo HCM2S
(STBA24) (ASME T23)
STBA24J1

Fig. 3 Development Progress of Ferritic Steels for Boiler

shows the development progress of ferritic steels of the 2Cr, 9Cr and 12Cr
series. Of them, HCM9Ml is a low carbon 9Cr-2Mo steel having service
experience over a period of 25 years since development, with about 2000 tons
having been produced specifically for superheater and reheater tubes and
steam pipes. The strength of this steel is between those of T 22 and TP 304H,
and it is used especially for reheater tubes in place of lSCr-SNi steels.
Tempaloy F-9,2 EM123 and T914 are improved 9Cr steels whose strengths
have been enhanced by adding carbide forming elements such as V and Nb.
Of these improved 9Cr-1Mo steels, T 91 has the highest allowable stress and
has already been extensively used allover the world as a material for heavy
section components such as headers and steam pipes (i.e., not limited to
superheater tubing). The emergence of this steel has made it possible to
fabricate high pressure components for ultra supercritical power plants up
to 593°C (1100°F) using a ferritic steel. NF616,5 having an even higher
allowable stress, was developed in 1990. This steel was obtained on the alloy
design basis of a substitution of W for Mo, decreasing the Mo content to 0.5%
and adding 1.S%W. This type of alloy design has been found to be excellent in
terms of creep strengthening, and this method is commonly used in the most
recently developed steels. Figure 46 compares the creep rate and strain
behaviors for T91 and NF616. NF616, the typical9Cr-W steel, exhibits a very
low creep rate even after ageing at 600°C and 650°C, in contrast to T 91, the
typical 9Cr-1Mo steel. However the creep deformation curves of both steels
behave in the same manner. This may indicate that tungsten strengthening is
more effective against creep resistance than molybdenum strengthening. It
38 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

10-5

\\i
\ iAged at 650'C:,104h

~\ Aged at 600'CX104h »> :: ~ ;:. ••••••••

- '\'
10-6 -> ..••..
~ •••

.•.. \, "" -..".-- ,~',~' .,,'"

~
.!
ca
'"
--- -'"'~~AS
' ••• '-'T91
Manufactured

a: 10-7
Q. Aged at 600°C X 1()4h
Z•.. Aged at 6S0°C X 104h
(J

10-8 As Manufactured

Tested at 650°C and 120MPa


10-9
0 0.02 0.04 0.06 0.08 0.10
Strain

Fig. 4 Comparison of Creep Rate vs Strain Behaviors of T91 and NF616

has already become possible to obtain 9Cr steels with remarkably high creep
rupture strength, but they tend to be inferior to 12Cr steels or austenitic steels
for superheater tubing applications in boiler furnaces. This is because 9Cr
steels cannot be used in a temperature range above 625°C, taking into account
the oxidation and corrosion resistance limiting temperature.
With respect to the 12Cr steels, HT91 (DIN, X20CrMoV121)7 has been
extensively used for superheater tubes, headers and steam pipes, with
extensive operating experience in Europe. However, this steel has not been
used in Japan or the u.s. because the carbon content (as high as 0.2%) leads to
poor weldability and creep strength has not been found to be particularly
good.
Meanwhile, improved l2Cr steels for boilers have recently been developed
by eliminating the drawbacks of conventional l2Cr steels. HCM128 and
HCM12A9 are examples of these improved l2Cr steels. HCM12 is a 12Cr steel
with 10/oMoand 10/oWhaving a duplex structure of 8-ferrite and tempered
martensite with improved weld ability and creep strength. The stability of the
creep strength of this steel has been designed by using precipitation strength-
ening with very fine VN precipitates, and high-temperature tempering at over
800°C. The allowable stress is found to be somewhat superior to that of T 91,
as described above. This steel has already accumulated service experience
over a period of more than 15 years and has been extensively used for
superheater tubes in chemical recovery boilers exposed to severe high-
temperature corrosion attack.
HCM12A is an improved type of HCM12, and the alloy design has been
NEW DEVELOPMENTS IN STEELS FOR POWER GENERATION BOILERS 39

undertaken so as to allow applicability for thick walled components such as


headers and steam pipes by eliminating a-ferrite in order to enhance the
toughness. Development of a new steel for practical application must take
into consideration not only creep strength but also oxidation resistance,
weldability and toughness, as shown in Fig. 5.9 Creep strengthening for

Corrosion Service Temperature


Resistance

Precipitation Strengthening
VN, Nb (C, N), Laves, JJ.

Creep Strength Solution Strengthening W, Mo

Stable Long-Term Strength

High Temperature Temper(High AC1)1======:;:>t __ ..-_ ••


F.,
L..-_W_e_ld_a_b_ili_ty_
......• , , .
L~------:'~__l ~~~!_~~~_~~ __f=¢i_~~~~_!~~~~~_~_~~i

Toughness Martensitic Structure


6 - Ferrite ~ 50/0
Heat Embritlement

0.1 C-12Cr-O.4Mo-2W-1 Cu-0.2V-0.OSNb-B-0.06N

Fig. 5 Alloy Design for HCM12A

HCM12A has been designed using the base material of the 12Cr steels
without compromising practical performance. Creep strengthening can be
achieved either by precipitation strengthening through the addition of V, Nb
and N, or by solution strengthening using Wand Mo. The Ni content has been
minimised to stabilise the long-term creep strength, and the Acl temperature
has been maintained at a higher level in order to allow high-temperature
tempering. In other words, 12Cr steels require additions of austenite forming
elements such as Ni, C and N to minimise 8-ferrite harmful to toughness,
which would be formed if the Cr equivalent were too high. HCM12A
therefore contains Cu instead of Ni, because Ni decreases the long-term
strength and greatly reduces the Acl temperature. This can be said to be a new
attempt in terms of alloy design because there is no precedent for Cu used in
9-12Cr heat-resistant steels.
The roles of Mo, W, V and Nb are extremely important in improving the
40 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

A : O.1C-12CrMoWVNb Creep Rupture Strength


B: O.2C-12CrMoWV at 600°CX104h

I
: •••. Increase6-Ferrite

120

I Low Toughness
I
I
I
I
A B Elements
I
I
o- W
I
()f:),. Mo

102--~--~1~~--~
I
I •• Mo+W
__ ~~
2 3 4 5
Mo + O.5W (mass %) Nb (mass 0/0)
(a) Effect of Mo and W (b) Effect of V and Nb

Fig. 6 Effect of Mo, W, V, and Nb on Creep Strength of 12Cr Steel for Boiler

creep strength of ferritic steels, and their effects are shown in Fig. 6.10 As
shown in Fig. 6(a), creep strengthening due to Mo and W shows the highest
effect when the W content is increased, minimising ductility, whereas
toughness declines while maintaining the Mo equivalent (Mo +0.5 W) at
about 1.5%. As shown in Fig. 6(b), optimal V and Nb additions are about
0.25% for V and about 0.05% for Nb. These values remain the same in both
Cr-Mo steels and Cr-W steels, as in the case with ger steels or 12Cr steels.
Although it was believed during the initial research period in the 1960s that
about 0.4% would be an appropriate Nb content, one-tenth of this percentage
can be adequate in terms of long-term creep strength. V and Nb produce
marked effects on precipitation strengthening because they form extremely
fine MX carbonitride which precipitates coherently on the ferrite matrix.
Because such precipitates are too fine to examine, their structures and
properties remain unknown. However, because the combined addition of V
and Nb shows more prominent strengthening than the single addition of
either one, it is postulated that some interaction may be at work, such as a
single precipitate (NbC, for example) of the two forming a nucleus for the
other precipitate.
Figure 7 compares the creep rupture strengths of four grades of the 12Cr
steel, RT91, RT9, RCM12 and HCMI2A. As shown in Table I, RT91 is the
base material of 12Cr steel with W content increased to 0.5%, 1% and 20/0.
Thus, although HT91 and HT9 belong to the 60 MPa class, the latter contains
O.s%W with the other compositions remaining the same. Also HCM12 is a
steel with a Mo equivalent of 1.5% using addition of the same quantities of
Mo and W, and HCM12A is a steel developed on the basis of the same concept
NEW DEVELOPMENTS IN STEELS FOR POWER GENERATION BOILERS 41

500

300

200

cu
0.
etn 100
tn
.•..!
en 70

50 • HT91
o HT9
• HCM12
30 o HCM12A

20
30 31 37
T(3S + log t) X10-3

Fig. 7 Comparison of Creep Rupture Strengths of 12Cr Steels for Boiler

as shown in Fig. 5. Figure 7 lists HCM12A, HCM12, HT9 and HT91 in


descending order of creep strength, and that the difference between these
steels becomes greater with increasing temperature and with increasing test
duration. However, a comparison between HT91 and HT9 shows that an
addition of O.s%W is effective in the improvement of creep strengthening
independent to temperature and time.
A variety tof approaches for further enhancement of creep strength are
being sought in ferritic steels, and, as shown in Fig. 3, two 180MPa class steels
in terms of 100 000 hour creep rupture strength at 600°C have already been
obtained from laboratory tests. Both have similar chemical compositions
containing an addition of Co and an increased W content. NF1211 contains
2.S%Co and 2.6%W, with a slightly increased B addition compared to
conventional Cr-W steels. On the other hand, SAVE1212contains equal 3%
additions of Co and W, featuring additions of Ta and Nd as well. It has been
shown that both Ta and Nd can enhance creep strength in the temperature
range of 600 to 6S0°C by producing fine and stable nitrides.'? The Nd used
here is an element of the lanthanoid series, and further strengthening can be
expected to be obtained by utilising the effects of new alloying elements such
as a refractory metals.
The findings of studies of 9-12Cr steels have been applied to develop a new
high strength low alloy steel. HCM2S,13a low carbon 2.2SCr-l.6W steel with
V and Nb, is a cost effective steel developed on the basis of the modern alloy
design concept. The creep strength of this steel at approximately 600°C is
roughly twice as great as conventional low alloy steel or T 22, and it requires
42 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

300

200

Ci
Q. 100
~
~ 70
!
tii 50
T91
30 o O.6%Re added HCM2S
• HCM2S
- T91
20 ••. T22
T22
10~~--~--~--~--~--~--~~
16 17 18 19 20 21 22 23 24
T(20 + logt}X10-3

Fig. 8 Creep Strength of HCM2S and Effect of Re Addition

neither preheat nor post weld heat treatment. Figure S shows the creep
rupture strength of HCM2S compared with conventional T22 and T91. This
figure also indicates that the addition of Re to HCM2S markedly enhances the
creep strength.

DEVELOPMENTS AND ALLOY DESIGN IN AUSTENITIC STEELS

Table 2 shows nominal chemical compositions of austenitic steels for power


boilers. Steels are classified into four groups: ISCr-SNi, 15Cr-15Ni, 20-25Cr
and High Cr-High Ni steels. Figures 9 and 10 compare allowable stresses for
18Cr-8Ni and 15Cr-15Ni steels, and for 20-25Cr and High Cr-High Ni steels
respectively.
Figure 9 indicates that Tempaloy A-l,14 Super 304H15 and TP347HFG16
(19Cr-SNi steels) have strengths equivalent to or higher than those of 15Cr-
15Ni steels such as 17-14CuMo, which was originally held to have had a high
strength. Also from Fig. 10 it is evident that in the 20-25Cr steels, HR3C,17
Tempaloy A-31B and NF70919 have high strength compared with conven-
tional TP310 and Alloy 800H. Figure 11 shows the development progress of
austenitic steels of the lSCr-8Ni series and the 20-25Cr series including Alloy
SOOH.Austenitic steels originated from AISI 302 (lSCr-SNi steel), and various
types were developed according to their intended service. It is seen from Fig.
11 that newly developed steels of the 18Cr-8Ni series have been generated,
aiming at precipitation strengthening by adding both Ti and Nb, or Nb alone,
NEW DEVELOPMENTS IN STEELS FOR POWER GENERATION BOILERS 43

;::l
U
o
cr)

\0 N C't')
o o
o
o
o
o
01 1 0 1 10
00 \0 00
io 0 C't') 0 l.!) M NO
00 00 o 0 00

0000000 000000 00
ooo\oo~oo oo~mmoo ocr)
M M M M M NNC't')MNM l.!)~

\000\0\0\0\0\0 \ONNl.!)OO
~o~~~~~ ~~~~~~
\oN\O\O\O\O\O l.!)
l.!)\o~l.!)~l.!)M
0000000 00 000000
00
ooOooNoooooo 00 \0 00 l.!)l.!)O\0 0
OMOMOOO 0000 MM 00
0000000 000000 00

z
00
z
l.!)
M U
~
I l.!)
~I
~ N
U U I
00 l.!) o
M M N
44 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

~
~ 100

550 600 650 700


Temperature CC)

Fig. 9 Comparison of Allowable Stresses of IBCr-BNi Steels and 15Cr-15Ni Steels


for Boiler

~
::?: 100
.•......

•.
UJ
UJ
!
en
CD
:c
;
.,g 50
<

550 600 650 700


Temperature CC)

Fig. 10 Comparison of Allowable Stresses of 20-25Cr Steels and High Cr-High Ni


Steels for Boiler
NEW DEVELOPMENTS IN STEELS FOR POWER GENERATION BOILERS 45

-C
1SCr-SNi,C<O.08 Heat Treatment( 147)
AISI304 I
1SCr-8NiNb I
ASME TP347HFG
Chemistry
18Cr-8NiTi
AISI321
o
timization (136)
18Cr-SNiNbTi
Tempaloy A-1
18Cr-SNiNb (SUS321J1 HTB)
AISI347 Cu Addition (168)
18Cr-8NiCuNbN
+Mo
18Cr-8NiMo Super304H
(SUS304J1HTB)
+ Cr AISI316
(80) (1S1)
+Ni
22Cr-12Ni 25Cr-20Ni I ~I 25Cr-20NiNbN I
AISI309 AISI310 HR3C
(SUS310J1TB)

(186)
20Cr-25NiMoNbTi
NF709
(SUS310J2TB)

(155)
22Cr-15NiNbN I
Tempaloy A-3
(SUS309J4HTB)
( ) designates 105 h creep rupture strengh at 600

Fig. 11 Development Progress of Austenitic Steels for Boiler

and that their additions are markedly lower than those of conventional 321H
and 347H. The addition of Ti or Nb in 321H or 347H was optimised in order to
fix carbon combined with Cr from the stand point of the prevention of
intergranular corrosion. Figure 1220 shows the effect of the (Ti + Nb)/C ratio
on the creep rupture strength of 18Cr-8NiNbTi steel. The (Ti + Nb)/C ratios
of the conventional 321H and 347H are remarkably high and far above the
ratios of about 0.2 to 0.3 at which creep rupture strength reaches its peak
value. For this newly developed steel, the additions of Ti and Nb have been
reduced relative to the C content in order to provide the highest creep
strength. Such an optimisation of chemical composition is called 'Under
stabilising' because it is insufficient for the complete stabilising of C. This is a
promising direction for austenitic steel development, placing emphasis on
creep strength. An example of the application of a new alloying element to
improve creep strength is Super 304H. This steel uses an addition of Cu of
about 3%, which is similar to the addition of Cu in 17-14CuMo steel.
Although the influence of Cu on creep strength has remained unknown from
the observation results of the microstructure, it has been verified that the Cu
addition can be remarkably effective in improving creep strength, because Cu
precipitates on the austenitic matrix in the form of extremely fine precipitates
called a 'Cu-rich phase', which remains thermally stable."
46 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

••......

.
cu
~ 120
'-'
~ 110
,.,.------' •..•..•..
,,
", ...:r .
;r
c " •..•..•..
~ 100

.
cu
.c " •..
m 90 /
""
'-- .....•

'.
c
e ,
ti)
••:.•.......
---<.
80
CI)

..,:;
Q.
70
/ / "
// 321H} .....
~ 60 / 3QH'
Q. /

~m 50
o.
.c 40
,..
it)
c
0.01 0.1 0.5 1.0 1.5 2.0
(Ti + Nb) I C Atomic Ratio
,,' , I ,I I I , I , ,

0.01 0.1 0.5 1 1.5 2 3 4 5 6 7 8


(Ti + 0.5Nb) I C Mass Ratio

Fig. 12 Effect of (Ti + Nb)/C Ratio on Creep Rupture Strength of 18Cr-8NiNb Ti


Steel

The 20-25Cr series steels are superior to the IBCr-BNi series in resistance to
high-temperature corrosion, but their creep strengths (except for Alloy 800H)
are lower than those of the IBCr-8Ni series steels. Thus, if the creep strength
of 20-2SCr series steels can be improved, they will become very useful boiler
steels, particularly for high temperature steam conditions. HR3C is an
improved version of TP 310 with respect to creep strength. NF709 and
Tempaloy A-3 also represent a new type of steel for which the Ni content has
been greatly reduced on the basis of the expensive Alloy 800H, with further
enhancements of their creep strengths. The general trend of alloy design
common to all of them lies in stabilising the austenitic structure by adding
0.2%N instead of decreasing the Ni content, as well as in precipitation
strengthening by the trace addition of Ti and Nb. The concept adopted here is
to bring about the stable austenitic structure and to improve creep strength by
precipitation of fine carbides due to 'Under stabilising'. In this steel group,
High Cr-High Ni steels HR6W21 has been developed by adding 6 W to a %

23Cr-43Ni austenitic steel to greatly improve the creep rupture strength.


However such High Cr-Nigh Ni steels including CR30A22naturally feature
high material costs due to the large amount of expensive alloying elements,
which make those steels difficult to put into practical use. SAVE2S,23the most
recently developed 20-2SCr steel, contains I.S%W and 3%eu following the
NEW DEVELOPMENTS IN STEELS FOR POWER GENERATION BOILERS 47

precedent of HR6W and Super 304H. Additionally, in order to stabilise the


austenitic structure and to obtain effective precipitation strengthening or
'Under stabilising', 0.2%N and 0.4SNb were also added. As a result, a large
amount of Ni was substituted for by Cu and N, and was reduced to 18%. This
steel is economical and exhibits over 120% of the strength of HR3C in a wide
range of temperatures due to the various strengthening mechanisms
employed.

CONCLUSIONS

The successive elevation of the steam conditions of power plants is due


largely to the achievements of research and development in realising heat
resistant steels for power applications. For the last several decades, the
progress of 9-12Cr steels and austenitic steels have been particularly remark-
able. Some of the newly developed steels have already been practically used
in power generation boilers. Development of such heat resistant steels has
been achieved through alloy design placing emphasis on creep strength
improvement without compromising other practical performance, such as
corrosion resistance, weldability and fabricability. For future developments of
power generation boilers, alloy design for creep strengthening should be
aimed at curtailment of material cost without the loss of other practical
performance. The verification of the stability of structures and strengths based
on long-term creep rupture tests over a duration of tens of thousands of
hours, as well as the clarification of strengthening mechanisms and the
development of new strengthening techniques, will also be needed in further
research and development work.

REFERENCES

1. T. Yukitoshi, K. Nishida, T. Oda and T. Daikoku: Trans. ASME, Pressure


Vessel Technology, 1976, 98, 175.
2. K. Kinoshita: NKK Technical Report, 1973, 62, 602.
3. M. Ivenel: Revue Gemerale Term, 1964, 555.
4. V. K. Sikka, C. T. Ward and K. C. Thomas: ASM Int. Conf Production,
Fabrication, Properties and Applications of Ferritic Steels for High Temperature
Applications, Warren, PA: 6-8 Oct. 1981.
5. M. Sakakibara, H. Masumoto, T. Ogawa, T. Takahasi and T. Fujita: Thermal
and Nuclear Power (in Japanese), 1987, 38, 84.
6. M. Ozaki, N. Nisimura and F. Masuyama: Abstracts of 120th Meeting of Japan
Inst. Metals, 1997, 183.
7. G. Kalwa, K. Haarmann and J. K. Janssen: Metall. Soc. of AIME, Topical
Conf Ferritic Alloys for Use in Nuclear Energy Technology, Snowbird, UT,
19-23 June 1983.
48 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

8. K. Yoshikawa, A. Iseda, H. Teranishi, F. Masuyama, T. Daikoku and H.


Haneda: Int. Conf. High Temperature Alloys, Petten, Netherlands, 15-17
June 1985.
9. A. Iseda, Y. Sawaragi, S. Kato and F. Masuyama: 5th Int. Conf. Creep of
Materials, Lake Buena Vista, FL., 18-21 May 1992.
10. K. Yoshikawa, A. Iseda, M. Yano, F. Masuyama, T. Daikoku and H.
Haneda: 1st Int. Conf. Improved Coal Fired Power Plants, Palo Alto, CA.,
19-21 Nov. 1986.
11. M. Ohgami, Y. Hasegawa, H. Naoi and T. Fujita: IMechE Conf. Trans.
1997-2, Advanced Steam Plant, IMechE, 1997, 115.
12. M. Igarashi and Y. Sawaragi: Proc. Int. Con! Power Engineering - '97, 1997,
Vol. 2, 107.
13. F. Masuyama, T. Yokoyama, Y. Sawaragi and A. Iseda: PVP-Vol. 288,
Service Experience and Reliability Improvement: Nuclear, Fossil and Petro-
chemical Plants, ASME, 1994.
14. Y. Minami, K. Kimura and M. Tanimura: ASM Int. Conf. New Development
in Stainless Steel Technology, Detroit, MI., 17-21 Sept. 1984.
15. Y. Sawaragi, K. Ogawa, S. Kato, A. Natori and S. Hirano: Sumitomo Search,
1992, 48, 50.
16. K. Yoshikawa, H. Fujikawa, H. Teranishi, H. Yuzawa and M. Kubota:
Thermal and Nuclear Power (in Japanese), 1985, 36, 1325.
17. Y. Sawaragi, H. Teranishi, H. Makiura, M. Miura and M. Kubota: Sumitomo
Kinzoku, 1985, 35, 166.
18. A. Toyama, Y. Minami and T. Yamada: CAMP-lSI!, 1988, 1, 9.
19. M. Kikuchi, M. Sakakibara, Y. Otaguro, H. Mimura, S. Araki and T. Fujita:
Int. Conf. High Temperature Alloys, Petten, Netherlands, 15-17 Oct. 1985.
20. T. Shinoda and R. Tanaka: Bulletin of Japan Inst. Metals, 1972, 11, 180.
21. Y. Sawaragi and K. Yoshikawa: Tetsu to Hagane, 1986, 72, S672.
22. M. Tamura, N. Yamanouchi, M. Tanimura and S. Murase: 1985 Expo. and
Symp. Industrial Heat Exchanger Tech., Pittsburgh, PA., 6-8 Nov. 1985.
23. H. Senba, M. Igarashi and Y. Sawaragi: Proc. Int. Conf. Power Engineering-
'97, 1997, Vol. 2, 125.
Section lA:
STEEL DEVELOPMENTS
Development of 12 Cr Heat Resistant %

Steel Plate (TEMPALOY F-12M) For


USC Boiler
K. HAYASHI, T. KOJIMA and Y. MINAMI
Materials & Processing Research Center, NKK CORPORATION, Kawasaki
Japan

ABSTRACT

This paper deals with newly developed 12 Cr ferritic heat resistant steel plate
%

(TEMPALOYF-12M) containing O.7Mo-1W-O.1Mn-B-Cu-Nb-V-N which is used


for hot reheat steam pipes and headers with large diameter and thick wall of ultra
super critical (USC) boiler. The steel has high steam oxidation resistance, and creep
rupture strength of more than 1.3 times higher as compared with Mod.9Cr-1Mo
steel (ASTMA387 Gr.91) above 600°C,which is attributed to strengthening by lower
Mn and B addition as well as precipitation strengthening of Nb, V carbonitride and
W strengthening. In addition, the steel plate consisting of fully tempered martensitic
structure exhibits enough notch toughness after not only PWHT but also a long term
ageing, and good hot and cold workability and weldability.

INTRODUCTION

In fossil fired power plants, high strength austenitic stainless steel tubes have
been widely used for superheater and reheater in power generation boilers.
However, these materials have been scarcely applied for the main and reheat
steam pipes and their headers with large diameter and thick wall because of a
high thermal expansion coefficient and the ease of oxide scale exfoliation, as
compared with ferritic steels. Accordingly, ferritic steels such as 2.2SCr-1Mo
steel or Mod.9Cr-1Mo steel has been applied for those parts.
In recent years, from the standpoint of world wide natural environment
and effective utilisation of limited resources, ultra super critical (USC) boiler,
in which steam temperature and pressure are higher than those in conven-
tional boilers, have been developed in the world in order to increase the heat
efficiency of fossil fired power plants. When considering the materials for the
main and reheat steam pipes and their headers, high Cr(9-12 mass'zs) ferritic
steels are required with respect to higher strength at higher temperature and
higher corrosion resistance as compared with conventional ferritic steels such
as Mod.X'r-TMo.!
On such a background, a new 12Cr ferritic heat resistant steel plate
(TEMP ALOY F-12M) was developed 2-4 as a material for the reheat steam

51
52 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

pipes and headers fabricated by bending and welding. This paper deals with
the concept and the performances including high temperature properties of
TEMPALOY F-12M steel plates.

OBJECTIVE

The objective of this research is to develop a steel plate having high creep
rupture strength and high steam oxidation resistance applicable to hot steam
pipes such as reheat steam pipes and headers with large diameter and thick
wall of USC boiler in which steam temperature of 630°C and the pressure of
300 MPa. Especially for the creep rupture strength, the goal of the maximum
allowable stress at 650°C is more than 1.3 times higher as compared with
Mod.9Cr-lMo steel (ASTM A387 Gr.91). It is, furthermore, intended that the
steel plate has enough hot and cold workability, weldability and cost
performance to meet material performances compatible with Mod.9Cr-lMo
steel plate.

EXPERIMENTAL PROCEDURE

Experiments were performed using several kinds of 20 mm thick laboratory-


produced 12 Cr steel plates with mainly different W, Mn and B levels to
%

investigate the effects of alloy elements on mechanical properties including


creep rupture strength. The chemical composition range are listed in Table I

Table 1Chemical compositions of steel examined (mass'zs)

C Si Mn P S Cu Ni Cr Mo W V Nb B N

0.12 0.150.05 0.003 0.001 0.50 0.28 9.9 0.35 0.68 0.19 0.050.002 0.064
-0.16 -0.23 0.83 -0.012 -0.004 -2.96 -0.36 12.2 -0.73 -2.00 -0.28 -0.13 0.010-0.082

where those were adjusted by controlling the balance of ferrite (ex) former
elements and austenite (-y) former elements in order to suppress 8-ferrite
formation. It is necessary for Cu to increase in the case where W content is
increased as mentioned below in detail. Notch toughness was also evaluated
using steel plates with different Cr levels.
The steel plates were normalised at 1080°C and tempered at 780-800°C.
Mechanical properties were evaluated after post weld heat treatment (PWHT)
at 740°C for 8 hours which may be encountered as a welded pipe.
DEVELOPMENT OF 12%CR HEAT RESISTANT STEEL PLATE 53

---a
~U)(3CU)
cf0Cu)~~
(O.SCU)

o 0.5 1.0 1.5 2.0 2.5 a 0.5 1.00 0.005 0.010 0.015
W (rnassss) Mn (mass ss) B (rnassss)

Fig. 1 Effect of W, Mn and B content on creep rupture properties

RESULTS AND DISCUSSION

Effect of Alloy Elements on Creep Rupture Strength


Figure 1 shows the effect of W, Mn and B content on the creep rupture
properties at 650°C. Creep rupture strength (time) tends to increase with
increasing Wand B contents and with decreasing Mn content. Although W is
the most effective element to increase creep rupture strength, the combination
effect of decreasing Mn content and increasing B content in the case of 1
mass': W or less is comparable with that of increasing W content from 1
mass" to 2 mass'ze.
Creep strengthening mechanism by W addition has been reported by many
researchers.v" which are solid solution strengthening, stabilisation of car-
bides, strengthening by precipitation of Laves or f.L phases along the grain
boundary or lath boundary of martensite. However, there needs further
experiments and discussions in this point.
As for creep strengthening mechanism by lowering Mn content, Fig. 2
shows the distribution of precipitates after isothermal ageing at 650°C for 104
hours with different Mn contents. It can be observed that decreasing Mn
content tends to suppress coagulation and coarsening of precipitates which
are considered almost M23C6 type carbide, and Laves phase in the figure.
Figure 3 shows the quantitative phase analysis" result of M23C6 type carbide
and Laves phase as a function of Mn content, just after PWHT and after
isothermal ageing at 650°C for up to 104 hours. There seems no significant
changes in the amount of M23C6 irrespective of before and after ageing and
Mn content. Adversely, Laves phase not existing after PWHT increases with
increasing ageing time at 650°C, however the quantities are very small in any
case. As a result, it can be assumed that the improvement of creep rupture
strength by decreasing Mn content is due to the stabilisation of precipitates
resulting from the stabilisation of martensite structure. B also contributes to
54 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

O.05mass% Mn 0.78 mass% Mn

Fig. 2 Transmission electron micrographs of extraction replica after ageing at 650°C


for 104 hours

~e B c_r ~ M
__O ~_D W o M__
n~
2.0~--~--~--~--~--~--~
as N-T ~ as N-T 650°C
-PWHT ~ -PWHT X3000h
] 1.5
en
Q)

~ 1.0
-J

(Therrno-calc.)
"E "E 0.5
::J
~ 1.0 o
E E
<t: -c
0.0 0.05 0.78 0.05 0.78 0.05 0.78 0.0 0.05 0.78 0.05 0.78 0.05 0.78
f\,1n ('!nnt,.::mt (m~~~o/,.) Mn content (mass%)

Fig. 3 Effect of Mn content on precipitates of M23C6 and Laves phase after ageing at
650°C

improve the creep rupture strength through stabilisation of M23C6 carbide


where B enters C site of M23C6 in place and forms M23(C,B)6 instead.l?

Effect of Alloy Elements on Microstructure and Toughness


In order to obtain enough toughness, it is of great importance to suppress
a-ferrite formation by controlling the balance of Q former elements and "I

former elements in adjusting of chemical composition.l! Cr equivalent is well


known for predicting the 8-ferrite formation of high Cr steels.F while a new
parameter Md which is also a method based on electron theory for predicting
it has been proposed.P
DEVELOPMENT OF 12
%
CR HEAT RESISTANT STEEL PLATE 55

Cr equivalent = Cr+6Si+4Mo+l.5W+11V+5Nb+12S.Al +8Ti


-(40C+30N+2Co+Cu+4Ni+2Mn) (mass'ze) (1)
Md= 0.825Fe+l.034Si+0.854Mn+l.059Cr+l.663Mo+2.335Nb+l.610V
+ 1.836W-0.230C+0.637Cu +0.661Ni +0.755Co-0.400N (at.%) (2)

15 ~~ 15
~~
$
·c
~
~ 10 ~ 10
Go Go
0 0
(5 (5
0 0
c: c:
0
.2 o oQJ 0 o@oo
t) 5 U 5
0 0
~ ~
Q) 0 Q)

E E
::s ::s
(5 0
0
> 1 11 12 13 14 > 0.851 0.852 0.853 0.854 0.855 0.856
Cr equivalent (masses) Md

Fig. 4 Effect of Cr equivalent and Md on volume fraction of 8-ferrite

Figure 4 shows the relationship between Cr equivalent and the volume


fraction of 8-ferrite, and between Md and the volume fraction of 8-ferrite.
Both parameters have good correlations with the 8-ferrite fraction respec-
tively, where it becomes volume below 1 vol.': when Cr equivalent is less
than 9 mass'zs, or when Md is less than 0.852. Figure 5 shows the effect of the

3.0
~
(J) 2.0
(J)
en 0.001
5 1.0

"*E
"0

0.0 fI.-.::::::::===:---- __ ~o.ooo~~====------


>
.~ -1.0
Q)
-0.001
~ -2.0

0.1 0.2 0.3 0.4 0.5 0.6 0.1 0.2 0.3 0.4 0.5 0.6
.6.M (rnassss) .6.M (masses)

Fig. 5 Effect of alloy element on Cr equivalent and Md

alloy elements on the Cr equivalent and Md. As is clear from the figure, W
addition increases both the Cr equivalent and Md, which promote to form
8-ferrite. Therefore 'Y former element such as Cu or Ni must be increased
when W content is increased under 12%Cr-0.2%Si.
56 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

It is of interest that Mn has no influence on the o-ferrite formation accord-


ing to Md on the contrary to the fact that Mn is considered to suppress
the 5- ferrite formation by the judgment from Cr equivalent. In fact, fully
tempered martensitic structure was obtained in this experiment for
the steel with 0.05 mass" Mn content where Md is equal to 0.852 and Cr
equivalent is 10.82 mass? where o-ferrite might not exist from the Md but do
exist from Cr equivalent. Consequently, the parameter of Md is more useful
for predicting the 5-ferrite formation rather than Cr equivalent especially
aboutMn.

o
1U
o~ 1t1
>-
o >-
C)
Q5
e>
Q)
c c
w W
u ~o u
Q)
o
-e
Q)
00 .c @~N-T-PWHT
(5
a
UJ
.c _&_!~r~~~ _ UJ
.c A\ Target
-----------
e--------__ 600·CX104h
----------------.--------------
« «
10 11 12 13 3
Cr (mass%)

Fig. 6 Effect of Cr and W content on Charpy impact property

Figure 6 shows the effect of Cr and W contents on the notch toughness of


12%Cr steels consisting of fully tempered martensitic structure. Absorbed
energy at DoCin Charpy impact test has a tendency to decrease as increasing
Cr and W contents. When W content is below 1 mass? where Cr content is
fixed 12 mass'zs, absorbed energy at DoCis much higher than 20 J, which is the
minimum value required, even if after ageing at 600°C for 104 hours.
It is well known that W promotes the precipitation of coarse Laves phase
during ageing or creep, where Laves phase mainly precipitates along the
previous austenite grain boundaries, thereby resulting in poor notch tough-
ness after ageing or creep.
Figure 7 shows the quantitative phase analysis 9 results of Laves phase of
steels with 1% and 2%W after ageing at 550-650°C for 104 hours in contrast to
the calculated equilibrium quantities of precipitates using Thermo-Calc (a
software for thermodynamic calculations). The quantities of Laves phase after
ageing increases with increasing W content especially at 650°C. According to
this calculation, Laves phase of steel with 2%W will be predicted to increase
more after ageing more than 104 hours. It is suggested that an excess W
addition is effective to improve creep rupture strength on the one hand, but
brings about deterioration of notch toughness after a long term ageing more
than 104 hours on the other hand.
DEVELOPMENT OF 12%CR HEAT RESISTANT STEEL PLATE 57

~
~ O.SMo-1.9W-2Cu
~ 3.0 o-

S :::?'- , , , , ,
Q) Calculated
~ 2.0 by Thermo-Calc
s:
o,
~
en
~ 1.0
ctS
-l

o.o~~~~~~~~~~~~~~~~~
450 500 550 600 650 700 750 800
Temperatu re (OC)
Fig. 7 Precipitated Laves phase after ageing for 104 hours

Effect of Alloy Elements on Hot Workability


As mentioned above, in order to avoid 8-ferrite formation, the addition of 'Y
former elements such as Cu, Ni, Co, N is necessary. When considering these
elements, Ni and Co cannot be added so much because Ni reduces ACl
temperature and Co is expensive. Furthermore, C and N tend to reduce
weldability and N content is also limited from the standpoint of manufactur-
ing process. In contrast, Cu is only an useful 'Y former element in this case, as
long as Cu is added to the extent where scratch and crack do not occur on the
plate surface during fabrication. Figure 8 shows the effect of B on the
reduction of area in high temperature tensile test. The figure indicates that the

100
;g
0
1Cu-1W
80 (0.003S)
ctS
~
Q)
(0.001 S)
«
"I-
60
a
c
a 40 (0.003S)
U::J
"0

Q)
a: 20
Heating:1250°C - Test: 1OOO°C

00 0.002 0.004 0.006 0.008 0.01


B (rnassss)
Fig. 8 Effect of B content on hot workability. (High temperature tensile test)
58 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

excess B addition reduces the hot workability, however B content less than
0.005 mass? doesn't reduce hot workability in the case of 1 mass') Cu
content. Moreover, S level was reduced as low as possible since it is well
known that S is harmful to hot workability.

ALLOY DESIGN CONCEPT OF TEMPALOY F-12M STEEL PLATE

On the basis of test results in terms of steam oxidation resistance, creep


rupture strength, toughness not only after PWHT but also after a long term
ageing, workability, weldability, and further cost performance, a new 12 Cr %

steel plate was developed and named TEMPALOY F-12M consisting of


12Cr-0.2Si-0.7Mo-1W-1Cu-0.1Mn-0.00SB-Nb-V-0.07N.

• High steam oxidation resistance -- High Cr (12%Cr-O.2%Si)

S
• High creep rupture 1preciPitation strengthening -- Nb, V, N
strength Solid solution strengtheningz Mo, W
Stabilisation of carbides Low Mn, B addition
• Good toughness 1suppreSSion of 8 -ferrite Balance of a formaer
and y former elements
(Md value<O.852)
Suppression of Laves phase Limitation ofW,Si

• Good hot workability Limitation ofCu, S, B


• Good weldability C~O.20%

~ I 12Cr-O.2Si-O.7Mo-lW-lCu-O.lMn-O.OOSB-Nb-V-O.07N I
Fig. 9 Alloy design concept of TEMP ALOY F-12M steel plate

Figure 9 shows the alloy design concept of TEMPALOY F-12M steel plate.
To begin, Cr and Si contents were fixed 12 mass': and 0.2 mass" respectively
to obtain high steam oxidation resistance at high temperature through the
preconsideration. From the standpoint of the creep rupture strength, proper
amount of Nb, V and N are necessary to utilise precipitation strengthening of
Nb, V carbonitride, and Mo and Ware added for solid solution strengthening
or stabilisation of carbide, and Mn is limited below 0.2 mass'l and B is added
for stabilisation of carbide.
With respect to the notch toughness on the other hand, the microstructure
must be controlled to be fully tempered martensitic structure not including 8-
ferrite associated with the deterioration of notch toughness by controlling the
balance of a former elements and ~ former elements according to the Md
DEVELOPMENT OF 120/oCR HEAT RESISTANT STEEL PLATE 59

parameter. Cu, Band S contents are also adjusted in order not to impair hot
workability necessary during plate fabrication and hot bend working.
Both of Wand Cu content were set 1 mass" where W is not so high level in
order to obtain good toughness and workability under 12 mass% Cr content.
It is noted that high creep rupture strength can be obtained by low Mn and B
addition instead of excess W addition more than 1 mass%. B content is set
0.005 mass% which is effective to improve creep rupture strength without
reducing hot workability.
Decreasing Mn content is also effective to improve creep rupture strength
without promoting 8-ferrite formation. In addition, the further improvement
of long term creep rupture strength is expected by heat treatment at a higher
temperature 11,14 because decreasing Mn content raises Acl temperature. In
this experiment, decreasing Mn content from O.B mass'zs to below 0.2 mass?
raises Acl temperature by approximately 30°C.

EXAMPLE PROPERTIES OF TEMPALOY F-12M STEEL PLATE

Test Materials
Table 2 shows the chemical composition of the developed steel plates
examined. Steel A and B with 20 mm in thickness were manufactured by a

Table 2 Chemical composition of developed steels examined (mass'zs)

Steel C Si Mn P S Cu Ni Cr Mo W V Nb B N

A 0.16 0.19 0.07 0.009 0.003 1.01 0.30 11.8 0.72 0.98 0.26 0.10 0.009 0.082
B 0.16 0.22 0.05 0.010 0.001 0.99 0.30 12.0 0.70 0.95 0.25 0.10 0.005 0.074
C 0.15 0.20 0.08 0.010 0.001 0.97 0.34 12.0 0.69 0.89 0.24 0.11 0.006 0.078
D 0.12 0.19 0.16 0.013 0.001 1.04 0.34 11.6 0.57 1.04 0.25 0.06 0.004 0.071
Steel A, B: Laboratory-produced (20 mm thick plate)
Steel C: Mill-produced (50 mm thick plate)
Steel D: Mill-produced (65mm thick plate)

laboratory melting (50 or 150 kg). Steel C and D with 50 and 65 mm in


thickness were manufactured by a commercial scale melting by electric
furnace (50 ton). The steel plates were normalised at 1080°C and tempered at
7BO-BOO°C, and then PWHT was conducted at 740°C for B hours to the test
materials.

Strength, Toughness and Microstructure


Table 3 shows the mechanical properties of the developed steel plates after
PWHT. All steel plates exhibit high 0.2% proof strength, high tensile strength
60 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Table 3 Mechanical properties of the developed steels

Tensile properties Toughness

Steel 0.20/0PS TS El. vE (DOC)


(MPa) (MPa) (%) (J)

A 589 771 24.6 57,51,49


B 634 812 22.5 76,64, 78
C 563 754 26.4 46,52,46
D 606 773 24.6 79,65,68
Spec. (Target) ~470 ~685 ~18 (~O)

(1/2t, L-direction)

and sufficient elongation which are satisfied with the specification listed in
the Table 3. The steels also have sufficient absorbed energy at O°Cin Charpy
impact test. Figure 10 shows an example of microstructure consisting of fully
tempered martensitic structure.

Fig. 10 Optical microstructure of developed steel (steel B, 1/2t)

Steam Oxidation Resistance


Figure 11 shows the steam oxidation resistance of Mod.9Cr-1Mo steel (ASTM
A 387 Gr.91), the developed steel (TEMPALOY F-12M) and SUS 304 steel at
650°C. The scale thickness of developed steel by steam oxidation after the
exposure at 650°C for 1000 hours is approximately 60 f.LID which is smaller
than that of Mod.9Cr-lMo steel, around 150 urn. It is obvious that the steam
oxidation resistance of the developed steel is improved upon Mod.9Cr-lMo
steel. Figure 12 shows a cross section microstructure of the scale of Mod.9Cr-
IMo steel and the developed steel. The scale of both steels was characterised
by two layers structure, and no exfoliation was occurred. Outer layer of the
DEVELOPMENT OF 12%CR HEAT RESISTANT STEEL PLATE 61

-E
~150
en
en
Q)

~100
o
:c
I-
0>
(ij 50
o
C/)

o L-..I.---'-'~
A 387 Gr.91 TEMPALOY F-12M SUS304
Fig. 11 Steam oxidation property

A 387 Gr.91 TEMPALOY F-12M

Fig. 12 Optical microstructure of scale by steam oxidation (650°C X SOOh)

scale is made of oxide containing mainly Fe, and inner layer of the scale is
made of oxide containing enriched Cr and Si by EPMA analysis. Especially,
the concentration of Cr and Si into the inner layer is remarkable for the
developed steel. It is concluded that the steam oxidation resistance of the
developed steel, which contains higher Cr than that of Mod.9Cr-1Mo steel, is
improved by forming stable oxide layer including Cr enriched in the inner
scale.

High Temperature Strength


Figure 13 shows the high temperature tensile strength of developed steel as
compared with Mod.9Cr-1Mo steel (ASTM A 387 Gr.91). The developed steel
62 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

o TEMPALOY F-12M
/:}. A 387 Gr.91
o
o
A
A

Q)

~200
c
Q)
~
o~~~~~~~~~~~~~~~
o 100 200 300 400 500 600 700 800
Temperature (OC)
Fig. 13 High temperature tensile properties

500~~~~~~~~~~~~~~~
400
300 ---__

*1~~
~
C/)
70-
60
50
40
30~~~~~~~~~~~~~~~
4
102 103 10 105
Rupture Time (h)
Fig. 14 Creep rupture properties

has higher tensile strength than that of Mod.9Cr-lMo steel for all tem-
perature ranges tested. Figure 14 shows the creep rupture strength of the
developed steel at the temperatures between 550°C and 700°C as compared
with Mod.9Cr-lMo steel. Figure 15 indicates the maximum allowable calcu-
lated from the high temperature properties including the data above. The
maximum allowable stress of the developed steel is higher than that of
Mod.9Cr-IMo steel at any temperature, and it is more than 1.3 times higher
as compared with Mod.9Cr-lMo steel above 600°C.
DEVELOPMENT OF 120/0CR HEAT RESISTANT STEEL PLATE 63

en
en
~
Q)

00100
Q)
::cro
~
.Q
«
E
::l
E
.~
100 200 300 400 500 600 700 800
~
Temperature CC)
Fig. 15 Maximum allowable stress

Other Properties
When manufacturing welded pipes with large diameter and thick wall, good
workability is required. The developed steel has approximately 10°/0 uniform
elongation which is sufficient to fabricate pipes by cold bend working, and
exhibits higher values more than 75°/0 in terms of the reduction of area in the
high temperature tensile test above 800°C which indicates that the steel has
sufficient hot workability to fabricate pipes by hot bend working.
As far as weldability is concerned, the preheating temperature of the steel
to avoid cold cracking was determined 175°C in the case of 50 mm thick plate.
As a result, it is noted that the developed steel has good cold crack resistance
comparable with Mod.9Cr-lMo steel.
With respect to the notch toughness after a long term ageing, absorbed
energy at O°C in Charpy impact test after 104 hours at the temperatures
between 550°C and 650°C is higher than 20 J. It can be said that the developed
steel has enough toughness for use.

CONCLUSION

12°/oCr heat resistant steel plate (TEMPALOY F-12M) containing O.7Mo-


1W-0.IMn-B-Cu-Nb-V-N was newly developed, which is applicable to
the reheat steam pipes and headers with large diameter and thick wall of USC
boiler. The steel has high steam oxidation resistance and creep rupture
strength more than 1.3 higher as compared with Mod.9Cr-1Mo steel (ASTM
A387 Cr.91) above 600°C, which is attributed to strengthening by lower Mn
and B addition as well as precipitation strengthening of Nb, V carbonitride
and W strengthening. In addition, the steel plate consisting of fully tempered
64 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

martensitic structure exhibits enough notch toughness after not only PWHT
but also a long term ageing, and good hot and cold workability and
weldability. It is strongly expected that this plate is applied to the reheat
steam pipes and headers of future plants.

REFERENCES

1. F. Masuyama: Tetsu-to-Hagane, 1994, 80, 587.


2. K. Hayashi, T. Kojima and Y. Minami: CAMP-lSI!, 1996, 9, 1318.
3. K. Hayashi, T. Kojima and Y. Minami: CAMP-lSI!, 1997, 10, 527.
4. K. Hayashi, T. Kojima and Y. Minami: CAMP-lSI!, 1997, 10, 1257.
5. K. Ryuu, T. Fujita: Tetsu-to-Hagane, 1987, 73, 1034.
6. K. Kimura, R. Ishii, T. Matsuo and M. Kikuchi: Report of the 123rd
Committee on Heat-Resisting Materials and Alloys, Japan Society for the
Promotion of Science, 1993, 34, 127.
7. Y. Tsuchida, K. Okamoto and Y. Tokunaga: lSI! International, 1995, 35, 317.
8. M. Igarashi and Y. Sawaragi: Report of the 123rd Committee on Heat-
Resisting Materials and Alloys, Japan Society for the Promotion of
Science, 1996, 37, 77.
9. H. Kutsumi, A. Chino and Y. Ishibashi: Testu-to-Hagane, 1992, 78, 594.
10. N. Takahashi, T. Fujita and T. Yamada: Tetsu-to-Hagane, 1975, 61, 2264.
11. A. Toyama, Y. Minami and Y. Ishizawa: CAMP-lSI!, 1993, 6, 1638.
12. P. Patriaca, S. Harkness, J. Duke and L. Cooper: Nuclear Technology, 1976,
28, 516.
13. H. Ezaki, M. Morinaga, K. Kusunoki and Y. Tsuchida: Tetsu-to-Hagane,
1992, 78, 1377.
14. H. Hayakawa, A. Yoshitake and M. Tamura: CAMP-lSI!, 1988, 1, 924.
The Commercial Development and
Evaluation of E911, A Strong 90/0
CrMoNb VWN Steel for Boiler Tubes
and Headers
J. ORR*, L. w. BUCHANANt and H. EVERSON§
* British Steel Swinden Technology Centre, Moorgate, Rotherham, South
Yorkshire S60 3AR, UK
t Mitsui Babcock Energy Limited, Technology Centre, High St, Renfrew, PA4
8UW, Scotland
§ British Steel Engineering Steels, PO Box 50, Aldwarke Lane, Rotherham,
South Yorkshire S60 IDW

ABSTRACT
The steel E911 (9% Cr, 1% Mo, 1% W + Nb + V + N) developed through an
experimental programme supported by ECSC funding is now an industrially
established steel. Tubes and pipes made from continuously cast billets have been
manufactured. Long-term testing, which is still continuing, demonstrates that E911
has a significant strength advantage over Steel 91, derived from the optimised
precipitation strengthening of VN and additional solid solution strengthening by
tungsten. Metallographic data demonstrate the stability of the microstructure and
therefore the long term strength of E911.
The commercial products made from this steel have been subjected to various tests
to assess its suitability for application in high temperature, high pressure boiler
systems. The paper reports on the success in developing welding consumables. The
creep rupture properties of the complete weldment have been assessed to determine
boiler component service and fabrication parameters. The effect of cold work on
creep properties and the material behaviour with respect to stress corrosion cracking
resistance have also been determined. Stress corrosion data for E911 in as-welded
and post weld heat treated conditions demonstrate that it can be fabricated easily
and used safely.
Preliminary results from a parallel programme involving the fabrication of a trial
header by conventional methods and by HIPping are encouraging.

1. INTRODUCTION

Several new steel grades, based on 9-12% Cr. have been developed in recent
years. The first of the series was Steel 91, developed in about 1985.1 The 'new'
steels were developed to meet the proposed demand by power generation
companies to increase efficiency by burning less fossil fuel, principally coal,

65
66 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

and thereby reduce costs and also meet the increasingly stringent environ-
mental requirements. The fact that in Europe, principally in the UK, these
latter requirements have been met over the last 5-10 years by gas burning
power stations, has not minimised the global requirements on power genera-
tion companies. This is because, in the longer term and especially world wide,
fossil fuelled power plants, burning coal (or coal-like substances), will
dominate in the power generation market.?
This paper describes the development and evaluation of fabrication and
manipulation processes of a steel, designated E911, which has been developed
by European steelmakers, tested and evaluated by boiler makers, welding
engineers and fabricators, with the aim of codifying the steel and its
properties for use as boiler tubes and headers.
The work described in this paper has been part-sponsored by the Energy
Technology Support Unit (ETSU) of the UK Government, Department of
Trade and Industry.

2. THE WHY AND HOW OF FERRITIC STEELS

Ferritic steels, or more strictly those with a tempered martensitic structure are
cost competitive and offer more flexibility in operation, than other high
strength steels which have austenite as the basic microstructure. The 9-12%
Cr based steels offer improved creep and fracture toughness over the low
alloyed steels still used extensively in power generation components. Their
higher creep strengths offer the possibility of achieving power generation at
higher efficiency levels than in current solid fossil fuel fired units.
Although, even higher creep strength and fracture toughness are available
from austenitic steels, some of their physical property characteristics, princi-
pally the lower thermal conductivity and higher coefficient of expansion
relative to ferritic steels, mean that thick section boiler components cannot be
operated with maximum flexibility if made in such steels. Austenitic steels
have a relatively expensive alloy content and a more costly conversion route
to tubular products.
Such developments do not only entail increasing the chromium content, say
from that of 2.25% Cr 1% Mo steel, to provide increased oxidation resistance,
hardenability and temper resistance, because by so doing the gamma loop in
the Fe-Cr-C diagram closes, thus leading to the possibility of forming delta
ferrite at critical processing temperatures. Hence, a careful balance of ferrite
forming and austenite forming elements is required to achieve a satisfactory
solidification process, a fully austenitic and hot workable microstructure at
primary processing, tubemaking and normalising heat treatment tempera-
tures and also to provide high creep resistance.
The key elements to be considered, apart from chromium, are carbon,
nitrogen, vanadium and tungsten.? The addition of a small amount of
THE COMMERCIAL DEVELOPMENT AND EVALUATION OF E911 67

niobium «0.1%) helps to achieve a fine prior austenite grain size for
normalising temperatures up to 1150°C,4 which promotes high toughness.
However, in weldments it seems that niobium is the principal element that
leads to lower toughness.f
Taking all these factors into consideration, the typical composition for E911,
within the ranges established by electric arc steelmaking, Table l(a) is just

Table lea) Compositions of E911 Steels

C Si Mn P S Cr Mo Ni Nb V W N

Likely 0.10 0.10 0.30 - 8.50 0.90 - 0.06 0.15 0.90 0.050
Range 0.13 0.30 0.60 0.020 0.010 9.50 1.10 - 0.10 0.25 1.10 0.080
Typical 0.11 0.20 0.45 0.015 0.005 9.00 1.00 0.20 0.08 0.20 1.00 0.060

within the acceptable envelope for efficient steelmaking and tubemaking.


