(B0708) R. Viswanathan, J. Nutting-Advanced Heat Resistant Steels For Power Generation-Maney Materials Science (1999) PDF

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
1 Carlton House Terrace
London SW1Y 5DB
© 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
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
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
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
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%.
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
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
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
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
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
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
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
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:
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
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
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
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.
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
750
0
0
(l)~ 725
~
Cii 700
Q;
0-
E
(l) 675
l-
t»
c 650
.~
0-
E
(l)
625
I-
600
575
0.5 5 10 50 100 500 1000
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
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
700
o
o
600
~
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ca
CD
c..
E
Q)
r- 500
0)
c
.~
c..
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r- 400
5 10 50100 5001000 5000

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
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
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
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-
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:
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
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
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

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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
10-5
\\i
\ iAged at 650'C:,104h
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Manufactured
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(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
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
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
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
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,
;::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
~
~ 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
-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."
••......
.
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
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.
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
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
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.
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.
~
~ 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)
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
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
-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
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
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.
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
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
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
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
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.
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
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.
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
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.
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
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
(a) General microstructure x28 000 (5319)
(b) Recovery & pinning particles x46 000 (5331)
Fig. 7 E911-17901 hours at 60QoC

(c) Small M23C6 particles x46 000 (5329)
(d) Laves phase + M23C6 particles x46 000 (5333)
Fig. 7 - continued
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)

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
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.
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.
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.
(?
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.
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
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
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
~
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
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.
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
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.
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
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.
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
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
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-
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.
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
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)
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
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-
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 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
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.
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
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.
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.
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.
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.
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,
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.
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.
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
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
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.
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.
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-
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

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
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
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:
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
...
,, \
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.
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
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
(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
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

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
(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
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.
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
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.
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
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
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
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.
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
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
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)
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
--- 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
: -:----:-----::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
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:
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
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
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
+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
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

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
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
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
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
(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
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.
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

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.
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.
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).
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
(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.
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
§: §:
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
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)
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

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
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
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
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
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%).
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
Table 3. Results from APFIM analyses of steel P92 after different times of ageing
(wt%).
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
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
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.
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).
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

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
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
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,
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:
(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)
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
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
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
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:
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
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
\
, .:
•
.. ,
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.
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.
--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.
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.
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
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.
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
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.
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
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.
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
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
(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"
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
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
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
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

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

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.
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)

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
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
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
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.
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
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.
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
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

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
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

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
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,
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
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
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
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

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'')
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.
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
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,
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)
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
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
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
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
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
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).
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

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
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)

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
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----~
....
~.-
AI o
-
1······
Creep fatigue crack
growth
e--
~A r-.
=0.1 h., IE I T
\-----. 11- t--r-_ .J..~ fI

GeometrylHold time (Frequency)
\ I""
fb
.
I ;,~
--A- Cs25 / 0.1 h (0.003 Hz)
1,E-02
:c 'lIIIII
, '-,, __
~ I. 0.32: ----M- Cs25 / 0.32 h (0.0009 Hz)
E A
.s .......
~~
;;? 'n
pJff --+- Cs25 / 0.32 h (0.0009 Hz)
1M
tH = 1 h II ; pre-cracked
~
cu
"C
1,E-03
.
.....
.... ..
IJ -A
l-\.';Y
g~ G -11- D60 /0.32 h (0.0009 Hz)
f!
l~~,
-~!
\..
~
0
~
"
-_.- Cs25 / 1 h (0.0003 Hz)
,~~[l C ~ t /
1,E-04 .- D60 /1 h (0.0003 Hz)
'"
"
s·
~~ ,
!
Z!
Creep crack growth
1,E-05
/1/ .~ I -- !;-- Cs25
100 1000 3000 --0·-- D60
Fig. 6 Comparison of the creep crack- with the creep fatigue crack growth data on
basis of the stress intensity factor KI, steel 30 CrMoNiV 4 II, T = 550°C
Creep fatigue crack

growth
Geometry 1 Hold time
, + ~-AI On. o (Frequency)
",tJi '. 0 rP 0
~~~8~:,~~~~~~3f£~SI~
-A- Cs25 1 0.1 h (0.003 Hz)
1,E-02 tl:.:.:.:~
..·.....
:~.·
..·.-.·
...
·.-..·tH;=O~.3;2
...
·.~
...If6f
:c ~~ -}lPS
In.......~.:mm-fd V' ..
b~ -I!t- Cs25 1 0.32 h (0.0009
E I··· •••• /.-:: .{,<JI-/-/

f ...•• ;Jl~} fDlU d..".-+ ...........• r-/ ~ f
Hz)
E
~~~~~~.~.nts~~l
tH=1 ~ ~ ~~ ~~0XJ !
----I§- 060 1 0.32 h (0.0009 Hz)
ca~" 1,E-03 t2~~~~;~~Jllltj!.,."

.:"'/ ~I ~.. ..~..... "._ . -k- Cs25 1 0.32 h (0.0009
,. O·········?l.f.FJ·····························+·········\·· ,..•1 .nnn·nn
Hz) pre-cracked
"? 1 ~ -+- Cs25 1 1 h (0.0003 Hz)
""I
1,E-04 _ _. . . _...::: ·····-·····>.I:-::.~~· .. . . . --e- 060 11 h (0.0003 Hz)
.1
.' Creep crack growth

.",1
1,E-05 --l-------+---.c---+----!---_--l-- __ -.i
--0-- 060 and Cs50 0 Hz
1,E-04 1,E-03 1,E-02 1,E-01 1,E+OO 1,E+01
--o---Cs25 0 Hz
C* (plain strain) [N(m mhr1]
Fig. 7 Comparison of the creep crack- with the creep fatigue crack growth data on
basis of the parameter C*, steel 30 CrMoNiV 4 11, T = 550°C
will take place when the ratio K]/un > 3 (mixed mode damage or crack tip
damage). The creep fatigue crack growth rate of specimen with dwell time
0.32h and 1.Oh (frequencies 0.0009Hz and 0.0003Hz) lies in between the
scatterband of the pure creep crack growth. The slope of single specimens are
approximately parallel to each other.
The creep fatigue crack growth rate da/ dN of specimen with a dwell time
of 0.1 h (frequency 0.003 Hz) do not show a unique behaviour. Two specimens
with high initial stress intensity factors lie in the scatterband but with a much
lower slope. Two other specimens with lower initial stress intensity factors lie
above the scatterband. They yield a much faster creep fatigue crack growth
rate. Their slope is approximately parallel to the curves of specimen with 0.32
and 1.0 h dwell time and pure creep crack data. These data shows a markedly
influence of the fatigue interaction on the creep crack behaviour. Also it can
be seen that with an increasing initial K] greater than 600 Nmm-3/2 the slope
of the creep growth rate decreases.
In Fig. 7 the crack propagation rate is plotted as function of the parameter
C*. As mentioned above, the specimens with a dwell time of 0.32 and 1.0 h
(0.0009 Hz and 0.0003 Hz) lie in the scatterband of the creep crack data. The
specimens with a dwell time of 0.1 h (0.003 Hz) also do not fit the scatterband
as in Fig. 6.
In cases of the description of the creep propagation behaviour as function of
the K] or C*no effect of the fatigue loading part can be indicated by dwell time
0.32h and 1.Oh.
In Fig. 8 the results of pure fatigue crack tests (solid data points) are
compared with creep fatigue crack tests (hollow data points) on basis of ilK]
1,E-01 ... .... ...... ........... Creep fatigue crack growth

.. ... :.
Geometry 1 Frequency (Hold time)

..
1,E-02 0.0003 . (tH=1 "I ~ ..

~ -.•.
=--::-:=
--A:-- Cs25 1 0.003 Hz(0.1 h)
Qi'
'I!II!I
(!Ii:' -e-- Cs25 1 0.0009 Hz (0.32 h)
pre-cracked
'0 f = 0.003 Hz· 0.0009 Hz (1,,=0.1· ~/
>. -III- Cs25! 0.0009 Hz (0.32 h)
~ 1,E-03
as E
····v \
daldN=12x10·11*LlK25
--II-- D 60 10.0009 Hz (0.32 h)
1 ~Fr~qUe~Cies -+- Cs25 ! 0.0003 Hz (1 h)

~ 1,E-04 0.05 Hz (tH=O h
A
(ij .-•.... D60 1 0.0003 Hz (1 h)
.~~it
"C
Hz (t.!=O h)
Fatigue crack growth
1,E-05
--.- Cs25 1 Hz
~~ ....:A....Cs25 0.05 Hz
1,E-06 ···.···D60 0.05 Hz

100 1000 3000
-e- Cs50 0.05 Hz
Fig. 8 Crack propagation rate da/dN of creep fatigue and fatigue tests versus cyclic
stress intensity factor L1K!, steel 30 CrMoNiV 4 II, T = 550°C
1,E-01 ..........................
.... Creep fatigue crack
growth
Geometry I Frequency (Hold

time)
1,E-02
.... ..... .. ...
-fr Cs25 1 0.003 Hz (0.1 h)
f .003 Hz
"i'
.•" ,
c:; f = 0.0009 \/\ 'A-fjtt,;T -III- Cs25! 0.0009 Hz (0.32 h)
~ 1,E-03
EoS
,
5' .. .....
_lIP'
Me; AllIIIIIIIP'
Wt .14'
..........
.-- '.
Fatigue crack growth
z
~ ,.
lM'O"·" ..••.
~ 1,E-04 16
MEl !lIE
--:A- Cs25 1 0.05 Hz
'C ,............
:;
--:A- Cs25 1 10Hz
J
r
1,E-05
s , ....
,
-e- D151 0.05 Hz
1,E-06 -+- D60 I 0.05 Hz
100 1000 3000
Fig. 9 Crack propagation rate da/ dN of creep fatigue and fatigue tests versus cyclic
stress intensity factor LlK], steel X 10 CrMoVNb 9 I, T = 600°C
for the 30 CrMoNiV 4 11 steel and in Fig. 9 for the X 10 CrMoVNb 9 1 steel.
The data sets from a common 'Paris law scatterband' given in Ref. (6) fit well
to the threshold values of the stress intensity factor LlKth which were
experimentally determined. The slope of single creep fatigue crack curves
with 0.32h and 1.0h dwell time are larger than that of pure fatigue crack
curves. The curves of specimen with 0.1h dwell time are approximately
parallel to the pure fatigue tests. The creep fatigue specimen shows the
tendency, that they have a faster creep crack growth rate than pure fatigue
tests. This can be seen in the scatterband, they lie in the upper range, more
obviously at higher initial values of dK1•
SUMMARY
Long term creep crack growth tests have been carried out on a 30 CrMoNiV 4
11 turbine rotor steel up to about 50 OOOhduration and crack growth rates
down to 2 X 10-5 mm h ". This big creep crack data base, covering the
influence of size and geometry, was correlated with the parameters KI and C*,
whereas the parameter C* provides smaller scatterbands than K1•
To determine the start up, shut down and other variable loading conditions
in power plant components, creep-fatigue crack growth tests have been
performed up to test durations of 8000h. The test results show that dwell
times of 0.1 h yield to a faster creep propagation rate than those with 0.32 h
and 1.0h. At these tests no faster crack propagation rate was determined in
comparison to creep crack tests. The determination of the transition time
Kl
tl = E' . C* . (n + 1) (4)
demonstrates, that the use of the parameter C* is critical for the short term
tests with a short dwell times of 0.1 h. This is presumably a reason of a
damage mechanism which is dominated by plastic stress distribitution and
therefore the description of the creep propagation rate by means of C* or KI
creates some problems, so they shouldn't be used.
The behaviour that specimen with an initial KI higher than 600 Nmm-3/2
have a decreasing slope of da/ dt can be explained with the assumption that
another damage mechanism takes place which is presumably influenced by
plastic stress-strain redistribitution at the crack tip.
The first test results of the X 10 CrMVNb 9 1 steel led to the assumption that
this steel shows the same behaviour as the 30 CrMoNiV 4 11.
ACKNOWLEDGEMENT
Thanks are due to the 'Bundesminister fur Wirtschaft' (AiF-Nr. 10 395N) and
to the 'Verein deutscher Eisenhuttenleute' for their support of this work and
further to the 'Arbeitsgemeinschaft Warmfeste Stahle' for the supply of test
material.
NOMENCLATURE
ao initial crack length (mm) KI stress intensity

Lla crack growth (mm) dKI cyclic stress intensity factor
B thickness (mm) n Norton's exponent
C* creep load parameter R stress ratio
CT compact tension t} transition time (h)
da/dt crack growth rate (mm/h) tc cycle time (h)
da/dN crack growth per cycle tH dwell time at maximum
(mm/cycle) load (h)
DENT double edge notch tension tR ramp time (h)
dv/dt load line displacement rate tr rupture time (h)
(mm/h) W width (mm)
E' specific youngs modulus an nominal stress (MPa)
(MPa) a net net stress (MPa)
f geometry function T temperature (OC)
FI minimum load (N) 0a major diameter (mm)
Fu maximum load (N) 0i inside diameter (mm)
g2 function depending on 0max maximum diameter (mm)
specimen type, stress state
and net stress
REFERENCES
1. J. Granacher,R. Tscheuschner, K. Maile and W. Eckert: 'Kriechrifsverhalten

typischer Kraftwerksbaustahle', Steel research, 1989, 60 (II), 514-521.
2. K. Kussmaul, K. Maile, J. Bareiss, K. H. Kloos, J. Granacher and R.
Tscheuschner: 'Creep Crack Investigation of Turbine Steels with Speci-
mens of Different Size', ASME-Conference, Denver, 25-29 July 1993.
3. J. Granacher, R. Tscheuschner, K. Maile and W. Eckert: 'Langzeitiges
Kriechrifsverhalten kennzeichnender Kraftwerksstahle', Mat.- Wiss. u.
Werkstofftechnik, 1993, 24, 367-376.
4. K. Kussmaul, K. Maile, J. Bareiss, K. H. Kloos, J. Granacher and R.
Tscheuschner: 'Creep crack investigation of turbine steels with speci-
mens of different size', Proc. of the ASME-Conference, Pressure Vessel
and Piping, Denver, USA, 25-29 July 1993, PVP-VoL 266, Creep, Fatigue
Evaluation and Leak-Before-Break Assessment, Y. S. Garud, ed.,
119-26.
5. J. Ewald: Internal paper of W14 working group, Arbeitsgemeinschaft fur
Warmfeste Stahle.
6. S. R. Holdsworth: 'High temperature fatigue crack growth', High tem-
perature crack growth in steam turbine materials, COST 505, J. B. Marriott,
ed., EUR 14678, Petten 1994.
Creep-Fatigue Characteristics of
Advanced High Strength Cr- W Steels
for Power Boiler Applications
M. SATO*, H. KIMURA*, M. ABE*, M. YAMAUCHlt and
M. FUJITA§
* Tohoku Electric Power Co. Inc., 3-7-1, Ichiban-cho, Aoba-ku, Sendai
980-0811, Japan
t Nagasaki Research & Development Centre, Mitsubishi Heavy Industries,
Ltd., 5-717-1, Fukahori-machi, Nagasaki 851-0392, Japan
§ Boiler Engineering Department, Mitsubishi Heavy Industries, Ltd., 3-3-1,
Minatomirai, Nishi-ku, Yokohama 220-0012, Japan
ABSTRACT
This paper describes the creep-fatigue characteristics of three advanced high

strength Cr-W steels, HCM12A, NF616 and HCM2S, newly developed for applica-
tion to boiler pressure parts at elevated temperatures. Uniaxial creep rupture, low-
cycle fatigue and fatigue-creep interaction tests were carried out. The data obtained
in these tests were compared with the data for Mod.9Cr-lMo steel and conventional
2.2SCr-lMo steel to demonstrate the improved strength of these new alloys. Creep-
fatigue life evaluation methods were discussed based on the Time Fraction Rule in
order to propose damage diagrams for use in creep-fatigue design. A life reduction
mechanism in uniaxial fatigue-creep interaction testing of these alloys was investi-
gated, and the FCl test showed that the effect of strain concentration on the life
reduction through progressive deformation, such as bulging and/or necking, which
is not permissible in service plant components, could be greater than the creep effect.
This information should be incorporated in the development of a creep-fatigue life
evaluation methods.
INTRODUCTION
In Japan, several types of Cr-Mo steel, including 2.25Cr-lMo, 9Cr-lMo-

V-Nb, 9Cr-2Mo, and 12Cr-1Mo-1W-V-Nb, have been widely utilised for
high temperature components, such as steam generators and pressure vessels
for power and chemical plants. Recently, however, new heat resistant ferritic
steels with higher high temperature strength are being developed by
Masuyama et al.) Naoi et al.2 and Iseda et al.3 through the optimisation of
alloying elements, such as vanadium and niobium, molybdenum and tung-
sten, as well as carbon and nitrogen, so as to apply them in advanced steam
plants such as ultra-supercritical pressure (USC) plants.
298
CREEP-FATIGUE CHARACTERISTICS 299
The adoption of advanced steam conditions with higher temperature and

pressure in power generation plants is highly effective both as a countermeas-
ure against environmental degradation and in terms of improved thermal
efficiency. Accordingly, there are urgent needs for the development of new
steels with improved high temperature strength. In this study, the creep-
fatigue characteristics of three new heat resistant ferritic Cr-W steels were
investigated.
MATERIALS
Creep-fatigue characteristics of three newly developed types of high strength

ferritic steel pipes of 350 mm outer diameter and 50 mm wall thickness,
known as HCM2S, NF616 and HCM12A, were investigated in this study.
HCM2S(0.06C-2.25Cr-1.6W-0.25V-0.05Nb) was developed by Masuyama et
al.: through the optimisation of chemical composition and heat treatment
based on conventional 2.25Cr-lMo steel, and has a tempered bainite struc-
ture with very fine carbides (VC) dispersed in a ferritic structure of tempered
Bainite. NF616(0.10C-9Cr-0.5Mo-1.8W-0.2V-0.05Nb-B) was developed by
Naoi et al.2 through the replacement of a portion of the Mo in 9Cr-2Mo steel
(NSCR9) with W, and by the optimisation of the V and Nb contents, and has a
fully tempered martensitic structure without 8-ferrite. HCM12A(0.10C-12Cr-
0.4Mo-2W -lCu-0.2V -0.05Nb) was developed by Iseda et al.3 based on 12Cr-
1Mo-1W-V-Nb steel (HCM12), and features higher corrosion resistance
than 9Cr steel and high creep strength, attained by the optimisation of the V
and Nb contents, and is characterised by a fully tempered martensitic
structure. These steels have been specified in ASME Code Case 2199 since
1995, 2179 since 1994 and 2180 since 1994 as T23 (HCM2S), T92(NF616) and
T122(HCM12A), respectively.
EXPERIMENTAL PROCEDURE AND CONDITIONS
Creep, low-cycle fatigue, and creep-fatigue tests were conducted by using

smooth-bar specimens. The size of gauge length was 6 mm O.D. X 25 mm L,
8 mm O.D. X 15mm Land 8 mm O.D. X 25 mm L for creep, low-cycle fatigue,
and creep fatigue specimens respectively. Creep tests were conducted at 550,
600, and 650°C for all steels in lever-type creep testing machines. Low-cycle
fatigue tests were conducted at 600 and 625°C for HCM2S, NF616 and
HCM12A, respectively, at a strain rate of O.l%/s in an electro-hydraulic
fatigue testing machine with an induction heating system. Creep-fatigue tests
were performed in servo-mechanical testing machines with electric furnaces
under the same temperature conditions as the low-cycle fatigue test for each
steel. In creep fatigue tests, strain-holds of 5, 15, and 30 minutes were
introduced at the tensile or compressive peak strains.
500
~ 300
een
en
e 100
U5
50
30~~~~~~~~~~~~~~~
500~~~~~~~~~~~~~~~
as
a.
6100
en
en 50
e
U5 30
102 103 104 105

Time to Creep-Rupture (h)
Fig. 1 Creep-Rupture Test Results
Creep-Rupture Test Results

Creep test results for HCM2S, NF616 and HCM12A are shown in Fig. 1.
Results for HCM2S are shown in Fig. l(a), as well as the NRIM data+ for
conventional 2.25Cr-IMo steel and SMI data'' for Mod.9Cr-IMo steel. The
creep-rupture strength of HCM2S is much higher than that of conventional
2.2SCr-IMo steel, and almost comparable to that of the Mod.9Cr-1Mo steel.
Results for NF616 and HCM12A are shown in Fig. l(b), as well as the SMI
data'' for Mod.9Cr-1Mo steel. The respective creep-rupture strengths of
NF616 and HCM12A are at almost the same level and superior to that of the
Mod.9Cr-1Mo steel.
Low-Cycle Fatigue Test Results

Low-cycle fatigue test results are shown in Fig. 2. Results for HCM2S are
shown in Fig. 2(a), as well as the NRIM data" for conventional 2.2SCr-1Mo
steel. The low-cycle fatigue strength of HCM2S is nearly comparable to that of
conventional 2.25Cr-1Mo steel.
Results for NF616 and HCM12A are shown in Fig. 2(b), as well as the NRIM
5
~ (a)
3
Q)
C)
c
as 0
a:
c
.~
Ci3 0.5
S 0.3
~
5
(b) o NF616 (625"C)
3 [J HCM12A(62S·C)
~ -Mod.9Cr+1Mo(SOO·C)(Ref.7)
Q)
C)
c
as
a:
c
.~ 0.5
Ci3
0.3
102 103 104 105

Cycles to Failure Nf (cycle)
Fig. 2 Low-Cycle Fatigue Test Results
data? for Mod.9Cr-1Mo steel. The low-cycle fatigue strengths of NF616 and
HCM2S are almost the same as that of Mod.9Cr-1Mo steel.
Creep-Fatigue Test Results

Creep-fatigue test results are shown in Fig. 3. Results for HCM2S are shown
in Fig. 3(a), as well as the data from the low-cycle fatigue test without strain-
hold (th == 0) previously shown in Fig. 2 and the NRIM data" for conventional
2.2SCr-lMo steel. Life reduction in the creep-fatigue tests compared with the
data without strain-hold was observed, and tensile-hold was found to be
more damaging than compressive-hold in this steel. However, life reduction
was less than that of the reference data for a conventional 2.2SCr-1Mo steel.
Results for NF616 are shown in Fig. 3(b) in a similar manner, together with
the NRIM data? for Mod.9Cr-lMo steel. Life reduction in creep-fatigue tests
compared with the data without strain-hold was observed and, compressive-
hold was found to be more damaging than tensile-hold in this steel. Life
reduction was almost the same as that of the Mod.9Cr-lMo steel.
Results for HCM12A are shown in Fig. 3(c). Life reduction in creep fatigue
tests was observed, but the difference between compressive-hold and tensile-
hold was not clear in this steel. Life reduction was almost same as that of the
Mod.9Cr-1Mo steel.
thT : Tensile-Hold
thC : Compressive-Hold
10 'I
~
~ 5 (a) HCM2S, 600°C o thT = Smin
6.thT = 1Smin
Q)
o thT = 30min
,.
C)
c • the= Smin
co A the = 1Smin
a: • the = 30min
c
~ ""~....•..., ''', .• th=O
-=
'e
en
0.5
.,...•..... ''''''
................. en
"\' 2.25Cr-1Mo,!hT = O.lh(Ref.6)

~
~ 2.25Cr-1Mo,thT = 1h(Ref.6)
0.1
10~~~~~~ ~~--~~ _
~
~ 5 o thT Smin
Mod. 9Cr, 600'C, thT = 6min(Ref.7) 6.thT 1Smin
...•... ~
Q)
C) o thT 30min
c • the Smin
co A the 1Smin
a: "~~th=O
<:~Q, 30min
c:
'een 0.5 1"~fI: • the
Mod.9Cr, 600'C, thT = 1h(Ref.7)

(ij
t§
0.1----~~~~~~~~~--~~~~
10 'I
(c) HCM12A, 625°C o thT Smin

Mod. 9Cr, 600'C, thT = 6min(Ref.7) 6.thT 1Smin
...../' c thT 30min
! .
....••...•..•• • the Smin
1Smin
~&thC 30min
=- thC
Mod.9Cr, 600'e, thT = 1h(Ref.7)
103 104 105

Cycles to Failure Nt (cycle)
Fig. 3 Creep-Fatigue Test Results
DISCUSSION
Creep-Fatigue Damage Diagram for Time Fraction Rule

Creep-fatigue damage (Dc - Df) diagrams according to the time fraction rule
were constructed for HCM2S, NF6l6, and HCM12A, and are shown in Fig. 4
together with the line for D; + D, = 1 and the lines specified in the ASME
Code,"
The diagram for HCM2S is shown in Fig. 4(a). The data for compressive-
hold and the data for tensile-hold were scattered near the D; + Df = 1 line and
the line specified by ASME for stainless steel, respectively. The difference
between the compressive-hold data and the tensile-hold data was clearly
distinguished, and the allowable damage for tensile-hold was smaller than
that for compressive-hold.
o
o thT =
5min
c thT = 15min
Il.
o thT =
30min
Q)
~ 0.8 • the =
5min
• the = 15min
~ 0.6 =
• the 30min
c
5r 0.4
Q)
U 0.2
o~--~----~----~--~~~~----~
o
1.2~--~----~----~--~~--~----~
o thT = 5min
=
thT 15min
Il.
=
o thT 30min
• the =
5min
• the = 15min
=
• the 30min
g. 0.4
~
o 0.2
O~--~----~~-a~~~~~~----~
1.2r-----~----~-----r-------,r----~----...,
o thT = 5min
o
Cl s: thT = 15min
o thT = 30min
the = 5min
Q)
~ 0.8 •
• the = 15min
~ 0.6 • the = 30min
Q
g. 0.4
~
o 0.2
o~--~----~~~~~~~~~----~
o 1.2
Fatigue Damage Of
Fig. 4 Creep-Fatigue Damage Diagram for Time Fraction Rule
The diagram for NF616 is shown in Fig. 4(b). Data for both compressive-
hold and for tensile-hold were scattered near the line specified by ASME for
Cr-Mo steel. The difference between the compressive-hold and tensile-hold
data was small, but the allowable damage for compressive-hold was less than
that for tensile-hold.
The diagram for HCM12A is shown in Fig. 4(c). All data showed wide
scatter below the D; + Df == 1 line and no difference between compressive-
hold and tensile-hold data was observed.
The effect of the strain-hold position, i.e., the difference between tensile-
hold and compressive-hold, on life reduction and on the Dc-Dfdiagram was
clearly seen among HCM2S, NF616 and HCM12A, and it was considered that
there might be factors other than creep responsible for the life reduction seen
in the creep-fatigue test. It was shown that the effect of specimen deformation
(necking or bulging) on life reduction in the creep-fatigue test was quite large
in the Mod.9Cr-lMo steel by Yamauchi et al.9 Therefore, the effect of

specimen deformation was also examined.
Effect of Specimen Deformation on Life Reduction in Creep-Fatigue Testing

First, the distribution of specimen diameter in gauge length after the test was
measured of equal intervals of 1 mm for all creep-fatigue specimens in order
to examine the effect of specimen deformation. The schematic for specimen
diameter measurement is shown in Fig. 5, and an example of the measure-
ment results is shown in Fig. 6. It was observed that the specimens should be
enlarged in diameter along larger lengths but also showed local necking.
The effect of diameter change on life reduction in the creep-fatigue test is
shown in Fig. 7 as a relationship between the strength reduction factor LlEpred/
LlEexp and the degree of specimen deformation dmaxldmin. Here, Eexp is an
experimental strain range applied to specimens in the creep-fatigue test, and
~, -
&E 2 1
d 3
dE 3 1
d 4
dE 4 1
d 5 dE 5 1
d 6 1
&E 6 1
d 7
&S 7 1
d 8
&E 8 1
d 9 1
&S 9 1
d10 1
ds10 1
d11 1
ds11 1
d12
&E12 1
d13
dE13 1
d14
ds14 1
d15 1
&E15 1
d16 1 6E:6 I,';;
Fig. 5 Schematic of Diameter Measurement of Specimen after Creep-Fatigue Test
9----------~---------T--------~
NF616, L\ E t=O.7%, thC=5min
'"C 8.5 l-
e:
G)
.§
~ 8 --.Q ---0 ---0--"0... ",0---0---0---<>--0--- ~
ar
".i) .•
0 .•.•'0"",,0 -, d
~ 7.5 f- _<>- After Test 1-

G)
E
ca
1-Before Test
(5
7~--------~'----------~'--------~
o 5 10 15
Location in Gage Length (rnrn)
Fig. 6 Example of Deformation of Specimen in Creep-Fatigue Test

CREEP- FATIGUE CHARACTERISTICS 305
2 I I
(a) HCM2S
1.5 ~ /j. -
W /j.
80
.•••....
~a. l- o~
•
.re • • o Tens. Et = 1.5% _
Co\) • Compo Et = 1.50/0
<J
o Tens. Et = 1.0%
0.5 l- • Compo Et = 1.0% -
/j.Tens. Et =0.7%
.Comp. Et = 0.70/0
0 I I
2 I I
(b) NF616
~
• • • •• •
1.5 /j.t -
W /j.
.•••.... 0
WI 008
/j. o Tens. Et = 1.5% 1 _
~a. I-
• Compo Et = 1.50/0
Co\)
o Tens. Et = 1.0%
<l
0.5 l- • Compo Et = 1.0% 1_
/j.Tens. Et = 0.7%
• Compo Et = 0.7%
0 I I
2
(c) HCM12A
- -
W
1.5
~ •
• D··
•
.•••....
,,~. 0 o Tens. Et = 1.5%
~a. l-
• Compo Et = 1.5% 1-
o Tens. s, = 1.0%
Co\)
<J
• Compo Et = 1.0%
0.5 l-
/j.Tens. Et = 0.7%
.Comp. Et = 0.7%
I I
1.05 1.1 1.15 1.2

dmaxl dmin
Fig. 7 Effect of Diameter Change in Specimen on Life Reduction in Creep-Fatigue

Test
L1Epred is a strain range in the low cycle fatigue test at the same life as in creep-
fatigue test. Respectively, dmax and dmin are the largest and the smallest
diameter in the gauge length of the specimens. A good correlation was
observed between ilEpred/ L1Eexp and dmaxldmin for HCM2S and NF616, but fairly
large scatter was seen in the data for HCM12A.
Second, the strain ranges in each of the sixteen portions shown in Fig. 5
were calculated using the following equations.
(1)
(2)
Here, 8Et,i, L1Ee,i, L1Ep,i and L1ui are total strain, elastic strain, plastic strain and
stress ranges in each portion, respectively, a and n are material constants

obtained from a cyclic stress-strain relationship, and E is an elastic constant.
The largest strain ranges, llEt,max, /lEp,max, and /lEe,max, and stress range /lU'max in
the gauge length were calculated using eqns (1) and (2).
Thirdly, creep strain Ee induced by stress relaxation during strain-hold was
calculated by using the following equation.
Ee= Ee,p + Ee,s (3)
Here,Ee,sis a secondary creep strain and was calculated by using Norton's
law for secondary creep rate obtained from the results of the creep test. Ec,p is a
primary creep strain and was estimated by means of comparison between
experimental relaxation data which included primary and secondary creep
strain and the calculated results of secondary strain, and assumed Ec,p = 0.05%
for all materials. However, estimated creep strain was below 0.10/ and was 0
very small compared with the plastic strain shown above. Therefore, the
effect of creep strain on the increase in inelastic strain assumed to be
negligible in the subsequent evaluation.
Finally, the largest inelastic strain range in the gauge length of the creep-
fatigue specimen was estimated by the summation of plastic strain and creep
strain calculated using eqns (1) to (3). The relationship between the largest
calculated inelastic strain ranges and the lives for the creep-fatigue test is
shown together with the nominal values of the experimental results in low-
cycle fatigue test results in Fig. 8. The calculated results for HMC2S were
found to have been overestimated when compared with the results of the
fatigue tests as shown in Fig. 8(a). However, they were in good agreement
with the results for service-exposed SCMV4 (2.25Cr-1Mo steel plate),lO and
this indicates that the effect of ageing during the creep-fatigue test on fatigue
behaviour may be comparatively large in HCM2S as well as in conventional
2.2SCr-1Mo steel. For NF616 and HCM2S, the calculated results for creep-
fatigue conditions were in good agreement with the low-cycle fatigue test
results as shown in Fig. 8(b) and (c).
The results shown above tend to suggest that the life reduction in the creep-
fatigue tests for HCM2S, NF616, and HCM12A can be attributed mainly to the
effect of strain concentration due to specimen deformation during creep-
fatigue testing, which cannot be expected to occur in service plants, and that
creep-fatigue lives can be evaluated by using an enhanced inelastic strain
range including creep strain and the Coffin-Manson relationship for low-
cycle fatigue test results.
CONCLUSION
(1) HCM2S and NF616/HCM12A have superior creep strength and compara-
ble low-cycle fatigue/creep-fatigue strength to these as conventional
2.25Cr-1Mo steel and Mod.9Cr-1Mo steel, respectively.
£ 10
o Creep-Fatigue Test
~ 5 • Results of Evaluation
<I
-0- Fatigue Test
Q)
C»
c:
-A-SCMV4 (Service Exposed) Fatigue IRef.l0)
cu
a:
c:
'e! 05
Ci5 •
(;)
~cu
CD
~ O.1~~~~~~-----~~~~--~~~~~
£ 10
W
c::
5
<I
~ 10
r:N 5
<I
Q)
C»
c:
~
c:
'e
Ci5
0.5
(;)
~CD
£ 0.1
102 103 104 105
Cycles to Failure Nf (cycle)
Fig. 8 Coffin-Manson Relationship for Creep-Fatigue
(2) Life reduction in the creep-fatigue test can be attributed mainly to the
strain concentration in the specimen due to deformation, such as bulging
and necking, induced during testing.
(3) There is a possibility that the creep-fatigue life of HCM2S, NF616, and
HCM12A can be evaluated using an inelastic strain range including creep
strain and the Coffin-Manson relationship obtained by means of a low-
cycle fatigue test without creep effect.
REFERENCES
1. F. Masuyama, T. Yokoyama, Y. Sawaragi and A. Iseda: Materials for

Advanced Power Engineering, Part 1, by Coutsouoradis et al., eds, Kluwer
Academic Publishers, Netherlands, 1994, 173.
2. H. Naoi, H. Mimura, M. Ohgami, H. Morimoto, T. Tanaka, Y. Yazaki and T.

Fujita: New Steels for Advanced Plant up to 620°C, by Metcalfe, ed., PicA
Publishing Services, UK, 1995, 8.
3. A. Iseda, A. Natoria, Y. Sawaragi, K. Ogawa, F. Masuyama and T.
Yokoyama: Thermal and Nuclear Power, 1993,45, 900.
4. SMI Creep Data Sheet (KA-STBA28), 1994.
5. NRIM Creep Data Sheet No. 3B (STBA24), 1986.
6. NRIM Fatigue Data Sheet No.7 (SCMV4), 1978.
7. NRIM Fatigue Data Sheet No. 78 (ASTM A387 Gr.91), 1993.
8. ASME B&PV Code, Sec. III Div. I, Subsection NH, 1995.
9. M. Yamauchi, T. Matsubara and H. Nakatani: Proc. 29th Symposium on
Strength of Materials at High Temperatures, Soc. Mater. Sci., Japan, 1991.
10. M. Yamauchi: Unpublished Data
Properties of a 12%CrMo V High
Temperature Turbine Steel Containing
FeWTiC
P. BATES, M. A. WALSH AND S. PRICE
Forgemasters Steel and Engineering Limited, P.O. Box 286, Brightside Lane,
Sheffield S9 2RW, UK
ABSTRACT
FeWTiC is a carbide containing powder which consists of fine WTiC particles in a Fe

matrix. The powder is designed to have a neutral buoyancy in steel to promote even
mixing and hence a uniform distribution in the final product. A stable fine
distribution of carbides is a pre-requisite for good mechanical properties and creep
resistance in high temperature turbine applications.
A novel method of improving carbide stability has been investigated by the direct
addition of FeWTiC powders into the molten metal of 12%CrMo V trial melts. The
microstructure, mechanical properties and creep resistance of advanced 12%CrMoV
steels containing varying volume fractions of FeWTiC additions are compared
against the base material.
INTRODUCTION
The demand for higher efficiency in electricity production has led to a

continuous rise in desired operating steam temperatures. Current designs of
supercritical plant operate at temperatures in the region of 600°C with next
generation units aiming for 650°C.The design requirements on steam turbine
rotors can be summarised as.!
• Ability to withstand centrifugal forces proportional to the rotational
speed.
• Ability to withstand transient thermal stresses at start-up / shut-down on
load changes.
• Good fatigue/notch toughness to withstand local stress concentrations
at blade attachment areas.
• Ability of medium pressure rotor to withstand creep loading due to high
temperatures caused by double re-heat.
Historically, for cyclic operation at steam temperatures up to 550°C,
1%CrMoV steels are preferred for the high temperature rotors due to their
creep resistance and 3.5NiCrMoV steels are preferred for low temperature
rotors due to their superior fracture toughness and through hardenability.
309
The initial drive towards higher steam temperatures for improved efficiency
concentrated upon the use of available creep resistant austenitic materials.
However, these materials introduced significant problems, thermal fatigue as
a result of low thermal conductivity and a high coefficient of thermal
expansion, susceptibility to stress corrosion cracking and cost.
The critical components in the turbine train with respect to creep loading
are the HP and IP rotors. The 9-12%Cr steels were developed in the late
1950s2 to satisfy the operating requirements for steam temperatures up to
500°C and have become the candidate material for 600-650°C conditions.
More recently COST 501, a European collaborative development pro-
gramme has investigated the use of 12%CrMoV materials for use as rotor
materials in either supercritical or combined cycle plant, mainly concentrating
on boron additions to improve high temperature properties. In 1987 the
project was expanded to investigate the effects of N,Nb,Mo and W.
Manufacturing trials were undertaken to produce full scale rotors in a
candidate 12%CrMoVNbN material. One rotor was produced using the above
base plus a 1%W addition by Saarstahl using the ESR process- whilst one
containing Mo,Nb and N2 was produced using modified secondary steel-
making processes by Forgemasters Steel and Engineering Limited+ This
composition, designated Rotor F, was used as the base to investigate the effect
of a carbide powder addition on the mechanical properties of an advanced
12%Cr rotor steel.
THE MICROSTRUCTURE OF 12%CrMo VNbN STEELS
The stability of carbides in a martensitic steel has been an area of much

research and is summarised in a review by J. Nutting.f The long term
microstructural stability of 9-12%Cr steels has also been investigated by V.
Foldyna et al.6,7 The general understanding is that in a 12°/oCrMoVNb steel the
initial microstructure is that of tempered martensite with fine M2X precip-
itates evenly distributed throughout the matrix with coarser M23C6 carbides
precipitated onto the prior austenite grain boundaries and martensite lath
boundaries. During exposure at 600°C the M23C6 coarsens rapidly at first but
then at a reduced rate. The M2X precipitates dissolve and are replaced by
secondary MX particles. This phase is also unstable and breaks down to form
a CrVNb rich nitride, Cr(V,Nb)N which is designated as Z phase. Dependent
upon the Mo content of the material laves phase (Fe2Mo) can also form
reducing the solid solution strengthening effect of Mo in the matrix.
The deliberate addition of nitrogen to the above alloy can be beneficial in
producing VxC and VN precipitation during tempering or exposure. The VN
is as effective as MX phase in improving creep properties.
The addition of Nb to a V containing steel is detrimental above 0.1°10 as it
reduces the amount of nitrogen in solid solution and therefore limits the
12%CRMoV HIGH TEMPERATURE TURBINE STEEL 311
amount of VN precipitation. Aluminium also has this same effect and

therefore its level is normally controlled to below 0.010%. A small quantity of
Nb in the range of 0.04-0.1% is however useful to control austenitic grain
size.
NEXT GENERATION STEELS
The next generation steels for operating temperatures up to 650°C are based
upon the additions of W,Co and B.B Increasing the Mo equivalent (%Mo +
O.s%W) and reducing carbon has been beneficial. The addition of B refines the
M23C6 by replacing up to 50°10 of the carbon. Boron is also known to segregate
on grain boundaries and stabilise them. As B has a high affinity for nitrogen
the nitrogen content is reduced or tied up by the addition of Ti. The addition
of Co improves solid solution hardening and acts as an austenite stabiliser
therefore assisting in the prevention of delta ferrite.
Summary of Current Research

The general aim of all development work in the field of 9-12°loCr steels is to
develop a material with the following properties:
1. Produce a martensitic structure with no appreciable B ferrite content.
2. Achieve a high dislocation density
3. Contain a stable distribution of carbides
4. Contain a high content of solid solution strengthening elements.
As mentioned previously the main problem with all of the current candi-
date materials is the stability of the carbides during creep exposure. The
Oswald ripening of carbides occurs generally in accordance with:
In Cr == 2V-y
c, rRT
where C, the solute concentration in the solvent when the particle has a radius
of curvature r.
C, is the solute concentration in the solvent when the particle has an
infinite radius of curvature, ie., a planar interface.
V is the volume/Mol of the dispersed phase
is the interfacial energy between the particle and the matrix
"y
R is the gas constant

T is the temperature in OK
In order to stabilise particles they should have a very low interfacial energy.
One way of producing a low interfacial energy is to introduce stable carbides
to the melt in the form of a powder.
THE USE OF FeWTiC
FeWTiC is a tungsten, titanium carbide (WTi)C produced by London &

Scandinavian Metallurgical Co Ltd. using a self propagating high tem-
perature synthesis technique. The carbide size is controlled by production
parameters and is generally supplied in the range 1-10 J-Lm.In order to allow
introduction of the carbide to liquid steel the carbide is encased in an iron
matrix to a carbide volume fraction of 75%. The resulting powder is crushed
and sieved to give granules of approx. 0.5 mm dia. suitable for adding to a
molten bath. The dissolution of the Fe(WTi)C on wetting occurs by melting of
the iron binder and distribution of the carbide particulates into the steel bath.?
The proportion of Wand Ti in the carbide is controlled in order to balance the
density of the particulate to that of the molten steel.
This investigation covers the addition of 1%, 3%, 5% FeWTiC to a
12%CrMoVNbN matrix, Rotor F.4 In addition a melt containing the base
chemistry with an addition of 0.9%Ti and 0.2%C has been produced to enable
the difference between adding stable particles of TiC and the precipites
produced by the addition of Ti to the matrix to be determined. A control melt
(0% FeWTiC) has also been produced to enable correlation to the full size
rotor trial data.
Laboratory vacuum induction melted ingots were produced in an 18 kg

furnace and subsequently poured into a 94/64 mm split cast iron mould. The
procedure consisted of melting the base charge with sufficient carbon to allow
refining by vacuum carbon deoxidation. Once refined the reactive ferro alloys
FeSi, FeV were added. An over-pressure of argon gas was then introduced
prior to the addition of Mn and high nitrogen FeCr. After a refine period the
FeWTiC powder was added via an airlock/bulk charger system in two
separate additions. A hold period of 15 minutes was given prior to tap. After
casting a slice was taken from the bottom of the ingot for analysis/micro
examination. The remaining material was hammer forged to 19 mm dia. test
bar. Heat treatment calibration trials were conducted on the control melt
L0159 in order to determine a tempering temperature to produce strength
levels in the small diameter test bar similar to that achieved in the full size
rotor.
In addition to the control melt, 10/0,3% and 5% FeWTiC additions were
produced. Allowance was made for the 0.95% free carbon contained within
the FeWTiC power when preparing the bulk material, to maintain the normal
amount of primary (thermal) carbide. In addition to the FeWTiC trial, a cast
containing 0.93%Ti, equivalent to the Ti addition made by a 3 FeWTiC %
addition was produced with increased carbon in order to promote TiC.

120/oCRMoV HIGH TEMPERATURE TURBINE STEEL 313
RESULTS
The analyses of the laboratory melts are given in Table 1, together with the
analysis of the full size rotor. The main deviations from the desired aim
analyses is that of aluminium and nitrogen. Although the carbon levels
reported are higher, this is due to the analytical method analysing for total C
i.e., C in matrix + Carbide.
The level of Al produced was surprising considering that the melt was
produced using pure metals and high quality ferro additions of known
chemistry.
The FeWTiC power was analysed for Al and was found to contain 0.36%.
Assuming that an Al figure of 0.005% is achieved in the matrix (see L0159) this
gave a total Al from the alloying additions of:
l%FeWTiC L0160 = 0.009%
3%FeWTiC L0161 = 0.016%
5%FeWTiC L0165 = 0.023%
It is apparent that just under half of the actual Al can be attributed to the
additions indicating that the balance came from the steelmaking refractories.
The nitrogen requirement for the control melt L0159 was just achieved with
a recovery of ,...,50%obtained. In the presence of the FeWTiC powder however
the solubility of nitrogen appears to be reduced with levels of N2 reducing
with increasing FeWTiC. There may be a contribution due to the increased
holding time/temperature encountered when adding in the FeWTiC powder.
The Ti containing melt L0164 also shows deviations in AI, C and N2 from aims
although Ti recovery was 1000/0with the aim level being achieved.
INGOT METALLOGRAPHIC EXAMINATION
Each ingot was examined prior to forge to determine the dispersion of the
FeWTiC particles within the melt. Examination revealed a good cleanness
was achieved in the control melt with a low level of oxides and Ti(C,N), (Fig.
1). The 1% to 5% FeWTiC casts demonstrate a fine dispersion of FeWTiC
carbides with occasional occurrences of TiCN particles associated with
carbide (Fig. 2.). The Ti bearing cast showed extensive dirty Ti(C,N) stringing,
(Fig. 3).
HEAT TREATMENT CALIBRATION
To enable comparison of the test data to that of the full size rotor F trial+ a heat
treatment trial was conducted on control melt L0159. Tensile blanks were
hardened for Ihr/1070°C/OQ followed by 4 hours temper in the range
600-72SoC. The results are shown in Table 2. The tempering temperature of
II)
o
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~~~~~~
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Of:'.,. \0 0 \0
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00 000000
00 000000
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000000
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000000
o OOf:'.,.~OON
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~ ~~~~~T"""'l
$-4
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l!J T"""'l crJ 0 T"""'l l!J cr;
T"""'l T"""'l T"""'l T"""'l T"""'l T"""'l T"""'l
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II) io II) II) II) II)
000000
OO"o:::t'l OOOOT"""'l 0'\
0000T"""'l0
000000
T"""'l1I)0f:'.,.l!J
~~~~~~
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OUuUU
]~~~~u
~~~~~,
<~~g;~~
Fig. 1 LOI59 control melt, as cast, unetched XIOO
Fig. 2 LOI60 IO/oFeWTiCmelt, as cast, etched XIOO
725°C was selected for the remaining laboratory ingots, after forging to %" dia.
test bar.
METALLO GRAPHIC EXAMINATION OF FORGED AND HEAT

TREATED BARS
The microstructure of the control melt was found to be completely martensitic

(Fig. 4). The FeWTiC containing melt also exhibited a completely martensitic
Fig. 3 L0164 base + Ti, as cast, etched X100
Table 2. Control Melt L0159 Heat Treatment Trial results

All Samples Hardened for 1 hour 1070°C then Oil Quenched.
Tempered for 4 hours at specified temperature then air cooled.
Tempering Temp °C Rp 0.2MPa RmMPa °/oEI %RA Hv
600 932 1078 17 65 353353

650 844 983 19 60 311320
700 794 928 19.5 65 308309
725 739 876 20 63 281281
Actual Rotor 731 872 18 54
Rotor treated as follows: Hardened 1070°C Oil Quenched

Tempered 570°C Furnace Cooled
Tempered 675°C Furnace Cooled
structure. The primary M2X precipitates were 70-150 microns dia./square.

The FeWTiC particles were semi-angular (Fig. 5), and in the size range <10-70
microns. Some slight banding of the FeWTiC was observed (Fig. 6).
The Ti bearing cast L0164 was found to contain a network of rounded TiC
precipitates mainly in the size range of 10-40 microns. There was also
considerable Ti(C,N) and associated oxide consisting of cuboidal precipitates
of 50-70 microns as stringers with an effective length of over 200 microns.
MECHANICAL PROPERTIES
The short term mechanical properties are presented in Table 3 and Fig. 7. The
control rotor F chemistry L0159 shows good agreement with results obtained
Fig. 4 L0159 control melt, forged + H.T., etched X400
Fig. 5 L0165 5 FeWTiC melt, forged + H.T., etched X400

%
from the full scale production rotor." The discrepancy between the charpy
impact values for the control melt and full size rotor reflects a section size
effect.
The l FeWTiC melt exhibited a reduction in tensile and proof strength
%
compared to the control melt but also showed a corresponding improvement

in impact toughness. The 3 FeWTiC addition cast was found to have very
%
similar impact properties to that of the control but still exhibited a slight
reduction in tensile strength. The 5%FeWTiC addition cast demonstrated a
reduction in impact toughness to 40J and a marginal increase in tensile
Fig. 6 L0161 3%FeWTiC melt, forged + H.T., etched X100
Table 3 Mechanical Properties
Actual
Rotor O%FeWTiC 1%FeWTiC 3%FeWTiC SOloFeWTiC Ti/C
Proof Strength (MPa) 731 739 562 592 644 281

UTS (Mpa) 872 876 766 817 908 462
°10 Elongation 16 20 22 19 16 28.5
Reduction of Area 49 63 62 53 34 71
Charpy Impact G) 39 78 103 80 34 9.9
Hardness (HB) 255 229 241 262 137
strength. The Ti bearing cast demonstrated a significant reduction in tensile

strength to almost half that of the control cast and exhibited very poor impact
values. The hardness results confirmed the effect of FeWTiC additions on
strength.
DISCUSSION
The short term tests conducted are somewhat surprising as it is normally

expected for tensile strength to increase with increasing volume fractions of
FeWTiCIOand for impact properties to reduce.
The reduction of strength and increase in toughness achieved with an
120/oCRMoV HIGH TEMPERATURE TURBINE STEEL 319
1000.....-----------------------
800
600
-.- Proof Strength (MPa)

400 -V- UTS (MPa)
---- Elongation ('Yo)
-<>- Reduction of Area ('Yo)
•.•••.• Charpy Impact (J)
.4.
100
.•..
50 0--
.:--- .--
. ' -<> ~
--'--<>, "... /
/0
'-.~
.
/
--
---------------
-·-···-------T-------·-.,-----...,.----,.-----.-----y------l
. - '.:...
----
.-----. -
Actual Rotor 0% FeWTiC t % FeWTiC 3% FeWTiC 5% FeWTiC Ti/C
Identification
Fig. 7 Short term mechanical properties
addition of 1 FeWTiC indicates that the FeWTiC powder is in some way

%
affecting the usual strengthening mechanisms in this alloy. Increased addi-

tions above the 1 level follow the usual trend predicted by the theory of
%
mixtures that strength and hardness increases in proportion to the second

phase. The reduction in impact properties with increasing FeWTiC additions
has been seen before in laboratory scale casts'? and is attributed to incomplete
dispersion of the FeWTiC. This is due to the small laboratory furnace having
no means of stirring the bath after the FeWTiC addition.
The FeWTiC carbides observed in the forged and heat treated alloy were
found to be semi-angular in appearance. The carbides in the original FeWTiC
powder are spherical, therefore the change in morphology is indicative of
some reaction between the (W,Ti)C and the liquid steel. The size distribution
of the particles however appears unaffected. This phenomena has been
observed previously? and appears to be normal in a low carbon matrix.
The reduction in strength with the initial addition of FeWTiC may be
caused by the Ti reacting with nitrogen in the liquid matrix to produce TiN.
This reaction reduces the soluble nitrogen available to form the sub micron
VN precipitates which normally decorate the martensite laths. At higher
levels of FeWTiC addition, the strengthening obtained by the introduction of
a second phase offsets the reduction caused by depletion of VN precipitate.
This is indicated by the Ti + C modified alloy L0164 which showed a
dramatic loss in strength. Using the same etching reagent for revealing
microstructure as used for the control and FeWTiC casts, no lath detail could
be produced in the martensite due to the lack of precipitation.
CONCLUSIONS
1. The addition of FeWTiC powder to an advanced 12Cr rotor steel has been
successful in laboratory trials.
2. Some change in carbide morphology was observed, however particle size
distribution was generally unaffected.
3. Addition of 1°loFeWTiC reduced tensile strength and increase impact
resistance but at 3°1oaddition properties similar to the base material were
obtained.
4. A 5°1oaddition gave an increase in strength but with an associated decrease
in impact resistance. This was considered to be due to the lack of stirring
facilities in the small laboratory furnace.
FURTHER WORK
A key requirement of any material operating in a high temperature environ-

ment is heat resistance. Further work is underway to examine the creep
properties of the FeWTiC containing steel for comparison with existing
10-12°/oCr steels.
REFERENCES
1. J. E. Bertilsson and B. Scarlin: 'Design Requirements and Materials for

Advanced Steam Turbines', High Ternperature Materials for Power Engi-
neering, Liege, Belgium, Sept. 1990,281-311.
2. D. L. Newhouse: 'Guide to 12Cr Steels for High and Intermediate Pressure
Turbine Rotors for the Advanced Coal Fired Steam Plant', EPRI Report
No. CS-S277, July 1987.
3. C. Berger, E. Potthast, R. Bauer and G. A. Honeyman: Development of High
Strength 9-12%CrMoV Steels for High Temperature Forgings, International
Forgemasters Meeting, Terni, Italy, June 1991.
4. G. A. Honeyman: '12°/oCrMoV Steels for Combined Cycle Plant Steam
Turbine Rotor Forgings', Materials for Combined Cycle Power Plant, 10-12
June, 1991, Sheffield, UK.
5. J. Nutting: 'The Structural Stability of Low Alloy Steels for Power Genera-
tion Applications', this volume, 12.
6. V. Foldyna, Z. Kubon, A. Jakobova and V. Vodarek: 'Microstructural
stability of Advanced 9-12% Chromium Steels', Creep Resistant Metallic
Materials, Proceedings of the 9th Int. Symposium, Hradec, Czech Repub-
lic, 23-26 Sept. 1997, 203-216.
7. A. Strang and V. Vodarek: 'Microstructural Stability Studies on a Creep
Resistant Martensitic 12CrMoVNb Power Plant Steel', Creep Resistant
Metallic Materials, Proceedings of the 9th Int. Symposium, Hradec, Czech

Republic, 23-26 Sept. 1996, 217-233.
8. T. Fujita: 'Future Ferritic Steels for High Temperature Service New Steels
for Advanced Plant up to 620°C', EPRI/National Power Conference, May
1995, London, UK, 190-200.
9. J. V. Wood, K. Dinsdale, P. Davies and J. L. F. Kellie: 'Production and
Properties of Steel - TiC Composites for Wear Applications', Materials
Science and Technology, 1995, 11 (12) 1315-1320.
10. L. Shaw: ALL VAC-SMP, Internal Correspondence.
The Effect of Heat Treatment on the
Properties of Forgings from Modified
Chromium Steels
A. JAKOBOVA, M. FILIP, V. FOLDYNA, V. VODAREK and
A.KORCAK*
Research and Development V1TKOVICE, a.s., Ostrava, Czech Republic
* Heavy Engineering V1TKOVICE, Ostrava, Czech Republic
ABSTRACT
The properties of chromium modified steels depend distinctly on heat treatment
parameters. In this paper the effects of normalising temperature and cooling rate on
microstructure and properties of steel 91 are reported. It has been shown that double
austenitising, i.e. quenching and normalising, results in a significant improvement of
proof stress and creep properties of steel 91. Microstructural investigations revealed
that microstructure after double austenitising was much finer than that after
conventional heat treatment. The results on microstructural evaluation in the course
of conventional and double austenitising heat treatments are reported. Micro-
structure is related to tensile properties at room temperature, Charpy impact energy
and creep properties.
1. INTRODUCTION
There are strong environmental and economic pressures to increase the

thermal efficiency of fossil fuel fired power stations. That is why much effort
has been devoted to the development of modified 9-12% chromium steels
with improved creep strength at 600°C. The advanced steels are needed
especially for critical steam turbine components including rotor forgings and
heavy castings.l-?
In recent years a great attention has been paid to the improvement of creep
resistance of steel 913 by increasing Mo and/or W contents.l-! optimising V,
Nb, and N contents-+" and adding Band Co.1,4,5,7,8Each of these modifica-
tions of chemical composition was more or less effective but the properties of
all modifications depended distinctly on heat treatment procedures.vl? In this
paper the effect of heat treatment of steel 91 on its properties and micro-
structure is discussed.
2. EXPERIMENTAL MATERIAL AND PROCEDURES
The chemical composition of steel 91 made in VfTKOVICE was as follows:

O.14%C, O.38%Mn, O.43%Si, 9.84%Cr, O.88%Mo, O.05%Ni, O.07%Nb, 0.240/0V,
322
EFFECT OF HEAT TREATMENT ON THE PROPERTIES OF FORGINGS 323
0.069 N. Both 20 mm bars and commercial forgings 470 mm in diameter were

%
used for heat treatment studies. Heat treatment variables included austenitis-
ing temperature and cooling rate from austenitising temperature. Double
austenitising procedure included quenching from 1200°C followed by nor-
malising at 1070°C and tempering.
The cooling rate was characterised by the cooling rate coefficient -v which
represents the logarithm of time in seconds for cooling down of material to
one half of the austenitising temperature. The cooling rates applied to
experimental material simulated the real cooling rates in the central part of
forgings with diameter in the range from 200 to 900 mm during cooling in
water, oil or air. The heat treatment variables are summarised in Table 1.
Table 1 Heat Treatment Procedures
Normalising Tempering
Heat Treatment Temperature, °C Cooling Rate, -v Temperature, °C
1040/1h 2.4, 3.0, 3.4, 3.9

Normalising + 1060/1 h 2.4, 3.0, 3.4, 3.9 760/2 h
Tempering
1080/1h 2.4, 3.0, 3.4, 3.9
Double Austenising + 1200/9 h/water
3.2,4.0 750/11h
Tempering (VI) 1070/10 h/air
Normalising and
1070.10h/ air 750/11h
Tempering (V3)
The effect of heat treatment procedures on material properties was evalu-

ated by comparison of tensile properties at room temperature, Charpy impact
energy and creep rupture properties at 600°C. Furthermore, detailed micro-
structural investigations were carried out in order to demonstrate micro-
structural evolution during heat treatment and creep exposure at 600°C.
Optical microscopy and analytical transmission electron microscopy studies
were conducted on heat treated material as well as on transverse micro-
sections taken from the fractured creep rupture testpieces. Electron micro-
scopy studies were carried out on carbon extraction replicas and thin foils.
Thin foil were prepared using a Tenupol twin jet electropolishing unit. Both
X-ray microanalysis and selected area diffraction were used for identification
of minor phases.
3. MECHANICAL AND CREEP PROPERTIES
The cooling rate from the austenitising temperature determines mechanical

properties at room temperature. For cooling rates up to -v = 3.4 we have not
observed a significant influence of austenitising temperature on tensile

strength, proof stress, elongation, reduction of area and Charpy impact energy.
Only for the slowest cooling rate -v = 3.9 mechanical properties were found to
be considerably affected by normalising temperature. Increasing austenitizing
temperature resulted in decreasing differences in mechanical properties
obtained in the whole range of cooling rates investigated. As expected softening
of normalised material increased with increasing tempering temperature.
Both normalising temperature and cooling rate have a distinct effect on the
transition temperature FATTsoand on a shift of this temperature. The effect of
cooling rate on the transition temperature decreases with increasing normal-
ising temperature, Table 2 and Fig. 1.
The results of mechanical tests at room temperature on material after
double austenitising treatment are given in Table 2, too. As evident this
regime of heat treatment resulted in significantly increased proof stress and
Charpy impact energy in comparison with conventional heat treatment.
Furthermore, improved creep resistance has been observed after double
austenitising. The steady state creep rate at 600°C/I00 MPa of material
Table 2. Mechanical Properties at Room Temperature
Heat Treatment Rpo,2 Rm As Z KV FATTso
MPa 0/0 J °C
1040°C -v=2.4
-v=3.0 535-568 718-754 21.8-23.6 228-240 -35
-v=3.4 67-72
+760°C/2 hi air -v=3.9 273 540 28.4 149 +65
1060°C -v=2.4
-v=3.0 561-570 731-753 21.7-23 221-229 -30
-v=3.4 70-71
+760°C/2 hi air -v=3.9 482 685 23 180 +10
1080°C -v=2.4
-v=3.0 569-631 751-798 20-22 209-240
-v=3.4 67-71 -30 -7 -40
+760°C/2 hi air -v=3.9 558 741 24 211
1200°C I water
+ 1070°C I air 619 756 20 69 222 +5
+750°C/air
1070°C/air
443 623 26.5 70 207 +3
+ 750°C/air
110
~
u
•.....• 90
T
C)
-v=3,9
." 70 T
0
~
~
50 T
<]
30 T
10 T
-10 T.
1020 1040 1060 1080 1100
Normalising temperature rOC]
Fig. 1 Effect of normalising temperature and cooling rate on LlFATTso
investigated, which had been heat treated by a standard procedure, was 8.2 X
10-10 sec" while in the case of material after double austenitizing this rate
reached 8.5 X 10-11 sec ". The established difference in steady state creep rate
proves the higher creep resistance of double austenitised material. The results
of creep tests at 600°C of steel 91 after conventional and double austenitising
treatments are shown in Fig. 2. The creep rupture strength at 600°Cjl0S has
been estimated to be about 15% higher for double austenitised material.
4. EVALUATION OF MICROSTRUCTURE
Creep resistant 9 to 12%Cr modified steels are usually used in the normalised
or quenched and tempered condition. The optimum austenitising tem-
perature depends on chemical composition of steels. The recommended
treatment for steel 91 is normalisation from 1040 to 1100°C.12With increasing
austenitising temperature increasing amount of minor phases dissolve in
austenite. Niobium is added to the modified chromium steels to retard the
austenite grain growth during austenitising. The solubility of niobium in the
matrix is very low and most primary NbX particles are not dissolved at
the solution temperatures up to 1100°C. Despite the benefit to strength, higher
temperatures produce coarser grain size and might develop delta ferrite in the
microstructure. 11, 12
The continuous cooling transformation (CCT) diagrams provide a sig-
nificant contribution to the understanding of transformation behaviour of
steels. An example of CCT diagram for steel 91 is shown in Fig. 3. As evident
austenite transforms in a wide range of cooling rates to lath martensite. The
10000
1000
100~~~~~~-+~~n---~r--+~-T'-rrH
10 100 1000
Stress []Y.[Pa]
Fig. 2 The results of creep tests at 600°C for commonly heat treated steel V3 (.) and
double austenitised steel VI (0)
formation of ferrite is significantly retarded. Martensite formed at inter-

mediate cooling rates exhibits a significant drop of hardness.P This hardness
decline is accompanied by a raise in M, temperature. Microstructural inves-
tigations revealed intensive precipitation of M3C particles in martensite laths
and especially in large plates."
AUSTENITIZING ,0tO°c
P91
900
800
CJ 600
~
.a~ sao
~
~ ~oo Ms
a
CJ '300
E-<
200
100
o--~~~~~~~~~~~~~~~~~~~
10' 102 10'3 101. 105 sec
I, ", , I , " ,
Time 1 2 I. 6 10 20· (°6010°200(00 1000 min

, , !, , , " ,
1 2 I. 6 10 201.060100 hours
Fig. 3 Continuous cooling transformation diagram for steel 91 (O.09C,8.3Cr,

O.84Mo, O.20V,O.06Nb, O.063N)
Tempering of martensite should be carried out near but still below ACl in
order to achieve a high stability of the microstructure.l+ At early stages of
tempering particles of M3C and M7C3 phases precipitate in the matrix. IS
However, those phases are at typical temperatures of tempering highly
unstable and they are very soon replaced by more stable minor phases. The
most important type of carbides in 9 to 12% chromium steels is M23C6 phase.
Particles of this phase nucleate predominantly at prior austenite grain
boundaries and along martensite lath boundaries.
During tempering particles of nitrogen rich phases precipitate in marten-
site, too. The type of minor phases depends on chemical composition of steels
and tempering parameters. In 12 Cr steels M2X particles form preferentially
%
at tempering temperatures below 700°C.16M2X particles usually have needle-

like morphology and preferentially nucleate on dislocations inside martensite
laths. Above 700°C MX phase precipitation is preferred.I" This phase is often
designated as secondary MX phase in order to distinguish it from undis-
solved NbX particles. The main substitutional solute in the secondary MX
phase is vanadium. Furthermore, it dissolves some niobium and chromium.
Particles of this phase nucleate preferentially on dislocations. It can be
speculated that inhomogeneous precipitation of both MX and M2Xphases is a

consequence of differences in dislocation density through the matrix."
In order to explain the differences in mechanical as well as creep properties
after heat treatment procedures investigated a detailed microstructural study
was undertaken. It was found that the cooling rate -v == 3.9 resulted in
formation of ferrite. In the case of austenitising temperature 1040°C austenite
transformed completely to the ferrite + carbide microstructure. Formation of
ferrite is responsible for a marked decline of mechanical properties of steel
investigated. The volume fraction of ferrite + carbide constituent in steel 91
after cooling at the rate -v == 3.9 decreased with increasing austenitising
temperature. No ferrite + carbide constituent was observed in material which
had been austenitised at 1080°C. The results of metallographic investigations
and mechanical tests indicate that optimum normalising and tempering
temperatures are 1080°C and 750°C, respectively. This regime of heat treat-
ment is beneficial for heavy forgings with very slow cooling rates in central
parts.
The effect of double austenitising procedure on microstructural evolution
of steel 91 was investigated in the as received state and after creep exposure.
Normalising temperatures 1050-1070°C which are typical for a conventional
heat treatment [V3] are high enough to dissolve completely M23C6 and
secondary MX particles but only a small fraction of NbX goes into solid
solution at these temperatures.17,18 In the course of subsequent tempering at
750°C M23C6particles precipitate mainly on austenite grain boundaries and
martensite lath boundaries. Furthermore, fine particles of secondary MX
phase precipitate on dislocations. Particles of this phase are thought to
contribute significantly to high creep resistance of chromium modified
steels.v''
The first high temperature austenitisation during double austenitisating
procedure (V1) supports dissolution of NbX precipitates. This results in a
significant coarsening of prior austenite grain size. Due to very low niobium
solubility in the matrix, NbX particles reprecipitate either during quenching
or in the course of the second austenitisation at lower temperature.l? A
pinning effect of such precipitates and a high density of nucleation sites in
lath martensite are in our opinion responsible for a pronounced austenite
grain refinement observed after the second austenitisation. Fine lath marten-
site microstructure results in high proof stress as well as a good level of
Charpy impact energy. Intensive dissolution of NbX at the first austenitising
temperature enhanced the amount of interstitial atoms in the solid solution.
An increased amount of nitrogen in the solid solution is a prerequisite for
intensive precipitation of secondary vanadium rich MX particles during
tempering and subsequent creep exposure.I" TEM investigations revealed
that the number of M23C6 particles per unit area was evidently higher in
double austenitised material. A number of M23C6particles was found inside
laths and/or sub grain. At the same time the number of MX particles was
Double quenching and tempering Common heat treatment
500x Optical micrographs 500x
O.5'pm O.5Jlm
TEM mi c r 0 g rap h s
Fig. 4 Material 91 - as received condition
higher in double austenitised material. Typical examples of microstructure of

steel 91 after heat treatment procedures investigated are shown in Fig. 4.
The effect of VI and V3 heat treatment procedures on microstructural
evolution during creep at 600°C was studied on following creep rupture
testpieces:
VI: times to rupture 198 hours (180 MPa) and 3556 hours (140 MPa)
V3: times to rupture 148 hours (140 MPa) and 4526 hours (110 MPa)
The results of TEM investigations indicate that creep resistance of double
austenitised material is higher due to an increased amount of secondary MX
particles and the precipitation of M23C6 particles in the finer form. High
density of particles of minor phases slowed down dislocation recovery and
the growth of subgrains. In double austenitised material a number of fine MX
particles decorated subgrain boundaries. It proves that fine MX particles

continued to precipitate during creep exposure. After about 3500 hours at
600°C large particles of Laves phase were identified in testpieces investigated
regardless heat treatment procedure.
5. CONCLUSIONS
It has been demonstrated that the optimum normalising temperature of steel

91 is 1080°C. Higher temperatures are not recommended because they
facilitate austenite grain coarsening and enhance the risk of delta ferrite
appearance in the final microstructure. Normalising at 1080°C results in a
high level of tensile properties at room temperature and the effect of the
cooling rate up to -v = 3.9 on values of Charpy impact energy and the
transition temperature is suppressed. This fact should be taken into account
mainly in the case of heavy forgings. The optimum tempering temperature is
about 750°C.
Proof stress as well as creep properties of steel 91 can be significantly
improved by double austenitising heat treatment. The beneficial effect of this
treatment can be summarised as follows:
- progressive dissolution of NbX particles at 1200°C and reprecipitation of
this phase either during quenching or the second austenitisation
- refinement of the austenite grain size due to both the pinning effect of
NbX particles and a high density of potential nucleation sites in lath
martensite during the second austenitisation
- intensive precipitation of secondary MX particles in the matrix and on
subgrain boundaries during tempering and subsequent creep exposure.
ACKNOWLEDGEMENTS
The authors acknowledge the Grant Agency of the Czech Republic for
financial support of the research in the field of chromium modified steels
(grant No.106/9710100).
REFERENCES
1. C. Berger et al: Materials for Advanced Power Engineering, Liege, 1994, 47.
2. B. A. Marlow: Advances in Turbine Materials, Design and Manufacturing, The
Institute of Materials, London, 1997, 36.
3. V. Foldyna et al: Creep Resistance Metallic Materials, Hradec n M., 1996, 203.
4. T. Fujita, T. Sato and N. Takashi: Trans. ISI/, 18, 1978, 115.
5. V. Foldyna and Z. Kubori: Proc. Materials Engineering in Turbines and
Compressors, Newcastle upon Tyne, 1995,353.
6. Z. Kuban and V. Foldyna: Steel Research, 1995, 66, 389.