This is characterised by the arithmetic difference between the weighted effects
for the ferrite and austenite forming elements, (also known as chromium and
nickel equivalent values, respectively). The difference for steels such as E911
lies in the direction of the chromium equivalent value(s) and hence the
positive numbers in Table l(b). Whilst there are several formulae available for

Table Ifb) Ferrite and Austenite Forming Calculations


(i) Schneider:

Cr + 2Si + 1.SMo + SV + 1.7SNb + 0.7SW - Ni - O.SMn - 30C - 2SN - O.3Cu


For E911 sum = + 7.6%
(I) Schaeffler:
Cr + Mo + 1.SSi + O.SNb + 0.7SW + SV + Ni - O.5Mn - 30 C - 30 N - O.3Cu (- Co)
For E911 sum is = + 6.6%
(iii) Newhouse:
Cr + 6Si + 4Mo + 1.SW + 11V + 5Nb - 40C - 30N - 2Mn - 2Co
For E911 sum = + 11.2%

such calculations, the results of which are indicated in Table 1(b), the most
generally used of these calculations is that attributed to Schneider, which
predicts the effects on the microstructure as shown in Fig. 1. Others shown in

Table l(c) E911 Weld Metal Composition

C Si Mn P S Cr Mo Ni Nb V W N

0.11 0.20 0.61 0.007 0.003 8.71 0.95 0.77 0.046 0.20 0.94 0.055
68 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

12

Aust + Mart

10

Ni
Equivalent
6

0
8 10 12 14 16 18 20

Cr Equivalent
BASE

A = -Nb C1 = +1.0 Co
B = E91l Match C2 = +1.7 Co
N1 = +0.5 Ni C3 = +2.2 Co
N2 = +0.8 Ni NCl = +0.5 Ni + 1.1 Co
N3 = +1.2 Ni NC2 = +0.9 Ni + 1.2 Co

Fig. 1 E911 weld metals (Schneider - see Table 1(b))

Table l(b), although giving different positive numbers, are modifications on


Schneider, produced to meet particular requirements. The Newhouse equa-
tion is used often in Japan and parts of Continental Europe. The Schneider
equation and diagram has been used in other sections of this paper.

3. MANUFACTURE AND EVALUATION PROGRAMME FOR E911


STEEL

The E911 steel composition was derived using funding by the European
Coal and Steel Community." Many steel compositions were tested and
the then optimum was found to be that of E911 (European 9% Cr, 1% Mo,
1% W).
Up to date four production casts of E911 steel have been produced ranging
from 25 to 90 tonnes. In the UK, the steel has been successfully produced by
continuous casting, thus leading to further cost efficiency.
The products of the E911 casts range from tube and pipe sizes of 31.8 X 5 to
THE COMMERCIAL DEVELOPMENT AND EVALUATION OF E911 69

490 X 70 mm (these representing the outside diameter and wall thickness of


the products respectively). The products were all made by hot deformation
processes in tube mills of British Steel, Dalmine, Mannesmann and Vallourec.
The products have been evaluated in several pan-European programmes,
under the umbrella of COST 501 (1993-1997), in which the UK programme
which forms the basis of this paper, was included.
The UK programme partnership, Table 2, with financial support from

Table 2 E911: UK Evaluation Programme-


,Advanced Cycle Component Testing (ACCT),
Lead Company: Mitsui Babcock Energy Limited
Partner Companies: British Steel plc
- British Steel Engineering Steels
- Swinden Technology Centre
Metrode Products Limited
Financial Assistance: Energy Technology Support Unit

ETSU, used the commercially produced tube and pipe sizes 44.1 X 7.1 mm
and 127 X 19 mm, heat treated by normalising from 1060 to 1100°C followed
by a stabilising temper at 760°C (Fig. 2). Lower tempering temperatures were
not considered, because for boiler components stress relieving/post weld
heat treatment temperatures, for steels such as E911, are typically around
750°C. (See Section 4.2.1).
The scope of the evaluation programme is shown in Table 3. The results
described in the following section are augmented by those measured for E911
steel components tested in other European countries in the COST 501
programme.

4. RESULTS OF EVALUATION PROGRAMME

4.1 Time Independent and Time Dependent Properties


Tensile properties have been established over the range ambient to 600°C and
stress to rupture properties, mainly at 600° and 650°C, but with other COST
501 programmes providing some data at 550, 575, 625 and 675°C. These data
all relate to isothermal constant load tests, but some iso-stress testing over the
range 600-700 C using stress values of 120 and 100MPa was included in the
D

COST 501 programmes.


Summaries of the UK and COST 501 data are shown in Figs 3 and 4. The
total data available have been assessed by recognised European procedures/-f
to determine minimum values for 0.2% proof strength and average values for
70 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

X
, ,
X
°c
NI060

HV30 0--- NII00


'\~O

\0\ 0
X \

\\
350
X \

\ 0
>sc \

~O\
XX\
300

250

17 18 19 20 21 22

Fig. 2 E911 tempering curves

stress rupture strength - these being the normal bases for design strength
values in codes. The outcomes of these assessments are shown in Table 4 and
Fig. 5, in comparison with similarly determined values for Steel 91 and 12%
CrMoV.
THE COMMERCIAL DEVELOPMENT AND EVALUATION OF E911 71

Table 3 Advanced Cycle Component Testing - Programme of Work


Task 1: (i) Manufacture of steel and tubes and pipes.
(ii) Heat treatment.
(iii) Stress rupture testing of heat treated tube and pipe at 600-650°C.
Task 2: (i) Weld metal development.
(ii) Manufacture weldments.
(iii) Cross-weld tests of weldments.
(iv) Determine effect of cold work.
Task 3: (i) Low cycle fatigue testing.
Task 4: (i) Manufacture welded header.
(ii) Manufacture E911powder.
(iii) HIP model header production.
(iv) Test and evaluate headers.
Task 5: (i) Manufacture weldments (see 2(ii».
(ii) Stress corrosion testing of as-welded and post weld heat treated materials.
Task 6: Evaluate and report all results.

RpO.2 700

2
N/mm
ZZZ} Cost 501 Data

600
• Steel 91 - Min . Values

500

400

300 Min.Values
E9l1
(Table 4.1)

a 200 400 600

Fig. 3 0.2%proof strength values

The data in Fig. 5 show that the strength of E911 steel at elevated
temperatures is significantly above that for Steel 91 and 12 CrMoV steel and
hence offers economic benefit to the users of E911 steel.
The data in Table 4 and Fig. 5 form the basis for the information required
72 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

x 0 B.S. Data

Cost 501

Mean Values (Table IV.2)

[] HIPped Bar

300

200 x

100

60

40

100 1000 10000 Hrs.

Fig. 4 E911 creep rupture data

for codification of this steel and thus allow it to compete fairly with the
P92/NF616 steel for which ASME Code Case 21799 applies.

4.2 Fabrication of E911


4.2.1 Welding
For 9-12% Cr alloy steels, it is generally accepted that weld consumables of
matching composition to the parent material should be used. Work on the
development of consumables for Steel 91 provided the basis for the develop-
ment of E911 consumables.'? For weld metal of the 9 CrMo + alloy type, the
requisite time independent (tensile) and time dependent (creep) properties
can be obtained fairly easily by control of the stress relieving/post weld heat
treatment temperature, but the subsequent effects on toughness and ductility
require more detailed attention. Hence for the development of an E911
consumable, particular attention was given to these properties, since stress
relieving can be achieved at ~750°C which is sufficiently below the ACI
temperature for E911 steel.
THE COMMERCIAL DEVELOPMENT AND EVALUATION OF E911 73

Table 4
4.1 Minimum 0.2% Proof Strength Values
For a room temperature minimum value of 470 MPa the following minimum values at
elevated temperatures are indicated:

°C 100 200 300 400 500 600

MPa 445 425 410 395 365 285

4.2 Average Stress Rupture Strength Values

MPa at durations (h)

°C 1000 3000 10000 30000 100000

550 240 225 209 194 176


575 206 191 175 159 141
600 173 158 141 124 106
625 141 125 108 92 76
650 110 95 80 68
675 83 71

300

N/mrn2

200

100

o
200 400 600
Temp. °c
Fig. 5 Design type curves
74 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Recognising that niobiumf and possibly tungsten in E911 might reduce the
toughness of weld metal, alloy development was concentrated on counter-
acting such effects. Thus additions of up to 1 nickel to improve toughness
%

and up to 2% cobalt to maintain a high enough AC1 temperature to allow


effective stress relief, individually and in combination, were investigated, see
Fig. 1.
Various sorting tests indicated that compositions containing cobalt did not
offer any significant advantages and that the optimum composition for
toughness and ability to stress relieve at -7S0°C, was the base composition
(see Table l(a)) with an increase in nickel to -0.7% i.e. similar to N2 in Fig. 1.
The optimum weld metal composition is shown in Table l(c).
Weld metal toughness is also sensitive to welding heat input, welding
process and the post weld heat treatment time (at 750°C for E911). A preferred
level of weld metal toughness, as defined by COST 501 is 50 J minimum at
ambient temperature (+20°C). For E911 weld metal, impact transition data
show that this can be achieved with a combination of a moderate heat input,
e.g. 1.2 kjmm", and a post weld heat treatment time of 2 hours. Welding with
higher heat input, e.g. 2.1 kjmm :t, can still achieve the desired toughness but
longer post weld heat treatment times are required, possibly up to 10 hours.
Thus the preferred welding condition is to use a moderate heat input which
allows short heat treatments to attain adequate toughness in the weld metal.
This then gives the optimum economics for fabrication.
Cross weld stress rupture tests on weldments using filler metal N2,
produced strengths from those similar to parent metal in short durations at
600-625°C (where fracture locations were at the parent/weld interface), to
reductions of strength of up to 30% at longer durations and at higher
temperatures. Such shortened durations are associated with fractures in the
'Type IV' position, i.e. that part of the HAZ where inter-critical zone
temperatures were experienced resulting in partial transformation and tem-
pering. These effects are demonstrated in Fig. 6. Results from tests up to
10 000 hours do not indicate any effects related to the welding process or the
consumable used.
The strengths of dissimilar metal welded joints, using E911 and austenitic
steel (Esshete 1250) are being assessed by 'pressure bottle' testing. The test
variables include internal pressure, end-load and weld metal (INC082 and
INC0625). The early failures in this test programme were at the 'Type IV'
position but could not be related to the weld metal type. Long term tests are in
progress.

4.2.2 Cold Bending


The assessment of the effect of 15% cold work, to simulate cold bending or
manipulation of tubes, shows that the stress rupture strength is reduced by
approximately 100/0over the range 600-650°C, see for example Fig. 6. This
behaviour is similar to that reported for both Steel 9111 and P92 steel.
THE COMMERCIAL DEVELOPMENT AND EVALUATION OF E911 75

100 1000 10000 100000


Hours

Fig. 6 E911 stress rupture - 625°C

4.2.3 Stress Corrosion Cracking


Stress corrosion cracking is of concern for some high strength martensitic
steels, because of the risk of cracking of the untempered martensite present in
the HAZ regions after welding.
Laboratory stress corrosion tests in water and saturated water vapour, have
been carried out on E911 weld metal and HAZ material, to rank these against
the performance of other power generation materials. Although some crack-
ing was observed in the laboratory results for E911 weld metal, this was less
severe than that for Steel 91. Experience with Steel 91 has shown that this can
be fabricated without risk of stress corrosion cracking after welding. There-
fore, it is concluded that for E911 weld metal a similar situation will exist.
Furthermore, since no cracking was observed in the laboratory for post
weld heat treated material, there is no risk of stress corrosion cracking during
service.

4.2.4 Model Headers


The possibility of eliminating welding by the use of hot isostatic pressing
(HIPping) for complex shaped components, potentially offers significant
advantages to the boiler maker/fabricator and user, in terms of cost, manu-
facturing time and reduction of stress concentration effects.
Therefore, to assess the potential for E911 material, two simple header
T-joint type components were made by a conventional manufacturing and
fabrication route and by HIPping (from powder made from the same base
material as the rolled pipe and welded header). These are on test at 600°C and
76 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

internal pressure of 273 bars (which creates a hoop stress of 77 MPa). No


failure has been observed for durations up to -4000 hours.
The stress rupture strength of HIPped bar material from the same source, is
similar to that of rolled bar material, (see Fig. 4).

4.3 Stability of Microstructure


Long term (100 000 hours) stress rupture values have been determined by
parametric data assessment procedures." to produce the values as in Table 4.
However, it could be concluded from Fig. 4 that the test data durations may
not yet be sufficient to fully support the longer term predicted stress values of
Table 4(b). Whilst this is recognised, and test programmes are in place within
the COST 501 Round III WP11 consortium to generate longer term data, other
means may be required to confirm the results of the parametric data
assessment to convince the potential users of E911 steel of its suitability.
Of note is the good agreement between the test data and the predicted
stress values, both in terms of position and trend, over the range of
temperatures shown in Fig. 4.
Examination of a section of the available data, by an independent assessor
and by other testing, resulted in a predicted stress value for 600°C - 100 000
hours of 105 MPa,12 which is close to that shown in Table 4.
The reliability of the values in Table 4 may also be confirmed by consider-
ing the detailed microstructure, of creep/time exposed materiaL Examples of
the microstructure of E911 material tested for -18 000 hours at 600°C are
shown in Fig. 7.
The particular features illustrated, which demonstrate the stability of E911
material, are:

- the tempered martensite structure is still evident in the lath structure and
remanent high dislocation density, Fig. 7(a).
- some recovery has occurred, but movements of boundaries are pinned
by the large number of small/intermediate sized particles, Fig. 7(b).
- M23C6 carbides produced during tempering remain fairly stable in size
and composition over long time periods.' Figs 7(c) and 8. Thus alloy
transfer from the matrix and therefore out of solid solution is not
significant.
- Laves phase does appear during test exposures at 600 (and 650°C4), Fig.
7(d). This is large and blocky and often directly associated with pre-
existing M23C6 particles. Examinations of the matrix adjacent to such
joint particles, indicates that the tungsten content has reduced from the
original 1 to around 0.5-0.60/0, Fig. 9.
%

- VN particles formed during tempering grow only very slowly and are
considered to be the principal precipitation strengthening agents in this
steel. 13
THE COMMERCIAL DEVELOPMENT AND EVALUATION OF E911 77

(a) General microstructure x28 000 (5319)

(b) Recovery & pinning particles x46 000 (5331)

Fig. 7 E911-17901 hours at 60QoC


78 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

(c) Small M23C6 particles x46 000 (5329)

(d) Laves phase + M23C6 particles x46 000 (5333)

Fig. 7 - continued
THE COMMERCIAL DEVELOPMENT AND EVALUATION OF E911 79

Cr Fe Mo W
X A 0 []
Alloy %
100

80
x
-----------------------X~
xx x~X
60

40

20

a
20 21 22 23
3
T(20+1ogt) x 10-

Fig. 8 M23C6 compositions

10

Tungsten
%

o Scan Distance S pm 10

Fig. 9 Tungsten in matrix and M23C6 (10 532 hr. at 650°C)


80 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

The metallographic data indicate therefore that although the tempered


martensite structure of E911 steel, as formed after normalising and tempering
at typically 1060°C and 760°C, respectively is not unexpectedly metastable,
the changes that occur during testing at 600-650°C do so quite slowly, with
the possible exception of the formation of the Laves phase.
Since Laves phase forms fairly quickly and without significant change in
composition+ as large particles, Fig. 7(d), it will not have any long term effect
on the creep strength after the initial decrease in the matrix content of
tungsten - see above.
It may however, have some negative effect on impact toughness, but this is
not a significant concern in boiler tubes.
It can be concluded therefore, that E911 material, in terms of, precipitates
present, stability of their composition and alloy content of the matrix, quickly
reaches a state of pseudo-equilibrium. Some decay in strength over long
durations must be expected, as indicated in Fig. 4, but for E911 this seems to
occur only slowly over long durations at temperatures relative to its potential
service range. One further observation, not seen in Fig. 7, but shown in other
tested material of E911, is the indication that additional VN particles form
during service/testing at 600-650°C.4 These will counteract the natural
softening of the originally formed tempered martensite and thus lead to
slower decay in strength with time.
Therefore the long term strength values of Table 4, which currently
lie beyond the range of actual test results, may be used with the confi-
dence because of the form of the test data and the stability of the micro-
structure.

5. DISCUSSION AND CONCLUSIONS

The data and information presented in this paper, demonstrate that E911 steel
has a useful strength advantage over existing codified steels used in boiler
manufacturing (see Fig. 5). It therefore has the potential to offer significant
manufacturing and operating benefits to the power generation industry as it
strives to obtain higher efficiency in energy conversion and (thereby) meet the
growing environmental pressures towards lower emissions of such as SOx
and CO2. Any advantages of a new alloy steel must address its long term
stability, e.g. after >100 000 hours. The results of parametric assessments of
data for the range 550-675°C, Fig. 4 (and ref. 12) and the metallographic data,
as for example in Figs 7-9 indicate that E911 attains a state of pseudo-
equilibrium after only a short test/service period and seems likely to
maintain this condition. Hence the stress values in Table 4(b) may be used
with confidence. These data, with the supporting test data, as in Fig. 4, will
form a significant part of the data package being prepared on behalf of COST
THE COMMERCIAL DEVELOPMENT AND EVALUATION OF E911 81

501, (representing European material producers and manufacturers), to


ASME for Code approval for E911. This will facilitate the formal adoption of
this steel by fabricators and users. It can be stated with confidence, that more
and longer term stress rupture data exist for E911 than there were available
when the ASME Code Case was granted for 9Cr2W steel."
The requirement for weld consumables and the effect of the welding
process on the toughness and high temperature strength of E911 has been a
significant part of the development programme.
An optimised weld metal composition has been established (see Table l(c))
(N2 in Fig. 1), which in the weld produces adequate toughness and high
temperature strength initially compatible with the parent material, Fig. 6.
However, as test durations increase, a decrease in weldment strength in
uniaxial tests occurs, predicted to be ,...,30%less than that of the parent
material, as failures occur in the Type IV zone of the HAZ. However, this is
not as significant as it first appears because for boiler manufacturing and
operation, the stress system is principally in the hoop direction, with the
associated longitudinal stress being ,...,50%of that in the hoop stress direction.
Longitudinal welds are usually avoided where creep is the major design
consideration. It is also necessary that end or system loads, as created during
manufacture and/or service are minimised. This is to ensure that the axial
stress across circumferentially placed welds, does not increase that already
existing, i.e. the 50% of the hoop stress created by the internal pressure. Under
these circumstances, the decreased stress bearing capacity of welded joints, as
indicated in Fig. 6, is not a design/service limitation. It should be noted that
this situation applies generally for other ferritic/martensitic steels used- in
welded constructions in boilers operated at elevated temperatures. Therefore,
the parent material strength can be used as reference point for comparison
purposes, (see Fig. 5).
The other fabrication data relating to cold manipulation effects, Fig. 6 and
the limited risk of stress corrosion cracking indicate that E911 steel tubes and
pipes can be manufactured into power generation components, without resort
to special procedures. Thus, E911 is at least in a similar category to that of
Steel 91, but with higher creep strength. Furthermore, both of these steels are
much more tolerant to manufacturing and fabricating conditions than the
long established 'X20' type steel which is significantly lower in strength, Fig.
5.
The potential for fabrication of complex shapes by HIPping has been
demonstrated in the manufacture and testing of experimental model headers,
the results of which indicate no significant property variations arising from
the metallurgical differences from that of conventionally fabricated headers.
The performance of the latter under simulated service conditions (equivalent
hoop stress of 77 MPa at 600°C) is giving encouraging results, which supports
the potential of E911 as a boiler manufacturing material of higher strength
and similar fabrication response to that of Steel 91.
82 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

ACKNOWLEDGEMENTS

The authors thank colleagues in their companies for technical assistance and
in particular Metrode Ltd. for supply of welding consumables.
The authors acknowledge the permission of Dr. K. N. Melton, Research
Director, Swinden Technology Centre, British Steel plc, Dr. J. M. Farley
Technology Centre Manager, Mitsui Babcock Energy Limited and Dr. 1. G.
Davies, Technical Director, British Steel Engineering Steels to publish this
paper.
The total programme was supported by finance from the UK Government
Energy Efficiency Office.

REFERENCES

1. P. Patriarcha, S. D. Harkness, J. M. Duke and L. R. Cooper: 'US Advanced


Materials Program for Steam Generators', Nuclear Technology, March
1976, 28, 516-536.
2. Institute of Materials Report: Requirements for Materials Rand D for Coal
Fuelled Power Plant: Into the 21st Century, D. Allen, S. M. Beech, L.
Buchanan and J. Oakey eds. Presented at Institute of Materials Seminar,
29 January 1998.
3. J. Orr and D. Burton: 'A Study of the Basic Constitution of 9-11 % Cr Steels
for Elevated Temperature Service', European Coal and Steel Community
Report, EUR 15843-EN.
4. J. Orr and L. Woollard: 'The Development of 9% CrMo Steels from Steel 91
to E911', Microstructural Development and Stability in High Chromium
Ferritic Power Plant Steels, The Institute of Materials, 1997, 53-72.
5. J. F. King et al.: 'Weldability of Modified 9Cr - 1Mo Steel', Oak Ridge
National Laboratory Report 6299, 1986.
6. ECSC Information Day Report: 'The Manufacture and Properties of Steel 91
for the Power Plant and Process Industries', Dusseldorf, 5 November
1992, J. Orr, ed.
7. Draft European Procedure for Determination of Minimum 0.2% Proof
Strength Values (under preparation).
8. Appendix to ISO 6303: 1981: Pressure Vessel Steels not included in ISO 2604
Parts 1-6: Derivation of Long Term Stress Rupture Properties.
9. ASME Code Case 2179: 'Seamless 9Cr-2W Material Section 1', Approval
date: 8 August 1994.
10. G. M. Evans: COST 501 Round III WP11 - Boiler Group, Minutes of
Meeting in March 1994, Appendix 8.
11. A. Iseda, M. Kubota, Y. Hayase, S. Yamamoto and K. Yoshikawa:
'Application and Properties of Modified 9CrlMo Steel Tubes and Pipes
for Fossil Fuelled Power Plants', The Sumitomo Search No. 36, May 1988,
pp.17-30.
THE COMMERCIAL DEVELOPMENT AND EVALUATION OF E911 83

12. P. J. Ennis: 'The Long Term Creep Rupture Properties of 9-12% Chro-
mium Steels', Advances in Turbine Materials, Design and Manufacturing, A.
Strang, W. M. Banks, R. D. Conroy and M. J. Goulette, eds, The Institute
of Materials, 1997.
13. Z. Kuban, V. Foldyna and V. Vodarek: 'Analysis of Strengthening
Mechanisms in 9-12% Chromium Steels', Microstructural Stability of
Creep Resistant Alloys for High Temperature Plant Applications, A. Strang, J.
Cawley and G. W. Greenwood eds, The Institute of Materials, 1998.
Alloy Design of Advanced Ferritic
Steels for 650°C USC Boilers
F. ABE, M. IGARASHI, N. FUJITSUNA, K. KIMURA and
S.MUNEKI
Frontier Research Center for Structural Materials, National Research Institute
for Metals (NRIM), 1-2-1 Sengen, Tsukuba shi 305-0047, Ibwaki, Japan

ABSTRACT
The alloy design of tempered martensitic high-Cr steels with sufficient creep and
oxidation resistance has been carried out for application to thick section boiler
components of 650°CUSC plants. The analysis of long-term creep rupture data in the
NRIM Creep Data Sheet Project suggests that for the improvement of long-term
creep rupture strength of ferritic steels, the stabilisation of initial microstructure is
required for up to long times. Thermo-calc calculation shows that the addition of
high-Cr or high-Si for the improvement of oxidation resistance causes the formation
of 8-ferrite. Of the austenite stabilising elements, high melting point elements Ir, Rh
and Pd are promising for strengthening and stabilising the martensite matrix as well
as for suppressing the formation of 8-ferrite. The creep rupture strength of
O.OBC-9Cr-3.3W-VNbBN steels with 2 and 40/0 Ir was larger than that of the steel
with 3% Co, although we have carried out only short-time tests so far. The
concentration of W can be maximised up to about 30/0 in 9Cr steels, where the steels
consist of tempered martensitic microstructure and W contributes to the improve-
ment of creep rupture strength for long periods of time.

INTRODUCTION

Since 1980s, the Electric Power Development Company (EPDC) has coordi-
nated the development of advanced coal-fired ultra-supercritical (USC) plants
in [apan.! Many steelmaking and plant manufacturing companies are
involved in the development programs. Figure 1 shows the increase in steam
temperature and pressure of coal-fired power plants in Japan. At present, a
60QoCUSC plant using Mod. 9Cr-1Mo steel for main steam pipe is operated
at Kawagoe, Japan. Field tests of newly developed high-strength ferritic
steels, NF616(9Cr-0.5Mo-1.8WVNb steel)? and HCM12A(11Cr-O.4Mo-
2WCu VNb steel)" are being now performed for application to boiler compo-
nents of 625°C plant.'
In 1997, National Research Institute for Metals (NRIM) started the research
and development project on advanced ferritic steels for application to
large diameter and thick section boiler components such as main steam

84
DESIGN OFADVANCEDFERRITICSTEELSFORUSC BOILERS 85

Present R&D (650 oC, 350atm


650 :. pressure)

~
e 625 °C plant test (NF616, HCM12A)
~ 600 Ultra- ~
8. supercritical 600 -c, 315 atm pressure
~ (USC) llants (Mod. 9Cr- 1Mo)

~ 550 .•

~ 1------------4.~
Supercritical plants
(538 -c, 246 atm pressure)
500~----~------~----~-----
1970 1980 1990 2000
Year

Fig. 1 Increase in steam temperature and pressure of coal-fired power plants in


Japan

pipe and header of USC plant at 650°C and 350 atmospheric pressure.
The project involves the development of tungsten strengthened 9-12Cr
steels with sufficient long-term creep rupture strength higher than
NF616 and HCM12A at 650°C. The 650°C plant is a final stage of the advanced
coal-fired USC power plant scenario in [apan.! Thermal efficiency is
enhanced from 39.8% in conventional plants operating at 538°C and 246
atmospheric pressure to 43.0% in the 650°C plant, resulting in lower fuel
consumption and lower carbon dioxide emissions. The later reason is
increasingly quoted to protect the global environment. The project has
received strong support from the Science and Technology Agency (STA),
the Japanese Government and was established as a sub-project within a
big R&D project to create non-traditional structural materials, designated
'ultra-steels', for the 21st century. In order to promote strategically the
project, NRIM founded the Frontier Research Center for Structural Materials
in 1997.
This paper describes an outline of the project, the alloy design philosophy
and the present status of steel development. The critical issues for the
development of ferritic steels for 650°C USC boilers are shown to be the
improvement of oxidation resistance as well as long-term creep rupture
strength. The alloy design philosophy of tempered martensitic high-Cr steels
with sufficient creep and oxidation resistance is described. Iridium (Ir),
having the maximum melting point of the austenite stabilising elements, is
superior to conventional austenite stabilising elements Ni, Cu and Co for
strengthening the martensite matrix. The maximisation of W concentration in
tempered martensitic 9Cr steels is also shown for the improvement of long-
term creep rupture strength.
86 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

(?
a.
5
en
en
Q)
L..
+""
en
Q)
z<tS 40
~
.Q
-e-- 2.2SCr-1 Mo
« ~
-e- 9Cr-1 MoVNb
9Cr-O.SMo-1.BWVNb
-ft -11 Cr-O.4Mo-2WCuNbV
0'---"'----'----'---...1.--........&..---.1
500 550 600 650
Temperature (oC)
Fig. 2 Temperature dependence of ASME allowable stress of some ferritic steels for
boilers

POTENTIAL OF CONVENTIONAL STEELS AND REQUIREMENTS


FOR 650°C THICK SECTION BOILER COMPONENTS

Figure 2 shows the ASME allowable stress for NF616 and HCM12A, compar-
ing with that for conventional 2.25Cr-1Mo and Mod. 9Cr-1Mo steels. The
allowable stress of NF616 and HCM12A is much higher than that of the
conventional Cr-Mo steels and exhibits only a small change with temperature
below 600°C. At temperatures higher than 60QoC,however, it should be noted
that the stress significantly decreases with temperature even for NF616 and
HCM12A. The allowable stress at 650°C is evaluated to be 48 and 43 MPa for
NF616 and HCM12A, respectively, which are approximately half of those at
600°C. On the other hand, the oxidation rates of 9-12Cr steels in steam
significantly increases above 600°C5 and many people consider that the
maximum temperature for use as main steam pipe and header, which is
restricted by oxidation resistance, is about 620 to 630°C for NF616 and
HCM12A. Therefore, the critical issues for the development of ferritic steels
for 650°C USC boilers are the improvement of oxidation resistance as well as
long-term creep rupture strength, superior to NF616 and HCM12A. The
resistance to thermal cycling and Type IV cracking strength loss in welded
joints is also serious for construction of thick section boiler components.
Figure 3 shows the creep rupture strength for a variety of ferritic steels as a
function of Larson-Miller parameter with a constant C = 20.6 These data have
been obtained in the NRIM Creep Data Sheet Project? At relatively short
times, the creep rupture strength differs from steel to steel depending on
strengthening mechanisms such as precipitation strengthening. However,
DESIGN OF ADVANCED FERRITIC STEELS FOR USC BOILERS 87

1000
700 • lCrlMoO. 25V
A 5CrO. 5Mo
rr-; 500 .9CrlMo
ro
0.... • l2Cr
300 • 12CrlMolWO. 3V
~<;» 200
100
70 O. Ol2C steel
50
30
o 0 . 2C 'V lCrO. 5Mo
20 OO.5Mo 0 l.25CrO.5MoSi
~ o. sc-o 5Mo 0 2. 25CrlMo

194 16 18 20 22 24
Larson-Miller parameter (T(K)· (20+log. tr(h»)) (103)

Fig. 3 Creep rupture strength of .carbon steels and Cr-Mo ferritic steels

with increasing time, agglomeration of carbides, recovery of excess disloca-


tions and coarsening of martensite lath subgrains occur during creep and the
strengthening effects become disappeared. The converging creep rupture
strength toward a common level at long times suggests that fully recovered
ferrite matrix of the steels is responsible for the fundamental creep strength.
The fundamental creep strength is an inherent property in the steels at long
times irrespective of different chemical compositions and has been named as
'Inherent Creep Strength'. 6, 8 The time to reach the Inherent Creep Strength
level depends on the rate of microstructural evolution during creep. There-
fore, for the improvement of long-term creep rupture strength of ferritic
steels, the stabilisation of initial microstructure is required for long periods of
time. Taking into account of highly oxidation-resistant steels, the suppression
of carbide agglomeration in high-Cr or high-Si steels would be required- for
the stabilisation of microstructure.

TASK GROUPS IN THE PROJECT

The present project consists of five tasks:


Task 1 - Alloy design and advanced thermomechanical controlled process
(TMCP)
Task 2 - Optimisation of heat affected zone (HAZ) and mechanical
properties of welded joints
Task 3 - Oxidation resistance in steam
Task 4 - Creep and rupture properties
Task 5 - Creep-Fatigue properties.
88 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Task 1 contains two programs; the optimisation of alloy compositions by


thermodynamic calculation using Thermo-calc and DICTRA and the optimi-
sation of tempered martensitic microstructure by means of advanced TMCP.
Task 2 is focussing on the mechanisms of Type IV cracking strength loss in
welded joints, toward the optimisation of HAZ microstructure. Task 3 is
concerned with the oxidation rate and the spalling of oxide scale in steam.
Main objectives of Task 4 are to assess the long-term creep strength properties
and to make clear strengthening mechanisms of tungsten-strengthened ferr-
itic steels, on the base of the analysis of creep deformation behaviour and
microstructural evolution. Task 5 investigates creep-fatigue properties taking
into account of the effect of oxidation. The thermal cycling capabilities of thick
section components in USC plants would be severely restricted by fatigue
damage.

ALLOY DESIGN PHILOSOPHY

Figure 4 shows the alloy design philosophy of high-Cr ferritic steels for 650°C
USC boilers, on the basis of a tempered martensitic microstructure. The
concentrations of alloying elements shown in the central part are the ones that
we are trying to begin at first but not optimised ones. We are trying to begin

~ ~
oxidation resistance +- 8 - ferrite formation
decrease * addition of austenite
* addition of SI stabilizing elements

~ ~
--. toughness decrease
------~ ~

--. creep strength decrease


-+ AC1 temperature decrease
*addition of Ir, Rh, Pd

oxidation resistance --. ~


carbide agglomeration

I
+-
decrease -+ acceleration of Fe2W
* addition of Y precipitation

~ ~ * fine dispersion
V = 0.2, Nb = 0.05, Ta = 0.01 ..0.02 of Me by TMCP

~ Increase In Me *
~ volume fraction
=
C 0.08- 0.10, N 0.03- 0.06, =
=
B 0.005- 0.008
creep strength +- --. carbide agglomeration
decrease --. weidablllty decrease

Fig. 4 Alloy design philosophy of high-Cr ferritic steels for 650°C USC boilers
DESIGN OF ADVANCED FERRITIC STEELS FOR USC BOILERS 89

from 9% Cr because of remarkable formation of 8-ferrite at high Cr9 and the


decrease in oxidation resistance at low Cr.s The oxidation experiments of
9-12Cr steels in steam at temperatures between 550 and 700°C showed that
the parabolic rate constant for oxidation decreases with increasing Cr and Si
concentrations and that the effect of Si on the decrease in oxidation rate is
much larger than that of Cr.s For the improvement of oxidation resistance, the
small addition of Si of about 0.5% is effective, while it needs at least gO/oCr.On
the other hand, the equilibrium phase calculation using Thermo-calc shows
that the addition of high-Cr or high-Si causes the formation of 8-ferrite during

O.08C-O/1Si-O.SMn-xCr-3W-
O.2V-O.OSNb-O.OOSB-O.OSN

O~~~--~--~----~--+
8 9 10 11 12 13
Cr (mass 010 )

Fig. 58-ferrite volume as a function of Cr concentration for the model steel with Si
of 0, 0.5 and 10/0

austenitisation at around 1100°C as shown in Fig. 5. This suggests that the


addition of austenite stabilising elements is required to prevent from the
8-ferrite formation for steels containing Cr higher than 9% or Si higher than
0.5%.
Ni, Cu and Co have been used as austenite stabilising elements in high-Cr
ferritic steels.v-" However, in order to exclude a possible influence that these
elements cause a decrease in creep rupture strength at 650°C and long times,
Ni, Cu and Co should be substituted with another austenite stabilising
element having sufficient capabilities of strengthening and stabilising the
martensite matrix. For strengthening and stabilising the martensite matrix,
the austenite stabilising elements should reduce diffusion rates and Ms
temperature and should increase Young's modulus of ferritic steels. Reducing
thermal expansion, scarcely reducing a' ~"Y transformation temperature and
Curie temperature and satisfying Hume-Rothery rule are also desirable.
Because diffusion rates and thermal expansion decrease with increasing
melting point of elements and Young's modulus increases with increasing
90 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Table 1Thermal and elastic properties of the austenite stabilising elements

Cu Ni Co Pd Rh Ir

Melting point (. C) 1083 1455 1495 1554 1966 2454

Diffusion rate Large Small

Thermal expansion Large Small

Young's modulus Small Large

T a'-'r I A Ci - 45 - 74 + 0.5 -9 - 14 - 11
(0 C I wt<'k n «3%Co)

Curie Temp I A Ci - 3 - 11 + 11 -3 -2 -2
(e C/wt% n

melting point, the austenite stabilising elements having higher melting points
are promising for strengthening and stabilising the martensite matrix (Table
1). Conventional austenite stabilising elements Ni, Cu and Co are located in
the first long period of the periodic table and the melting points of these
elements are lower than that of iron. On the other hand, Ir, Rh and Pd are also
austenite stabilising elements but the melting points of these elements are
much higher than or the same as iron. Furthermore, Ir, Rh, Pt and Pd reduce
the Ms temperature of iron, like Mo and W, while V and Nb increase the Ms
temperature (Fig. 6).11 This suggests that Ir, Rh, Pt and Pd dissolved in the
matrix can cause a strengthening effect resulting from martensitic transforma-
tion induced strain as can be expected for Mo and W. Ir, having the maximum
melting point of the austenite stabilising elements, is the most promising for
strengthening and stabilising the martensite matrix.
The effect of W on the creep rupture strength was examined for the simple
9Cr-0, 1, 2 and 4W steels containing 0.1% carbon.l- The creep tests were
carried out for up to about 104 h at 550, 600 and 650°C. The creep rupture
strength of the steels is shown as a function of Larson-Miller parameter LMP
with a constant C = 20 in Fig. 7(a), together with the data for solute-modified
9Cr-WVTa steels which will be described later. The W concentration depend-
ence is shown for the simple 9Cr-W-0.IC steels in Fig. 7(b), where the
logarithm of creep rupture strength log <T at LMP = 20079, 20952 and 21825,
corresponding to 103, 104 and 105 h at 600°C, respectively, is plotted as a
function of W concentration. The log increases linearly with increasing W
(J'

concentration up to about 3%, where the steels consist of tempered marten-


site. The contribution of W to the increase in creep rupture strength ~log
<T / ~Cw, where the Cw is the concentration of W, is evaluated to be 0.15, 0.17
and 0.18/wt%W at LMP = 20079,20952 and 21825, respectively. The values of
~ log (J' / Cw mean that the creep rupture strength of tempered martensitic
~
DESIGN OF ADVANCED FERRITIC STEELS FOR USC BOILERS 91