7. L. Karlsson: Acta metall. mater., 1988, 36, 13.
8. K. Spiradek et al: Proc. Materials for Advanced Power Engineering, Liege, 1994,
251.
9. J. Orr and D. Burton: ibid, 263.
10. A. [akobova et ai, Proc. Creep Resistant Metallic Materials, Hradec n. M.,
1996, 306.
11. C. Rasche, W. Bendick and J. Orr: ECSC Information Day,VDEh Dussel-
dorf, 1992, paper 2.2.
12. J. Orr, D. Burton and C. Rasche: ibid, paper 2.3.
13. O. Wachter: 'Investigation of the Properties of the 9% Cr Steel of the Type
9Cr-O.5Mo-l.8W-V-Nb with Respect to its Application as a Pipework
and Boiler Steel Operating at Elevated Temperarures'. PhD Thesis.
Technische Hochschule, Aachen, 1995.
14. J. Hald: TEM Investigations in New 9-12% Cr Steels for High Temperature
Applications, ELSAM ELKRAFT,The Technical University of Denmark,
1998.
15. H. K. D. H. Bhadeshia and J. W. Christian: Metallurgical Transactions, 1990,
21A, 767.
16. V. Vodarek: Unpublished Results, 1996.
17. J. Orr and D. Burton: Proc. Materials for Advanced Power Engineering, Liege,
1994, 263.
18. V. Foldyna, A. [akobova, V. Vodarek and Z. Kuban: ibid, 453.
Effect of Trace Elements on the Creep
Properties of Ferritic Steels for Steam
Turbine Rotors
Y. MURATA*, M. MORINAGA*, R. HASHIZUMEt,
T. AZUMA§, Y. TANAKA§ and T. ISHIGURO§
* Dept. of Materials Science and Engineering, Graduate School of
Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603,
Japan
t Materials Research Section, Technical Research Center, The Kansai Electric
Power Company Inc., 11-20 Nakoji 3-chome, Amagasaki 661-0974, Japan
§ Muroran Reseach Laboratory, The Japan Steel Works, Ltd., 4 Chatsu-machi,
Muroran 051-0006, Japan
ABSTRACT
For high performance high Cr ferritic steels designed for steam turbine rotors, the
roles of nitrogen, carbonitride forming elements and some impurity elements as they
affect the creep properties were elucidated. Also, it was found that there was a
relationship between Acl temperatures and the creep rupture lives of the steels. In
addition, a clear difference in the creep strength was observed between 650°C and
700°C.
1. INTRODUCTION
There has been a strong need to develop advanced ferritic steels which can be
utilised even in ultra super critical (USC) conditions of power plants.' We
have proposed a new method- for developing ferritic steels on the basis of the
DV-Xa molecular orbital calculations.v+ Two alloying parameters are
obtained from this calculation.I One is the d-orbital energy level (Md) of
alloying transition element, M, in bee Fe. This Md parameter correlates
with the electronegativity and the atomic radius of element, M. The other
is the bond order (Bo) which is a measure to show the covalent bond
strength between Fe and M atoms in bee Fe. The Bo parameter increases
with increasing covalent bond strength between atoms. It is known that
both the parameters change following the positions of elements, M, in the
periodic table. The usefulness of these two electronic parameters has
already been presented for the design of ferritic steels for turbine boilers- and
rotors.f
However, since this calculation has been performed mainly on alloying
332
EFFECT OF TRACE ELEMENTS ON THE CREEP PROPERTIES 333
transition elements, as yet the effects of non-transition elements and some

impurity elements are not known on the creep properties of ferritic steels. The
purpose of this study was to investigate experimentally the roles of nitrogen,
carbonitride forming elements and some impurity elements in the high-
temperature creep strength of the high Cr steels. In addition, the effect of Cr,
Re and Ni was reexamined on the creep properties.
2. EXPERIMENTAL STEELS
In this study, twelve kinds of ferritic steels, NJK1,...,NJKI2,were newly made

by modifying the composition of a high performance ferritic steel (TK4) for
steam turbine rotors developed in our previous study.> This TK4 steel was
designed following the criteria, 1.-5.
1. The 8 ferrite formation is suppressed using the electronic parameter,

Md. Here, Md is the compositional average of the Md value for each
transition element in the steel. This Md parameter gives a better
prediction for the 8 ferrite formation than the conventional Cr-equiva-
lent parameter.?
2. The Acl temperature should be as high as possible so as to improve the
creep resistance of steels.
3. The alloy composition should be selected so that the bond order, Bo,
becomes large, since the bond order probably correlates with the creep
properties.? Here, Bo is the compositional average of the Bo value for
each transition element in the steel.
4. The contents of Si and Mn in the steel are reduced as largely as possible
in order to improve the fracture toughness.
5. The compositional ratio of the MC-type carbonitride-forming elements
such as Nb and V to carbon and nitrogen is chosen to be about 0.45 in the
mol" unit.
The TK4 steel was modified and the chemical compositions and the
electronic parameters of the experimental steels are listed in Table 1 together
with the composition of TK4. Here, NJK2 had the composition close to that of
TK4. For these experimental steels except for NJK4, Cr content was adjusted
in order to obtain a good combination of refractory metals and also to
suppress the 8 ferrite formation in them. As a result, the experimental steels
had a similar values of the two electronic parameters, Md and Bo.
NJKl, NJK2 and NJK3 contained different nitrogen levels of 0.008%, 0.015%
and 0.027%, respectively. For NJK4, only the amount of Cr in NJK2 was
lowered to 10%. Also, NJK5, NJK6 and NJK7 were made by the addition of
0.02%Ti, 0.04%Zr and 0.05%Ta, respectively, to NJK2. In these steels the Nb
content was also modified slightly, following the criterion of 5. A part of Co in
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NJK2 was replaced by Ni and it was named NJK8. In addition, NJK9 and
NJK10 were made by adding 0.3 Re and 0.6 Re, respectively, into NJK2.
% %
All the NJK1"-'NJK10were high purity steels of very low concentrations of

impurities (e.g., As, Sn, Sb). Also, the concentrations of Si and Mn were
suppressed at the low level in them. In contrast to these ten steels, both NJK11
and NJK12 contained these elements and Ni in the commercial level, since Ni
is an element involved inevitably in the recycled scrap. In addition, NJK12
contained O.3 Re. This was prepared since Re may affect the alloy properties
%
in a different way when these various impurity elements coexist.
The 50 kg ingots of the twelve steels were prepared by vacuum induction

melting, and then processed by hot-forging in a conventional way. The slab
size was 35 mm thick, 130 mm wide and 1000mm long. In order to control the
grain size, each slab was heat treated at 1100°C for 5 hrs, followed by the
annealing at 720°C for 20 hrs. Subsequently, it was austenitised at 1070°C for
5 hrs and then tempered at 570°C for 20 hrs at the first step followed by the
second temper at 680°C for 20 hrs. The heating and cooling rates employed in
the present heat treatment were 20°C/h and 100°C/h, respectively. These
rates were set by assuming a thermal hysteresis which will undergo in the
central part of a large-scaled rotor. It was confirmed from microstructural
observations that no 8 ferrite was present in any experimental steels after
normalisation, in agreement with the prediction of the Md parameter. After
the second temper treatment they were cut into the size suitable for individ-
ual experiments.
The creep-rupture test and the Charpy impact test were performed in
conventional ways. Also, the Ac1 and the Ms temperatures were measured.
The precipitates in the steel were observed with transmission electron
microscopy.
4. RESULTS
4.1 Transformation Temperature and Fracture Toughness

The measured transformation temperatures of the present steels are sum-
marised in Table 2. The concentrational dependence of the Ac1 and the Ms
temperatures is shown in Fig. 1. There was similar dependence between these
temperatures irrespective of elements except for Nand Re. The results of the
Charpy impact test are shown in Table 3. Fracture appearance transition
temperature (FATT) was in the range of 79°C to 103°C, and all the steels
exhibited more than 100J for the upper shelf energy (USE). The FATT and the
Table 2 Measured transformation temperatures
Steel
NJKl 367 817

NJK2 353 813
NJK3 348 817
NJK4 370 819
NJK5 357 820
NJK6 358 826
NJK7 364 832
NJK8 330 804
NJK9 354 815
NJKI0 347 817
NJKll 348 802
NJK12 330 794
860 860
370
0
~
360~
~CD
Q.
350 ~
t-
U)
340 ~
330
370
Ni, masss Re, mass%
Fig. 1 The concentrational dependence of the Acl and the Ms temperatures

Table 3 Results of Charpy impact test
Steel FATT/OC USE/J
NJKl 79 169.5
NJK2 91 157.8
NJK3 85 102.9
NJK4 81 177.4
NJK5 83 157.8
NJK6 103 131.3
NJK7 101 158.8
NJK8 84 151.0
NJK9 91 140.1
NJKI0 97 141.1
NJKll 96 140.1
NJK12 101 142.1
USE changed with the concentration of alloying elements as shown in Fig. 2.

The steel number, X for NJKX(X = 1,...12), was put near the data point in Fig.
l(a),...(f)and Fig. 2(a),...(f),for comparison between the steels.
These alloying effects may be summarised for respective elements as
follows:
N: The content of N did not affect the Acl temperature, but lowered the Ms
temperature abruptly (Fig. l(a): NJKl, 2 and 3). This was consistent with
the well-known fact that both C and N decrease the Ms temperature. The
USE decreased with the N addition, but the FATT showed a maximum at
about O.018 N (Fig. 2(a).
%
Cr: Cr lowered both the Acl and the Ms temperatures (Fig. l(b): NJK2 and
4). The FATT increased and the USE decreased with increasing Cr content,
indicating that Cr is an element to make ferritic steels brittle (Fig. 2(b». This
may be related to the fact that the Cr addition increases the Bo value, i.e.,
the average covalent bond strength increases by the Cr addition into ferritic
steels.
Ti, Zr, Ta: The addition of a small amount of Ti, Zr or Ta increased largely
both the Acl and the Ms temperatures (Fig. l(c): NJK2, 5, 6 and 7). Since
these elements are strong M(CN) carbonitride-forming elements, they fixed
C and N atoms to the carbonitrides, resulting in the increase of both the
Acl and the Ms temperatures. Both Ti and Ta did not affect the USE value,
but Zr decreased it significantly. On the other hand, the FATT increased by
the addition of Zr and Ta, but decreased by the Ti addition (Fig. 2(c».
Ni: As is well known, the substitution of Ni for Co lowered steeply the Acl
temperature and also the Ms temperature, since Ni stabilises the austenite
phase more effectively than Co (Fig. l(d): NJK2 and 8). Also, the Ni
substitution for Co lowered both the FATT and the USE (Fig. 2(e». This
200
100
0
i=
J
ill 140 90
en «
:::> 12 11-
100
~ 140
W
(f)
:::> 12
80
0.0 0.4 0.0 0.2 0.4 0.6 HP OP OP

Ni, mass% Re, mass% 1m uri +Re
Fig. 2 The concentrational dependence of the FAIT and the USE
decrease of the USE may be due to higher Cr content in NJK8 than in

NJK2.
Re: The Ms temperature increased by the 0.3 Re addition, but decreased
%
by the 0.6 Re addition. In contrast to the Ms temperature, the Acl

%
temperature increased monotonously with increasing Re content (Fig. l(e):

NJK2, 9 and 10). Also, as shown in Fig. 2(e), Re acted to enhance the
brittleness, as Cr did.
Impurity: The presence of minor or impurity elements such as Mn, Si, P, As,
Sn, Sb and Ni in the steel lowered both the Acl and the Ms temperatures
(Fig. l(f): NJK2 and 11). Here, both Mn and Ni are austenite stabilising
elements, and hence they lowered the Acl and the Ms temperatures.
Furthermore, the Re effect in the steel containing commercial levels of
impurities was different in some way from the results obtained from high
purity steels (NJK9 and 10). Thus, the 0.3 Re addition decreased both the
%
Acl and the Ms temperatures (Fig. l(f): NJKll and NJKI2). Also, as might
be expected, the ordinary purity steels exhibited lower fracture toughness
than the high purity steels (Fig. 2(f»).
100 1000
t/h
Fig. 3 Stress rupture strength of the steels containing different N levels
100 1000
: -0- NJK2(650)
~ --e-- NJK2(700)
~ --6- NJK4~650)
200
-------------r-----l"--l-Tl! I !i
100
90
:t:m
cffiffil
1
\;I : : : 70
: : :::
··············t········t····t···t···t··i·t·t·i···············~·······t····t····!···~··i"·
80 L...-_-.&-_..&..- __ ...r...-a.--'--I •.•..•.•..•..
__ --"-----'_""'---"-.A... ...•.....•
100 1000
t Ih
Fig. 4 Stress rupture strength of the steels containing different Cr levels
4.2 Creep Rupture Test