Ms To

G
ferrite stabilising; austenite stabilising;
TOlJ To Dr

~~~~~~
M
Ms To
Gh ~~~--~~T
Ms To
~~--~~~
To

V, Nb
! W, Mo
! !
Ir, Rh, Pt, Pd

Fig. 6 Change in Gibbs-free energy curves with alloying elements for Pe-Smol'zsX
(X = V, Nb, W, Mo, Ir, Rh, Pt, Pd) alloys

400
(a

200

as
n, 100 (/)

6 (/)

; 105h
(/)
UJ
60 en~ 60
~
en 40 -&-9Cr
-6-9Cr-1W
~600°C\
40
-a-9Cr-2W •..•.• 103 h (LMP = 20079)
-Si1-9Cr-4W
20 -e--9Cr-l WVTa •..•.• 104 h (LMP = 20952)
-.-9Cr-3WVTa
...•.• 10sh (lMP = 21825)

10~~--~--~--~--~--~
17000 19000 21000 23000 o 2 4
(a) Larson-Miller parameter (C = 20) (b) W concentration (wt%)

Fig. 7 (a) Creep rupture strength as a function of Larson-Miller parameter with a


constant C = 20 and (b) its W concentration dependence for 9Cr-W steels
92 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

phase increases by 1.4-1.5 times per Iwt" W and that the improvement of
creep rupture strength by the addition of W is effective for long periods of
time. The 9Cr-4W steel contained 10 vol': 8-ferrite in the matrix of tempered
martensite and the creep rupture strength scarcely increased no more. On the
other hand, and the precipitation of Fe2W Laves phase as well as the
formation of 8-ferrite at high W concentrations decreased toughness. The
present results suggest the maximum concentration of W in 9Cr steel is
considered to be about 3%. The creep rupture strength of solute-modified
9Cr-WVTa steels with 1 and 3% W were also examined.P This was originally
aimed to develop high-strength gCr steels for up to about 600°C. From Fig. 5,
the creep rupture strength at LMP = 20952, corresponding to 105 h at 600°C, is
evaluated to be 145 MPa for the 9Cr-3WVTa steel, which is nearly the same as
that of NF616 and HCM12A. The longest test time for the 9Cr-3WVTa steel
was 65 453 h at 600°C.
The optimisation of carbon, nitrogen and boron is one of the most
important factors for the improvement of long-term creep rupture strength of
ferritic steels. The optimisation involves two factors; the compositions of these
elements and the distributions of carbo-nitrides with or without boron in the
matrix and along lath boundaries and along prior austenite grain bound-
aries.

PRESENT STATUS OF STEEL DEVELOPMENT

(1) Effect of Iridium on Microstructure and Resistance to Softening During


Tempering
The effect of Ir on microstructure has been investigated for 0.OBC-9Cr-
3.3W-0.2V-0.05Nb-0.00SB-0.OSN steels with 0, 1, 2 and 4% Ir, comparing
with the results on the steel with 3% CO.14According to the concentration of
Ir and Co, the steels are designated the base steel, 1Ir, 2Ir, 4Ir and 3Co steels.
The steel rods were prepared by vacuum melting in a high frequency
induction furnace to ingots of 5 kg in each steel, homogenising at 1200°C for
1 h, hot forging and hot rolling to square rods having a cross section of 14 by
14 mm. After normalising at 1100°C for 30 min, only the base steel contained
10 vol.S 8-ferrite in the matrix of martensite, while the lIr, 2Ir, 4Ir and 3Co
steels exhibited full martensite. No precipitate containing Ir was present. The
present results indicate that Ir is dissolved in the matrix and has sufficient
austenite stabilising potential similar as Co. The softening during tempering
after normalising shifts to higher temperatures with increasing Ir concentra-
tion as shown in Fig. B. This suggests that the recovery of excess dislocations
produced by martensitic transformation during cooling is delayed with
increasing Ir concentration. Because the recovery of excess dislocations occurs
by dislocation climbing, self-diffusion rates in the steels decrease with
increasing Ir concentration.
DESIGN OF ADVANCED FERRITIC STEELS FOR USC BOILERS 93

400
fI.:I
r;I'J

~ 350
"0

~
~
..c 300
~
fI.:I

Q.)

~ 250
;;
200

150~~~~~~~~~~~~~
550 600 650 700 750 800 850 900
Tempering temerature (OC )

Fig. 8 Change in Vickers hardness during tempering for the O.08C-9Cr-


3.3W-O.2V-O.OSNb-O.OOSB-O.OSNsteels with 1, 2 and 40/0 Ir, after normalising at
1100°C

(2) Effect of Iridium on Creep Strength


The effect of Ir on creep strength properties has also been investigated for the
base steel, 1Ir, 2Ir, 4Ir and 3Co steels mentioned above.l+ The creep tests were
carried out after normalising and tempering, using specimens of 6 mm gauge
diameter and 30 mm gauge length. Figure 9 shows the creep curves for the
2Ir, 4Ir and 3Co steels at 650°C and 200 MPa. Although we have carried out
only short-time tests so far, the creep rupture time shifts to longer times and

0.25

0.2

0.15
c::
·ro
s....
...., 0.1
V)

0.05

Fig. 9 Creep curves for the O.08C-9Cr-3.3W-O.2V-O.OSNb-O.OOSB-O.OSNsteels


with 2 and 40/0 Ir at 650°C and 200 MPa, comparing with the results on the steel
with 3% Co
94 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

the creep rate decreases with increasing Ir concentration. It should be also


noted that the creep rupture strength of the 2Ir and 4Ir steels is larger than
that of the 3Co steel. At present, long-term creep tests have been continuing.

CONCLUSIONS

1. The critical issues for the development of ferritic steels for 650°C USC
boilers are the improvement of oxidation resistance as well as long-term
creep rupture strength.
2. The long-term creep rupture strength of ferritic steels depends on the rate
of microstructural evolution during creep. For the improvement of long-
term creep rupture strength of ferritic steels, the stabilisation of initial
microstructure is required for long periods of time.
3. The equilibrium phase calculation using Thermo-calc shows that the
addition of austenite stabilising elements is required to prevent from the
8-ferrite formation for the steels containing Cr higher than 9% or Si higher
than 0.5%.
4. Of the austenite stabilising elements, the high melting point elements Ir, Rh
and Pd are promising for strengthening and stabilising the matrix of
martensite from thermodynamic considerations. Indeed, the creep strength
of O.08C-9Cr-3.3W-0.2V-0.05Nb-O.005B-0.05N steels increased with
increasing Ir concentration and that of the steels with 2 and 4% Ir was
larger than that of the steel with 3% Co, although we have carried out only
short-term tests so far.
5. The logarithm of creep rupture strength of simple O.lC-9Cr-W steels
increased linearly with increasing W concentration up to 3% W for up to
long times at temperatures between 550 and 650°C, suggesting that W can
be maximised up to about 3% in the 9Cr steel.

REFERENCES

1. K. Miyashita: Proc. Intern. Conf on Advanced Steam Plant, IMechE Con-


ference Transaction 1997-2, 1997, 17.
2. H. Naoi, H. Mimura, M. Ohgami, H. Morimoto, T. Tanaka, Y. Yazaki and T.
Fujita, Proc. 'The EPRI/National Power Conference', London, UK, 1995,
8.
3. Y. Sawaragi, A. Iseda, K. Ogawa, F. Masuyama and T. Yokoyama: Proc.
'The EPRI/National Power Conference', London, UK, 1995,45.
4. F. Masuyama: 'The EPRI/National Power Conference', London, UK, 1995,
30.
5. Y. Fukuda, K. Tamura and K. Suzaki: Proc. Intern. Symp, On Plant Aging and
Life Predictions of Corrodible Structures, Sapporo, Japan, 1995, 835.
DESIGN OF ADVANCED FERRITIC STEELS FOR USC BOILERS 95

6. K. Kimura, H. Kushima, K. Yagi and C. Tanaka: Aspect of High Temperature


Deformation and Fracture in Crystalline Materials, The Japan Institute of
Metals, 1993, 309.
7. F. Abe, H. Araki and T. Noda: Mater. Sci. Technol. 1990, 6, 714.
8. K. Kimura, H. Kushima, F. Abe and K. Yagi: Mater. Sci. Eng, 1997,
A234-236, 1079.
9. F. Abe and K. Yagi: Advances in Turbine Materials, Design and Manu-
facturing, The Institute of Materials, 1997, 750.
10. M. Igarashi and Y. Sawaragi: Proc. Intern. Con! on Power Engineering-97,
Tokyo, The Japan Society of Mechanical Engineers, 1997, 107.
11. M. Igarashi, S. Muneki, H. Kushima, K. Kimura, N. Fujitsuna and F. Abe:
Report of the lSI! Meeting 10, The Iron and Steel Institute of Japan, 1997,
1250.
12. F. Abe and S. Nakazawa S: Metall. Trans, 1992, 23A, 3034.
13. F. Abe: Mater. Sci. Eng. 1997, A234-236, 1045.
14. S. Muneki, M. Igarashi and F. Abe: Report of the lSI! Meeting 10, The Iron
and Steel Institute of Japan, 1997, 1251.
Development and Application of
2.25Cr-l.6W (HCM2S) Steel Large
Diameter and Thick Section Pipe
N. KOMAI*, F. MASUYAMA*, I. ISHIHARAt and
T. YOKOYAMA§
Mitsubishi Heavy Industries Ltd.
* 5-717-1, Fukahori-machi, Nagasaki 851-0392, Japan
t 180, Koyagi-cho, Nishisonogi-gun, Nagasaki 851-0392, Japan
§ 3-1, Minatomirai 3-chome, Nishi-ku, Yokohama 220-8401, Japan
Y. YAMADERA:t:, H. OKADA:t:, K. MIYATA<JI and
Y. SAWARAGI<JI
Sumitomo Metal Industries Ltd.
t 1, Nishino-cho, Higashimukojima, Amagasaki 660-0856, Japan
CJ[1-8,Fuso-cho, Amagasaki 660-6891, Japan

ABSTRACT

A tungsten strengthened low C-2.25Cr-l.6W-V-Nb (HCM2S) steel has been jointly


developed by Mitsubishi Heavy Industries Ltd. and Sumitomo Metal Industries Ltd.
for power boiler applications. In this study large diameter and thick wall HCM2S
steel pipes were manufactured in trials to investigate the material properties and the
ease of fabrication such as welding with matching consumable and induction
bending.
It was found that the pipes met their specifications for mechanical properties and
exhibited the same material properties as P22, but with 1.8 times the creep strength,
as well as good weldability. The large diameter and thick wall pipe was welded and
bent without difficulty, and it was demonstrated that the properties of the fabricated
metal were satisfactory for practical applications.
HCM2S steel has excellent creep strength and weldability, suggesting strong
potential demand as a substitute for conventional P22 and P91 for the superheater
headers and main steam pipings of power boilers with advanced and conventional
steam cycles.

INTRODUCTION

From the view point of environmental protection and energy savings, the
steam conditions of recently constructed power plants have been raised to
higher temperatures and pressures. Many high strength ferritic 9-12Cr steels
have been developed for use in boilers with elevated steam conditions.l + On
the other hand, reduction of construction costs for power boilers has also been

96
DEVELOPMENT AND ApPLICATION OF 2.25CR-l.6W (HCM2S) 97

increasingly demanded. A new low alloy steel known as HCM2S was


therefore jointly developed by Mitsubishi Heavy Industries Ltd. and Sumi-
tomo Metal Industries Ltd.5,6 HCM2S has excellent creep rupture strength
and weldability, and it is expected to be used as a substitute for conventional
2.2SCr-lMo and Mod. 9Cr-1Mo steels. Tubes made of this steel were
approved by the ASME Boiler and Pressure Vessel Code Committee for use in
Section I construction under SA-213 T23 in Code Case 2199 on 5 June, 1995. A
field service test of these steel tubes in the tertiary superheater of a 156MW
utility power boiler has been conducted since April 1993.7,8Data packages for
pipes, forgings and plates of this steel have also been submitted to ASME to
obtain approval for use in Section I. This paper describes the development of
large diameter and thicker wall HCM2S pipe and the results of fabrication
tests such as welding and induction bending.

DEVELOPMENT AND PROPERTIES OF HCM2S PIPE

The base composition of HCM2S steel is 2.2SCr-1.6W-O.2SV-O.OSNb, which


was developed by examining the effects of alloying elements such as Mo, W,
C, Nand B on creep strength and material properties. The chemical composi-
tions of two heats of HCM2S pipes are shown in Table 1. There are no
remarkable differences in chemical composition between them, and the
compositions satisfied their specifications. The two heats were used for the
investigations described below. They were first melted in a 20 ton electric
furnace, followed by VOD refining, and then casted as ingots. Pipes with a

Table 1 Chemical composition of tested pipes

Heat

A B
Elements (0350 X t50 mm) (0350 X t50 mm) Specification

C 0.05 0.05 0.04-0.10


Si 0.21 0.26 ~O.50
Mn 0.49 0.51 0.10-0.60
P 0.015 0.010 ~0.030
5 0.001 0.003 ~0.010
Cr 2.17 2.42 1.90-2.60
Mo 0.11 0.11 0.05-0.30
W 1.59 1.56 1.45-1.75
V 0.23 0.26 0.20-0.30
Nb 0.05 0.05 0.02-0.08
N 0.008 0.006 :::;0.030
Sol.A.e 0.008 0.003 :::;0.030
B 0.0042 0.0045 0.0005-0.006
98 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Fig. 1 Appearance of HCM2S pipe of Fig. 2 Microstructure of tested pipe as


diameter 350 mm, thickness 50 mm received
and length 5500 mm

350 mm outside diameter and a 50 mm wall thickness were manufactured by


the Ehrhardt push bench process. HCM2S pipes were mist cooled after
normalising at 1050°C for 1h and then tempered at 770°C for 1 h. Figure 1
shows the appearance of the heat B pipe which was tested. The micro-
structure of the as-received heat A pipe in cross section is shown in Fig. 2. The
microstructure consisted of homogeneous tempered bainite, and the grain
size of these pipe steels was slightly coarser than that of HCM2S tubes.
The tensile properties of HCM2S pipes satisfied their specifications, and the
Charpy impact properties of this steel were also sufficient for practical
application. Figure 3 shows the creep rupture properties of HCM2S pipes,
and creep rupture strength is compared with that of HCM2S tubes in Fig. 4.
The allowable stresses for HCM2S pipes have not yet been determined by
ASME, but are expected to be almost the same as those for tubes. This is
because, as shown in Fig. 4, the pipes have almost the same creep rupture
properties as the tubes. ASME allowable stresses for HCM2S tubes at various

400 r--T--rT"TT'T'I'1T""--r-r-rrT~--,--.rTTTTl"Tr--r-r-T"I"TTTT1

300
300

200 200
i
~ 100
~ 100
~
(J) 70
70

50
50
30

30 '--0 --L-I-..&....I.L.IJ1W-..:02;;--L-.L-I-LJ.L.W10-=-3
-J.....L...J....L.L.1J1.lL..:04:-'-L..L.1.LLUl105
1 18 19 20 21 22
Time to rupture (h) PLM, (273 + T)(20 + log t) X 1 0-3

Fig. 3 Creep rupture properties of Fig. 4 Comparison of creep rupture


HCM2Spipes properties of HCM2S pipes and
HCM2Stubes
DEVELOPMENT AND ApPLICATION OF 2.25CR-l.6W (HCM2S) 99

140

120

i
~ 100

en
en 80
e
en
CD 60
:0
as
,g
== 40
< 20

10-2
450 500 550 600 650 700
Average cooling rate from 800'C to 300'C ('CIs)
Temperature CC)

Fig. 5 Comparison of allowable Fig. 6 The relationship between


stresses of piping steels hardness and cooling rate after
normalising

temperatures are shown in Fig. 5, showing a comparison with conventional


ferritic boiler steels. The allowable stresses of this steel are over 1.8 times
higher than those of P22 at 600°C; at around 510°C they are superior to those
of P91. Thinner wall pipes could be designed by employing these high
allowable stresses, resulting in the benefits of large reductions in thermal
stresses as well as lighter components.
Figure 6 shows the relationship between the hardness and the cooling rate
after normalising in comparison to that of 2.25Cr-1Mo steel. HCM2S as
quenched was softer than 2.25Cr-1Mo steel under cooling rate conditions of 2
X 100°Cs-l and above. HCM2S also showed a constant level of hardness over
a wide range of cooling rates. This behavior is desirable in terms of
mechanical properties because hardness deviation along the walls of thick
walled components can be controlled so as to be low after normalising.
HCM2S exhibited excellent weldability, to the extent that cracking does not
occur in the y-groove weldment even at room temperature. Such excellent
weldability is accomplished with approximately 50HV lower welding hard-
ness than that of 2.25Cr-1Mo steel. This fact shows that neither pre- nor post-
weld heat treatment would be required for the welding of HCM2S.

WELDING AND PROPERTIES OF PIPE WELDMENTS

Welded joints were made by GTAW for root pass and subsequent weldings
(SMAW, SAW or MAG) using a matching filler metal that was concurrently
developed. Table 2 shows the welding conditions and the grooving configura-
tions. Figure 7 illustrates SMAW, SAW and MAG welding of HCM2S pipes.
The welded joints were post-weld heat treated at 715°C for 2 hours prior to
tensile tests, side bend tests, metallography examination, hardness measure-
ments, Charpy impact tests, and creep rupture tests.
100 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Table 2 Welding conditions for HCM2S large diameter and thick wall pipe
Welding method SMAW SAW MAG
Electric GTAW 65"-' 80 GTAW SO"-' 90 GTAW 80"-' 85
current (A) SMAW 70"-'185 SMAW 80-170 SMAW 65"-' 75
SAW 510-550 MAG 110-350
Preheat 150 or 200 100 or 200
temperature (CC) 150 or 200

PWHT 715OCX2h 715CCX2h 715CCX2h

Grooving
configurations

a) SMAW b) SAW

c) MAG

Fig. 7 Welding of HCM2S pipes


DEVELOPMENT AND ApPLICATION OF 2.2SCR-l.6W (HCM2S) 101

TS
586MPa

586MPa

) SMAW
TS .
591MPa

576MPa

Side bend test

TS
596MPa

592MPa

Tensile test Side bend test


c) MAG

Fig. 8 Results of tensile test and side bend test for HCM2S weldments

Figure 8 shows the appearances of the tensile test and the side bend test
specimens after the respective tests. All of the tensile test weldment speci-
mens ruptured in the base metal, and the base metal tensile strength exceeded
the specified minimum value. The side bend test also showed satisfactory
results.
Figure 9 shows the macrostructures and microstructures observed on the
longitudinal sections of the weldments. No defects or unusual structures were
seen in the macrostructures of the weldments. The weld metal and heat
affected zone exhibited homogeneous bainitic structures, as did the base
metal structures.
Figure 10 shows the hardness traverse at the midwall of the weldments.
The hardness of the weld metal in the SMAW and SAW joints was higher than
that in the MAG joint, with a maximum hardness of approximately 260HV.
The hardness in the heat affected zone was fully softened by PWHT, and the
softening area was seen in the heat affected zone adjacent to the base metal, as
is typically observed in the weldments of Mod. 9Cr-1Mo steel." The hardness
102 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

N N
<
:c
<C
:c

~ CI:J

~ Q)

S
"'d

Q)
~
Cf)
C".I

~
...I
u..
...I
La.
U
::c
~ 0
CI:J
;...
Q)

::I
~u
::I
CJ ~;...
~ <t CI:J
;...
UJ ~ 0

,.....
·s
u
~.c
o
"'d

ro
~
CI:J
;...
Q)
:E :E
3: ~u::I
== ::I
~;...
CI:J
;...
0
u
ro
~
0\
bb
~
DEVELOPMENTANDApPLICATION OF2.25CR-l.6W (HCM2S) 103

280

260

>
6 240 ~
til
~
til .c
Go)
c 220 C,
'E c
as
.c 200
e
u;
til
oS!
~u 180 '(;;
c
s {!
160
1mm
L-I

140
Weld metal Fusion line Base metal
Temperature rei
Fig. 10 Hardness traverse at midwall Fig. 11 Tensile strength of HCM2S
of SMAW, SAW, and MAG pipe weldments
weldments of HCM2S pipes

change in the weldments on the outer and inner sides was the same as that at
the midwall.
Figure 11 gives the results of the elevated temperature tensile test of the
weldments. Specimens for the tensile test were taken from the midwall of the
weldments, and a fusion line was placed at the centre of gauge length. As
seen in Fig. 11, the tensile strength of the weldment was approximately
equivalent to that of the base metal of the pipe. All tensile test specimens
ruptured in the base metal.
The notches used in the Charpy impact tests were placed in the weld metal,
fusion line, heat affected zone, and the base metal, and the tests were
performed at O°C.The results are shown in Fig. 12. The heat affected zone in
the SMAW and SAW weldments showed high impact values, exceeding
200Jcm-2. The impact values in the weld metal of the MAG weldrnent were
the highest among these three weldments. The impact values in the weld
metal of the SMAW weldment were lower, and were almost the same as those
of the P91 weldment.?
The creep rupture tests were conducted using specimens which were taken
from a weldment with the centre of each specimen placed at the fusion line.
Creep rupture strengths using of the Larson-Miller method for SMAW, SAW
and MAG weldments are given in Fig. 13. The creep rupture strengths of the
weldments were almost the same as that of the base metal up to 20.5 X 103 in
the Larson-Miller parameter, but it was seen that the strengths tend to
deteriorate in comparison with that of the base metal beyond the value of 20.5
X 103 in the Larson-Miller parameter, indicating higher temperature and
longer test duration. The ruptured locations in almost all specimens in long
term and high temperature tests were in a soft zone of the heat affected zone.
It seems that the reduction of degradation of creep rupture strength in the soft
zone caused the deterioration of creep rupture strength in the weldments. The
104 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

400 500
~
CJ 350 300
3
0 300 200
0
o
is 250 l 100
CD
::::s
200
~
70
~ U)
U)

tsco ! 50
a.
150 en
30
.5 100
>-
a. 20
:a
.c
50
0
0 10
17 18 19 20 21 22 23
PLM, (T + 273) X (20 + log t) x 10-3

Fig. 12 Charpy impact properties of Fig. 13 Creep rupture properties of


HCM2S pipe weldments HCM2S weldments

extrapolated lash creep rupture strengths of the base metal and the welded
joints at various temperatures were calculated; the weldment was weaker
than the base metal in 10sh creep rupture strength. However the reduction
ratio of creep rupture strength in the weldments was similar to that of the
weldment of Mod. 9Cr-1Mo steel."

INDUCTION BENDING AND PROPERTIES OF BENT METAL

Induction bending was applied to HCM2S pipe as shown in Fig. 14. The pipe
was heated circumferentially by a high frequency induction heater followed
by bending. The heating temperature was controlled such that the tem-

Fig. 14 Induction bending of HCM2S pipe


DEVELOPMENTANDApPLICATION OF 2.25CR-l.6W (HCM2S) 105

perature of the outside surface was maintained at about 1030°C, and the
bending speed was approximately 0.3mms-1. The pipe was bent to the angle
of 60° and the bending radius was 1400mm (4D, with D designating the
outside diameter of the pipe). The bent pipe was normalised and tempered
after bending under conditions of 1050°C X 1 hAC + 770°C X 1h, which was
the same condition as for the base metal.
The results of wall thickness measurements show that there is a slight
decrease in wall thickness at the extrados and an increase at the intrados. Such
changes in wall thickness are normal," and the reduction of wall thickness is
about 6% at maximum.
Figure 15 shows the cross-sectional microstructure of the bent metal at the

Extrados Neutral Intrados

Fig. 15 Microstructures at midwall after normalising and tempering of HCM2S bent


pipe

midwall of the extrados, neutral, and intrados after post-bend heat treatment
(PBHT). The microstructure of the bent metal was homogeneous tempered
bainite over the entire sections observed. The grain size was slightly coarser
than that of the base metal.
The hardness traverse were measured along the wall thickness for both as-
bent and PBHT conditions. The hardness at the outer surface region of as-bent
pipe is relatively high, because of the transformation caused by heating at a
temperature above Ac3. Normalising and tempering of bent pipe reduced the
hardness to that of the as-manufactured pipe, and the hardnesses were made
uniform along the wall.
The tensile properties of the bent metal after PBHT were examined at the
extrados, neutral, and intrados, and were found to be almost the same. as
those for the base metal. The properties were circumferentially uniformed.
The Charpy impact properties for the bent metal are shown in Fig. 16,
providing a comparison with as-manufactured pipe metal. For Charpy impact
tests the bent metal was not only air-cooled but oil-quenched in order to
accelerate the cooling rate after normalising. The impact properties of the air-
cooled bent metal deteriorated due to bending and inappropriate heat
treatment. The deterioration in impact properties was possibly due to coarse
grain structures. In contrast the tests of the bent metal which was oil-
106 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

500
• Base metal
~ 6. N{AC)-T
E 400 o N(OQ)-T
~
3-

0
~
(1)

'iii 300
•..u
>
co
Q.
200
.5
..
~
Q.

co
.c 100
0

0
-100 -50 0 50 100
Temperature ee)
Fig. 16 Charpy impact properties of HCM2S bent pipe after normalising and
tempering

Fig. 17 Microstructure after oil-quenching and tempering at extrados of midwall of


HCM2S bent pipe

quenched after normalising revealed extremely high impact values for fine
grain structures as shown in Fig. 17, in which many fine blocks composed of
bainitic lath were observed. Accelerated cooling after normalising thus
provided many fine blocks in the grain. It seems that fine blocks in bainitic
structure effectively work to improve the impact properties in the same
manner as a fine grain structure. As for hardness after quenching, it was
found to be almost the same as that of the air-cooled bent pipe due to the dull
hardenabilities of HCM2S steel. For practical use, it is recommended that
accelerated cooling not only by oil quenching but also by blast air cooling
after normalising be undertaken to obtain better toughness.
DEVELOPMENTANDApPLICATION OF2.25CR-l.6W (HCM2S) 107

300
200

l!. 100
t/) 70
t/)
~ 50
u;
30 6.N(AC)-T
o N(OQ)-T
20 - Base metal

10~--~----~--~~~~--~--~
17 18 19 20 21 22 23
PLM, (T + 273)X (20+ log t) X 10-3

Fig. 18 Creep rupture properties of HCM2S bent pipe

The creep rupture properties of the bent metal after PBHT are shown in Fig.
18. The bent pipe after PBHT showed a slightly greater creep rupture strength
than the base metal; oil-quenched and tempered bent pipe also showed nearly
the same strength. From these results it can be seen that the accelerated
cooling of bent pipe after normalising can remarkably improve toughness,
while creep strength is maintained at a satisfactorily high level.

CONCLUSION

A large diameter and thick walled HCM2S steel pipe has been developed.
This pipe, manufactured on a commercial basis, has excellent creep strength
and weldabilities, comparable to those of tubes. Fabrication trials of this large
diameter and thick walled HCM2S pipe were carried out for main steam pipe
and headers, and it was confirmed that there was no difficulty from the
standpoint of welding and induction bending. Fabrication procedures were
developed, and the properties of the fabricated metal were found to be
satisfactory for practical applications as demonstrated by test results. HCM2S
pipes have excellent creep strength and weldability, which is likely to result in
a higher demand for use of this steel in place of P22 and P91.

REFERENCES

1. V. K. Sikka, C. T. Ward and K. C. Thomas: ASM Int. Conf Production,


Fabrication, Properties and Application of Ferritic Steels for High-Temperature
Applications, Warren, PA., 6-8 Oct. 1981.
108 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

2. M. Igarashi and Y. Sawaragi: Proc. Int. Conf on Power Engineering-97, Vol. 2,


1997, 107.
3. Y. Sawaragi, A. Iseda, K. Ogawa and F. Masuyama: Materials for Advanced
Power Engineering, Part I, D. Countsouradis et al., eds., Kluwer Academic
Publishers, Netherlands, 1994, 309.
4. H. Naoi, M. Ohgami, Y. Hasegawa and T. Fujita: Materials for Advanced
Power Engineering, Part I, D. Countsouradis et al., eds., Kluwer Academic
Publishers, Netherlands, 1994, 425.
5. F. Masuyama, T. Yokoyama, Y. Sawaragi and A. Iseda: Materials for
Advanced Power Engineering, Part I, D. Countsouradis et al., eds., Kluwer
Academic Publishers, Netherlands, 1994, 173.
6. F. Masuyama, T. Yokoyama, Y. Sawaragi and A. Iseda: PVP-Vol. 288,
Service Experience and Reliability Improvement, Nuclear, Fossil and
Petrochemical Plants, ASME, 1994, 141.
7. F. Masuyama, N. Komai, T. Yokoyama, A. Iseda, S. Yamamoto and M.
Igarashi: Proc. Conf. Materials issue in Heat Exchangers and Boilers, 1995,
119.
8. F. Masuyama, N. Komai, T. Yokoyama, S. Yamamoto, K. Miyata and M.
Igarashi: Proc. Int. Conf. Power Engineering-97, Vol. 2, 1997, 95.
9. H. Haneda, F. Masuyama, S. Kaneko and T. Toyoda: Proc. Int. Conf.
Advances in Materials Technology for Fossil Power Plants, 1987, 231.
The Development of Steel Grade 92 for
Large Thick Section Components for
Advance Coal Fired Power Plant
S. PRICE and M. A. WALSH
Technical Director, Forgemasters Steel and Engineering Limited, PO Box 286,
Brightside Lane, Sheffield S9 2RW, UK.

ABSTRACT

Energy utilisation throughout the world has seen a significant transformation over
the past 30 years. Factors such as economic considerations and environmental
impact have become key drivers in the trend towards power generation plant which
is both efficient and clean. Consequently, energy derived from renewable sources
such as hydro, wind and solar, has seen a rapid rise in utilisation by some 145%and
today accounts for 15% of the total world energy demand.
Conventional fuels, however, such as coal still account for 40% of world electrical
power generation and are predicted to continue to be a major energy source.
However, they have also been influenced by environmental pressures which has
seen the development of advanced clean coal technologies incorporating advanced
steam cycles to increase efficiency and reduce emissions.
Essential to clean coal technology is the development and availability of cost
effective steels which can be used for thick section components and which are
capable of operating at elevated temperatures in corrosive atmospheres. Much of the
work in materials development for these applications has centred around the 9-12%
Cr family of steels.
This paper describes the development, manufacture and properties of an
advanced 9% Cr steel containing tungsten (Grade 92) for thick section forged
components up to 425mm for use in advanced high temperature power plant
applications.

INTRODUCTION

It is, perhaps, not surprising that the past few decades has seen a growing
requirement for primary energy. Throughout the world energy represents a
significant sector of the economy. In the UK, for example, it represents 4.6% of
GDP, 12% of total UK investment and, more importantly, 44% of UK
industrial investment. In terms of electrical power generation, the past 30
years has seen it grow from a segment representing 15% of the total world
energy in 1960 to some 30% in 1990.1Future energy trend predictions suggest
a rise in demand by some 2 to 3% per year over the next 15 years.2
The passage of time has also seen some interesting developments within

109
110 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

180 Other
Nuclear
160
Hydro
G) 140
0 Natural
"t:J
.c 120 Gas
c:
100
~
:E 80 Coal

60
40
Oil
20
01
1976 1980 1985 1990 1994

Fig. 1 World primary energy demand

Ocean Thermal Energy .---------, ,....------ __ Coal & Lignite

Wave Energy _-------, ----tl_ Natural Gas

Fig. 2 Fuel types available for energy production

the energy and power generation sectors as traditional fossil based fuels have
become substituted by non-fossil fuels such as geothermal, hydro, solar, wind
etc." Indeed, since 1976 the demand for non-fossil derived primary energy has
seen the greatest rise by some 145% and today accounts for some 15% of the
total world energy requirement (Fig. 1).
Almost all of the fuels shown in Fig. 2 are viable for conversion into
electrical power, however, the choice is dependent upon a number of factors
including:
• Economic considerations
• Availability
• Geographic distribution
• Environmental impact
These factors and other considerations such as the prevailing social and
political climate are key determinants of the strategic energy policies of the
THE DEVELOPMENT OF STEEL GRADE 92 111

world regions. Environmental impact, in light of fears over global warming


and a world-wide concern for the environment and conservation, has become
increasingly significant over the last decade in driving the growth in use of
'environmentally friendly' fuels.
Coal is still by far the greatest contributor to the world's electrical power
demand. In 1995, the world total electricity demand was 12000 TWh and
power generation, utilising coal, accounted for some 4800 TWh, equivalent to
40% of world demand. In terms of its future, there are proven reserves of coal
in excess of 200 years'' and with 90% of coal generated in each country
consumed by that country, then its potential use for power generation,
particularly in high energy demanding, coal rich, developing countries such
as China and India, is clearly indicated. Indeed, power generation is pur-
ported to offer the fuel the best opportunity for expansion, with a projected
demand of 7800 to 8000 TWh by the year 2010 and a continued heavy reliance
upon coal) However, the projected reliance upon coal, combined with
increasing environmental pressure, has given rise to a renewed emphasis for
new coal fired generating capacity, which is both clean and efficient+
Considerable improvements in gaseous emission control from fossil based
fuels have resulted through the development of technologies which minimise
both the amount of acid gases produced in the process and the amount
released to the atmosphere. For example 'Clean' combustion technologies
such as flue gas desulphurisation (FGD) and selective catalytic removal (SCR)
have been developed and established for the removal of acid gases, resulting
from coal combustion (sulphur dioxide and oxides of nitrogen, NOx) with
removal of up to 900/0 of S02 and NOx from the flue gas now achievable.vf
Carbon dioxide emissions are a function of plant thermal efficiency. The
tonnes of carbon dioxide per GWh generated according to plant type are
shown in Fig. 3 and illustrate the environmental impact of each.6
The predicted growth in energy demand, and in particular electrical energy
supply, combined with environmental pressures to reduce CO2 emissions to
contain the problem of global warming, has been highlighted to be a

Coal 964
Oil 820
Gas 484
Geo-thermal 57
Micro-Hydrro 8.0
Nuclear 7.8
Wind 7.4
Photovoltaics 5.4
Large-Hydro 3.1

Fig. 3 Tonnes of CO2 generated per Gwh for different plant types (Source: WEe
Survey of Energy Resources 1995)
112 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

significant driver of power generation technology. As stated above, efficiency


is the key determinant of the level of CO2 emission from power plant. To this
end, significant developments have been made to improve efficiency in order
to reduce the levels of emission from plant. The economic desirability to
utilise freely available fossil fuels such as coal and gas, combined with
environmental pressures, have led to developments such as advanced coal
fired power plant technologies with renewed interest in utilising supercritical
steam cycles, and combined cycle plant, both giving reduced emissions and
improved thermal efficiencies and reinforcing gas and coal as fuels for the
future. The influence that such technological developments have had on
increasing thermal efficiency and reducing CO2 emissions is illustrated in
Table 1.

Table 1 Efficiency of Various Types of Power Plant

Station Thermal Efficiency (%) Station Type Tonnes CO2 per GWh

38 Oil-Fired 820
39 Coal-Fired 960
36 Nuclear 7.8
49 Supercritical 366
58 Combined Cycle 380

The design and construction of advanced power plants utilising super-


critical steam cycles relies heavily on the availability of materials which are
capable of operating under arduous conditions of temperature, stress and
environment. Under such operating conditions heat resistance is of primary
importance and, therefore, properties such as creep strength, high tem-
perature oxidation resistance and thermal fatigue are critical to the applica-
tion.
International Development programmes have, therefore, focused on devel-
oping materials for critical components such as:
• Water panels
• Headers and pipework (thick section components)
• Superheaters
in the boiler, and turbine components such as:
• Rotors forgings
• Casings and steam chests
Parallel developments, in the USA (EPRI), in Japan (EPDC) and in Europe
(COST) have been carried out to develop creep resistant ferritic material
which are cost effective and can meet the more demanding requirements of
advanced supercritical steam conditions of 600-650°C, 325 bar.'
Many of the new steels developed under the umbrella of these programmes
THE DEVELOPMENT OF STEEL GRADE 92 113

have since been applied on a commercial scale and have been installed into
supercritical plant such as the Skaerbaek and Nordjlland 415 MW power
stations in Denmark.
One of the advanced alloy chemistries developed is the Tungsten containing
9%Cr 1%Mo steel referred to as Grade 92. This steel has been evaluated as part
of an extensive validation exercise, culminating in it obtaining ASME Code
approval.f The EPRI programme in which the steel was developed involved
partners from Japan, UK, USA and Denmark and produced several 9-12%
steel compositions (Grade 92 and 122) which satisfied the advanced super-
critical criteria for temperatures up to 620°C. The steels have been evaluated
for application to thick section boiler components and have, in addition, been
used in full size superheater header fabrication trials for installation into one
of the 415 MW supercritical plants under construction by the Danish utility
ELSAM. Further, more demanding tests of the capability of the two steels are
also planned to evaluate the material behaviour under conditions more
typical of the eventual application. A header will be fabricated using both
steels by ABB Combustion Engineering and International Combustion Lim-
ited and will be tested at high temperatures under accelerated conditions in a
high pressure cell operated by Mitsubishi Heavy Industries.
The improvement in creep rupture strength of these new alloys by some
40% over modified 9%Cr 1%Mo steel at 600°C, 105 hours" has given consider-
able interest in the application of Grade 92 steel to large thick section forged
components for both conventional and supercritical steam cycles according to
design conditions.
This paper describes the manufacture and characterisation of one of the
largest forgings produced in Grade 92 steel by Forgemasters Steel and
Engineering Limited. The results of mechanical, chemical and metallographic
characterisation of the forging are presented.
Other evaluations are also ongoing but are not reported in this paper.
Sections of the forging described in this paper have been supplied for
inclusion in a joint research programme including ABB, GEC Alsthom and
Siemens A.G. The programme is designed to examine the creep and relaxa-
tion behaviour of high temperature pipe flange assemblies." Scaled down
flange assemblies incorporating Grade 92 steel are to be internally pressurised
and exposed to temperature fluctuations. The readings obtained are then used
to refine existing numerical finite element models of the flange assembly
behaviour.
In addition some material has been further forged to enable the manu-
facture of components for the fabricated header trials which will undergo
high pressure testing within the EPRI RP1403 project.
There is also considerable interest in Grade 92 steel in Denmark where it is
being considered for application to outlet headers, mainsteam pipework and
hot re-heat steam pipework of future ultra supercritical power plant.
A summary of material manufactured by Forgemasters Steel and Engineer-
114 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

u*
INGOT

t
FORGING

f
Flange Header Material
t
Bending
t
Material

: ~~~on - ~i~tal
Assemblies Components Characterisation Trials Characterisation
and Including Elevated
Materials Tempcrature
Characterisation Properties
Homogeneity
Metallography
Fracture
Toughness
Creep Testing

Fig. 4 Summary of steel Grade 92 manufactured and on-going evaluations

ing Limited and current evaluations which are ongoing are illustrated in Fig.
4.

MANUFACTURE OF STEEL GRADE 92

Steelmaking
Melting was carried out in a 25 tonne Electric Arc Furnace. Approximately 23
tonnes of high chrome scrap was charged to the furnace together with small
additions to trim tungsten and control the oxygen level of the bath. On
completion of primary melting the steel was transferred to a Vacuum Arc
Degassing unit for secondary refining and reduction of hydrogen under
vacuum. Final trimming additions were made prior to tapping and up-hill
teeming (with argon protection), two multifluted ingots of 850 mm mean
diameter.

Forging
On completion of solidification the ingots were stripped from their moulds
and one of the ingots was delivered to the 10 000 tonne press where it was
direct forged to a 440 mm diameter bar with a forging reduction of 4:1.

Heat Treatment
After forging the bar was transferred for primary heat treatment. Slow
cooling to below 180°C was followed by annealing at 650/700°C for 10 hours
and furnace cooling to ambient.
THE DEVELOPMENT OF STEEL GRADE 92 115

The forging was then rough machined and assessed by ultrasonic examina-
tion which showed it to be clean and sound.
Quality heat treatment for properties was carried out at 1070°Cfor 8 hours.
In order to ensure through hardening and freedom from delta ferrite cooling
was carried out through the application of an oil quench to below 150°C.This
was followed by tempering at 750°C for 12 hours. The forging was then
further skimmed and a full ultrasonic examination was performed. This
confirmed the earlier findings that the forging was both clean and sound.

MATERIAL TESTING

Material for basic mechanical testing was taken from the top and bottom end
of the forging at locations shown in Fig. 5. In addition to basic mechanical

Top of Ingot End Bottom of Ingot End


150mm
~:~
i :
~ 1--<150~
I
C~- -BSS
1MR
.
~:"
- L;::~~:~~::oj
I
I l>~J- -BMR

TC -~-~-~-L?~?}--'---'--'-'-'--'--l-'-----'-'-'-'--'-I-~,= -,!\~
In
1
II

D = Diameter at quality heat treatment = 425 mm


SS = Sub-Surface
MR = Mid-Radial
C=Centre
T=Top
B=Bottom

Fig. 5 Schematic of Grade 92 steel forging showing test locations

testing, long term testing was initiated within other development pro-
grammes, however, data was unavailable at the time of writing this paper.
The full testing matrix for the forging is shown in Table 2.
The results of Chemical analysis are given in Table 3 and demonstrate
specification compliance and good uniformity of chemistry throughout the
forging.
Microstructural examination revealed a tempered Martensitic structure
throughout the forging, as shown in Fig. 6.
The results of mechanical testing at locations throughout the forging are
detailed in Table 4.
The results indicate good hardenability in steel Grade 92 in sections up to
116 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Table 2 Test Matrix for Grade 92 Forging

Location (Ref. Fig. 5)

Test TSS TMR TC BSS BMR BC

Chemical Analysis .I X .I .I X .I
Microstructure .I X .I .I X .I
Tensile (RT) .I .I X .I .I X
Elevated Tensile (350°C) .I X X X X X
Charpy (RT) .I .I X ./ .I X
Fracture Toughness X X ./ X X X
Creep X X X X X .I

Table 3 Cast and Product Analyses of Grade 92 Forgings

ASMECode
Case
Specification

Cast Top Top Btm. Btm.


Element Min Max Analysis (5. Surf) (Core) (5. Surf) (Core)

C 0.07 0.13 0.09 0.09 0.09 0.09 0.08


Si 0.50 0.02 0.02 0.02 0.02 0.02
Mn 0.30 0.60 0.51 0.52 0.S3 0.S2 O.Sl
P 0.02 0.01 0.01 0.01 0.01 0.009
S 0.01 0.005 0.005 0.005 0.005 0.004
Cr 8.S0 9.S0 8.98 8.99 9.05 8.98 8.91
Mo 0.30 0.60 0.51 0.51 0.52 0.51 0.5
Ni 0.40 0.09 0.08 0.08 0.08 0.08
V 0.15 0.25 0.19 0.19 0.19 0.19 0.19
Al 0.040 0.011 0.010 0.008 0.010 0.013
Cu NS NS 0.05 0.05 0.05 O.OS 0.04
Sn NS NS 0.006 0.006 0.007 0.006 0.006
W 1.50 2.00 1.89 1.89 1.88 1.89 1.90
Nb 0.04 0.09 0.050 0.053 0.057 0.053 0.046
B 0.001 0.006 0.0023 0.0023 0.0025 0.0020 0.0021
N2 0.03 0.07 0.038 0.041 0.042 0.040 0.037
NS = Not Specified

425 mm with minimal difference in both strength and toughness from surface
to centre. The uniformity in strength and toughness is also clearly demon-
strated with the maximum variation in tensile strength being 20 MPa
throughout.
THE DEVELOPMENT OF STEEL GRADE 92 117

Fig. 6 Tempered martensitic microstructure (location - BC [x200])

Table 4 Summary of Mechanical Test Results

Test Location Orientation Rm (MPa) Rp 0.2 (MPa) A (%) Z (%) KCV (Avg. 3) (J)

TSS Transverse 643 480 25 65 76


TSS Longitudinal 646 474 27 69 146
TMR Transverse 635 465 26 66 75
TMR Longitudinal 628 460 27 70 129
BSS Transverse 624 450 26 58 75
BSS Longitudinal 626 446 28 70 167
BMR Transverse 632 451 27 65 74
BMR Longitudinal 627 446 27 68 125
Specification 620 440 20 41 (L)
min min min 27 (T)

(Note: All tests performed at room temperature).


Rm - ultimate strength; Rp 0.2- 0.2% yield strength; A - % reduction of area; Z - %
elongation; KCV - Charpy Notch Energy
118 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

SUMMARY

A high quality 425 mm thick section forging in Grade 92 steel has been
successfully manufactured by Forgemasters Steel and Engineering Limited
using conventional melting technology. The forging has been shown to be
uniform in chemistry, microstructure and properties. Further characterisation
of the material is ongoing in a number of European development pro-
grammes, examining the long term properties and its potential application to
large forgings in conventional and supercritical steam power plant.

REFERENCES

1. Materials Technology Foresight for the UK Power Generation Industry, The


Institute of Materials Strategy Commission Report 1995.
2. Technology Foresight; Advanced Combined Cycle and Gas Turbine Technology,
Office Science and Technology, DTI 1997.
3. Energy in Profile, Shell Briefing Service Number two, 1995.
4. S. B. Gibbs: Prospects for Advanced Coal-fuelled Power Plant and the Require-
ments for Materials Research, Development and Demonstration, Draft Report,
March 1996.
5. Survey of Energy Resources, World Energy Council, 1995.
6. Mini Hydropower Group: 'Mini Hydro: Policy and Practice', Supplement
in the International Journal on Hydropower and Dams, 1995.
7. R. Blum: 'Materials Development for Power Plants with Advanced Steam
Parameters - Utility Point of View, in Materials for Advanced Engineer-
ing', Proceedings of a Conference held in Liege, Belgium, October 1994,
pp 15-30.
8. E. Metcalf, W. T. Bakker, R. Blum, P. Bygate, T. Gibbons, J. RaId, F.
Masuyama, H. Naoi, S. Price and Y. Sawaragi: 'New Steels for Advanced
Coal Fired Plant up to 620°C', Ind. Conference on Advanced Steam Plant,
London, 21-22 May 1997.
9. H. Purper, H. Konig and K. Maile: Experimental and Numerical Determination
of Creep and Relaxation Behaviour of High Temperature Pipe Flanges.
Development of 9Cr-2W Cast Steel for
the Valves in Elevated Temperature
Fossil Power Plants
T. HONDA, T. KUSANO, T. OSADA, K. HIRANO and
K. TAKEMOTO
Okano Valve Mfg Co., 1-4, Nakamachi, Moji-ku, Kitakyushu-shi, Fukuoka,
Japan 800

ABSTRACT
We have already developed power plant valves made of the modified 9Cr-1Mo
ferritic cast steel for use up to elevated temperatures of 866 K in 1986. These cast
steels were specified as ASTM A 217 Grade C12A in 1997. However, there is a future
need for valves for use over 866 K. The cast steels which have the strength equivalent
to that of rolled 9Cr-2W materials specified in ASME code case 2179 have now been
developed, to meet this roll.
Eight heats of the 9Cr-2W cast steels have been cast as disk specimens and one
heat cast for the actual gate valve body, and the properties of these cast steels have
been investigated.
Topics include the relationship between 8-ferrite and Cr equivalent, the tensile and
creep rupture properties of the cast steels and weldment, and also the soundness of
the valve body cross section. The cast steels show good mechanical properties
including V-notched Charpy impact property, and the creep strength of these cast
steels are almost equivalent to that of the 9Cr- 2W rolled steel. The optimum method
for controlling the alloying elements in the cast steel is determined to suppress the
8-ferrite formation and to improve other properties.

INTRODUCTION

The improvement of thermal efficiency is required for fossil power plants.


The emphasis of the current development in a three-phase program (Table 1)
has been placed on increasing the steam temperature and pressure.

Table 1 Pressure and temperature conditions of power plant

Temperature/K

Step Pressure/Mpa Main steam 1st Reheater 2nd Reheater

31.0 839 839 839


II 31.0 866 866 866
III 34.5 923 866 866

119
120 ADVANCEDHEAT RESISTANTSTEELSFORPOWERGENERATION

A major aim of this program is to develop the materials suitable for high
temperature service. For the third stage of this program there is a need for
austenitic stainless steels to be developed. However, the NF616 steel has been
developed by Fujita! and Nippon Steel CO,2and this steel is usable for the
third step, i.e. temperature up to 923 K. The NF616 steel has been specified as
the 9Cr-2W for use in tube and piping materials in ASME code case 2179.
The expanded application of ferritic steels is advantageous not only for
reducing construction costs but also for plan design, due to their smaller
thermal expansion coefficient and larger thermal conductivity, compared
with those of austenitic steels.
The 9Cr-2W ferritic steel having a higher strength at elevated temperature
than that of the 9Cr-1Mo steel which is used up to 866 K. Therefore, the
development of 9Cr-2W cast steel for valves is also required to fit to the
adjacent piping and to retain the advantages of ferritic steel. The development
of the 9Cr-2W steel produced by forging or rolling has almost been com-
pleted. However, the development of this steel in cast form has not.
The following concerns have been recognised to overcome the deficiencies
in castings.
1. The specification for 9Cr-2W calls for chromium and tungsten contents
of 8.50-9.50 wt? and 1.50-2.00 wt%, respectively. These elements are
ferritic phase making elements and so is Si. It is not desirable to let the Si
content decrease below 0.10 wt% otherwise the steel develops blow-
holes. Therefore, the difficulty in suppressing the formation of 8-ferrite
in cast products remained.
2. Usually, cast produces have a lower fracture toughness than that of
wrought products with the same chemical compositions. Therefore,
adequate toughness of the cast material is also a concern.
This study makes an attempt to develop sound castings with almost the same
chemical compositions as the original NF616 and the ASME code case 2179.
The essential metallurgical estimation in our study includes the considera-
tions of chemical compositions of the castings, and also the mechanical,
tensile, and impact properties; the creep rupture strength and weldability.

EXPERIMENTAL PROCEDURE

A total of nine heats consisting of 8 test castings each of 980 N in weight for
disk specimens and one valve body casting of 4.3 kN in weight were melted in
a high-frequency furnace. The disk specimen with an outer diameter of 350
mm and thickness of 120 mm and the other test coupons specified by Japanese
standards JIS G 0307 were cast from heats Al to D1. The gate valve body,
diameter 150 mm and the test coupons were cast from heat D2. The shape and
dimensions of the gate valve body are shown in Figs 1 and 2.
DEVELOPMENT OF 9CR-2 W CAST STEEL 121

Fig. 1 Dimension of the gate valve body

Fig. 2 The appe,arance of gate valve body

EXPERIMENTAL RESULTS

Table 2 shows the chemical composition specified in the ASME code case 2179
for each heat melt. The relation between Cr equivalent and 8-ferrite can be
obtained for each heat. Where, Cr equivalent is obtained by the following
equation.'

Cr eq=Cr+6Si+4Mo+l.5W+11V+SNb
+ 12Al-40C-2Mn-4Ni-2Co-30N-Cu (1)

Figure 3 shows these relations, as well as the 8-ferrite range determined for
the deposits of 9% Cr shielded metal-arc welding."
As shown in Fig. 3, 8-ferrite contents of NF616 type cast steels are changed
with Cr equivalent, and the larger the Cr equivalent, the larger the 8-ferrite
content. It was also found that the 8-ferrite content of the cast steels almost
agree with the o-£errite range in the 9% Cr steel weld deposits.
122 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Table 2 Chemical composition of cast steel

Chemical composition/ wt%

Heat C Si Mn Cr Mo W Ni V Nb N Al B

Al 0.11 0.18 0.33 8.39 0.54 1.73 0.100 0.20 0.06 0.030 0.020 0.006
A2 0.08 0.09 0.34 8.90 0.54 1.72 0.100 0.20 0.06 0.034 0.010 0.005
B1 0.14 0.28 0.65 8.38 0.51 1.79 0.19 0.17 0.07 0.038 0.034 0.006
B2 0.10 0.07 0.75 8.25 0.51 1.77 0.04 0.15 0.05 0.038 0.013 0.002
C1 0.11 0.08 0.54 8.60 0.48 1.69 0.30 0.17 0.03 0.041 0.017 0.004
C2 0.11 0.22 0.50 8.64 0.48 1.70 0.30 0.17 0.03 0.036 0.013 0.003
C3 0.12 0.33 0.49 8.66 0.47 1.72 0.29 0.16 0.03 0.032 0.012 0.002
D1 0.10 0.59 0.53 9.30 0.56 1.85 0.06 0.21 0.07 0.0370.046 0.006
D2 0.12 0.46 0.59 8.88 0.41 1.57 0.40 0.20 0.06 0.038 0.034 0.005
9Cr-2W 0.07 max. 0.30 8.50 0.30 1.50 max. 0.15 0.04 0.030 max. 0.001
(Case 2179) -0.13 0.50 -0.60 -9.50 -0.60 -2.00 0.40 -0.25 -0.09 -0.070 0.040 -0.006

40 ----------------.

35 Cast steel
/
30 q; j 0
ffl
~ 25 ~/
JJI
~! ~&
·S
Q)
::;,/
20 ~ r I ~
~ f .' I!:;
t.O 15 r~ / ,,~
'-' I~

10 ~!I
0.. I " ~
~

/ 00
5 I I ~
0,
O~~_~~~~--~--~~--~
o 5 10 15 20
Cr equivalent %

Fig. 3 Relationship between Cr equivalent and 8-ferrite

Table 3 shows the mechanical properties of the cast steel. Both strength and
ductility of the cast steel are satisfied for the values specified in ASME code
case 2179. Charpy impact values of the cast steel are also satisfied with those
of European specification.
Figure 4 shows the relation between Si content and Charpy impact values.
DEVELOPMENT OF 9CR-2 W CAST STEEL 123

Table 3 Mechanical properties of cast steel

Impact/J
0.2010 yield D.T.S. Reduction
Heat strength/MPa /MPa Elongation/DID of area/DID Hardness/HB 273K 293K

Ai 459 631 29 68 211 62 84


Bl 517 705 26 60 213 43
B2 500 648 25 67 197 60
Cl 476 654 23 63 202 41 57
C2 495 680 22 60 200 35 46
C3 484 675 28 58 198 35 54
D2 528 700 21 56 211 41 52
9Cr-2W
(Case 3179»440 >620 >20 <250 >41*

* European spec.
Heat treatment; Diffusion annealing: 1343 K X 18 ks, Normalising: 1343 K X 18 ks,
Tempering: 1033K X 18ks

100
o 273K
~ D 293K
D
80 • Estimated
0
::s at 293K
~ II 41J spec.
>
~o 60 () 0 at 293K
~
.~a
LI D • D

~ 40 - -0- - -0- ~ -0. -- - - - -- - .• - --


~
~ o 0
U
20

0
0 0.2 0.4 0.6
Si content wt%
Fig. 4 Variations of Charpy impact values with Si content

The impact values of the cast steel vary with Si content and the values
increase when Si content decreases below 0.2 wt%, but almost no changes
were observed for a Si content higher than 0.2 wt%.
Figure 5 shows the appearance of the cross section of the valve body tested
by the liquid penetration method (the inlet and outlet parts of the valve are
supplied for the welding test). There are no significant defects in the cross
section of the valve body.
124 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Fig. 5 The cross sections of the valve body tested by the liquid penetration method

50f-.Lm

Fig. 6 The microstructure of the valve body

Figure 6 shows that the microstructure of the valve body has a tempered
martensite structure.
Figure 7 shows the 0.2% yield, tensile strength and ductility of the cast
steels at room and elevated temperatures. The minimum values of strength
determined by the ASME committee for all rolled NF616 heats? are also
shown in this figure.
It was found that the 0.2% yield strengths of the cast steels are higher than
the ASME specified minimum values for all testing temperature ranges,
293-973 K. However, the tensile strengths of the cast steels were close to the
minimum value and below at 923 K. At present, the reason for this cannot be
described clearly. However, the tensile strength is remarkably affected by the
heat treatment conditions and the cast steels are tempered for relatively long
DEVELOPMENT OF 9CR-2W CAST STEEL 125

ro 800
~
~
Minimum tensile strength
/'

B! B2 D2 (valve body)
Tensile strength 0 ~ 0
Yield strength~ I1A Ii
O~~ __ ~ __ ~ __ ~ __ ~ __ ~ __ ~~
200 400 600 800 1000
Temperature K
(a) Yield and tensile strength

~ 100----------------.
B! B2 D2 (valve body)
Reduction in area 0 ~ 0
Elongation (I) £. III

Minimum reduction in area

a ~~ __~_~_~ __~_~_~~
200 400 600 800 1000
Temperature K
(b) Elongation and reduction in area

Fig. 7 Strength and ductility of cast steels

times such as 18 ks to 32.4 ks at 1033 K. It seems that this is one of the reasons
for the lower tensile strength of the casts than that of rolled steels which are
tempered for 3.6 ks or 7.2 ks.
As shown in Fig. 7(b), the elongation of the castings are sufficiently large,
126 ADVANCEDHEAT RESISTANTSTEELSFORPOWERGENERATION

500~--------------------------------~

100

~Weld 0 Bl
A. Tube ~ B2
UI Pipe 0 D2(valve body)
~ Plate
10~ ~ __~ ~~~ __~ __~ __~~
35 37 39 41 43 45
T( 40+1og t) X 10-3
Fig. 8 The master-rupture curve of the cast steels (Tubes, pipes and plates data are
refered to Nippon Steel Co., 2nd edition for NF616(2))

but the reductions in area are close to the minimum values of the rolled
NF616 at room and elevated temperatures. However, these values are no
problem for practical use in power plants.
Figure 8 shows the rupture master curve for the cast steels, as compared
with the tubes, pipes and plates of NF616.
Results show that the creep-rupture strength of the cast steels are almost
equivalent to that of rolled NF616. However, weld joints of which the base
metal is B1 cast steel show rather lower values especially at lower stress
conditions, although it is only one result. All of the welded test pieces
ruptured in the heat effected zone.
Figure 9 shows the appearance of the portion of weld joint with the valve
body inlet and outlet for D2 heat, as well as the cross section. There are no
visible defects in the welded portions.
Figure 10 shows that the hardness changes near the welded portion which
is subjected to stress relieving heat treatment at 1018K for 18ks. The hardness
in the weld deposits are 260-270 Hv which are slightly larger than those of
the specified base metal of 250 Hv. On the other hand, the hardnesses in the
heat affected zones are 195-210 Hv which are smaller than those of the base
metal.
The weldability tests according to the MITI specification were conducted
for the weldment of the valve body weld joint. As a result, tensile and impact
properties of the welded portion satisfied the values specified in the MITI
specification.
DEVELOPMENT OF 9CR-2 W CAST STEEL 127

Appearance in the portion of weld joint Cross section of the weld joint
Fig. 9 The weld joint with the value body inlet and outlet for D2 heat

300~------------------------~

Distance mm
Fig. 10 Variations of hardness of welded portions

DISCUSSION

Table 4 shows the range of the chemical compositions of NF616. The chemical
compositions of NF616 has been frequently improved from the original
NF616 which was developed by Fujita in 1986. The final chemical composition
range which was proposed by Naoi and Ogami in 1991 is also shown in Table
4. The chemistry range for each element specified in ASME code case 2179 are
not relatively wide. The aim of the ASME committee for determining these
ranges was to estimate the following.
128 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Table 4 The changes of chemical compositions of NF616

Chemical composition/wt':

References C Si Mn Cr Mo W Ni V Nb N Al B

Fujita/
O13 0 05 0 50 10 5 0.2 1.3 0.7 0.17 0.04 0 05 0.005-
19861 . . . . -0.7 -2.2 -0.21-0.07'
Naoi et all 8.0 1.50- 0.10 01 0.02
19914 <0.15 <0.50 <1.00-13.0 <1.0 -2.50 -0.30 < . -0.15
ASME/ 0.07 <0.50 0.30 8.5 0.30 1.50 040 0.15 0.04 0.030 0 04 0.001
1994 -0.13 -0.60 -9.5 -0.60-2.00<' -0.25-0.09 -0.070 < . -0.006
GTAW/
0.065 0.20 1.01 8.94 0.48 1.62 0.36 0.09 0.042 0.032 -
19942
SMAW/
0.080 0.36 1.66 8.73 0.56 1.68 0.64 0.23 0.059 0.034 -
19942

(1) The limitations of C content: maximum 0.13% to improve the weld-


ability
(2) The limitations of Cr content: minimum 8.5% to maintain a good anti-
oxidising property
(3) The limitations of Nb and N content: minimum 0.04% and 0.030%,
respectively to maintain strength at elevated temperatures
(4) The limitations of Mn content: 0.30-0.60% to maintain the strength at
elevated temperatures
On the other hand, welding rods decrease the C content up to the lower level
to maintain good weldability and this causes the increase in the Cr equivalent.
Therefore, it must be necessary to increase the Mn content over ASME
specification for the suppression of 8-ferrite formation.
It is considered that Cr equivalent must be lower than 9.5% at least to
suppress the formation of 8-ferrite. To produce castings with a weight larger
than the tested valve body in our work, it seems necessary to decrease the Cr
equivalent. These heavier castings delay the solidification time, and thereby
have the tendency to form more 8-ferrite than lighter castings with the same
Cr equivalent.
To produce castings free from the blowholes, Si content should be higher
than about 0.3% and N should be lower than 0.050/0.For example, when the
compositional fluctuations are considered, the ASME chemical composition
ranges should be selected for castings.
For chemical compositions of 0.12%C, 0.4%Si, 0.5%Mn, 8.7%Cr, 0.4%Mo,
1.7S%W, 0.3%Ni, 0.2%V, 0.06%Nb, 0.04%N and 0.03%Al, the Cr equivalent
result is 10%. This Cr equivalent is rather high to suppress 8-ferrite formation.
Therefore, it seems necessary to modify the chemistry ranges of the ASME
DEVELOPMENT OF 9CR-2 W CAST STEEL 129

specification to produce the cast steels industrially. The cast steel valves are
mainly used for the steam line and not exposed to the fire flame such as boiler
tubes. Therefore, the Cr content does not necessarily have to be so high a level
as tubes and therefore a B.D%Cr may be allowable for example. Another
reason to decrease the Cr content in the cast steels is that Si acts as anti-
oxidising element. There is concern about the equation for the oxidation of
NF616.2 According to this equation, O.l%Si and 9%Cr steel is equivalent to the
O.3%Si and gO/oCr steel. Furthermore, welding is applied to only two parts
which are the seat ring/valve body and the valve/pipe. The welding of these
are not so difficult, therefore, the higher content of C such as 0.15% may be
allowable for castings. These modifications make the cast steel valves easier to
produce and also reduce the production cost of cast steels.

CONCLUSION

The cast steels equivalent to the rolled NF616 have been developed and
evaluated. The main results are as follows:
1. 8-ferrite of the cast steels vary with the Cr equivalent according to the
proposed equation. The variation of the 8-ferrite with Cr equivalent is
similar to that of the weld deposits of 9%Cr steels. However, in actual
castings which are larger and heavier than that of the tested castings, the
amount of 8-ferrite is expected to be higher for the same Cr equivalent
conditions.
2. The mechanical properties of the cast steels meet the requirements of the
ASME code case 2179, and Charpy impact values also meet the Euro-
pean specification of 41 J at 293 K.
3. The weldability of the cast steels satisfy the MITI specifications and
mechanical properties satisfy the 9Cr-2W specification in ASME code
case 2179.
4. The cast steels which have the strength equivalent to the rolled NF616 at
the elevated temperature up to 973 K can be produced commercially.

REFERENCES

1. T. Fujita: Cost-EPR! Workshop, 19B6, 13.


2. Nippon Steel Co.: Data Package for NF616 Ferritic Steel, 1994.
3. P. Patriarca, S. D. Harkness, J. M. Duke and L. R. Cooper: Nuclear
Technology, 1976, 28, 525.
4. H. Naoi, M. Ogami, S. Araki, T. Ogawa, H. Yasuda, H. Masumoto and T.
Fujita: Nippon Steel Technical Report, 1991, 50, 7.
Section IB:
SERVICE EXPERIENCE
New 9-12%Cr Steels for Boiler Tubes
and Pipes: Operating Experiences and
Future Developments
w. BENDICK*, F. DESHA YESt, K. HAARMANN§ and
J.-C. V AILLANT<JI
* Mannesmann Research Institute, D 47251 Duisburg, Germany
t Vallourec Research Center, F 59620 Aulnoye-Aymeries, France
§ Vallourec & Mannesmann Tubes, D 45466 Millheim an der Ruhr, Germany
Yl Vallourec & Mannesmann Tubes, F 92103 Boulogne-Billancourt, France

ABSTRACT
Starting on 1 October 1997 the activities of Mannesmann and Vallourec in the field of
hot-rolled tubes and pipes for power plants have been combined in a joint venture
called Vallourec & Mannesmann Tubes (V&M Tubes). Therefore the opportunity is
taken to jointly present the experience of these two companies in the production and
development of new 9-120/0 Cr steels.
The development of new 9-12% Cr steels started in the USA with T 91 IP 91 being
standardised in 1983/84. From that time on large research and development
programs have started at Mannesmann and Vallourec. In 1986 Vallourec received
the first commercial order for cold drawn tubes of T 91 from India. Mannesmann's
first deliveries were P 91 pipes for a replacement of P 22 headers in the USA. Since
then T 91 /P 91 material has been used in numerous power plants, both for retrofit-
ting actions and the construction of new plants. Operating experiences and advan-
tages to conventional materials are highlighted, e.g. weight and cost savings,
increases in operational flexibility and efficiency.
Advanced materials are needed for a further increase of steam parameters.
Mannesmann and Vallourec have been engaged in the development of new 9% Cr
steels with tungsten addition: ASTM standardised T92/P92 (1.75% W) and the
new European steel grade E 911 (1% W). Creep tests (with times exceeding 48 000 h
for E 911) show a substantial increase of creep rupture strength with respect to
T 91 IP 91. In addition to tube and pipe production, weldments as well as hot and
cold bends have been made and tested. Several tubes and induction bends have
already been installed in running power plants in order to get first operational
experiences. The standardisation of T 92/P 92 is now effective and that of E 911 is
under preparation.

INTRODUCTION

Major steps to improve the high temperature creep strength of ferritic steels
for boiler applications were taken by Mannesmann and Vallourec in the late

133
134 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

1950s, when they introduced the ferritic-martensitic steels X20CrMoV12-11


and EM 12.2 X20CrMo V12-1 has been used for superheater tubes as well as
for steam pipes and thick section components, whereas EM 12 has only been
used for superheater tubes. Their chemical compositions are given in Table 1.
These steels have been in service for many years in most European and many
other countries.

Table 1 Chemical Composition of 9-120/0 Cr Steels Used in Power Plant Tubing and
Piping

EM 12 X20 T91jP91 T92/P92 HCM12A E911


(T122)

C max. 0.15 0.17-0.23 0.08-0.12 0.07-0.13 0.07-0.13 0.09-0.13


Si 0.20-0.65 max. 0.50 0.20-0.50 max. 0.50 max. 0.50 0.10-0.50
Mn 0.80-1.30 max. 1.00 0.30-0.60 0.30-0.60 max. 0.70 0.30-0.60
P max. 0.030 max. 0.030 max. 0.020 max. 0.020 max. 0.020 max. 0.020
S max. 0.030 max. 0.030 max. 0.010 max. 0.010 max. 0.010 max. 0.010
Ni max. 0.30 0.30-0.80 max. 0.40 max. 0.40 max. 0.50 0.10-0.40
Cu 0.30-1.70
Cr 8.50-10.50 10.00-12.50 8.00-9.50 8.50-9.50 10.0-12.5 8.50-9.50
Mo 1.70-2.30 0.80-1.20 0.85-1.05 0.30-0.60 0.25-0.60 0.90-1.10
W 1.50-2.00 1.50-2.50 0.90-1.10
V 0.20-0.40 0.25-0.35 0.18-0.25 0.15-0.25 0.15-0.30 0.18-0.25
Nb 0.30-0.55 0.06-0.10 0.04-0.09 0.04-0.10 0.06-0.10
Al max. 0.040 max. 0.040 max. 0.040 max. 0.040
N 0.030-0.070 0.030-0.070 0.040-0.100 0.050-0.090
B 0.001-0.006 max. 0.005 0.0005-0.005

After a phase of stagnation, the development of the steel T 91 /P 91 in the


USA has led to a revival in the field of developing new steels for power plant
tubing and piping.3,4 Shortly after its ASTM/ ASME standardisation in
1983/84, large research and development programs have started at Man-
nesmann and Vallourec. In 1986 Vallourec received the first commercial order
for cold drawn tubes of T 91 from India. Mannesmann's first deliveries were
P 91 pipes for a replacement of P 22 headers in the USA.s Since then increasing
amounts of T91/P91 have been produced by both companies and were
delivered world-wide. In addition R&D work continued in the field of
9-12% Cr steels. Starting on 1 October 1997 the activities of Mannesmann and
Vallourec in the field of hot-rolled tubes and pipes have been combined in a
joint venture called Vallourec & Mannesmann Tubes (V&M Tubes).

PRODUCTION AND APPLICATION OF T 91/P 91

The steel T 91 jP 91 has been the subject of extensive R&D programs through-
out the world. Also at Mannesmann and Vallourec a large number of
NEW 9-12%CR STEELS FOR BOILER TUBES AND PIPES 135

investigations have been carried OUt.6,7 Considering the material properties,


similarities with X20CrMoV12-1 have been found concerning transformation
behavior, microstructure as well as processing by hot and cold bending and
by welding. Besides those common features there also are important differ-
ences resulting from the different chemical composition. While the lower
carbon content is of advantage in processing and welding, creep strength is
increased by the precipitation hardening due to V /Nl? carbonitrides.
The outstanding feature for the application of T91jP91 is its higher creep
strength compared to the ferritic-martensitic steels used in the past (Fig. 1). At

90

40

30 ~------~------~------~------~
500 525 550 575 600
Temperature in °c
Fig. 1 Creep Rupture Strength of Heat Resistant Steels compared to P91

550°C the creep rupture strength of the well-known ferritic steel 10CrMo9-10
(P22) amounts to only 45% of that for T91/P91. And there is also a
considerable difference in strength regarding X20CrMoV12-1. This difference
in creep strength can be used to reduce the wall thickness of heavy compo-
nents. An example is given in Fig. 2. Regarding the whole steamline system
this can add up to considerable savings in weight. In planning the two
800 MW units of the VEAG power station at Boxberg, where a comparison
was carried out between X20CrMoV12-1 and P91, the total saving was
estimated at 173 t per unit amounting to a total saving of cost of around 2.6
million DM. This figure does not include saving of welding costs and for line
supports.
136 ADVANCEDHEAT RESISTANTSTEELSFORPOWERGENERATION

o
o
,....

32WTmin. I
• j
0800 ••
I 42WTmin .
4-

Design Pressure: 70bar; Design Temperature: 5650C

Fig. 2 Comparison of the Size of the Reheater Ball Piece in XI0CrMoVNb91 (P91)
with that in X20CrMoV121 for use in the VKR Power Station at Schopau

An essential part of the R&D work on T91/P91 has been to obtain


procedures for processing, fabrication and construction including bending
and welding. The qualification of welding has been extended to dissimilar
metal welds with X20CrMoV12-1 and lOCrMo9-10, thereby making
T91/P91 to be a candidate material not only for applications in new power
plants but also for replacements during retrofitting. Usually replacements are
made by the material originally used. However, the use of T91/P91 with
higher creep strength can be of great benefit, because it allows constructions
with thinner walls improving the flexibility of operation. This can be of
importance for exchanging a whole line system as well as for replacing single
components with extreme wall thickness. An example of the latter case is the
replacement of the P22-header in an American power station, as mentioned
before.' Also whole line systems have been replaced by P 91, e.g. at VKR units
in Scholven replacing 14MoV6-3.
Regarding Fig. 1, the use of T91/P91 becomes even more attractive for
higher temperatures. In fact this steel allows the construction of plants
with higher than conventionally used steam conditions. However, units with
higher steam conditions operate with higher efficiencies, which is both of
economical and ecological importance. Table 2 gives an overview on such
new power plants and projects built or to be built in Germany and Den-
mark.
In conclusion T91/P91 has turned out to be an excellent material that can
NEW 9-12o/oCR STEELS FOR BOILER TUBES AND PIPES 137

Table 2 Application of P 91 in New Power Plants/Projects in Germany and


Denmark

Power Station Utility Unit Size Main Steam Hot Reheat Efficiency

Schkopau'U VKR 2 X 450MW 550°C/285 bar 565°C/70bar "",40.5%


Kirchm6ser(2)(3) VKR 160MW 540°C/85 bar "",50%
Altbach(2)(3) Neckarwerke 330MW 545°C/285 bar 568°C/75 bar "",42%
Schwarze Pumpe'D VEAG 2 X 800MW 552°C/284 bar 570°C/66 bar "",40.5%
Nefo(2) Nordjyllands- 425MW 587°C/310 bar 580°C/100- -47%(4)
vaerket 30bar
Skaerbaekw Skaerbaek- 425MW 587°C/310 bar 580°C/100- -470/0(4)
Gas or Oil vaerkert 30 bar (49%)
Boxberg'D VEAG 2 X >800MW 550°C /285 bar 583°C/67bar -41%
Lippendorf (1) VEAG 2 X 930MW 559°C /285 bar 588°C/67bar -42%
Lubecki" PREAG 425MW 590°C / 300 bar 607°C/70bar -45.7%
HeBler(2) VKR 700MW 585°C / 300 bar 605°C/70bar -45%
Frimmersdorf (1) RWE 950MW 585°C/286 bar 605°C/70bar "",43%
Bexbach'f Saarberg 750MW 583°C/300 bar >78 bar -44%
Franken'f (3) Bayernwerke 600/150MW 575°C/285 bar 595°C/78 bar -43%

(1) Lignite Coal, (2) Hard Coal, (3) Combined Cycle, (4) Seawater Cooling.

be used for retrofitting actions, building of new power plants with conven-
tional steam conditions and also for new advanced plants with supercritical
steam conditions and high efficiencies. Vallourec and Mannesmann have
delivered tubes and pipes in this grade allover the world. Table 3 gives a
short overview containing only the main deliveries.

QUALIFICATION OF NEWLY DEVELOPED 9°1o CR STEELS WITH


W-ADDITION

New power plants with improved thermal efficiency can make a significant
contribution to reduce the overall CO2 emissions. Moreover the operation of
such high efficient power plants have proved to be of economic interest. Both
factors have been the driving force to continue with R&D programs in order
to develop new ferritic-martensitic steels for even higher steam temperatures,
i.e. steels with higher creep strength. Activities in this field are concentrated in
Japan, Europe and USA.8 Present steel developments based on T91/P91 are
characterised by Tungsten additions. They are the ASTM standardised steel
T92/P92, Japanese steel HCM12A (T122) and the European development
E911 (Table 1). TIle 9 Cr steels T92/P92 and E911 differ mainly by their W-
%

and Mo-contents. HCM12A (T122), however, is a 12°/oCr steel with similar


w- and Mo-contents as T92/P92. A special feature of this steel is a high Cu-
content of about 1 to obtain a fully martensitic microstructure after
0
/0

normalisation.
138 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Table 3 Reference List for V &M Tubes Main Deliveries of grade 91 (1993-1997)

Project/Utility Country Customer Application

Southern California Edison USA ABB/CE (USA) Superheater tubes


Public Service Colorado USA AB/CE (USA) Superheater tubes
Clinch River USA Babcock & Wilcox (USA) Superheater tubes
Big Rivers USA Foster Wheeler (USA) Superheater tubes
Black Point Hong Kong Mitsui Babcock (UK) Superheater tubes
and pipes
Keadby Project UK Mitsui Babcock (UK) Superheater tubes
Ferry Bridge UK NEI (UK) Piping
Frimmendorf Germany D. Babcock (Germ.) Superheater tubes
and pipes
Lippendorf & Boxberg Germany EVT (Germ.) Superheater tubes
and pipes
Baudour Belgium GEC Alsthom (France) Superheater tubes
Cordemais II France Babcock Entreprise Superheater tubes
(France)
Fuzhou China Mitsui Babcock (UK) Superheater tubes
and pipes-
Piping
Dangdong-Dalian China Mitsui Babcock (UK) Superheater headers
- Piping
LuoHang China GEC Alsthom (France) Superheater tubes
Rizhao China Babcock (Germ.) Piping
Yang Zhou China Babcock & Wilcox (USA) Superheater tubes
Xigu China Chinese Ministry of Piping
Electricity
Poryong Korea Hanjung (Korea) Superheater pipes
UlsanPower Korea Hyundai (Korea) Superheater pipes
Map Taphu Indonesia Foster Wheeler (Finl.) Superheater tubes
and pipes
Sual Indonesia GEC Alsthom (France) Superheater tubes
and pipes
Pagbilao Indonesia Mitsubishi a
apan) Superheater tubes
Port Kelang 1 & 2 Malaysia B. F. Shaw (USA) Piping
Tuas Malaysia Connex (USA) Piping
Tuxpan (Lopez Mateos) Mexico GEC Alsthom (France) Superheater tubes
Cerrey (Mexico) and pipes

The newly developed Tungsten bearing steels have some similarities, but
also different features. A more detailed characterisation is given elsewhere.v?
Their creep rupture strengths are assumed to be very similar (Fig. 3).
Compared to T91/P91, an increase of 20-300/0 is realised at 600°C and lOsh.
This increase in creep strength is equivalent to an increase in maximum steam
temperature of lS-2SoC.
NEW 9-12%CR STEELSFORBOILERTUBESAND PIPES 139

105 h creep rupture strength, MPa:


150
\

,,
\ Inconel617
V
,
X8CrNiMeNbV 1613
100

50

.1
X 20 Cr Me V 12 1

I-Austeniti~1
l---Ni-base alloy~
o
500 550 600 650 700 750
Temperature.vo

Fig. 3 Materials for Main Steam Lines in Power Plants

Vallourec and Mannesmann have dedicated some work to qualify for the
production of tubes and pipes in grade 92 and E911.
These steels have been studied under the European COST 501 program
with participation from 13 European countries, including steel and tube/pipe
manufacturers, boilermakers, electrode manufacturers, utilities and research
institutes.lv P Both Mannesmann and Vallourec have been active partners of
the COST program. Due to the large number of more than 50 participants,
many data on both steels are available; in the case of E 911, the total data base
is now considered to be larger than the data bases for the Japanese steels
which have been developed earlier. Figures 4 and 5 show the V&M creep test
results at various temperatures for E 911 and grade 92, respectively. The test
data include 8 products from 6 different casts in E911 and 9 products from 8
different casts in grade 92; the testing times have reached more than 48 000 h
for E911.
The main advantage of the co-operation in COST is the fact that E911 and
grade 92 have been characterised in a most comprehensive manner. Not only
the properties of the base material were investigated, but also workability like
hot and cold bending and welding, including the development of optimised
consumables. Figure 6 shows the example of creep tests carried out on one
submerged-are-weld on E 911. The figure includes the mean values of the base
material for comparison. Up to test duration of 10 000 h rupture occurs only in
the base material at 575 and 600°C. At higher temperatures rupture in the
HAZ has been observed for longer testing times, leading to a decrease in
creep rupture strength. Figure 7 presents cross-weld creep tests on a shielded-
140 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

1000

----- - L.-.

Ii
co
•~ - -- ~P-
D. ~ ~ ~~ 1"'- ~ ~~
-
j

k ~ ~ ...H 600°C
",""t- I-~~
:E t""'"l
~i- i'. •.", ~ ..•. ~ ~
.5 100
:g •.... -
e ~ •...•. Irll
en
-~ - Mean Values
1650°C ]

.- Ruptured
4) ~
~~~ning I