A series of creep rupture tests was performed at 600°C, 650°C and 700°C in
the stress range of 109.8MPa to 360 MPa. Of these, some results of 650 and
700°C are shown in Figs 3-8. In every figure, the rupture lives of NJK2 are
shown as a reference. It was stressed here that NJK4 containing no Re had the
longest creep rupture life among the present steels and that the life was about
5 000 hrs at 650°C under the applied stress of 157 MPa, as shown in Fig. 4.
It is considered that the creep properties should be discussed using the data
of longer rupture lives. Therefore, the data of rupture lives obtained from the
lowest stress conditions of 157MPa at 650°C and of 110MPa at 700°C was
employed here in order to examine the concentrational dependence of the
rupture life. The results are summarised in Fig. 9(a)-(f).
········llTIJI! i!
::::: : .~~r-I
200
··~·~T'·
~~~~ 7qO·q~~
-lHlr:::::::::::;::::::r::rlllll!:::::::::::::I::::::+=::I:::J:::
100
90
80 ~~~----~--~~--~~----~~~~
100 1000
tlh
Fig. 5 Stress rupture strength of the steels containing carbonitride forming
elements, Ti, Zr and Ta
100 1000
-o-NJK2!65Ol
.. -e-NJK2700
~6~pt~
--6- NJK8 650
-.-NJK8700
200
· . .
············--y-·······r···rr·1~ ! 1 !
:· 7~·O·C·
: . :'::::
.... .. :
::
~ ~ ~ ~ ~ ~ ~:.
100
90
80 ~----~~--~~~~~----~~--~~
100 1000
tlh
Fig. 6 Stress rupture strength of the steels containing different Ni levels
100 1000 -0- NJK2(650)

r__---..-------.--r---r--r-"'T"'-r-I"_r__---i NJK2(700)
--A- NJK9(650)
--.t.-
NJK9(700)
-0- NJK10(700)
____ NJK10(650)
1000
tIh
Fig. 7 Stress rupture strength of the steels containing different Re levels
100 -0- NJK2(650)

p.;;;..-----.....-....---..---.--.~----I -e- NJK2(700)
-6- NJK11 (650)
--A- NJKll (700)
. . . -Q-NJK12(650)
200 ..............., , , t···I· 1••. j . ......... -ll-NJK12(700)
l~
100 i ····i i J.····i.. ~.. i·.~·i.···············i········
······i····~····
90
80 L-
··············+········~·····+···T··+·T··~··f+···············~·········i······~····1····
~~ __ ~~~~~ ~~ __ ~~
100 1000
tlh
Fig. 8 Stress rupture strength of the steels containing impurity elements in the
commercial level
102~~~1~~1~~1~1~~~1--~~1~~1~~1~~
0.01 0.02 0.03 10.0 11.0 0.0 O.O~L._ 0.04
N mass% Cr mass% Others
------1-------------1------ ------I------------:T.-----------:l"-------------l------ ------1-------------1-------------1---
~{:dr~~~:~~~~~~~~:::::
:::(er~::::~:::::::::~:::::::::::~::::::~:::::::::
::(f):::::::::::::::::::::::::::~
--------------------------- --------------------------9-----------------10----- ------------------1-~----------12--
i103::::~::::::::::~::::::::::~:
I I I I I I I 1 I
0.0 0.4 0.0 0.2 0.4 0.6 HP OP OP
Nit mass% Re mass% Impurit~ +Re
Fig. 9 The concentrational dependence of the creep rupture life. The open circles
and the closed circles represents the results of 650°C under the stress of 157Mpa
and 700°C under the stress of 110Mpa, respectively
It was found that the concentrational dependence of the rupture life at

650°C exhibited the reverse tendency at 700°C, except for Ni shown in (d). For
example, as the Cr content increased, the rupture life decreased at 650°C, but
increased at 700°C, as shown in Fig. 9(b). It was also true that the steel
containing impurities in the commercial level (NJK11) showed a longer
rupture life than the high purity steel (NJK2) at 650°C, but this trend reversed
at 700°C (Fig. 9(£). As shown in Fig. 9(c), this was also observed even in the
steels containing Re. These results are probably related to the temper
temperature, 680°C, employed in this study, as discussed below.
In the case of the N addition, the rupture life at 650°C increased monoto-
nously with increasing N content, but when the test temperature was raised
to 700°C, it exhibited a maximum in the range of 0.015%-0.02%N. Also, Ti, Ta
and Zr did not affect the rupture life at 650°C, but these elements decreased
the rupture life at 700°C.
5. DISCUSSION
5.1 Microstructural Evolution During Creep

There is a series of information on the microstructure which is generally
accepted in high Cr ferritic steels.
1. The microstructure is the tempered martensite.

2. In the tempered steel, M23C6 carbide precipitates significantly in the
matrix together with a small amount of Nb(CN). In fact, there was a
large amount of fine M23C6 carbide and a small amount of NbC carbide
in the tempered TK4 steel, as shown in Fig. 10(a).
3. M23C6 is stable below the Acl temperature but unstable above this
temperature."
4. The Laves phase appears in the specimen after holding for about
1000hrs at 650°C when the steel contains a relatively high level of the
refractory elements such as Mo and W, as shown in Fig. 10(b).
5. The critical temperature for the Laves phase precipitation is about
650-750°C.6-9
These microstructures change in high Cr ferritic steels in the course of creep

test at high temperatures. The possible changes are summarised as follows:
(I) Recovery of dislocation structures in the martensite lath.

(II) M23C6 carbide precipitation.
(III) M23C6 carbide dissolution.
(IV) Coalescence of M23C6 carbide.
(V) Transformation from M23C6 carbide to other phases (e.g., the Laves
phase and M6C carbide).
Fig. 10 Transmission electron micrographs of extraction replica taken from TK4

steel. (a) as temper, and (b) after creep rupture test at 650°C (tr = 1357h) under the
stress of 173 MPa.
In order to understand the observed creep strength, it is necessary to discuss

in detail these microstructural evolutions during creep.
5.2 Temperature Effect on Creep Strength

The microstructural changes are considered to depend largely on the Acl
temperature and the temper temperature as well. For example, when the
Fig. 11 Relationship between Ac1 temperature and creep rupture life at 650°C
under the stress of 157Mpa and 700°C under the stress of 110 MPa.
creep temperature is below the temper temperature, (II), (IV) and (V)
reactions probably occur in the steeL When the creep temperature is above the
temper temperature, the reactions (I) and (III) will occur in it. The temper
temperature employed in this study was 680°C, which was intermediate
between the two creep test temperatures, 650°C and 700°C.
In order to proceed with the above discussion, the rupture lives at 650°C
and 700°C are replotted against the Ac1 temperature, as shown in Fig. 11.
Interestingly, the rupture lives showed a C curve at each test temperature,
and the C curve at 650°C was reverse of the C curve at 700°C. This
phenomenon observed in Fig. 11 was supposed to occur due to the following
reasons:
i. When the steel is held at a temperature close to the Acl temperature, a
part of M23C6 carbide will dissolve into the matrix and also the
reaction (I) takes place, resulting in reducing the creep rupture life.
This is the case of the 700°C creep test of steels having low Ac1
temperatures (for example, the steels near the A region in Fig. 11).
ii. When the steel has a much higher Ac1 temperature than 700°C, the
reactions of (I), (IV) and (V) will occur quickly at 700°C. This
corresponds to the steels near the B region in Fig. 11.
iii. At 650°C the reactions of (II), (IV) and (V) occur mainly in the steeL
The reaction (V) makes the microstructure coarse, resulting in reduc-
ing the rupture life of the steeL This is probably related to the fact that
the creep rupture life becomes shorter than the extrapolated one from
the rupture lives measured under the high stress conditions (see Figs.
3-8). But the critical temperature of the reaction (V) is not so high, and
it is supposed to be about 650-750°C, which increases with the Ac1
temperature in high Cr ferritic steels. The reaction (V) shows a C curve
against time as the usual transformation-temperature curve does.
Therefore, when steels have a low Ac1 temperature, the creep tem-
perature of 650°C is very close to the critical temperature for the
reaction (V), leading to the slow reaction (V) and hence to the larger
rupture life. This corresponds to the steels near the C region in Fig. 11.
Also, when steels have high Ac1 temperatures, 650°C is still low for
the onset of the reaction (V), so that the reaction (V) must be slow.
Instead, since the reaction (II) takes place via carbon diffusion, it
occurs faster than the (V), so the life becomes longer. This is the case of
the steels near the D region in Fig. 11.
It may be said that the 700°C creep test corresponds to the test in the full
annealing conditions for steels, whereas the 650°C creep test corresponds to
the test in the midway to the full annealing. Also, it is stressed here that if
700°C is above the critical temperature for the Laves phase formation, then
the 700°C creep test will yield large microstructural changes in the steel, so
that such a creep test will be very different from the 650°C creep test, although
the temperature difference is only 50°C between them. In other words, the
700°C creep test is not a simple acceleration test of being extrapolated from
the 650°C creep test.
5.3 Effect of Carbide Forming Elements on Creep Strength

The explanation mentioned above in (i), (ii) and (iii) is based on the carbide
reaction, and hence when strong MC carbide forming elements exist in the
steels, the character of the rupture life will not obey in the same manner as in
(i), (ii) and (iii). This is the case of NJK5, NJK6 and NJK7 as marked by E and F
in Fig. 11. Since carbon and a part of nitrogen were fixed to the M(CN)
carbonitride in these steels, effective carbon and nitrogen contents in the
matrix decreased by the addition of the transition elements, Ti, Zr and Ta.
Therefore, the Ac1 temperatures become higher in these steels than in other
steels, resulting in the different rupture life-Ac1 curve from the others.
For the present steels, in the case when Ti, Zr and Ta were added, the Nb
content was reduced in order to keep a balance in the compositional ratio of
carbide-forming elements to carbon and nitrogen. Among three elements, Ti
and Zr are more effective in forming carbides than Ta. In view of the carbide
formation, the compositions of O.02mass%Ti, O.04mass%Zr and O.05mass%Ta
were estimated roughly to be O.023mol%, O.025mol% and O.15mol%, respec-
tively. Thus, Ta behaves as if its concentration is about a half of the other two
elements for the carbide formation. However, the Ms and the Ac1 tem-
peratures change reasonably with the Ta addition as shown in Fig. l(e). This is
because Ta has a similar atomic radius to Nb and if Ta coexists with Nb, a
complex carbide, (Nb,Ta)C is formed instead of NbC.I0 Furthermore, Zr tends
to form oxides strongly, and a part of Zr may form Zr02. This may be one of
the reasons why the USE decreased by the Zr addition.
6. CONCLUSION
The alloying and micro alloying effects on the creep properties were investi-
gated for high performance ferritic steels designed in our previous study. The
roles of individual elements including impurity elements in the creep proper-
ties were shown in a concrete way, in view of the microstructural evolution
during creep.
REFERENCES
1. W. Schlachter and G. H. Gessinger: High Temperature Materials for Power

Engineering 1990, E. Bachelet et ale eds. The Kluwer Academic Publishers,
The Netherlands, 1990, 1-24.
2. M. Morinaga, R. Hashizume and Y. Murata: Materials for Advanced Power
Engineering, Part I, D. Coutsouradis et ale eds. Kluwer Academic Pub-
lishers, The Netherlands, 1994, 319-328.
3. J. C. Slater: 'Quantum Theory of Molecules and Solids', vol. 4, McGraw-Hill,
New York, 1974.
4. M. Morinaga, N. Yukawa and H. Adachi: J. Phys. F:Met. Phys., 1985, 15,
1071-1084.
5. Y. Murata, M. Morinaga and R. Hashizume: Advances in Turbine Materials,
Design and Manufacturing, A. Strang et ale eds. The Institute of Materials,
1997, 270-282.
6. Y. Kadoya, R. Magoshi, H. Kawai, I. Tsuji, T. Tsuchiyama, S. Takeuchi and
Y. Yasumoto: Proc. of 5th Inter. Conf. on Clean Steel, Balatonfured,
Hungary, vol. 2, 1997.
7. J.Hald: Steel Research 1996, 67, 369-374.
8. H. Kutsumi, A. Chino and Y. Ishibashi: Tetsu-to-Hagane (J. Iron Steel Inst.
Japan), 1992, 78, 594-600.
9. Y. Funahashi, S. Tanimoto, N. Yoshida, Y. Matsumura and A. Sasaki: Tetsu-
to-Hagane (J. Iron Steel Inst. Japan), 1992, 78, 1472-1479.
10. Y. Murata, K. Suga and N. Yukawa: J. Mater. Sci., 1986,21,3653-3660.
Section 3A:
TURBINES
European High Temperature Materials
Development for Advanced Steam
Turbines
D. V. THORNTON* and K. H. MAYERt
* GEC ALSTHOM Large Steam Turbines Rugby, UK
t GEC ALSTHOM Energie GmbH, Nuremberg, Germany
ABSTRACT
The newly developed 9-10 /oCrMo(W)VNbN(B) steels permit an increase in inlet
0
steam temperatures of the order of 50-60°C over traditional 1%CrMo V and

12%CrMo V steels and thus an improvement in thermal efficiency of up to approx. 8%
with a simultaneous rise in live steam pressure. 'The development and qualification of
the new steels were essentially a result of the joint European research programme
COST 501. The improved creep strength was verified up to max. 80 000 test hours. The
greatest increase in strength results from further alloying with approx. 100ppm of
boron. Besides enhanced creep strength, the new turbine steels are characterised by an
increase in fracture toughness and low-cycle fatigue strength. Turbines featuring
these steels are thus suitable for operation in the medium-load and peak-load ranges.
The newly developed steels are already used in 12 new European power stations with
inlet temperatures of up to 600°C. The experience gained in the production of compo-
nents for these power stations is decidedly positive. The aim of current and future
tests is to achieve inlet steam temperatures of up to max. 650°C while continuing to
use mainly ferritic-martensitic steels for the rotor shafts and casings of the turbines.
Modern microstructural test methods are becoming increasingly important in further
enhancing the creep strength of the ferritic-martensitic steels.
INTRODUCTION
Growing economic demands on coal-fired power stations and ever increasing

environmental restraints will continue the drive towards more advanced
supercritical steam conditions. An improvement in thermal efficiency of the
plant improves the economic utilisation of fossil fuels and thereby reduces
both the plant life-time fuel costs and the release of 502 NOx and CO2
emissions. The latter is very significant in view of the world-wide agreements
to reduce CO2 emissions by 2010 and the fact that a 1 increase in efficiency
%
of an. 800 MW machine would lead to a life-time reduction in CO2 approach-

ing one million tonnes.
Natural evolution of steam turbine design, such as the application of high
performance controlled-flow blading which can lead to a 10% increase in HP
or IP turbine efficiency, together with optimisation of the overall steam/water
349
cycle and improvements in combustion and boiler design, have all led to a
gradual improvement in the efficiency of fossil power plant. However, the
most direct way of increasing efficiency is by increasing the main and reheat
steam temperature.' A 1% improvement in relative efficiency can be gained
from a 20°C rise in steam temperature, while an increase in the steam pressure
is also advantageous. Prior to 1990 the majority of central power station fossil-
fired plant operated at sub critical steam conditions, i.e. the steam pressure
was less than 221.2 bar. The main steam temperature was standardised
throughout the world at 540°C, although 565°C has for many years been the
standard for coal-fired plant in Europe, particularly in the UK with the main
steam pressure typically being 180 bar.
However, there were notable exceptions where high temperature plant
were built in the 1950s and 1960s. In Europe a considerable number of low
power rating (3 to 125 MW) plant for the chemical industry were built with
steam temperatures of 600°C and 650°C and pressures of 180 to 330 bar. A few
larger utility supercritical power plant were built in the USA (Eddystone I,
325 MW) and in the UK (Drakelow C, 375 MW) to explore this technology.
The exploitation of the greater creep strength of austenitic steels was critical in
the design of this plant and significant problems were experienced in the
application of these steels to thick section boiler and steam turbine compo-
nents. This resulted from their higher thermal expansion, low thermal
conductivities and low yield strength leading to high thermal stresses in start-
up and creep damage during relaxation as well as to thermal fatigue cracking,
dimensional instability and structural collapse. Some of these machines have
continued to operate, often with downrated steam conditions and operational
limitations, but interest in the application of advanced conditions was lost for
some time.
Further development of conventional thermal power stations aimed at
increasing thermal efficiencies was essentially precipitated by the second oil
crisis. EPRI initiated a study of the development of more economic coal-fired
power plant in 1978. This study re-awakened world-wide interest in
advanced steam plant and resulted in a number of research and development
studies involving US, Japanese and European steam plant manufacturers. The
research programmes focused on developing further the existing high-
temperature-resistant ferritic-martensitic 12%CrMoV steels for the produc-
tion of rotors, casings and chests, pipes and headers capable of operating at
inlet steam temperatures of up to 650°C. Figure 1 gives an overview of the
objectives and the participants of the international research programmes
aimed at the development of turbine materials.
The manner in which this development work has been conducted has
differed greatly from one country to the next. In the USA and Japan the
initiative came from the R&D institutes EPR! and EPDC of the power station
operators while in Europe the impulse was provided by the power plant
manufacturers in the context of COST programmes. In Japan specific alliances
EUROPEAN HIGH TEMPERATURE MATERIALS 351
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have been forged between each plant manufacturer and a steel maker leading
to each having their own alloys for the critical components. In Europe,
material developments have stemmed from collaborative studies. The COST
501 project involves 65 partners (manufacturers, utilities and institutes) from
13 European countries. The large number of collaborators has enabled a
significant amount of long-term high temperature creep testing to be per-
formed aimed at establishing a comprehensive database for the various
candidate materials. This is of particular importance when examining the
long-term stability of these newly developed steels which will determine the
load carrying capacity of the critical high temperature components and plant
reliability over the projected 200 000 hours operational life-time.
GOALS OF THE TURBINE MATERIALS PROGRAMME
Generally speaking, materials development work under the COST 501 pro-
gramme concentrated on the competitiveness of the new generation of fossil-
fired thermal power stations compared with the existing plant and the
combined gas and steam-fired power stations on the basis of the following
requirements:
- operational capability in the medium and peak-load ranges
- life expectancy of at least 200 000 h
- high availability
- long intervals between overhauls
- short overhaul periods
- short manufacturing times and
- competitive production costs
These requirements mean that the application of the newly developed
steels must not involve any additional risks. This implies, among other
things,
- long testing times to predict reliably the creep strength for 200 000 h
- high ductility of the steels under conditions of creep stressing
- high fracture toughness of the steels in the new condition and following
prolonged operational stressing
- satisfactory manufacturability of the new steels in terms of melting,
casting, forging, hot forming and welding
In contrast to boiler components, these requirements must also be met for
very large components. Figure 2 demonstrates the relevant dimensions with a
global comparison of the cross-sections of boiler tubes, headers, turbine rotors
and turbine inner casings. The alloying of the steels has to be tailored to the
manufacture of the components to ensure the strength, ductility and tough-
ness of all component zones.
14------ 220~mm ---~.I

Header I
Rotor Turbine Casing

up to 40 1 up 10 60 1
Fig. 2 Comparison of Sections of Steam Plant Components
~ 800------------------------------------~
~ !:! 0,8
.: E M: for 5 000 lCF·Cycles
~ E
E-
:J ~ 600
NO
c"r"
"C .::
s:: u
~~
.••• tn 400
C)tn
s:: Cb
~.c s::
Cb
en ~
~ {:.200
Q.~
:s :s
0::1:)
2"E
~LL
o
o 100 200 300 400 500 600
Temperature in °c
Fig. 3 Design Criteria for HP lIP Rotor Steels l%CrMoV
Figure 3 shows, by way of example, the essential material characteristics for

the design of HP and IP turbine rotors as a function of the component
temperature for the l%CrMoV steel used for inlet steam temperatures up to
approx. 560°C, viz.
- the fracture toughness
- the 0.2-limit
- the low-cycle fatigue strength and
- the 100 000 creep rupture strength.
The development of a new rotor steel must guarantee the presence of a
100 000 h creep strength of approx. 100 MPa at the max. possible rotor
temperature and that the other properties coincide at least with those of the
l CrMoV steel. These requirements also apply to the newly developed cast
%
steel grades; satisfactory casting and welding characteristics must also be

ensured.
Table 1 European 9-12%Cr-Rotor Steel Development of COST 501-1/2, Test Melts

Parameters N -Typ B -Typ W-Typ Mo/w- Typ Mo - Typ
C .072 .090 .10 .17 .12 .12 .16 .11 .13 .15 .13 .17 .10
Si .20 .30 .18 .07 .07 .08 .12 .05 .04 .06 .05 .05 .05
Mn .65 .57 .55 .06 .55 .48 .49 .51 .49 .49 .52 .55 .49
Chemical Cr 9.30 12.20 9.21 9.34 11.1 10.3 11.3 11.1 10.2 11.8 10.2 9.6 10.6
W .14 - - - 1.79 1.81 1.80 .51 .90 .46 -
Composition Mo 1.04 .98 1.50 1.55 .30 32 .32 1.13 1.10 1.10 1.49 1.14 1.89
Co - - - - - -
(wt - %) Ni .77 .20 .11 .12 .81 .81 .79 .80 .77 .54 .61 .62 .61
V .21 .24 .23 .27 .22 .20 .22 .20 .20 .22 .18 .12 .26
Nb .060 .070 .063 .064 .05 ..06 .06 .06 .014 .030 .06 .03 .49
N .11 .11 .015 .015 .06 .07 .06 .05 .07 .05 .05 .05 .05
(ppm) B - 180 100 - - <5 - 30 17 30
Austenitisation °C 1120 1080 1100 1020·1070·1120 1020·1070·1120 1070
Pre-tempering °C - 590 570 570 570
Tempering °C 690 720 730/780 700 685 up to 730 690 up to 720 720
0.2 - Limit MPa 655 734 692/440 651 630 up to 786 640 up to 750 579 554 544
FATTso °C -23 +20 20J/51J(1) +60 -8 upto+41 -5 up to +20 ·14 -14 +7
Creep Strength ® ©© ©© ® s ® e ©
(1) at room temperature
DEVELOPMENT OF ROTOR MATERIALS
Table 1 provides an overview of the chemical composition, heat treatment

data and mechanical properties of the test melts examined during short and
long-term tests in Rounds 1 and 2 of COST 501 which were aimed towards
inlet steam temperatures of 600°C. Compared with the classical 12°/oCrMoV
steel the C and Cr and V contents were, as a rule, reduced and further alloyed
in all cases with approx. 0.060/0 Nb. The Mo, W, N and boron contents in
particular were varied in specific cases.?
The melts were characterised in line with the specific further alloying of
nitrogen (N type), boron (B type), tungsten (W type), tungsten-molybdenum
(Mo/W type) and molybdenum (M type). In total, the tests involved 13
different melts which, in some cases, were in different conditions of heat
treatment.
The maximum creep strength values are exhibited by the boron-alloyed
melts and the lowest by the nitrogen and tungsten variants. Figure 4
illustrates examples of the creep strength of a number of test melts which was
determined at 600°C. For the comparative purposes the creep strength is also
shown for pipe steel P 91 and a test melt CT from the cast steel programme
which is alloyed with approx. 1% Mo and 1% W corresponding to the Mo /W
type (see Table 4).
It is characteristic of all tungsten-alloyed melts that they feature relatively
high creep strength below 10 000 h which, however, declines in the long-term
range. This is particularly pronounced in the case of those melts alloyed with
1.8°/0 W which all show a substantial drop in creep strength after approx.
10 000 h. This reduction is less pronounced in the case of melts alloyed with
EUROPEANHIGH TEMPERATUREMATERIALS 355
Test temperature 600 e

D
400~----------~----------~-----------
m
Q.
300~----------~----------~--------~
:iE
.5:
C, 200
.c
s::::
~In
e
:::l
0..
2 100
<>
Q.
B-Typ
e
CD
80 0 W-Typ P 91
(J
~ MoW-Typ (mean value)
60 0 Mo-Typ
40
100 1000 10000 100 000
Time to rupture in h
Fig. 4 Creep Rupture Strength of COST 501 Test Melts at 600°C
approx. 1 Wand approx. 1 Mo, their creep strength being more or less of
% %
the order encountered with pipe steel P 91 at 100 000 h. The boron-alloyed
variants BO and B2 exhibit the greatest stability and/ or highest creep strength
in the long-term range. Compared with the traditionally used 12 CrMoV, BO %
and B2 feature only approx. 9 Cr, 1.5% Mo and approx. 0.06% Nb and boron
%
contents of 180 or 100 ppm but no tungsten. The relatively stable behaviour
results mainly from the presence of the boron.
In order to ascertain the causes of the differing creep strength values and to
optimise the chemical composition of the most promising candidate steels,
extensive microstructural tests were carried out in Round 3 (e.g. 3-8). The
following state-of-the-art test methods were used:
- transmission electron microscopy (TEM)
- energy dispersive X-ray spectroscopy (EDX)
- atom-probe field-ion microscopy (APFIM)
- energy filter transmission electron microscopy (EFTEM)
- thermodynamic equilibrium calculations (Thermo calc)
- microstructural modelling of creep
The following microstructural parameters were systematically determined for
all the relevant materials in the virgin condition and following long-term
creep stressing:
- hardness
- grain size
- primary phase description (martensite, delta ferrite etc.)
- secondary phase description
- species (M23C6, MX, Laves Phase etc.)
- size distribution
- location (inter granular, cell boundaries etc.)

- chemical composition
- interparticle spacing
- dislocation (random, sub-cells etc.)
- cell size and shape
- dislocation density
Detailed results:
- The tungsten-bearing D melts contain no MX and M2X precipitations in
the virgin condition.
- Laves phases appeared in nearly all the steels; however in the tungsten-
free steels M, their appearance was delayed for several thousand hours
at 600°C and they were not observed at all in the creep specimens tested
at 650°C.
In the boron steel Laves phase was seldom encountered
- The boron-free steels with a relative high creep rupture strength exhibit a
higher volume fraction of MX and M2X particles, which increase sig-
nificantly during the creep process.
- The boron steels exhibit predominantly very stable M23C6 carbides and
very small MX precipitates with a low-volume fraction.
- In the boron steels boron was found in M23C6 in the virgin condition and
remained there during creep testing (APFIM).
MANUFACTURING AND TESTING OF PILOT ROTORS
Table 2 gives details on the chemical composition, heat treatment and

mechanical properties of the pilot rotors which have been produced up to
now and are undergoing testing. Three of them correspond to the boron-
Table 2 European 9-12%Cr- Rotor Steel Development of COST 501, Pilot Rotors
Parameters TypBO Typ B2 Typ FB4 Typ E TypF
Diameter mm 600 900 1200 1200 1200
C .10 .17 .18 .12. .11
Si .18 .07 .08 .10 03
Mn .55 .06 .76 .45 .52
Chemical Cr 9.21 9.34 9.20 10.39 10.2
W - - - .81 -
Comosition Mo 1.50 1.55 1.49 1.06 1.42
Ni .11 .12 .15 .74 .58
(wt-%) V .23 .27 .255 .18 .18
Nb .063 .064 .05 .045 .050
N .015 .015 .012 .052 .056
B .018 .010 .008 .0002 .001
Austenitisation °C 1080 1100 1100 1070 1070
Pre-tempering C 590 570 570 570
Tempering °C 730 700 700 690 680
0.2-Limit MPa 692 651 663 745 730
FATTso °C 20J(1) +60 +46 +5 +40
Creep Strength ©© e e © e © ©
alloyed steel type 'B' with outer diameters of 600 - 900 - 1200 mm. The other
two pilot rotors exhibit the chemical composition and heat treatment of those
test melts which in the case of test variants 'E' (1°1oMo/1°/0 W) and 'F' (1.5°/0
Mo) revealed the most favourable operating properties. With the exception of
the pilot rotor 'FB4', which was not manufactured until 1997, creep test results
for samples from these rotors are available up to approx. 80 000 h. The tests
likewise focused on fracture toughness and long-term embrittlement behav-
iour as well as low-cycle fatigue. 9, 10
Steel C Cr Mo W V Nb N B (Weight%)
a) .28 1.0 0.9 .30
.21 12.0 1.0 .30
.12 10.0 1.5 .20 .05 .05
.s:: .12 10.0 1.0 1.0 .20 .05 .05
C,
*
e) .18 9.0 1.5 .25 .05 .02 .010
r::::
~
Q5 200
e
:s .>
,c/d: X12CrMo(W)VNbN101(1)
g. MPa ->
n::
c..
e 100
Q)
0
.s::
0
0
0
0 0
~
0
500 550 600 650
Temperature in °C
Fig. 5 100 000 h Creep Rupture Strength of Turbine Rotor Steels
Figure 5 gives details on the creep rupture strength applicable to 100 000
hours and the chemical composition of both the traditionally used rotor steels
and the newly developed rotor steels." A creep strength of 100 MPa, decisive
for the sizing of the rotors, serves as a guide to assessing the steels. This
strength is achieved by the new steels in the 595°C to 620°C range.
Figure 6 illustrates, by way of example, a comparison of the fracture
toughness of the rotor type steels 'E' and 'F' in comparison to the traditional
rotor steels." The new HP and IP rotor steels lOo/oCrMo(W)VNbN feature a
substantially greater fracture toughness than the l°loCrMoV and 2%CrMo-
NiWV HP and IP rotor steels used up to approx. 550°C and, in addition, tend
to show greater fracture toughness compared with the conventional
l2°loCrMoV HP and IP rotor steel.
The gain in low-cycle fatigue strength of the newly developed rotor steels
100/oCrMoVNbN versus the lO/oCrMoVrotor steel is shown in the left half of
Fig. 7. The additional lower thermal expansion of the lO%CrMo VNbN steels,
compared with the low-alloyed steel, also has beneficial effects on the
permissible startup gradient of the turbine units. The right half of Fig. 7
demonstrates the relative gain in permissible rate of temperature change at
250 BODO
3/2
N/mm
200 12%CrMoV
~co 6000
a.
:E
.: 150
u
':Z 4000
VI
VI
Q) 100
c
.c
C)
:::s
0
I- 2000
e :::s
50
'0
~
u.
-1BO -120 -60 60 120

Temperature in °C
Fig. 6 Fracture Toughness of Turbine Rotor Steels
LOW-CYCLE FATIGUE STRENGTH ALLOWABLE RELATIVE RATES OF

SURFACE TEMPERATURE CHANGE
2,0
10 %CrMoVNbN
Hot Start
1,5
//
/ (550'C)
2.0 -r--------r-------,
eft.
.5 1,0
c
'i! 0,8 ~
en a:
m Q)
.~ 1.0
'0 0,6
I- 1U
a; 1 CrMoV
1 %CrMoV a:
(530'C)
0,4
0,3 o
102 103 104 400 450 500 550 600
Cycles to Crack Temperature in - C
Fig. 7 Low-cycle Fatigue Strength and Permissible Rate of Temperature Change of

lO/oCrMoVand lO%CrMoVNbN HP and IP Rotors
ca 800~==::_1_0_%_C_~_O~(~~V_Nb_N --_-_-_--~1o/c~oC~rM_o~v ~
a.
~~ 0,8
.: E
~ E
~ ~ 600
-- .....
----!:.~
-'---~--L:-----_.....
No
0-
'C .:
; .2 , v .----..
I
, .
,
0,2-Limit --~ •••••
,
:5 ~
tnVl
c Q)
400
~ "\\
~g,
C
I" ~
Q)
Fracture J',
~ {!. 200 ~ Toughness ~c ~',
~~
:::s :::s
,," Creep Rupture ,
tr:t; Strength 105 h "
Q,ca
~U:
o o 100 200 300 400 500 600
Temperature in °C
Fig. 8 Comparison of Design Criteria of HP and IP Rotor Steels Manufactured by

lO/oCrMoVand lO%CrMo(W)VNbN Steels
the rotor surface for a hot start for a specific shaft dimension for both these
types of steel.l?
On the basis of the design criteria of rotor steels, Fig. 8 demonstrates the
advances made with the 10 /oCrMo(W)VNbN steels in the form of an
0
overview for 600°C applications, the range of which has been extended
significantly not only at high and low component temperatures, but also by
means of increased permissible stresses.
NEW ROTOR TEST MATERIAL OF COST 501, ROUND 3
Table 3 provides data on the chemical composition, heat treatment and

mechanical properties of various melts which are being tested with a view to
Table 3 European 9-12%Cr- Rotor Steel Development of COST 502-3, Test Melts
Parameter Typ FB 2 Typ FN 2 Typ FN 3 Typ FN 4 Typ FN 5
c .13 .13 .13 .12 .11
Si .05 .12 .08 .06 .06
Mn .82 .96 .96 .86 .55
Chemical Cr 9.32 10.2 10.2 11.5 11.2
W - 1.91 1.85 1.81 2.63
Composition Mo 1.47 .54 .47 .48 .26
Co .96 - 1.98 1.90 2.66
(wt-& ) Ni .16 .25 .24 .275 .40
V .20 .23 .22 .21 .22
Nb .05 .065 .062 .065 .065
N .019 .042 .041 .060 .027
B .0085 .0047 .0058 .0049 .010
Austenitisation °C 1100 1100 1100 1100 1100
Pre-tempering °C 570 570 570 570 570
Tempering °C 710 685 710 685 710 700 720 715 735
O.2-Limit MPa 714 722 612 747 649 688 598 767 621
FATT50 °C +14 +7 -12 +10 +10 +70 +5
Creep Strength © © © e © © © e © e
producing rotor steels for inlet steam temperatures of 620°C. They differ from
the rotor steels of Round 2 in that they are all alloyed additionally with boron
and, with one exception, have cobalt contents of between 1% and 2.7%. Creep
test values up to approx. max. 20 000 h were obtained by the end of 1997. The
most favourable response has hitherto been shown by the tungsten-free FB 2
melt and the FN 5 variant which has a chemical composition corresponding to
HR 1200. Under the new COST Action 522 pilot rotors will be manufactured
from the most promising candidate materials.
CAST STEEL DEVELOPMENT
Table 4 shows details on the test materials which have been investigated up to
now in COST 501. In Round 2 100 mm thick plates were manufactured from
Table 4 European 9-12%Cr-Cast Steel Development of COST 501, Test Melts and
Pilot Components
Parameter TypC TypCT rve cr Typ CB 1 Typ CB 2 Typ CD 2 Typ CE 2 Typ CF 2
Component 100mm 100 mm 5t 5t 200mm 5t 150mm 5t
Plate Plate Pilot Valve Step Block Plate Step Block Plate Step Block
C .13 .13 .13 .12 .12 .06 .11 .10

Si .42 .33 .29 .24 .20 .31 .21 .31
Mn .58 .52 .60 .94 .88 .88 .86 .77
Chemical Cr 10.6 10.5 10.6 9.42 9.20 9.54 9.39 9.60
W - 1.01 .96 - - 1.94 .97 -
Composit: Mo 1.02 1.03 .96 1.50 1.49 .43 .98 1.32
Co - - - .93 .98 1.07 1.52 .93
(wt-%) Ni .87 .86 .91 .14 .17 .10 .15 .22
V .21 .23 .22 .24 .21 .21 .22 .23
Nb .07 .07 .08 .08 .06 .04 .05 .06
N .05 .05 .05 .02 .02 .045 .05 .04
B - - - .004 .011 .004 - -
Austenit. °C. 1100 1100 1100 1050 1100 1100 1100 1100
Tempering °C 730 730 730 730 730 740 730 730
PWHT °C 720 720 730 730 730 730 730 739
0.2-Limit MPa 582 592 586 483 547 512 513 553
FATTso °C 87 J(1) 42J(1) 45 20 32 22J(1) 10 33
Creep Strength @ @ @ @ @@ ? © e
melts C and CT and subjected to comprehensive testing. Both melts largely

correspond to pipe steel P 91 as regards their chemical composition, differing
only in that the CT melt still features approx. 1 tungsten. This type of melt %
was used to manufacture a 5t pilot valve after obtaining the results from creep
tests up to approx. 10 000 h and specimens from different cross-sections were
tested exhaustively by the following means:
- metallographic tests
- tensile and impact energy tests
- creep tests
- long-term embrittlement tests
- low-cycle fatigue tests
Except for the creep tests, which are being performed over a period of
40 000 h, all the tests have been completed. The long-term creep strength
which will be achieved at 600°C roughly corresponds to that of the P91 steel-
see also test result for CT in Fig. 4. As with the rotor steels this
10 /oCrMoWVNbN steel is better in all respects than the l CrMoV cast steel
0 %
which is used up to approx. 550°C.

The other test materials listed in Table 4 were alloyed so as to enhance creep
strength for 620°C applications. Optimisation was achieved by reducing the
nickel content, by further alloying with cobalt and, in some cases, by a boron
addition while, at the same time, matching the nitrogen content.
150-200 mm thick plates were cast as well as 5t step blocks with cross-
sections of 150-300-500 mm. They were subjected to the following tests:
- metallographic tests
- tensile and impact energy tests
- creep tests
- long-term embrittlement tests
The tests are more or less complete apart from the creep tests which have
reached the 20 000 h stage. The test material CB 2 in particular, which is
alloyed with 100 ppm boron, exhibits a distinct increase in creep strength. The
testing period for the CD 2 material, which corresponds to the pipe material
Nf616 except for the approx. 10/0 cobalt content, does not yet permit any
conclusions to be drawn.
NEW GENERATION POWER STATIONS
The success of the COST 501 materials development programmes is already

being reflected in the form of new orders for advanced fossil-fired thermal
power stations in Europe. Table 5 gives an overview of new power stations in
Table 5 European Thermal Power Stations with Advanced Steam Parameters
Steam Commissioning Fuel Output Live Reheat Thermal

Plant MW Steam Steam Efficiency
bar/oC °C 0/0
Skaerbaek 1997 Gas 400 290/582 580/580 49

Nordjyland 1998 Coal 400 290/582 580/580 48
Avedore 2000 Biomass, Oil 530 300/580 600 47
Schkopau A,B 1995 Lignite 450 285/545 560 40
Schw.Pumpe A,B 97/98 Lignite 800 268/545 565 40.6
Boxberg Q,R 98/99 Lignite 818 268/545 583 41.7
Lippendorf R,S 99/00 Lignite 900 268/554 583 41.7
Frimmersdorf Lignite 950 268/580 580 42.3
VKR (Study) 2002 Coal 500/900 270/605 625 47
RWE (Study) 2004 Coal 550 300/640 660
which the newly developed steels are being applied to achieve elevated steam
parameters.
The gas and coal-fired Danish power stations at Skaerbaek and Nordjyland
have a double reheat cycle with inlet steam temperatures of 580°C and a live
steam pressure of 290 bar. The Danish plant at Avedore, which is fired on
biomass and oil, features a reheat temperature of 600°C and live steam
conditions of 300 bar and 580°C.
In the case of a lignite-fired power stations, which only have a single reheat
cycle and, with one exception, are located in eastern Germany, the max.
reheat temperature is 600°C at live steam conditions of 270 bar and 580°C. The
positive response of power plant operators to the successful work being
carried out under the materials development programmes can also be seen in
the steam parameters of studies carried out by two German power plant
operators who invited comments from the manufacturers on the subject of
building thermal power stations with inlet steam temperatures of max. 625°C
or 660°C. Based on the present state of the art, a live steam temperature of
approximately 625°C can be achieved now.
The experience gained so far in the manufacture of components for the
above-mentioned power stations is decidedly positive. By way of example, a
steel foundry has already manufactured more than 40 large castings made of
the new steel grades.l- The production of turbine rotors has proceeded in a
similarly positive fashion.l'' The properties of the production components
correspond largely to those of the pilot components and the trial casts
determined in the research programmes. Long-term creep tests on specimens
from production components were commenced in 1996 under a VGB pro-
gramme in order to obtain a more extensive database for future power plants
with even higher steam parameters.
A new COST programme expected to start in 1998 is geared towards
achieving an inlet steam temperature of 650°C based on the predominant use
of ferritic-martensitic steels.
Other joint private and national programmes are concerned with
- determination of the creep strain behaviour
- long-term low-cycle fatigue behaviour
- multi-axial creep behaviour
- creep ratchetting behaviour
- creep and creep fatigue crack behaviour
of the newly developed steels.
SUMMARY AND CONCLUSION
During the last 15-20 years ferritic-martensitic 9 to 12% chromium steels have
been developed under international programmes which permit inlet steam
temperature for fossil-fired thermal power stations up to approx. 610°C,
pressures of up to about 300 bar and reheat temperatures up to about 625°C.
The result has been improvements in thermal efficiency of around 8% versus
conventional steam parameters.
The objectives of the European research programme COST 501, which
today involves 65 partners from 13 different European countries, have been
coordinated so that the turbines of the new generation of power stations allow
the same flexible and cost-effective operation as the conventional units.
The new steels are already being used in 12 European power stations with
inlet steam temperatures of up to about 600°C. The experience which has been
gained in the production of components for these power stations is extremely
positive. The properties of the production components correspond almost

entirely to those of the pilot components of the research programmes.
Current and future tests will be aimed at achieving inlet steam tem-
peratures up to max. 650°C, using mainly ferritic-martensitic steels for the
highly stressed turbine components.
REFERENCES
1. B. A. Marlow: 'Advanced Steam Turbines', Advances in Turbine Materials,

Design and Manufacturing, The Institute of Materials, London, 1997,
36-45.
2. C. Berger, R. B. Scarlin, K.-H. Mayer, D. V. Thornton and S. M. Beech,
'Steam Turbine Materials: High Temperature Forgings', 5th Liege COST
Conference - Materials for Advanced Power Engineering 1994, Liege,
Belgium 3-6 October 1994.
3. R. W. Vanstone, H. Cerjak, V. Foldyna, J. Hald and K. Spiradek: 'Micro-
structural Development in Advanced 9-12%Cr Creep Resisting Steels -
A Collaborative Investigation in COST 501/3 WPll', 5th Liege COST
Belgium, 3-6 October 1994.
4. K. Spiradek, R. Bauer and G. Zeiler: 'Microstructural Changes during the
Creep Deformation of 9%Cr-Steel', 5th Liege Conference - Materials for
Advanced Power Engineering 1994, Liege, Belgium, 3-6 October 1994.
5. S. Straub, D. Henes, P. Polcik, W. Blum, K.-H. Mayer and J. Hald: 'Vergleich
der Mikrostruktur der martensitischen Stahle X16CrWMoVNbN 11 2,
X12CrMoWVNbN 10 11 und X18CrMoVNbB 9 1 nach Zeitstandbean-
spruchung', 19. Vortragsveranstaltung Langzeitverhalten warmfester Stahle
und Hochtemperaturwerkstoffe, Verein Deutscher Eisenhuttenleute
(VDEh), Dussledorf, 1996.
6. L. Lundin: 'High Resolution Microanalysis of Creep Resistant 9-12%
Chromium Steels', Thesis for the Degree of Doctor of Philosophy, Depart-
ment of Physics, Chalmers University of Technology and Coteborg
University, Sweden, 1995.
7. H. Cerjak, P. Hofer and B. Schaffernak: 'Beitrag zur Quantifizierung der
Entwicklung betriebsedingter Ausscheidungen in neuen 9 bis 12%Cr-
Stahlen', 20. Vortragsgesellschaft Langzeitverhalten warmfester Stahle und
Hochtemperaturwerkstoffe, Verein Deutscher Eisenhiittenleute (VDEh),
Dusseldorf, 1997.
8. J. Hald: Berechnungen mit dem Programm THERMOCALC, Department of
Metallurgy, Technical University of Denmark, Lyngby, Denmark 1996.
9. K.-H. Mayer, W. Bendick, R.-U. Husemann, T. Kern and R. B. Scarlin: 'New
Materials for improving the Efficiency of Fossil-Fired Thermal Power
Stations', VGB Power Tech 1/98, 22-27.
10. D. V. Thornton and K.-H. Mayer: 'New Materials for Advanced Steam
Turbines', Advances in Turbine Materials, Design and Manufacturing, The
Institute of Materials, London, 1998, 203-226.
11. K.-H. Mayer and H. Konig: 'Creep-Fatigue Behaviour of Newly Devel-
oped Heat-Resistant 9-10 /oCrMoVNbN Turbine Steels', International
0
Conference Creep Resistant Metallic Materials, Hradec and Moravici,

Czech Republic, 23-26 September 1996.
12. A. N. Patterson, G. Simonin and H. Neft: 'Steam Turbines for Advanced
Conditions', GEC ALSTHOM Monte Carlo Conference, 1994.
13. R. B. Scarlin, C. Berger, K.-H. Mayer, D. V. Thornton and S. M. Beech:
'Steam Turbine Materials: High Temperature Castings', 5th Liege COST
14. F. Schuster, A. Buberl, R. Hanus and H. Cerjak: 'Erfahrungsbericht tiber
die Herstellung von Turbinen- und Ventilgehausen aus den neuen 9%Cr
StahlguJ3sorten G-X12CrMoWVNbN 10 11 und G-X12CrMoVNbN 9 I',
Tagungsbericht VGB-Konferenz Werkstoffe und Schweifltechnik im Kraft-
werk 1996, 8-9 October 1996, Cottbus, Germany.
15. M. Taylor and D. V. Thornton: 'Experience in the Manufacture of Steam
Turbine Components in Advanced 9-12% Chromium Steels', Inter-
national Conference on Advanced Steam Plant - New Materials and Plant
Design and their Implications for Future CCGT and Conventioanl Power
Stations, London, UK, 21-22 May 1997.
Manufacturing and Properties of 2%Cr
Family Steels for a Large HP-LP Rotor
Forging
T. NAKADA, T. TSUCHIYAMA, M. MIYAKAWA,
O. MATSUMOTO, H. NAKASHIMA, O. ISHIYAMA and T. ABE
Steel Casting and Forging Plant, Kobe Steel, Ltd. 2-3-1, Shinhama, Arai-cho,
Takasago City 676-8670, Japan
ABSTRACT
Two large high pressure (HP)-low pressure (LP) combined rotor forgings were
manufactured from 2.5Cr1.2Mo1.5NiV. A HP-LP combined rotor of maximum size
rotor forging with 1862mm diameter in the LP section was manufactured from 2.
25CrMoV. This rotor forging had a 0.2% yield strength of 735MPa with a FATT of
6°C in the surface of barrel of the LP section. A second production rotor forging of
1625mm diameter had a 0.2% yield strength of 830MPa with a FATT of 36°C in the
centre of the LP section.
Both rotors show a comparable creep rupture strength with CrMo V steel in the HP
section.
1. INTRODUCTION
A HP-LP combined turbine had been widely used in combined cycle

generation. A combination HP-LP rotor forging is required to have good
creep rupture properties in the HP section and a high yield strength and
toughness in the LP section. Recently, a diameter requirement of rotor
forgings has steadily increased to cope with the increases in the turbine
output. It is difficult to get to the required high strength and toughness in case
of rotors of more than 1600mm diameter. Therefore, HP-LP combined rotors
tend to be manufactured in 2CrMoNiV steels instead of CrMoV steels. A
2Cr1.7Mo1.5NiV steel with good mechanical properties and creep rupture
strength for a HP-LP combined rotor forging has previously been devel-
oped.' The new 2.5Cr1.2Mol.5NiV steel was developed to further improve
the properties.' A production rotor forging with 2.5Cr1.2Mo1.5NiV steel was
manufactured and showed excellent mechanical properties for LP section and
got a comparable creep rupture strength with CrMoV steel in the HP section.
Kobe steel made a HP-LP combined rotor forging with the maximum
diameter with 1862mm from 2.25CrMoV steel. This paper describes the
results of production rotors which were manufactured from 2.5Crl.2Mo-
1.5NiV steel and 2.25CrMoV steel.
365
Heat Treatment)
STEEL INGOT WE IGHT MAX. ROTOR D i a.

A 89ton l/J 1625
I--- 2.5Cr1.2Mo1.5NiV
B 73ton l/J1417
C 2. 25CrMoV 122ton l/J 1862
Fig. 1 Manufacturing process of HP-LP combined rotor forging
2. MANUFACTURING PROCESS FOR HP-LP COMBINED ROTOR
The manufacturing process of the production HP-LP combined rotor forging

is given in Fig. 1. The selected raw material was melted by basic electric
furnace and the molten steel was refined by the vacuum carbon deoxidation
(VCD) method. The ingot was forged on a 13 000 ton press, subsequently a
preliminary heat treatment was performed.
To satisfy different required mechanical properties in the HP and LP
sections, a differential heat treatment was applied. Figure 2 shows the
schematic illustration of the differential heat treatment. The quenching
temperature and the tempering temperature in HP section and LP section
were changed. Figure 3 shows the pattern of differential heat treatment.
3. MANUFACTURING RESULTS
3.1 Manufacturing results of 2.5Cr1.2Mo1.5NiV Rotor Forging

3.1.1 Chemical Composition
The chemical composition in various positions of the forging with a thickness
of 1625 mm in the LP section are given in Table 1. The chemical compositions
were uniform over the entire sample. The impurities of P, S were of a
sufficiently low level.
MANUFACTURING AND PROPERTIES OF 2%CR FAMILY STEELS 367
Heating Process Quench i ng Process Temper i ng Process
Quench ing (Q) Temper i ng (T)

HP 9500e 653°e
A
LP o
9l0 e 6240C
HP 9500e 6600e
B
LP o
9l0 e 6300e
HP 955°e ssrc
C
LP sure 635°e
Fig. 2 Differential heat treatment
HP : To
HP : TT
LP : TT
Quenching Tempering
Fig. 3 Quality heat treatment of HP-LP combined rotor forging
3.1.2 Microstructure
Figure 4 shows the microstructures in various positions of the forging with a
diameter of 1625mm. The microstructure in all positions was bainite; ferrite
was not found. The grain size was 4-5 in ASTM number in the HP section and
8-9 in the LP section. The grain size in the centre of the barrel in the LP
section was 6.
(Top)
HP LP
~ (Bot. )
•• S3 S2
,-
85
84
iii
~i
-e. °1 81
r -s.
C2 Cl
l
Table 1 Chemical composition of 2.5Cr1.2Mo1.5NiV with 1625 mm Dia.
(unit: mass%)
C 5i Mn P 5 Ni Cr Mo V
Ladle 0.24 0.05 0.45 0.005 0.001 1.45 2.42 1.15 0.25
51 0.24 0.06 0.43 0.005 0.001 1.43 2.46 1.14 0.23
52 0.25 0.06 0.43 0.004 0.001 1.44 2.48 1.12 0.23
53 0.25 0.06 0.44 0.004 0.001 1.45 2.48 1.13 0.23
54 0.25 0.06 0.44 0.005 0.001 1.43 2.47 1.15 0.24
55 0.25 0.06 0.44 0.004 0.001 1.46 2.52 1.15 0.24
C1 0.24 0.06 0.43 0.005 0.001 1.43 2.47 1.15 0.24
C2 0.24 0.06 0.43 0.004 0.001 1.40 2.45 1.12 0.23
(Top)
---I------.;~.LP
HP ...•.•• (Bot. )
S3 S2
S4
GS 4.3 GS 5.6 GS 8.3
Fig. 4 Microstructures at various locations of 2.5Cr1.2Mo1.5NiV forgings with

<1>1625
MANUFACTURING AND PROPERTIES OF 20/oCR FAMILY STEELS 369
Table 2 Mechanical properties of the forging with 1625mm diameter
0.2°/oP5 T5 E1 RA vE20 c
0 FATT
(MPa) (DID) (J) (OC)
51 T 778 895 20 72 171, 176, 174

52 T 777 906 19 71 195, 187, 195
S3 T 788 900 20 74 187, 190, 192
L
P L 816 931 19 69
Cl
R 136, 122, 162 5
L 821 946 16 61
C2
R 39,42,52 36
H 54 T 686 814 19 72 159,174,187

P 55 T 694 821 18 69 82,93,82
*T: tangential, R: radial, L: longitudinal
3.1.3 Mechanical Properties

The mechanical properties of the forging with a diameter of 1625mm are
given in Table 2. The FATT in the centre of the barrel's LP section was +36°C
with a 0.2% yield strength of 834 MPa.
Table 3 shows the mechanical properties of the forging with 1417mm
diameter. The FATT in the journal centre of the LP section was -19°C with a
0.2% yield strength of 778 MPa.
These results showed enough high strength and excellent toughness for a
large HP-LP rotor forging.
3.1.4 Creep Rupture Strength

Figure 5 shows the results of the creep rupture strength of the surface in the
HP section have been plotted with the Larson-Miller parameter. The creep
rupture strength of 2.5Cr1.2Mo1.5NiV steel and 2.25CrMoV steel were
comparable to that of CrMoV rotor forging. The rupture elongation was
20-49% and the reduction in area was 80-96%. It was found that the forging
had high creep rupture ductility.
3.1.5 Fracture Toughness

The results of the fracture toughness test ill the LP section are given in Fig. 6.
The test was performed by the JIC method, and the value of KIc was obtained
by conversion from the value of JIC' The fracture toughness of 2.SCr1.2Mo-
1.SNiV steel obtained a value close to 3.5NiCrMoV steel which is used for LP
rotor forging.
(Top) Sl (Bot. )
S2
S•.•3 ~
I- 1:1
Cl
Table 3 Mechanical properties of the forging with 1417mrn diameter
0.2%P5 T5 E1 RA vE20 C 0 FAIT
(MPa) (%) (J) (OC)
51 T 758 880 19 72 187, 187, 187

L
P L 786 903 19 71
C1
R 171, 171, 168 -19
H 52 T 670 804 17 69 154, 154, 154

P 53 T 677 801 18 69 157, 162, 159
T: tangential, R: radial, L: longitudinal
500
CrMoV
• 2.5Crl.2Mol.5NiV
((j) 1625nm)
0 2.5Crl.2Mol.5NiV
((j) 1417nm)
300
2.25CrMoV
co
e,
::liE
(I)
(I)
Q)
L.
~
CI) 158MPa
100
80 •
IS66°C-10 h I
60
18 18.5 19 19.5 20 20.5- 21 21.5 22

P = (1+273) (20+log t) / 1000 T °C
t : hr
Fig. 5 Comparison of creep rupture strength
MANUFACTURING AND PROPERTIES OF 2%CR FAMILY STEELS 371
9000
•
••
8000
-
7000
~ 6000 •
E 5000
E
~ 4000
'::Z • : the center core in the LP sect i on r---
3000
2000 • : the surface in the HP sect i on I---
1000
a
a 20 40 60 80
Temperature eC)
Fig. 6 Fracture toughness of the HP - LP combined rotor forgings
(Top) HP ~---t---~-2A""
• LPI (Bot. )
~'-r-t-·
~r·
55 54 -51----,
52B
56 .[--==--=--=--=--=-_1 · 83 ~I _-_~~-_-
"S
Table 4 Chemical composition of 2.25CrMoV HP-LP rotor forging (unit: mass'ze)
C 5i Mn P 5 Ni Cr Mo V
Ladle 0.23 0.08 0.72 0.004 0.001 0.84 2.25 1.14 0.24
51 0.23 0.08 0.69 0.004 0.001 0.80 2.22 1.14 0.24
52A 0.24 0.09 0.70 0.004 0.001 0.83 2.24 1.16 0.24
52B 0.25 0.10 0.71 0.004 0.001 0.83 2.25 1.16 0.24
53 0.24 0.09 0.69 0.004 0.001 0.80 2~23 1.15 0.24
54 0.25 0.09 0.70 0.004 0.001 0.82 2.25 1.16 0.24
55 0.24 0.09 0.69 0.004 0.001 0.83 2.24 1.13 0.24
56 0.26 0.10 0.71 0.004 0.002 0.84 2.25 1.16 0.24
3.2 Manufacturing Results of Maximum Size Rotor Forging (2.25CrMo V)

The chemical composition in various positions of the forging with 1862mm in
the LP section are given in Table 4. The chemical compositions were uniform
over the entire sample.
The microstructure of the forging with a diameter of 1862mm in all positions
was bainite; ferrite was not found. The grain size was 5 in ASTM number in
the HP section and 9 in the LP section.
Table 5 Mechanical properties of 2.25CrMoV HP-LP rotor forging
0.2%P5 T5 EI RA vE20 c0 FAIT
(MPa) (%) U) (OC)
51 R 735 853 22 71 161 -8

L
P 52A R 735 853 22 70 174 -10
52B R 735 853 21 70 60 6
53 R 666 784 23 71
H 54 R 617 745 23 72
P 55 R 608 735 22 73 144 0
56 R 637 774 21 66
R: radial

The mechanical properties of the forging with a diameter of 1862 mm are
given in Table 5. The FATT in the surface of the barrel in the LP section was
+6°C with a 0.2% yield strength of 735 MPa. These results showed enough
high strength and toughness for a large HP-LP rotor forging.
3.2.4 Creep Rupture Strength

Figure 5 shows the results of the creep rupture strength of the surface in the
HP section. The creep rupture strength of 2.25CrMoV was agreed approxi-
mately with those of new 2.5Crl.2Mo1.5NiV steel, and it was comparable to
that of CrMoV rotor forging.
4. EVALUATION OF 2.SCr AND 2.25Cr ROTOR FORGING
Figure 7 shows the relationship between FATT and yield strength as com-
pared with 2CrMoNiV rotor.2-3 The quenching cooling rate of the centre is
decreased as the diameter of the barrel is increased, and FATT is generally
increased. Nevertheless it was found that the mechanical properties of
2.5Cr1.2Mol.5NiV steel were higher in strength and toughness than the
2CrMoNiWV steel.
5. MANUFACTURING RESULTS OF COMBINED HP-LP ROTOR

FORGINGS
Kobe steel manufacturing experiences of combined HP-LP rotor forging in

2-2.5CrMoV steel are given in Table 6. Kobe steel has been manufacturing
MANUFACTURING AND PROPERTIES OF 2
%
CR FAMILY STEELS 373
50
40
30
e
I-
20
10
I-
~ 0
-10 .: 2.5Cr1.2Mo1.5NiV
o : 2CrMoN iIV (rP 1266)
-20
• : 2CrMoN iIV (rP 1750, rP 1647)
-30
550 600 650 700 750 800 850
O. 2% YS (MPa)
Fig. 7 Relation between FATT and 0.2% YS of centre in LP section
Table 6 Manufacturing experience of HP-LP rotor forging (2.5CrMoV)
No. Steel Barrel Dia. Shipping Delivery

(mm) Weight (ton) (Year)
2.25Cr1MoV
2Cr1.7MoV
2.25Cr1MoV
2.25Cr1MoV
8 2.25Cr1MoV 1260 19 1995

9 2.25Cr1MoV 1150 15 1995
10 2.25Cr1MoV 1325 20 1997
11 2.25Cr1MoV 1340 18 1997
Rotors 6, 7 and 12 were described in this paper
approximately 40 pieces of combined HP-LP rotor forgings, and twelve

rotors out of about forty has been manufactured from 2-2.5CrMoV steel.
6. SUMMARY
The production of combined HP-LP rotor forgings with 2-2.5CrMoV steel

were manufactured and show excellent mechanical properties.
1. Different mechanical properties in the HP and LP sections were satisfied
by the application of differential heat treatments.
2. The balance of strength and toughness in the 2.SCr steel was extremely
good.
3. Kobe steel has so far manufactured twelve HP-LP rotors.
ACKNOWLEDGEMENTS
The authors would like to express their great appreciation to Fuji Electric Co.,
Ltd. and Mitsubishi Heavy Industries, Ltd. for their cooperation.
REFERENCES
1. T. Tsuchiyama, M. Miyakawa, M. Okamura, M. Morita, T. Yamamoto and

S. Nishida: Clean Steels Technology, 1992, 181.
2. 13th International Forgemasters Meeting, 1997, Manufacturing of a HP/LP
combined rotor forging from a 2.5Crl.2Mol.5NiV steel.
3. 12th International Forgemasters Meeting, 1994, Advanced 2% CrMoNiWV
Steel for Combined Rotors.
Experience in Manufacturing and
Mechanical Properties of Turbine Rotor
Forgings and Discs in Improved 10%
CrMoWVNbN Steel
K.-H. SCHONFELD and H. WAGNER
Saarschmiede GmbH Freiformschmiede, Volklingen, D-66330, Germany
ABSTRACT
Within the COSTprogramme, a new steel X12CrMoWVNbN 10-1-1 (classed as type

E), has been developed and evaluated. In this study several rotor forgings of this
steel for steam turbine and many discs for gas turbine application were manu-
factured. Experience in manufacturing at Saarschmiede are described in this paper.
Rotors and discs were made from an ESR ingot with diameter up to 2300mm and
weight up to 160t. Turbine shafts were manufactured up to diameter 1300mm with
weight up to 38t and discs up to diameter 2000mm. Different quality heat
treatments were performed in view of the need for different application properties.
Results of mechanical testing are reported.
INTRODUCTION
Within the European COST programme it was undertaken to develop high

temperature steels for advanced steam cycles. In the first stage the aim was to
improve the ferritic 9-12% Cr steels to higher creep rupture strength at
temperature up to 600°C. Extensive investigations of a lot of trial melts have
enabled three candidate steels, named COST B, COST E and COST F-steel, for
further investigations.
COST E-steel full scale rotor was manufactured by Saarschmiede and tested
by European turbine builders and research institutes. In the meantime COST
E-steel forgings were made as rotors for steam turbine, but also successfully
as discs for gas turbine applications, which demand other properties.
STEAM TURBINE APPLICATION (TURBINE ROTORS)
Goals within the European COST 501 programme were
• 100 000 h creep rupture strength at 600°C of about 100 MPa

• good creep rupture ductility (>10% elongation) and no notch sensitivity
375
• through hardening up to at least 1200 mm diameter

• minimum yield strength of 600 and 700 MPa
Based on a review of existing grades of 9-12% Cr steels five grades of steel
were identified as candidates, then modified and manufactured as trial melts
for further investigations. These results in selection of three grades of steel for
full scale forgings.1-4
Cr Mo Ni Al W
0/0 % % 0/0 0/0
0.10:s; 0.40:S; :s; 10.0 1.00 0.60:s; 0.040 0.0040 0.15 0.95
0.14 0.100 0.60 0.015 0.007 11.0 1.20 0.80 0.010 0.060 0.0060 0.25 1.10
Fig. 1 Chemical composition of steel X12CrMoWVNbN 10-1-1 (COST E steel)
COST E steel forgings were manufactured by Saarschmiede. Figure 1 shows

the target chemical composition of COST E steel, DIN X12 CrMoWVNbN
10-1-1 and Saarschmiede grade 1.4926 X2.
Rotor E with a heat treatment diameter of 1150mm was manufactured from
a 42 ton ESR ingot with diameter of 1300 mm. After heating up to forging
temperature the soaked ESR ingot was forged on a 60 MN forging press by
double upsetting and forged into shape with a maximum diameter of
1250 mm. After preliminary heat treatment and premachining the quality heat
treatment was performed by austenitising at 1070°C, hardened in oil and
double tempering at 570°C and 690°C to obtain a yield strength of about 700
MPa and than tempered at 715°C for a lower yield strength of about 600 MPa.
Results of mechanical testing are summarised in Figs 2 and 3.1-3
Other mechanical properties such as creep rupture properties, behaviour
after ageing, yield strength/temperature behaviour are reported.l f
Specimen orientation
Near surface - tang
Center - axial x
Fig. 2 Mechanical properties of trial rotor E, yield strength ,..,630 MPa2

PROPERTIESOFTURBINEROTORFORGINGSANDDISCS 377
Fig. 3 Mechanical properties of trial rotor E, yield strength --750 MPa2
Up to now several shafts and shaft ends were manufactured by Saarsch-

miede, e.g. turbine shaft with maximum diameter of 1260mm and appro 45
tons in weight. These rotors are also made to ESR-quality. First melting was
performed in a 125 tons electric arc furnace, cast into electrodes and
subsequently remelted into a 126 tons ESR ingot with 2300 mm diameter. The
forging sequence is outlined in Fig. 4.
After forging the rotor was transformed in the pearlite phase at 760°C.
Before quality heat treatment the forging was premachined. The heat treat-
ment contour is shown in Fig. 5. The rotor was vertically austenitised at
1070°C and hardened in oil. Double tempering was performed at 570°C and
690°C.
Typical test locations are shown in Fig. 6: left for rotors, right for shaft
ends.
RESULTS
Chemical composition
Figure 7 shows the result of chemical analysis of all forgings (melt analysis) as
average value with standard deviation. The melts are in a small scatterband
which expect homogeneous mechanical properties.
Mechanical properties
Mechanical properties, yield strength 0.2% and impact, are summarised in
Figs. 8a and Fig. 8b as statistical analysis of actual production results of rotors
and shaft ends.
r::; lopmingot
M=mjddlc:
a= [Jni1tll'l1 of 1I1}fm:
T MB
Fig. 4 Forging sequence of turbine rotor
GAS TURBINE APPLICATION
COST E steel was developed first for steam turbine application as rotor
material. The mechanical properties results and long term behaviour were the
reasons for looking into its applications for gas turbine parts. The background
and the requirements which are vastly different to steam engine application
are reported+ Siemens has tested COST E steel for gas turbine discs and based
on these results a prototype disc was manufactured and investigated. Suc-
cessful properties were reached which resulted in designing COST E steel as
an improved material for gas turbine discs.
PROPERTIES OF TURBINE ROTOR FORGINGS AND DISCS 379
Fig. 5 Heat treatment contour of turbine rotor
t¢M.tt,\mpfe
T 2
Fig. 6 Typical test locations of rotors and shaft ends
C Si Mn P S Cr Mo Ni Al As
0/0 % % % % % % % % %
mean 0.119 0.096 0.427 0.0072 0.0011 10.456 1.045 0.747 0.008 0.0075
standard
0.006 0.015 0.019 0.0011 0.0002 0.091 0.009 0.024 0.001 0.0044
deviation
Co Cu N Nb Sb Sn V W H
% % % %
0/0 0/0 % %
ppm
mean 01017 0.036 0.0550 0.0456 0.0006 0.0038 0.186 0.97 2.62
standard
0.006 0.007 0.0036 0.0031 0.0001 0.0008 0.011 0.03 0.52
deviation
Fig. 7 Chemical composition of 36 melts in X12 CrMoWVNbN 10-1-1 (COST E

steel)
Manufacturing of typical gas turbine discs

Up to now a lot of discs different in size and weight were manufactured by
Saarschmiede. Typical diameter sizes are 1606 to 1925 mm and thickness 240
to 553mm.
The steel is melted and remelted in the same manner described before for
rotors. Depending on the sizes of the discs and ordered quantities ESR ingots
-;J.
~ 25~-----------------------------
~
i~ 20+-------------------------------
~
Q 15~--------------
~
5 10~--------------
~=
C'"
'=
0
\0
\0 0
\0
0
00 oc;
0
0
0
0
N
N ~r--
0
~r-
0
\0
t- ~r-
0
00
t-
'0
_0
0000 0
0
N
00
c::i ~
0
00
0
"<:t"
00
t- t-
V \0
\0
\0 t- t- r- 00 00
1\
yield strength, MPa
Fig. Sa Yield strength 0.2% of rotors and shaft ends in X12 CrMoWVNbN 10-1-1
(COST E steel)
16~----------------------------------------------------~
-;J. 14+-----------------~@rr_---------------------------------1
i 12~-----------------~@rn------
~
= lO~-----------------~J!n----------------~.----------------
~ 8+-----------------~Hi%~-------------k'I-------------------1
~
Q
~ 6--f-----
~
& 4
I"'"
~
-~-- ---------n --
-1------I$~I____It""I--(-$iI--_E:,::d----H)':'I-H:nI----
~ 2--f-U~&I-~%1-lm!~-lt0i1-~',~-----lid-~,M~--r~ml-
I"'Z1
11'11 -1:111
~ s ~
o
0
;Q 0
V)
~ :g 0 V) 0
e-- V) 0 V) 0 V) 0
V) V)
r-:- 0;>
~
C'I V)
~
V)
~
\0
~
\0 00 0'\
~~ ~
N
V
~ -=
0 \0
;:;; ~ ~ ~ :g \0 r::: \0
C;; \0
c; 1\
~
\0 r- 00 \0 \0
N N 0'\
impact, J
Fig. 8b Impact of rotors and shaft ends in X12 CrMoWVNbN 10-1-1 (COST E
steel)
of diameter 1300 and 2300 mm are used. The forging sequence of discs made
from these two ingots are shown in Fig. 9 and Fig. 10.
The discs are forged using a 6000 tons press. After forging the discs are
transformed to the pearlite phase. Prior to quality heat treatment the forgings
are premachined. Quality heat treatment is performed by austenitising at
1070°C and hardened in oil, followed by double tempering at 570°C and 640 to
660°C. The quality heat treatment contour and the test location of typical
turbine discs are shown in Fig. 11.4
RESULTS
Chemical composition
Chemical composition of COST E steel gas turbine discs are the same for
forgings for steam turbine parts. Results of the chemical analysis are shown in
Fig. 7.
PROPERTIESOFTURBINEROTORFORGINGSANDDISCS 381
EJ
T ""Top. Df ingot
M'fflmiudle
B == ao1tom of in!1ot
M B
M
---t!--- -
B
•
-n=- EP.' .....
--~
~~~~~~~M ~
o. •
-{I]EUJl--- !l--]fP--
M ••••• ~
Fig. 9 Forging sequence of gas turbine discs in X12 CrMoWVNbN 10-1-1 (COST E
steel)
Mechanical properties of disc material are summarised as statistical analysis
of actual production results of more than 50 discs with the above mentioned
sizes. Figures 12a, band c show the frequency of values for yield strength
0.2%, impact and FATT.
The correlation between yield strength 0.2% and FATT is shown in Fig. 13.
Really there is no strong influence probably due to the small scatterband of
yield strength.
FURTHER INVESTIGATIONS
In view of further improved properties, especially creep rupture, there are