10 II
10 100 1000 10000 100000
Time in h

Fig. 4 V&M Creep Test Results on E 911 Base Material

metal-arc-weldment on P 92; similar behavior as for E 911 is observed, that is a


decrease in creep strength due to failure in the HAZ.
Within COST a total of 24 welds on E911 and 9 on grade 92 have been
produced and tested, including for E911 19 similar metal welds and 5
dissimilar welds with P91, X20CrMoV12-1, P92 and the austenitic steel
XSCrNilS-9.

1000

~
•........•..
~
--
-~ "''''"'~ -re--. a -~•.. --....•.
...
"""-
1""-111- I-~
.
--gg:
I-- I-- ~ iii..c II .•.
1-"-
~ r"-'~" ~ ~ ~r ~ ~
e ~ ••• - ~~~ ........-.
lIP
~ ~
625 C
- -~650°C
L__ J

--- "" Mean Values


•• .4 ruptured
... ,.,.
c> ~~ .runnlnq

10 I
10 100 1000 10000 100000
Time in h

Fig. 5 V&M Creep Test Results on Grade 92 Base Material


NEW 9-12%CR STEELS FOR BOILER TUBES AND PIPES 141

1000

-
-- -- - -=-- ...-
---
- -- ----
I--

....
~I"-
r-- :""-1"- --!..

---
r--I'-
r---- 9.'---- Lf?'7soc
- ---
r-- ~["l
-- f-- 1'-- __

---
100
r--I-
~ A ~
I•••
~600~
1-
625°C I
I""" 11

.
.••..•.....•..

iL650°C.J
r-- Mean Values
U I ~ \. Weld (Rup)

"0 [~ Weld (Run)

10 III
10 100 1000 10000 100000
Time in h

Fig. 6 V&M Creep Test Results on E 911 Weld

T92jP92 has been standardised in ASTM/ ASME. T122 is included in


ASME under Code Case 2180. E911 has been approved by the German TDv
and is included in a VdTOV material data sheet. Different ASTM committees
have been contacted for approval of different product forms in E 911, too. The
compilation of a data package for ASME approval is in preparation. The
commercial use of E 911 in Europe is planned for the near future.

100000-,--------,-------,--------,------,

g
~ 1000
i=

10+-----~-----_r----+_---~
1,06 1,08 1,1 1,12 1,14
10001T (KA.1)

Fig. 7 V&M Iso-Stress Creep Test Results on P92 Weld at 120MPa


142 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Field tests of single components have already started on the newly


developed steels in order to get experience in their service behavior. An
overview on tests performed in European power stations is given in Table 4.

Table 4 Application of New W-Bearing Steels in European Power Stations

Power Station Material Grade Size Component Steam Conditions Installa tion

Vestkraft P92 (NF616) ID 240 X 39 Straight Pipe 560°C/250bar 1992


Unit 3 Main Steam

N ordjyllands- P92 (NF616) ID 160 X 45 Header 582°C/290 bar 1996


vaerket HCM12A (T122)
Schkopau E911 ID550 X 24 Induct. Bend 560°C/70 bar 1996
UnitB Hot Reheat
Staudinger E911 ID 201 X 22 Induct. Bend 540°C/213 bar 1996
Unit 1 Main Steam

Skaerbaek E911 ID 230 X 60 Induct. Bend 582°C/290 bar 1996


Unit 3 Main Steam

GKKiel P92 ID 480 X 28 Header 545°C / 53 bar 1997


YEW E911 OD 31.8 X 4 Superheater 650°C 1998
Westfalen E911 ID 159 X 27 Steam Loop 650°C/180 bar 1998
Westfalen P92 ID 159 X 27 Steam Loop 650°C/180 bar 1998

Components made of NF616 and HCM12A were produced in Japan. All


other components were produced by Mannesmann and V&M, including the
P 92 components. In fact the replacement of a damaged header at GK Kiel by a
new header made of P 92 was the first commercial application of this steel
grade in Europe; it received an individual approval for this project from
TOY.

CONCLUSIONS

Two new steel grades have been emphasised in this document: T92/P92,
already ASTM/ ASME standardised and European E 911, standardisation of
which is under progress. Both are Tungsten modified 90/0Cr steels with 1 %

Tungsten for E911 and 1.75% for T92/P92. Tube manufacture and fabric-
ability of pressure parts (bending and welding) can be performed under the
same operating conditions as for T91/P91. Thanks to improved creep
properties (+20/30%) compared to conventional T91/P91, it is believed that
these steels will fulfill increasing needs for pressure components of advanced
new projects, or for retrofitting of large conventional units.
NEW 9-120/0CR STEELS FOR BOILER TUBES AND PIPES 143

REFERENCES

1. P. Bettzieche: Mitt. VGB 57, 1958, 393.


2. M. Caubo and J. Mathonet: Revue de Metallurgie, May 1969.
3. V. K. Sikka, C. T. Ward and K. C. Thomas: Ferritic Steels for High Temperature
Applications (Proc. Conf.), American Society for Metals, 1983, pp. 65-84.
4. D. A. Canonico: 'Technical Program and Data Package for Use of Modified
9Cr-1Mo Steel, ASME Sect. I and VIII, April 7, 1982'.
5. C. P. Belanca, J. Infield, M. Zschau and K. Haarmann: 1992 ASME Pressure
Vessel & Piping Conference, New Orleans.
6. W. Bendick, K. Haarmann, G. Wellnitz and M. Zschau: VGB Kraftwerk-
stechnik (English Issue), 1993, 73, 73.
7. F. Pellicani, J. C. Vaillant, H. Godinot and J. Roger: 'Welding of Pipe in
ASTM A335-P91', COST Conference, Liege, October 1994.
8. R. Blum, J. Hald, W. Bendick, A. Rosselet and J.-C. Vaillant: VGB
Kraftwerkstechnik (English Issue), 1994, 74, 553.
9. W. Bendick, K. Haarmann, G. Wellnitz and M. Zschau: 3R international,
1994, 33, 411.
10. W. Bendick, K. Haarmann, M. Ring and M. Zschau: VGB Kraftwerkstechnik
(English Issue), 1997, 77, 380.
11. B. Lefebvre, J. C. Vaillant and F. Pellicani, 'Manufacture and Properties of
Tubes and Pipe in New W-Modified 9CrMo Steel', COST Conference,
Liege, October 1994
12. F. Pellicani, J.-C. Vaillant and H. Godinot: 'Proprietes d'Emploi et de Mise
en Oeuvre de Tubes en Acier a 9°1o Cr et 0,5 Mo Modifie au W
%

(T92/P92)" AFIAP, Paris, October 1995.


Properties After Service Exposure of
2.25Cr-l.6W-V,Nb (HCM2S) and
12Cr-O.4Mo-2W-ICu-V,Nb (HCM12A)
Steel Tubes in a Power Boiler
Y. SAWARAGI*, K. MIYATA* and S. YAMAMOTO+
Sumitomo Metal Industries, Ltd.
* 1-8, Fuso-cho, Amagasaki 660-0891, Japan
t 1, Nishino-cho, Higashimukojima, Amagasaki 660-0856, Japan
F. MASUYAMA§, N. KOMAI§ and T. YOKOYAMA~
Mitsubishi Heavy Industries, Ltd.
§ 5-717-1, Fukahori-machi, Nagasaki 851-0392, Japan
YI 3-1, Minatomirai 3-chome, Nishiku, Yokohama 220-8401, Japan

ABSTRACT
Two kinds of ferritic heat resistant steels, 2.2SCr-1.6W- V,Nb(HCM2S) steel and
I2Cr-0.4Mo-2W-ICu-V,Nb(HCM12A) steel, have been developed for boiler tubes
and pipes. Both steels have already been approved by the ASMEBoiler and Pressure
Vessel Code Committee for use in section I construction. The allowable tensile
stresses at 600-62SoC of HCM2S(T23) and HCM12A(T122/P122) are remarkably
higher than those of conventional steels, T22 and T9I, respectively. The high creep
rupture strengths of these steels were accomplished by substituting W for a part of
Mo. The superheater and reheater tubes manufactured from these new steels were
put into a field service experience in a large utility power boiler since April 1993.The
tubes were removed to investigate the properties after one-year and three-years
service. The field service test results demonstrated that the practical performances of
both these steels were good, ensuring the superior corrosion resistance and less
material degradation.

INTRODUCTION

It is a general trend that fossil fired power plants need to reduce CO2
emissions. At the same time, the reduction of power generation costs requires
low-cost and high-strength steels. Considering these circumstances, the
research and development of high-strength ferritic steels have been carried
out. Tungsten stengthened 2.2SCr steel (HCM2S)1 and 12Cr steel (HCM12A)2
have been developed for fossil fired boiler materials by Sumitomo Metal
Industries Ltd. and Mitsubishi Heavy Industries Ltd. Both steels have already
been approved by the ASME Boiler and Pressure Vessel Code Committee for

144
PROPERTIES AFTER SERVICE EXPOSURE 145

use in section I construction. The allowable tensile stresses at 600-650°C of


HCM2S (T23) and HCM12A (T122/P122) are remarkably higher than those of
conventional steels, T22 and T91, respectively. Furthermore, the field expo-
sure tests on both steels have been carried out in a large utility power boiler in
Japan since April 1993. The superheater and reheater tubes were removed
after one-year and three-years services in order to investigate the materials
properties and deterioration due to long term exposure. This paper describes
the results.

DEVELOPMENT PHILOSOPHY AND SPECIFICATION

Figure 1 shows the philosophy for the development of low C-2.25Cr-


1.6W-V-Nb steel (HCM2S). The carbon content was lowered to less than

Weidabil ity Creep strength

Fig. 1 Development philosophy of HCM2S steel

0.10/0in order to improve the weldability and applied under the as welded
condition without pre-weld and post-weld heat treatment. The maximum
quenched hardness should be controlled below Hv 350. The excellent creep
rupture strength of this steel was accomplished by substituting W for a part of
the Mo and the addition of a slight amount of boron. The optimum amounts
of solution strengthening elements (W, Mo) and precipitation stengthening
ones (V, Nb) were considered to be 1.6W-O.IMo-0.25V-0.05Nb (wt.%). The
microstructure in normalised and tempered condition for this steel consists of
fully tempered bainitic structure, which leads to the sufficient toughness.
Figure 2 shows the philosophy for the development of 0.1C-11Cr-
2W-0.4Mo-lCu-V,Nb steel (HCM12A) which can be applicable to large
diameter and thick walled pipes. Considering the corrosion resistance, the Cr
content in the steel was increased compared with P91 steel. The excellent
creep rupture strength of this steel was accomplished by substituting W for a
part of Mo and the addition of slight amount of boron, as well as HCM2S. The
146 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

VN, stable & effective


Nb(C,N), grain refine-
ment

W,stable

Stable
long-term strength

Fig. 2 Development philosophy of HCM12A steel

content of C, which is an effective element for suppressing 8-ferrite formation,


was reduced in order to improve the weldability. The formation of 8-ferrite
should be suppressed by the control of Cr equivalent less than 9 wt. in order%

to keep the toughness for large diameter and thick walled pipes. The lowering
of Cr eq. was accomplished by the addition of Cu. While, in the case of tubes,
this steel contains a slight amount of 8-ferrite due to the increase in Cr content
which is effective to improve the hot corrosion resistance.
Based on the above consideration, the specifications of chemical composi-
tions of the developed steels were determined as shown in Table 1.

PROPERTIES

Allowable Tensile Stresses


The allowable stresses for HCM2S and HCM12A are shown in Fig. 3. The
allowable stress at 600°C for HCM2S is 1.8 times higher than that of T22 and
slightly lower than that of T91. It was demonstrated that the solid solution
strengthening effect by W in HCM2S is larger than that of Mo in 10/0 Mo steel
such as T22.3 The allowable stress at 600°C of HCM12A is 1.3 times stronger
than T91. It was clear that the increase in W content was effective in order to
suppress the softening and/ or recrystallisation.I
PROPERTIES AFTER SERVICE EXPOSURE 147
0 I 0
M ~ 0
0 OM
Z VI 0 00

I
Lf)0 0
o \.0 Lf)
00 0
00 0
~ 00 VIO

I I
N 00 ~ 0

Z 00 OM

-.~~
00 00

0 I I
£ :> 00
N M
00
Lf)0
MM
00
<
N
M
~ I I
U Lf)Lf) 00
~ ~ r-, Lf)Lf)

'"d
~ ~ ~ ~N
~cd
UJ I I
C'l Lf)0 Lf)Lf)
0 OM C'l\.O
~ ~ 00 00
U
~
<...+--4
0 I
I 00
rfj 00 0Lf)
~0 ~ 0\ \.0
ON
U ~N MM
:E rfj
0
0
~0 Z VIO
Lf)

u
~u
's
I
00
Mt-...
;J
...c:
OJ
U O~
u
..8~ 0 0
M M
rfj 0 0
~ UJ VI 0 VI 0
,9
~ cd
u 0 0
Su M
0
N
0

c,
OJ ~ VI 0 VI 0
UJ
~ I
CIJ
....-4
,.0
00
M \.0 r-,
0

«l
Eo-!
~ 00 VIO

0 0
io Lf)
(J) VI 0 VI 0

I I
~0 0
M
t--..~
OM
U 0 0 00

] UJ
<
N
M
~
~OJ~ ~ ~
U u
::E ~ :r:
148 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

120
as
~100
rn
rn
! 80
1;)
CD
15 60
'~"
~ 40

20

o~------~--------~------~
400 500 600 700
Temperature (Ge)

Fig. 3 Comparison of allowable tensile stresses between the developed steels


(HCM2S, HCM12A) and conventional steels for boiler

Long Term Ageing Properties


The Charpy impact properties at DoCfor aged materials were shown in Fig. 4.
The impact value for HCM2S tend to decrease according to the increase of
ageing duration when the ageing temperature is 550°C. However, this steel is
found to have enough values even after long term exposure. As for HCM12A,
the impact value tends to decrease according to the increase of ageing

300~------------------~ 100--------------------------~
10x 10,2mmVnotch
!
N N 1Ox 10,2mm V notch
250>- ----0..- ~ooe ~
3. 80
o As NT
P , P 6 550
o o
1U 200 ~ ,, 600 e 0
<, '6 0 600
CD
:::l
, : 60 ~, ....- -- - -- --Q ~.--'---65-0--I'
''Q. :J
~ 150 ~
',,;50 e
o

~c. ~c. 40
.s 100
"0
.~
~
as 50
e:as 20
fj s
o AsN.T. 1000 3000 10000
Aging time (h)

(1) HCM2S (2) HCM12A

Fig. 4 Charpy impact properties at O°Cafter ageing for HCM2S and HCM12A
PROPERTIES AFTER SERVICE EXPOSURE 149

...
,, \

80
\
,
\

. .
1

\ T91 T22
, \

\
Cracking ratio C , (2 25Cr-1Mo) \
~ 60 h ,(Mod.' \/P91
C=t:r x 100(%) \)Cr-1MO) /
OJ
~40 .\,
o \
as
020 ~\ \
\
\
HCM2S \
/ \
50 1 0 150 200 250 300 350 50 150 200
Preheating temperature (OC) Preheating temperature (OC)

(1) HCM2S (2) HCM12A

Fig. 5 Comparison of y-groove weld cracking ratio between the developed steels
and conventional steels for boiler

temperature and/or ageing duration. However, this steel is found to have


enough values even after long term exposure.

Weldability
The results of y-groove restraint cracking test for HCM2S and HCM12A are
shown in Fig. 5. The cold cracking susceptibility for HCM2S with low carbon
is superior to that for T22. This suggests that the HCM2S can be applicable
under the as welded condition without pre-weld and post-weld heat treat-
ment. The cold cracking susceptibility for HCM12A is superior to that for P91
by controlling the amount of carbon to less than 0.14%.
The original matching welding consumables (GTAW, SMAW, SAW) for
both steels have already been developed.v-

FIELD EXPOSURE TEST

The field exposure test for HCM2S; and HCM12A was conducted by instal-
ling test tubes into the superheater and reheater sections of a 156 MW utility
boiler. Table 2 shows the main specifications of the boiler. The installed
locations and tube dimensions of the test tubes are shown in Fig. 6.
After 1 year and 3 years service exposure, the test tubes were removed from
the boiler. The net service exposured times are 9 200h and 20 S09h, respec-
tively.
Dimensional measurements, evaluation of mechanical properties and cor-
rosion resistance, and microstructural observation were performed on the
removed tubes.
150 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Table 2 Specifications for the boiler

Items Contents

Boiler Type Forced Circulation Type


Maximum Operating Pressure Superheater: 19.2MPa
Reheater: 4.2 MPa
Steam Temperature Superheater Outlet: 574°C
Reheater Outlet: 543°C
Feed Water Temperature 267°C (at Economiser Inlet)
Amount of Main Steam Flow 510 000 kgf/h (at Maximum Continuous Loading)
Amount of Reheater Steam Flow 427770 kgf/h (at Maximum Continuous Loading)

Q) TP347H + HCM12A + TP347H (<1>38.1x t7.4)


@ TP347H + HCM2S + T22 + T91 (<1>42.7x T9.4)
@ HCM9M + HCM12A + TP347H + TP321H + HCM9M (<1>54x t6.0)

Fig. 6 Installed location of HCM2S and HCM12A tubes

Chemical Compositions
The results of chemical composition analysis for the removed tubes are shown
in Table 3. Each element satisfies the specification.

Metallography
Figure 7 shows the microstructure after 3 years service for HCM2S and
HCM12A. HCM2S consists of fully tempered bainite without ferrite. While,
HCM12A consists of tempered martensite containing a small amount of
PROPERTIES AFTER SERVICE EXPOSURE 151

Table 3 Chemical compositions of 3 years serviced tubes (wt.%)

Steel C Si Mn P S Cu Ni Cr Mo V Nb W N

S HCM12A 0.10 0.30 0.53 0.011 0.001 0.85 0.35 12.40 0.35 0.20 0.047 1.89 0.052
r
hupt - HCM12A 0.10 0.29 0.53 0.011 0.001 0.85 0.34 12.30 0.35 0.20 0.046 1.88 0.052
ea er TP347H 0.08 0.64 1.49 0.024 0.001 0.10 12.40 18.40 0.19 - 0.74 - 0.049

Super- HCM2S 0.06 0.19 0.48 0.021 0.001 - 2.25 0.13 0.26 0.047 1.66 0.006
heater T22 0.11 0.25 0.38 0.016 0.010 - 2.10 0.93 - 0.008

HCM9M 0.08 0.31 0.55 0.013 0.006 - 9.20 2.07 - 0.016


Re- HCM12A 0.07 0.28 0.54 0.012 0.001 0.48 0.20 12.20 0.36 0.21 0.048 1.85 0.052
heater TP347H 0.09 0.47 1.51 0.024 0.001 - 12.72 18.53 - 0.86 - 0.045
TP321H 0.08 0.49 1.67 0.023 0.001 - 10.75 17.15 - Ti: 0.51 - 0.008

(1) MCM2S(S/H) (2) HCM12A(S/H) (3) HCM 12A(R/H)

Fig. 7 Optical microstructure of 3 years serviced tubes

8-ferrite. There were little differences in optical microstructures between


virgin materials and serviced ones. The electron microstructural observations
demonstrated that the main precipitates were V(C,N), M23C6 and M7C6 for
virgin and used HCM2S. While, in case of HCM12A, the intermetallic
compound which consists of Fe and W took place during exposure.

Mechanical Properties
The tensile test results at room temperature for removed tubes are shown in
Fig. 8. With respect to HCM2S, there were little changes in tensile strength
and 0.2% proof stress due to exposure durations. The strength levels for
removed tubes of HCM2S are higher than those for T22. While, HCM12A
showed a difference in the tensile strength and 0.2% proof stress between the
152 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

(i
D.. 800 ~ ~ Ci 800 ~
D.

~---=:----:
~ ~
s:
c,
f-
f-
J::.
C,
c:
e 600
en
f-
!600 f-
~
..! en
~
&---- ~----A& 0 HCM12A
'ec:n I-
'enc: r-

6 HCM9M
Q)
0 HCM12A {E. 400 - • TP347H
F 400

I-
TP347H • TP321H
6 HCM2S

J I I I I
T22

~ 600 "£ 600 ~


~ ~
UJ
~ -
UJ
e ~ e ~
6__ ~
!o !o 400 -
1..----1.._--,..
400 I-

----6
o
o
a: ~ A
.~;a..::::-e.------"
a: - e_-- __ --- -
cP- cP-
d 200 - 'ML---" C\I
d 200 '-

I I I I I I
o 10000 20000 o 10000 20000
Service duration (h) Service duration (h)

(1) Superheater (2) Reheater

Fig. 8 Tensile strength and 0.2% proof stress at R.T. for removed tubes

materials used in the superheater and in the reheater. The one with lower Cu
content used in the reheater contained more 8-ferrite. However HCM12A
superheater and reheater tubes showed that there were no remarkable change
in tensile strength and 0.20/0proof stress between 1 years service and 3 years.
The change of hardness behaviour for each steel was almost similar to the
change of tensile behaviour as shown in Fig. 9.
The Charpy impact properties at O°Cfor removed tubes are shown in Fig.
10. The Charpy impact value for both steels deteriorated after 1 years service,
however they tended to saturate after 3 years. It can be said that both steels
have kept good enough values even after 3 years exposure from the view
point of practical applications.

Creep Rupture Properties


The creep rupture properties of removed tubes are shown in Fig. 11 and Fig.
12. The results for HCM2S indicated that the creep rupture strength at 550°C
was laid along the lower band of virgin material, while the strength at 600°C
was almost the same as the average strength of the virgin material. There
were no differences in creep rupture strength between 1 year and 3 years
service. The creep rupture strength behaviour of removed HCM12A tubes
PROPERTIES AFTER SERVICE EXPOSURE 153

r--. o

l:1
HCM12A
TP347H ~'~'----------
HCM2S 0
6.
HCM12A
HCM9M
c;

• T22
c;; TP347H
~ 250 -
>
~
g~--Q:S:O
--~> 250 •
E TP321H

rn
m
c::
200
"'C

«;
::r:
150 f- A- - - -~- - - - - ~ 150
I I I

o 10000 20000 o 10000 20000


Service duration (h) Service duration (h)

(1) Superheater (2) Reheater

Fig. 9 Hardness at R.T. for removed tubes

150----------------
8tH: 10x5x2mmV RIH
A/H:10x 2.5x 2mmv • :S/H
It): I
300~---------------~

O~~O---1-0-0~O-O----20-0~O-0~ O~~------~------~~
o 10000 20000
Service duration (h) Service duration (h)
(1) HCM12A (2) HCM2S

Fig. 10 Charpy impact properties at O°Cfor removed tubes

was almost similar to HCM2S. It was demonstrated that the both steels have
little degradation in creep rupture strengths after 3 years exposure.

Steam Oxidation Resistance


The relationship between the steam oxidation scale thickness and the service
duration for removed HCM2S and HCM12A tubes is shown in Fig. 13. The
scale formed on both steels consisted of a two layer structure, and there was
no exfoliation in their scales. The steam oxidation resistance of HCM2S was
slightly superior to that of T22 steel, although the Cr contents in both steels are
the same. The growth rate of the scale on HCM12A in the superheater seemed
to be slower than that of HCM2S and T22. It was demonstrated that the steam
154 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

o 600°C
<> 650 e
0

y 575°e

(if
n, 200
~
UJ

e
UJ

en
100

50

10 102 103 104 105


Rupture time (h)

Fig. 11 Creep rupture properties for removed HCM2S tubes

500
0 550°C
0 600°C
400 6S00C
700 e G

300

l200
~
UJ
UJ
e
Cii
100

c: • : 3-years service
50

10 102 103 104


Rupture time (h)

Fig. 12 Creep rupture properties for removed HCM12A tubes

oxidation resistance of HCM12A with 12 Cr was superior to that of HCM9M


%

with 9 Cr. While, the scale thickness on austenitic steels such as TP347H and
%

TP321H were thinner than ferritic steels, but the exfoliation phenomenon was
observed in TP321H after 3 years service.
PROPERTIES AFTER SERVICE EXPOSURE 155

140 0 HCM2S
140 o HCMl2A

• T22 • HCM9M

120 b. HCM12A 120
TP347H

~ 100
UJ
• TP347H
Il00
UJ
• TP321H

mc: 80
UJ
Q)
t: 80
-"o -"o
~
Q)
60 5
Q)
60
ro
(.)
Cij
o 40
en en
20

---
20
.•_----A
0~-0~---1-0~0-00--~20~0~O~0~ 0
0 10000 20000
Service duration (h) Service duration (h)

(1) Superheater (2) Reheater

Fig. 13 Steam oxidation resistance for removed tubes

CONCLUSIONS

The field exposure tests of HCM2S and HCM12A steels with high allowable
tensile stress have been carried out by installing the test tubes in the
superheater and reheater sections of a Japanese utility power boiler.
The test tubes were removed after one-year and three-years services in
order to investigate the materials properties and deterioration due to long
term exposure. The results obtained are as follows.

1. The tensile strength for HCM2S become higher according to the increase
of service duration. While, there was little change in tensile properties
for HCM12A between virgin and serviced materials.
2. The Charpy impact value at aoc deteriorated after 1 years service for
both steels, however they tended to saturate after 3 years service. It can
be said that both steels have kept good enough values even after long
term exposure.
3. The creep rupture strength for both steels were found to be good and no
degradation even after 3 years service.
4. The steam oxidation resistance of HCM2S was slightly superior to that
of T22 steel. The steam oxidation resistance of HCM12A was found to be
superior to that of TP321H austenitic steel in consideration of the scale
exfoliation.
5. Judging from the above results, it may be concluded that the practical
performances of both steels are good and they can be applicable for
superheater and/ or reheater tubes, replacing conventional steels such as
T22 and/or T91.
156 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

REFERENCES

1. F. Masuyama, T. Yokoyama, Y. Sawaragi and A. Iseda: PVP-vo1.288, Service


Experience and Reliability Improvement: Nuclear, Fossil and Petrochemical
Plants, ASME, (1994), 141.
2. A. Iseda, Y. Sawaragi, S. Kato and F. Masuyama: Proc. 5th Int. Conf on Creep
Materials, Lake Buena Vista, FL., 18-21 May, 1992, 389.
3. Y. Sawaragi, A. Iseda, F. Masuyama and T. Yokoyama: Proc. 2nd Int. Conf
on Heat Resistant Materials, Gatlinburg, Tennessee, 11-14 September
1995,277.
4. K. Ogawa, A. Iseda, Y. Sawaragi, F. Masuyama and T. Yokoyama: Proc. Int.
Conf. on Power Engineering-95, Shanghai, 22-26 May 1995, 1065.
Use of X 10 CrMoVNb 9-1 Steel in
Power Plant Retrofitting Applications-
Experience and Application Potential
B. HAHN, V. BAUMHOFF and M. ZSCHAU
Mannesmann Demag AG, Energie und Umwelttechnik, Theodorstr. 90,
Dusseldorf, Germany

1. INTRODUCTION

The harmonisation and the imminent opening of the national energy markets
on the one hand and the constraints imposed by environmental protection
requirements on the other hand have led in recent years to rethinking in the
field of power plant technology. As well as the requirement for increasing the
thermal efficiency of fossil fired power plants, the demand for increased
reliability at reduced maintenance costs determine the future progress of
development in this field. In Eastern Europe and in the emerging Asian
markets, retrofitting the existent plants, as well as the building of new plants
are being carried out in parallel. This situation requires an effective use of
materials. Following the qualification of X 10 CrMoVNb 9-1 for use in
conventional power plants, new methods have been developed to raise steam
parameters and improve thermal efficiency. The high creep-rupture strength
and good fabricability of this steel enables it to be used effectively in
retrofitting old power plants in Eastern and Western Europe. This paper is
intended to report on this experience.

2. MATERIALS USED SO FAR AND OPERATIONAL EXPERIENCE

While the selection of materials for use in power plants in Asia is based on the
ASMEI ASTM standards, which is in good agreement with the selection of
materials in accordance with DIN 17175,1 the steels used in Eastern Europe
are mainly Russian steels, which have undergone their own course of
development.'
Table 1 gives an overview of the materials frequently selected for boiler and
pipework applications in Western and Eastern Europe. Until the political
change in late 80s, the Russian steels were used in the power plants in the
then Eastern-bloc and also in China and India. For applications in the creep
range, CrMo V steels were preferentially selected. In the years before, the
boiler and pipework components operated in the temperature range between
525°C and 560°C were mainly made of 12Ch1MF. This steel is similar to 14

157
158 ADVANCEDHEAT RESISTANTSTEELSFORPOWERGENERATION

Table 1Overview of materials used so far for boiler and pipework components
operating in creep range

Material Delivery to: Country of Origin Main Temp. of Application

13 CrMo 4-4 DIN 17175 FRG Up to 520°C


10 CrMo 9-10 DIN 17175 FRG Up to 540°C
14MoV 6-3 DIN 17175 FRG Up to 545°C
X 20 CrMoV 12-1 DIN 17175 FRG Up to 550°C
RF*
12ChlMF TU-14-346-75 Up to 560°C
(formerly USSR)
RF*
12Ch2MFSR TU-14-346-75 Up to 560°C
(formerly USSR)
RF*
15ChlMIF TU-14-346-75
(formerly USSR) Up to 550°C
(15 CrMoV 5-10) vdTOv-WB 506
FRG
RF*
12ChllV2MF TU-14-346-75 Up to 585°C
(formerly USSR)
Steel 15 128
N 415128 Chechnya/Slovakia Up to 550°C
(CrMoV)
* Russian Federation

MoV 6-3 in strength and fabricability. Following satisfactory experience


gained with the use of this steel in the VEAG power plants in the new federal
states of Germany, it has become popular under the designation 15 CrMoV
5-103 in Germany. The Mannesmann pipe mills have processed so far more
than 10 000 t of this steel. It was originally developed with the designation
15CIMIFL and frequently used as cast turbine casings in the Russian turbine
designs. The first use of this steel as pipework in the turbine interior was also
made in these designs. It is very similar in chemical composition to cast steel
GS 17 CrMoV 5-11. From the point of view of the application spectrum of the
Russian boiler steels, 12Ch2MFSR has not gained much importance. It is
microalloyed with boron and aimed to serve as a material for superheater
tubes in the boiler, for higher temperatures up to 620°C. In our opinion, the
chemical composition of this steel is not suited to fulfil such a requirement.
This has been indeed confirmed in practice. 12Chl1V2M (EI 756), which is a
11% Cr steel, is also limited in its use, although this steel is reported to
provide satisfactory performance when used as a superheater tube for
temperatures up to 585°C4,5and has been in use satisfactorily in six 210 MW
units of Boxberg II power plant in Eastern Germany. It is similar in chemical
composition to X 20 CrMoVW 12-1, except for its lower carbon content and a
higher tungsten content of 2%.
It has been thought for a long time that the above-mentioned set of
USE OF X 10 CRMoVNB 9-1 STEEL 159

materials are well established and there is no need for steel development
beyond X 20 CrMoVNb 12-1. Increased environmental awareness and an
economic need for increasing the thermal efficiency of fossil fired power
plants prompted Mannesmann in the mid-eighties to make arrangements for
using P 91 - which was originally developed in the USA for fast breeder
applications - in conventional power plants. Ever since its first commercial
use in 1991 as part of a qualification programme, there has been no new
power plant in Germany in which this steel has not been used for main steam
pipework systems.

3. PROPERTIES OF X 10 CrMoVNb 9-1/P 91

Extensive information on the properties and fabricability of X 10 CrMoVNb


9-1 has been published earlier.6-10 Therefore, only the essential characteristics
of this steel needs to be presented here.
The transformation characteristics and the microstructure of this steel are
similar to those of X 20 CrMoV 12-1, because of their similar alloy designs.
Owing to the lower carbon content, its martensite start and finish tem-
peratures are raised by about 100°C. For the same reason, the hardness of this
steel in the as-quenched martensitic condition is reduced by about 150 HV 10.
Fig. 1 shows a continuous cooling transformation diagram for this steel. It is
more readily viable to fabrication. For instance, it is markedly less susceptible

chemical C Si Mn P S N AI Cr Ni Mo V Nb
composition
in% 0.10 0.36 0.42 0.017 0.004 0.058 0.024 8.75 0.13 0.96 0.20 0.07

1000

900
Ac1b = 810°C A+K

t 800

700
normalizing temperature 1040°C
(- 1.~~-
F+K
~
-
600 holding time 20 min
.S

---- h[e-
grain size after quenching ASTM 10
:;
Q)
500
e
Q)
a.
400 I---

Ms 410
E
.$ 300 ~I
200
M
100
1 101 102 105
seconds ~
cooling time between 800 and 500°C

10 100
reduced wall thickness S (1 -a-> in mm for air cooling
Fig. 1 Continuous cooling transformation diagram for X 10 CrMoVNb 9-1
160 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

austenitization 1050 °C 1 h a.c.


1,200 r--Y""'"----..--,----T--r---.,...-...--__._-_ 250

t 1000~~~ri-~--~-+--+-~~~ 200

1:E
Z
800 150 t
Q)
::;
.5 o
E
a:
600~~~4-~~~~~+-~~~ 100 :s-
<l
"c
'~ 400~~~~~~~~~+=~~~ 50
%
a:
o
650 675 700 725 750 775 800 825 800
temperature for 1 h tempering in °C --..

Fig. 2 Tempering behaviour of X 10 CrMoVNb 9-1

to stress corrosion cracking in the hardened condition after hot working or


welding. The threat of cold cracking during cooling after welding is nearly
precluded. Consequently, unlike the components made of X 20 CrMoV 12-1,
the components made of X 10 CrMo VNb 9-1 may be allowed to cool to room
temperature, provided that certain precautionary measures are adopted.
The tempering behaviour of X 10 CrMoVNb 9-1 is shown in Fig. 2. The
upper limit for tempering temperature is given by the Aclb temperature. The
heat treatment of the steel consists of austenitising for 1 h at 1050°C followed
by air cooling and subsequent tempering between 750°C and 770°C. Temper-
ing studies of finished components showed that extended tempering times
(>25 h) do not significantly reduce the strength, compared to the starting
condition. Of great advantage in the context of welding, particularly when
making dissimilar metal welds between X 10 CrMoVNb 9-1 and low-alloy
steels, is the high toughness of X 10 CrMoVNb 9-1. Fig. 3 shows a comparison
of the toughness of this steel with that of other high temperature steels.
X 10 CrMoVNb 9-1 has a higher creep-rupture strength than that of X 20
CrMo V 12-1, especially in the higher temperature range, as can be seen in Fig.
4. The difference in 100 DOD-hourcreep-rupture strength at 600°C between the
two steels is about 53%. The advantages that can be derived from this high
creep-rupture strength in component design are obvious. For instance,
components can be designed with a lighter weight. The resultant reduction in
thermal stresses during non-steady plant operation enables the components
to perform more favourably, thereby increasing their service lives.

4. PROCESSING OF X 10 CrMoVNb 9-1

Extensive work has shown that X 10 CrMoVNb 9-1 responds favourably to


hot and cold working as well as to welding.v l'' Figures 5 and 6 show the
USE OF X 10 CRMoVNB 9-1 STEEL 161

Specified minimum
- individual value

Fig. 3 Comparison of the impact toughness of various high temperature steels

200

i
a.m
:E 100
.s
fn
fn
80
cu
...,
J.

fn 60 64A:P91

o o • : X 20
40
o :X 20 average values
to DIN 17175

2~OO 2 5 101 2 5 102 2 5 103 2 5 104 2 5 1052 5 106


time~

Fig. 4 Comparison of the creep rupture strengths of X 10 CrMoVNb 9-1 and X 20


CrMoV 12-1

tensile properties and impact toughness of a hot induction bend in the post-
bend hardened and tempered condition. Cold bends were also studied in the
same fashion and good results were obtained. The use of these bends is
however limited to small pipework sections only.
162 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

1000 100

900
EJ-- ~-1l!I
90

...- -
UTS
--
- -- ..•.- ,--
\ -
800 80
-II
700 70

t
\ reduction of area
600 ~ ~
I
60

t
....,
0
<,: 0.2 o/~ offset YS
N 500 50

--
E
cf.
~ 400
'-'
----r-----= 40

300 .6- 30
-~.
-6_ fr-
f--lr--
tr--
200 \ 20
elongation (A5)
100 10

o 0
starting extrados entrados neutral extrados entrados
pipe zone
test temperature: RT test temp.: 600°C

Fig. 5 Tensile properties of an X 10CrMoVNb 9-1 induction hot bend in the post-
bend hardened and tempered condition

ISO V-notch specimens


260

240

t<l>

.- -
'S 220
-,
-~
0

.s
~ ~
>- ----
E>
<l>
c:
<l>
200
t>~
a.
.S
180

160
starting pipe tension zone compr. zone neutral zone

Fig. 6 Impact toughness of an X 10 CrlvloVNb 9-1 induction hot bend in the post-
bend hardened and tempered condition

The steel has also been studied for its amenability to welding by all relevant
welding methods (TIG, manual metal arc and submerged-arc). The studies
confirmed that the steel has an improved weldability, as expected on the basis
of its chemical composition. As already mentioned, the welds are charac-
terised by reduced hardness and improved impact toughness, compared to
welds in X 20 CrMoV 12-1. Table 2 shows, by way of example, the hardness
USE OF X 10 CRMoVNB 9-1 STEEL 163

Table 2 Hardness (HV 10) distribution in filler and cap passes of a submerged-arc
weld in comparison with that in a manual metal arc weld after a PWH of 4 h 750°C,
AC (base material: X 10 CrMoVNb 9-1)

Welding position Base material Heat-affected zone Weld metal

Grain-coarsened Sub critic al


HAZ HAZ

SAW (flat position) 206-215 253 195 232-253


Manual PF 232-253
metal PE 206-215 254 197 233-252
arc PA 241-255

distribution in filler and cap passes of the welds deposited by submerged-arc


welding and manual metal arc welding. The creep-rupture strength of a
matching composition weld in 10 CrMoVNb 9-1 is compared with the creep-
rupture strengths of X 20 CrMoV 12-1 and 10 CrMoVNb 9-1 base materials in
Fig. 7. It can be seen that the creep-rupture strength of the weld metal is
significantly higher than that of X 20 CrMoV 12-1 base material.
To facilitate broad use of X 10 CrMoVNb 9-1, especially in retrofitting
projects, the behaviour of dissimilar metal welds between X 10 CrMoVNb9-1

Stress, MPa
103 , I I , " I I I I , , I I I I I
8 ~f-

- Parent material P 91 (MFI extrapolation)


6 -f-

-- Parent material X20 Cr Mo V 12 1


4 I I I
I I
3
/5500C"'-1-
I I --r..a:-~ ~
j)j~~ ~
2
.
600°C ---r-.."",-
•...r---. ~~~
650°C b,.•
" " .•. ....
~, ~
r--........... '

~~ 0
0
1'<0... o :->••••
o ......
".'"
"""

1'0.,
II 0'" I"'"
'. ~,
Cross weld specimens
4 (unnotched, tempered 2h 750oCAC) 0 ...•...• "
3
e,A Rupture in parent material " •.
2 '.
0,0 Rupture in HAZ
0-, fx. Specimens still running
I I I I I I I I I I I I I
10.1' 100 10' 102 103 104 105
Time, h

Fig. 7 Comparison of the creep-rupture strength of a matching composition weld in


X 10 CrMoVNb 9-1 with the creep-rupture strengths of X 10 CrMoVNb 9-1 and X
20 CrMoV 12-1 base materials
164 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

and particularly low alloy steels requires special attention. The welds
between X 10 CrMoVNb 9-1 and X 20 CrMoV 12-1 do not present any
problems because both the steels belong to the same alloy type. In the case of
welds between X 10 CrMoVNb 9-1 and a low alloy steel such as 10 CrMo
9-10, 14 MoV 6-3 or 15 CrMoV 5-10, attention should be paid to the effects of
carbon migration. Weld metals matching either X 10 CrMo VNb 9-1 or the low
alloy steel in composition may be used. Mannesmann's experience indicates
that when an X 10 CrMoVNb 9-1 weld metal is used, the creep-rupture
specimen breaks in the decarburised area of the HAZ in the low alloy steel. By
comparison, when a low alloy steel weld metal is used, the fracture occurs in
the decarburised weld metal zone closer to the X 10 CrMoVNb 9-1 base
material. Adequate strength was however measured in both welds. When a
low alloy steel weld metal is used, the high initial impact toughness of X 10
CrMo VNb 9-1 enables the tempering temperature of the weldment to be
matched to the tempering temperature appropriate to the low alloy steel,
without any degradation of the properties of the X 10 CrMoVNb 9-1 base
material. Table 3 gives an overview of the impact energy values measured on
dissimilar metal welds between X 10 CrMoVNb 9-1 and X 20 CrMoV 12-1 or
between X 10 CrMoVNb 9-1 and 10 CrMo 9-10, for different weld metals.
The ISO V-notch impact energy values measured on a dissimilar metal weld
deposited with 14 MoV 6-3 between X 10 CrMoVNb 9-1 and 14 MoV 6-3 are
shown in Fig. 8. Such a high level of toughness has never been achieved in a
dissimilar metal weld between X 20 CrMoV 12-1 and 14 MoV 6-3. For this
reason, in practice a transition section made of 10 CrMo 9-10 is incorporated

.•.- .•. POt.:·O·


0······0 Pos.: ·s·
x······ x Pos.:· o·

(O)The highest single value: 266J


250

Q)
:; 200

-,o
C
';>150

~g
0)1

•..s
(J
-100

ctI
0.;
(O)The lowest single value: 68J
.5 50

\
\

specimen loaction

Fig. 8 Impact toughness of a dissimilar metal weld between 14 MoV 6-3 and X 10
CrMoVNb 9-1 after PWHT of 2h at 720°C (350mm ID X 12mm WT)
USE OF X 10 CRMoVNB 9-1 STEEL 165

o o
Lf) N
t""""4 t""""4

I I
00 o
~ ('f)

o
t""""4
o
t""""4

0\ 0\
o o
~ ~
U U
o
t""""4
o
t""""4

00 o o
r-,
\0 Lf)

o
Lf)
I
\0
N
I
~I
Lf)

o
t""""4
0\
o
~~
U
o
t""""4

+
u uu u
< « <
cJ
o
cJ cJ cJ
o 0 0
o 00 0
~ ~1:!2 ~
...c: ...c:...c: ...c:
N N N N
166 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

--- aB 105 (s = 1,5) Operating pressure: 148 bar


Operating temperature: 540°C
Design pressure: 166 bar
- - - - - aB 2 x 105 (s = 1,25) Design temperature: 548°C

Fig. 9 Configuration of a 14MoV 6-3/X 20 CrMoV 12-1 weldment adopted, for


example, in connection with the replacement of a main stream line

into such a joint (see Fig. 9). There is no need of such a measure in the case of
X 10 CrMoVNb 9-1.
This brief outline of the properties of X 10 CrMoVNb 9-1 clearly shows the
spectrum of advantages associated with using X 10 CrMoVNb 9-1, also in
retrofitting and revamping old power plants.

5. OPTIMUM SELECTION OF MATERIAL FOR MAINTENANCE AND


RETROFITTING OPERATIONS

Each maintenance or retrofitting operation requiring replacement of individ-


ual components or assemblies involves the work of selecting optimum
materials for that particular operation. For use as power plant pipework
operating in the creep range, i.e. at temperatures above 500°C, a number of
low-alloy steels and two high-alloy martensitic steels, namely X 20 CrMoV
12-1 and X 10 CrMoVNb 9-1 (P 91), are available in Europe. The data in Figs
10-1210 facilitate the selection of materials for a given application. Fig. 10
shows the differences in the strength of 10 CrMo 9-10, 14 MoV 6-3,
12ChlMF, 15 CrMoV 5-10 (15Ch1M1F), X 20 CrMoV 12-1 and X 10
CrMoVNb 9-1, using a plot of the maximum allowable design stress (azul.)
according to TRD against design temperature (TR) for design lives of 100 000
hours and 200 000 hours. The differences in the strength of the materials can
also be demonstrated by plotting corresponding maximum allowable internal
pressure (PR) against design temperature (TR) for any given pipe size. Fig. 11
shows, by way of example, such a plot for a seamless pipe with a wall
USE OF X 10 CRMoVNB 9-1 STEEL 167

: -:----:-----::1::::::: r::::::l::::::r::::::r::::::: r::::T:::::r:::::i


: : : : : : : :
-.r:.r;-.!",,,~,oo!~~,~~'

-;----T--;::r::::r:::::r:::::r::::F:::::1
180 I I I I I I ,

,140
! ,I ii"
nI 120
0-
:E
_L -- --1-- -- ---r-------r-------i
.5 100
-----r-------!
J eo -----1
eo

40

2OT---~------r-----~-----~r_--~--~-----~------T-----~----~
500 S10 S20 sse sea S30 So4O 570
TR In °C ~

Fig. 10 High-temperature design for pipework components. Dependence of the


maximum allowable design stress «J" zul) according to TRD 300 on design
temperature (TR) for the various high temperature steels and for two different
design lives

C1I
.c
~ 80~~~~:..::.:
a.

500 ~ ~ ~ m ~ m ~
TRin"C ~

Fig. 11 High temperature design according to TRD 300 for seamless pipe.
Dependence of the maximum allowable design pressure (PR) according to TRD 300
on design temperature (TR) for the various high temperature steels and two
different lives, when s,/ di = 0.04 (e.g. d, = 400 and s = 16)

thickness to diameter ratio of sv/di == 0.04. The minimum wall thickness


required at the various combinations of pressure, temperature and time that
require a minimum wall thickness of s = 16 mm for an X 10 CrMoVNb 9-1
pipe with d, = 400 mm are shown in Fig. 12 for the remaining five steels. In
the pressure range of main steam, the favourable high-temperature strength
168 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

TR ('C) 500 510 520 530 540 550 560 570 5110 !580 eoo
PR (bar) 130 120 110 101 112 83 7'.5 118.5 58 52.1 48

PR(bat) 154 144 132 121 110 88.5 sa 80 70.5 112.1 55,5
TRI"C) 500 510 520 530 540 550 580 570 5110 5eO eoo

Fig. 12 High temperature design according to TRD 300 for seamless pipe.
Minimum design wall thickness (s-) required by TRD 300 for the various high
temperature steels at different combinations of pressure, temperature and time that
require a minimum wall thickness of 16mm in the case of X 10 CrMoVNb 9-1 pipe
with 400mm internal diameter (di)

of X 10 CrMoVNb 9-1 can be utilised to design and manufacture components


with a thinner wall for operation at temperatures down to 500°C. For hot
reheat systems operating in the lower range of pressure and temperature, the
extent of utilisation of the advantages of X 10 CrMoVNb 9-1 is limited by the
smallest s to d ratio that can be realised in production. For this range, a
meaningful alternative is the use of X 10 CrMoVNb 9-1 in combination with
15 CrMoV 5-10 for the pipework system. The fittings/distributors in the
pipework system are made of 10 CrMoVNb 9-1. Because of its high strength,
it is possible to adopt the same section thickness for 15 CrMoV 5-10
components and for the fittings which would have otherwise required a
thicker section. From the welding point of view, the resultant dissimilar metal
joints do not pose any fabrication or reliability problems. Fig. 13 shows, by
way of example, the design of a four-branch spherical fitting in X 10
CrMoVNb 9-1 to be used in combination with 15 CrMoV 5-10 pipe. Fig. 14
shows the four-branch spherical fitting and the adjoining pipe section ready
for departure from the workshop.
Before a pipework system in 14 MoV 6-3 is completely replaced, there is
often a need for replacing highly stressed fittings. Figure 15 shows the
component size reduction that could be achieved when a steam mixing fitting
in 14 MoV 6-3 is replaced with a steam mixing fitting in X 10 CrMoVNb 9-1
as part of a retrofitting operation. When the pipework system was renovated
later, the X 10 CrMoVNb 9-1 fitting could be readily incorporated into the
new system.
The technical and economic advantages that can be derived by the use of X
10 CrMoVNb 9-1 in retrofitting applications are the following:
USE OF X 10 CRMoVNB 9-1 STEEL 169

15 CrMoV 510

Welding Connections
Shop Welds @1.4909/1 .4903
Site Welds (91.4903/1.7745 g
Site Weld @ 1.4093/1.7380 .:t

Fig. 13 Example of the design and dimensions of an X 10 CrMo VNb 9-1 four-
branch spherical fitting in a 15 CrMo V 5-10 hot reheat line (49bar /530°C -
200 000 h)

Fig. 14 X 10 CrMo VNb 9-1 four-branch spherical fitting adjoining pipe section in
15 CrMoV 5-10, as finished in the workshop
170 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

4 X composite weldments
X 10 CrMoVNb 91 /14 MoV 63
as erection welds

2500

\1"1
N

new:

--~-----
o

14MoV63 '&
old:

1.0. 800 of sphere I

Fig. 15 Replacement of a creep-damaged steam mixing line in the hot reheat system
of a 340 MW coal-fired power plant (60bar, 545°C) - comparison of the old thick
wall design in 14MoV 6-3 with the new thin wall design in X 10 CrMoVNb 9-1

- reduced wall thickness for components, the older dimensions of which


limited the rate of temperature change during a start-up;
- reduced pipe mass with attendant reduction in the cost of heating during
a start-up and a shorter heating time;
- faster cooling rates, which in the case of repair enable a quicker start of
repair and a shorter period of shutdown to be achieved;
- reduced end forces and moments on the end components of the boiler
and turbine;
- reduced cost of supports for replacement pipework and reduced loads
on supporting steel structures.

6. SUMMARY

Following a brief description of the materials used for power plant compo-
nents operating in the creep range in Western and Eastern Europe, attention is
drawn to the use of a new materials concept in retrofitting applications.
X 10 CrMoVNb 9-1 is a material that facilitated the construction of new
power plants with advanced steam parameters. The use of this steel also
provides technical and economic advantages when retrofitting old plants and
replacing, where necessary, highly stressed boiler and pipework components
such as fittings and steam headers individually. Combined use of X 10
CrMo VNb 9-1 and 15 CrMo V 5-10, which is a material of Russian origin, also
provides interesting economic and technical advantages when replacing
USE OF X 10 CRMoVNB 9-1 STEEL 171

components in the hot reheat system operating at steam temperatures up to


545°C. This approach would be of great interest in the context of the imminent
need for retrofitting the power plants in Eastern Europe and Asia, where a
large number of power plants of Russian design are being operated.

REFERENCES

1. DIN 17175. 'Nahtlose Rohre aus warmfesten Stahlen', Technische Lieferbe-


dingungen.
2. TU 14-3-460-75/TU 14-3-190-82, 'Nahtlose Rohre fur Dampfkessel und
Rohrleitungen', (russischer Fachbereichsstandard).
3. VdTOV-Werkstoffblatt 506, 'Warmfester Stahl 15 CrMoVNb 9-1'.
4. E. I. Krutasova: Die Zuoerlassigkeit des Metalles von Energieanlagen, Moskau,
Verlag Energoizdat, 1981.
5. Ju. M. Gofman: Bewertung der Beiriebezuoerldssigkeit des Metalles von Energie-
bauteilen, Moskau, Verlag Energoatomizdat, 1990.
6. F. Bruhl, K. Haarmann, G. Kalwa, H. Weber and M. Zschau: 'Verhalten des
9% Cr-Stahles X 10 CrMoVNb 9-1 im Kurz- und Langzeitversuch, Teill:
Grundwerkstoff', VGB Kraftwerkstechnik, 1989, 69, S. 1214-1224.
7. F. Bruhl, H. Cerjak, H. Musch, K. Niederhoff and M. Zschau: 'Verhalten des
9% Cr-Stahles X 10 CrMoVNb 9-1 im Kurz- und Langzeitversuch, Teil2:
SchweiBverbindungen'.
8. K. Niederhoff, G. Wellnitz und M. Zschau: 'Erfahrungen mit der Ver-
arbeitung des warmfesten Chromstahles X 10 CrMoVNb 9-1', 3R
international 30, 1991, S. 426-432.
9. M. Zschau und K. Niederhoff: 'Rohrleitungen mit dem neuen Stahl P 91
einschliefslich Induktivbiegungen', VGB Kraftwerkstechnik, (1994), 74, S.
150-157.
10. B. Hahn, V. Baumhoff, K. Peters and M. Zschau: 'Effektiver Werk-
stoffeinsatz in Kraftwerksrohrleitungen im Rahmen von Kraftwerksneu-
bauten und Ertuchtigungsvorhaben', VGB Kraftwerkstechnik, 1997, 77, S.
214-220.
Service Experience with the Application
of Advanced Materials in Improved
Coal Fired Power Plants Operating in
the Range 593-610°C
I. KAJIGAYA*, K. YAMAMOTO*, M. YUUKIt and
G. NAKAYAMAt
Ishikawajima-Harima Heavy Industries Co., Ltd., (IHI) Toyosu 3-1-16,
Koto-ku, Tokyo, Japan
* Power Plant Division, t Research Institute

ABSTRACT
There has been a steady advance in the design of Ultra-Super Critical (USC) plants in
recent years. Such improvements have been largely sustained by the development of
new materials. Currently various types of modified 9Cr-1Mo steels are used for the
main pressure components working to 593°C. But for the USC units operating above
593°C, the application of advanced 9 to 12Cr ferritic steels developed in Japan seem
to be the key to reducing tube or pipe wall thickness and material costs. In the design
of USC boilers, material costs need to be carefully evaluated as well as material
reliability and longevity. This paper summarises the items to be considered by the
new materials and recent experiences of their practical application.

1. INTRODUCTION

Means by which more efficient utilisation of coal for electricity generation is


being emphasised in Japan and considerable research has been directed into
developing technologies for protecting the environment from NOx and SOx
emissions. At the Kyoto, in December 1997, conference concerning measures
to prevent global warming, targets were set to reduce CO2 emissions in the
future. Through better thermal efficiency, Japanese power plants should
make CO2 emission as low as possible.
Based on these considerations, IHI has been developing a coal fired USC
boiler since 1980. IHI has successfully supplied the first 700 MW coal fired
USC boiler of 593°C to the No.3 unit of the Hekinan Power Station of the
Chubu Electric Power Co. in 1993.1Means for improving steam conditions at
new plants have been sought, such operating temperatures exceeding 593°C.
A coal fired USC boiler with the largest operation capacity to date under
optimal steam conditions at Tachibanawan No.1 unit of the Electric Power
Development Co., Ltd. (EPDC) is now being constructed. Nominal capacity is

172
IMPROVED COAL FIRED POWER PLANTS 173

to be 1050MW with 25MPa at 600/610°C.2 The first Japanese pressurised


fluidised bed combustion (PFBC) combined cycle power plant with capacity
of 71 MW and reheat steam temperature of 593°C was constructed by IHI in
1996. This is a new type of coal utilisation system, providing a higher thermal
efficiency. The plant was followed by another PFBC combined cycle power
plant with the world's largest capacity of 360MW and steam conditions of
25MPa and 566/593°C.3 For better thermal efficiency the steam conditions at
these plants should be improved. Also new heat resisting alloys at lower cost
should be made available. Modified 9Cr-1Mo steels are extensively used in
main high pressure components at the Hekinan No. 3 unit to lessen their
weight and improve reliability by thermal stress reduction+ Ferritic heat
resisting alloys and the modified 9Cr-1Mo alloy are particularly used at new
plants owing to their inherent characteristics. New alloys of 9 to 12% Cr
content, and austenitic alloys of higher strength and lower cost are also being
developed. Material selection and the use of appropriate alloys for USC plants
are discussed in the following.

2. STEAM CONDITIONS AND HEAT RESISTING ALLOYS FOR USC


BOILERS

Figure 1 shows the history and future trends in steam conditions at Japanese
thermal power plants. Steam conditions, thermal efficiency and dates of
commercial operation of USC plants for the past and future are presented in
Fig. 2. Figure 1 clearly indicates that the steam conditions of power utilities
are fixed to be at a supercritical condition of 24.1 MPa and 538/566°C in the
past thirty years since around 1960. During these years, all engineering efforts
have been focused on enlarging capacities of plants and improving operation

35 650
,-.... 32. 2MPa
~:---.-.-----
I I
....
,-....
ro 0
o, 30 -
Kawagoe #1,#2 1593 C ~OC
0

600 '-'
0

:E
<:»
25 - 566 °C 25.:..l~?~~--.- •• --•••• ---.---j CD
S-
CD :J
1.-

20
53S0C ~ Hekinan #3 550 +-'
::l ro
(j)
(j)
17rf!~Ar- S-
CD
CD 15 Tachibanawan # 1 a.
1.-
500 E
a. r-'
r~
Q)

10 - ---_••_.-Steam pressure +-'


E
ro
OJ
4. 6MP.C!J---- -- Steam temperature 450 E
ro
+-' 5 CD
en ~
en
0
1950 1960 1970 1980 1990 2000
Year

Fig. 1 History of turbine throttle steam conditions of thermal power plants in Japan
174 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

+6r--..-----.------.----~~~--~~--~--~
~ 650/650°C

.~ +5 t--t--t---~-H+f+++++H"""7::":~~~I__-~--__4-
rn
Q)
~
"-""
+4r-~~~~~--~~~~~~~-~---_4--
.•...•
c:::
~Q) +3r--r~~~~~-_r----~~~--~---_4--
>
[ +2~~T_--~~~-_r---~~~--~~mn~~

2rn +1 t---t-::t-

.•...•
"-
ell

I
Q) Or-~T_-~4----_r----~~~~~r_-_4--

1990 1995 2000


Main Steam Pressure (MPa) Records or planning
of commercial operation
(Calender year)

Fig. 2 Plant thermal efficiency improvement by applying USC steam cycle

capabilities. Furthermore, the figure indicates that after the steam condition of
593°C at Hekinan No. 3 unit is adopted, the steam condition is steadily
advancing to 600 and 610°C. Under the leadership of EPDC, the development
program has already started an application test of various candidate alloys
and trial manufacturing of full size models of pressure components for an
USC boiler that operates at 30MP /630°C.5
Usually, steel for boiler applications can be classified to carbon steel, low
alloy steel, 9 to 12 Cr steel and austenitic steel.
Advanced 9 to 12 Cr and austenitic alloys of high strength produced at low
cost have recently been developed. The choice of alloy is made based on the
results of examination of the properties, reliability tests and assessment of
corrosion resistance in the environment. Table 1 shows major alloys under
consideration for USC boilers with specifications and compositions. Stress
data are indicated in Fig. 3. Figure 4 shows the results of a study of major
pressure components of a USC boiler. The application of advanced 9 to 12 Cr
and austenitic alloys to USC boilers is discussed in the following section.

3. MATERIAL SELECTION AND ADVANCED 9 TO 12 Cr ALLOY


APPLICA TION

9 to 12 Cr alloys are being increasingly used, owing to their superior strength


at elevated temperatures. This is because of the fact that in designing USC
IMPROVED COAL FIRED POWER PLANTS 175

Table 1 Material for USC boiler major components

Category Steel Grade Main Component ASME standard Developer

Low alloy MITI STBA24Jl 2.25Cr1.6WNbV SA213-T23 Sumitomo


steel TEMPALOY F-2W 2CrO.6MoWVTi NKK
MITI STBA29 9CrO.5Mol.8WNbV SA213-T92 NSC
.. TEMPALOYF-12M 12CrO.7MoO.9WlCuNbV - NKK
Ferritic steel MITI SUS410J3TB 12CrO.4Mo2WICuNbV SA213-T122 Sumitomo
NF12 llCr2.6Wl.8CoMoNbV - NSC
MITI SUS304JIHTB 18Cr9Ni3CuNbN Sumitomo
MITI SUS321JIHTB 18CrlONiNbTi NKK
Austenitic XA704 18Cr9Ni2.5WNbV NSC
Steel MITI SUS310Jl TB 25Cr20NiNbN SA213-TP310CbN Sumitomo
MITI SUS310J2TB 20Cr25NiMoNbTi NSC
SAVE25 23Cr19Ni3.5Cul.5WNbN - Sumitomo
Remarks
Sumitomo: Sumitomo Metal Industries, Ltd
NKK: NKK Corporation
NSC: Nippon Steel Corporation

IOU
180

160 160

140 140
ITI STBA29 (NF616)
C/)
120 120
~
C/) c/).
C/)

u; ~!
v.;:
.92 100 100
"en .92
c "en
2 c
Q.)
80 2 80
::ces Q.)

:cct:!
~
.Q ~
60 .Q 60
~ ~
40 40
SA213-TP347H

20 20
SA213-TP316H
(reference)
0
a ------------------------~
500 550 600 650 700 750 800 500 550 600 650 700 750 800
Temperature (OC) Temperature (OC)

(Ferritic steel) (Austenitic steel)

Fig. 3 Comparison of allowable stress for high temperature materials


176 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Main steam and reheat steam

A temperature
538 566
(turbine inlet)
593
(DC)
625
A. Pressure vessels
Water separator.)
( Separator tank

B. SH tube
(heating area)

c. SH tube
(non-heating area)

D. Main steam pipe

E. Hot reheat pipe

F. High temperature valvs,


Safety valves

r==J
_
Austenitic steel
Low alloy steel (ferritic)
[==:J 9-12C r steel (ferritic)

Fig. 4 Study of material selection for major pressure components

plants, the superior strength of these alloys at elevated temperatures make the
wall thickness of pipes of main pressure components to be smaller and that
larger merits are expected to be realised with using the alloys with respect to
design and non-destructive inspection of the pipe systems. The history of the
development of these alloys is shown in Fig. 5.6 The modified 9Cr-1Mo alloy
is presently used worldwide. IHI started application works in 1984 as IHI is

e
!
600 0
x 1aSh Creep rupture strength
35MPa class 60 - 80MPa Class 100MPa class 140MPa class

~~- •••. 19Cr-2MoVNb I


~--~ EM12
Optimized -Mo
....------,V.Nb
t--~ 9Cr-1MoVNb 9Cr-O.SMo-1.BWVNb
ASMET91 MITI STBA29 (NF616)

+Mo
12Cr 12Cr-O.SMo-1.BWVNb

ANSI 410 -C T812


+W +W

+Nb -112Cr-1Mo-1WVNb ~ 12Cr-O.SMo-2WVNbCu I


HT9 HCM12 Min SUS41OJ3TB (HCMl2A)

Fig. 5 Development process of 9-12Cr steels?


IMPROVEDCOAL FIRED POWERPLANTS 177

one of the first to have recognised the superior position of this alloy?
Characterisation, fabrication and demonstration tests using full size models
are conducted for alloy evaluation in coordination with the Oak Ridge
National Laboratory in the USA that developed the alloy as well as with
many other leading steel manufacturers in Japan. Thus, IHI has succeeded in
establishing design practices for all grades of the modified 9Cr-1Mo alloys.
The first USC plant of 593°C that adopted the alloy has reduced the
thicknesses of pipes. Piping material costs are also reduced by establishing a
fabrication technology of a pipe of larger diameter and smaller thickness+ The
alloy is used at existing USC plants extensively, but a larger wall thickness is
required for steam temperatures higher than 600°C. Advanced alloys of
higher strength at elevated temperature have been developed as HCM12A,8
NF616,9 and TEMPALOY F12M.I0 These advanced 9 to 12 Cr alloys have
allowable stresses 1.3 times better than the modified 9Cr-1Mo alloy at
temperatures above 600°C. Main pressure components of USC plants operat-
ing above 600°C can be designed so that pipe thickness is approximately the
same as that for lower operating temperatures under the condition that
advanced 9 to 12 Cr alloys are used. All advanced alloys utilise precipitation
hardening phenomenon of Nb and V additions similar to that as in the case of
modified 9Cr-1Mo alloy in which Mo is incorporated as a solid-solution
strengthening element. Advanced alloys contain W at about 2% to get the
same result.
IHI has worked on establishing engineering practices for the actual utilisa-
tion of the following advanced alloys.

• HCM12A (MITI SUS410J1TB and MITI SUS410J3TP)


• NF616 (MITI STBA29 and MITI STPA29)

Figure 6 shows the results of the application of NF616 tubes to reheater outlet
headers for a USC boiler designed at 25 MPa and 600/610°C. Figure 7 shows
the application test for submerged arc welding of large diameter piping made
of HCM12A. Design issues in applying these advanced 9 to 12 Cr alloys are
summarised with those for the conventional modified 9Cr-1Mo steel:

1. The high temperature strength of the advanced alloys is essentially the


same as that of austenitic alloys. But corrosion resistance is less than that
of austenitic alloys. This parameter of advanced 9 to 12 Cr alloys must be
evaluated prior to application to high temperature parts.
2. Post weld heat treatment (PWHT) is always required for welded joints
of advanced 9 to 12 Cr alloys to ensure minimal stress and optimal
ductility. Design must be made to reduce field heat treatment as much
as possible to keep production and PWHT costs minimal.
3. In the weldment of dissimilar alloys, material selection must be based on
consideration of PWHT temperature. For example, the 9Cr-1Mo alloy
and STBA22 steel (lCr-O.SMo) would not be acceptable materials for a
178 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Fig. 6 Reheater outlet header with NF616 tubes (25 MPa, 600/610°C)

Fig. 7 Appearance of submerged arc welding for HCM12A piping

joint since the PWHT temperature for 9Cr-lMo alloy would exceed the
Al point of an STBA22 tube.
4. Creep-rupture strength of welded joints is generally less at a higher
temperature compared with the base metal. This would not be a matter
for small diameter tubes and radial joints of larger diameter pipes. But in
IMPROVED COAL FIRED POWER PLANTS 179

the case of joints in a longitudinal direction, measures must be taken to


consider the behaviour of welded joint creep rupture strength.

4. MATERIAL SELECTION AND ADVANCED AUSTENITIC ALLOYS


APPLICATION

4.1 Measures for coal ash corrosion


Superheater and reheater tubes of USC boilers are exposed to very severe
operating conditions and thus must be made using austenitic alloys with
superior strength at elevated temperatures and superior resistance against
high temperature coal ash corrosion.
On the contrary, austenitic alloy application is limited owing to its high
cost. At conventional Japanese boilers using high quality bituminous coal
with sulphur content as low as 10/0 and below, there has been no incident of
coal ash corrosion. However, temperatures at USC boilers, particularly those
of superheater and reheater tubes are essentially the same as those for the
formation of complex compounds of alkaline sulphates from coal ash.
Extremely high temperature corrosion would thus appear to occur depending
on a particular component metal temperature. Measures to prevent corrosion
are quite important.l1, 12 Japanese power plants generally use different grades
of coal from various sources. Studies for candidate superheater alloys for all
kinds of coal must be conducted at the design stage of USC boilers. A method
for assessing coal ash corrosion has already been established, which is
presently in use.P Figure 8 compares corrosion tests and corrosion prediction
results of an austenitic alloy for superheater tubes; the results were obtained
jointly by IHI and the Foster Wheeler Corporation for three boiler units of the

300MW Gallatin Station Unit2 350MW Crist Unit6


(Sulfur percent in used coal = 3%) (Sulfur percent in used coal = 3%)

0.300 0.300

E 0.250 0.250
.§ E
E.
0.200 0.200
en en
en
..Q en
0.150 ..Q
0.150
c c
0 0
'w 0.100 0.100
'w
e 0.050
e(5
0 0.050
o o
0.000 0.000
0 5000 10000 15000 20000 0 5000 10000 15000 20000
Time [h) Timerhl
Remark Material: MITI SUS31OJITB Temperature: 700°C

Fig. 8 Comparison of in-site coal ash corrosion test results and estimated corrosion
loss based on IHI's corrosion index
180 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

100
Test units Testing time: 4000h""""16000h .
90 + Gallatin Station Unit2 0 Sulfur percent in used coal: 0.5 3.0%
x Crist UnitS
80 o Pawnee Station
:2
0
70
-
0
0
T""
.c.
(.) 60
c
~
en
50
en
..Q
c
40
0
'en 30 +
e 0
0
0 20

10 ~
:
+
o 1

10 15
1

is 30
1

35
5 20

Cr content (wt%)

Fig. 9 Effect of chromium content on coal ash corrosion resistance to attack'<

R&D Project for Improved Coal Fired Power Plant, (RP-1403) sponsored by
EPRI of the USA. Estimated corrosion using a higher calcium content coal was
less than that obtained by actual corrosion tests. Therefore equations to
provide a more accurate estimation should be established for high calcium
coals. Corrosion caused by ordinary bituminous coal can be predicted fairly
well by the developed corrosion index. Figure 9 shows the relationship
between ash corrosion of various alloys in superheater and reheater tubes
versus alloy Cr content.l+ This suggests that high temperature corrosion due
to high sulphur content coal ash could be suppressed by using austenitic
alloys with a Cr content exceeding 25 0/0. Figure 10 shows the relationship
between Cr content of austenitic and ferritic alloys and allowable stress of
various heat resistant alloys at 625°C. Various alloys were developed in Japan
to specify allowable stress and corrosion resistance at elevated temperature.
Appropriate material selection is based on the tube thickness shell required,
the extent of corrosion and tube production cost.

4.2 Weld joint


To ensure maximum use of austenitic alloys in USC boilers, effective
measures to prevent hot weld cracking and realise and maintain optimal
welded joint strength must be implemented. Thus, development of highly
satisfactory welding materials and means for producing welded joints with
greater strength are primary considerations. Measures to prevent stress-
corrosion cracking of weld joints must be also considered in designing 18-8
type stainless alloys. Figure 11 shows stress-corrosion cracking long Fermi
tests facility at the Ryukyu University test facility for assessing environmental
IMPROVED COAL FIRED POWER PLANTS 181

(N/mm2)
140 [Ferritic] [Austenitic]

120 Mod.9-12Cr
steel
I T SAV~5
I
MI
I SUS310J2TB

cP 100
LO
N
MITI SUS3J4J1 HTB,

-cu,IIN,~.n& - - I •t
+Cr,Ni,W,Cu j
MITI SUS310J1TB
I
co II,lXA704
I +Cr, Ni,' Nb, N
I
ro Js
NF12
'+w. c~ .-co
+W,V,N
80