several investigations, with different grades of creep resistant 9-12% Cr
steels, to be looked at.
T B
T =- Top of ingot
M=middle
B = Bottom of ingot
T B
Fig. 10 Forging sequence of gas turbine discs in X12 CrMoWVNbN 10-1-1 (COST
E steel)
test ring T1 bore test ring R1
test Ring R2
Fig. 11 Quality heat treatment contour and test location of gas turbine discs in X12
CrMoWVNbN 10-1-1 (COST E steel)
16
'$. 14
t 12
~
= 10
~o~
--
8
~
-
tJ
5 6
=
~ 4
~
2 I I I -
o Ifiil Ilitl flit III III

0
II
0
on 0 V) 0 0 V)
0
oc; ~ N
00 ~ V)
00
r-
00
00
00
0\
00
0\
00
v II
V)
C;;; c::i
00
\0
N
00
~
\0
00
~
00
\0
["--
00
\0
gg
yield strength 0.20/0, MPa
Fig. 12a Yield strength of turbine discs in steel X12 CrMoWVNbN 10-1-1 (COST E)
25~-------------------------------------------------------
~
~
~ 20-~----------~~~3-------------------------------------------~
=
~ 15-.----------m~~~I------------------------------------------1
~e
~
~ 10 -J------HN.---.iI£J
~
=
~ 5+-----~~mdl~~~I~~~t+~8~·W~--------------------------------~
r.=
V) 0 V)
0;'
0
V)
~ ~ ~ 0
~
V)
~
~
00 0\
impact, J
C;;; 00 ~ \0
0\
~
§ ~
- ~ E
Fig. 12b Impact of turbine discs in steel X12 CrMoWVNbN 10-1-1 (COST E)
0
~ g trl 0
V)
-::t" S;
';
trl
N ('f")
~ 0
N
~
N
;;; \0
('f")
~ ~
\0
FATT,oC
Fig. 12c FATT of turbine discs in steel X12 CrMoWVNbN 10-1-1 (COST E)
890
•
..~.• •
880
870
~
•• • •
~
~
--. ~ 4. • ~~
• •• •
6
860
~ • ••
N •• * .~
•• ...•.
=~
.
850
• ..•..
• t • • ••
.~ ••
• ••
d
840
•
830
•
~~
•
•
~6
~
~ ~
..•..
• •• • ••
~
820
• 0
•
810
15 20 25 30 35 40 45 50
FATT,OC
Fig. 13 Relationship yield strength 0.2% and FATT of turbine discs in steel X12
CrMoWVNbN 10-1-1 (COST E)
80
• • •
I.--
70
yield strength 0.2 % =
832 MPa (mean value) • • • •
60 -
U
0
~
E-i
50
-<
~ 40 range or FAIT for discs without
boron
30 - range of yield strength 0.2% =
81&-&&7MPa
20 -
10 ,
0 10 15 20 25
B-content, ppm
Fig. 14 Influence of Boron on FATT in steel X12 CrMoWVNbN 10-1-1 (COST E)
One of the results of improvement for better creep rupture strength is the
alloying of Boron. Some initial investigations have been made with boron
alloyed COST E steel.
In Fig. 14, FATT-values of boron alloyed to boron free COST E steel are
compared. The yield strength of 0.2% is in the same range for both types. The
FATT of boron alloyed COST E steel is remarkably higher than the boron free.
Boron alloying of 5 to 23 ppm has no significant influence on FATT.
SUMMARY
The published properties of trial melts and full scale rotors in COST E steel
have resulted in the application of several shafts and shaft ends for steam
turbine application. Manufacture and testing of full scale forgings have

confirmed the earlier published results for the COST E steel. More recently the
use of the steels for gas turbine discs has been proposed. Many discs have
been in successful operation in Siemens' combustion turbines.
REFERENCES
1. C. Berger, E. Potthast, R. Bauer and G. A. Honeymann: Development of high

strength 9-12% CrMoV steels for high temperature rotor forgings, 11th
International Forgemasters Meeting, Terni/Spoleto, Italy, 11-14 June
1991.
2. C. Berger, K. H. Mayer, S. M. Beech, D. V. Thornton and R. B. Scarlin: High
Temperature Rotor Forgings of High Strength 10% CrMoV Steels, 12th
International Forgemasters Meeting, Chicago, USA, 11-16 Sept. 1994.
3. C. Berger, R. B. Scarlin, K. H. Mayer, D. V. Thornton and S. M. Beech:
'Steam Turbine Materials: High Temperature Forgings', 5th Interna-
tional Conf. Material for Advanced Power Engineering, Liege, Belgium, 3-6
October 1994.
4. T. U. Kern and K. H. Schonfeld: Improved 10% CrMoWVNbN Steel for gas
turbine application - manufacturing and properties, 13th International For-
gem asters Meeting, Pusan, Korea, 12-16 Oct. 1997.
Metallurgical Procedure and Results
Melting of Boron Alloyed lOwt% Cr
ESR Steel for Power Generation
Machinery
M. MAURISCHAT, N. BLAES, K. LANGNER and
H.WAGNER
Saarschmiede GmbH Freiformschmiede, D-66330 Volklingen, Germany
ABSTRACT
As a part of the COST 501 program Saarschmiede GmbH Freiformschmiede is

involved in the development of advanced 10wt% Cr steels for application in power
generation machinery. In this context, Saarschmiede has produced, among others
also some 10wtO/o Cr electro slag remelted (ESR)steels with elevated boron contents
and, in particular, a pilot rotor for the VGB (Technische Vereinigung der Gros-
skraftwerksbetreiber e.V.) program.
This paper deals with equipment and procedures at Saarschmiede for the
production of 10wt? CrB ESR steel ingots. Basic thermodynamic data for oxidation
reactions of alloying elements that have an affinity for oxygen are adapted to the
practical process by means of some trial melts.
The paper reports data for three ESR melts produced in a crucible of 1.3m
diameter controlled by continuously sampling slag and steel chemistries during
melting. On the basis of these trial melt, a 45 t ESRingot for a pilot rotor application
was produced with excellent homogeneity of the alloying elements that have an
affinity for oxygen such as B, Si and AI. The homogeneity of these elements in a 23 t
ESR ingot is demonstrated by longitudinal and cross sectional samples. A nominal
boron analysis of 93ppm ± 9 ppm in the pilot rotor is based on a sufficient number
of melt samples taken during remelting.
INTRODUCTION
The higher efficiency of advanced steam plants requires continuous develop-

ment of steel grades for application in power generation machinery. This is
essential in context of steam turbine construction. Saarschmiede GmbH Frei-
formschmiede, Germany has participated in the COST 501/11 program for
several years developing advanced steel grades.l-? Figure 1 shows two Ifl wt"
Cr steels produced by Saarschmiede for application at temperatures of
620°C.
Using the steel grade X18 CrMoVNb 9 1 with a boron content of 90 ppm a
pilot rotor with data shown in Fig. 2 was produced by Saarschmiede under
386
METALLURGICAL PROCEDURE AND RESULTS MELTING 387
Steelgrade COST Producer C Cr Mo Ni W V Nb N B

501/11 0/0 % % % % % % % 0/0
Typ
X12 CrMoWVNbN 10 1 E-Typ Saarschmiede 0.12 10.3 1.0 0.8 0.8 0.18 0.05 0.005 -
X18 CrMoVNbB 9 1 B-T Saarschmiede 0.18 9.5 1.5 0.5 - 0.25 0.05 0.010 0 .010
yP Bonler
Fig. 1 Advanced 10wt% Cr turbine rotor steels in Saarschmiede - COST SOl/II
Weight, as shipped 23t

Diameter, as shipped 1142mm
Length, as shipped 4200mm
Forging diameter 1200mm
ESRweight 45t
ESR diameter 1300mm
1 Exchange electrode FSR
Average melt analysis:
0.0057 0.0116 0.258 0.0093
Fig. 2 VGB pilot rotor, X18 CrMoVNb 9 1
the VGB - Technische Vereinigung der Grosskraftwerksbetreiber e.V. (Tech-

nical association of large power plant operators) - program, Germany,
together with the power plant manufacturers ABB, GEe Alsthom Energie and
Siemens.
EQUIPMENT AND PROCEDURE
Outfitted with all equipment for steel production Saarschmiede is able to melt
and manufacture high quality steel grades. Figure 3 shows some conventional
melting devices, such as:
- 1 X 125 t electrical arc furnace (EAF) with eccentric bottom tapping
(EBT), max. primary power 55 MVA.
- 1 X 125 t ladle furnace (LF), max. primary power 18 MVA.3
- 1 x 125t tank degassing station (VD) with additional oxygen equipment
(VOD) and alloying facility.
- The casting pits enable bottom pouring up to 110t ingots and pouring
from the top up to 150 t ingots.
- Additionally there are two 150 t vacuum ingot casting tanks available.
125 tEAF 125tVDNOD 165 tESR

Fig. 3 Main melting facilities in Saarschmiede
- Beside these installations there are facilities for ladle deslagging, wire
feeding and cleanliness rinsing.
The range of production includes steel grades for power generation
machinery, general machinery, construction, tooling, and material for the
aerospace industry. Figure 4 shows a cross sectional sketch of the ESR
equipment+ The ESR process enables meeting the highest quality require-
ments concerning segregation and non metallic cleanlinessf The ESR equip-
ment consists of two melting stands. Stand No. 1 has a withdrawable base
plate while stand No.2 has a fixed base plate. In stand No. I, 1.0 m, 1.3 m and
2.3 m diameter ingots having lengths up to 5.5 m can be produced. In stand
No.2, cross sections of 0.35 meters square as well as 0.5 m and 0.75 m
diameter ingots can be made. Stand No. 1 enables ingot weights of 20-165 t.
---- Bectrode
•....•..
--Hood
-:-----liQuid Metal Pool
Gap Locking Device

__ ,,~Wor1<ing Platform
•..
---~-Spindle Suspension
--+t--- ESR Ingot
!!t---H--- Base Aate
~~--++--- Slatting Block
a.t---H--- Hydraulic Cylinder
Spindle
---+!I--- 8ectric Conlad Plate
~--- Supporting Table
~----~r---~~
Spindle Drive
Fig. 4 ESR cross section

With the special adaption of peripheral devices, ingot weights up to 180t may
be made.
The remelting electrodes are guided by four columns with 2.3 MVA
primary power each. The equipment operates in the range of 0-10 Hz. The
melting process is computer controlled with an automated melting report.s
The bath is covered by a 250mm slag layer of 20wt% CaO, 20wt% A1203
and 60wtO/oCaF2. All materials additions, especially deoxidation agents, are
computer controlled. Application of predried media ensures low hydrogen
contents after remelting. In 1995 the electrical part of the ESR equipment was
updated with a new power supply, a digitally controlled processing unit and
a digitally controlled electrode feeding a base plate withdrawal system. These
technical improvements and continuously sampling slag and melt chemistries
results in sufficiently improved homogeneity of the ingot composition and
diminished the delay rate simultaneously. An automatic weighing and
charging system guarantees a steady melt and slag deoxidation.
FUNDAMENTALS
During remelting, it is important to maintain the melt/ slag equilibrium of the

alloying elements that have an affinity for oxygen. In this context, the
elements AI, Si, Ca are especially interesting. These equilibrium essentially
determine the content of boron in the melt and slag.
Figure 5 shows schematically some oxidation reactions in boron containing
turbine ESR steels. Additionally, oxidation equilibrium are influenced by the
atmospheric oxygen.
The thermodynamic data of Fig. 6 give a good quantitative survey of the
reactions between melt and slag. By influencing the alloying elements AI, Si
Fig. 5 ESR melt-slag reactions

aB10J - 35500 + ILl3

2[B]+3[O]~(B103); KB10J =-1--3 =10 T
a B xao
a 64000
2[ AI] + 3[0] ¢:> ( Al2 03
); K A/20) a 2 A/~O)a3 10
--T-+ 20.57
Al 0
a SiO _ 31084 + 12.02
[Si]+2[0]<::>(Si02}; KSi~ =--2 =10 T

as; x «:
_12590 -5.53
[Mn]+[O]¢:> {MnO}; K MlIO aMnO 10 T
a/vIII x ao
_25800 +10.7
10 T
44040
--+19.42
10 T
_ 73400 +23.3
10 T
Fig. 6 Basic thermodynamic equilibrium data of the ESR process
and Ca that have the greatest affinity for oxygen by corrective deoxidation
during the remelting process, the operational equilibrium of the remaining
elements of the system, such as boron, can be stabilised. For this reason it is
important to approach these theoretical equilibrium to the operational charac-
teristics empirically. This will be described in the following chapter. Taking
into account these fundamentals it is possible to ensure constant boron
content in length and cross direction of the ESR ingot.
PRODUCTION PROCEDURE
Figure 7 shows the composition of four ESR heats with elevated boron
contents from 18 ppm up to 300 ppm, which were remelted at Saarschmiede.
Adapting the theoretical equilibrium data of the first three heats to the
operational results, good homogeneity of the boron content in the last heat
used for the VGB pilot rotor was achieved.
The production procedure of these ESR heats is pointed out in Fig. 8 in the
form of a pictogram. Selected raw materials were melted in the EAF to a low
phosphorous content heat. Main alloying additions and deoxidants were
added during tapping. Tapping was followed by deslagging of the ladle. The
carried over slag was then replaced with a synthetic basic slag. Fine correction
of the melt chemistry and temperature was performed in the ladle furnace.
Hydrogen and sulphur removal as well as nitrogen content correction was the
result of the vacuum treatment. Final cleanliness rinsing ensured low non-
Heat Ingot C Si Mn P S Cr Ni Mo V N Al W B Nb
No. weight % % % % % % % % % % % % % 0/0
t
1 22 0.47 0.39 0.34 0.025 0.001 13.3 0.24 0.20 0.039 0.019 0.009 - 0.010- 0.014
0.030
2 55 0.12 0.09 0.43 0.007 0.001 10.8 0.73 1.04 0.185 0.047 0.008 1.0 0.0018 0.058
3 23 0.19 0.12 0.78 0.006 0.001 9.2 0.14 1.44 0.254 0.013 0.007 - 0.0087 0.061
pilot 45 0.19 0.09 0.77 0.007 0.001 9.2 0.14 1.45 0.258 0.012 0.006 - 0.0093 0.066
rotor
Fig. 7 Boron containing trial melts
EAF Tapping Deslagging Met. Slag Ladle Vacuum Electrode Electro Slag
Addition Furnace Degassing Casting Remelting
Fig. 8 Melting procedure of ESR material
metallic inclusion contents. ESR electrodes having a 635mm diameter were

cast conventionally from the bottom.
The lOwt% Cr steels with elevated boron content of this paper were
remelted in a 1.3m diameter crucible with a withdrawable base plate. The
ESR process was started by melting a sufficient quantity of synthetic slag.
Multiple simultaneous and continuous sampling of the melt and the slag
phase ensured a well adapted slag deoxidation and a steady analysis of the
alloying elements that have an affinity for oxygen in the steel.
The remelting process was computer controlled. Online analysis of the
samples and running slag temperature control as well as continuous measure-
ments of the carried off energy and control of the ingot withdrawal rate
resulted in a process with a constant melting rate.
To minimise the ESR ingot head solidification cavities, a hot topping
procedure was used at the end of the ESR process. Hot topping works by
decreasing the remelting rate considerably for diminution of the liquid pool.
Non steady solidified parts were eliminated by scrapping sufficient quantities
of the head and the foot after the forging process.
1,000 2 [8 I' (M nO) + (5;0,) 0 [M n I' [5 f 1+ (8,0,) _

A,HeatNo 1
CHeat No 2
~
log rB,= ~IOgr all! lS [S!l: [~ollJ.: III lS (" 1- 10g(I.)+ (~- 1,316)
OHeatNo 3
• VGB pilot rotor
I
0,100 I
~
.Jc'-
f§:
theoretical equilibrium
I
I
0,010 ~ operational equilibrium approach of BIB203
I
I
I
I
l
I
I ••.... J
I ··
I
~
~
- I I
I
I
I
·
I
0,001
0,000 0,002 0,004 0,006 0,008 0,010 0,012 0,014
activity of B103 in the slag
,* all Boron contents are adapted to the Si- and Mn-contents of the VGB pilot rotor
Fig. 9 Adaption of the theoretical equilibrium to the practical procedure
Remelting of the LOwt': CrB steel was controlled on basis of the above
described themodynamic data. Figure 9 points out the adaption of the
theoretical data to the practical results of the first three trial melts from the
above Fig. 7.
Additionally, Fig. 9 shows the results of the VGB pilot rotor remelting
process. Good agreement was obtained with the practical curve. Use of the
practical curve of Fig. 9 gives a good chance of sufficient analysis adjustment
at remelting begin. Continuously sampling during the EST process has been
the basis for corrective deoxidation actions.
RESULTS
Trial melts
The boron content of the melt samples are plotted in Fig. 10 for trial melts No.
2, No.3 and the pilot rotor. To enable the adaption of operational character-
istics in a wide range, trial melt No.1 was produced with boron contents from
100 up to 300 ppm. For this reason these values were not used in Fig. 10.
As schematically shown in Fig II, the 23 t ingot of melt No.3 was cut for
sampling. A total of 180 samples were investigated. All interesting compo-
nents of steel were analysed.
The boron distribution for the length and cross direction of the ingot is
shown in Fig. 12. After cutting the head and foot scrap from the ingot, a rather
constant average boron content of 86.5 ppm ± 12.5 ppm was found. This
pattern also includes the boron distribution in the ingot cross direction.
Approximately constant contents of the alloying elements that have an
affinity for oxygen of the melt face steadily increasing oxide activities. That is
140
120 -e- [B]-VGB pilot rotor
100
e
Co
Co
.•.. 80
.sc 60
c
0
u
~ 40
20
0
0 10 20 30 40 50
weight of ESR ingot, t
Fig. 10 Boron distribution in three ESR ingots
Jl
•
I
~
:l
~
~E-
.
•
.-- ... ...

_
0
C
M
~
.s
(',l
Ci)
~
-l
@ •
U •
"
••• Diameter: 1300mm
•••
Fig. 11 Sampling, 23 t heat No.3 ingot
caused by oxidation due to atmospheric oxygen and simultaneous corrective

deoxidation actions.
VGB Pilot rotor

In Fig. 13 the steady course of the related oxide activities of the alloying
elements that have an affinity for oxygen such as B, AI, Si, Mn, Ca, Fe and Cr
are plotted following the total remelting length of the VGB pilot rotor.
Especially in the course of FeO, the influence of the intermediate deoxidation
actions is perceptible.
This kind of slag control leads to the homogeneous melt composition in Fig.
14. The figure shows the distribution of the melt components B, AI, Si, Mn, Mo
120
100
80
E
Q.
Q. 60
B
40
____
--+-0 200 ----M-150
20 -- • --350
- - - - ..400 -- • - ·550
- -)E - 600
0
0 2 4 6 8 10 12 14 16 18 20 22
Fig. 12 Boron distribution in length and cross direction of the 23 t heat No.3 ingot
2,5
]
:5
2
0
~
~
~~
.s 1,5
~ y
0
~
~~
0,5
0 10 15 20 25 30 35 40 45
Fig. 13 Activity ratio of slag component in the VGB rotor
and Cr in the length direction of the pilot rotor based on samples taken from
the melt. An average boron content of 93 ppm ± 9 ppm was measured. This
good boron homogeneity is also an indication that the other alloying elements
are homogeneously distributed. Low deviations in the analysis results along
the length direction of the rotor usually indicate sufficient homogeneity in the
cross direction.
After the ESR production, the 45 t ingot was forged, preliminarily and
quality heat treated. Then, about 4 t of metallurgical scrap was cut off from the
head and about 3 t from the foot.
0,020
H
----.-[B] - - 0 - -[AI] ~[Si]/10
t
0,018
0 - -0 - [Mn]/IOO -IE-[Cr]/IOOO --+-[Mo]/IOO
0
...•. .. ..
0,016
~ .•...•. ..•. ..•.... ... ...
..•. .... ..•.
..•.
.•...•....•. ..•..•. ..•..
..•.
..•..
.•.
A
.•.
A A
.•. ..•. ..•.
..•.
..•. ...
..•.
'i:'
~ 0,014
g-~
-~_.u ~
0,012
~ 0 ••.
•...•.....•..
•.. ~ ,.., -- - -- ~
-0
-- - -v--u-
Co
~s. 0,010
.,..,,.., ,..,
-=
..&.
s.~
U#
..,
•. 0
- "'Zr' II'" 9"
-- ..
0,008 ---u-o-u" -v- - r.J ~ v- 'u-
~"--
FUV- V OiiiiiQ--o- V- 4 - -0- (
~ .•. "V
~ 0,006 .•. ,,-tr rD--O .... ) .... " "[ -O[]-C-
C D - DC- []- -C-o[]- -0" C- [
0,004
~
~ 0,002
0,000
o 500 1000 1500 2000 2500 3000 3500 4000
lenght of pilot rotor, mm
Fig. 14 B, AI, Si, Mn, Cr and Mo concentration in the VGB pilot rotor
SUMMARY
The paper contains the production procedure of a 10wt Cr steel grade with %
90 ppm boron content. Four heats of 10 wt? CrB steel have been melted. The
conventional and ESR melting facilities of Saarschmiede are presented.
Thermodynamic data are adapted to the operational procedure. The metallur-
gical results, especially of a 23 t ESR trial melt and a 45 t ESR melt for a 22 t
VGB pilot rotor, are presented. These results show excellent homogeneity of
alloying elements that have an affinity for oxygen such as Ai, Si, Mn, Cr and
Mo. The pilot rotor contains an average boron content of 93 ppm ± 9 ppm.
Closer investigations of the trial melt No.3 lead to excellent constant boron
values in the cross direction. The above melting procedure allows Saarsch-
miede to produce advanced 10wt% Cr steels with elevated boron contents
reliably.
ACKNOWLEDGEMENTS
The production of the pilot rotor was achieved by use of development funds
of Technische Vereinigung der Grosskraftwerkssetreiber e.V. (Technical
Association of large power plant operators), Essen, Germany in the scope of
the VGB-R&D program No. 158.
REFERENCES
1. C. Berger, K. H. Mayer and R. B. Scarlin: VGB Kraftwerkstechnik, 1994, 74 (3),

338-45.
2. C. Berger, E. Potthast, R. Bauer and G. A. Honeyman: 11. International

Forgemasters Meeting, Terni 1991, Proceedings IX, 5.
3. F. Regnitter, K. Langner and W. Ottmar: Stahl u. Eisen, 1987, 19, 881-883.
4. R. Jauch, A. Choudhury, H. Lowenkamp and F. Regnitter: Stahl u. Eisen 95,
1975, 9, 408-413.
5. A. Choudhury, R. Jauch, H. Lowenkamp and F. Tince: Stahl u. Eisen 97,
1977, 18, 857-866.
6. H. Heilig and S. Wienecke: Stahl u. Eisen 106, 1986, 2, 57-62.
High Purity 9CrMoVNiNbN Rotor
Forging for Advanced High Pressure-
Low Pressure Steam Turbine
Y. TANAKA, T. AZUMA, Y. SHUDO, S. ONO, Y. IKEDA and
T.ISHIGURO
The Japan Steel Works, Ltd., 4 Chatsu, Muroran, Hokkaido, Japan
ABSTRACT
9CrMoVNiNbN steel has been developed for large high pressure-low pressure
steam turbine which will be needed in the near future. Based on the laboratory
investigation results, a trial rotor forging with LP section diameter of 1750mm and
HP section diameter of 1200mm was manufactured and evaluated. The results
showed the rotor forging to have excellent strength versus toughness balance and
good creep strength equivalent to that of conventional 12CrMoV steel.
INTRODUCTION
In order not only to conserve the resources but also to reduce CO2 emission on
the standpoint of global climate change, improvement thermal efficiency of
power plant is desired.' To meet this need, new types of high efficiency power
generation plants such as ultra super critical (USC) power plants and
combined cycle power plants have been designed and are being constructed.
The high pressure-low pressure combination (HLP) rotor shafts are widely
used in the steam turbine side of the combined cycle power plants, since the
HLP turbine has the advantages in cost of construction, space in the plant and
maintenance. Recent increases in power generation capacity of the combined
cycle plants promotes the enlargement of size of HLP turbines and it is
predicted that the diameter may reach around 2000 mm in the near future. In
order to attain the material requirements of such large HLP turbines, several
low alloy steels with 2.0 to 2.25CrMoNiV composition have been developed
successfully.cf However, further increases of section size results in higher
stresses and require superior toughness in the centre portion, which can't be
satisfied by using low alloy steels. In order to attain this target, materials
based on the 9CrMo V steel have been investigated for the larger HLP turbine.
The laboratory investigation to optimise the chemistry was performed and a
trial rotor was successfully produced. The present paper introduces the
development of a 9CrMoVNiNbN material and properties of the trial rotor
forging made of this steel.
397
C,AfoV Stee' caJ