W'" II
en MITI SUp" 1OJ3TB MIT,I SUS~21 ~1
en
~
(j)
Q)
:cCO
60
MITI ST,A29
\+W .. MO F-12M Nb.l1.N I
~~~~~~~:'TP347HT

MITI ST,BA28 +Cr,W,Cu SA213-TP321 H etc,


3: 40 MITI STBA24J1
.Q
:a: , I +Cr,V,Nb

i+w,v, I

Nb
20
J IS STBA24 etc.'

00 10 20 30
Cr content (0/0)_

Fig. 10 Comparison of allowable stress at 625°C for various new materials

Fig. 11 Appearance of stress corrosion cracking test for austenitic steel

corrosion of welded new alloys. Figure 12 presents accelerated test results of


stress-corrosion cracking sensitivity of welded joints of MITI SUS304J1HTB
and conventional TP316H tube which was shown to be sufficient for long
term use. MITI 304JIHTB has less stress-corrosion sensitivity compared to
182 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

1000~------------~-------
o SA213-TP316

C 800 - 6 MITI SUS304J1HTB


o
o
C3
°E 600 o
..c:
0..
Q) o
"'0

~o
CO
o

250
Cycle

Fig. 12 Combined cyclic external stress corrosion test result

conventional TP316H steel tubes. It should be possible to sufficiently prevent


stress-corrosion cracking of MITI 304JIHTB tubes through conventional
production procedures.

5. CONCLUSIONS

The basis for selecting newly developed alloys and their application to USC
boilers are explained and discussed. Japanese material technology is con-
sidered to greatly contribute to the development of USC plant technologies in
Japan. Advances in material technology are beneficial for increasing steam
conditions of PFBC combined cycle power plants, and coal gasification
combined cycle power plants as well as USC plants. Furthermore, the
material technology can be applied for enhancing reliability and durability of
presently operating thermal power plants. For thermal power plants to
operate at higher efficiency and more economically, further efforts in
advanced material technology should be made.

REFERENCES

1. R. Ishimoto, M. Ozawa, M. Kuwahara, et al.: 'Operating Results of 700 MW


Coal Fired Supercritical Boiler with 593°C Reheat Steam Temperature',
International Conference on Power Engineering-93 (ICOPE-93), Tokyo,
1993.
2. S. Ando, 1. Kajigaya, M. Ozawa and Y. Mochizuki: 'Outline of 1050MW
60QoC USC Boiler', International Conference on Power Engineering-97
(ICOPE-97), Tokyo, 1997.
IMPROVED COAL FIRED POWER PLANTS 183

3. K. Ornata and I. Anderson: 'Karita 360MW PFBC an imminent prospect',


Modern Power System, April, 1997, P33.
4. H. Umaki, 1. Kajigaya, T. Kunihiro, et al.: 'Application of Large Diameter
Seam Welded Pipes and Header of Super 9Cr Steel for 700MW Coal
Fired Boiler with 593°C Reheat Steam Temperature', Ishikawajima-Harima
Engineering Review, September 1991, 31 (5).
5. K. Muramatu: 'Development of Ultra-Super Critical Plant in Japan', this
volume 543-559.
6. R. Ishimoto, 1.Kajigaya, H. Umaki and O. Abiko: 'Applicability of Modified
9Cr-1Mo Steel', The Thermal and Nuclear Power, 1985, 36 (9).
7. T. Yokoyama and F. Masuyama: 'Application of Boiler Material for Ultra-
high Temperature and High Pressure Power Plants', The Thermal and
Nuclear Power, 1994, 45 (11).
8. Y. Sawaragi, K. Ogawa, F. Masuyama and T. Yokoyama: 'HCM12A pipe
production, properties and welding consumable development', The
EPRIjNational Conference, New Steel for Advanced Plants up to 620°C,
London UK, May 1995, P45.
9. H. Naoi, H. Mimura, M. Ogami, H. Morimoto, T. Takana, Y. Yazaki and T.
Fujita: 'NF616 Pipe production and welding consumable development',
ibid., p. 8.
10. K. Hayashi, T. Kojima and Y. Minami: 'Properties of 12Cr-1W-0.1Mn-
B-Cu-Nb-V-N steel', The Iron and Steel Institute of Japan CAMP-ISIJ
P1257, 1997, 10.
11. S. Kihara and Nakagawa: 'Simulating test results for fireside corrosion of
superheater & reheater tubes operated at advanced steam condition in
coal-fired boilers', High Temperature Corrosion in Energy System, M. F.
Rothman ed. TMSj AIME, 1985, 361.
12. S. Kihara, K. Nakagawa and W. Wolowodiuk: 'Laboratory coal ash
corrosion tests', EPRI CS 6449, 1989.
13. J. Shigeta, Y. Hamao, H. Aoki and I. Kajigaya: 'Development of a Coal Ash
Corrosivity Index for High Temperature corrosion', ASME 86-JPJC-
FACT-3.
14. J. Blough, G. Stanko. M. Krawchuk, W. Wolowodiuk and W. Bakker: 'In-
situ Coal-ash Corrosion Testing for 2 Years at Three Utilities', Inter-
national Symposium on Improved Technology for Fossil Power Plants - New
and Retrofit Applications, Washington, March 1993.
Effect of Microstructure on
Intergranular Corrosion of Weldments
of Co-Based Alloys for Power Plant
Valves
T. HONDA, H. TAKAKU and T. SAKUMA
Okano Valve MFG Co., 1-14 Nakamachi, Moji-kushi, Fukuoka, Japan 800
Central Research Institute of Electric Power Industry, 2-11-1, Iwado Kita,
Komae-shi, Tokyo 201-8511 Japan

ABSTRACT

The influence of heat treatment conditions on intergranular corrosion (IGC) has been
investigated for the weldments of the Co-based Stellite alloys, welded by the oxy-
acetylene gas welding method. The Stellites are susceptible to IGC when they are
heated in the range from 693 to 973K after welding.
The result of this study showed that the IGC susceptibility of weldments which are
subjected to post-weld heat treatment is due to the formation of the grainboundary
Cr depletion zones resulting from precipitation of the M~3 type Cr-carbides.
Heating above 1000k suppresses the IGC susceptibility due to formation of
secondary W-Co-Cr-C type M23C6 carbides which result in reduced levels of Cr
depletion.

INTRODUCTION

Numerous valves are used in electric power plants, chemical plants, and other
types of plants. For example, approximately twenty thousand valves are
installed in a typical fossil and or nuclear power plant. In many cases, valve
sheets for power plant applications are clad by a Co-based alloy of Stellite.
Stellite is a cladding/ overlaying material which is specified as RCoCr- A by
the American Welding Society (AWS), and its main chemical composition is
composed of Co, Cr, C, Wand Fe. For its good corrosion and wear resistance,
the weld-overlayed Stellite is widely used as the hardfacing material of
various machinery components and parts, as well as the above-mentioned
power plant valves.
The method of welding Stellite is mainly by oxy-acetylene gas welding
(hereafter, gas welding). However, electrode welding such as plasma transfer
arc (PTA) have been performed recently. It is reported that valve sheets made
of Stellite have experienced erosion damages in feedwater valves of fossil
power plants,' and that this results in erosion-corrosion in preferred regions

184
EFFECT OF MICROSTRUCTURE ON INTERGRANULAR CORROSION 185

adjacent to the precipitated carbides.P-' It is also reported that the main cause
of damage is due to the same mechanism as that of type 300 austenitic
stainless steels in which the inter granular corrosion (IGC) is induced by the
formation of Cr-depleted zones near the carbide-precipitated grainboundary
(sensitisation phenomenonj.! However, the systematic estimation of the IGC
has not been conducted for valve sheets of Stellite. This maybe due to the
different conditions for heat treatments and also due to their various behav-
iours in each plant for Stellite valve sheets.
On the other hand, systematic investigation has been reported concerning
the microstructure of Co-based alloys (Co-Cr-Fe-C) under the thermal
equilibrium conditions.> However, there exist deficiencies in the knowledge
of both corrosive and mechanical properties, because Stellite is mainly used as
the functional performance material.
Results are reported on the changes in microstructural and mechanical
properties due to the solution effects of substance materials (mainly Fe) into
the Stellite by the electrode arc welding and other methods.v? However, the
comprehensive knowledge on the ICC of Stellite are insufficient. Further-
more, the estimation of properties for not only the functional performance but
also structural material characteristics are required for Stellite, in order to
reduce/suppress the damages of components and parts.
In this paper, we investigated the correlation between IGC and micro-
structural change due to heat treatments, and also the appropriate heat-
treatment conditions for the improvement of IGC in SteIlite which is welded
with a gas welding and includes no Fe diffused from the molten substrate
materials (a carbon steel).

EXPERIMENTAL PROCEDURES

Test Specimen and Heat-treatment Conditions


The shapes and sizes of test specimens are shown in Figs 1 and 2, for the two
kinds of test specimens. Figure 1 shows the product specimen which is
equivalent to an actual power plant valve sheet, and Fig. 2 shows the bar type

<1>200

Stellite

Carbon steel (S25C)

Fig. 1 Shape and dimensions of product specimen


186 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Fig. 2 Shape and dimensions of bar specimen

specimen composed of the Stellite overlayed by gas welding and a substance


(carbon steel, S25C).
The welding aspects of product specimen and bar specimen are the two-
layers (passes), and multi-layers weldings, respectively. The pre-heat tem-
perature of these specimens in welding is 923 K, after welding the specimens
were air-cooled.
As shown in Figs 1 and 2, thermocouples are inserted into the hole with
diameter 3mm, for measurements of temperature of the Stellite adjacent to the
substance during welding. The test samples (Stellite) were cut from the
above-mentioned specimens, their sizes being 30X20X3 for product type and
3X16 dia. for bar type.
The main chemical composition of Stellite is shown in Table 1, and all these

Table 1 Main chemical composition of specimens

Specimen Chemical composition [mass 0/0]

C Cr W Co

Product specimen 1.30 27.7 4.9 bal.


Bar specimen 1.35 29.2 5.0 bal.
R CoCr-A spec. 0.9-1.4 26.0-32.0 3.0-6.0 bal.

contents satisfy the AWS specification. Conditions of heat-treatments for


Stellite samples after welding are shown in Table 2, the heating-up rate is
2.5 K/ s with a holding-time of 14.4ks for all heat-treatments.
From Table 2; 923 K and 1323K are the recommended post-welding
temperatures, for Stellites overlayed on carbon steel and on type 300 aus-
tenitic stainless steels, respectively. The heating time of 14.4 ks is the
equivalent time for the actual power plant productions with a substance
thickness of 100 mm.
EFFECT OF MICROSTRUCTURE ON INTERGRANULAR CORROSION 187

Table 2 Conditions of heat treatment

Specimen Temperature (X14.4 ks)

As weld, 773K, 823K, 873K, 923K, 973K, 1023K, 1173K, 1223K,


Product specimen
1343K
As weld, 693K, 773K, 873K, 923K, 973K, 1023K, 1048K, 1173K,
Bar specimen
1223 K, 1273 K, 1343 K

Measurement of Hardness and Microstructural Tests


The fundamental tests for material properties of weldments, changes in
hardness and microstructures due to heat-treatments were performed. The
hardness was measured by a micro-hardness tester. The microstructural tests
were conducted by an optical microscope (OM), electron-probe X-ray ana-
lyser (XMA), X-ray diffractor and transmission electron microscope (TEM)
including electron beam diffraction.

Intergranular Corrosion Tests


The inter granular corrosion test is conducted according to JIS-G 0575, in
which specimens are immersed in boiling H2S04-CUS04 aqueous solution
(Strauss solution). The test duration periods are 57.6 ks as specified in this JIS,
as well as the longer 259.2 ks and 540 ks periods for the accelerated immersion
tests. After these corrosion tests, the measurement of depth of inter granular
corrosion and the OM observation near the corroded portions were con-
ducted.

EXPERIMENTAL RESULTS

Heat- Treatments and Microstructures


Temperature change in weldments with heating-time
Figure 3 shows the results of heat-histories of weldments during the welding
processes. Weldments of the Product specimen are subjected to a heat-up over
1273K twice, in accordance with two-layer weldings. And thereafter, these
weldments were cooled at a rate of 1.8 ks in the temperature range of
973 K-693 K, this temperature is very important in relation to the precipita-
tion of carbides.
On the other hand, the holding time in the temperature range at
973 K-693 K is extremely short, about 0.3 ks, for the Bar specimen weldments.
As discussed later in this article, the above-mentioned heat-histories deter-
mine the behaviour of carbide precipitations and the IGC susceptibility of
Stellite (weldments).
188 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

1800~--------------------------~

1500

g 1200
~
E 900
a
Q)

~
Bar specimen
300

o 2 4 6 8 10
Time [ks]

Fig. 3 Variations of welding temperature with time

Change in hardness
The hardness change of the Bar specimen was due to the heat-treatment
shown in Fig. 4, as compared with that of the as-welded specimen. The
heating of Stellite weldments to temperatures of 923 K and 1048K increases
the hardness, as compared with that of the as-welded. The heating to 1173K
and 1223K reduces the hardness of weldments, but the hardness is increased
again by the 1343K heating.

Microstructural changes due to heat-treatment


Generally, the microstructure of Stellite is composed of the matrix of aus-
tenitic phase/ E- phase and carbides precipitated during the cooling process of
its solidification (i.e. primary carbides), and also of the carbides precipitated
by the post-weld heating (i.e. secondary carbides).

600------------------------~

'>
t;
~ 500

V
(l,)

1400
~
o
®
As weld

>
900 1200 1500
Heat treatment temperature [K]

Fig. 4 Variations of hardness with heat treatment temperature for Bar specimen
EFFECT OF MICROSTRUCTURE ON INTERGRANULAR CORROSION 189

(a) As weld (b) 923 K

(c) 1048 K (d) 1173 K

(e) 1223K (f) 1343 K 20f,Lm

Fig. 5 Changes in microstructure due to heat treatment temperature

Figure 5 shows the microstructure of bar specimens in each heat-treatment,


including that of the as-welded specimen. In comparison with the as-weld
specimen, small amounts of particle-like secondary carbides are observed in
the specimens heading at 923 K and 1048K, and also it is observed that the
latter heating condition promotes the precipitation of the secondary carbides
than that of the former heating.
At the higher heating temperature above 1173K, the decomposition of the
primary carbides induces new precipitation of the particle-like secondary
carbides around the matrix, where previous primary carbides also coexisted.
Furthermore, heating higher than 1223K promotes the coarsening of particle-
like secondary carbides and the slender networks of primary carbides. At the
highest heating of 1343K, observed the solution of the carbides into the
matrix and the re-precipitation of carbides during the cooling process.
190 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Distribution of main elements


The result of surface analyses with XMA for Bar specimens is shown in Fig. 6.
The networks composed of Cr and C are observed remarkably well in both as-
weld and the 923 K-heated specimens. Most of these networks are expected to
correspond with primary carbides, and no difference in the distribution of
these network carbides is observed between the as-weld and the 923 K-heated
specimen.

Identification of carbide structures


The X-ray and electron-beam diffractions are conducted for carbides extracted
from the Bar specimens, which have undergone the following heat-treatments
are as-weld, 923 K, 973 K, 1023 K, 1173 K and 1343 K. All structures of carbides
except for the 1023 K heat are identified as M7C3. The carbide structure of the
1023 K heat shows a mixture of M7C3 and M23C6.
The results obtained from the electron-beam diffraction method for the
extracted-carbide replica samples are the same as from X-ray diffraction. The
results from TEM observations show that secondary M23C6 carbides with
needle-like shapes together with the secondary M7C3 carbides, form in the
1023K-heated samples.
Figure 7 shows the variations of Cr / Co /W contents in the primary and
secondary carbides with heat-treated temperatures. Almost no changes in
compositional atomic % of primary carbides were observed for all heat-
treatment conditions. Compared with the primary carbides, the atomic %
composition of secondary carbides heated at 923 K includes a slightly higher
Cr content 89.4-93.6%, a slightly lower Co content 2.84-6.40% and a slightly
higher W content 3.54-4.220/0.
On the other hand, it has been identified that the type-M23C6 secondary
carbides produced by heating to 1023 K are composed of the lower Cr content
74.2-77.80/0 and the higher Co content 14.4-19.0%. The above-observed
results, especially Cr content of carbides, show a close connection with the
IGC behaviour of Stellite, as-discussed in the latter section.

ICC Behaviour
Results from short-term tests
The IGC results tested according to the JIS-specified test time of 57.6 ks are
summarised in Fig. 8 for both the specimens of Product and Bar types.
For the Product type specimen, IGCs are observed in the as-weld condition
and also the post-weld treatments heated for 14.4 ks at temperatures of 773 K,
823 K, 873 K and 923 K.
However, the specimens heat-treated at a temperature higher than 973 K
have no IGC susceptibility. For Bar specimens, the heat-treated conditions of
973 K and 1048 K have no IGC susceptibility, but the IGCs are observed in
EFFECT OF MICROSTRUCTURE ON INTERGRANULAR CORROSION 191

§: §:
If.)

I=:
QJ

,SU
c,
QJ

If.)

~ro
..0
~0
•..•....

<
~
:>...
..0
~UJ
-e
~ QJ
'i:"' 'C 'i:"'
Q. ~,... If.)
:>...
~ CD
;: X
caI=:
UJ
~ ro
« C') ~rJl

~ C\I
0) I=:
e
QJ

E
QJ
Q)
I=:
';
E
•..•....
0
I=:
0
'.0
;j
~~
~
is
rJl
'0 '0
~ ~
'-'>
ob
~
oP"'4
192 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

100
[§] a..•.2nd
90 , carbides
--Q " Q
80 ot st carbides "
" 'Q
~ 70
~
+-J

20
en

:e~
(J)
"'0
15
/
~
10 ~~~~
llil
0
.S .,,.
+-J

(J)
$:l 5 ~ ~;nd carbides
+-J
$:l
u
0 a
10

8 ~ 2nd carbides
,- ~
6 <II-
<II;

4 ID'-'
o 1st carbides
2
Q 0
a
As weld 923K 1023 K
Heat treatment temperature

Fig. 7 Variations of Cr, Co and W content in 1st and 2nd carbides with heat
treatment temperature

o
1.0 ,..----------------.
Product specimen
D Bar specimen

0.2

600 700 800 900 1000 1100


Heat treatment temperature [K]
Fig. 8 Depth of IGC by Strauss tests (test duration: 57.6 ks)
EFFECT OF MICROSTRUCTURE ON INTERGRANULAR CORROSION 193

specimens heated at lower temperatures of 693 K-923 K, and the IGC depth
becomes especially large up to 0.5-0.6 mm in length.

Results from accelerated long-term tests


The cross-sectioned aspects of specimens after ICC tests for the Product and
Bar type specimens are shown in Figs 9 and 10, respectively.

(a) As weld (c) 1023 K x 14.4 ks

Fig. 9 Observations of IGC after 540 ks for product specimen

(a) As weld

(b) 923 K x 14.4 ks (c) 1048K x 14.4ks 100f,Lm

Fig. 10 Observations of IGC after 259.2 ks for bar specimen


194 ADVANCEDHEAT RESISTANTSTEELSFORPOWERGENERATION

As shown in Fig. 9, in the immersion tests for 540 ks for the Production
specimens, the IGCs are so severe as to penetrate the full thickness of
specimens in both the as-weld and the 973 K-heated specimen after welding,
although the specimens heated at 1023K show extremely slight IGC of
0.02 mm depth.
The IGCs are no longer observed when the specimens are heated over
1023K. For the Bar specimens which are immersed for 259.2ks, only the
923 K-heated specimen has the IGC susceptibility.

DISCUSSION

IGC Susceptibility
From the results obtained by a series of IGC tests previously described, it is
clear that the lower limit of heat treatment conditions after welding, by which
the ICC of Stellite materials will be actualised, is approximately 693 K, and
that the upper limit is about 1023K.
The difference in IGC susceptibility between Product specimens and Bar
specimens for as-welded Stellite may be due to the cooling times after
welding which are about 1.8 ks for the former and about 0.3 ks for the latter as
shown in Fig. 3. This may suggest that the gas welding condition as
experienced by actual power plant valves with a large heat capacity will
induce the IGC susceptibility in the cooling process after welding.
Although the microstructure of Stellite is composed of austenitic phase/
e-phase and precipitated carbides, from a series of our test results it would
appear that the primary carbides which are precipitated, in the solidification
process of the weldments, have no influence on ICCs.
The reason for the low cooling velocity after welding for the Product type
specimens, in our study, results from the high temperature effect of the pre-
heating and pass-to-pass heating at approximately 923 K in the gas welds. On
the other hand, it is expected that the ICC behaviour of the as-weld Stellite
welded by the gas method may be different from that of the low temperature
pre-heating and pass-to-pass heating of about 573 K for such as electrode
welding (PTA).

Correlation between Hardness and Microstructure


As compared with those of the as-welds, the hardnesses of the post-weld
heat-treated Stellites are increased in the heating temperature range of
923K-1048K, decreased in the range 1173K-1223 K and increased again for
1343K.
From the results observed by the optical microscopy and TEM, it is
deduced that the coarsening of the particle-like secondary carbides induces
the lowering of hardness by heating between 1173K-1223K, and that the
EFFECT OF MICROSTRUCTURE ON INTERGRANULAR CORROSION 195

solution of carbides into the matrix and re-precipitation of the secondary


carbides result in the increase in hardness by heating at 1343 K.
It is also considered remarkable that the precipitation of the fine particle-
like secondary carbides in the matrix due to heating at 923 K-1048 K causes
the increase in hardness, as compared with that of as-welds.

Correlation between Precipitation Behaviour of Carbides and ICC


It is identified that all crystal structures of primary and secondary carbides in
Stellites which are as-welds and also those heated at up to 1243 K after
welding are M7C3, except for the 1023 K heat. This result corresponds with the
thermal equilibrium phase diagram determined by D. Coutsouradis et al.1
However, the difference between our results from their phase diagram is
the existence of the M23C6 carbide in addition to M7C3 carbide for the
1023 K-heated Stellite. Concerning the precipitated carbides in Co-Cr-C
alloys, K. Lobl reported that the maximum amount of precipitated secondary
carbides is observed by heating at 998 K for 1.8 ks and the precipitation of
secondary carbides becomes small by heating at over 998 K.9 His knowledge
suggests the limitations for the existence of ICC correspondent with
973-1023 K heating in our investigation. It is considered that the precipitation
of M23C6 carbides may be thermally unsteady or a transient one. However,
detailed understanding of this precipitation behaviour cannot be obtained.
From our results, it is estimated that the precipitation of secondary carbides
with high Cr content promotes the ICCs due to the formation of severe Cr-
depleted zones which are adjacent to precipitated secondary carbides, and
that the primary carbides, existing in the as-welds and the weldments heated
at 923 K and 1023 K have no IGC sensitivity because of the mitigation of
formation of Cr-depleted zones.
It is considered that no IGCs in weldments heated at temperatures higher
than 1023 K attribute to the disappearance of Cr-depleted zones due to the
high temperature thermal diffusion.

CONCLUSION

1. Stellite has the IGC susceptibility when it is heated at temperatures from


693 K to 973 K after welding. It has been clarified that this IGC susceptibil-
ity of Stellite weldments is induced by the formation of Cr depletion zones
which are related to the precipitation of secondary carbides during the
processes of its cooling and post-weld heating. This phenomenon is
independent from the precipitation of primary M7C3 type carbides which
are precipitated during the solidification process of Stellite weldments.
2. It has also been observed that grainboundary precipitation of secondary
M23C6 type carbides consisting of the complex Co-Cr-W-C which are
196 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

produced by heating over around 1000 K suppresses the IGC in Stellite


equivalent to actual productions because of the mitigation in the formation
of Cr-depleted zones.
3. The primary and secondary carbides in Stellite have the M;C3 type
structure which is the equilibrium phase for the as-weld and the concerned
post-weld heat-treatments. The M23C6 type carbides are precipitated in
addition to M7C3 carbides when heated at 1023 K. It is considered that this
M23C6 type carbides may be precipitated under the thermally unsteady /
transient condition and may be related with the formation of the complex
carbides including Cr and W.

REFERENCES

1. A. J. Shiiki: Turbo machinary, 1990, 18(10), 598.


2. V. G. J. Resh: VGB Kraftwerkstechnik, 1979, 59,212.
3. D. R. Rush: Power, 1991, 22, 30.
4. V. H. Bischof: VGB Kraftwerkstechnik, 1984, 64, 248.
5. D. Cutsouradis: Cobalt, 1961, 13, 4.
6. L. V. Muysen: Cobalt, 1972, 55, 67.
7. H. Matsumoto: J. Welding Technics, 1981, 8, 64.
8. L. C. Webb et al.: EPRI Report, TR-l02285.
9. K. Lobl: Cobalt, 1968, 38, 29.
Section 2:
MICROSTRUCTURES
Microanalysis of 9-12% Chromium
Steels P92 and P122
M. H.A.TTESTRAND, M. SCHWIND and H.-O. ANDREN
Department of Physics, Chalmers University of Technology, SE-412 96
Goteborg, Sweden

ABSTRACT

The 9-12% chromium steels P122 and P92 have been investigated using atom probe
field ion microscopy (APFIM) and transmission electron microscopy (TEM).The two
steels are similar in composition with the exception of an addition of copper to P122,
allowing a higher chromium content. The investigated materials were tempered at
770°C and isothermally aged at 600°C for times ranging from 0 to 10000h. The
matrix and precipitates of type M23C6,MX and Laves phase have been analysed with
APFIM. Steel P122 contains 0.9% copper and it was found that the matrix concentra-
tion of copper drops during ageing from 0.4% to an equilibrium level at about 0.1%.
No copper was found in M23C6M , X or Laves phase. Instead copper forms a separate
phase, that was identified by TEM. During ageing the amount of tungsten in the
matrix drops due to formation of Laves phase. This process is faster in steel P122
compared to steel P92, indicating an accelerating effect of copper on the nucleation of
Laves phase. In both steels, enhanced concentrations of boron were found inside
M23C6carbides. Phosphorous was found to segregate to a very narrow region at the
carbide/matrix interface. The role of different alloying elements in the two steels is
discussed.

INTRODUCTION

The thermal efficiency of fossil fired power plants can be increased by raising
operating pressure and temperature. The most important limiting factor turns
out to be the creep and thermal fatigue properties of the materials used in
thick section boiler and turbine components. Ferritic alloys are preferred
because of their higher thermal conductivity and lower thermal expansion
coefficient compared to austenitic alloys. Advanced 9-12% chromium steels
have been recognised as the key material.l= For the most advanced, so called
ultra super-critical plants in use today, operating at 580°C/28.5 MPa (285 bar),
grade P91 can be used. However, to improve operating conditions beyond
this, there has been a need for further alloy development. The two Japanese
grades NF616 and HCM12A have creep properties superior to P91 and have
both been approved by ASME under the designation P92 and PI22, respec-
tivelv." These two steels contain about 2% tungsten, 0.5% molybdenum (wt%)
and small amounts of boron, which distinguish them from P91 regarding

199
200 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

composition. Steel P122 additionally contains 0.9°10 copper, allowing a higher


content of chromium, which is important for corrosion resistance.
This work concerns the microstructural evolution of the two steels P122 and
P92 during isothermal ageing at 600°C for up to 10 000 h. Hald has performed
a TEM investigation of the same materials as studied in this work.f-" He
showed that the steels in the as-received condition (annealed and tempered)
had the expected microstructure of tempered martensite, consisting of ferritic
sub grains with precipitates of type M23C6 on sub grain boundaries and
precipitates of type MX inside the subgrains. During ageing the most
significant change in microstructure was the precipitation of Laves phase
particles of relatively large size. Iseda et al. investigated test materials with
various compositions." In material containing 2 wtOlo Cu they found fine Cu
phase precipitates. This phase was not found in material with less than 1 wtOlo
Cu. To obtain a deeper understanding of the microstructural changes in the
materials, APFIM has been used in this work to monitor the redistribution of
elements, at the highest possible spatial resolution, during tempering and
isothermal ageing.

ATOM PROBE FIELD ION MICROSCOPY

Atom probe field ion microscopy (APFIM) is a combined technique for


imaging and chemical analysis with extremely high spatial resolution.l'' The
basic principles of the field ion microscope is shown in Fig. 1. The needle
shaped specimen, with a tip radius of about 100 run, is placed in a vacuum
chamber, which is filled with an inert gas, e.g. neon or helium. A phosphor
screen at ground potential is located a few centimetres away from the
specimen tip. If the specimen is raised to a high enough positive potential, the
field strength above the specimen surface will induce field ionisation of the
inert gas atoms. This process will take place at sites above prominent surface
atoms. After ionisation, the positively charged ions will be repelled from the
specimen towards the phosphor screen, where a highly magnified projection
of the surface atoms is obtained. The field ion microscopy (FIM) image
contains both crystallographic and chemical information and precipitates can

image intensifier
specimen gas atoms + phosphor screen • gas atoms

\/
r8§§§§§§~
( specimen ,

Fig. 1. Basic principles of field ion microscopy (FIM)


MICROANALYSIS OF 9-12% CHROMIUM STEELS P92 AND P122 201

Fig. 2. (a) Field ion micrograph of an M23C6 carbide (arrowed) in steel P92. The
diameter of the image is approximately 100 run. (b) A specimen for APFIM analysis
with an M23C6 carbide close to the end of the tip (TEM micrograph)

often be seen as either bright or dark areas. Figure 2a shows a FIM image of an
M23C6 carbide in steel P92.
The basic phenomenon involved in operation of the atom probe is field
evaporation, when atoms from the specimen surface are removed and ionised
due to the strong electric field. In practise, the process takes place when high
voltage pulses are applied to the specimen already exposed to to a high DC
voltage. The evaporated ions are then analysed with a time-of-flight mass
spectrometer. The analysis procedure is straightforward (see Fig. 3). Ionised
atoms from the specimen surface accelerate towards the phosphor screen.
There is a small hole in the screen, which only permits ions from a small area
on the specimen surface, a few nm in diameter, to enter into the mass
spectrometer. The analysed area can be chosen, while watching the FIM
image, by tilting the specimen until the hole in the screen falls over the image
of the area of interest. The mass-to-charge ratio of each ion entering the
spectrometer is derived from the flight time needed to travel from the

phosphor screen single ion


movable specimen with aperture detector

~ 0_0: ~ol
Fig. 3. The atom probe technique
202 ADVANCEDHEAT RESISTANTSTEELSFORPOWERGENERATION

specimen to the detector. Conservation of energy yields the following


relationship:

neV = m(d/t)2 / 2 (1)

where n is the charge state of the ion, e the elemental charge, V the applied
voltage during the pulse, m the ionic mass, d the flight path from the specimen
to the detector and t the time of flight.

EXPERIMENTAL

The investigated material came from two thick section pipes (350 mm outer
dimension and 50 mm wall thickness) originally supplied by Sumitomo
Metals Industries (P122) and Nippon Steel (P92). The composition of the steels
is shown in Table 1. Both materials had been annealed and air cooled,

Table 1. Composition of the two investigated steels P122 and P92.

Fe Cr Mn Ni Mo W V Nb Cu C B N Si P

P122 bal. 11.0 0.56 0.32 0.42 1.94 0.19 0.05 0.B7 0.11 .001 0.05 0.02 .013
P92 bal. 8.96 0.46 0.06 0.47 1.B4 0.20 0.07 - 0.11 .001 0.05 0.04 .OOB

followed by tempering at 770°C for 1-2 h. Ageing experiments were per-


formed by Hald on samples used for mechanical tests? The samples were
isothermally aged at 600°C for 1000, 3000 or 10 OOOh.
The APFIM instrument and the data evaluation system used in this work
are described elsewhere.11,12,13 The atom probe analyses were carried out at
specimen temperatures between 60 K and 80 K. The residual gas pressure in
the UHV chamber was kept below 7.10-8 Pa and the evaporation pulse
amplitude was 20% of the standing voltage. These are standard conditions for
APFIM analysis of steel. Electropolishing was used to prepare the needle
shaped specimens. To get precipitates close to the end of the tip, in a position
suitable for analysis, pulsed electropolishing was used to remove material in a
controlled manner. Figure 2b shows a specimen of steel P92, with an M23C6
carbide positioned for analysis.
Analytical TEM was used to confirm the presence of a copper phase in steel
P122. Because of problems with preferential etching during electropolishing,
ion beam milling was used to produce thin foils. The TEM work was carried
out on a Philips CM200 FEG instrument equipped with a LINK EDX-system
and working at 200 kV accelerating voltage.
MICROANALYSIS OF 9-12% CHROMIUM STEELS P92 AND P122 203

RESULTS

APFIM analyses of matrix and other phases present were performed for
different ageing conditions of the two steels P122 and P92 and the results are
presented in Table 2-3. In the case of one single analysis of a phase, the error
estimation is calculated as one standard deviation of the counting statistics. If
more than one analysis is used, the mean value of the individual analyses and
one standard deviation are given. Matrix analyses showed that in both steels
the chromium content and the vanadium content had decreased during
tempering because of precipitation of M23C6 and MX, respectively. Precipita-
tion of Laves phase in the two steels is reflected in a decrease of molybdenum
and tungsten contents during ageing. The difference in tungsten content after
1000 h of ageing indicates that this process is faster in steel P122 compared to

Table 2. Results from APFIM analysis of steel P122 after different times of ageing
(wt%).

Fe Cr Mn Ni Mo W V Nb Cu C B N Si P

P122
Matrix
b I 9.2 0.6 0.3 0.43 1.60 0.10 0.02 0.37 0.12
Oh
a. ±1.0 ±0.1 ±0.1 ±.07 ±.60 ±.03 ±.02 ±.19 ±.03
b I 9.2 0.6 0.4 0.30 0.95 0.16 0.02 0.11 0.10
1000h
a. ±1.1 ±0.2 ±0.1 ±.05 ±.50 ±.02 ±.02 ±.10
10000h b 1 9.3 0.7 0.3 0.26 0.82 0.11 0.08 0.10
a. ±1.0 ±0.1 ±0.1 ±.10 ±.11 ±.02 ±.01 ±.02

22.7 55.6 0.8 0.4 3.5 11.3 0.5 0.07 5.0 0.02 0.04
±0.5 ±0.8 ±0.1 ±0.1 ±0.1 ±0.2 ±0.1 ±.07 ±0.1 ±.01 ±0.1
21.8 52.8 0.8 0.4 3.5 15.1 0.5 0.03 5.1 0.02 0.01
1000h
±0.7 ±0.2 ±0.1 ±0.1 ±0.2 ±0.2 ±0.2 ±.01 ±0.2 ±.01 ±.01
10000h 17.9 58.9 1.2 0.4 2.7 13.5 0.3 0.03 5.2 0.03 0.01
±0.8 ±1.2 ±0.2 ±0.1 ±0.4 ±1.3 ±0.1 ±.02 ±OA ±.02 ±.01
Laves
31.4 8.3 0.6 0.2 8.3 49.2 0.2 0.5 0.08 1.0 0.24
1000h
±1.5 ±0.3 ±0.1 ±0.1 ±1.3 ±2.5 ±0.1 ±0.2 ±.02 ±0.1 ±.03
10000h 28.6 6.4 0.6 0.2 8.6 54.0 0.1 0.3 0.04 1.0 0.20
±1.4 ±0.5 ±0.1 ±0.1 ±0.7 ±3.S ±0.1 ±0.3 ±.01 ±0.4 ±.10
MX
1.3 15.2 57.4 10.6 15.5
Oh
±0.4 ±1.3 ±3.2 ±1.4 ±0.8
4.0 86 2.9 6.9
lOOOOh -
±1.0 ±8 ±O.7 ±1.0
204 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Table 3. Results from APFIM analyses of steel P92 after different times of ageing
(wt%).

Fe Cr Mn Ni Mo W V Nb Cu C B N Si P

P92
Matrix
8.2 0.50 0.1 0.47 1.92 0.07 0.01 0.03
Oh bal.
:to.2 :t.Ol :t.06 :t.02 :t.ll :t.Ol :t.Ol :t.Ol

bal. 8.1 0.4 0.2 0.47 1.41 0.05 0.01 0.01


1000h
±0.2 ±O.l :to.l :t.05 :t.46 ±.03 :t.Ol :t.Ol

bal. 7.3 0.4 0.2 0.30 0.75 0.04 0.05 0.02


10000h
±0.2 :to.l ±O.l :t.ll :t.34 :t.02 ±.Ol :t.02
M23C6
26.4 50.0 0.4 0.3 3.8 11.5 0.9 6.0 0.03
Oh :t1.0
±2.l :t2.4 :to.2 ±0.2 ±2.3 :to.4 ±O.9 ±.O3
18.9 57.0 1.0 0.1 4.2 12.2 0.4 6.2 0.04
10000h
±0.7 ±0.9 ±0.2 ±.OS ±O.4 ±1.0 :to.l ±O.4 :t.Ol

steel P92. The matrix concentration of copper in steel P122 drops during
tempering and ageing to an equilibrium level at about 0.1%.
The composition of M23C6 precipitates measured by atom probe analysis is
given in Tables 2-3. Apart from chromium, the carbides contain relatively
large amounts of iron, tungsten and molybdenum. During ageing, the iron
concentration decreases and the concentration of chromium increases. Copper
was not found in this phase. A clear enrichment of boron in the M23C6
carbides was found in both steels, but a difference was noticed regarding the
distribution of boron within the carbides. This is illustrated in the concentra-
tion profiles in Figure 4a-b. In steel P92, the boron is homogeneously
distributed within the carbide, while in steel P122, the boron concentration is
enhanced in the near surface region of the carbide. This observation was
made in several analyses through matrix/carbide interfaces. Selected area
analyses deep inside carbides also confirmed that the boron concentration
was low in the interior of the carbides in steel P122. Segregation of phosphor-
ous to the matrix/carbide interface, which is illustrated in Figure 4a-b, was
found in both steels.
Three MX particles were analysed, all in steel P122; two were vanadium-
rich nitrides in the unaged material and one a niobium-rich carbo-nitride in
the material aged for 10 000 hours. The compositions of the particles are found
in Table 2. Both kinds of particles were far from stoichiometry; the combined
amount of carbon and nitrogen was in both particles about 42 at.%. No boron,
phosphorous or copper was found, neither inside the particles nor at
MICROANALYSISOF9-12% CHROMIUMSTEELSP92 AND P122 205

100

~
0 50

]
25

10 12 14 16
Distance [nm]

~
0
v
u,

10 12 14 16
Distance [nm]

~
c::
0

J:
p
10 12 14 16
Distance [nm]

Fig. 4. (a) Concentration profiles through a matrix/ carbide interface in steel P122
aged for 10 000 h. The boron concentration is enhanced within the carbide in a
region close to the surface

interfaces between the particles and the matrix. Laves phase precipitates were
analysed in steel P122 and the results are given in Table 2. The composition is
close to (Fe,Cr)2(Mo,W). Relatively high concentrations of silicon and phos-
phorous were found in these precipitates. Also, it can be seen that some
carbon is dissolved in the Laves phase. Neither copper nor boron was
detected in this phase. The copper phase in steel P122 was not analysed with
APFIM. Instead TEM was used to confirm the presence of this phase. In
material aged for 10 000 h, copper-rich particles were found in subgrain
boundaries in connection with both M23C6 carbides and Laves phase. This is
illustrated in Fig. 5. EDX analysis of this copper-rich particle revealed a
copper content of more than 90 wt%. Also an enrichment of manganese was
detected (1.9 wt%).
In steel P122 four phases are present in the martensitic matrix after 10 000 h
of ageing, that is M23C6, Laves, MX and Cu. The redistribution of elements
measured in this investigation makes it possible to roughly estimate the
206 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

100

~c
0 50

tt

25

10 15 20 25 30 35
Distance [om}

~
c
0

J:
B
10 15 20 25 30 35
Distance [nm]

~c
0

10 15 20 2S 30 35
Distance [om]

Fig. 4. (b) Concentration profiles through a matrix/ carbide interface in steel P92
aged for 10000 h. Boron is enriched and evenly distributed within the carbide

volume fraction of the different phases. Such a calculation yields; M23C6-


2.4%, Laves-T.S'zs, MX-0.2%, Cu-0.7%.

DISCUSSION

Copper is primarily added to steel P122 to suppress the formation of 8-ferrite


during solution treatment and allow a higher chromium level. This effect has
been verified in previous investigations but the distribution of copper has not
been clarified.v? This work has shown that copper forms a separate phase
during tempering and ageing and that this process affects the precipitation of
other phases. Other types of steels alloyed with copper have been studied
previously with the atom probe technique, e.g. a maraging steel'! and neutron
irradiated pressure vessel steels." In both cases it was shown that the
solubility of copper in ferrite is low and that copper precipitates as a separate
phase. In the case of the maraging steels, it was also found that the copper
particles play an important role for the nucleation of intermetallic phases."
MICROANALYSISOF9-12% CHROMIUMSTEELSP92 ANDP122 207

Fig. 5. Precipitation of copper in steel P122 aged for 10000 h. A copper-rich particle
(a) is located between an M23C6 carbide (b) and a Laves phase particle (c)

The present investigation has shown that copper is not contained in


M23C6, MX or Laves phase. The copper particles found in material aged for
10 000 h were located in subgrain boundaries and in contact with both
M23C6 and Laves particles. If copper particles are formed rapidly in the ferrite
they might work as nucleation sites for other phases, which can explain the
observed difference between the two steels in the rate of Laves phase
precipitation.
Previous investigations have shown that M23C6 carbides form very rapidly
during tempering of 9-12% chromium steels." The change in iron content
during ageing reflects the higher equilibrium iron content at tempering
temperature (770°C) than at ageing temperature (600°C). Regarding the
behaviour of the trace elements phosphorous and boron, a similar investiga-
tion has been carried out earlier of a boron containing 9% chromium steel.l?
Lundin and Richarz found pronounced segregation of phosphorous to the
matrix/ carbide interface, while boron was enriched and evenly distributed
inside the carbide. The present investigation has revealed the same behaviour
of phosphorous and boron in steel P92. In steel P122 the boron concentration
is enhanced in the surface region of the carbides and the concentration of
boron in the interior of the carbides is low. The reason for this discrepancy is
not clear, but a hypothesis is that the rate of nucleation of M23C6 is higher in
P122, possibly because small copper precipitates work as nucleation sites.
This would allow less time for boron diffusion from primary grain bound-
aries in the beginning of the growth of M23C6• It has been showed previously
208 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

that boron segregates to austenite grain boundaries during cooling.l'' If it is


assumed that all carbon is tied up in carbides and the carbon and boron are
distributed in the carbides according to their nominal ratio it is possible to
estimate the total amount of boron contained in M23C6. A straightforward
calculation yields that about 50-70% of the total amount of boron is contained
in carbides. In steel P122 this estimation is of course uncertain because of the
inhomogeneous distribution of boron. Lundin et al.19,20 got the same result for
two other chromium steels, both with higher boron content than 10 ppm. The
amount of boron in the carbides thus increases with higher boron content in
the steel, but still not all of the boron seems to be incorporated in carbides.
The presence of boron in M23C6 might be beneficial for creep properties if the
coarsening rate of this phase is decreased. Recent experimental results
indica te that this is a true effect.21
Two kinds of MX particles were analysed; VN and Nb(C,N). Even if the
Nb(C,N) precipitate was analysed only in material aged for 10 000 h it can be
assumed that the carbon-rich MX particles are formed early, possibly prior to
or during the solution treatment, before precipitation of M23C6 early during
tempering. Pure vanadium nitrides are believed to form later during temper-
ing and ageing. It is interesting to note the high chromium content and the
low nitrogen content in the vanadium nitride particles. A similar composition
of MX precipitates has also been reported by Lundin.P A possible explanation
for the observed composition is that chromium diminishes the lattice parame-
ter of MX, which implies smaller misfit between the coherent precipitates and
matrix. The dispersion of MX particles inside the sub grains is critical for the
creep properties and a key question is the role of boron in this case.19,20,22 If
boron effects nucleation and coarsening of MX particles, this could have a
positive effect on long term creep properties. Lundin et al. have suggested a
mechanism called latent creep resistance, where small MX precipitates are
dynamically nucleated on dislocations and dissolved during creep.19,20Boron
could possibly take part in this process if it segregates to dislocations. Even if
most of the boron is tied up in carbides there might still be some available in
the matrix as discussed above. No boron was found neither inside the MX
precipitates nor at the MX/matrix interface but this fact does not exclude the
possibility that boron plays an indirect role in the nucleation of MX phase on
dislocations.
The composition of Laves phase close to (Fe,Cr)2(Mo,W), with additional
small amounts of silicon, phosphorous and carbon, is in agreement with
earlier investigations of this phase.P The drop in tungsten concentration in
the matrix during ageing reflects the kinetics of Laves phase precipitation.
Hald modelled this process in steel P92.7,8 The result is shown in Fig. 6
together with values measured by Nippon Steel used to calibrate the model.
In the figure are also shown data from the present investigation on the two
steels P92 and P122. There is a significant difference between the two steels in
the amount of precipitated tungsten after 1000 h. Possibly copper is responsi-
MICROANALYSISOF 9-12% CHROMIUMSTEELSP92 AND P122 209

--- -Ps50!~
1,6

••L
1,4

..--. / ~", rrrr


600°CJ
1,2
~
~
c
01

I- •
II' ~,.
~~ / [IJJ
l650°C ;:;:

r.> »< ~ ( rn
"'0 /
~ 0,8
I
.0-
.~ ~~
ct 0,6
L,..oo~ L.o~1;
I
V 1.0""

~ V t:::~~ ~..,...
y-' .-r--.--
17000CJ
i 0,4

0,2
~
..
~ ~ ~'- .....
~ ~
~ ~
-
f"""W

~ -~
..•~ ~

o
10 100 1000 10000 100000 1000000
Time (hJ

Fig. 6. Calculated amount of tungsten precipitated in steel P92. Squares are


measured values (Nippon Steel) used to calibrate the model. Results from the
present investigation are shown as triangles (steel P92) and circles (steel P122).
Original figure from reference?

ble for this by affecting the nucleation of Laves phase. Small copper precip-
itates might work as suitable nucleation sites in this case.

CONCLUSIONS

1. In steel P122 copper is present at fairly high concentrations in the unaged


matrix, but the concentration drops during isothermal ageing at 600°C to
an equilibrium level at about 0.1%. Copper is not contained in M23C6, MX
or Laves phase. Copper instead forms a separate phase.
2. During ageing the amounts of molybdenum and tungsten in the matrix
drop due to formation of Laves phase. The tungsten concentration equili-
brates faster in steel P122 compared to steel P92. This indicates faster
precipitation of Laves phase in steel P122, possibly caused by the presence
of copper particles in this steel.
3. Enhanced concentrations of boron were found inside the carbides in both
steels. In steel P122 the boron was located close to the carbide/matrix
interface, while in steel P92 the boron was homogeneously distributed. The
reason for this difference is not clear. In both steels, phosphorous segre-
gates to a very narrow region at the carbide/matrix interface.
4. Two different types of MX particles were analysed ill steel P122; vanadium
nitride and niobium carbo-nitride. Both kinds of particles are sub-stoichio-
metric with respect to nitrogen and carbon. The vanadium nitride contains
a relatively large amount of chromium. No boron or phosphorous was
found neither inside the precipitates nor at the MX/matrix interface.
210 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

5. The composition of Laves phase in steel P122 is close to (Fe,Cr)2(Mo,W)


with small additions of phosphorous, silicon and carbon. No boron was
found in this phase.

REFERENCES

1. C. Berger, R. B. Scarlin, K.-H. Mayer, D. V. Thornton and S. M. Beech:


Materials for Advanced Power Engineering, D. Coutsouradias et al. eds,
Kluwer Academic Publishers (Dordrecht), 1994.
2. T. Fujita: Materials engineering in turbines and compressors, R. D. Conroy, M. J.
Goulette and A. Strang, eds, The Institute of Materials, London, 1995,
493-516.
3. D. V. Thornton and R. W. Vanstone: Materials engineering in turbines and
compressors, R. D. Conroy, M. J. Goulette and A. Strang, eds, The Institute
of Materials, London, 1995, 135-153.
4. D. V. Thornton and K.-H. Mayer: Advances in turbine materials, design and
manufacturing, A. Strang, W. M. Banks, R. D. Conroy and M. J. Goulette,
eds., The Institute of Materials, London, 1997, 203-226.
5. E. Metcalfe and W. T. Bakker: New steels for advanced plant up to 620°C, E.
Metcalfe, ed., EPRI, 1995
6. F. Masuyama: New steels for advanced plant up to 620°C, E. Metcalfe, ed.,
EPRI, 1995.
7. J. Hald: New steels for advanced plant up to 620°C, E. Metcalfe, ed., EPRI,
1995.
8. J. HaId: steel research 1996, 67 369.
9. A. Iseda, Y. Sawaragiu, S. Kato and F. Masuyama: Fifth international
Conference on Creep of Materials, ASM International, Materials Park, OH,
1992.
10. M. K. Miller, A. Cerezo, M. G. Hetherington and G. D. W. Smith: Atom
probefield ion microscopy, Clarendon Press, Oxford, 1996.
11. H.-O. Andren and H. Norden: Scand. J. Metallurgy, 1979, 8, 1979, 147.
12. H.-O. Andren: J. de Phys., 1986, 47(C7) 483.
13. U. Rolander and H.-O. Andren: J. de Phys., 1989, 50(C8), 529.
14. K. Stiller, F. Danoix and A. Bostel: Appl. Surf Sci., 1996, 94/95, 326.
15. M. K. Miller and M. G. Burke: J. Nucl. Mat., 1992, 195, 68.
16. A. Bjarbo and M. Hattestrand: TRITA-MAC-0601, Report, Materials
Research Center, The Royal Institute of Technology, Stockholm, 1996.
17. L. Lundin and B. Richarz: Appl. Surf. Sci., 1995, 87/88, 194.
18. L. Karlsson and H. Norden: Acta Metall., 1988,36, 13.
19. L. Lundin, S. Fallman and H.-O. Andren: Mat. Sci. Tech., 1997, 13,233
20. L. Lundin: High resolution microanalysis of creep resistant 9-12% chromium
steels, Ph.D. Thesis, Chalmers University of Technology, G6teborg, 1995,
Paper 8.
MICROANALYSIS OF 9-120/0 CHROMIUM STEELS P92 AND P122 211

21. P. Polcik: Universitat Erlangen-Niirnberg, personal communication.


22. V. Foldyna, Z. Kubon, A. Jakobova and V. Vodarek: Creep resistant metallic
materials, J. Purmensky, ed., Vitkovice, a.s., Ostrava, 1996.
23. L. Lundin: Scripta Mater., 1996, 34, 741.
Forecasting Microstructural Change in
Austenitic Steels for Boiler Applications
R. G. FAULKNER*, D. MEADE*, c. c. GOODWIN*,
M. w. SPINDLER**, and R. HALES**
* Power and Aerospace Materials Group, IPTME, Loughborough University,
Loughborough, Leics., LE11 3TU
** Nuclear Electric plc, Barnett Way, Barnwood, Glos GL43RS

INTRODUCTION

Earlier Carolan and Faulkner model-based methods for forecasting the


kinetics of grain boundary precipitate growth have been modified and
extended. The system being investigated is intergranular M23C6 in Type 316
Austenitic steel.
The original grain boundary precipitation models of Aaron and
Aaronsson.! Caisley and Paulkner.? Carolan and Faulkner" assumed a lenticu-
lar shaped precipitate morphology and a constant collector plate size in the
solute supply equation. Some consideration of a variable collector plate size
was made by Carolan and Faulkner, who concluded that this model was
applicable only at temperatures close to the precipitate solvus. Mass transfer
to assist growth was assumed to take place by a combined lattice and grain
boundary diffusion controlled mechanism. Nucleation was also included in
the kinetics appraisal and for the case of M23C6 in an austenitic steel matrix
the nucleation kinetics were lattice diffusion controlled. Other work on
aluminium alloys by Aaronson's group highlighted the importance of grain
boundary diffusion in this process, but this was probably because the
precipitate matrix interfaces (8-prime in AI-Cu) were semicoherent in their
work.
More recently Jiang and Faulknerv'' have taken the Carolan models further
and applied them to high strength 7000 series aluminium alloys. Specifically
the improvements to the model include the following.
• Abandonment of analytical equations to describe the kinetics in favour
of an iterative approach, dividing the precipitate growth into a series of
small steps and changing the driving force in accordance with the
precise conditions applicable at each step.
• Inclusion of grain boundary segregation, using models of Seah and
Hondros'' for equilibrium segregation and of Faulkner? for non-equilib-
rium segregation. This modifies the solute supply rate.
• Application of classical nucleation equations to define the activation

212
FORECASTING MICROSTRUCTURAL CHANGE 213

energy to form the critical nucleus at the ageing temperature; this is used
to calculate the nucleation site density, the reciprocal of which is the
collector plate area at the onset of growth.
• Assumption of coalescence: this is quantified by calculating the change
in collector plate area as a function of time assuming a normal statistical
distribution of precipitates. Increasing the collector plate size increases
the solute supply rate accordingly.
• Allowance for site competition on the grain boundary during segrega-
tion so that the nucleation and growth kinetics are controlled by an
equilibrium interface concentration which is now time dependent.
• Inclusion of the Gibbs-Thompson effect, which allows for the effects of
interface curvature on solute solubility in very small precipitates.
• Coarsening kinetics have been included.

We have incorporated this approach into a new model dedicated to


describing M23C6 grain boundary precipitation in Type 316 Austentic
steel.

MODELLING DETAILS

Non-Equilibrium Segregation Calculations


The model begins by describing the amount of non-equilibrium segregation
of solute (chromium) created at the grain boundary during the quench and
during subsequent ageing. The quench process is defined by an effective time
taken to reduce the temperature from the starting temperature to 400°C. The
heat treatment is divided into small increments of time, a, such that at any
time step, i, that total time is given by i.A, The time is calculated assuming that
the heat treatment is at a constant temperature, taken as the temperature of
the material at the start of the quench, i.e., the solution treatment temperature.
The quench conditions set the solute concentration expected on the boundary
as a result of non-equilibrium segregation, and the definition of Ci, can be
found in eqn (7) in the paper by Faulkner? Two regions, the solute concen-
trated layer (SCL) and the solute depleted layer (SDL) are created near to the
boundary (see Fig. 1). These originate from solute being taken into the SCL by
solute-vacancy complex diffusion during each time step: the widths of the
layers are adjusted at the end of each step. The width of the SCL increases
with time until the temperature drops below the temperature at which non-
equilibrium segregation is expected to cease, usually about O.55Tmp' where
Tmpis the absolute melting point of the material. After this time no more non-
equilibrium segregation is expected to occur and the SDL is gradually filled
up by solute diffusion down the concentration gradient formed by the non-
equilibrium segregation process (Fig. 2).
214 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

100.-----------------------------------------~

Ci 10
U
::c
£
c
o
:t:i
~
C
Q)
o
c:
o
U 0.1
~SDL

1----------------------------1
0.01
Distance from GB (y)

Fig. 1 Segregation profile after quench

100~----------------------------------------~

'Ci 10
U
::c
£
c:
o
~ •....
C
Q)
o
c:
o
U 0.1 ~ After quench

1.---------------------------.....1
0.01
Distance from GB (y)

Fig. 2 Segregation profile after ageing

The equations describing these curves are as follows. During cooling or


during ageing where ageing temperature, T, T>T0.55mp:

Y-WI
C(y,teff) = Cb exp( - ay2) + Cg if WI < Y '5: W
W

C(y,teff) = Cb exp( - ay2) + Cg ify> W


FORECASTING MICROSTRUCTURAL CHANGE 215

where:
_Cg~ _ 2WZ(Cb - Cg)
Wz - C ' W - C I
(1)
b g

During ageing where ageing temperature, T, T<T0.55mp, we assume now that


the time is real time, t, at the ageing temperature. The segregation profile is
now determined from the following equations.

C(y,t) = Cb exp( -a'y2) if y < Wz


C(y,t) = Cb exp( -a'y2) + CI(y,t) + CII(y,t) + CIII(y,t) + CIV(y,t) if Y 2 WI
where:
_ C (y - WI)Cg fY - Wz 2ffiJCg -(y - WZ)2
CI
(y,t ) - g + W er 2~Dct + VitW exp 4Dct

__ ~ ( W +Y - WI W - Y + WI)
CII(y,t) - 2 erf 2~Dct + erf 2~Dct

_ -YDJcg [ -(w +Y - WI)2 -(w - Y + WZ)2]


CIII(y,t) - - VitW exp 4Dct + exp 4Dct

__ yCg ( W +Y - Wz _ W - Y + WZ)
Cly(y,t) - 2w erf 2~Dct erf 2~Dct

_ Cg~ _ 2WZ(Cb - Cg) ,_ 1tC~


WI - Cb I W - Cg I a - 8DcitqC~ (2)

The key requirement of this part of the model is to provide information at any
stage in the heat treatment about the amount of segregated solute on the grain
boundary, which can then be used as an enhanced supply parameter in
subsequent calculations of precipitate growth kinetics. The amount of extra
solute at any time t is given by
1 fOl
(3)
Xui = 81 0 C(y,t)dy

where

81 = ~2DIt (4)

Equation 2 is used for this part of the calculation of C(y,t).

Nucleation
Nucleation is important for two reasons. First, it defines the nucleation site
density on the grain boundary (GB) which is crucial to predicting the
216 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

interparticle spacing and hence the collector plate area at the onset of growth.
Second, it is important for determining the nucleation time, which is needed
to describe the total time necessary to grow a precipitate to a given size.

Collector Plate Area


The initial collector plate size is given by the reciprocal of the nucleation site
density function, No, given by Russell.''

No=-exp N (-~G*)
Xe
--
kTage
(5)

where N is the number of atoms on a unit area of grain boundary given by

(6)

where Xe is the atomic fraction of solute in the nucleating phase, do is the grain
boundary width, and Pa is the molar density of the matrix

3
*- 41tO'int ( _ 3
an d ~G - 3~G~ 2 3 cos 'I' + cos '1') (7)

where 'Jf is the contact angle between the tangent to the nucleating precipitate
and the GB plane, and O"int is the effective interfacial energy change created by
replacing the grain boundary with a cap-shaped precipitate, whose shape is
'I'
defined by the angle above. Details of the calculation of this value are in the
Discussion section.
The driving force for the transformation ~GV1 is given by

(8)

where R is the gas constant, Tage is the absolute ageing temperature, Vi} is
molar volume of the precipitate phase, and Xb is the segregated solute
concentration on the GB (= Cb).
The only unknown factor in eqn (8) is X~~age' and this is the equilibrium
concentration existing between the precipitate phase and the matrix at the
ageing temperature, which we are assuming to be the nucleation temperature.
This can be calculated from the solubility product equation found, for
example, in Faulkner and Caisley.3
FORECASTING MICROSTRUCTURAL CHANGE 217

6
a~ 1 - 28800 23
XaTage = [ Cc exp ( RTage - 0.9 )] (9)

The only method by which the collector plate size can increase is through
particle coalescence and coarsening. Coalescence can be important and we
have considered it by assuming that there exists a normal distribution of
collector plate sizes about the mean that we have calculated from the
reciprocal of eqn (5). This is given by eqn (10), where Av is the variable
collector plate size defined by the normal distribution, no, where

_ ~ [_ (Av - Amo)2]
no - 2Vitcr exp 2a2 (10)

Amo is the starting collector plate size given by

1
Amo == No (11)

a is the standard deviation, taken as

1
Amo == No

(Amo - Amin)
a= (12)
3

where Amin == 2 X 10-18 m2

The Av term in eqn (10) becomes the variable collector plate size as a
function of time. This is determined by assessing the reduction in number of
precipitates per unit area as a result of coalescence. The probability of
coalescence occurring is assessed from eqn (10) and coalescence is assumed to
occur when any collector plate is smaller than the precipitate size. This can be
described by eqn (13), which calculates the mean collector plate area at any
time, assuming that coalescence is occurring.

r}
1
(13)
Amn = No;[{ {I _ 0.2S[ erf ( Ami - ~ Ami,,) - erf ( Ami -~ 4Lt)

Nucleation time
The nucleation times are generally very short at typical ageing temperatures,
218 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

i.e., <600°C. They are calculated from the Van der Velde et al.,9 eqn (14) for cap
shaped nuclei.

_ 32kTagea4crfntNA
(14)
't - Dbnucdoxb V~~G~ sin \If

where k is Boltzmann's constant, a is the lattice parameter of the matrix, Dbll11C


is the grain boundary diffusion coefficient, do is the grain boundary width, O'int
is the modified particle-matrix interfacial energy (eqn (7)), NA is Avogadro'S
number, Xb is equivalent to Cb created by the quench, and ~Gv is the driving
force for growth given by eqn (8).
This time is added to the calculated growth time for the specified heat
treatment, which will be discussed in the next section.

Growth

The precipitate growth is again treated in a series of steps, i.S, with each step
adding to the size calculated from the sum of the preceding steps. The
representative equation for the precipitate radius, L, is given by

L. =
2A ml._ I D1I/2(XaaTage
t} )[t'1/2_(t'-ot)I/2]p
a + L3 }1/3 (15)
1
{ Pt}1t3/2J(\If)(Xt} - X~¥age) l-1

Xai is given by the segregation parameter (eqn (3)). Ami is given by eqn (13), Xt)
is the solute concentration in the precipitate, 1('1') is a geometrical para-
meter, dependent on the particle shape, Pt} is the molar density of the
precipitate phase, and DI is the lattice diffusion coefficient at the ageing
temperature.
In principle, the model can be used not only to calculate precipitate size as a
function of quenching and ageing treatments, but also to calculate inter-
particle spacing, through 1/(Ai)1/2 and any precipitate-free zone width from
an assessment of the shape of the curve given in Fig. 2, which is described by
eqn (2). In this case we have only used the model for precipitate size
forecasting.

Coarsening

The precipitate size at any time, t, during coarsening, L(t), is given by:

= [9doDbnuc(jaf3x~~age Ve(t - tcc) L4]!


L( ) (16)
t 32ABRT + g

where Lg is the precipitate size at the onset of coarsening, tcc is the critical time
for the onset of coarsening, calculated from:
FORECASTING MICROSTRUCTURAL CHANGE 219

(17)

A =~(1-~)
3 crap
(18)

(19)

where f is the fraction of the grain boundary covered by precipitates, given


by:

f= nq (20)
Amg

RESULTS

Data used in the calculations are given in Table 1. The intergranular M23C6
precipitate growth curve at 550°C, 600°C and 650°C is shown for alloy A in
Fig. 3. Included on the figure are experimental observations made by

Table 1. Data used in models

Parameter Value

r, (K) 1323
T.55xTmp (K) 1023
teff (s) 4
d (m) .000005
'I' (0) 57
1 X 10-9
do (m)
a (m) 3.649 X 10-10
aI (m? 8-1) .0000063
QI (J K-1 mol-1) 243000
abnuc (m- 8-1) .003
~nuc (J K-1 mol-1) 191000
a, (m28-1) .00083
o, (eV) 1.96825
Eb (eV) .0361
Efv (eV) 1.6
Pa (mol. m -3) 140920
Pi} (mol. m ") 5496
Vi} (m") .000181932
Xi} (at. fr.) .78
O'a~ (J m-2) .668
O'~~ (J m-2) .835-0.00089T (at l060°C)
220 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

1E-6~----------------------------------~

~
.1 ~ --""_·1.
I(J)
:::::s
1E-7

1E-8
•••••••• H •.••••••••
-_J----_
r;::::................................. -.•............•..... ....•...•. _ .
:0
~
a.
a.

1E-9

1E-10 -+-~----r---_r---- --.....----..,...--........---r--_----._--.-----1


o 20000 40000 60000 80000 100000 120000
Ageing time (hrs)

Fig. 3 Precipitate growth as a function of time for Alloy A at 550,600 and 650°C.
Square symbols depict experimental values

transmission electron microscopy for the same alloy taking measurements


from approximately 200 precipitates per heat treatment.
The predictions in Fig. 4 show the effect of carbon content, alloy A has a
0.034% C content whilst alloy B contains 0.0830/0 carbon. Experimental
observations for the alloys concerned are included. Full compositions of
alloys A and B are given in Table 2.

4E-7...,.----------------------------------,

1E-7~--------------~-------------------------~

6E-7-'--- ----_----.------r-----r------,--------r----l
60000 70000 80000 90000 100000
Ageing time (hrs)

Fig. 4 Effect of Carbon content on precipitate growth. Square symbols depict


experimental values
FORECASTING MICROSTRUCTURAL CHANGE 221

Table 2. Compositions of Type 316 Steels (wt.%)

Alloy C Si Mn P S Cr Mo Ni B Nb Ti V N Co

A .034 .18 1.87 .021 .013 16.62 2.3 10.45 .0043 .01 .006 .02 .033 .035
B .083 .35 .77 .033 .016 16.7 2.52 11.7 .0001 .083 .035 .77 .0285 .09

DISCUSSION

At lower temperatures, 500-700°C, lower growth rates observed here with


higher C material (Fig. 4) reflect the fact that the nucleation is more difficult
with lower C contents. This leads to larger collector plates at the early stages
of growth and this results in a higher solute supply to individual grain
boundary precipitates. Interparticle spacings are much greater in the low C
material, reflecting the point that low C and solute contents result in isolated
large grain boundary precipitates.
The choice of interfacial energy in the nucleation site density calculation is
very sensitive to the model predictions (crint in eqn (7)). Values of M23C6/
austenitic steel interfacial energy have been studied by Murr.l" This relation
has to be incorporated in the following equation to obtain the full interfacial
energy term.
crint = crap + crapc.f(\fI1) - crp~.
!(\fI1) is the ratio of the surface area of the cap-shaped precipitate to the circular
area of grain boundary on which the precipitate sits. This depends on \fI, the
angle between the tangent to the precipitate and the GB at the precipitate
edge. crape is the interfacial energy of the curved part of the interface; craJ3 is the
interfacial energy of the flat interface parallel to the grain boundary. In this
case it turns out that the increased interfacial area of the curved interface
cancels out the reduced interfacial energy associated with the curved, as
opposed to the flat, interface. Therefore the first two terms on the right hand
side of the above equation are equal. crJ3J3is the GB energy, and Murr estimates
that this term is equal to 0.835 J m? at 1060°C and that the temperature
dependence is -0.00089 J m? K-1. We have assumed that a constant
temperature of 600°C applies to this term in all the predictions used in this
work
The choice of Amin in eqn (12) is made as a suitable value describing the
average critical nucleus area. This parameter is not greatly sensitive to the
predictions and so the same value as indicated for eqn (12) is used through-
out.
Reasonable fits between experiment and predictions are seen in Figs 3 and
4. Closer matching would be obtained if the true temperature dependence of
the GB energy were taken into account for each of the ageing temperatures
considered. The pictures in Figs 3 and 4 also clearly indicate a transition to
222 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

coarsening kinetics at around 50 000 hours. The transition is rather abrupt and
it may be that the transitory kinetics in this period need refining somewhat.

CONCLUSIONS

The introduction of a new iterative modelling approach to prediction of grain


boundary precipitation kinetics has been applied to austenitic steels. The
results for M23C6 in Type 316 Austenitic steel are shown here for the first time,
and reasonable fits between experimental data and predictions are seen.
Carbon content is shown to be a sensitive parameter when considering the
overall growth behaviour. Intergranular precipitation rates are higher for
lower C contents. However, the precipitates formed at these low C levels are
very isolated and lumpy.

REFERENCES

1. H. B. Aaron and H. I. Aaronson: Acta Metall., 1968, 16, 789-798.


2. R. A. Carolan and R. G. Faulkner: Acta Metall., 1988, 36, 257-266.
3. R. G. Faulkner and J. Caisley: Metal Science, 1977, 11, 200-207.
4. H. Jiang and R. G. Faulkner: Acta Mater., 1996,44, 1857-1864.
5. H. Jiang and R. G. Faulkner: Acta Mater., 1996,44, 1865-1871.
6. M. P. Seah and E. D. Hondros: Int. Met. Rev., 1977, 222, 262.
7. R. G. Faulkner: Acta Metall., 1987,35,2905-2914.
8. K. C. Russell: Acta Metall., 1969, 17, 1123.
9. G. Van der Velde, J. A. Velasco, K. C. Russell and H. I. Aaronson: Metall.
Trans., 1976, 7A, 1472-1473.
10. L. E. Murr, G. I. Wong and R. J. Horylev: Acta. Met., 1973, 21, 595-60.
Precipitation Reactions in 3Crl.5Mo
Power Plant Steel
N. FUJITA and H. K. D. H. BHADESHIA
Department of Materials Science and Metallurgy, University of Cambridge,
Pembroke St, Cambridge CB2 3QZ

ABSTRACT

A method has recently been developed to estimate the speed with which precipita-
tion reactions occur in power plant steels. It is based on Avrami theory but with an
adaptation that allows the treatment of simultaneous reactions. A number of
approximations and inconsistencies in the theory have been eliminated in the
present work. The modified theory is shown to successfully predict new experi-
mental data on 3Crl.5Mo steel.

1. INTRODUCTION

Steels for use at elevated temperature rely on a variety of precipitates for their
resistance to creep deformation. The precipitation process in the vast majority
of creep-resistant steels occurs in a complicated manner, beginning with
phases which are easy to nucleate but which are metastable. It is only after
prolonged aging (e.g. many decades at 600°C) that the equilibrium phase
mixture might be obtained. This is just as well because the equilibrium
microstructure is unlikely to be useful in creep applications.
Steels destined for power plant applications might contain any of the follow-
ing precipitates: iron base carbides or carbonitrides (M3C, M2.4C etc.), M2C,
M7C3, M23C6, MSC2, M6C, graphite and Laves phase. It is obviously difficult to
design a steel with specific particles in mind given the complexity of the
precipitation events. A theory has recently been proposed (Robson and Bhade-
shia.l-' Jones and Bhadeshia") which adapts the classical Avrami+" model to
enable simultaneous precipitation reactions to be tackled. Although this new
theory has been applied to power plant steels, it has only been tested against
limited data and it contains a number of important approximations, some of
which may not be generally valid. The purpose of the present work was firstly
to make the theory more rigorous in its application, and secondly, to test the
model against some critical new experimental data for 3er1.SMo steel.

2. EXPERIMENTAL PROCEDURE

The 3Cr1.5Mo (Table 1) steel studied in this work was vacuum-melted as a 15


kg ingot, heated at 1250°C for 30 minutes in an argon atmosphere, hot-rolled

223
224 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Table 1 Concentration in wt% of the major alloying elements in 3Cr1.5Mo steel

C Mn Cr Mo

3Cr1.5Mo 0.10 0.98 2.98 1.50

to 15 mm thick plate and quenched from a finishing temperature of about


900°C. Specimens of 3 and 8 mm diameter were then machined and sealed in
silica tubes under a partial pressure of argon (about 150 mm Hg) to prevent
decarburisation and oxidation. Phase diagram calculations using MTDATA9
predicted that only austenite is present above 1200°C in 3Cr1.5Mo steel.
Therefore, the samples were homogenised at 1250°C for 3 days followed by
water quenching to produce a martenistic microstructure. The specimens
were then sealed again and tempered at 600°C for times up to 1000 h, and
then quenched into water. .
The microstructures were characterised using optical and transmission
electron microscopy (TEM), the latter using carbon extraction replicas. Elec-
trolytically extracted residues were analysed using X-rays.
The number densities of precipitates were determined using the method of
Ashby and Ebeling.l" The particle sizes were determined by averaging at least
100 measurements in each case.

3. RESULTS

3.1 Microstructural observations


The microstructure of 3Cr1.5Mo following heat treatment at 1250°C for 3 days
followed by water quenching was martenistic.
When the specimen was tempered at 600°C for 0.05 h (Fig. 1), only M3C
could be detected and most particles appeared to be in the form of plates.
Figures 2 to 4 show a set of transmission electron micrographs and associated
diffraction analysis for 3Cr1.5Mo samples tempered for 0.7, 10 and 100 h
respectively. M7C3started to precipitate at 0.7 h (Fig. 2). As shown in Fig. 3, at
10 h, the M3C particles are smaller than was at the case after 0.05 h, implying
that they had started dissolving. A small amount of M3C persisted in the
microstructure even after 10 h of heat treatment at 600°C. As the tempering
time was increased to 100 h, M2C needles and M23C6 particles were clearly
observed (Fig. 4).

3.2 X -ray analysis and precipitation sequences


Table 2 shows a summary of X-ray analysis results of electrolytically extracted
residues.
PRECIPITATION REACTIONS IN 3CR1.5Mo POWER PLANT STEEL 225

Fig. 1 Transmission electron micrograph of 3Crl.SMo steel tempered at 600°C for


O.OSh

Zone axis: [II5)


Fig. 2 Transmission electron micrograph for 3Cr1.5Mo steel tempered at 600°C for
O.7h, (a) image of M7C3 particle and (b) electron diffraction pattern from M7C3.The
arrow in (a) indicates the particle from which the electron diffraction pattern was
obtained. In the diffraction pattern, there were streaks characteristic of M7C311

The results of both TEM and X-ray analysis are in good agreement. M2C
followed the formation of M7C3 which occurred at 0.3 h of tempering.
Between 10 h and 100 11 tempering, M23C6was clearly detected and the X-ray
intensity from M3C decreased. This implied the beginning of M3C dissolution.
According to both TEM observations and X-ray analysis of extracted residues,
the precipitation sequences at 600°C for 3Crl.5Mo steel can be summarised as
follows:
226 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Zone axis : [ 3 0 1 ]
Fig. 3 Transmission electron micrograph of 3Cr1.5Mo steel tempered at 600°C for
lOh, (a) image of M3C particle and (b) electron diffraction pattern from M3C. The
arrow in (a) indicates the particle from which the electron diffraction pattern was
obtained

Table 2 The results of X-ray analysis for extracted residues of 3Crl.5Mo steel
tempered at 600°C (V5, 5, W and VW mean very strong, strong, weak and very
weak X-ray intensities, respectively)

Precipitates detected

Tempering condition

1250°C-3 days normalised w


600°C-O.05h tempered W
600°C-O.3h tempered V5 W
600°C-O.7h tempered V5 vw 5
600°C-IO h tempered 5 w 5 W
600°C-IOO h tempered W s 5 S

4. DISCUSSION

4.1 Comparison between experiment and theory


Figure 5 shows a calculation using the Robson and Bhadeshia model!
compared against experimental data for 3Crl.5Mo steel. Table 3 shows how
each precipitate is treated. Although the calculations are qualitatively correct,
PRECIPITATION REACTIONS IN 3eRi.sMo POWER PLANT STEEL 227

Fig. 4 Transmission electron micrograph of 3Crl.5Mo steel tempered at 600°C for


lOOh, (a) image of M23C6 particle and (b) electron diffraction pattern from M23C6,
(c) image of M2C particles and (d) electron diffraction ring pattern from an array of
M2C particles. The arrow in (a) indicates the particle from which the electron
diffraction pattern was obtained

Table 3 The main assumptions in the Robson and Bhadeshia model!

The microstructural parameters Diffusion-controlled growth

Constant number of pre-existing M3C Parabolic law for spherical precipitation


particles
(Constant initial number density of Lengthening with constant
particles)
Constant thickness of M3C and aspect aspect ratio for needle precipitation
ratio ofM2C
Use mean particle size
Both are controlled only by Cr diffusion
Interfacial energies
228 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

0.025
--M C
23 6
--- .....
M C
7 3
0.020 - - - • M2C

c
-------~ I
----- M3C

.9
to.015
~
c::
~
9 0.010
Q
> I
\
, .:

.. ,

,\
0.005

.,:' - .•."
\

.,i
0.000
1e-02 1e-Ol le+OO le+Ol le+02
Time / h
Fig. 5 The predicted precipitation sequences' along with experimental data for
3Crl.5Mo steel tempered at 600°C

100 3Cr1.5Mo steel


tempered at 600°C
o On lath boundaries
• Within laths
5 80
c

U
ff')

~
c..,
60
e
VJ

~c
VJ

..::.= 40
:c
Cj

4~
f-. 0
20
•• j~

f 0

~ 0.2 10.1 10° 101 102 103

Tempering time at 600°C/ h

Fig. 6 The thickness of M3C on lath boundaries and within laths as a function of the
tempering time at 600°C
PRECIPITATIONREACTIONSIN 3CRi.5Mo POWERPLANT STEEL 229

there are some obvious discrepancies. The approach to equilibrium is gen-


erally much slower than predicted by the model.

4.2 Difficulty 1: The thickness of M3C particles


M3C particles have been assumed to be uniform in size for the calculations
presented in Fig. 5, with the particle thickness set to 1 /-LID, a value which is
inconsistent with the measured thickness. Fig. 6 shows the thickness of M3C
on martensitic lath boundaries and within laths, as a function of tempering
time at 600°C. The error bars correspond to two standard deviations. After 10
h of heat treatment, it became difficult to find enough M3C particles for
meaningful measurements with error bars. Because less than 20 particles were
measured, the distribution of thicknesses was so small that only the average
measured values are plotted in Fig. 6. The size does not seem to change for
times less than 10 h. The thickness of particles on lath boundaries was about
twice that of those within the laths.

4.3 Difficulty 2: The number density of M3C particles


For the purposes of the calculations in Fig. 5, the number density of M3C
particles was assumed to be 5.49 X 1021 m", which was assumed to be
independent of steel composition in the original work.l- However, the total
volume fraction of M3C must be a function of the carbon concentration. As
emphasised in Fig. 6, the thickness is approximately constant before the
dissolution of M3C, so that the initial number density N, of M3C particles
must be a function of the carbon concentration. The average measured value
of N, in specimens tempered at 600°C for times where only M3C exists was
1.23 X 1021m-3 for O.lC-3Cr1.5Mo steel. To create an empirical expression for
N, as a function of the carbon concentration, measurements were also made
on O.15C-2.25CrlMo steel tempered at 600°C, in which case N, = 2.35 X 1021
m-3•13 If the effect of other alloying elements is neglected, then it is expected
that N, increases with carbon concentration. Therefore, N, (m :') was
assumed to increase in proportion to the carbon concentration C (wt%) as
follows:

Nv = 2.23 X 1022C - 1.0 X 1021 (1)

4.4 Difficulty 3: The aspect ratio of M2C


The aspect ratio (length/width) of M2C needles was assumed to be constant at
50. However, the measurements indicated values between 10 and 20, so that
the aspect ratio was set at 15 for the present work.
230 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

4.5 Difficulty 4: Avrami theory


One difficulty in the application of Avrami theory is that the conversion of
extended space into real space, necessary to account for impingement,
prevents the calculation of anything but the average particle size. Given that
the total fraction of precipitates is small, this difficulty can be avoided by
neglecting impingement altogether. It should then be possible to estimate size
distributions.

4.6 Difficulty 5: Diffusion controlled-growth in a multicomponent steel


The original model treats the growth of all precipitates other than M3C in
terms of the diffusion of chromium alone, with the interface composition
given by a tie-line passing through the mean alloy composition (c). The
analysis of diffusion-controlled growth therefore involves just one condition
for mass conservation at the interface which is moving with a velocityv:

v (c~~ - cc~) = DCr(accrl ax)x = Xl (2)


where c~~ and cc~ are the equilibrium concentrations of chromium in ~
(precipitate) and ex (ferrite) phases respectively, DCr is the diffusion coefficient
of chromium in ex phase and (accrlax)~=x is the chromium concentration
gradient in the ex phase at the ex I J3interface.
As emphasised in the classic work of Kirkaldy-" and Coates.l'' this binary
treatment is inadequate for ternary or higher order steels. This is because the
diffusion coefficient of the interstitial solute can be many orders of magnitude
greater than that of the substitutional solute. A second mass conservation
equation must be simultaneously satisfied:

(3)
But to do this and maintain local equilibrium at the moving interface, a tie-
line must be chosen which reduces the driving force for carbon diffusion so
that the slower moving chromium can keep pace with the carbon. Such a tie-
line will not in general pass through c. Indeed, the tie-line defining the
interface compositions will not be constant but will shift towards E as
precipitation progresses (Fig. 7).IS Notice in Fig. 7 that the effective value E' of
c at the point where alloy carbide precipitation begins is the composition of
the ferrite after the precipitation of cementite by a paraequilibrium mech-
anism.

5. THE MODIFIED MODEL

The measured microstructural parameters used in the modified model are


shown in Table 4. Table 5 shows the comparison of assumptions between the
PRECIPITATION REACTIONS IN 3CRl.5Mo POWER PLANT STEEL 231

e
;
=
e=
l-
alloy
~ composition
C
e
•..
Col

I Ferrite + Carbide
I

c' c
C concentration

Fig. 7 The schematic drawing for tie-line shifting in Fe-Cr-C system

Table 4 The measured values used in the modified model

The microstructural parameters The values in use

Number density of sites for M3C at 600°C 1.23 X 1021 m-3


Thickness of M3C on lath boundaries 5.0 X 10-8 m
Thickness of M3Cwithin laths 2.0 X 10-8 m

Aspect ratio for needles of M2C 15.0

Table 5 The comparison of assumptions used on both models

The original model The modified model

Based on Avrami theory Nucleation and growth but no treatment of impingement


Using mean particle size Particle size distribution due to
different nucleation times and growth rates
Cr diffusion-controlled growth Diffusion-controlled growth in Fe-Cr-C system

original and modified models. The results for 3Crl.5Mo are shown in Fig. 8
along with the experimental observations.
Comparison with Fig. 5 shows that the modified model is in better
agreement with experimental data. However, M3C precipitation is still under-
estimated.
232 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

--M C
23 6
•.•••.•.
M C
7 3
- - _. M C
0.020 2
----- M3C

.~=
~ 0.015
\

~
\
\

~
~
~'--"
; 0.010
"0
;;>
,.( \ \.

0.005 t':,
I:
I •
.../ : .

le-Ol le+OO le+Ol le+02 le+03

Time / h

Fig. 8 The calculation of multiple precipitation reactions at 600°C by the modified


model for 3Cr1.5Mo steel

M3C forms by a paraequilibrium mechanism but the cementite during


aging enriches with chromium. The chromium enrichment was calculated in
the model using published thcory.l" it stops when the cementite achieves its
equilibrium composition. Cementite begins to dissolve when the chromium
concentration in ferrite falls below its equilibrium with cementite, as alloy
carbides precipitate and consume solute. The diffusion distance for this was
assumed to be a mean distance between all particles. A concentration gradient
therefore arises between the cementite and alloy carbide. This assumption
may not be realistic and the problem needs a more rigorous analysis.

6. CONCLUSIONS

New experimental data have been generated on the precipitation reactions in


3Crl.5Mo steel which was tempered from a martensitic state. These results
indicated a need to modify a theory for the prediction of the kinetics of
precipitation reactions. In particular, a multicomponent treatment of the
diffusion-controlled-growth of alloy carbides has introduced a proper con-
servation of mass in the model. The new calculations have been carried out
without the Avrami conversion of extended space into real space, a sat-
isfactory approximation given the minute fractions of precipitates involved.
The new model shows better agreement with experimental data.
PRECIPITATION REACTIONS IN 3CR1.5Mo POWER PLANT STEEL 233

REFERENCES

1. J. D. Robson and H. K. D. H. Bhadeshia: Mat. Sci. Tech., 1996, 13, 631.


2. J. D. Robson and H. K. D. H. Bhadeshia: Mat. Sci. Tech., 1996, 13, 640.
3. S. J. Jones and H. K. D. H. Bhadeshia: Acta. Metall., 1996,45, 2911.
4. A. N. Kolmogorov: Bull. Accad. Sci. USSR Phys. Ser., 1937, 3, 355.
5. W. A. Johnson and R. F. Mehl: Trans. Am. Inst. Min. (Metall.) Engrs., 1939,
135,416.
6. M. Avrami: J. Chern. Phys., 1939, 7, 1103.
7. M. Avrami: J. Chern. Phys., 1940, 8, 212.
8. M. Avrami: J. Chern. Phys., 1941, 9, 177.
9. S. M. Hodson: MTDATA-Metallurgical and Thermochemical Databank,
National Physical Laboratory, Teddington, UK, 1989.
10. M. F. Ashby and R. Ebeling: Trans. Metall. Soc. AIME, 1966, 236, 1396.
11. J. Beech and D. H. Warrington: J. Iron Steel Inst., 1966, 204, 460.
12. J. D. Robson: Ph.D. Thesis, University of Cambridge, UK, 1996.
13. N. Fujita: Unpublished work, University of Cambridge, UK, 1997.
14. J. S. Kirkaldy: Can. J. Phys., 1958, 36, 907.
15. D. E. Coates: Metall. Trans., 1973, 4, 2313.
16. H. K. D. H. Bhadeshia: Mat. Sci. Tech., 1989, 5, 131.
Ageing Embrittlement of Fe-12Cr Steels
T. ANGELIU, E. L. HALL, M. LARSEN, A. LINSEBIGLER and
C.MUKIRA
GE Corporate Research and Development Center, Schenectady, NY 12309,
USA

ABSTRACT
When aged for long times at elevated temperatures, Fe-12Cr steels can experience a
significant decrease in the fracture toughness as observed by an increase in the
fracture appearance transition temperature (FATT). The mechanism responsible for
this decrease in toughness has never been unequivocally explained, but it has been
generally attributed to the precipitation of second phases and/or impurity segrega-
tion. The objective of this study was to characterise the microstructural changes in
conventional and super clean, electroslag remelted (high purity) MI52 steel aged
between 343°C and 510°C up to 50Khrs for correlation to the toughness changes.
Analytical electron microscopy techniques were used to characterise the micro-
structure and segregation of impurities. After thermal ageing at 454°C, conventional
MI52 contained large quantities of alpha prime (Cr-rich, bee structure) in addition to
Cr-rich M23C6carbides and complex Cr-Fe-Mo-Ni-Si rich precipitates. The micro-
structure of the high purity MI52 aged at 454°C was similar to the conventional
material, except for the absence of the Si-rich precipitates. Microstructural analysis
after ageing at 343°C revealed the same phases as in the as-tempered material
(primarily M2X and M7X3). Auger analysis of the prior austenitic grain boundaries
revealed Sn segregation in the aged conventional material, with equivalent levels of
P segregation in both the conventional and high purity materials. A de-embrittling'
I

treatment of 600°C/2hrs restored much of the original toughness. Microstructurally,


the de-embrittling treatment reduced the amount of alpha prime and lowered the
hardness by several Rockwell C points. The analytical electron microscopy study is
still in progress, but the initial results suggest that the degradation in toughness with
ageing is a combination of second phase precipitates (notably, alpha prime) and
impurity segregation (Sn).

INTRODUCTION

For Fe-12Cr steels, the mechanism responsible for the decrease in fracture
toughness with long term ageing has never been unequivocally explained,
but has been generally attributed to grain boundary impurity segregation
and/ or the precipitation of second phases.l=!" The idea that impurities effect
the long term ageing embrittlement is based on the strong role of phosphor-
ous on the temper embrittlement of Fe-12Cr steels=" and one study on long
term ageing." Microstructural studies have indicated that carbides and/or

234
AGEING EMBRITTLEMENT OF FE-12CR STEELS 235

Laves phases degrade the toughness of Fe-9 to 12Cr steels upon long term
thermal ageing?-10 In one study of Fe-9Cr-1Mo steel, the degradation in
toughness was consistent with both grain boundary segregation and micro-
structural changes." In another study, the pronounced growth of carbides on
lath and prior austenitic grain boundaries was concluded as being responsible
for the decrease in toughness with ageing." However, the effect of segregants
was not evaluated. After ageing at 600°C, Laves intermetallic phase has been
reported as the main embrittler of Pe-lOCr9 and 9Cr-2Mo10 steels aged for
10 Khr and 2 Khr, respectively.
In response to the long term ageing embrittlement of Fe-12Cr steels, GE
developed a high purity version of M152 that is ESR processed and super
clean.'! This high purity material has been shown to have improved resist-
ance to ageing embrittlement as compared to the conventional material,
suggesting that impurities playa strong role in the embrittlement.P However,
high purity materials are still susceptible to embrittlement upon ageing. The
increase in FATT of high purity M152 is about 35% of that exhibited by the
conventional material after identical thermal treatments.12,13 The purpose of
this study was to perform microstructural characterisation of M152 steels to
determine the causes of long term ageing embrittlement.

EXPERIMENTAL PROCEDURE

Materials
Conventional and high purity heats of M152 were aged between 343°C and
510°C (650°F and 950°F) for times up to 50Khrs in furnaces exposed to air.
The conventional materials (GG-265 and BWS-O, Table 1) were fabricated
over 15 years ago and were obtained from sections of gas turbine wheels prior
to service. The high purity heats (F and J, Table 1 and 'super clean', containing
low levels of Mn, Si, P, S, Sn, Sb and As and containing a low number of
inclusions from electroslag remelt processing. The chemical compositions of
these alloys are shown in Table 1.

Charpy Impact
At designated times, blocks of M152 materials were removed from ageing
furnaces for impact toughness evaluation. Charpy impact experiments were
conducted according to ASTM E23 to determine the fracture appearance
transition temperature (FATT), or the temperature at which there is 50%
fibrous (ductile) and 50% brittle (cleavage) failure on the Charpy specimen
surface. Typically, 5 to 6 test specimens were used with and uncertainty in the
PATT of about ±14°C (25°P). After impact testing, the fracture surfaces were
examined using scanning electron microscopy (SEM). The amount of inter-
granular (IG) fracture was quantified by placing a grid on a collage of SEM
236 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Table 1 Chemical compositions of M152. GG-265 and BWS-O are conventional


heats, F and J are super clean and ESR processed (high purity)

alloy Fe Mn Si Cr Ni Mo V

GG-265 bal. 0.68 0.20 11.8 2.65 1.61 0.28


BWS-O bal. 0.63 0.28 11.6 2.65 1.58 0.29
F bal. 0.020 0.014 11.9 2.80 1.60 0.26
J bal. 0.023 0.041 11.0 2.8 1.7 0.030

alloy C N P S As Sb Sn

GG-265 0.10 NA 0.013 0.005 NA NA NA


BWS-O 0.12 NA 0.012 0.004 NA NA NA
F 0.102 0.031 0.007 0.001 0.0024 4e-4 0.003
J 0.10 0.027 0.005 0.001 0.004 1e-5 <0.002

photomicrographies taken at 30X and counting the number of IG intersections


and dividing by the total number of intersections. Regions containing IG
appearance in the photos were verified by SEM analysis at higher magnifica-
tion.

Phase Extraction
Bulk phase extraction was used to dissolve away the matrix and capture the
remaining residue for analysis. This was conducted by wrapping a 10 gram
specimen of M152 with Pt wire and immersing into a solution of 10% HCI in
methyl alcohol. A current density of 0.02 A cm-2 was applied to the specimen
versus a Pt flag counter electrode. The specimen and solution was placed in a
continuous ultrasonic bath to assist with particle detachment. At the end of 24
hours, a vacuum filtration system was used to separate the residue from the
solution and rinse the residue with two 100 ml portions of methyl alcohol.
After the liquids were filtered, the filter and residue were allowed to dry prior
to weighing. The extracted residue was analysed by SEM and transmission
electron microscopy (TEM).

Microscopy
Optical microscopy
Specimens were prepared for optical microscopy by grinding to 4000 grit SiC
on paper and then through a series of fine polishing to 0.04 mm silica slurry.
The specimens were etch-polished using a dilute solution of Fry's reagent
consisting of 5 grams CuCI2, 40 ml HCI, 30 ml distilled water and 25 ml ethyl
alcohol. This solution was diluted by 1 part Fry's to 3 parts ethyl alcohol.
AGEING EMBRITTLEMENT OF FE-12CR STEELS 237

After etch-polishing, the specimens were etched with the same dilute solution
of Fry's reagent for ,...,20seconds. The polished and etched mounts were
photographed optically up to 1000X and examined using SEM.

Auger electron microscopy


Characterisation was conducted at Physical Electronics in Eden Prairie, MN
using a PHI model 680 Field Emission Scanning Auger Nanoprobe. The
specimens were 4mm by 4mm by 19mm with a V-shaped notch approxi-
mately 3 mm deep. The specimen was cooled using liquid nitrogen, fractured
in situ and analysed immediately. For the high purity specimen, IG fracture
was promoted by hydrogen charging the specimen in a 1 litre solution of 1 N
sulfuric acid + 0.25 gram of NaAs02. The specimens were masked with stop-
off lacquer so that only the notch was exposed to the solution. The charging
current was 0.4 A em- and the specimens were charged up to 2 weeks. After
charging, all of the specimen surfaces were quickly (within 10 minutes)
completely ground with 600 grit SiC paper to remove sulfur from the
surfaces. The specimens were cooled with liquid nitrogen or dry ice and
stored until analysis.

Transmission electron microscopy


The majority of the transmission electron microscopy was conducted using a
Philips EM430 (300kV) analytical electron microscope (AEM) equipped with
an Oxford SATW X-ray analysis system and a JOEL 2010 AEM (200kV)
equipped with an Oxford SATW X-ray analysis system and a Gatan Imaging
Filter (GIF). For analysis of the extracted residue, material was scraped off of
the filters and dispersed using a ultrasonic dismembrator, with a drop of
solution being placed in a thin carbon film supported by a Cu grid. Thin foils
were prepared from cut slices (typically from Charpy specimens) ground and
electropolished in a solution of 20% perchloric acid in methanol at -40°C to
-50°C, 25 to 30 V, 60 to 80 rnA. Difficulties with imaging and analysing the
residue material (due to agglomeration of the precipitates) and the thin foils
(complex microstructure) lead to the fabrication of extraction replicas from
the metallurgical mounts. Three replication techniques were utilised, (a) two-
stage plastic/ carbon, (b) one-stage carbon and (c) two stage plus immersion.
The one stage carbon process was the most successful in extracting a
representative description of the particle distribution as verified with thin foil
TEM. In this method, the specimen was immersion etched in Villella's
solution (picric acid + HCI + methanol) for 45 seconds. A heavy coating of
carbon was evaporated onto the etched surface. The surface was scored and
placed back into the etchant for 1 hour, rinsing with water every 15 minutes,
followed by a 2 minute immersion in a 20% perchloric acid in methanol
solution. The carbon coating floats off and is captured on a 400 mesh Cu
grid.
A limited amount of field emission gun scanning transmission electron
238 ADVANCEDHEAT RESISTANTSTEELSFORPOWERGENERATION

microscopy (PEGSTEM) was conducted at AEA Technology in Harwell, UK.


The instrument used was a Vacuum Generators, HB501 PEGSTEM with a
beam diameter of 2 run. Compositional analysis was conducted using an
Oxford Instruments LZS windowless energy-dispersive X-ray detector.

RESULTS AND DISCUSSION

Fracture Appearance Transition Temperature (FATT) and Fractography


Table 2 and Figs la and b summarise and compare the FATT behaviour of
conventional and high purity M152 alloys evaluated in this study. These

Aging Temperature (OC)


Aging Temperature eC)
325 350 375 400 425 450 475 500 525
325 350 375 400 425 450 475 500 525 700 ~...........,..,........,..,.. """T'""""'"~.............-- ...•...•.......
•...•...•...•. ~.......,..............,-.....,
700..,..........,......,....,....,...........,.......,........-rrr-""""'-T"TTT"T"T'"T"'T'""""""""'TT"T"'T'"1'""T'T'T'"'1
50Khr
conventional M152 BWS-O, 50Khr 600 -+-conventional
600 300
300 . ·e· 'HP heat J. all20Khr
500 500 c HP heat F, 38Khr . nal
• HP heat F, 38Khr + DE
200 400 200
~
.- 400
"Tj G::' impurities
~ 300 segregants
~ ~3oo silicides?
-e
~
~ 200

100
100.-
n ~
--
200

100 -a.higJ;Urity
o- ••••
o o20Khr . . . alpha prime 0
o o (J............ •
[3....•..• 0 .... 0
-100 as-i-ecclved - - - - - - - -
-100
aged+DE -100 -100
-200L.............J.-L..L..J'-'-'--'-
..•..•..•......•..•...•...•...•.•.........•..•..•...•..•..•...•..
~ ...•...•........•........•...• _200t....................L..o.............J.
..•..•.•...
......L........-......I-o ••..•••.••. ~ ••.•....•..••.•.•..•.••.• L.....o........;j
600 650 700 750 800 850 900 950 1000 600 650 700 750 800 850 900 950 1000
Aging Temperature eF) Aging Temperature eF)

(a) (b)

Fig. 1 (a) FATT response of conventional M152 as a function of aging time and
temperature and de-embrittling treatment of 600°C/2hrs and (b) FATT response of
conventional and high purity M152. Notes suggest the possible contribution of the
various microstructural features to the differences in the FAIT response

figures show that the FATT increases as the ageing temperature increases up
to 454°C (850 P). A de-embrittling treatment of 600°C/2 hours restores the
0

PATT of the conventional M152 aged up to 427°C (800 P) back to the original 0

PATT response. When aged at 454°C (850°F), not all of the original toughness
is restored for either the conventional or high purity materials. The restora-
tion of the toughness after the de-embrittling treatment suggests that impu-
rity segregation may be responsible for the increase in the FATT. However,
hardness measurements show a noticeable reduction in the hardness of all
materials after the 600°C/2 hour treatment, Table 2. The importance of the
material hardness is illustrated in Table 2. When the high purity materials
was thermally treated at 1100°C for 2 hours and quenched to produce virgin
AGEINGEMBRITTLEMENTOF FE-12CR STEELS 239

Table 2 Summary of M152 FATT, fractography, hardness and extraction results

Heat Aging Time FATT FATT Fracture Rc Phs Extr TEM Auger
(OC) (Khrs) (OC) (OF) (%IG) wt.?

AR -47 -53 34 1.4



343 36 -34 -30 0 34 1.5
F 1.6
36 + DE -47 -53
High
Purity 454 32 31 87 0 36 2.6 • •
32 + DE -11 13 0 31 2.0 •
1100 2 hrs 132 270 14 42 0.1

GG-266 AR 37 1.26

AR -41 -42
357 17 8 46 trace 40 1.3
17 + DE -63 -82 0 34 1.5

399 28 NA NA trace 42 1.35


GG-265 28 + DE NA NA 0 35 1.17
427 28
28 + DE
76
-64
169
-83
1
0
42
35
1.4
1.6

454 25
25 + DE
129
-9
264
15
45
0
39
35
3.3
2.0

510 38 10 50 34

AR 10 50
BWS-O 454 50 342 647 86 36 2.9 • •
50 + DE 137 279 56 32 3.2 • •
DE = de-embrittling treatment of 600°C/2 hrs

martensite, the hardness increased from Rc 34 to 42, with an increase in the


FATT of over 165°C (300°F), producing 140/0IG fracture on the Charpy impact
specimen surface.
The differences in the FATT between the conventional and high purity
material are shown in Figure lb. The high purity material starts with a lower
FATT than the conventional material and the FATT does not increase to the
same extent as the conventional material with ageing. However, the FATT
still increases noticeably, in agreement with other results.12,13 These results
indicate that while high purity M152 is more resistant to ageing embrittle-
ment than the conventional material, it is still somewhat susceptible.
The fracture mode was studied by examining the fracture surfaces and
quantifying the amount of IG fracture morphology. Table 2 shows that the
amount of IG fracture increases with ageing temperature for the conventional
240 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

material, while none of the long term aged high purity specimens exhibited
IG fracture. For both materials, there is a significant increase in the FATT
without the observation of IG fracture, indicating that the segregation of
impurities to prior austenitic grain boundaries is not solely responsible for the
decreased toughness. To help determine the contribution of impurity segrega-
tion and second phase precipitates have on the long term ageing toughness,
Auger and TEM characterisations were conducted.

Impurity Segregation
Figure 2a shows a representative fracture surface from the Auger in situ
fractured BWS-O (conventional) material aged at 454°C/50 Khrs. Figure 2b

grain boundary facets


0.3 BWS-O, 850°F/50Khr
• •
: • •
0.25 • • •
~ •
~ 0.2 •
s=
rJ'} 0.15

0.1
• bulk Ni is 2.5 wt. ~
0.05 1....&...I...~ •..•.••.•.••....J...,.o...a-'-'-'~ ...•....•....•....•...•...•.
-'-'-'-""'-'-'-~ .•...•
7 7.5 8 8.5 9 9.5 10 10.5
Ni (at. %)
1 gain boundary: Sn 0.24 at.% ±
0.06. 2 internal surface: Sn 0.10
at. % ± 0.04

(a) (b)

Fig. 2 FEGAuger results showing (a) a representative fracture surface with both
grain boundary facets and internal surfaces (cleavage) and (b) segregation of both
Sn and Ni on grain boundary facets

shows that both Sn and Ni have segregated significantly to the prior austenitic
grain boundaries and that the amount of segregated Sn and Ni appear to be
related to one another. This is a significant observation as Sn is well known as
the most potent embrittler of steels.l" This suggests one strong reason why the
high purity material, with very low levels of impurities, is more resistant to
ageing embrittlement than the conventional material. These results were
verified by the very limited FEGSTEM results that showed segregation of Ni
and Sn, as well as Cu, Mn and As on one boundary in BWS-O, 454°C/50Khr,
Fig. 3. Arsenic'> has been reported as a grain boundary embrittler of steel,
while the role of Ni, Mn and Cu segregation directly embrittling steel is less
clear.
AGEING EMBRITTLEMENT OF FE-12CR STEELS 241
12 ..
conventional M152 i ~ .
BWS-O,4S4C/SOKhrNNi 1 !

o """r"""
-20 -10 0 10 20 -20 -10 0 10 20
distance (nm) distance (nm)
(a) (b)

Fig. 3 FEGSTEM profiles from a boundary in BWS-O, 454°C/50 khr

Table 3 Summary of FEGAuger results. All data are from IG facets in units of 0/0
atomic concentration with ± 1 standard deviation

BWS-O* BWS-O** F (high purity)**,-"


454°C/50 Khr 454°C/50Khr + DE 454°C/32 Khr Comments

P 1.7 ± 0.4 1.4 ± 0.5 0.8 ± 0.4


S <0.1 <0.1 <0.1 only in inclusions
Sn 0.24 ± 0.06 <0.1 <0.1 higher in inclusions
Sb <0.1 <0.1 <0.1 only in inclusions
As <0.1 <0.1 <0.1 only in inclusions
Ni 9.1 ± 0.8 9.1 ± 1.5 6.1 ± 0.4
Cu 1.4 ± 0.2 1.5 ± 0.3 <0.1
Si 3.9 ± 0.5 3.9 ± 0.5 <0.1
Mn <0.5 <0.5 <0.5 only in inclusions
Cr 17.2 ± 2.2 17.2 ± 2.6 13.4 ± 2.4
4.2 ± 0.7 4.1 ± 1.5 6.4 ± 3.3
Mo
15 facets 14 facets 6 facets

* Data collected in multiplex mode (higher signal to noise ratio); **survey mode (lower
ration)
-" Specimen was hydrogen charged prior to fracture

Table 3 summarises the grain boundary impurity segregation results of the


conventional and high purity materials aged at 454°C. Noted first is the effect
of the de-embrittling treatment, which reduced the level of segregated Sn
with the other levels of impurities remaining relatively the same. Comparing
the conventional to the high purity results, there is significantly more Sn, Cu,
Si and Ni and slightly more P segregated to the prior austenitic boundaries of
242 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

the conventional material than high purity heat. From the literature on low
alloy steels, Sn is believed to be the most notable segregant in terms of its
degrading effect on the fracture toughness. Phosphorous has also been shown
to be detrimental, however the differences displayed as a function of the de-
embrittling treatment and bulk composition do not indicate that P is playing
much of a role. While the presence of Ni, Cu and Si are significant, there is no
basis to indicate what their role may be.
The only other significant observation was the lack of S-rich inclusions in
the high purity material, attributed to super clean nature and ESR process-
ing.

Second Phase Precipitation


Optical and scanning electron microscopy revealed little detailed information
regarding the microstructural changes occurring in these materials. As a
result, extensive TEM characterisation was conducted, with the results
summarised in Table 4. The as-received and low temperature aged micro-
structures of both materials were very similar. Each contained a fine and
uniform dispersion of M2X and M7X3, with M being mostly Cr and X mostly
C. After ageing at 454°C, the carbides had changed to M23C6 and were very
uniformly distributed on the prior austenitic grain and martenistic lath
boundaries. There was also a large and uniform distribution of Cr-rich
precipitates, Fig. 4a. The diffraction pattern from these precipitates was bee

Table 4 Summary of TEM microstructural characterisation

Conventional F, high purity

Condition Carbides ex' Silicides Condition Carbides ex' Silicides

GG-266 M2X,M7X3 no no M2X, M7X3 no no


as-received as-received
GG-265 M2X,M7X3 no no M2X, M7X3 no no
357°C/ 17khr 343°C/36 khr
GG-265
454°C/25khr M23X6 yes yes 454°C/32khr M23X6 yes no
BSW-O
454°C/50 khr
BWS-O M23X6 less yes 454°C/32khr+ less
454°C/50 khr+ DE DE
GG-265 no yes
510°C/38khr

(M = Cr, X = C, N, 0)
DE = de-embrittlement treatment of 600°C/2hrs
AGEING EMBRITTLEMENT OF FE-12CR STEELS 243

(a)

Fig. 4 (a) TEM photomicrograph of alpha prime and (b) bee diffraction pattern
consistent with alpha prime. BWS-O,454°Cj50 Khr

and consistent with the alpha prime phase, Fig. 4b. This phase was identified
in both the conventional and high purity materials and was observed in lesser
quantity after the 600 C/2 hour de-embrittling thermal treatment. No alpha
D

prime was observed in the conventional material aged at S10 C/38 Khr which
D

is consistent with the temperature at which alpha prime is reported to be


stable, ,...SOODC and below.l" The presence of alpha prime was also verified in
the high purity material using thin foils and energy filtered compositional
mapping. Precipitates suspected to be alpha prime were found to be Cr-rich,
but absent in C. This confirmed that over a larger number of particles that
these precipitates were not carbides and most likely alpha prime. The only
other significant microstructural observation was the presence of a variety of
complex precipitates (containing Cr, Mo, Fe, Ni, and a large amount of Si) in
the conventional material, that were absent in the high purity material.
Electron diffraction analysis did not successfully identify the crystallographic
phase of these precipitates, but they are thought to be complex metal silicides.
The absence of these precipitates in the high-purity material is attributed to
the low level of Si.

Embrittlement Mechanisms
The results from this study do not unequivocally explain the mechanisms
responsible for the long term ageing embrittlement of Fe-12Cr steels. How-
ever, two important observations have been made. The first is the segregation
of potent embrittlers to the prior austenitic grain boundaries in the conven-
tional material. The second is the presence of alpha prime, which is a well
known embrittler of higher Cr-containing steels'? and Ni-base alloys.l"
244 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

These observations permit some insight into the long term ageing embrit-
tlement of M152. The long term ageing embrittlement of both conventional
and high purity materials are partially attributed to the precipitation of alpha
prime. Although the roles of the carbides and Ni silicides have not been fully
rationalised, the decrease in the FATT with the de-embrittling treatment
coinciding with the disappearance of the alpha prime phase in the micro-
structure, strongly infers that the alpha prime phase is playing a strong role.
The segregation of impurities to the grain boundaries dramatically worsens
the situation for the conventional material, consistent with reports of a
synergistic relationship between the amount of segregants and hardness on
the toughness of steels.'? The hardness or strength level of the material is
believed to be very important to the susceptibility to ageing embrittlement.
Fe-IOCr alloys developed in the COST program for steam turbine applica-
tions have not reported significant increases in the FATT upon thermal ageing
at 475°C and above." However, these materials possess a lower strength than
M152 and thus should be more tolerant of alpha prime phase precipitation.
These materials also contain a lower Cr content, which Grebner"? has shown
to be the most critical element in determining whether alpha prime will form.
At some point there is a critical Cr content (or Cr equivalent) below which
alpha prime will not form in a reasonable amount of time.

CONCLUSIONS

1. The increase in FATT of conventional M152 with ageing is greater than that
of the high purity M152 material, although both materials are susceptible
to long term ageing embrittlement.
2. The decrease in toughness with ageing of conventional M152 is attributed
to the precipitation of second phases, notably alpha prime and impurity
segregation, notably Sn.
3. The decrease in toughness with ageing of high purity M152 is attributed to
the precipitation of second phases, notably alpha prime.

ACKNOWLEDGEMENTS

The authors acknowledge the useful discussions with Dr Graham Honeyman


of Forgemasters Steel and Engineering, Sheffield, UK, who suggested examin-
ing for alpha prime phase and general discussions with Prof. Clyde Briant of
Brown University. We acknowledge the assistance of Suzie Manning and
Rebecca Casey with the bulk phase extractions, Ray Schnoor with metal-
lography, Mike Pollick and Mitch Hammond with hydrogen charging,
v. (Ravi) Ruvikumar with the energy filtered transmission electron micro-
scopy (all from GE CRD), Dennis Paul and Lori LaVanier at PHI for the
AGEING EMBRITTLEMENT OF FE-12CR STEELS 245

FEGAUGER, and Ian Vatter and Simon Dumbill at AEA Technology, Har-
well, UK for the FEGSTEM.

REFERENCES

1. J. Z. Briggs and T. D. Parker: The Super 12% Cr Steels, Climax Molybdenum


Co., 1965, 16.
2. S. Mandziej, A. P. von Rosentiel, H. Goretzki, M. Weiss and B. H. Kolster:
'Transmission Electron Microscope and Scanning Auger Investigations
of Temper-Embrittled 12% Cr Steel', Fresenius Z Anal Chem, 1987, 329,
335-341.
3. H. Goretzki, A. P. von Rosenstiel and S. Mandziej: 'Small Area MXPS- and
TEM- Measurements on Temper-Embrittled 12% Cr Steel', Fresenius Z
Anal Chem., 1989,333,451-452.
4. R. Guillou, M. Guttmann and Ph. Dumoulin: 'Role of Molybdenum in
Phosphorous-Induced Temper Imbrittlement of 12% Cr Martensitic
Stainless Steel', Metal Science, 1980, 63-72.
5. Ph. Lemble, A. Pineau, J. L. Castagne, Ph. Dumoulin and M. Guttmann:
'Temper Embrittlement in 12% Cr Martensitic Steel', Metal Science, 1979,
496-502.
6. K. Sato, 1. Kitagawa, K. Soeda, K. Morinaka and A. Fujita: 'Manufacturing
of High Purity 12% Cr Rotor Forgings', Proceedings of the Robert 1. Jaffee
Memorial Symposium on Clean Materials Technology, ASM Materials Week,
1992, 145-151.
7. M. Wall, B. C. Edwards and J. A. Hudson: 'Thermal Ageing Studies of 9%Cr
1%Mo Steel', International Atomic Energy Agency International Work-
ing Group on Fast Reactors Specialist Meeting on Mechanical Properties of
Structural Materials Including Environmental Effects, Chester, 10-14 Octo-
ber 1983.
8. J. W. Schinkel, P. L. F. Rademakers, B. R. Drenth and C. P. Scheepens: 'Heat
Treatment, Ageing Effects and Microstructure of 12%Cr Steels', Ferritic
Steels for High-Temperature Applications, ASM, Metals Park, OH, 1982,
131-149.
9. C. Berger, E. Potthast, R. Bauer and G. A. Honeyman: 'Development of
High Strength 9-12%CrMoV Steels for High Temperature Rotor Forg-
ings', 11th International Forgemasters Meeting, Terni/Spoleto, Italy, June
1991.
10. Y. Hosoi, N. Wade, S. Kunimitsu and T. Urita: 'Precipitation Behavior of
Laves Phase and Its Effect on Toughness of 9Cr-2Mo Ferritic-Martensitic
Steel', J. Nuclear Materials, 1986, 141-143, 461-467.
11. U.S. Patent 5320687, 'Embrittlement Resistant Stainless Steel Alloy', 14
June, 1994.
12. K. Orita, J. Taira, T. Azuma, Y. Tanaka and C. Furstoss: 'Development and
246 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Production of High Purity 12% Cr Steel for Gas Turbine Disc Material',
Chicago Forging Conference 1994.
13. I. B. Kim, S. T. Kang, Y. S. Song, J. S. Lee, H. S. Chang, H. M. Kim, M. C.
Jeong and S. J. Kim: 'Manufacturing and Properties of Superclean M152
Steel Gas Turbine Wheel', 13th International Forgemasters Meeting vol. 1,
1997, 495-502.
14. A. K. Cianelli, H. C. Feng, A. H. Ucisik and C. J. McMahon: 'Temper
Embrittlement of Ni-Cr Steel by Sn', Metallurgical Transactions A, 1977,
SA, 1059-1061.
15. R. I. Jaffee, T. Ohhashi, O. Watanabe and P. Machner: 'Development of
Super Clean 3.5 NiCrMoV Low-Pressure Steam Turbine Rotor Forging
Steel', Trans. ISS, 1989,45-51.
16. V. P. Itkin: 'Cr-Fe', Phase Diagrams of Binary Iron Alloys, H. Okamoto, ed.,
J\SM, 1993, 102-129.
17. P. J. Grobner: 'The 885°F (475°C) Embrittlement of Ferritic Stainless Steels',
Metallurgical Transactions A, 1973, 4, 251-260.
18. J. F. Radovich: 'Effect of Alpha Chromium on Long Time Behavior of
Alloy 718', 5uperalloys 718, 625, 706 and Various Derivatives, E. A. Loria
ed., The Minerals, Metals and Materials Society, 1997, 409-415.
19. R. J\. Mulford, C. J. McMahon, D. P. Pope and H. C. Feng: 'Temper
Embrittlement of Ni-Cr Steels by Phosphorus', Metallurgical Transactions
A, 1976, 7A, 1183-1195.
Microstructure and Creep of a T91 Steel
s. SPIGARELLI, E. CERRI, E. EVANGELISTA and
P. BONTEMPI*
INFM/Department of Mechanics, University of Ancona, Ancona, Italy
* ENEL-CRAM, Cologno Monzese, Italy

ABSTRACT
The creep response and the microstructural evolution of a T91 (9Cr-1Mo- NbV) steel
were investigated during high-temperature exposure. The conventional power law
equation was found to describe the minimum creep-rate dependence on applied
stress; the stress exponent increased as temperature decreased. The microstructure
was investigated after rupture or interruption of the test. Two different families of
particles were identified; the kinetics of coarsening was analysed, and the effect of
applied stress was incorporated in the Ostwald ripening law.

INTRODUCTION

The creep properties and microstructure of 9Cr-lMo-NbV and 9Cr-lMo-


NbVW steels have been studied extensively.l" by contrast, there are rela-
tively few investigations on the correlation between creep response and
microstructural evolution.v V
The microstructure of 9Cr-lMo steels after heat treatment (normalising
and tempering) consists of an elongated substructure characterised by high
dislocation density. During creep, this substructure evolves to form equiaxed
sub grains, with low dislocation density; 1, 2,5,13during tempering, the subgrain
boundaries and the prior austenite grain boundaries are the sites of an
extensive precipitation of carbides, mainly M23C6(where M is a metal such as
Cr or Fe). Another family of particles, MX (where M is Nb or V, and X is C or
N), precipitates during tempering and/ or creep.
According to the majority of the studies carried out on these steels,
M23C6 particles stabilise the sub grain boundaries and retard sub grain
growth, substantially contributing to creep strength.v" Additional sources
of strengthening are the secondary intragranular MX, since these precipitates
are sufficiently fine to interact with dislocations. The strengthening effect
produced by MX has been quantified in terms of Orowan stress.!'
Particle coarsening is thus one of the major degradation processes operating
in these steels. The present study was devised to quantify the effect of the
coarsening processes on the short-term creep response of a 9Cr-lMo-NbV
steel.

247
248 ADVANCEDHEAT RESISTANTSTEELSFORPOWERGENERATION

EXPERIMENTAL

The material investigated in the present study had the following chemical
composition (wt.%): C = 0.091, Cr = 8.76, Mo = 0.94, Nb = 0.07, V = 0.19, N
= 0.064, Al = 0.35, Ni = 0.11, Mn = 0.46, Fe bal. Heat treatment consisted of
normalising at 1050°C for 15 min., followed by tempering at 750°C for 1 hr.
Constant-load creep rupture tests were carried out at 575, 600, 625 and 650°C.
A number of interrupted tests were performed in order to study the
microstructural evolution during creep. Transmission electron microscopy
(TEM) was used to investigate the effect of creep exposure on substructure
evolution (subgrain size, dislocation density) and particle coarsening. The
particle equivalent diameter was measured by image analysis; interparticle
spacing, A, was calculated by means of the following relationship:

where d is the average equivalent diameter and f is the volume fraction of the
population of precipitates being studied.

RESULTS

Typical creep curves of strain, E, vs time, t, are reported in Fig. 1. They show
the occurrence of a relatively short primary stage, followed by a very brief
quasi-steady-state condition and then an extended tertiary stage. The brief
nature of the secondary stage is clearly illustrated in Fig. 2, which shows some
of the creep data obtained at 600°C and re-plotted in the form of instantaneous
creep rate, E vs t. In Fig. 3 the values of the measured minimum creep rate, Enll
are plotted as a function of the applied stress IT; inspection of Fig. 3 reveals
that the creep response of the material can be described by means of the
conventional power law equation:

(1)

where A is a temperature-dependent parameter, and the stress exponent, n,


decreased from 14 to 9 as temperature increased from 575 to 625°C.
Figure 4 plots the time to rupture, tR, and the time to minimum creep rate,
t~, as a function of Em; Fig. 4 clearly shows that both tR and tm exhibit a similar
dependence on minimum creep rate which can be expressed in the form of the
Monkman-Grant relationship:

(2)
MICROSTRUCTURE AND CREEP OF A T91 STEEL 249

0.06
9Cr-1Mo-NbV
600·C

0.04

0.02

0.00
o 1000 2000 3000

t [h]

Fig. 1 Creep curves for different test conditions at 600°C

9Cr-1 Mo-NbV
600·C

10-2

••.:S 10-3
-\II

10-4

10-5

10-6
10-2 10-1 10° 101 102 103 104

t [h]

Fig. 2 Creep curves at 600°C in differential form


250 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

9Cr-1Mo-NbV

• 6S0·C
• 62S·C
• 600·C
• 57S·C

-
r.5

10 100 1000

CT [MPa]

Fig. 3 Minimum creep-rate dependence on applied stress

4
9Cr-1 Mo-Nb V

-02
•...
.2

o
-6 -5 -3 -2

Fig. 4 Time to minimum creep rate and time to rupture as a function of Em


MICROSTRUCTURE AND CREEP OF A T91 STEEL 251

Fig. 5 Structure after heat treatment and prior to creep testing

and

(3)

where a ;::::I, while Cm and CR are constants.


Following heat treatment, inspection by TEM revealed the structure illus-
trated in Fig. 5, where the elongated sub grains formed by fragmenting
martensite laths and particles on subgrain boundaries are easily detected.
Figure 6 shows the histogram of size distribution of the particles precipitated
during tempering. This population of particles should include a majority of
M23C6 and a lower number of primary undissolved MX, since M3C precipi-
tated during normalising are not stable at the tempering temperature.f
Inspection by TEM after creep testing revealed the occurrence of substantial
evolution of the substructure (Fig. 7); dislocation density strongly decreased,
and well-equiaxed subgrains evolved from the original elongated structure.
Both subgrains and particles precipitated during tempering coarsened during
creep exposure; in particular, there was evidence for a direct relationship
between interparticle spacing and sub grain size (Fig. 8).
Exposure to high temperature during creep resulted in a fast precipitation
of fine particles (MX) (Fig. 9a), while the volume fraction of large precipitates
(M23C6) remained substantially unchanged. The precipitation of fine intra-
granular precipitates was complete at t<tm, and both particle families coars-
ened during creep, as clearly suggested by a direct comparison of Figs. 9a and
b. These observations were confirmed by the TEM analyses carried out at 575
and 600°C.
252 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

20
9Cr-1Mo-NbV
after heat treatments

15

E
>-
o
c:: 10
CD
::J
tT

d [Ilm]

Fig. 6 Size distribution of particles precipitated during heat treatments

Fig. 7 Microstructure after creep at 600°C-130 MPa (rupture, tR = 2741 h)


MICROSTRUCTURE AND CREEP OF A T91 STEEL 253

2.00
9Cr-1Mo-NbV
1.75
~ 57S·C
• 600·C
1.50
• 650·C
E
3- 1.25
CD
N
Ow
1.00
c
0ij
"-
OJ
.0 0.75
::J
CIJ

0.50

0.25

0
0.04 0.08 0.12 0.16 0.20

Fig. 8 Interparticle spacing and subgrain size under different test conditions

30 30
9Cr-1Mo-NbV 9Cr-1Mo-NbV
600°C - 130MPa 600°C - 130MPa
504h 2741h

.....• 20 •.....•20
~ ~
>. >.
o o
c: c
(J) (J)
::J :::J
0- 0-
(J) (J)

J:: 10 .::: 10

o o

(a) d [pm] (b) d [11m]

Fig. 9 Typical bimodal distribution resulting from the precipitation of fine MX


during creep, and from coarsening of both M23C6 and MX: (a) 600°C-130 MPa-
S04h; (b) 600°C-130MPa-2741 h (rupture)

DISCUSSION

The analysis of Pig, 8 indicates that the degradation of the microstructure,


expressed in terms of recovery of the initial high dislocation density, can be
directly related to coarsening of the strengthening secondary phases. In
254 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

particular, low applied stresses resulted in long exposure time and marked
coarsening of the precipitates, while high applied stress (i.e. 200 MPa at 600°C)
resulted in partial recovery of the substructure, with a relatively high
dislocation density. In this condition, short exposure time reduced the
coarsening of the secondary phases and very fine and numerous MX could be
detected. Therefore, the analysis of the kinetics of the degradation mecha-
nisms is a primary concern.
The coarsening process (Ostwald ripening) results in a decrease in the
number of precipitates per unit volume, while mean dimension and inter-
particle spacing for a given volume fraction of secondary phase increase. This
mechanism is currently described6,9,lO,13by means of an equation proposed
by Wagner-! and Lifshitz.l"

(4)

where do is the initial dimension of the precipitates, and the coarsening


constant, K, can be expressed in the form:

_ 64Do)'cc V m2
K - 9RTv exp
(_ Q)
RT (5)

Do being a constant, 'Y the interfacial energy, Cc the equilibrium concentration


of the alloying element in the matrix, Vm the molar volume of the particle, and
v a factor that depends on the stoichiometry of the precipitate, while R and T
have the usual meaning and Q is the apparent activation energy of the
coarsening process. The experimentally-measured dimension of large (M23C6)
and fine (MX) precipitates, obtained at a given stress at 600°C for different
exposure times, were analysed to calculate the K constant for the two families
of particles. The best fit for do = 70nm (for M23C6 ) and do = 20nm (for MX)
gave the value of K reported in Fig. 10. While 70 run is an estimation of the
initial dimension of the large precipitates that is substantially in agreement
with Fig. 6, the value do = 20 nm for MX simply represents a best-fit value (i.e.
an 'apparent' initial dimension), since the precipitation of these particles
occurs at the beginning of the tests, and eqns 4-5 cannot describe this stage of
the process (Fig. 11).
The decrease in K with applied stress clearly indicates that applied stress
increases coarsening rate even though the underlying mechanism has not yet
been investigated; this effect could however be described assuming that the
increase in the applied stress produces a decrease of the apparent activation
energy for coarsening.16-17 Such behaviour could be quantified by means of
an equation in the form:
MICROSTRUCTURE AND CREEP OF A Tcr STEEL 255

10-25
9Cr-1Mo-NbV
28
10- 600·C

10-27

10-30

10-31

10-32
o 50 100 150 200

u [MPa]

Fig. 10 K dependence at 600°C on applied stress (105, 130 and 175 MPa); the value
at 37 MPa was estimated from the particle dimension in the heads of samples tested
under 105MPa

(6)

where p and k are constants, and Qo is the activation energy of the coarsening
process for pure ageing. The best fit of the K values by means of eqn 6 is
shown in Fig. 10; however, since only data at 600°C are considered in the
present study, the value of Qo cannot be estimated.
Assuming that the combination of eqns 4-6 provides an acceptable simula-
tion of the coarsening process for different families of particles, interparticle
spacing can be easily calculated (the measurements of the number per unit
volume of particles suggested that once the precipitation of MX was com-
pleted, the volume fraction of precipitates remained substantially stable);
thus, an estimation of the strengthening effect of the particles, expressed in