.,20 ModIfied
() C,AfoV Stee' C4
..!•.
0
.•..I
0
80
!
•.
0
e
40
!
c:
CD
e
.•..
II
0
II;
=
700 800 900 .•
000 .,
.0•0
Tensile Strength, MPa
Fig. 1 Strength versus FATT balance of the materials for HLP turbine
MATERIAL REQUIRMENTS FOR THE LARGER HLP TURBINE
Since the service temperature range of HLP turbine includes those of low
pressure turbines and high pressure turbines, the material should have good
toughness versus strength balance in the LP section and, good creep strength
equivalent to that of CrMoV steel in HP section, simultaneously.
Figure 1 shows the relationship between 50% fracture appearance transition
temperature (FATT) of the material at the centre of forging approximately
1750mm dia and strength for various HLP turbine materials. The figure
demonstrates that the low alloy steels have superior strength versus tough-
ness balance compared with the conventional CrMoV steeL These materials
are going to be operated in advanced combined cycle power plants. However,
in order to attain further increase of turbine size, much better toughness
versus strength balance will be required. The requirements for materials of
such HLP turbine is not defined so far, but the authors assumed that the
centre toughness will be less than 20°C with a strength level of above
880 MPa. On the other hand, the required creep strength level should be
equivalent or better than that of conventional CrMoV steel.
LABORATORY INVESTIGATION TO DETERMINE THE OPTIMUM

CHEMISTRY
On the stand point of alloy design, the addition of alloying elements to

increase the toughness generally decreases the creep strength. In order to
HIGH PURITY 9CRMoVNINBN ROTOR FORGING 399
Table 1Chemistry of the laboratory heat materials (wt%)
C Si Mn Ni Cr Mo v Nb N
0.10 0.05 0.08 0.2 7.0 0.7 0.18 <0.01 0.010
0.19 0.25 0.50 2.5 10.5 1.8 0.27 0.05 0.056
optimise the chemistry to attain the good toughness and creep strength
simultaneously, thirty seven heats of laboratory ingots in the chemistry range
shown in Table 1 were prepared and investigated. Each steel was melted by
vacuum induction furnace and cast into a 50 kg ingot. The ingots were
hammer forged into plate with l40mm width and 35mm thickness. After
preliminary heat treatment, the materials were subjected to the quenching
from l050°C, with a Cooling rate of 100°C/h. After quenching, the first
tempering was conducted at 570°C followed by the second tempering. The
second tempering temperature was controlled so that the material had a
tensile strength level of 880 MPa. Mechanical, impact and creep rupture tests
were performed after the heat treatment.
Effects of Si, Mn and Ni contents on toughness and creep rupture strength
are shown in Fig. 2. From the figure, addition of Ni contents increases the
toughness but reduces creep rupture strength. Decrease in the Mn content has
no effect on the toughness. Reduction of the Si and Mn content is effective in
.. 10-2
J:
..
!
l!
•
Q.
b•
10-3
~
.§
•
.5
10-4
40
20
()
0
•. 0
~
~ ·20
·40
2.5 3.0
Hi contant, mass%
Fig. 2 Effect of Si and Mn content on FATT and creep strength

Table 2 Effect of chemical elements
Element Temper Resistance Toughness Creep Strength
C Increase Increase Decrease

Si Increase Decrease Decrease
Mn Increase No Effect Decrease
Ni Decrease Increase Decrease
Cr Increase 9.5% 10.00/0
Mo Increase 1.35% Increase
V 0.21% 0.21 % No Effect
Nb Increase No Effect Increase
N Increase Decrease Increase
increasing the creep rupture strength. Similar investigations were performed

for steels having various C, Cr, Mo, V, Nb and N contents. The investigation
reveals the effects of each chemical element as summarised in Table 2.
Addition of C improves the toughness through the formation of a fine lath
martensitic structure. Increase of Ni also improves toughness by decreasing
transformation temperature to have a fine lath structure. On the contrary,
addition of Si and N decreases the toughness. Mn and Nb have no significant
role on the tougness. On the other hand, an increase of C, Si, Mn, and/or Ni
content reduces the creep strength. Additions of Nb and/or N are effective in
improving the creep strength. Vanadium has no significant effect on the creep
properties in the materials tested. Based on these investigations, the high
purity 9CrMoVNbN steel with the addition of Ni, as shown in Table 3, is
determined to be the optimum composition for the trial HLP rotor forging
material.
MANUFACTURING OF THE TRIAL ROTOR FORGING
Desired Chemical and Mechanical Properties

Based on the fundamental investigation, the aimed for chemical composition
of the trial rotor forging is shown in Table 3. The desired tensile strength and
FATT are determined to be 880 MPa and less than 20°C, respectively.
Table 3 Optimum chemistry determined by laboratory investigation (wt%)
c Si Mn Ni Cr Mo V Nb N P,S,Al,As,Sn,Sb
0.16 <0.1 <0.1 1.3 9.8 1.4 0.21 0.05 0.040 Superclean
800
HP Portion
Bottom Top
¢ 1750 ¢1200
Fig. 3 Dimensions of the trial rotor forging
Dimensions of the Trial Rotor Forging

Figure 3 shows the dimension of the trial rotor forging. Diameter of LP section
is selected to be 1750mm that is typical in the advanced type HLP rotor.
Diameter of HP section is 1200mm which is also typical for the conventional
IP rotor.
Manufacturing Process of the Trial Rotor forging

Steel was refined in the basic electric furnace followed by the ladle refining to
attain a high purity melt. Then the steel was cast and forged to make the
electrode of electro slag remelting (ESR) process. By the ESR process, an ingot
with 1800mm dia. and 65 ton weight was made. Forging was performed by
using 8000 ton and 10 000 ton presses. In order to attain sound and
homogeneous microstructure, repetition of upsetting and cogging was per-
formed before the final forging. After forging and preliminary heat treatment,
quality heat treatment was performed, the austenitising temperature being
1075°C and quenching in oiL Tempering was performed twice to obtain a
stable microstructure. The first tempering temperature is 580°C and the
second tempering temperature is 650°C.
After the heat treatment, ultrasonic examination was performed and no
indication was found. Figure 4 shows the appearance of the trial rotor
forging.
Evaluation of the Trial Rotor Forging

Chemistry
Table 4 shows the result of chemical analysis at various portion in the trial
rotor forging. The locations IA' to IT' of the materials are shown in Fig. 5.
Homogeneous distribution of chemical composition was confirmed in the
whole trial rotor forging. Phosphorus and sulphur contents are less than
50 ppm and 10ppm, respectively. The contents of the other residual elements
Fig. 4 Appearance of the trial rotor forging
Table 4 Distribution of chemical composition (wt%)
C Si Mn P S Ni Cr Cu Mo V Nb Al As Sn Sb N 0
A .15 .07 .09 .005 .0007 1.22 9.74 0.06 1.36 .22 .05 <.005 .005 .004 .0010 .0426 -
B .15 .09 .09 .004 .0005 1.22 9.70 .05 1.37 .22 .05 <.005 .005 .004 .0011 .0400 .0011
C .15 .10 .09 .004 <.005 1.22 9.81 .05 1.36 .22 .05 <.005 .004 .004 .0011 .0403 -
0 .16 .09 .09 .004 .0005 1.22 9.75 .05 1.37 .22 .05 <.005 .004 .004 .0009 .0410 -
E .16 .10 .09 .004 <.0005 1.22 9.74 .06 1.36 .22 .05 <.005 .005 .004 .0009 .0409 .0015
F .16 .09 .09 .004 <.0005 1.22 9.69 .05 1.36 .22 .05 <.005 .004 .003 .0011 .0423 -
I .15 .10 .09 .004 .0005 1.22 9.68 .05 1.36 .22 .05 <.005 .004 .004 .0009 .0409 -
J .15 .09 .09 .004 .0005 1.21 9.69 .05 1.35 .22 .05 <.005 .003 .003 .0009 .0397 .0012
K .15 .08 .09 .005 <.0005 1.21 9.68 .05 1.36 .22 .05 <.005 .004 .004 .0010 .0407 -
L .16 .09 .09 .004 <.0005 1.22 9.66 .05 1.36 .22 .05 <.005 .004 .003 .0010 .0412 -
M .15 .10 .09 .004 .0005 1.22 9.69 .05 1.36 .22 .05 <.005 .004 .004 .0010 .0410 .0015
N .16 .07 .09 .005 .0005 1.21 9.69 .05 1.35 .22 .05 <.005 .004 .004 .0011 .0402 -
Q .15 .07 .09 .004 .0005 1.22 9.71 .06 1.35 .22 .05 <.005 .004 .004 .0012 .0422 -
R .15 .08 .09 .004 .0006 1.21 9.69 .05 1.35 .22 .05 <.005 .004 .003 .0012 .0423 .0009
S .14 .06 .10 .004 <.0005 1.19 9.55 .05 1.32 .21 .04 <.005 .004 .003 .0010 .0338 .0013
T .13 .06 .10 .004 <.005 1.18 9.51 .05 1.31 .21 .04 <.005 .004 .003 .0010 .0365 -
such as As, Sn and Sb were controlled at a low level. Oxygen content is

around 15ppm.
Sulphur Print and Macrostructure

Sulphur print and macrostructure of the cross section of 1750mm dia LP
section and 1200mm HP section were examined. No indication of Sulphur is
0.02YS:685MPa
0.2YS :743MPa
T.S. :867MPa r-0-.0-2Y-S-:6-9-7-M-P....,a
EI. :20.8% 0.2YS :756MPa
R.A. :60.1°~ T.S. :884MPa
fATT :·2OC(O) EI. :19.6%
: OOCII) R.A. :58.5%
U.S.E. :15&1 FATT :+4OC(O)
:+4°CII)
U.S.E. :157J
0.02YS:708MPa O.02YS:659MPa 0.02YS:669MPa O.02YS:688MPa

O.2YS :758MPa 0.2YS :723MPa O.2YS :723MPa O.2YS :743MPa
T.S. :882MPa T.S. :870MPa T.S. :866MPa T.S. :867MPa
EI. :20.4% EI. :24.7% EI. :24.1% EI. :20.5%
R.A. :60.5% R.A. :57.6% R.A. :59.0% R.A. :60.9%
FATT :·6OC FATT :·3OC FATT :·7OC FATT :·15OC
U.S.E. :134J U.S.E. :128J U.S.E. :149J U.S.E. :153J
Fig. 5 Tensile and impact properties at various location in the rotor forging
observed in the sulphur print. The macrostructure showed a fine solidifica-

tion structure and with no defects.
Microstructure
The microstructures of the surface and the centre location of the LP section
were examined. A homogeneous tempered martensitic structure with a prior
austenite grain size of around 3.5 were obtained at both locations.
Tensile and Impact Properties

Figure 5 shows tensile and impact properties at various locations. Tensile
properties are uniform in the whole forging from the surface to the centre.
Impact properties satisfy the target value of less than 20°C. The FATT at the
centre portion of LP section is -3°C. These results yield the toughness versus
strength balance at the centre portion of LP section as shown in Fig. 6. In the
figure, the results obtained from the simulation heat treated materials are also
plotted in order to clarify the correlation of the wide strength range. This
figure demonstrates that the considerably good toughness can be attained in
the high strength region compared with the low alloy steels.2-8 It should be
noted that the HP section material showed similar strength versus toughness
balan.ce.
Creep Rupture Strength

Figure 7 shows the creep rupture test results obtained from surface material
of HP section and from laboratory heat materials. The rupture curve of the
CIMoV Steell8J
ModtIecI
1-'120 CrMoV Steel C4J
700 800 900 1000 1100

Tensile StrengIh , APa
Fig. 6 Tensile strength versus toughness balance
500
400
l:I
.•.
.c: 300
c.
c:
IV) CrMoVsfee'
.•.e::I
(Smooth)
200
t•.
l- f). : Lab. heats,
e
S6re
" : Lab. heats , 6500e
0 o: Tria. rotor, S6re
~ o: Tria. rotor, aoooc
I <> : Tria. rotor, 6300e

•.. Open: Smooth
Solid :Notch
100
400 450 500 550 600

Temperature, °C
Fig. 7 Creep strength of the 9CrMoVNiNbN steel

HIGH PURITY9CRMoVNINBN ROTORFORGING 405
developed material exceeds that of CrMo V steels and falls on the average
curve of conventional 12CrMo V steels. This suggests that the material can be
used for a HP steam temperature of 566°C.
Fracture Toughness
Figure 8 shows the fracture toughness transition properties of materials from
the centre of HP and LP sections. The fracture toughness at the room
i~ •..
300 •
0
LP portion
HPporfion
~
200
50 100 150 200

Temperafure, DC
Fig. 8 Fracture toughness of the material
temperature is high uppershelf toughness and this should increase the

serviceability of the rotor forging.
Low Cycle Fatigue Strength

Figure 9 shows the results of low cycle fatigue test. The result shows the low
cycle fatigue strength of the material at room temperature and 538°C is
equivalent to that of the conventional CrMo V steels.
Temper Embrittlement
Figure 10 shows the change in FATT of the material for 30 OOOhaging. No
significant increase of the FATT occurred up to 30 000 h. This suggests that the
material is insensitive to the temper embrittlement or carbide embrittlement
occurred in the temperature range tested.
SUMMARY
The 9%CrMoVNiNbN steel for future HLP turbine has been developed and a
trial rotor forging has been manufactured and evaluated. The results are
summarised as follows.
103--~~~~~--~~~~~~~~.u~
102 103 104 105
Cyc'. to Fal.ure at 53rC
Fig. 9 Low cycle fatigue strength of the material at 538°C
100
Aging Temper.ture
80
_e-
-.- 343°C
38.·C
60 -A- 454·C
-6- 454·C
C) -v- 482°C
0 40
I- 20
l-
e
I&. 0
·20
-40
·60
As QT 1000 10000 100000
Aging tim e , hrs
Fig. 10 Change in FATT due to the isothermal ageing at various temperatures
1. gO/oCrMoVNbN steel with 1.3% Ni is determined to be the optimum

chemical composition on the standpoint of toughness and strength
balance for the LP section and creep strength for the HP section.
2. A trial rotor forging with 1750mm diameter LP section and 1200mm HP
section was manufactured with homogeneous metallurgical and
mechanical properties.
3. The LP centre has excellent strength versus toughness balance and HP
section material has creep strength equivalent to that of 12CrMoV steels,
which meets the aim of the present research.
4. Uppershelf fracture toughness is attained at room temperature.
5. The material is proved to be insensitive to the temper embrittlement.
REFERENCES
1. K. Kogami and H. Isaka: Testu to Hagane, 1990, 76, 1403.

2. M. Yamada, Y. Tsuda, O. Watanabe, M. Miyazaki, Y. Tanaka, T. Takenouchi
and Y. Ikeda: Proc. Clean Materials Tech., Chicago, USA, November 1992,
161.
3. Y. Fukui, M. Shiga, K. Hidaka, R. Kaneko and T. Tan: ibid., 249.
4. Y. Kadoya, T. Kitai, 1. Tsuji, A. Matsuo, Y. Tanaka, T. Azuma and Y. Ikeda:
Testu to Hagane, 1993, 79, 980.
5. E. Potthast, J. Poppenhanger, W. Wiemann and K. Mayer: Proc. 11th
Forgemasters Meeting, Terni, Italy, June 1991, NO. IX-8
6. Y. Tanaka, Y. Ikeda, K. Ohnishi, S. Kawaghuchi, O. Watanabe, A. Kaplan,
R. C. Schwant, R. I. Jaffee and G. Poe: ibid., No. IX-7.
7. K. Kimura, T. Azuma, Y. Tanaka and T. Ishiguro: CAMP - The Iron and Steel
Institute of Japan, 1991, 4, 2032.
8. V. P. Swaminathan, J. W. Steiner and A. Mitchell: Advanced Rotor Forging
I
for High Temperature Turbines', EPRI Report CS-4516, Vol. 2, 1986.

Development and Manufacturing of
Advanced 12%Cr Rotor Forgings for
Ultra High Temperature Steam
Conditions
T. TSUCHIYAMA, O. MATSUMOTO, O. ISHIYAMA,
Y. YASUMOTO and T. ABE
Kobe Steel Ltd, 2-3-1 Shinhama Araicho, Takasago City, Hyougo, Japan 676
ABSTRACT
The need to improve the thermal efficiency at steam power plant, will require
increasingly higher temperature and pressure for the steam. Since CrMoV steel
forging and conventional 12%Cr steel forgings have insufficient creep rupture
strength at the steam temperature of 593°C and above, 12%Cr rotor forgings with
higher creep rupture strengths have been needed. Kobe steel has developed 12 Cr
%
steels named TMKI and TMK2, with higher creep rupture strength for the steam
temperature of 593°Cand above and these rotor forgings have been used at power
stations of 1000MW class.
1. INTRODUCTION
The coal-fired Ultra Super Critical (USC) power generation is now drawing
attention as one of the methods for saving energy resources and reducing the
dependence on oil. The steam temperatures of current fossil power turbines is
538°C or 566°C. The raising of steam temperature to 593°C and above is
expected to greatly enhance thermal efficiency. In particular, the steam
turbines with high efficiency at coal-fired power stations are needed to
mitigate global warming.
In view of this need Kobe steel has developed the TMKl1,2 and TMK23
forgings with higher creep rupture strength for the steam temperature of
593°C and above. These new 12 Cr forgings have been practically manu-
%
factured for a Ultra Super Critical power plant. Kobe steel has also manu-
factured 12 Cr steel forgings from X22CrMoV121 steel for 566°C and HRll00
%
steel for 593 or 600°C steam temperature. However, the 12%Cr steel rotor is of
inferior properties for bearing journals, and the abnormal wear at the journal
occurred+ Accordingly, the countermeasures such as shrunk-on sleeves,
metal plating and overlay welding have been applied for the journal portion
of the turbine rotor. Kobe steel performed the overlay welding by submerge
arc welding (SAW) due to high reliability.f
408
MANUFACTURING OF ADVANCED
%
12 CR ROTOR FORGINGS 409
This paper describes the manufacturing experience of 12 Cr %

steel rotor
forging and overlay welding in Kobe steel.
2. MANUFACTURING EXPERIENCE OF 12%CR ROTOR FORGINGS

IN KOBE STEEL
Table 1 shows the manufacturing experience of 12%Cr rotor forgings in Kobe

steel. Twenty-one 12 Cr rotor forgings have been manufactured
%
from
X22CrMoV121, TMKl, TMK2 and HRl100 steels through ESR process.
Table 1 Manufacturing Experience of 12% Cr Steel Rotors in Kobe Steel
Steam Capacity Steel

Temperature Plant (MW) Overlay Delivery Number
EPDC Ishikawa No.1 156 X22CrMoV Yes 1983 2

EDPC Ishikawa No. 1 156 X22CrMoV Yes 1983 2
566°C
Tohoku Noshiro No.1 600 X22CrMoV Yes 1990 1
Taiwan 600 X22CrMoV Yes 1995 4
EPDC Wakamatsu 50 TMKl 1985 1
Chubu Hekinan No.3 700 TMKl 1990 1
593°C Hokuriku Nanaoota No.1 500 TMKl 1991 1
EPDC Matsuura No.2 sooo TMKl Yes' 1994 2
Chugoku Osaki 250 HRII00 ' Yes 1995 1
Chugoku Misumi No.2 1000 TMK1/2' Yes 1995 2
600/610°C Tohoku Haranomachi No.2 1000 HR1100 Yes 1995 2
EPDC Tachibana bay No.2 1050 TMK2 Yes 1998 2
The EPDC's Wakamatsu rotor was the world's first 12%Cr steelrotor for
use at the steam temperature of 593°C. This rotor was successfully operated in
the demonstration USC plant for two years.
The Chubu Electric's Hekinan No.3 is the world's first commercial power
plant for the steam temperature of 593°C. TMK1 steel forging was applied to
the intermediate pressure rotor and has been smoothly operated since 1993.
TMK1 steel forging is also being evaluated as Steel Eat the COST program so
far." The TMK2 steel forgings were applied to the Misumi and the Tachibana-
bay power stations with a steam temperature of 600°C.
The improvement of bearing characteristic is important in enabling the use
of a 12 Cr steel forging. An overlay welding teclmique was developed and
%
applied to eighteen 12 Cr rotor forgings. The improvement of welding

%
method from Metal Arc Gas (MAG) to Submerge Arc Welding (SAW) was
performed to obtain high quality in the welded portion. The quality of
submerged arc welded rotors showed high level and high stability.
Steel Melting and

Casting of Electrode Heat Treatment
Electroslag
l Remelting Machining
I F)ging I
Cold Rolling
Fig. 1 Manufacturing Process of TMK1/TMK2 Rotor Forging
3. MANUFACTURING AND QUALITY OF TMK1ITMK2 ROTOR

FORGINGS
3.1 Manufacturing Process

Figure 1 shows the manufacturing process of TMKl12%Cr rotor forgings. The
electrode which was refined by the vacuum carbon degassing (VCD) were re-
melted by electro slag remelting (ESR) method. The ESR ingot was 72 tons in
weight and 1750 mm in diameter for 1000 MW class IP rotor forging. The ESR
ingot was forged on a 13 000 ton capacity press to half its height, and then it
was forged to about four times its length. After the preliminary heat treatment,
the quality heat treatment was carried out. The maximum rotor diameter
during the quality heat treatment was 1220 mm. The rotor forging was oil-
quenched from 1090°C and tempered at 550°C and 665°C. (in case of TMK2
steel forging, oil-quenched from 1050°C and tempered at 550°C and 685°C).
3.2 Properties of TMK1 Rotor Forgings

Table 2 and Fig. 2 show the chemical analysis results at various positions of
the TMK1 rotor. The chemical analysis are almost same as the target ones. In
Table 2 Chemical Composition of TMK1 Rotor Forging for Hekinan #3
C Si Mn P S Ni Cr Mo V Nb N Al
0.14 0.07 0.51 0.008 0.001 0.60 10.28 1.46 0.17 0.056 0 .046 0.003
MANUFACTURING OF ADVANCED 12%CR ROTOR FORGINGS 411
TOP....---_---li
~
e
"""
.•...
0.16
0.14 --•.
I-
• • e--~ • m•
0.12 I-
c
Q)
-------- .
E
... • []]
Q)
(j)
0.05
\f-
a
0.04 l-
• •
Q)
C)
co
.•...
[E§J
e--------.
c
0.06 .e-
•• • • •
Q) l-
0
l-
Q)
0- 0.05 I-
.•...
..c
C)
0.04
-.
0(i)
~ /Mol
1.50 •.... • • • • -e-
1.40 I-
Location
Fig. 2 Distribution of Chemical Composition of TMKl Rotor Forging for Hekinan

#3
spite of the large ingot, the change in composition with position is not
noticeable and thus the advantages of ESR are fully confirmed.
The macrostructures at the top of the ingot and the centre core, indicate no
abnormal structures, such as freckles or ghosts. The microstructures at
various positions in the rotor are martensitic. Delta ferrite and eutectic Nb
carbide are not evident. The grain size number is No. 3-4 as per the ASTM
method. This means that the grains are fine for this type of rotor.

Figure 3 shows the mechanical properties in the centre core of MATSUURA
IP rotor for a 1000 MW power station in comparison with WAKAMATSU and
HEKINAN rotors. The 0.20/0 yield strengths and tensile strengths are 76-80
kgf/rnm- and 90-93 kgf /mm-, respectively. The strength differences between
the top and the bottom are very little. In addition, the Sa%FATT of these three
rotors are 35°C or lower even at the centre core. They can be said that these are
very excellent values as IP or HP rotors.
3.2.4 Creep Rupture Properties

Figure 4 shows the creep rupture strength of the centre core of HEKINAN
rotor as a function of the Larson-Miller parameter in comparison with the
Top
d I D----r-, Bottom
cri
~ c- 90
- - --- .
-, 80
'cri E
a.: E
~
N ~ 70
0
i 60
'-'
<I. 50
a:
~ 20 (jOn - .•••---.A.~ ...»:::::~ ....-~ ...-:.:
..::-:::::.-::I-
10
80
e 60
~ 40
u.
20
o
EQ
10
6 5
~ o
Location
Fig. 3 Mechanical Properties of TMKl Rotor Forgings
50
··'6
40 ........... ~
• .~
30 ··~~ ..lPl Notched I
I Plain I t..,~...-.f:.
".
·Li·...
'-, ~
CIJ
CIJ
E • Hekinan # 3
-,
en
10 6. Wakamatsu
23 24 25 26 27
T (25 + log t ) Xl 03
Fig. 4 Creep Rupture in the Centre Core of Hekinan #3 Wakamatsu Rotors
-3
T (25 + log t ) Xl 0
Fig. 5 Comparison of Creep Rupture Strength at the Surface and Centre Core
results of the WAKAMATSU rotor. It can be seen that they are nearly equal to
the latter. Furthermore, the notch strengthening is also shown. Figure 5 shows
the creep rupture strength of the centre core and the surface. The latter is
slightly higher than the former, but the difference is little. Thus, it can be said
that TMK1 rotor has good and uniform creep rupture strength.
3.3 Property of TMK2 Rotor Forgings

Figure 6 shows the chemical composition distribution and mechanical proper-
ties of the centre core of TMK2 rotor forging. This rotor forging was
manufactured for an IP rotor from 55 ton ESR ingot. TMK2 rotor forging
contained 1.8 W. The distribution of C and W contents shows high homo-
%
ginity. The mechanical properties showed high uniformity and superior

values in Charpy impact properties in particular.
4. QUALITY OF OVERLAY WELDING TO JOURNAL PORTION
A SAW welding method is considered to provide superior quality and

workability than other welding methods for this purpose, thus the SAW
process was selected.
4.1 Trial Welding

The overlay welding by newly developed welding process by SAW were
performed to materials of TMK1 and TMK2 having the almost same diameter
414
n=cD--iJ
ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION
Bottom Top
c: ~ 90 I-
~. 0--0----0---0
u5 s
0...
~
S 80
-.
bO 70
l-
I--
0---0--0---0
C\.l
0
c· 60
r"-. 0-----0----0--0
2R
<;»
60 -
<
Ct:::
50 -
r<:
2R
<;» 20 - 0--0--0--0
&3
r<
10 -
~
<;»
40 -
~E-c 20 I-
-c 0- ~
~ - 20 -
S be
15 -
0--.0--0--0
~
'-../
10 -
Z 5 -
>
() 0
r"- 0.15I--
2R 0--0---0--0
'-" 0.10 f-
u
r--..
1.85 f-
0----0-0---0
2R
<:»
1.80 I-
Fig. 6 Mechanical Properties and Chemical Compositions Distribution of TMK2

Rotor Forging
to the production rotors. Extensive tests have been performed to verify the
quality of welded portion.
4.1.1 Non-destructive tests

Ultrasonic, magnetic particle and dry penetration tests were conducted to
evaluate the quality of overlay welding. Some indications of 0.4-1.0mm in
FBH were observed and it was found that they were not cracks but blow holes
of slag inclusions.
4.1.2 Distribution of Cr content

In order to enhance bearing characteristic, the Cr content should be less than
2.0%. The changes of chemical composition of weld deposite for TMKI and
TMK2 steels are given in Figure 7. According to this result, the Cr content of
less than 2.0% was obtained at the depth of 8 mm from groove.
MANUFACTURING OF ADVANCED 12o/oeR ROTOR FORGINGS 415
-+oJ
ai
-+oJ
3
c:
o
o 2
o
- 2 a 2 4 6 8 '.0 12
Distance from groove bottom (mrn)
Fig. 7 Changes of Cr Content in the Welded Deposit
II)
II)
C)
c:
"E
CQ
J:
Distance
Fig. 8 Hardness Changes of Welded Regions
90
en
.... roE 80
en
a..
~
-,
E
C) 70
N
0
0 60
>0- 10
C)
Gi 8
c:
E
(1)
'"C 01 6
Q)
..c ~
g
..c
4
~ 2
Weld Bond Base Weld Bond Base

Metal Metal Metal Metal
Fig. 9 Mechanical Properties of Welded Regions

4.1.3 Mechanical properties

The hardness changes of welded region for TMKl and TMK2 are given in Fig.
8. The hardness of welded deposit is Hv 215 to 240 and the maximum
hardness in HAZ is Hv 340 to 350.
The tensile and impact properties of the overlay welded regions of TMKl
and TMK2 are shown in Fig. 9. They met the requirement for a rotor journal. It
was thus clear that the overlay welding by SAW process could be successfully
performed.
4.2 Application to Production 12% Rotor Forgings

4.2.1 Overlay Welding
Figure 10 shows the schematic illustration of welding work. During the
process of preheat-weld-postheat, the entire rotor was also set on the turning
roller and heated uniformly. The welding workability was excellent.
Flux feeder
Heating furnace
Turning rollers Gas burner
Fig. 10 Schematic Illustration of the Overlay Welding Operation
4.2.2 Quality of Overlay Welding Portion

Ultrasonic, magnetic particle and dry penetration tests were conducted. All of
the indications were small. In the more recent rotors, no indication exceeding
0.7mm (equivalent of flat bottomed hole) have been in overlays applied to
TMK1 and TMK2 forgings.
CONCLUSION
Kobe steel has successfully manufactured twenty-one 12 Cr rotor forgings

%
from ESR ingots of TMK1, TMK2, HR1100 and X22CrMoV121 steels. Of these,
overlay welding to the journal portions have been applied to eighteen rotors.
Further studies are in progress to develop rotor forgings for even higher
temperatures and pressures.
ACKNOWLEDGEMENTS
We would like to thank greatly Mitsubishi Heavy Industries, Fuji Electric and
Hitachi Ltd.
REFERENCES
1. A. Hizume, Y. Takeda, A. Suzuki, S. Kinoshita et al.: 1987, 109, 319.

2. T. Tsuchiyama, K. Kiyoshi, M. Masayoshi, H. Arihara, M. Okamura and H.
Ohizumi: 11th Forgemaster meeting, 1991.
3. M. Kamada, A. Fujita, Y. Takeda, T. Fujikawa. H. Yokota, T. Tsuchiyama
and M. Miyakawa: Material Engineering in Turbines and Compressors,
Third International Charles Parsons Turbine Conference, 1995.
4. A. Hass, A. Zimmerman and H. Termuehlem: First International Con-
ference on Improved Coal-Fired Power Plant, EPRI, 178.
5. T. Tsuchiyama, Y. Murai, M. E. Murakami, M. Miyakawa and M. Okamura:
12th Forgemaster meeting, 1994.
6. C. Berger, S. M. Beech, K. H. Mayer, R. B. Scarlin and D. V. Thornton: 12th
Forgemaster meeting, 1994.
Development of Heat Resistant
12%CrWCoB Steel Rotor for USC Power
Plant
K. HIDAKA, Y. FUKUI, S. NAKAMURA, R. KANEKO*,
Y. TANAKAt and T. FUJITA§
Hitachi Research Lab., Hitachi, Ltd - Saiwai-cho 3-chome, Hitachi-shi,
Ibaraki-keu, Japan 317
* Hitachi Works, Hitachi, Ltd
t The Japan Steel Works, Ltd
§ Professor Emeritus, The University of Tokyo
ABSTRACT
The creep rupture strength of HP (high pressure) and IP (intermediate pressure)
turbine trial rotors made of HR1200 steel for the 1000MW class was evaluated.
Initially optimisation of Co, Band N contents was investigated by 50kg ingots
prepared by vacuum induction melting. The ESR(electroslag remelting) method was
then used for the trial rotors to control the segregation of the alloying elements.
Weights of the ESRingots were 20 tons for the HP rotor and 80 tons for the IP rotor,
respectively. Thermal treatment was carried out for the machined rotors before
evaluation of the creep rupture strength. Both rotors satisfied the target value of
creep rupture strength, 100 MPa, at 650°Cfor 100000 hours from the Larson-Miller
plots (LMP) with C == 40.
1. INTRODUCTION
Preservation of natural environment and fossil fuel has become a global

concern. In response to this growing demand for a cleaner environment we
have offered the USC (ultra-supercritical) steam power generation besides
new power generation systems, since coal is a major energy source among the
fossil fuels. Blum and Raldl compare thermal efficiency of USC, PFBC
(pressurised fluidised bed combustion) and IGCC (integrated coal gassifica-
tion combined cycle) power generations, and they concluded that the most
feasible solution is the USC concept.
Since the USC concept critically depends on the materials development
rather than new designs, the improvement of creep resistance is a key
technology of materials development. Hidaka et al.2 suggested the possibility
of an all-ferritic steel steam turbine, whose high temperature components
were all invented by Fujita, aiming for a target operating temperature of
650°C for the future USC power plant. This paper mainly describes the
418
DEVELOPMENTOF HEAT RESISTANT12%CRWCoB STEELROTOR 419
evaluation of the creep rupture strength of 12°loCrWCoB steel applicable for

turbine rotor (HR1200). Boiler materials are also mentioned.
2. MATERIAL DEVELOPMENT
2.1 High W (tungsten) Content

Common alloying elements for heat resistant 12%Cr steel are Mo (molyb-
denum), V (vanadium) and Nb (niobium). It is well known that these ferrite
formers improve the creep rupture strength of ferritic steels. However, V and
Nb cannot be added in large amounts because of their low solubility in steel.
Higher solubility in steel is required for better creep resistance with an
increase of the amount. The regression analysis of Mo and W contents on
creep rupture strength was obtained at 500°C and 550°C for conventional
12%Cr steel as
(fsoo0c(MPa)= 195.15 + 67.37(OloMo) + 55.90(%W) (1)
(fsso0c(MPa)= 117.19 + 29.32(OloMo) + 82.96(OloW) (2)
If the coefficients are compared in eqns (1) and (2), W shows larger
coefficient at higher temperature. It can be concluded that W affects better
creep resistance than Mo at higher temperatures. Fujita'' pointed out the
optimum composition of Mo equivalent is given at 1.5 by (Mo eq.) = (OloMo) +
O.5(%W).Tsuda et al.4 and Kadoya et al.s reported their optimum composition
of Wand Mo for new 12°loCr rotor is 1.8wtOlo and O.6wtOlo, respectively.
However, Fujita determined the optimum composition of Wand Mo for
HR1200 as 2.6 wtOlo and 0.2 wt%, respectively.
2.2 Optimum Chemical Composition

Although the increase of ferrite former content improves the creep strength,
the excess amount of ferrrite former addition may deteriorate the mechanical
properties because of delta-ferrite formation. Suppression of delta-ferrite
formation can be estimated by calculation of Cr equivalent. The Cr eq. is
expressed by the equation:
Cr-eq. = (%Cr) + 6(%Si) + 4(%Mo + 1.5(%W)+ 11(%V) + 5(%Nb)

-40(%C) -2(%Mn) - 4(%Ni) -2(%Co) -30(%N). (3)
Although the ferrite formers are all positive coefficients in eqn (3), the Cr eq.
must be reduced for suppression of delta-ferrite formation. Co (cobalt) is a
new additive as delta-ferrite inhibitor in 12°loCr steel. Pickering= mentioned
that B (boron) improves hardenability of the 12%Cr steels because small
Table 1 Chemical composition of the 50 kg ingots (wt%)
No. C Cr Mo W N Co B Cr-eq. Target
1 0.08 10.9 0.21 2.57 0.004 <0.01 <0.001 11.90

2 0.08 10.8 0.21 2.55 0.023 1.05 0.015 9.51
3 0.08 11.0 0.21 2.59 0.022 2.09 0.015 7.68 Co
4 0.09 10.7 0.24 2.62 0.023 2.68 0.015 5.79
5 0.09 11.0 0.22 2.63 0.022 4.17 0.017 2.91
6 0.08 10.9 0.20 2.55 0.021 2.52 <0.001 6.65
7 0.08 11.1 0.22 2.59 0.026 2.61 0.005 6.56
8 0.08 11.0 0.22 2.55 0.022 2.57 0.010 6.56 B
9 0.09 10.7 0.24 2.62 0.023 2.68 0.015 5.79
10 0.09 10.7 0.22 2.65 0.024 2.65 0.027 5.71
11 0.07 11.1 0.20 2.57 0.020 2.50 0.017 7.20
12 0.07 11.1 0.20 2.58 0.029 2.50 0.016 6.95 N
13 0.07 11.1 0.21 2.62 0.041 2.50 0.013 6.58
amount of B addition stabilises its austenite. As the formation of BN

(boronnitride) may reduce the effect of Band N (nitrogen) content is also the
concern for this alloy system.
The optimum amount of Co, Band N was determined by 50 kg ingots
prepared by vacuum induction melting (Table 1). The thermal treatment of
the 50 kg ingots was carried out by the following way
(i) Austenisation for five hours at 1050°C

(ii) Isochronal cooling at 100°Cjh
(iii) First tempering for twenty hours at 570°C
(iv) Second tempering for twenty hours at 720°C.
Effect of eo
The suppression of delta-ferrite can be performed by addition of any austenite
formers in 12%Cr steel. However, most austenite formers may deteriorate the
creep rupture strength. Figure 1 (a) shows delta-ferrite formation to 12%CrW
steel. The delta-ferrite disappeared with 1.05wt% Co addition to the 12%CrW
steel. When Co is alloyed to the 12%CrW steel, the Cr equivalent changed
from 11.90 to 9.51 and the delta ferrite was completely eliminated.
As the effect of Co addition on creep strength to 12%Cr steel is not well
known, the quantitative investigation was performed. The Co addition on
creep rupture strength shows inverse effect from common austenite formers
(Fig. 2). It can be concluded that Iwt? Co addition is good enough to
eliminate the delta-ferrite formation, but up to 3 wt% Co content is required to
increase the creep rupture strength.
DEVELOPMENT OF HEAT RESISTANT 12%CRWCoB STEEL ROTOR 421
Fig. 1 Optical micrographs showing suppression of delta-ferrite by 1.05% Co

addition
(A) Co free and (B) 1.05% Co addition
120~------------------~
•
•
40~--~--~--~--~--~
o 2 3 4 5
Co Content (wt%)
Fig. 2 650°C X 105 hrs. Creep Rupture Strength as a Function of Co Content
Effect ofB
The small amount of B addition to the 12 Cr steels enables the martensitic
%
transformation even lower cooling rate, because the B addition to the 12 Cr %
steels shifts the pearlite start to longer time scale and stabilises the austenite.
The B addition is preferable to the turbine rotors, because the stable martens-
itic transformation can be obtained for large heat capacity.
The remarkable increase of creep rupture strength can be obtained by the B
addition up to 0.01 wt" (Fig. 3), but a plateau is reached at higher boron
levels.
Effect ofN
Figure 5 shows the creep rupture strength obtained from the LMP with C =
40. The peculiar effect can be seen by the comparision of (A) B free and (B) B
added 12%Cr steels. If 12 CrWCoB steel is compared to conventional 12 Cr
% %
120
110
ca-
o,
~
';;; 100
•
en
~
US
90
0.03
8 Content (wt%)
Fig. 3 650°C X 105 hrs. Creep Rupture Strength as a Function of B Content
Fig. 4 Colour mapping of Band N with back scattering image
steel, the creep rupture strength shows inverse relationship as a function of N

content. It can be considered that the excess amount of N addition may
promote BN formation which offsets both Band N effects (Fig. 4).
3. ROTOR FORGING
3.1 HP Rotor Forging

The trial manufacturing of 1000 MW class HP turbine rotor was carried out
for the evaluation of the mechanical properties. Temperature control of
upsetting is an important part of the forging process. Figure 6 shows the
determination of maxmum temperature for the upsetting as a result of
fracture ductility from tensile examination at high temperatures.
Thermal history of the HP rotor (Fig. 7) was determined by coupon
specimens obtained from girth of the drum portion.
Chemical composition of the HP rotor was analysed from bottom, medium
and top sections of the drum portion at diagonal position as shown in Fig. 8.
300 140
(A)8 Free (8)8 Added
130
'@'
~ 250 a..
6- ~
en en 120
en en
~ ~
Ci5 200 en
110
150 100
0 0.02 0.04 0.06 0.08 0.1 0.02 0.03 0.04 0.05
N Content (wt%) N Content (wt%)
Fig. 5 100000 hours. Creep Rupture Strength as a Function of N Content

(A) B Free Conventional 12Cr Steel (Test Temperature: 550°C)
(B) B Added High W Content 12%CrCoB Steel (Test Temperature: 650°C)
100 ~
R.A.
co
Q)
(ij 50
'5
c
o
U
::J
"'0
Q)
a:
o
500 1000 1500
Test temperature (OC)
Fig. 6 Determination of the upsetting temperature as a result of reduction of area

from the tensile examinations at high temperatures
uO FC
Fig. 7 Thermal history of the HP rotor

SOh
FC
RB1 RM1 RT1
Fig. 8 Chemical composition (wt%) analysed from six sections of HP rotor girth
The gravitational segregation, such as Wand B, was suspected during steel

making process, because these elements show highly different atomic density
from Fe. However, the gravitational segregation was not detected in the HP
rotor. Thus, the ESR method was successfully utilised in the ingot making. It
can be concluded that an introduction of ESR method realised the homoge-
neous distribution of all alloying elements through entire region of the HP
rotor.
3.2 Creep Rupture Strength of HP Rotor

The creep rupture strength was evaluated by the specimens prepared from
the HP rotor girth (RB, RM and RT) as shown in Fig. 9.
It can be concluded that the creep rupture strength of the HP rotor satisfies
the target value of 100 MPa at 650 after 100 000 hours exposure obtained by
0
the LMP with C = 40. The arrows attached to the data points designate the
present situation of proceeding creep examination in Fig. 9.
3.3 Reconsideration of Ni (nickel) Content

It is well known that Ni addition to 12 Cr steel is required to sustain the
%
mechanical properties at room temperature. However, Ni addition tends to

DEVELOPMENTOF HEAT RESISTANT12%CRWCoB STEELROTOR 425
50
cr f0-
E
E 10-
~ 0
~ o 0
en 00
en
~ f0-
00
Ci) 00
:J
Q)
15..
::J
a: 10
LMP = 41.54 (650°CX100,OOO hours)

I I I I I
5
37 38 39 40 41 42 43 44
P = T(log t + 40)/1000
Fig. 9 Creep rupture strength evaluated from HP rotor girth by LMP
deteriorate creep rupture strength. Strang et al.7 reported that the creep
rupture strength of 12 CrMoV steel with high Ni content shows fast
%
degradation after long time exposure during examination.

The quatitative analysis of Ni content on creep rupture strength was
studied by three levels of the amount of Ni to the 12%CrWCoB steel ingots
(Table 2).
Table 2 Chemical analysis of 50 kg ingot (WT%)
C Si Mn Ni Cr Mo V Nb W Co B N
0.08 0.02 0.54 0.21 10.7 0.23 0.23 0.07 2.58 2.66 0.016 0.021
0.09 0.02 0.55 0.80 10.7 0.24 0.24 0.07 2.62 2.68 0.015 0.023
0.09 0.02 0.53 1.17 10.8 0.23 0.25 0.07 2.59 2.67 0.016 0.022
The negative slope of the creep rupture strength is obtained as a function of

Ni content to the 12 CrWCoB steel (Fig. 10).
%
It can be concluded that lower Ni content to the 12 CrWCoB steel increases %
the creep rupture strength. This result was used for the trial manufacturing of
IP rotor.
3.4 IP Rotor Foging

The chemical composition of IP rotor was modified after determination of the
amount of Ni addition as listed in Table 3. The steel making process of IP
rotor was followed by the same way as that of HP rotor.
8~----~----~------~----~----~
0.2 0.4 0.6 0.8 1.2
Ni (wt%)
Fig. 10 Creep rupture strength of 12%CrWCoB steel as a function of Ni content
Table 3 Chemical composition of IP rotor (wt%)
C Si Mn Ni Cr Mo V Nb W Co N B
0.10 0.06 0.46 0.25 10.21 0.14 0.21 0.07 2.51 2.44 0.017 0.013
3.5 Creep Rupture Strength of IP Rotor

The creep rupture strength was evaluated by the specimens prepared from
the IP rotor girth as shown in Fig. 11. Both HP and IP rotors satisfied the
target value of 100 MPa at 650°C after 100 000 hours exposure from LMP.
50
I 0: HP Rotor
• : IP Rotor
N
E
E
•
B,
~
en
en
~
U5
~ 10 ~
a. 90
::l
a: 00
LMP=41.54 (650 CX105hrs.)! 0
0
I I I I I ~
5
36 37 38 39 40 41 42 43
P = T(log t + 40)/1000
Fig. 11 Comparision of creep rupture strength evaluated from HP and IP rotors by

LMP with C = 40
DEVELOPMENT OF HEAT RESISTANT 120/oCRWCoB STEEL ROTOR 427
Table 4 Chemical composition of Boiler steels
Steels C Si Mn Ni Cr Mo W V Nb Ti Co B N
(A) Low Alloy High

0.10 0.2 1.2 - 0.6 0.5 - 0.06 0.02 - 0.004 0.002
Tension Steel
(B) High Strength Cr-
0.08 0.5 0.1 - 2.5 0.15 2.5 0.3 0.03 - 0.004 0.002
W-Mo-V-Nb-B Steel
(C) High Strength 1.2 0.005 0.050
0.10 0.4 0.5 - 10.5 0.15 2.5 0.2 0.06 -
11Cr Steel
(D) High Strength
0.05 0.5 2.0 13 18 0.2 3.0 0.2 0.30 0.06 - 0.005 0.12
Austenitic Steel (I)
(E) High Strength 0.05 1.0 1.0 25 22 0.2 3.5 - 0.35 0.06 - 0.005 0.12
Austenitic Steel (II)
4. BOILER MATERIALS
One of the authors proposed the possible application of the high strength
steels for the USC boilers as shown in Tables 4 and 5.
CONCLUSIONS
The results obtained in the present study are summarized as follows;

(1) Both HP and IP rotors satisfied the target value of 100 MPa at 650°C
after 100 000 hours exposure from LMP with C = 40.
(2) It can be said that the application of HR1200 and the proposed boiler
steels could realise the large scale USC plant with steam conditions of
35 MPa/ 650°C/ 650°C/650°C.
REFERENCES
1. R. Blum and J. Hald: 'Development of high-efficiency USC power plants in

Denmark', International Conference on Advanced Steam Plant, IMechE,
London, 21-22 May 1997, 3-16.
2. K. Hidala et al.: 'Development of 9-12% Cr steels for all-ferrite steam
turbine at target temperature of 650°C', International Conference on
Advanced Steam Plant, IMechE, London, 21-22 May 1997, 99-113.
3. T. Fujita: 'Current progress in 9-12%Cr ferritic heat resistant steels', Third
International Charles Parsons Turbine Conference, The Institute of Materials,
Newcastle upon Tyne, 25-27 April 1995, vol. 2, 493-516.
4. Y. Tsuda et al.: 'Development of High Strength 12% Cr Ferritic Steel for
o 0 o
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t.r)
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V
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io
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00
C't')
Turbine Rotor Operating above 600°C', International Conference on Power

Engineering-97, J5ME, A5ME and CSPE Joint, Tokyo, 13-17 July 1997,
131-136.
5. Y. Kadoya et al.: 'Alloy Design and Production of an Advanced 12Cr Steel
Rotor Applicable to Elevated Steam Temperatures', Fifth International
Conference on Clean Steel, Balatonfured, Hungary, 2-4 June 1997, Vol. 2,
167-177.
6. F. B. Pickering: Physical Metallurgy and the Design of Steels, Applied Science
Publishers Ltd., 1978.
7. A. Strang et al.: 'The Effects of Nickel on the Precipitation Characteristics
and Microstructural Stability of Creep Resistant Martensitic 12CrMoV
and 12CrMo VNb Turbine Steels', Microstructural Stability of Creep Resist-
ant Alloys for High Temperature Plant Applications, The Institute of Materi-
als, London, 1998.
Development of High Strength,
Corrosion Resistant Ferritic Steels for
Large Size Forgings in Gas- and Steam
Turbines with High Efficiency
A. GOECMEN, P. ERNST, P. HOLMES and C. TOENNES*
ABB Corporate Research Ltd., 5405 Baden - Dlittwil, Switzerland *ABB
Kraftwerke AG, 5405 Baden, Switzerland
SUMMARY
The development of ferritic steels with higher performance and improved

reliability for advanced gas- and steam turbines is a demanding and challeng-
ing task. This paper describes the development of a new class of corrosion
resistant, high nitrogen ferritic steels providing yield-strengths above
1000MPa up to 550°C.
Normalised and tempered 12% chromium steels containing 0.1 to
0.25wt.°loC are commonly used materials for large size forgings in gas- and
steam turbines. This class of steels may not meet the requirements for future
high efficiency gas turbines with increased loadings. As a result, they may
have to be replaced by modified higher strength 12°10 chromium steels or by
Ni-based alloys, such as IN706. The development of higher strength ferritic
steels with operation temperatures between 400 and 550°C demands partic-
ular attention to microstructural stability in order to achieve the required
toughness at a high strength level and to minimise the risks for significant
softening and embrittlement during operation.
New high temperature capable, high nitrogen variants of the steels have
been developed with improved heat treatment characteristics, which are
suitable for large size forgings. Particular emphasis was given to an effective
distribution of about 0.8 wt. °10 of vanadium nitrides during steel processing
and heat treatment. The low solubility and the resulting high coarsening
resistance of vanadium nitrides is used to increase the effectiveness of grain
refinement during forging and normalising as well as to increase tempering
resistance and microstructural stability during operation.
The newly developed class of martensitic steels are characterised by the
following features:
1. The nitrogen content is in the range between 0.15 to 0.18 wt.°lo and can be
introduced into 12°10 chromium steels at ambient pressure during
melting. Vanadium is slightly over stochiometrically alloyed to nitrogen
(O.6-0.8wt.%). This combination of nitrogen and vanadium has been
430
HIGH STRENGTH, CORROSION RESISTANT FERRITIC STEELS 431
shown to provide grain size limitation below 50 urn up to normalising

temperatures of 1200°C and a distinctly increased tempering resistance
in the tempering range between 600 and 700°C. The tempering charac-
teristics can be modified by a controlled isothermal ageing of the
austenite (ausageing) before the martensitic transformation producing
an ultrafine dispersion of vanadium nitrides.
2. Optimised ausageing was found to increase the yield-strength at ele-
vated temperatures. As an example, a yield-strength exceeding
1000MPa at 550°C can be realised with particle hardening of 0.9 wt. of %
vanadium nitrides. This is evidence, that precipitation hardening of

martensitic steels with vanadium nitrides is more effective at elevated
temperatures than with any previous precipitation hardening reaction.
3. Nitride strengthened ferritic steels are anticipated to be very cost
effective rotor materials in advanced high efficiency gas turbines with
operation temperatures between 400 and 550°C. Further optimisation of
ausageing towards an increased creep resistance promises to increase
the high temperature capabilities of ferritic steels for steam turbine rotor
applications.
Section 3B:
OXIDATION
Materials for Advanced Boilers
w. T. BAKKER
Electric Power Research Institute, 3412 Hillview Avenue, Palo Alto,
California 94304
ABSTRACT
One way to increase the efficiency of pulverised coal-fired stations, is to increase the
steam temperature and pressure. To do this without decreasing the reliability and
service life of the boiler, advanced materials are needed in critical areas. Major areas,
where advanced materials are needed, are high pressure steam piping and associ-
ated headers, superheater tube banks, and waterwalls.
Conventional heavy section materials do not have sufficient creep strength and
thermal fatigue resistance for service in ultra supercritical (USC) boilers. A number
of high strength creep resistant, 9-12Cr martensitic steels were therefore developed
and evaluated for this application. Two of the steels have obtained ASME boiler code
approval.
Higher metal and fluegas temperatures can lead to increased superheater corro-
sion for some types of coal. Extensive laboratory and field tests were carried out with
different coal types. This enabled the section of suitable alloys, depending on coal
quality.
At ultra supercritical pressures, waterwall temperatures will exceed the limits for
presently used low alloy steels. Replacement alloys are commercially available, but
need field testing. Waterwall corrosion may be a problem for some fuels, when low
NOx combustion systems are used. This may require the use of high chromium weld
overlays or coatings in affected areas.
Results from the studies described above indicated that future USC power plants
can most likely be built, and operated successfully, using commercially available
materials.
INTRODUCTION
Improvements in the efficiency of pulverised coal (P.C.) fired boiler/steam

turbine power plants have been implemented since the introduction of P.C.
fired boilers in the 1920s. This culminated in the late 1960s with the
introduction of supercritical boilers operating at about 570°C superheat/
reheat temperatures and 24 MPA pressure. Due to initial operating difficul-
ties, efficiencies then decreased at lease in the USA as most utilities preferred
subcritical units with steam conditions of about 535°C/17 MPA. The introduc-
tion of emission control devices, such as scrubbers, further decreased plant
efficiency.
The energy crisis and subsequent sharp increase in fuel prices gave new
impetus towards the development of more efficient P.C. power stations. The
435
development of ultra supercritical power plants has been vigorously pursued

ever since. Initial studies indicated that the construction of supercritical
boilers with a 60QoC superheat/reheat temperature and 31 MP A pressure
would be feasible with only minor, evolutionary improvements in materials
technology. This type of plant has since become the holy grail of boiler
development and boilers presently under construction or in design are
nearing this goal. Materials developments, since that time indicate the
feasibility to increase the goal to 620°C/34MPA, without revolutionary
changes in materials practice. The presence concern about C02 emissions has
further increased the urgency to raise plant efficiency.
The early studies also indicated the main areas, where further materials
development was required to achieve the desired performance goals. They
are:
• High pressure steam piping and headers. These components are preferably
made from ferritic/martensitic steels, because of their lower thermal
expansion and lower cost. Much of the operating problems with earlier
supercritical boilers were related to the use of austenitic headers, or very
thick walled P-22 type low alloy steels.
• Superheater/reheater tubing; Materials used in earlier supercritical plants
in the USA, selected for their high creep resistance, quite often suffered
from excessive corrosion, caused by liquid iron-alkali sulphates in the
tube deposits. This concern may be more urgent in the USA, where high
sulphur, corrosive coals are more frequently used then elsewhere, where
low sulphur, less corrosive merchant coal is usually the fuel of choice.
• Waterwall tubing; The concern here is twofold. High supercritical pres-
sures and the use of high heat release furnaces will increase the
waterwall temperatures to the point that easily weldable low alloy steels
such as T-ll (l.2SCr, O.SMo) have insufficient strength. Higher strength
steels such as T-91 are available, but require postweld heat treatments.
The other concern is waterwall corrosion. Recent results in the USA on
boilers retrofitted with low NOx burner systems, using overfire air,
indicate that the present low alloy steels can suffer from excessive
corrosion, as high as 2 mm/yr.
In this paper we will review the present state of development of materials
technology in the 3 areas outlined above, with some speculation about what
the future may bring.
HIGH PRESSURE STEAM PIPING AND HEADERS
These components have traditionally been made from low alloy steels such as
P-22 in the USA Even in conventional boilers, such headers can fail pre-
maturely due to thermal fatigue cracking, caused by frequent cycling. The use
of higher pressures and temperatures can only increase the problem. Previous
MATERIALS FOR ADVANCED BOILERS 437
attempts to use austenitic steels here have not been particularly successful due
to the high thermal expansion of these steels. Fortunately a 9Cr martensitic
steel was developed by Combustion Engineering and the Oak Ridge National
Laboratory in the late seventies for use in liquid metal cooled nuclear reactors,
which turned out to be eminently suitable for use in heavy section boiler
components.' It was approved by the ASME boiler code committee for various
uses between 1983 and 1986 as T,P,F-91. Since that time the alloy has found
applications worldwide and is available from many sources, since the compo-
sition is not proprietary. It is especially popular in Europe, where it proved
superior in creep strength as well as weldability, compared to the well known
X20CrMoV121 steel, used in supercritical boilers.
The high creep strength of grade 91 steel is due to small additions of V, Nb
and nitrogen, which lead to the precipitation of M23C6 carbides and MX (Nb,V)
carbonitrides, in addition to solution strengthening by Mo. Very extensive
studies were made world wide to evaluate the suitability of P-91 for heavy
section components. These included manufacturing studies, welding trials,
both similar and dissimilar, bending trials, both hot and cold, and various
mechanical tests, on both virgin and aged samples.v ' The net result of all these
tests is that P-91 is now the preferred heavy section materials for supercritical
boilers world wide. However most designers feel the use of P-91 will probably
be limited to steam conditions of about 580°C/25 MPA, a little short of the goal
of 600°C/31 MPA. This is especially the case in Europe, where the allowable
creep strength is about 10% lower than in Japan and the US.
Fortunately, Professor Fujita in Japan discovered that the creep strength of
9-12Cr, Mo, V, Nb steels can be raised by about 30% through partial
substitution of Mo by W.4 This has spawned another round of intensive alloy
development and evaluation worldwide+ Two of these steels, a 9Cr steel
developed by Nippon Steel (P-92) and a 12Cr steel developed by Sumitomo
Metals (P-122) have been approved for use in boiler heavy section compo-
nents by ASME. Another W containing steel E-911 is in advanced develop-
ment in Europe. The allowable strength of the new steels at 600°C is about
25% higher than that of P-91. Thus these steels should allow steam tem-
peratures up to 620°C and pressures up to 34 MPA.
Figure 1 shows a plot of the 100 000 hr creep strength of various piping
steels, as presented by Mayer," This figure clearly indicates the enormous
advances in materials technology which have been made in the last 20 years.
A very interesting fact is that application of the new steels may actually result
in a capital cost reduction. Figure 2 shows the allowable design stresses and a
comparison of the relative wall thicknesses at various temperatures." From
these, section thicknesses and materials costs can be calculated as a function
of temperature and pressure. Figure 3 shows the results for a pressure of
31 MPA (4500psi). The cost of using high strength steel becomes lower than
that of P-22 steel at about 520°C. The cost of using the W containing steel is
lower than that of P-91 above about 550°C. These relations do not change very
438 ADVANCED HE'AT RESISTANT STEELS FOR POWER GENERATION
Steel
Composition C Cr Mo W V Nb N B (Weight %)
a} 0.10 2.50 1.00 -
b} 0.20 12.00 1.00 - 0.30
c) 0.10 9.00 1.00 - 0.20 0.05 0.05
d) 0.10 9.00 1.00 1.0 0.20 0.05 0.07
e} 0.10 9.00 0.45 1.8 0.20 0.06 0.05 0.002
200
~:J
15.
~m
a.Q..
Q):2:
o s 100
Q)-
000>
L...t:
..c:~
0-
000
a I
c5
a I ca. 25°C I
T""
I· -I
I ca. 50°C
I·
O~--------~----I------~--------~
500 550 600 650
Temperature -c
Fig. 1 100 000 hr creep rupture strength of pipe steels
140
120
m
0.. 100
6
00
00
~ 80
en
CD 60
zsas
~
..Q 40
«
20
0 L..J
500 525 550 575 600 625 650 300mm
Temperature (CO)
Fig. 2 Comparison of allowable stresses and cross sections of main steam pipes
much with decreasing pressure down to 20 MP A (3000psi). Actual fabricated

and installed cost differences should be even larger as the thinner pipes need
less welding and are easier to instalL
SUPERHEATER TUBING
Several advanced superheater tube steels are either commercially available

i.e. code approved, or in an advanced state of development. Table 1 lists a few
200.---------------------~------~
o~--~--~--~----~--~--~--~
300 350 400 450 500 550 600 650
Temperature (C)
Fig. 3 Cost of P-22, P-91 and P-122 steels header material as a function of
temperature at 31 MP A steam pressure
Table 1Advanced Superheater Alloys
100000hr
Material creep strength
Designation Material Composition (wt.%) MPA 650°C
Cr Ni Mo W Nb Ti Other
SS 347 Fine grain 18 10 1.0 103

NF709 20 25 1.5 0.25 0.05 N 130
HR3C 25 20 0.4 N 114
of them. For the lower temperature parts of the superheaters the tube version
of advanced martensitic piping steels should be satisfactory, while several
austenitic steels are available for higher temperatures, based on creep
strength considerations alone. The question is will they resist liquid ash
corrosion, which according to the literature is most prevalent in the
550-650°C range.9/10 To investigate this EPRI, IHI and Foster Wheeler carried
out extensive laboratory and field tests in 3 boilers, 2 fueled with somewhat
corrosive Eastern bituminous US coal, one fueled with a supposedly non-
corrosive Western low sulphur subbituminous coal.l! The experiments were
carried out using air cooled, retractable probes, inserted in finishing super-
heater or reheater areas. Metal temperatures were maintained in the
600-690°C range (1250-1300 P). Exposure time was 16 000hrs with samples
0
removed after 4000, 12000 and 16000hrs. The composition of the alloys
exposed are given in Table 2. Figure 4 shows metal losses observed in one of
the boilers, using an Eastern bituminous coal, Fig. 5 those observed in the
Table 2 Alloys Used in Superheater Corrosion Field Tests
Material
Designation Material composition (wt. 0/0)
Cr Ni Fe Other
T-91 9 tr bal. Mo(2), V, Nb, N

17-14 CuMo 15.5 14 bal. Cu3, Mo 2.4
304 18-20 8-12 bal.
347 17-19 9-13 bal. Nb + Ta. = 10 X C. (min)
800HT 19-23 30-35 bal. Al + Ti = 0.8-1.2
310Nb 24-26 19-22 bal. O.OlC,0.25 Nb
Cr30A 30 55 bal. Mo 2, Ti, Zr
80 2.00
0
0310 Nb
0347
60 o 17-14 CuMo 1.50
• CR30A
E
.s
~ - 800H
gen 40 en
s
1.00 -.J
en
0
-.J Jg
Q)
~
20 0.50
4000 8000 12000 16000

Time (h)
Fig. 4 Metal losses of various superheater steels in a boiler using bituminous

Eastern US coals
100 2.0
0310
o 17-14 CuMo
80
.304 1.5
o T91
~ E
g 60 -800H g
(J) CI)
(J)
0 1.0 ~
-I -I
(ij 40 (ij
CD CD
~ ~
0.5
20
0 0
0 4000 8000 12000 16000
Time (h)
Fig. 5 Metal losses of various superheater steels in a boiler using subbituminous

Western US coals
boiler using subbituminous Western coal. The losses observed were about the
same but the corrosion mechanisms were different. Tubes from the boilers
using Eastern bituminous coals showed the classic liquid ash corrosion in the
10 and 2 o'clock positions of the tube, where sulphur rich fly ash impacts on
the tube. K rich sulphate was found in the ash deposits, and metal wastage
was caused by internal oxidation and sulphidation, because a fully protective
Cr203 scale could not form in the presence of sulphur rich deposits. With
increasing Cr content in the alloy the Cr203 scale became more protective, but
in all alloys internal oxidation and sulphidation occurred in Cr depleted
zones below the scale.
The corrosion morphology of the tubes from the boiler using Western
subbituminous coal was similar, but the area of major attack was on the side
of the tube facing away from the flue gas stream, where deposits rich in very
fine CaS04 were found.
From the results presented above it may be concluded that substantial
superheater corrosion can occur, especially in high strength austenitic alloys
with a low Chromium content. For most coals high strength modified Alloy
800 type alloys such as NF709, will probably have sufficient corrosion
resistance, while for more corrosive coals modified SS 310 type alloys, e.g.
HR3C, should give an extra margin of safety. It is of interest to note here that
the T-91 sample exposed in the low sulphur coal fueled boiler had a corrosion
loss similar to SS 347, which is considerably less than that of SS 304 and
17-14CuMo. A probable reason is that scales and deposits usually adhere
tight to ferritic/ martensitic steels, but spall readily from all austenitic steels.
WATERWALLS
Metal Temperature Concerns

This issue has been discussed recently by Blum.l- In boilers operating at
625°C/32MPA maximum midwall temperatures can be as high as 500-525°C,
depending on magnetite deposits at the inside of the tube. This means that the
standard low alloy ferritic steels such as T-ll are not adequate. Originally
T-91 steel was the only suitable substitute. Under the COST program= it was
demonstrated that this material can be fabricated into waterwalls. However a
postweld heat treatment is required, which is difficult to do in the field. Two
steels containing 2.5 and 12Cr % respectively developed by Sumitomo and
MHI are more promising in that they do not require preheat or postweld heat
treatment.lv-! Both steels have creep strength in the same range as T-91 and
use similar precipitation strengthening mechanisms. Especially the 2.5Cr steel
appears promising for this application. It also has recently been approved by
the ASME boiler code committee as T-23. Test panels are now in service in
various boilers.
Waterwall Corrosion Concerns

Recent reductions in NOx emissions, mandated by the Environmental Protec-
tion Agency in the USA have led to the introduction of deeply staged
combustion systems, in which the air/fuel ration is significantly less than 1,
and additional combustion air is added above the burners via overfire air
ports. Several boilers in the USA retrofitted with such systems have reported
severe corrosion of low alloy steel waterwalls, with metal losses in the 1-3
mm/yr range. Supercritical units are generally more severely affected than
sub critical units and there is a good correlation between corrosion loss and
the sulphur content in the coal. The highest corrosion losses are found in
regions where H2S rich substiochiometric flue gas mixes with air from the
overfire air ports. Laboratory studies indicate that the high corrosion rates
cannot be explained by the presence of H2S and CO in the flue gas alone.
Work by Kung15 has shown that corrosion rates in gasmixtures, actually
found in boilers, containing 500-1500 ppm H2S and 5-10% CO, are generally
less than 0.5 mm/yr at 450°C. More recently it was shown that the presence of
FeS deposits can greatly increase the corrosion rate, but only under alternat-
ing oxidising/reducing conditions or oxidising conditions alone. Figure 6
shows corrosion losses of a low alloy steel, T-91 and SS-304 in the presence of
FeS containing deposits and a gasmixture containing 1% oxygen. Although
the corrosion rates are probably artificially high, because of the short duration
of the test, it is clearly demonstrated that low alloy steels will corrode quite
rapidly in the presence of FeS deposits and an oxidising gas. The tests further
show that clad dings or weld overlays containing at least 18 and preferably
120 .------------------, 10.2

c::::::J By weight loss
100 ~ By descaled thickness 8.5
E
..=;
80
-
fZZllnner
By x-section thickness
scale thickness 6.8 E
t
en cD
~ 60
-I
5.1 ~
c:
(ij o
·00
~ 40 3.4 e
o
o
20 1.7
o
~cv &
~
(Qrti s
!!,.0
~
~
!(0
~
r;iV
s
~
s~
!!,.0
~
!!,.0
~
~
!!,.0
~ ~
~~ ~~
~
s:~ ~~ ~ ~~
~ ~t...;, §
~
Fig. 6 Corrosion of steels containing 0.5-18% Cr under FeS containing deposits in
oxidising flue gas
more than 20 Cr are needed to assure acceptably low corrosion rates. Field
%
trials are presently in progress to substantiate these preliminary findings.
CONCLUSIONS
1. The materials technology needed to construct ultra supercritical boilers

with steam temperatures in the 600-620°C range and steam pressures in
the 30-34 MPA range is largely available, most of it in the form of
commercial, code approved, products.
2. For heavy section piping and headers the widely accepted P-91 steel will
suffice for moderately advanced steam conditions, while the recently
code approved, tungsten strengthened steels P-92 and P-122 steels will
be more than sufficient for boilers with 600°C/31 MPA steam condi-
tions.
3. Superheater materials, with sufficiently high creep and corrosion resist-
ance are also generally available, although some of the promising
candidates still need code approval. There may be a need for more
corrosion resistant materials, for corrosive, generally high sulphur
coals.
4. The concern about weldable high temperature waterwall materials has
largely been eliminated by the introduction of T-23 steel. However field
experience is needed to confirm its suitability.
5. Corrosion of waterwalls in supercritical boilers may be a problem for
some fuels and low NOx combustion systems. This area is the subject of
intensive R&D in the USA Promising laboratory results are awaiting
confirmation by field trials, which are in progress.
REFERENCES
1. B. W. Roberts and D. A. Canonico: 'Candidate uses. for modified 9Cr-lMo

steel in an improved coal fired power plant,' Proc. 1st Int. Conf on
Improved Coal Fired Power Plants, 19-21 Nov. 1986, Palo Alto, CA, EPR!
report CS-5581-SR, 5-57.
2. T. Topoda et al.: 'Development of thick walled pipes and headers of
modified 9Cr steel,' Proc. Second Int. Conf on Improved Coal Fired Power
Plants, 2-7 Nov. 1988, Palo Alto, CA, EPR! report GS-6422, 36-1.
3. B. W. Roberts et al.: Thick Section Welding of Modified 9Cr-1Mo (P-91) Steel,
EPR! report TR-I01394, September 1992.
4. T. Fujita et al.: 'Development of a ger steel,' Reference I, 5-201.
5. E. Metcalfe ed.: Proc. New Steels for Advanced Power Plants, 11 May 1995,
London, EPR! report TR-I04952.
6. K. H. Mayer: Presentation Workshop on Tungsten Strengthened 9-12 Cr Steels,
Amagasaki, Japan, 21 Oct. 1997.
7. F. Masuyama and F. T. Yokoyama: 'NF616 fabrication trials in comparison

with HCM12A,' Reference 5, 30.
8. Z. Yang et al.: 'Steels for thick section parts: Comparison of economics of
usage in a typical design,' Reference 5, 174.
9. L. Cain and W. Nelson: 'Corrosion of Superheaters and Reheaters of
Pulverized Coal Fired Boilers,' from ASME series A83 461, 1961.
10. R. W. Borio et al.: The Control of High Temperature Fireside Corrosion in Utility
Coal Fired Boilers, OCR R&D report no. 41, 1969.
11. J. L. Blough et al.: Superheater Corrosion: Field Test Results, EPRI report TR-
103438, November 1993.
12. R. Blum: 'Materials development for power plants with advanced steam
parameters. Utility point of view,' Proc. Materials for Advanced Power Eng.
1994, 3-6 Oct. 1994, Liege, BeIg., Kluwer Ac. Publ. Dordrecht, The
Netherlands, 15.
13. C. J. Franklin and C. Henry: 'Materials developments and requirements
for advanced boilers,' Reference 12, 89.
14. F. Masuyama, Y. Sawaragi et al.: 'Development of a tungsten strengthened
low alloy steel with improved weldability,' Reference 12, 173.
15. S. C. Kung: 'Prediction of corrosion rate for alloys exposed to reducing/
sulfidizing combustion gases,' Corrosion 97, NACE 1997, 97-136.
Low Alloy Steel Tl.I - Austenitic
Stainless Steel 347H Bimetallic Tubes
for Corrosive Environments in Steam
Power Plants
J. A. BERROETA*, J. VALLE*, E. AYALAt, M. A. ROMANt,
J. DE LUIS§, X. COMEZ<jf and J. ECHEBERRIA 1[
* Tubacex, Tres Cruces, 8, 01400 Llodio, Alava, Spain
t Babcock Wilcox Espafiola (BWE), 48510 Galindo, Vizcaya, Spain
§ Iberdrola, P" Virgen del Puerto, 53, Madrid, Spain
YI Centro de Estudios e Investigaciones Tecnicas de Gipuzcoa (CElT),
P" Manuel de Lardizabal, 15, 20009 San Sebastian, Spain
ABSTRACT
The results shown in this paper make reference to a research project in which are
involved different companies from the Basque Country (Spain): Tubacex, Babcock
Wilcox Espanola (BWE)and Iberdrola, and the research centre, Centro de Estudios e
Investigaciones Tecnicas de Gipuzcoa (CElT). The objective of this project was the
fabrication by co-extrusion of bimetallic tubes for corrosive environments at high tem-
peratures. Although in this project three different combinations have been studied, in
this paper only the results from one of these combinations are taken into account: Low
Alloy Steel TIl inside with an outside cladding of Austenitic Stainless Steel 347H.
The microstructures of the bonding obtained by co-extrusion, have been compared
to those obtained in the laboratory by diffusion bonding using hot plain strain
compression and hot isostatic pressing (HIP). In all cases the interdiffusion of the
different elements through the interface and the microstructure of both the as-
processed and after heat treatment products have been analysed by scanning
electron microscopy (SEM).On the steel side, as a result of the diffusion of nickel and
chromium from the stainless steel to the steel, a precipitation free austenitic band is
observed. While a profuse precipitation, mainly of NbC is found in a region near the
interface on the stainless steel side.
The optimum heat treatment performed has taken into account the best combina-
tion of mechanical strength and corrosion resistance. This heat treatment consists of
an austentisation at l050-1100°C + water quenching and a stabilisation treatment at
850-900°C.
In order to study the behaviour in industrial conditions the tubes have been
installed in the reheater of a supercritical boiler manufactured by BWE of an Electric
Power Plant of Iberdrola in Asturias.
1. INTRODUCTION
In many industrial applications, materials are subjected to both high stresses
(including high temperatures) and high corrosive environments. Materials
445
having both properties are very scarce and therefore bimetallic combinations,
for instance a high strength and low cost carbon steel with a cladding of a
high corrosion resistance alloy (stainless steel or nickel alloys), are necessary
to cope with both requirements. In the case of bimetallic tubes, co-extrusion is
a well established technique! for an economical way of fabrication.
In the context of this project a very interesting industrial application was
found, in which the behaviour of the bimetallic tubes could be evaluated in
operation. The supercritical boiler of the Lada IV Electric Power Plant. In
several zones of the reheater specially where the abrasive action of both the
blowers and the combustion gases takes place, the first tubes of the coils, in
the gas flow direction, suffer noticeable thickness losses. With time, stainless
steel shields were installed shielding the tubes. This solution presents several
inconveniences, high cost, heat transference losses, inspection costs and shield
fly up. The substitution of bimetallic tubes, with the compliance of the ASTM
A213 standard is presented as a very valid option.
The present work describes the microstructural and mechanical properties
obtained during bonding a low alloy steel TIl lining to a Nb stabilised
austenitic stainless steel 347H by hot industrial co-extrusion and compared to
the laboratory diffusion bonding experiments. Inspection of the bimetallic
tubes substituted in the reheater has been carried out.
Table I shows the chemical composition of the materials used: Low Alloy
Steel SA-213 (Til) and Austenitic Stainless Steel 347H. The selection of 347H
steel was made to have a compatible heat treatment of both alloys. In this
sense, the Nb present in 347H stainless steel avoids the precipitation of
chromium carbides both during processing and in operation, which can
reduce the inter granular corrosion resistance.
The laboratory diffusion bonding experiments were carried out using HIP
at IIOO-IISO°C and 200MPa, and hot plain strain compression (HPC) at
1200°C, following the procedure reported elsewhere.? The bimetallic tubes
were produced by Tubacex S.A., using 190mm TIl bars and 234mm dia.
347H tubes. The TIl bars were located inside the holes of 347H tubes, and
Table 1 Chemical composition of steels used, wt-%.
Material C Mn Si Cr Mo Ni Cu Fe
T11(*) 0.10 0.46 0.54 1.04 0.49 0.13 0.28 Bal.