terms of Orowan stress as a function of time, can be directly derived from d, f
and A. An example of such a procedure is shown in Fig. 12, in the form of the
Orowan stress for M23C6 (f = 0.0345) and MX (f == 0.0005) as a function of
time under different stresses. For each experimental condition, the value of tm
can be used to calculate the Orowan stress when E = Em (broken line in Fig.
12); thus, Fig. 12 suggests that the decrease of applied stress results in a loss of
strength due to particle coarsening. This behaviour, in turn, could explain the
256 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

150
9Cr-1Mo-NbV
600·C


100

E
.s
-0

50

o
o 500 1000 1500 2000 2500 3000

t [h]

Fig. 11 Evolution of particle size at 600°C-130MPa; solid lines represent eqn (4), the
broken line is a qualitative description of the precipitation process for MX

450 200
9Cr-1Mo-NbV 9Cr-1Mo-NbV
600·C 600·C
M23Ca MX
400
150
fij C;;
o,
0-

~ 350 z
8 b
0

100
300

- - - - Gor at t=tm - - - - O"Or at t=t.

250 50
10 100 1000 10" 10 100 1000 10"
t [h] t [h]

Fig. 12 Orowan stress as a function of applied stress and time; the figure shows
also the value of the Orowan stress as calculated at t = tm; the coarsening process is
accelerated by the increase in applied stress in agreement with eqns 4 and 6. The
volume fraction of precipitates was for M23C6! = 0.0345 for M23C6, and! = 0.0005
forMX
MICROSTRUCTURE AND CREEP OF A T91 STEEL 257

reduction of the n exponent with stress that is frequently observed in these


steelsf

CONCLUSIONS

The investigation of the short-term creep behaviour of a 9Cr-lMo-NbV steel


revealed the dependence of the stress exponent in the classical power law
equation on temperature. An extensive microstructural evolution during
creep led to coarsening of the substructure and of the precipitated phases.
Increasing applied stress was found to increase the kinetics of coarsening; the
loss of strengthening effect due to this process was quantified by calculating
the Orowan stress for both M23C6 and MX at times corresponding to the
minimum creep rates. This calculation confirmed that at long exposure times
the strengthening effect of the precipitates is substantially reduced.

LIST OF SYMBOLS

A = interparticle spacing (m)


d =average particle equivalent diameter (m)
f = volume fraction of precipitates
E = true strain

t = time (h)
E = strain rate (h-1)
(J = applied stress (MPa)

n = stress exponent
tR = time to rupture (h)
tm = time to minimum creep rate (h)
do = average equivalent diameter of precipitates at t = 0 according to eqn. 4
K = coarsening constant (m ' s -1)
Q = activation energy for the coarsening process (kJ I mol)
Qo = activation energy for the coarsening process at zero stress (kJ/mol)
E = Young modulus
(JOr == Orowan stress (MPa)

REFERENCES

1. V. Sklenicka, K. Kucharova, A. Dlouhy and J. Krejci: Materials for Advanced


Power Engineering, D. Coutsouradis et al., eds., Kluwer Academic Pub-
lisher, Netherlands, 1994, 435.
2. V. Foldyna, Z. Kuboii, A. Jakobova and V. Vodarek: Creep Resistant Metallic
Materials, R&D Division of Vitkovice a.s., Ostrava, Czech Republic, 1996,
203.
258 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

3. V. Foldyna and J. Pumersky: Czech. J. Phys. 1989, B39, 1133.


4. J. Orr and D. Burton: Materials for Advanced Power Engineering, D. Coutsour-
adis et al., eds., Kluwer Academic Publisher, Netherlands, 1994,263.
5. K. Spiradek, R. Bauer and G. Zeiler: Materials for Advanced Power Engineer-
ing, D. Coutsouradis et al., eds., Kluwer Academic Publisher, Nether-
lands, 1994, 251.
6. V. Foldyna, A. Jakob ova, A. Gemperle and R. Riman: Creep Resistant
Metallic Materials, R&D Division of Vitkovice a.s., Ostrava, Czech
Republic, 1996, 507.
7. A. Jakobova, V. Foldyna and V. Vodarek: Creep Resistant Metallic Materials,
R&D Division of Vitkovice a.s., Ostrava, Czech Republic, 1996, 306.
8. P. J. Ennis, A. Zielinska-Lipiec, O. Watcher and A. Czyrska-Filemonowicz:
Acta mater, 1997, 45, 4901.
9. S. Straub, T. Hennige, P. Polcik and W. Blum: Steel res., 1995, 66, 394.
10. S. Straub, P. Polcik, W. Besigk, W. Blum, H. Konig and K. H. Mayer: Steel
res., 1995, 66, 402.
11. K. Hamada, K. Tokuno, Y. Tomita, H. Mabuchi and K. Okamoto: lSI! Int.,
1995, 35, 86.
12. J. Cadek, V. Sustek and M. Pahutova: Mater. Sci. Eng., 1997, A225, 22.
13. J. Bursik, A. Orlova, K. Kucharova and V. Sklenicka: Creep Resistant
Metallic Materials, R&D Division of Vitkovice a.s., Ostrava, Czech Repub-
lic, 1996, 234.
14. C. Wagner: Z. Elektrochem., 1961, 65, 581.
15. J. M. Lifshiz and V. V. Sloyzov: J. Phys. Chern. Solids, 1961, 14 35.
16. J. Bursik and N. Merk: 'Quantitative Microstructural assessment of P91
Ferritic Steel after long term creep at high Temperature', NATO Seminar
Mechanical Behaviour of Materials at High Temperature, Sesimbra, Portugal,
1995.
17. V. Foldyna: 'Microstructural stability of ferritic 9-12% Chromium Steels',
Cost report Contract COST-94-0076-CZ (DG12CSMC), 1996, 96.
Effects of Tungsten on Mechanical
Properties and Microstructure in
9Cr-O.SMo- W Steels
H. NAOI*, M. OHGAMIt, Y. HASEGAWAt, H. MIMURAt
and T. FUJITA§
* The University of Hosei, t Nippon Steel Corp., § The University of Tokyo

ABSTRACT
Partial substitution for molybdenum in 9-12Cr-Mo steel by tungsten effectively
increased the creep rupture strength and several new ferritic tungsten containing
heat resistant steels as NF616, TB12M and HCM12A have been developed. In
this study, 9% chromium steels which contained 0.1, 0.95, 1.24, 2.00, 2,45, and
2.95% tungsten were manufactured. Creep rupture test, tensile test at room and
elevated temperature, and Charpy impact test were conducted. Creep rupture
strengths were analysed by the Larson-Miller parameter method. The steels
were aged at up to 600°C for 3000 hours and 650°C for 1000 hours. Precipitated
tungsten after ageing was measured by the extracted residue method. The
amounts of precipitated tungsten were compared with the Johnson-Mehl-Avrami
formula.

INTRODUCTION

Fossil fired power stations are operated at increasingly higher steam tem-
perature and pressure to improve the electricity generation efficiency. Aus-
tenitic stainless steels have a higher elevated temperature strength than
ferritic steels. Since their thermal expansion coefficient and thermal con-
ductivity are relatively high, austenitic stainless steels are subjected to high
thermal stress at start-up and shut-down. For these reasons, demand is
mounting for high-chromium ferritic steels as materials for supercritical and
ultra supercritical boiler plant. ORNLI developed a modified 9Cr-1Mo steel
(P91) standarised in ASME SA 213. The authors- " developed a new ferritic
tungsten containing steel NF616, which had a higher creep rupture strength
than austenitic steel and modified 9Cr-lMo steel. Three tungsten containing
ferritic steels, NF616 (P92), TB12M, and HCM12A (P122) evaluated by EPRI
project RP1403-504 and two of them were approved by ASME. Under this
background, the effects of tungsten on the mechanical properties and micro-
structure were studied.

259
260 ADVANCEDHEAT RESISTANTSTEELSFORPOWERGENERATION

Table 1 Chemical compositions of specimen (mass 0/0)

Steel C Si Mn Cr Mo W V Nb N Creq.

O.OlW 0.10 0.08 0.49 9.00 0.50 0.01 0.21 0.05 0.0760 6.80
0.95W 0.10 0.08 0.48 9.00 0.48 0.95 0.21 0.04 0.0675 8.35
1.24W 0.10 0.08 0.47 9.02 0.49 1.24 0.20 0.04 0.0693 8.70
2.00W 0.10 0.10 0.49 9.24 0.49 2.00 0.21 0.03 0.0675 10.26
2.45W 0.09 0.09 0.48 9.32 0.49 2.45 0.21 0.03 0.0693 11.32
2.95W 0.09 0.09 0.48 9.28 0.49 2.95 0.20 0.03 0.0774 11.67
NF616 0.10 0.10 0.50 9.00 0.50 1.80 0.20 0.05 0.0500 8.75

MATERIALS AND EXPERIMENTAL PROCEDURES

9% chromium steels with tungsten content were melted" by vacuum induc-


tion furnace. The chemical compositions and Cr equivalent (Creq.) are shown
in Table I, compared with those of NF616. Creq. were calculated by using GE
formula eqn (1). The amounts of 0.01, 0.95, 1.24, 2.00, 2.45 and 2.95% W were
added to 9% Cr-0.5 Mo-Nb-V base steels. Casted into 20 kgf ingots, being
%

reduced to plates with a thickness of 15 mm. The plates were normalised at


1060°C followed by air cooling and tempered at 780°C. Specimens were
machined from the centre of the plates in the longitudinal direction.

Creq.=
Cr+6Si+4Mo+1.5W+11V+5Nb+12Sol.AI-(40C+30N+2Ni+2Mn) (1)

Creep rupture tests were conducted at 600, 650, and 700°C. Tensile tests
were carried out at room temperature, 500, 600, and 700°C. The plates were
aged at 600°C for 3000 hrs and 650°C for 1000hrs. Charpy impact tests were
conducted at -60, -40, -20, 0, 20, 40 and 60°C using 2 mm V notched full
size specimens in the as tempered and after aged conditions.
Microstructures were analysed by optical microscope and transmission
electron microscope (TEM). The residues extracted from the tempered and
aged specimens were examined by chemical and X-ray diffraction analysis.

MECHANICAL PROPERTIES

Creep rupture
Figure 1 shows the creep rupture plot of at 600, 650, 700°C compared with
that of NF616. The longest data point being 6013hrs at 650°C. There was an
obvious difference in the creep rupture strength between the six steels. The
creep rupture strength of 2.00W steel was almost the same as that of NF616.
Figure 2 shows the rupture elongation and reduction of area, comparing with
EFFECTS OF TUNGSTEN ON MECHANICAL PROPERTIES 261

1000
NF616 I

- ,,~~ .a ~r ~
-- c -~~I
~ It
~
--
r-:
II ~ . lA ill

~ i~ ~- ~-~
[J
I'-~ -"!II

~
CI.l
CI.l

CI.l
100
I]
~ III )(-(
~-~
•.. ,,-•..
~ ~~ 600c
'"0 ~
.s ~ 650C
L ~"'::!
r--
oO.OIW trAi ~ i"-
"a
c::l..
-
- oO.95W "'"-.. ..••.
<: 1l.1.24W 700C
xz.oow
r--

-
e 2.45W
x2.95W
10
0.11 10 100 1000 10000 100000
Time to rupture (h)

Fig. 1 Creep rupture plot of 9Cr-0.5Mo-W steels

~
o
c
100
n ~~<~- ~ ~t It ~ JiirIJl ~ IL R. .•...!." I ...... ......::::; II
.g 80
"~I1' I •..•P' ~ r'1 ~1Ir Lf~ J.
V/
(,J
Reduction of Area "i\ o O.OIW
.g ~ ...e."
!

60 oO.95W
~~ NF616
e x ~ ~~ ..n.r sr-r-~ Il. 1.24W
g~
.~
40 I~
20
1) ~»
~ ~ ~~~ ~~ ~o~ ~I~~

~
"-o.~
'" 1 I>
- ........•....
x2.00W
<> 2.45W
IElongation I x2.95W
=o
fil 0 IIIII III
o 10 100 1000 10000 100000
Time to Rupture(h)

Fig. 2 Creep ductility at 600, 650, 700°C of 9Cr-0.5Mo-W steels

that of NF616. There seemed to be a little difference in the elongation and


reduction of area. The elongation and reduction of area decreased with
increasing W content in the steels. By using the Larson-Miller parameter
(LMP) and regression analysis, the creep rupture strength of the six steels
with tungsten were investigated. The LMP analysis is shown in the eqn. (2).
Parameter constants PC, regression coefficients CI, c, C3 and C4 were
determined by regression analysis. Figure 3 shows the creep rupture strength
at 600°C for 1000, 10 000, 30 000, and 105 hrs estimated by LMP analysis for the
six steels. The creep rupture strength increased with increasing W content in
the steels. The 105 hrs creep rupture strength at 600°C for 2.00W steel is 134.5
MI'a, being close to 132 MPa for NF616, estimated by ASME.
T*[PC+ log(tr)==CI +Cz*log a + C3*[log a]Z[+C4*[log a]3 (2)
where, T: temperature, K, tr: time to rupture, H, a: applied stress, MPa, PC:
parameter constant, Cl, Cz, C3 and C4: regression coefficient.
262 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

250
~ Italic numbers are
='2 200 MPafor 105 hrs at
~~
fI.)~

Q,) -- 150 600C


5U
~g 100
o 1000 hrs
fr~ 50 fa 10000 hrs
C 0 E3 30000 hrs
DIl100000hrs
0.01 0.95 1.24 2.00 2.45 2.95
AmountofW(%)

Fig. 3 Creep rupture strength at 600°C estimated by LMP method

800 ~--~--~----~--~--~--~
Solid line;
700 ~--~---+~--~~~==~~~ Tensile strength
~ 600 Dotted line;
N-.. 0.2% Proof stress
~ ~ 500 r-~~~~~~~~~==~==~
~ ~ 400
~ ~ 300 _____Room temp.
rIJ
~ 200 ~===d--===::::i!:~t=:::t====~==~===!1 -11-500 C
fI.)

E 100 ~~-"-'=-~~--+----+-----+------I
---A-600c
E-4 -+-7OOC

0.0 0.5 1.0 1.5 2.0 2.5 3.0


Amount of W (mass%)

Fig. 4 Tensile strength and proof stress at elevated temperature

Tensile
Figure 4 shows the tensile strength and 0.2% proof stress at room and
elevated temperature. They increased slightly with increasing W content in
the steel at all the tested temperatures. This phenomenon was considered to
be due to the effect of solid solution hardening of W. Figure 5 shows the
elongation and reduction of area at room and elevated temperature. They
both had almost same values at the same temperature. So the difference of
ductility in the 0.01-2.95% W steels was not observed.

Toughness
Figure 6 shows the Charpy impact value vs temperature, comparing the after
aged condition with the as tempered one. The impact values decreased with
increasing W content and increasing ageing time. Figure 7 shows Charpy
impact value at 20°C of the steels which were tempered, aged at 600°C for
3000 hrs, and aged at 650°C for 1000hrs. The impact values after ageing were
EFFECTS OF TUNGSTEN ON MECHANICAL PROPERTIES 263

td
100
~
<+-i
Solid line;
0
80 Elongation
~0 Dotted line;
•.;:3
0
.6,- 60 Reduction of area

~---
(j)~

c<3 40
-0-- Room temp .
.§ -o-500C
~eo 20
-A-600C
§
fil 0 -4-700C
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Amount of W (mass%)

Fig. 5 Elongation and reduction of area of tensile test

Dotted line: As temperd


Solid line: After aged
600c*3000hrs

-o-O.OlW
-o-O.95W
-tr-1.24W
-x-2.00W
--.-2.45W
o ----*- 2.95W
-80 -60 -40 -20 0 20 40 60 80
Temperature (C)

Fig. 6 Charpy impact value vs. temperature

0.0 0.5 1.0 1.5 2.0 2.5 3.0


Amount ofW (mass %)

Fig. 7 Charpy impact value at 20°C vs. W content


264 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

decreasing with increasing W content, gradually up to 0.95% W steel and


remarkably at over 2.00% W. The impact values aged at 650°C for 1000 hrs
were a little lower than those aged at 600°C for 3000 hrs. In order to compare
the aged at 650°C for 1000 hrs with the aged at 600°C for 3000 hrs, the LMP
and the tempering parameter (TP) were used. In the eqn (2) the parameter
constant PC = 36.1 and in the eqn (3) the tempering parameter C = 16.0. The
aged at 650°C for 1000hrs condition was calculated to correspond to being
aged at 600°C for 170 000 hrs and 12 000 hrs respectively. Consequently it
meant that the impact values at 650°C for 1000hrs might be saturated.

TP = T*[C+log(t)] (3)

where, T: temperature, K, t: tempering time, h, C: tempering constant.

MICROSTRUCTURE

Microstructure
Figure 8 shows the microstructures of 0.01Wand 2.95W steel in the as
tempered condition. The microstructures of all six steels were comprised of

Fig. 8 Microstructures of 0.01 Wand 2.95 W steel in the as tempered condition

typical tempered martensite without delta-ferrite. As shown in Table I, Creq.


values of O.OlW and 2.95W steels were 6.80 and 11.67%, respectively. The
value of 11.67% was considered to be border line for delta ferrite appearance.
However, because of its laboratory manufacturing process, the microstructure
might be very uniform and micro-segregation was minimised, resulting in the
microstructure of fully tempered martensite.

Precipitation
Fig. 9 shows TEM observation of extracted replica of 2.00W steel in the as
tempered and after ageing at 600°C for 3000 hrs. The precipitates in the as
EFFECTS OF TUNGSTEN ON MECHANICAL PROPERTIES 265

Fig. 9 Precipitates of 2.00W steel by TEM extraction replica

tempered condition were finely dispersed in a matrix of tempered martensite.


The precipitates in the after aged condition agglomerated along the prior
austenite and sub grain boundary with an increase in ageing time. However,
the size of the precipitates in the after aged condition were relatively fine and
stable, being no bigger than those in the as tempered condition. The relatively
fine and stable precipitates contributed to the high creep resistance of W
containing steels.

Extracted residue
Figs 10 and 11 show the amount of extracted residue of alloying elements in
the as tempered condition and in the after aged at 600°C for 3000 hrs
condition, respectively. The alloying elements were determined by chemical
and X-ray diffraction analysis. They consisted of Cr, Mo, W, V, Fe, N, Ti, AI,
Mn, and the rest. The 'others' element indicated in the Figs 10 and 11
consisted of N, Ti, AI, Mn and the rest. The alloying elements in the extracted
residue in the as tempered conditions, even if the W contents were different,

[ITlOthers
DFe
IIJV
IiW
DMo
IIJCr

o
0.01 0.95 1.24 2.00 2.45 2.95
Amount ofW (mass%)

Fig. 10 Amount of extracted residue alloying elements as tempered


266 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

DOthers
DFe
IIV
OW
OMo
OCr
o
0.01 0.95 1.24 2.00 2.45 2.95
Amount of W (mass%)

Fig. 11 Amount of extracted residue alloying elements after aged at 600°C for
3000hrs

were almost the same in quantity. The main alloying elements were Cr, Fe
and V. They might come from M in the M23C6 and MX type carbonitride,
being estimated from the analysis of NF616.5 The amount of extracted residue
of Wand Fe elements in the after aged at 600°C for 3000 hrs condition
increased with W content, resulting in the increase of precipitates. An
alternative explanation, is they come from the elements of Fe and W in Laves
phase (Fe2W). Figure 12 shows the amount of precipitated W and solved W in

0.0 0.5 1.0 1.5 2.0 2.5 3.0


W content of steel (%)

Fig. 12 Amount of precipitated and solved W after aged at 600°C for 3000 hrs

the after aged at 600°C for 3000 hrs condition. As the amount of precipitated
W for 2.95% W steel reached 0.95%, the amount of solved W was reduced to
2.00%. Consequently, the W strengthening mechanism changed from solution
hardening to precipitation hardening with the increase of ageing time.

Precipitated W
The authors" analysed the phase diagram of 9%Cr-0.5Mo-0.07%Nb-
0.2%V-O.1%C-O.05%N-W steel by using Thermo-Calc. and experimental
EFFECTS OF TUNGSTEN ON MECHANICAL PROPERTIES 267

1300

1200

1100

0'
~ 1000
e
~!. 900

E 800
~
700

600

500

A 0 0.5 1.0 1.5


W (ma •• %)
2.0 2.5 3.0

Fig. 13 Phase diagram of 9%Cr-0.5%Mo-0.07%Nb-0.2% V-0.1 %C-O.Os%N- W steel


by Thermo-Calc

data, as shown in Fig. 13. It was shown that MX, M23C6 and Laves phase
[(Fe,Cr)2(W,Mo)] precipitated below 1200, 890, 730°C, respectively. The equi-
librium of tungsten distribution between bee, M23C6, MX and Laves phase
were calculated. J. Hald? and the authors" investigated the behaviour of Laves
phase in the aged and crept specimen of NF616. In order to calculate the
amount of Laves phase, the mathematical model was established by using
long term data, Thermo-Calc., and the Johnson-Mehl-Avrami equation. The
model was based on several simplifying assumptions. One of the important
assumptions was that Laves phase precipitation was determined by W.
diffusion, because of the high stability of M23C6 carbide. Johnson-Mehl-
Avrami equations were shown in the eqns (4), (5) and (6).

w(t) = 1-exp[-(t/T)n] (4)

(5)

D = Do*exp-Qo/(RT)] (6)

where, w(t): relative amount of W precipitated at time t, Co: W concentration


in ferrite.Ss, C/x: equilibrium W concentration in ferrite.Ss, Ce~: equilibrium W
concentration in Laves phase.X, Do: 0.29 cm2/sec, Qo: 55.1 kcal/mol, R: gas
constant, 1.98 cal/ (mole*K), T: temperature, K, N: nucleation site number,
1/cm3, n: exponent.
The change in the amount of precipitated W was analysed using the
mathematical model. Equilibrium W concentration in ferrite Ceu and equilib-
rium W concentration in Laves phase Cel3 were determined from the NF616
data." The exponent n, 1/1' and N were determined 0.698, 2.58*10-8 (1 sec-I),
0.56*1010 (1 cm='), respectively, being referred to the analysis of precipitated
W with ageing time at 600°C.6,7 The change in precipitated W with ageing
time at 600°C were calculated by the Johnson-Mehl-Avrami equation,
268 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

by Thermo-Calc.
3.0 r---------------.
Calculated value
--2.95W
- - 2.45W
2.00W
-1.24W
0.95W

10 100 1000 10000 100000


Aging time (h)

Fig. 14 Change in precipitated W with ageing time at 600°C

compared with measured values, as shown in Fig. 14. From this figure it was
predicted that precipitated W with ageing time would be saturated at over
about 105 hrs.

CONCLUSIONS

9% chromium steels with tungsten were investigated. The effects of tungsten


on mechanical properties and microstructure were clarified as follows.
1. The creep rupture strength, estimated by LMP analysis, increased with
increasing W content. The tensile strength at elevated room and tem-
perature increased, and the toughness decreased with increasing W
content.
2. The alloying elements of precipitates after ageing were measured. The
change in precipitated W with ageing time at 600°C were analysed by
the extracted residue and the Johnson-Mehl-Avrami equation.

SYMBOLS

Creq. = Cr equivalent (%)


T = temperature (K)
tr = time to rupture (h)
IT = applied stress (Mpa)

PC = parameter constant
CI, C2, C3 and C4 = regression coefficients
t = tempering time (h)
C = tempering constant
w(t) = relative amount of W precipitated at time t
EFFECTS OF TUNGSTEN ON MECHANICAL PROPERTIES 269

Co = W concentration in ferrite (%)


C/x = equilibrium W concentration in ferrite (0/0)
Ce(3 = equilibrium W concentration in Laves phase (%)
Do and D = diffusion coefficient (cmv/sec)
Qo = activiation energy (kcal/mole)
R = gas constant (cal/Imole=K)
N = nucleation site number (1/cm'')
n = exponent

REFERENCES

1. C. R. Brinkman, D. J. Alexander, and J. Maziasz: ASME/IEEE Power


Generation Conf., San Francisco, 1991.
2. T. Fujita: COST-EPRI workshop, Scaffhausen, 1986.
3. H. Naoi, H. Mimura, M. Ohgami, H. Morimoto, T. Tanaka, Y. Yazaki, and T.
Fugita: EPRI/National Power Conf, London, 1995, 8-44.
4. E. Metcalfe and W. T. Bakker: EPRI/National Power Conf., London, 1995,
1-7.
5. H. Yasuda, M. Sakakibara, T. Takahashi, H. Naoi, and H. Masumoto: Fossil
Fired and Nuclear Power Generation of Japan, 1988, 39(5), 517-524.
6. H. Mimura, M. Ohgami, H. Naoi, Y. Yazaki, and T. Fujita: Proceedings of
CSME-JSME-ASME Inter. Conf on Power Engineering, ICOPE95, 1070-
1075.
7. J. Hald: EPRI/National Power Conf., London, 1995, 152-173.
8. M. Ohgami, H. Mimura, and H. Naoi: Proceedings of Fifth Inter. Con! on
Creep of Materials, Florida, 1992, 69-73.
Simulation of Carbo-Nitride Coarsening
in Multicomponent Cr-Steels for High
Temperature Applications
A. GUSTAFSON, L. HOGLUND andJ. ACREN
Materials Science and Engineering, Royal Institute of Technology, S-100 44
Stockholm, Sweden

ABSTRACT
Coarsening of cubic M(C,N) particles has been simulated for multicomponent 10%
chromium steels. These steels are used as high temperature parts in steam turbines.
The simulation has been made with the DrCTRA software that fully takes into
account the multicomponent thermodynamic and diffusional effects. The multi-
component coarsening is treated numerically for a maximum particle assuming that
the particle size distribution obeys the Lifshitz-Slyozov-Wagner distribution. The
model was tested in ternary systems for four different carbides .in austenitic matrix
where both experimental measurements and analytical solutions existed. These
carbides were Cr7C3,Mo6C, VC and NbC. A good agreement of the simulations with
the experiments and the analytical solutions was found. This is however not only a
test of the model. The result also depends on the thermodynamic data and the
diffusivities. The simulations of coarsening of M(C,N) in the chromium steel give a
result that is in agreement with observations.

INTRODUCTION

Fine sized carbide and nitride particles may have a large effect on the creep
strength of metallic materials. Ti(C,N), V(C,N) and Nb(C,N) are often used in
austenitic stainless steels and in ferritic Cr steels. The strengthening effect is
stronger the finer the particle dispersion is and consequently the coarsening
of particles, i.e. Oswald ripening, causes a decrease in creep strength. In order
to predict the lifetime of components exhibited for creep at elevated tem-
peratures one should thus first predict the coarsening and then couple such
predictions with creep models.
Lifshitz and Slyozovl-? and Wagner-' developed analytical solutions for
Oswald ripening in binary systems. For a-phase particles in a ~ matrix
consisting their analysis yields:

(1)

Ycis the average particle radius at time t, Yo the initial radius, (J is the interfacial
energy, V~ the molar volume of the a-phase, D~ is the diffusion coefficient of

270
SIMULATION OF CARBO-NITRIDE COARSENING 271

the A atoms in the J3-phase, the composition of the J3-phase in the


x(X~~

boundary to the a.-phase in mole-fraction, V~ the molar volume of the


J3-phase, R the gas constant, T the temperature and finally z= and x~ are the
compositions of the a. and J3phase respectively in mole-fraction of A. All units
are in 51.
Bjorklund et al.4 were first to analyse how the addition of a third element
affected the rate of Ostwald ripening of cementite in steel. Under some
simplifying assumptions there were able to derive analytical solutions for
ternary systems for the case when one of the elements is an interstitial
solute.

MODEL

The Oswald ripening model in DICTRAs uses the assumption that coarsening
of a system can be described by performing calculations on a particle of
maximum size at the centre of a spherical cell. According to Lifshitz, Slyozov
and Wagner the maximum particle size is 1.5 times the average size. In
DICTRA the full multicomponent thermodynamic behaviour as well as the
multicomponent diffusional effects are considered.
In the model a contribution from the interfacial energy is added to the
Gibbs energy function for the particle, see Fig. 1.

LlG = 2aVm (2)


m
r

ITis the interfacial energy in J m -2, r the radius of the particle in m and Vm is
the molar volume in m3 per mole substitutional atoms. Locally at the cell

Moving phase interface with CI.. and ~ Equilibrium as defined by the


in local equilibrium. average composition in the system
2 crVrn Interfacial energy contribution 2 crVrn Interfacial energy contribution
-r;- added to the a phase. r added to the a. phase.
Fig. 1 A schematic picture of the coarsening model in DICTRA5
272 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

boundary, equilibrium between particles of average size and the matrix is


assumed. A contribution of the interfacial energy is also added to the Gibbs
energy function of the particles of average size. The particle of the maximum
size will then have a smaller Gibbs energy addition than the particles of
average size. The composition close to the interface between the maximum
particle and matrix and the outer cell boundary will thus differ in such way
that the maximum particle will always grow. In order to maintain the total
composition in the cell its size will increase accordingly.

COMPARISON WITH EXPERIMENTS

The model yields satisfactory agreement with experimental results reported


in literature. So far we have only considered ternary systems although the
model can handle any number of components. First, coarsening of 'V' particles
in Ni rich matrix in ternary Ni-AI-Mo is considered. In Fig. 2 a comparison

10+-~--~~--~~--~~--~

9
Alloy A2
AExperimental points, Fahrmann et al.
7 - - - Dictra - same compositions
-- Dictra - same fractions of y'

Alloy A3
[!] Experimental points, Fahrmann et al.
4
-- - Dictra - same fractions of y'
3
Alloy AS
2
~ Experimental points, Fahrmann et al.
1 - - - - - - Dictra - same fractions of y'
E-21
O~~--~~~~~~~~~+
o 50 100 150 200 250 300 350 400
Time (hours)

Fig. 2 Comparison of the coarsening model in DICTRA with experimental data


from Fahrmann et al.6 Coarsening of -particles in Ni-AI-Mo at 872 is considered
"I'
0

between calculation and experimental data from Fahrmann et al.6 is shown.


The cube of the radius is plotted as a function of time.
Unfortunately the thermodynamic description from Saunders," the only
one available to use, does not seem to be in good agreement with the
observations by Fahrmann et al.6 Several of their alloys, which are obviously
two-phase alloys are predicted to be one-phase 'V when Saunders' database is
used. One should thus modify Saunders' database taking the new informa-
tion into account. As a first attempt we have used Saunders data but adjusted
the alloy composition in order to have the same fraction 'V' as observed by
SIMULATION OF CARBO-NITRIDE COARSENING 273

Table 1 Comparison of the molybdenum and aluminium contents and fractions of


"I' at 872°C reported by Fahrmann et aI.6 and used in the simulations (from
Saunders"), Compositions are given in atomic-percent and fractions in mole-
fraction

Fahrmann et aI.6 In simulations (from Saunders")

Alloy Mo Al fraction "I' Alloy Mo Al fraction "I'

A2 5.0 9.9 0.12


A2 5.0 9.9 0.19 A2 5.0 10.6 0.19
A3 7.9 7.7 0.12 A3 7.9 8.8 0.12
AS 13.0 5.3 0.07 AS 13.0 7.3 0.07

Farmann et al.6 This gave a small difference in composition compared with


Fahrmann et al. For the alloy A2 it was possible to use the actual composition
in the simulations but then the fraction of ~' became slightly lower than the
real one. Table 1 shows the compositions and fractions of ~' reported by
Fahrmann et ale and used in the simulations respectively. In Fig. 2 one can see
that the simulations agree well with the experimental data. For alloy A2 it was
possible to use the actual composition in the simulations but then the fraction
of ~' became slightly lower than the reported one. Figure 2 reveals that the
simulations agree quite well with the experimental data. There is, however, a
larger discrepancy for alloy AS. It should be noticed though, that the real
discrepancy is not as severe as it may seem from the figure because the cube
of the radius is plotted in the figure and the discrepancies are enlarged
accordingly. The difference between the experimental points and the simula-
tions on the radius is then around 50%. It must be emphasised that the
uncertainty in the diffusivities may be of that order of magnitude.
A comparison was also made with experimental data from Wey et al.8 They
investigated different carbides in austenite. The carbides were Cr7C3, Mo6C,
VC and NbC. The result can be seen in Fig. 3. The simulations do not fit the
experiments very well. The difference is around 200/0 and that is most
probably due to the diffusivities. As already mentioned, a factor of two in
difference in the diffusion coefficient is not unrealistic. The effect of carbon on
the chromium diffusion in austenitic or ferritic iron has not been investigated.
This is also the case for molybdenum, vanadium and niobium.

RESULT

Coarsening simulations were performed for carbo-nitrides in a 10% Cr steel.


The most important alloying elements in the steel are 10.S%Cr, 1%W, l%Mo,
0.14%C, 0.2%V, 0.06%Nb and O.06 N. The phases appearing in the steel at
%

600°C is a matrix of martensite with MX, M23C6and Laves phase as secondary


274 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

1.0
Experimental points from Wey et al.
0.9
x Cr7C3
S 0.8 e Mo6C
~ m VC
CJ'.l
0.7
:.a::s ~ NbC
Cd
0.6
'""
(1) Lines = DICTRA simulations
U 0.5
.~
c, 0.4
(1)
eo
Cd 0.3
'""
Q)
>
-c 0.2

0.1

0
0 20 40 60 80 100
Time1l3(sll~

Fig. 3 Comparison of the coarsening model in DICTRA5 with experiments from


Wey et al.8 at 1373 K. 1003 seconds is close to 11.5 days

phases. MX is the carbo-nitride of interest in this work and it consists mainly


of vanadium and nitrogen but also some niobium. The steel has a martensitic
matrix which was approximated as ferrite in the DICTRA calculations. The
simulations were made on the 4 component system: Pe-V-Nb-N. The steel is
annealed at 750°C before usage in the high temperature parts in steam
turbines at 600°C. The result of the coarsening simulation of the carbo-nitrides
in the 10% Cr is shown in Fig. 4.
One problem with calculating the coarsening of the carbo-nitrides is to

• Measured value after


2 months
64
-5
~ 3.5 x Starting point: Size of the
o
.~ 3 critical nucleus from
~ nucleation simulations.
~ 2.5
Cd

~
Cd
2
tM
o

873 K

1 101 102 103 104 105 106 107 108 109


Time (s)

Fig. 4 Simulation of coarsening of (V,Nb)N in ferrite (Fe). The starting point was
taken from the result of modelling of nucleation (Gustafson and Agren'')
SIMULATION OF CARBO-NITRIDE COARSENING 275

obtain the correct initial size of the particles. The particles are too small to be
observed in a transmission electron microscope before they have grown. The
nucleation of these carbo-nitrides were modelled recently by Gustafson and
Agren9 and in the present calculation the initial particle size was taken from
their work. When the particles have nucleated they will grow but the growth
stage lasts just for a few minutes and the coarsening process takes over.
Unfortunately we have, so far, only one experimental observation on the
average particle size for the carbo-nitrides made by Lundin.l" The size of the
carbo-nitride particles was measured on a sample that was creep tested for
1496 h, i.e. around two months. This single experiment was included in Fig. 4
and falls close to the calculated curve. According to the predictions the
average size of the particles increases from 1.1 nm to slightly over 4 nm after
11 years in 600°C.

DISCUSSION

The present model has been capable of representing experimental data


reasonably well. We have already concluded that an uncertainty in the
diffusivities would immediately yield a corresponding uncertainty in the time
dependence. The discrepancies would when comparing the calculations with
experimental data may thus very well be explained from less well-determined
diffusivities. It should be emphasised that we have not made use of any
adjustable parameters in the calculations. We may thus conclude that the
accuracy of the predictions should be regarded as satisfactory and form a
basis for modelling of creep.

ACKNOWLEDGEMENTS

The authors gratefully acknowledge the financial support from the Swedish
National Board of Technical and Industrial Development and the National
Energy Administration.

REFERENCES

1.1. M. Liftshitz and V. V. Slyozov: Soviet Physics JETP, Feb. 1959,35 (8), No.2,
331-339.
2. I. M. Liftshitz and V. V. Slyozov: Chern. Solids, 19 (1/2), 35-50.
3. C. Wagner: Zeitshrift fur Elektochernie, 1961, 65 (7/8),581-591.
4. S. Bjorklund, L. F. Donaghey and M. Hillert: Acta Met., 1972, 20, 867-874.
5. J-O. Andersson, L. Hoglund, B. Jonsson and J. Agren: Fundamentals and
Applications of Ternary Diffusion, G. R. Purdy, ed., Pergamon Press, New
York,~, 1990, 153-163.
276 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

6. M. Fahrmann, E. Fahrmann, T. M. Pollock and W. C. Johnson: Metallurgical


and Materials Transactions A, 1997, 28A, 1943-1945.
7. N. Saunders: Superalloys 1996, R. R. D. Kissinger et al., eds, TMS, Warren-
dale, 1996, 101.
8. M. Y. Wey, T. Sakuma and T. Nishizawa: Transactions of the Japan Institute of
Metals, 22 (10), 733-742.
9. A. Gustafson and J. Agren: Acta Mat. 1998,46 (1), 81-90.
10. L. Lundin: Chalmers University of Technology, G6terborg, Sweden,
private communication.
The Effect of Tungsten on Creep
Properties of High Chromium Steels for
Steam Turbine
R. ISHII, Y. TSUDA, M. YAMADA and M. MIYAZAKI
Toshiba Corporation, 2-4 Suehirocho, Tsurumi, Yokohama, Japan

ABSTRACT

The effect of tungsten addition on creep properties and microstructure was studied
for high chromium ferritic steels with various tungsten contents. Tungsten was
distributed among matrix, Laves phases and carbides during high temperature
exposure. The tungsten content in the matrix was reduced down to about 0.5 mass?
during creep and/or ageing for more than 10 000 h at 60QoC regardless of the initial
tungsten content. Solid solution strengthening due to about 0.5 mass': tungsten was
maintained during long-term creep. Laves phase precipitated at martensitic lath
interfaces, grain boundaries and in lath during high temperature exposure. At
martensitic lath interfaces and grain boundaries, continuous formation of Laves
phases and M23C6 carbides was recognised. This morphology played a role to
suppress the collapse of lath shape, and contributed to maintain the long-term
rupture strength. On the other hand, fine Laves phases precipitated in lath contrib-
uted to increase the short-term rupture strength. In order to obtain higher creep
rupture strength throughout the long-term, it is important not only to obtain the
appropriate amount of Laves phase but also to maintain the high amount of solid
solution elements in the matrix. This purpose was realised by doping rhenium or
increasing the molybdenum equivalent to over 1.5.

INTRODUCTION

Advanced high chromium ferritic steels have been developed as materials for
high efficiency fossil-fired power plants. The advanced steels, which have
recently been developed,l-3 are expected to increase the allowable steam
temperature above 600°C.
It is well established that the creep resistance of ferritic heat resisting steels
are greatly improved by precipitation strengthening due to fine carbides.
Tungsten, which has been regarded as one of the solid solution elements, is
also alloyed for better creep strength in current high chromium steels. In
addition, detailed investigations on phase stability and modelling of the
microstructure for these steels have been carried out with combined use of
thermodynamic calculation by Mimura et al.4 and Hald.f They revealed the
distribution of each element at each temperature with time. Furthermore,
recent studies on high chromium steels suggested that the creep resistance

277
278 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

was also improved by intermetallic phase precipitated during high tem-


perature exposure.v" However, the relation between precipitation morphol-
ogy and creep properties is not clear. A deeper understanding of the
behaviour of tungsten and intermetallic phase on creep properties has
therefore been required in high chromium ferritic steels.
This paper describes the fundamental investigation results, mainly on the
effect of tungsten addition to high chromium ferritic steels.

SOLID SOLUTION STRENGTHENING DUE TO TUNGSTEN

Solid solution strengthening due to tungsten was studied by using TOS2022


and TAF650.1 Typical chemical compositions and creep rupture strength of
both steels are shown in Table 1 and Fig. 1, respectively. TAF650 indicated
higher creep rupture strength than that of TOS202 at high Larson-Miller
parameter values.
Figure 2 shows the tungsten content in the matrix and the amount of
extracted residue of TOS202 after being aged or creep. All specimens show
depletion of tungsten in the matrix down to about 0.5 mass': for more than
3000 h and the extracted residue gradually increased. Figure 3 shows the

Table 1 Typical chemical compositions of TOS202 and TAF650 (mass'zs)

C Si Mn P S Ni Cr Mo W V Nb Co N B

TOS202 0.16 0.07 0.5 <0.01 <0.01 0.8 11.0 1.0 1.1 0.2 0.20 - 0.040 0
TAF650 0.11 0.07 0.5 <0.01 <0.01 0.5 11.0 0.15 2.6 0.2 0.07 3.0 0.025 0.015

TOS202: 1120°C X 3h~O.Q. + 570°C X 4h~A.C. + 650°C X 4h~A.C.


TAF650: 1100°C X Ih~O.Q. + 750°C X 2h~A.C.

400

300 .
TOS20~
~ 250
~
~
200
en"
en
.•...
C1)

V5 150

100 '--_"""--_-'--_....o.-_--'--_-""-~---'-------'
23,000 24,000 25,000 26,000 27,000

larson-Miller parameter (C=25)

Fig. 1 Creep rupture strength of TOS202 and TAF650


THE EFFECT OF TUNGSTEN ON CREEP PROPERTIES 279

7
: 600°c
6 ... : .630°C.
"O~

a~ Amount of residue
.~ 8 5
~

Q)
~
Q)~

.~
4 .
:+ <. <6
.: /'
v
~~ +
..d 0
;; tse
fIl

3
.~
Q 2 .
~ §

~>* +
W content in the matrix
8 ~ 1
~ 0
As tempered 100 1,000 10,000

Creep / Ageing time, h

Figure 2 Change in the W content in the matrix and the amount of extracted
residue in TOS202with time

"'0

·0

~
m
><
~fIl

~
0'
::s
7

5
.*:•
/) : 600°C
.650~C
: 700°C

+ <./~\
~
/t>
.. C> ()<>
Amount of residue

• ••
Q) :9 4
w£i fIl
e
..
.S C+-4
e C
0
3
6
·0·
• • •+..
Q)

C ::s
0
u ~
ctS
~
0
As tempered 100 1,000 10,000
Creep / Ageing time, h

Figure 3 Change in the W content in the matrix and the amount of extracted
residue in TAF650 with time

analysis results for TAF650. In this steel, almost the same results were
obtained for more than 1000h except that the amount of residue was larger
than that of TOS202. They have a tendency to become almost stable in both
steels for more than 3000 h. Since the tungsten content in the matrix reaches a
constant value at each temperature regardless of its initial content, there is no
difference between both steels in the amount of tungsten content contributed
to solid solution strengthening during long-term creep.
Kimura et al.9 proposed 'inherent creep strength' which was independent
on creep time. They also made clear that the strength was affected by the
small content of molybdenum in the matrix. Assuming tungsten's effects are
similar to those of molybdenum, the increase of the inherent creep strength,
280 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

which is associated with the stable amount of tungsten in the matrix, is


expected during long-term creep. It can be speculated that the solid solution
strengthening due to stable amount of tungsten is also independent of creep
time.

INTERGRANULAR PRECIPITATION STRENGTHENING

'Intergranular precipitation strengthening' due to secondary phase was


quantitatively confirmed in nickel-base alloys.l'' In this strengthening mech-
anism, the secondary phases precipitated at grain boundaries playa role to
suppress the dislocation movement during creep regardless of the kind of
precipitates. The higher the grain boundary covering ratio is, the higher the
creep resistance of the alloy is. It can be speculated that lath interfaces playa
similar role to grain boundaries.
Figure 4 shows the carbon extracted replicas and thin foil observation
results for TOS202 and TAF650 ruptured at the same testing condition. The
rupture time of TAF650 was about twice as long as that of TOS202. The
feature in the microstructure of TAF650 was that the precipitates at lath
interfaces suppressed the collapse of the lath shape.
Kimura et al.6 and Igarashi et al.7 suggested that the precipitates at grain

Fig. 4 Microstructure of crept specimens at 650°C-176.4 MPa. (a), (b) TOS202 tr =


1004.2h, (c), (d) TAF650 tr = 1883.7h (arrow marks: identified Laves phases)
THE EFFECT OF TUNGSTEN ON CREEP PROPERTIES 281

Table 2 Chemical compositions of the matrix of the steels studied (mass'ze)

Ni Cr Mo W V Nb Co

Steel A (matrix) 0.49 9.39 0.06 0.81 0.15 <0.01 2.97


Steel B (C, Nand B free) 0.51 9.15 <0.01 0.62 0.15 0.03 2.95

Steel A: 1100°C X 1h-70.Q. + 680°C X 3h~A.C. + 750°C X 3000h-7A.C. + 650°C X


3000h-7A.C.
Steel B: 1100°C X 1h-70.Q. + 680°C X 5h~A.C.

Fig. 5 Optical micrographs of the specimens. (a) Steel A: Fully annealed steel, (b)
Steel B: Single-phase steel

boundaries had an effect on increasing the creep resistance in high chromium


ferritic steels. In order to confirm this concept, two specimens were prepared.
Chemical compositions of the matrix and optical micrographs of the speci-
mens are shown in Table 2 and Figure 5, respectively. Steel A is fully annealed
TAF650 manufactured with double ageing (750°C X 3000h + 650°C X
3000 h). The coarse precipitates agglomerated at grain/sub-grain boundaries
in Steel A. Steel B is a ferritic single-phase steel which has a composition
similar to that of the matrix of TAF650 after being aged for 10 000 h at 600°C.
Both steels indicated about same values of Vickers hardness and tungsten
content in the matrix, respectively.
Figure 6 shows the creep rupture strength of these specimens. The creep
rupture time for Steel A was twice to five times as long as those of Steel B. The
difference between both steels was independent of stress.
From these results, it is expected that continuous formation of coarse Laves
phases and M23C6 carbides contribute to increase the inherent creep
strength.

PRECIPITATION STRENGTHENING IN LATH

In high chromium ferritic steels, fine MX carbo-nitrides are recognised in the


martensitic lath. Since MX is stable during high temperature exposure, it is
282 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

400

300

C'j
~ 200
~
(/.)""
(/.)
150
~
en
100 .

80
19 20 21 22 23 24 25 26

Larson- Miller parameter/l 000 (C=25)

Fig. 6 Creep rupture strength of fully annealed and single-phase specimen

360

340
~
rn 320
CIJ

=
(1)

300
~~
..d

~
(1)
280

~ 260
~
240
As tempered 1,000 3,000 10,000 30,000

Aging time at 600°C, h

Fig. 7 Change in Vickers hardness of TOS202 and TAF650

one of the important factors to maintain the creep rupture strength during
long-term creep. In high tungsten containing steels, however, fine Laves
phases were recognised in the martensitic lath in addition to MX.
Figure 7 shows the change in Vickers hardness of TOS202 and TAF650 as a
function of ageing time at 600°C. The increase in the hardness was recognised
in TAF650 up to 3000 h. This increase correlated with the increase in the
precipitation density of fine Laves phase. This phenomenon was not recog-
nised in TOS202.
Figure 8 shows the creep rate-time curves of TAF650 at 700°C-176.4MPa.
The minimum creep rate of the specimen pre-aged for 1000h at 60QoCwas
about half of that of the tempered specimen, although the dislocation density
of the former was lower than that of the latter because of pre-ageing. It can be
THE EFFECT OF TUNGSTEN ON CREEP PROPERTIES 283

lE-2 r---------------------...

Oe:

i
0: 0 :
e' •.
lE-3'- .. . ~ 0 0 Astempered}

lE-4 1- ...

...
e:.......
:OO&OO~~ CD.
........••................
:
.:
: ..

Pre-aged at 60QoC for 1,OOOh

0.1 0.3 3 10 30 100 300

Time, h

Fig. 8 Creep rate-time curves of as tempered specimen and pre-aged specimen

Fig. 9 Carbon extracted replicas of TAF650 crept at 700°C-187.4MPa. (a) As


tempered tr = 63.9 h, (b) Pre-aged at 600°C for 1000h tr = 83.5 h

speculated that the decrease in creep rate was caused by fine Laves phases
precipitated in lath during pre-ageing and/or creep.
Figure 9 shows the carbon extracted replicas of TAF650 crept at
700°C-176.4MPa. The precipitation density after creep for pre-aged specimen
was larger than that of as tempered one. Fine Laves phases precipitated
during pre-ageing and/ or creep has the pinning effect such as other fine
precipitates. The effect, however, seems to disappear in the relatively short-
term because of its instability during high temperature exposure as shown in
Fig. 7. Therefore, it is expected precipitation strengthening due to fine Laves
phases in lath as long as new Laves phases continue to precipitate.

INCREASE OF THE SOLID SOLUTION ELEMENTS

The feature in chemical composition of the advanced ferritic steels is that the
balance between molybdenum and tungsten contents has been modified within
284 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

1.5 of the molybdenum equivalent. Laves phases necessarily precipitate and


have the above mentioned effects in high tungsten containing steels. In order to
attain more stable long-term rupture strength, however, higher amounts of
solid solution elements remained in the matrix are required. Two methods,
rhenium addition and over 1.5 in molybdenum equivalent, were investigated.
Rhenium is well known as one of the solid solution elements in nickel-base
superalloys. In addition, authors" and Murata et al.11 reported rhenium
addition to ferritic steels increased the creep rupture strength.
In case of rhenium doping with tungsten, rhenium distributed along the
Laves phases, M23C6carbides and matrix. Figure 10 shows both tungsten and

3 W at 600, 650°C llCr-O 2Mo-2.6W-CoVNbNB steel

/'

2- ~

~
~ 1
aa.>
-5
.5 0 : Re free stee]

~ O.~ Re at 600, 630, 650·C


~
'0
..Eg
o
tI)
0.6

0.4

-t
:9
"0
CIl 0.2

o~~------~--~~~--~~----~
As tempered 100 1,000 10,000
Creep / Aging time, h

Fig. 10 Change in the Wand Re contents in the matrix with time

rhenium content in the matrix of rhenium containing steels and rhenium free
steel. One of the features of the former was to keep a higher tungsten content
in the matrix than that of the latter. The rhenium content remained in the
matrix was less than about 0.2 mass': during creep. These results indicate that
the rhenium addition has the role of not only solid solution strengthening due
to itself but also maintaining high content of tungsten in the matrix. It is
presumed that this phenomenon results in the suppression of 'sigmoidal
behaviour' throughout the long-term.
Both molybdenum and tungsten content in the matrix reaches about 0.5
mass% during high temperature exposure in case of containing over 0.5
mass? in their initial content. Increasing the initial tungsten content under
THE EFFECT OF TUNGSTEN ON CREEP PROPERTIES 285

2~--------~------~--------------~
600°C

:O.SMo-2.5W

Fig. 11 Change in Molybdenum equivalent in the matrix with time at 600°C

the condition within molybdenum equivalent 1.5, the total amount of molyb-
denum and tungsten remained in the matrix results is small after long-term
exposure. Figure 11 shows the change in the molybdenum equivalent with
time and actual 10 000 h creep rupture strength for three steels. (Basic
compositions were shown in the figure.) The higher the initial molybdenum
equivalent of the steel is, the larger the amount of solid solution elements in
the matrix. The creep rupture strength was dependent on molybdenum
equivalent after exposure for 10 000 h at 600°C. It can be speculated that there
is no necessity to adhere to a molybdenum equivalent within 1.5 in order to
maintain high amount of solid solution elements after long-term exposure.
Therefore, the adding of both elements of 1.5 in molybdenum equivalent is
one of the ways to increase the solid solution elements remained the matrix
during long-term creep. It is presumed that this modification is also able to
suppress the sigmoidal behaviour throughout the long-term. This concept
including the effect of precipitates is schematically drawn in Fig. 12. In the

Steel containing high amount


of solid solution elements

"6'bl)
o
C
• Continuous formation
of precipitates
• Stable amount
of solid solution elements

Time (log tr)

Fig. 12 Schematic drawing of the concept to obtain high creep rupture strength
286 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

steel containing high amount of solid solution elements, it can be speculated


that the high and stable creep rupture strength is attained by four items
shown in the figure.

CONCLUSION

The effect of tungsten addition to high chromium ferritic steels on creep


properties and microstructure were studied on tungsten containing high
chromium steels. The results are summarised as follows.
1. Solid solution strengthening due to about 0.5 mass% tungsten was
maintained during long-term creep regardless of the initial tungsten
content.
2. Continuous formation of Laves phases and M23C6 carbides at grain
boundaries and martensitic lath interfaces were one of the important
factors to maintain the creep rupture strength.
3. Precipitation strengthening due to find Laves phase in the lath was
expected as long as new Laves phases continued to precipitate.
4. Maintaining a high content of tungsten in the matrix was attained by not
increasing the initial tungsten content within 1.5 in molybdenum equiv-
alent but doping with rhenium.
5. Maintaining high content of solid solution elements in the matrix was
also attained by their initial content being over 1.5 of the molybdenum
equivalent.

REFERENCES

1. T. Fukita: Proc. of 3rd Intern. Charles Parsons Turbine Conf., Newcastle, UK,
1995,493.
2. Y. Tsuda, M. Yamada, R. Ishii and O. Wantanabe: Advances in Turbine
Materials, Design and Manufacturing, The Institute of Materials, London,
1997,283.
3. F. Metcalfe, W. Bakker, R. Blum, R. Bygate, T. Gibbons, J. Hald, F.
Masuyama, H. Naoi, S. Price and Y. Sawaragi: IMechE Conference
Transactions, Intern. Conf. on Advanced Steam Plant, London, UK, 1997,
189.
4. H. Mimura, M. Ohgami, H. Naoi and T. Fujita: Materials for Advanced
Engineering, Part I, Liege, Belgium, 1994,361.
5. J. Hald: The EPRI/National Power Conf., New Steels for Advanced Plant up to
620°C, London, UK, 1995, 152.
6. K. Kimura, R. Ishii, T. Matsuo and M. Kikuchi: 123rd committee on Heat
Resisting Metals and Alloys Report, 34, 1993, 127, (written in Japanese).
THE EFFECT OF TUNGSTEN ON CREEP PROPERTIES 287

7. M. Igarashi and Y. Sawaragi: 123rd committee on Heat Resisting Metals and


Alloys Report, 25, 1994, 285, (written in Japanese).
8. R. Ishii, Y. Tsuda and M. Yamada: Steel Forgings 2nd Volume, STP1259,
ASTM, 1997, 317.
9. K. Kimura, H. Kushima, K. Yagi and C. Tanaka: Creep and Fracture of
Engineering Materials and Structures, The Institute of Materials, Swansea,
UK, 1993, 555.
10. T. Matsuo, K. Nakajima, Y. Terada and M. Kikuchi: Mater. Sci. and Eng.,
1991, A146, 261.
11. Y. Murata, M. Morinaga and R. Hashizume: Advances in Turbine Materials,
Design and Manufacturing, The Institute of Materials, London, 1997, 270.
Creep Fatigue Crack Behaviour of Two
Power Plant Steels
C. BERGER*, J. GRANACHER*, M. TRAMER*,
K. MAlLEt and G. SCHELLENBERGt
* Institutefor Materials Technology, University of Technology Darmstadt
t Staatliche Materialprufungsanstalt, University of Stuttgart, High
Temperature Department

ABSTRACT

The creep crack initiation and propagation under constant load conditions are
relatively well investigated on conventional power plant steels of types IO/oCrand
12%Cr. Comparable investigations on modern 9 to lOa/oCrsteels have been started.
However, only few data are available for creep-fatigue crack initiation and propaga-
tion in these steels. Nevertheless, the creep-fatigue crack behaviour is important for
life assessment and integrity of power plant components operating under start up,
shut down and other variable loading conditions. These characteristics can not be
substituted by pure fatigue or creep crack data. Therefore, a comprehensive test
programme was started to investigate the creep fatigue crack behaviour of a
1%CrMoNiV turbine rotor steel (30 CrMoNiV 411) at 550°Cand a new 9%CrMoVNb
pipe steel (type P 9 1) at 600°C.Double edge notch tension (DENT)-specimens with
15 and 60mm thickness as well as side grooved compact tension (CT)-specimens
with 25 and 50 mm thickness were tested to determine possible influences of
geometry and thus to check the transferability of the data to components. Long term
experiments under cyclic tension load (R::=:: 0.1) are planned with test durations up to
10000 h and dwell times from 0.1 to 10 h.
The main aim of the programme is to obtain a description of creep fatigue crack
growth which is independent of the load level and the specimen geometry. On the
basis of first test results, the cycle dependent crack propagation rate da/ dN can be
described by the parameter dKI with the frequency or dwell time as a parameter. The
time dependent crack propagation rate da / dt can also be described by the parameter
dKI and by the parameter C*.

TEST PROCEDURE

Test Materials
The steels under investigation in this study are the bainitic 1%Cr-turbine rotor
steel 30 CrMoNiV 4 11 which is mainly used for heavy forgings like rotors
and discs for temperatures up to 540°C. The second steel which is focused on
in this study is the martensitic 9%Cr pipe steel X 10 CrMoVNb 9 1 for
pipework with steam temperatures up to 600°C. The chemical composition of

288
CREEP FATIGUE CRACK BEHAVIOUR OF Two POWER PLANT STEELS 289

Table 1 Chemical composition of the test materials (weight'ze)

C Si Mn P S Al Cr Ni Mo V Nb N

30 CrMoNiV 411 0.3 0.24 0.73 0.009 0.018 - 1.04 0.58 1.05 0.30 -
X 10 CrMoVNb 9 1 0.1 0.30 0.46 0.015 0.003 0.019 8.30 0.17 0.94 0.21 0.066 0.049

Table 2 Product forms and heat treatments

Product, dimension Heat treatment

Turbine 0max = 790mm 950°C/7h/ Air


30 CrMoNiV 411
shaft Length e = 5800mm 700°C /15 h/Furnace
0a = 492mm 1050°C/10 mini Air
X 10 CrMoVNb 91 Pipe
0i = 332mm 750°C/70min Air

both steels are given in Table 1. The product forms and heat treatments are
given in Table 2.

Test Specimens
In this study test specimens form the type compact tension (CT) with side
grooves were used with 25 and 50 mm thickness as well as double edge notch
tension-specimen (DENT) with 15 and 60mm thickness, Fig. 1. All specimens
were spark eroded with a notch tip (Radius = 0.1 mm) as crack starter front.
The different specimen sizes with a varity of the cross sections from nearly
240 mm? up to 4800 mm- allows the determination of possible effects of size
and geometry on the crack growth behaviour. Also, it will allow to check the
transferability of the test data to components.

+-+-4~t.-t B(mm)

W(mm)
Cs25 Cs50

25

50
50

100
D15 D60

15

10
60

50

ao/W 0.55 0.55 0.2 0.2

Fig. 1 Specimen geometry


290 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

Test Techniques
Most of the small scaled specimens were tested at 1fW Darmstadt using the
interrupted test technique. For each stress level, a series of up to 15 specimens
were tested under the same loading conditions in a multiple creep test
machine. After reaching predetermined proportions of the expected 'rupture
time' t- which are choosen between 10% and 800/0 the specimens were
unloaded. During this interruption the load line displacement of all speci-
mens was measured and some specimens of the series fractured at low
temperature. The crack length of these specimens were fractographically
determined. Thus a high accuracy of data is guaranteed taking into account
also the scattering of the material characteristics and inhomogeneousness.
The large scaled specimens were tested at MPA Stuttgart as well as some
tests on small specimens were performed as single tests in servo hydraulic
test machines. During these tests, an online measurement of the load line
displacement was performed by means of a high temperature strain gauge.
Also the crack propagation was measured online with the electric potential
drop (AC) technique. At the end of each test the potential drop device was
calibrated with the final crack length observed in the fractured specimen.

Test Conditions
In this study long term test under cyclic tension load (R:::::0.1) conditions were
performed in the load controlled mode with dwell times at maximum load
from 0.1 up to 10h. With test durations up to 10 OOOhit is planned to come
near to real service conditions of components. The tests are still ongoing
whereas test results from maximally 1.0h dwell time are presented in this
paper. In Fig. 2 a scheme of the load cycle is depicted and in Fig. 3 the
variation of the test parameters.
All tests with the low alloyed steel 30 CrMoNiV 4 11 were performed at
550°C and with the martensitic steel X 10 CrMoVNb 9 1 at 600°C. These
temperatures are in the upper range of practical use.

tH
F, --- --------1 1
..•••
4II-----~~ tR! ..••• -

I..... tc ~I
Fig. 2 Scheme of the applied load cycle
CREEP FATIGUE CRACK BEHAVIOUR OF Two POWER PLANT STEELS 291

Test
duration
1 000 h

3200 h

10000 h

30 CrMoNiV 4 11 X 10 CrMoVNb 9 1
T = 550 °C • T = 600 °C

Figure 3 Planned test conditions

Pure fatigue tests with a frequency up to 10 Hz were also performed with


CT-specimen. The data from creep crack tests were taken from.1-4

TEST RESULTS

Creep Crack Growth Rate


The results of long term creep crack growth test presented in this paper have
been already published.l= If the linear elastic stress intensity factor KI is used
for the description of the creep crack growth rate da/ dt a relatively large
scatterband (factor 65) results in Fig. 4. KI is in accordance to ASTM E 399-83
for CT-specimen given by

(1)

Within this scatterband the larger specimens show the lower creep crack
growth rates but at smaller initial nominal stress values higher creep crack
growth rates. The slope of single creep crack growth curves for individual
specimens is not parallel to the slope of the overall scatterband.
By using the parameter C* the scatterband for the description of the crack
growth rate can be markedly reduced as shown in Fig. 5. For the calculation of
the C*-parameter on CT-specimens the following equation in accordance with
ASTM E 1457-92 was used:

C* == iJ . Unet • g2 (a/w.n.~). (2)


292 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION

1
10 ~----------------~--------------,-------------,-------------------,

30 (rHoNiV 4 11,AHA,~.550·C

scatterband up to CT 100
and for O'nO > 11;: 137 N/mm% : /

t- /'
o
, /209 /
scatterband mean value; /139 (838l 11249 - It I

(759) 415
scatterbandfactor 65 192 lIZ J 41
/144 (77~) 140
/' 17281 232326(894)
/ 301 lld·561 H957~
10-2 -t---- (6381(489) ,
297
(5261

10-10

Is !l!1 CllOO (15


n.es 0,55 0,2 0,'
() dl II (t
I" • -<:>- ~ 10'"
n9 ms 060
,/ o/W U,2 n.4 0.05 0,4 0.6 D,l 0.2 0.'

+ ~ ~ ~
"
.0-
$ -e- . 10'11
/
fatigue_crack pre-loaded ;
1O-6+---~-------------4--------------~----~--~~~-------r-----.----r
,/ : *)

200 500 1000 2000 4000 5000

Fig. 4 Creep crack growth rate da/dt versus stress intensity factor KI,
steel 30 CrMoNiV 4 11, T = 550°C.3

101

30 frHoNiV , 11.AHA,{t"S50·C
(I
-
K-r'
- scatterband up to CT 100
M.d for (1no > ~ 137 N/mm2 a
_. _. - scatterband mean value
./ .It'
m" -
I
scatterbandfactor 17 208
(t 0501
173
to'Z

m"-

(s 25 Cs 50 Cs 55 eTlOO CI5
iO" 0,2 0.4
0.55 0.55') 0.4 0,55 0.45 0,55

145
ISSOI
0 CD C> <t (J'
• ~ $ to-II

09 015 060
10's ./
./ o/W 0,2 0.4 0.05 0,4 0,6 0.1 0,2 0,4
./ -0 <) ~ ~ & ~ -e-
+ _ 10-11

*) fatigue crack pre-loaded


10'6
5.10-5 10-' to°J 10,1 10-1 100 101 t; (N/{mmhll 101

Fig. 5 Creep crack growth rate da/ dt versus parameter C*,


steel 30 CrMoNiV 411, T = 550°C.3
CREEP FATIGUE CRACK BEHAVIOUR OF Two POWER PLANT STEELS 293

For plane stress condition C* is approximately

C* ~ 2 . n +
n
1 . v. . Unet· (3)

The slope of the overall scatterband (~0.9) which is similar to a theoretical


slope of n/ (n + 1) is parallel to the slopes of individual test results. Nearly all
curves of the single specimens lies parallel to each other. The creep crack
growth rate for the CT-specimens are within the upper range of the overall
scatterband and in the middle and lower region for the DENT-specimen. No
significant influence of the specimen size on the crack propagation behaviour
described by C* could be observed.

Creep Fatigue Crack Growth


In Figs 6 and 7 the creep fatigue data (solid data points) and the creep crack
data (hollow data points) of the low alloyed lCr-steel are shown.
The evaluation of all data takes into account, that for technical use the most
important range of crack growth data starts at the so called 'technical crack
initiation', which is defined for CT-specimen by the criteria Lla = 0.004Wand
0.01 W for DENT-specimens up to a crack length of Lla = 2mm. For the
calculation of KI and C* for the cyclic creep crack tests Fmax = Fu was
considered. In Fig. 6 the crack propagation rate da/ dt is plotted as function of
the parameter K1• The lower bound of the scatterband is similar to that in Fig.
4 but the upper one was adjusted by a suggestion of Ewald" that the failure

1,E-01 .....................

./
I----~
....
~.-