347H(**) 0.046 1.05 0.44 17.20 0.34 9.20 0.30 Bal.
* 190mm bars produced by Tubos Reunidos

**0 = 234 mm, t = 22 mm tube produced by Tubacex
Low ALLOY STEEL TIl - AUSTENITIC STAINLESS STEEL 347H 447
subsequently sealed, following the procedure patented by Tubacex S.A.3 The

assembled items were heated by low frequency induction heating to l200°C
and pierced in a vertical hydraulic press. After reheating, the pierced
assembled items were extruded to 88.9 mm dia. tubes having a total wall
thickness of lOmm (Tll: 7mm, and 347H: 3mm). Finally, they were cold
rolled to final dimensions of 50.8 mm dia. and 6 mm wall thickness (4.5mm of
T11 and 1.5mm of 347H). The tubes were heat treated before cold rolling in
order to obtain the suitable structure and mechanical properties.
Different heat treatments were performed to determine the optimum heat
treatment taking into account the best combination of mechanical strength
and corrosion resistance. Quenching in water after austenitising at 950-
1100°C for 30 min. Subsequent stabilisation treatment at 600-900°C and air or
furnace cooling were tried.
Specimens were cut from the laboratory diffusion bonded samples and
from the bimetallic tubes (as-processed and heat treated) and prepared using
conventional techniques for optical metallography and for examination in a
Philips XL30 scanning electron microscope (SEM). Two different etching
procedures were used to reveal the microstructure and carbide precipitation
in the 347H side: electrolytic etching with an aqueous solution of 10% oxalic
acid at 6V; and second for 3 mm dia. discs with the interface at the centre were
etched (abbreviated as foil etching) in a Struers Polipower unit using a
solution of 5% perchloric acid in acetic acid at a current of 150-200 rnA.
Variations in chemical compositions close to interface were studied by
energy-dispersive X-ray microanalysis (EDS).
In order to study the behaviour of the bimetallic tubes in industrial
conditions, the tubes have been installed in the blower zone of the reheater of
the supercritical boiler. In Fig. 1 is shown the blower zone (IK 35-36), and the
tube sections substituted by the bimetallic tubes. These sections have been
selected because they are subjected to the high erosion effect of the blowers.
Before the tube installation, cold and hot bending performance and welding
procedures have been carried out at BWE.
3. RESULTS AND DISCUSSION
3.1 Microstructural Analysis

Figure 2 shows optical micrographs of the interface and the regions close to it
formed during coextrusion. The tubes were observed after the heat treatment
performed before cold rolling, austenisiting at 900°C, slow cooling to 680°C,
and then air cooling. The carbides precipitation (in black contrast) in a region
close to the interface at the stainless steel side (Fig. 2a), indicates a profuse
carbon diffusion from the steel. EDS analysis carried out in the SEM indicate
that carbides are rich in Nb, This precipitation takes place both inside the
'+
Fig. 1 Blowers zone, inside the reheater, of bimetallic tubes substitution
grains and at the grain boundaries, but for greater distances from the last
precipitation. This could be due partly to the fact that boundary diffusion is
more rapid than bulk diffusion and partly to the fact that a lower carbon
supersaturation is required to form precipitates by heterogeneous nucleation
at the grain boundaries+ In contrast, on the steel side, as observed in Fig. 2b, a
(a) (b)
Fig. 2 Interface of bimetallic tube after coextrusion. (a) 347H side; (b) Tll side
Bimetallic Tube
.' .~~.....
%Fe %Cr%Ni %Fe
.....
HIP 1150°C %Cr %Ni
100 20 100 ~~~~----·----------~20
:
80 ••••• [] 0 C
16 80 16
•
•• DOC [J C
C :
: []
• .. •
60 0 12 60 '[] 12
40
It
• • 40
~
: .A···...
c:.
•
c .•
20 4 20 4
D .:
•
[] [J [J
0
0
-20 -10 0 10 -20 -10 0 10
T11 Distance hlm) 20 30
Distance (Ilm) 347H
(a) (b)
Fig. 3 Concentration profiles close to the interface: (a) bimetallic tube; (b) HIP at
1150°C
higher ferrite volume fraction band, of approximately 300 J-Lmwidth, can be

observed close to the interface implying steel decarburisation in this region.
Figure 3a shows clearly the inter diffusion of substitutional elements form
the 347H stainless steel to the TIl steel, and of Fe from the TIl to the 347H.
The distance diffused by these elements is ,....,5 J-Lm.Although, carbon can not
be analysed, and it is not included in this concentration profile, the presence
of the precipitates on the 347H side and the decarburated band on the TIl
side indicate faster carbon diffusion in comparison with substitutional ele-
ment diffusion, from the steel to the stainless steel. Although, in other
bimetallic combinations analysed like Carbon Steel/lncoloy 8255 or
4
AISI4130jlncone1625 ,6 a precipitation free austenite band has been found on
the steel side, close to the interface, in this case it is not found because as seen
in Fig. 3a the Ni concentration present in this zone is not high enough to
stabilise the austenite at room temperature.
Fig. 4 Microstructure of the 347H side (a) Optical micrograph after HIP; (b) SEM
micrograph after HIP and (c) SEM micrograph after HIP + HPC
The microstructure of the interface formed during the diffusion bonding

experiments using HIP, after furnace cooling, is shown in Fig. 4. In compari-
son with the microstructure corresponding to the bimetallic tube (Fig. 2), it is
found that by HIP, as a consequence of the isostatic pressing, the plastic strain
is at a minimum scale, and the grain size of 347H stainless steel is larger, since
recristallisation has not taken place. Like in extruded tubes, it can be observed
a profuse carbide precipitation close to the interface on the 347H side. As the
holding time at temperature and pressure is much higher in HIP (1 hour) that
in extrusion, the extension of diffusion is larger in HIP. As seen in Fig. 4a the
intragranular precipitation of carbides takes place up to greater distances.
This greater extension of diffusion, compared with extruded tubes is shown
in the concentration profiles included in Fig. 3. Whilst during extrusion the
diffusion of substitutional elements extend up to 5 urn, during HIP the width
of the zone affected by the diffusion is up to 15 urn for Cr, due to, according
with other works," its higher diffusion coefficient.
Figure 4b shows a SEM micrograph obtained by backscattered electron
contrast after foil etching. The niobium rich carbides appear in white contrast
due to its high atomic number. As shown in this micrograph the carbides,
mainly those ones precipitated inside the grains, look finer than in the optical
micrographs (Figs 3a and 4a). This difference is due to the more aggressive
effect of the oxalic acid etching used in optical microscopy pulling out the
carbides and leaving holes instead.
Low ALLOYSTEELTil - AUSTENITICSTAINLESSSTEEL347H 451
As shown in Fig. 4b, in contrast to the interface formed during extrusion,

after HIP a precipitation free austenite band, between 5-6 p.m in width, is
formed on the steel side in a direction parallel to the interface. As seen before,
the Ni diffusion is more extensive than during extrusion and is enough to
stabilise the austenite at room temperature.
Finally, the hot plain strain compression (HPC) after HIP, has been used to
simulate in a more approximated way the extrusion process. The micro-
structure of the stainless steel side after quenching is shown in Fig. 4c. It is
very clear in this figure that, in the same way as in hot extrusion and as a
consequence of the hot plastic strain, dinamic recristallisation has taken place.
Besides, there is a small amount of precipitation due to rapid cooling from the
experiment temperature (1200°C).
3.2 Heat treatments

The heat treatment performed must lead to the best combination of mechan-
ical strength and corrosion resistance, taking into account the different
properties of both alloys, the low alloy steel (T11) and the austenitic stainless
steel (347H). Therefore, this heat treatment has to be carried out in two steps.
First, an austenisation at temperatures higher than 1050°C to recristallise the
austenite grains of 347H and to dissolve the carbide precipitates formed
during its processing in an uncontrolled manner. Then, quenching in order to
avoid on cooling chromium carbide precipitation, responsible of intergra-
nular corrosion. The second step consists on a stabilisation treatment at
temperatures between 800-925°C to precipitate the desirable carbides, i.e.,
NbC. These carbides fix all the carbon of the matrix, avoiding sensitisation at
temperatures where chromium carbide can be formed. The later cooling must
be slow enough (furnace cooling) in order to optimise the mechanical
properties of T11 alloy.
In Table 2 are outlined the mechanical requirements of the standard
specification, ASTM A213, for seamless ferritic and austenitic alloy-steel
tubes."
A summary of the mechanical properties of bimetallic tubes after different
heat treatments are included in Table 3. In this table are included only the
results obtained after austenitising at 1050°C, since there are no differences
with the results obtained for 1100°C. The mechanical properties outlined in
this table are those corresponding to the as quenched state, and after different
Table 2 ASTM A213 standard.
Hardness (HV) Yield Stress (MPa) Tensile Stress (MPa) Elongation (%)
170 205 415 30

4S2 ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION
Table 3 Mechanical properties of bimetallic tubes after different stabilisation

treatments. Air and furnace indicate cooling performed.
Heat TIl Hardness Yield Stress Tensile Stress Elogation

Treatment (HV) (MPa) (MPa) (%)
As quenched 373
BOO°C-Air 188 255 599 31
BOO°C-
Furnace 163 290 580
B50°C-Air 177 265 612 30
B50°C-Furnace 158 31B 572 33
900°C-Air 189
900°C-Furnace 157 300 531 32
stabilisation treatments. 347H alloy hardness (18S-190 HV) is not included,

since it is independent of the stabilisation treatment.
A feature of interest shown in this table is that the variation in strength of
the bimetallic tube is related to the different response of the low alloy steel
TIl to the heat treatment, since the mechanical properties of the austenitic
stainless steel 347 are independent of the stabilisation treatment. As shown in
Table 3, and in comparison with the ASTM standard (Table 2), the T11
hardness after air cooling is higher than 170 HV and does not fulfil the
standard. Therefore, cooling after the stabilisation heat treatment has to be
slow enough in order to obtain a suitable ferrite-perlite structure in the low
alloy steel. Depending on mechanical properties the best recommendable heat
treatment is austenitising at 10S0-1100°C, quenching and a stabilisation
treatment at 8S0°C.
The variations of microstructure of bimetallic tubes with heat treatment are
shown in Fig. S. As a reference in Fig. Sa it is shown the microstructure of the
347H side in the as-cold rolled condition. As it is observed in this figure, the
austenite grains present a strained morphology, and a poor NbC precipitation
in zones far away from the interface. In Fig. Sb can be observed the
recristallised grains and the profuse precipitation of NbC (in white contrast)
obtained after a stabilisation treatment at 900°C during 2 hrs.
It is worth emphasising that chromium carbide precipitation can be
avoided only if the time at the stabilisation temperature is enough to assure a
profuse NbC precipitation. Only in this case there will not be carbon available
in the matrix to form chromium carbides at lower temperatures. An insuffi-
cient time of stabilisation leads to scarce NbC precipitation, therefore, C left in
the matrix is enough to form chromium rich carbides at temperatures in
which these carbides are harmful to inter granular corrosion. For instance, as
shown in Fig. Sc, if the stabilisation treatment at 900°C is performed only
during 30 min. the stainless steel is sensitised, and a heat treatment at
Low ALLOY STEEL Til - AUSTENITIC STAINLESS STEEL 347H 453
Fig. 5 (a), (b), (c) Microstructures of 347H side (a) after cold rolling; (b) 900°C, 3hrs;
(c) 900°C, 30 min. + 600°C 100hrs. (d) Microstructure of TIl side: 900°C + furnace
cooling
operation temperatures, for instance IOOhrs at 600°C, produces a copious

precipitation of chromium carbides (in grey contrast). Finally, Fig. 5d shows
the microstructure of the TIl side. From the interface, after the ferrite rich
band, it appears the ferrite-perlite microstructure formed after the stabilisa-
tion treatment at 900°C + slow cooling, that provides the optimum proper-
ties.
3.3 Industrial Testing

Before the installation of the bimetallic tubes cold and hot bending perform-
ance and welding procedures were carried out in order to define the tubes
workability.
Bending behaviour and welding procedures

Bending tests reveal that bimetallic interfaces are not detached in extreme
conditions of cold bending with curvature radius equal to the diameter and in
hot bending with curvature radius equal to half the diameter. On the other
hand, the increase of hardness produced as a consequence of the strain
induced during bending, is removed after the heat treatment.
300
Heterogeneus tensile test

270 TS: 548 MPa (brocked in b.m.)
(f)
YS: 406 MPa
(f) A%: 13
~ 240 E%: 54.2
o
~~ Bended (4t) 1800
:J: Faced and root: well
:;:r:
o 210
180
--=g;z !,I~ I I I" I I
150+-+-~-r-+-+-;~r-r-+-~~-r-r-+-;~
o 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
POINT
Fig. 6 Mechanical properties, hardness; and macro graph of a Tll///Tll-347H butt

joint
In Fig. 6 are reported the results obtained in one of the welding procedures
analysed (T11///Tll-347H butt joint).5 In this figure the mechanical proper-
ties and hardness of the weld joint and a macro graph of the specimen are
shown.
Tubes inspection
The bimetallic tubes were inspectioned after 3000 hrs of operation. In the
inspection performed there was not appreciated any kind of etching on the
bimetallic tube surface, still noticing the small superficial imperfections
caused by the fabrication process. Neither there was not any indication of
superficial erosion to the touch. Figure 7 shows the aspect of the bimetallic
surfaces at the maximum blower action zone. It can be observed as well the
shields of the adjacent tubes. Additionally, the welds did not show any
indication of superficial defects.
The measured external diameters of the bimetallic tubes ranged between
50.9 and 51.0mm, the same as fabricated. It was tried to measure the stainless
steel thickness, but the results were not reliable because the measured
thickness depended on the tube superficial finishing. Therefore, it can be
Fig. 7 Superficial aspect of bimetallic tubes implanted in the reheater
deduced that the behaviour of the bimetallic tubes located in the reheater has
been excellent and avoiding the danger of shields fly up.
4. CONCLUSIONS
Ultrasonic wave inspection and bending tests carried out on bimetallic tubes
show than an excellent metallurgical bond is obtained by hot extrusion. The
observed microstructural characteristics of the interfaces obtained by hot
extrusion and by laboratory diffusion bonding are very similar, indicating
that diffusion bonding experiments can be used to reproduce the metallurgi-
cal bond obtained by extrusion.
The interdiffusion of the different elements across the interface leads to a
profuse precipitation, mainly of NbC, in a region near the interface at the
stainless steel side, and a ferrite band close to the interface on the steel side.
Only on HIPed specimens, a precipitation free austenitic band is observed
parallel to the interface.
The optimum heat treatment determined, which takes into account the
different properties of both alloys, TIl and 347H, consists of an austenitisa-
tion at 1100°C + water quenching, and a stabilisation heat treatment at 900°C
for 2 hours, followed by slow cooling.
Inspection of bimetallic tubes after 3000 hrs of operation indicates that their
behaviour in the reheater has been excellent. The bimetallic tube substitution
in comparison with shields has important additional advantages, as are: its
lower cost, higher heat transference, and avoidance of shields fly up.
ACKNOWLEDGEMENTS
The authors gratefully acknowledge financial support from the Departamento

de Industria del Gobierno Vasco.
REFERENCES
1. E. P. Latham, D. B. Meadowcroft and L. Pinder: Mater Sci. Technol, 1989,

813.
2. J. A. Berroeta, J. Valle, E. Ayala, M. AvRoman, J. de Luis, X. G6mez and J.
Echeberria: Bimetallic Tubes for Corrosive Environments at High Tem-
peratures Applications, Proyecto de Cooperaci6n VET. Technical Report,
1996.
3. Tubacex SA: Eur. Patent no. 508733 and Certificate of Addition 517832.
4. B. 'Lopez, X. Gomez, J. Echeberria, I. Gutierrez, and J. J. Urcola: CMMC'96,
San Sebastian, 1996, 695.
5. J. A. Berroeta, J. Valle, E. Ayala, M. A. Roman, J. de Luis, X. G6mez and J.
Echeberria: Bimetallic Tubes for Corrosive Environments at High Tem-
peratures Applications, Proyecto de Cooperaci6n VET. Technical Report,
1997.
6. I. Gutierrez, J. J. Vrcola, J. M. Bilbao and L. M. Villar: Mat. Sci. and
Technology, 1991, 761.
7. B. Lopez: Doctoral Thesis, 1993.
8. Standard Specification for Seamless Ferritic and Austenitic Alloy Steel
Boiler, Superheater and Heat-Exchanger Tubes. ASTM A213/ A216M.
p.112.
The Effects of Oxidation on the Service
Life of 9-12% Chromium Steels
P. J. ENNIS, Y. WOUTERS and W. J. QUADAKKERS
Research Centre [uelich, Institute for Materials and Processes in Energy
Technology (IWV-2), 52425 [uelich, Germany
ABSTRACT
The extrapolation of experimental creep rupture data, usually determined in air, to

required service lifetimes is generally performed assuming that there is no influence
of the service environment on the deformation behaviour and failure. For thin-
walled components operating for long service durations, however, oxidation effects
may need to be taken into account. The oxidation behaviour of the advanced 9Cr
steels in simulated service atmospheres that contain water vapour (test gases for
simulating combustion gas and the steam side) has therefore been compared with
that of the martensitic 12CrlMoV steel and the stainless steel 316LN. The 9°1o Cr
steels exhibited high oxidation rates in such test gases, whereas in air, highly
protective oxide scales were formed. The 316LN austenitic steel behaved similarly to
12CrlMoV in simulated combustion gas and in air, with very low oxidation rates,
but exhibited high oxidation rates in Ar-SOo/o02 and scale spalling occurred.
The formation of oxide scales and the subsequent spalling of the scales lead to loss
of load-bearing cross-section and thus to an increase in the operating stress, and an
associated decrease in service life. Based on experimental data concerning the
oxidation behaviour, the magnitude of the oxidation effect on the stress rupture life
of the steel P92 representing the 9Cr steels was calculated for different tube
component wall thicknesses. It is shown that for the 9Cr steels, the oxidation effects
need to be taken into account when the tube component wall thickness is about
6 mm. For 12CrlMo V, the wall thicknesses at which the service lifetime is reduced
due to oxidation are below 0.5mm, provided that the Cr content is near the upper
limit of the steel specification.
INTRODUCTION
The development of power plant towards higher thermal efficiency can make
a significant contribution to achieving the aims of low emissions and
conservation of fossil fuel supplies. Higher thermal efficiencies may be most
easily achieved by increasing the temperature and pressure of the primary
steam entering the turbine. This, however, requires steels which can with-
stand the increased temperature without the need for large increases in the
wall thickness of components. In recent years, three new steels have been
developed which exhibit sufficiently high creep rupture strength to be of
interest for advanced power plant operating at steam temperatures of
575-625°C. The compositions of the steels are given in Table 1.
457
Table 1Nominal compositions of the steels tested (wt%)
element P91 E911 P92
C 0.10 0.10 0.10

N 0.05 0.05 0.05
Cr 9 10 9
Mo 1 1 0.5
V 0.2 0.2 0.2
Nb 0.06 0.06 0.06
W 1 1.8
The steel P91 has become a well established constructional material for
power station components.' Extensive and reliable design data are available,
and the steel is covered by the American standards ASTM 213 and 335.2 P92
was developed by Nippon Steel" in Japan under the designation NF616 and is
also included in ASTM 335 as P92. E911 was developed first as a rotor steel in
the European COST 501 Round II activities+ and is under further investigation
in continuing COST programmes as a pipe and tube steel.
In the development of these steels the main emphasis was on increasing
creep rupture strength. In long-term creep tests carried out in air, the
specimens exhibited excellent oxidation resistance and so little attention was
given to the oxidation behaviour in the envisaged service environments of
steam and combustion gas. In the work reported here, the oxidation behav-
iour of the 9Cr steels was investigated and compared to that of the martensitic
steel 12Cr1MoV (Fe12Cr1MoO.2VO.2C) and the austenitic steel 316LN
(Fe17Cr13Ni3MoO.03CO.15N). Experiments were aimed at elucidating the
mechanisms of oxidation and determining the rate of oxidation in service-
relevant atmospheres, so that estimates could be made of any influence of
oxidation on the service lifetime of components. Using the oxidation data, a
mean rate of wall thickness reduction due to scale formation was derived and
the consequence of the resulting increase in stress for the component service
lifetime was calculated.
Table 2 gives the details of the heats tested.

Rectangular specimens 20 X 10 X 2 mm'' in size were ground to 800 grit
surface finish prior to the exposure in simulated combustion gases consisting
of 1 vol %02, 14C02, 0.lS02, 0.01 HCI (Rest N2) with a water vapour content
of 7 or 12%. The exposures were carried out for up to 10 000 h at 600 and
650°C whereby the specimens were cooled to room temperature every 250 h
for weight measurements. For fundamental studies, some additional expos-
ures were carried out in N2-1 %02 with different H20 contents. Additionally a
OXIDATION ON THE SERVICE LIFE OF 9-12°10 CHROMIUM STEELS 459
Table 2 Chemical compositions of the steels tested (wt%)
12CrlMoV 12Cr1MoV
element P91 E911 P92 (high Cr) (low Cr) 316LN
C 0.10 0.12 0.11 0.20 0.20 0.02

N 0.05 0.06 0.049 0.12
Si 0.38 0.20 0.04 0.28 nd 0.38
Mn 0.46 0.51 0.45 0.56 0.50 1.66
Cr 8.10 8.85 8.96 11.60 10.20 16.48
Ni 0.33 0.24 0.06 0.69 0.70 12.80
Mo 0.92 0.94 0.47 0.87 0.90 2.25
V 0.21 0.20 0.21 0.27
Nb 0.07 0.065 0.075
W 0.94 1.84
number of exposures for up to 3000 h at 650°C were carried out with selected
materials in an Ar-50 vololo H20 mixture, a gas which is expected to yield
data relevant for pure steam oxidation.f After exposure the corrosion prod-
ucts were analysed by optical metallography, scanning electron microscopy
(SEM), energy dispersive X-ray analysis (EDX) and X-ray diffraction (XRD).
The oxidation data were used to estimate the loss of load-bearing cross-
section during exposure at service temperatures in simulated service environ-
ments. The resulting increase in the stress acting upon the component was
calculated and the service life taking oxidation effects into account was
estimated.
Behaviour in simulated combustion gas

Figure 1 shows a typical example of weight change data obtained for the
various steels during exposure at 650°C in a simulated combustion gas. The
results at both 600 and 650°C showed a clear separation in the behaviour of
the 9Cr steels and that of the more highly alloyed steels 12CrlMo V and
316LN. A detailed discussion of the results has been published.s
Figure 2 shows the microstructures of the scales formed on P92 (representa-
tive for the 9Cr steels), 12CrlMoV and 316LN after 10 000 h exposure at 600°C
in N2-1°10 O2-14°10 CO2-O.1°10 S02-0.01°10 HCl. In agreement with the weight
change data, 12CrlMoV and 316LN formed thin oxide scales, the scale
thickness for 12CrlMoV being even slightly smaller than that of 316LN. All
three 9Cr steels exhibited high weight gains and formed thick corrosion scales
which were generally multi-layered structures, the outward growing scale
consisting of FeZ03 and Fe304 and the inward growing layer being mainly
composed of Fe304 with thin bands of (Fe,Cr,Mn)304. Cr and Mn were only
50~----------------------------------
test gas composition in vol%:
~
N2 -102 -14C02 -7H20 - 0.1502 - 0.01HCI
40
N
'e
o 30
C,
s
.5
cu
20
D)
.E
.~ 10
CD
~ 316LN
12Cr1MoV
-10 '------'-------'------lL-.- ..&..- -I
o 2000 4000 6000 8000 10000

time, h
Fig. 1 Weight changes for P91, E911, P92, 316LN and 12Cr1MoV steels exposed at
650°C in simulated combustion gas (N2-1%02-14%CO-Oo/0502-0.01%HCI-
7 H20)
%
Fig. 2 Microstructures of the scales formed on P92, 316LN and 12Cr1MoV steels
exposed at 600°C for 10 OOOhin simulated combustion gas N2-1%02-14%CO-
0.01%502-0.01 %HCI-7%H20 (The light etching layer above the oxide scale is the
nickel plating applied to protect the oxide scale during metallographic preparation)
found in the inner sub-layer, with neither Cr nor Mn being found in the outer
part of the scale. In the inward growing part of the scale on P92, small
particles of a W-rich phase were found. Beneath the thick oxide scale, internal
oxidation was observed, with (Fe,Cr,Mn)304 penetrating along the prior
austenite grain boundaries and the martensite lath boundaries of the matrix
structure (Fig. 3). The Cr-depleted matrix remaining between the internal
OXIDATION ON THE SERVICE LIFE OF 9-12% CHROMIUM STEELS 461
Fig. 3 Microstructure of P92 steel showing the inward growing region of the scale
formed during exposure at 650°C for 1000h in N2-1 %02-14%COO.l %502-
0.01%HCI -7%H20
-8------~--------------------------------~
ferritic steels
austenitic
steel
-16 +--_---..--...-- ---r--_-......----.----...

o 4 10 12 14 16 18
Cr concentration, wt%
Fig. 4 The effect of chromium content on the oxidation rate of steels at 600 and
650°C in simulated combustion gas (N2-1%02-14%CO-0.l%502-0.01%HCI-
7%H20)
oxide fingers then oxidised, forming Fe304. These two steps were con-
tinuously repeated forming the layered structure seen in Fig. 3.
In Fig. 4 the parabolic rate constants determined at 600 and 650°C in
simulated combustion gas for the steels investigated are plotted as a function
of chromium content. The rapid decrease in the rate constant between 9 and
110/0Cr should be noted, bearing in mind the specified chromium composi-
tion ranges of the steels. This means that a nominally 12Cr steel may exhibit
corrosion rates similar to the 9Cr steels if the actual chromium content is at the
bottom end of the specified range which is 10-12.5%, as will be discussed
later.
A change of the water content from 7 to 12% did not fundamentally change
the oxidation mechanism and no indications were found that S or CI had
participated significantly in the corrosion process. Exposure in environments
with an HCI content of only 0.001% did not lead to significantly different
oxidation rates. These observations indicated that the fundamental differ-
ences in behaviour of the 9Cr steels in air and in combustion gas are not
primarily caused by the presence of HCI and/or S02 in the combustion gas,
but to the presence of water vapour.
Enhanced oxidation by water vapour

The tests in simulated combustion gas had shown that the critical water
content above which a protective oxide could not be formed on the 9Cr steels
lay below 7%. Figure 5 presents weight change data obtained for P91 after
10--------------------------------------------------------~
P91 steel exposed at 650"C for 250 h

in N2"10/00% with different H20 contents
10
water vapour content, vol%
Fig. 5 The effect of water vapour content on the weight change of P91 exposed at
650°C for 250 h6
isothermal oxidation at 650°C for 250 h in N2-10/002 containing different

levels of water vapour." In the dry gas, an extremely slow oxidation rate
occurred. The SEM analysis showed that a thin oxide layer with a thickness of
about 1 urn, appearing compact and adherent, had formed. The EDX analysis
revealed that the scale consisted mainly of iron with a small amount of
chromium and minor amounts of manganese, molybdenum and silicon.
Using X-ray diffraction, only the Fe203 structure could be detected?
The microscopic observations of the specimens oxidised in the wet gases
showed oxide scales similar to those formed after exposure in the simulated
70--------------------------------------~
steel P91 exposed in N2 -1%02
with different water vapour
60 contents for 250 h at different
temperatures
~
~50
~
'c40
~
co
S30
e
c
.2
~20
";;C
o
10
O~----~----~----~~--~~~--~----~
550 600 650 700 750 800 850
temperature, °C
Fig. 6 The oxidation rate at 100h for P9l exposed at different temperatures in
N2-l%02 with H20 contents of 0,2 and 40/0
combustion gases, that is, porous scales which consisted of Fe203 and Fe304 in
the outer scale, and Fe304 and (Fe,Cr,Mn4)304 in the inner scale. However, the
enhancement of the isothermal oxidation by the presence of water vapour
does not continuously increase with increasing temperature, as shown in Fig.
6. For 2 and 4% H20, a bell shaped temperature dependence was observed
with oxidation rate maxima at 650 and 700°C. At 800°C, a protective scale was
formed, irrespective of the H20 content (0, 2 and 4%) of the test gas. At these
high temperatures the diffusion of chromium and manganese into the scale is
sufficiently rapid to allow a protective scale consisting of (Fe,Cr,Mn)304 and
Fe203 to form.
Oxidation in steam
Figure 7 presents weight change data in Ar-500/0 H20 mixture at 650°C.
Comparison of the results with the data in Fig. 1 reveals that the oxidation
rates for the 9Cr steels were quite similar to those measured in simulated
combustion gas. The microstructures of the scales formed were also similar
(Fig. 8). The austenitic steel, in contrast, exhibited significantly higher corro-
sion rates in Ar-500/0 H20 than in the simulated combustion gas, leading after
only relatively short exposure times to scale spalling indicated by significant
weight losses. Indications were found that the corrosion resistance of the
austenitic materials in steam not only depended on the exact alloy composi-
tion, but also on alloy grain size and surface preparation. The ferritic
12Cr1MoV steel with 11.6% Cr also behaved as in simulated combustion gas,
that is, the corrosion rate was so small that it is hardly relevant for component
design. However, a second batch of this material, which contained only 10.2%
~ ~--------------------------------------~
P92
~
5 ~
__.•. --_r ~~~
Een ~ __ _--- •..
GS ,-~-
g' »>" P91
co " •••••
13 10 J'rI' ••••••••••••••••••• :':~:: : .••••.•••
- I ...••...•.......•.... _ ...••.
- .••. -.- 12Cr1MoV (lowCr)
~ I ..•......... ._..-.-"
.~ 0 ~:fj;': •. <""::-.::~: 12Cr1MoV (high Cr)
,... -. - _ ..•...•.AISl316LN
- ..•....•.
-10 "-------1--------'------ -------"
o 500 1000 1500 2000 2500 3000 3500
exposure time, h
Fig. 7 Oxidation of various steels in Ar-50% H20 at 650°C
316LN
Fig. 8 Microstructures of P92 and 316LN exposed at 650°C for 1000h in Ar-50%
H20
Cr, exhibited a much higher corrosion rate, which was not significantly lower
than that of the 9% Cr steels; Fig. 9 compares the oxide scales formed on the
two 12Cr1Mo V heats.
Effect of oxidation on service life-time

The calculations of the effect of oxidation on the creep rupture strength of P92
were carried out as follows. Based on the experimental corrosion data, an
annual wall thickness loss of 0.1 mm on both the outside and the inside
surfaces of the tube was assumed. The stress increase factor S, the ratio of the
load-bearing cross-sections before and after exposure, is given by
11.6% Cr 10.2% Cr
Fig. 9 Microstructures of 12CrlMo V steels (high Cr and low Cr versions) after

exposure for lOOOhat 650°C in Ar-50 %
H20, showing protective and non-
protective oxide scales
w
S = w - 2aw
where w is the tube wall thickness and aw the loss of wall thickness on each
side. Note that the factor is independent of the initial tube diameter.
For each year of service, a mean stress was calculated from the arithmetic
average value of the stresses at the start and at the end of the year when the
wall thickness had been reduced by 0.2 mm. The rupture life for this average
stress was obtained from the extrapolated rupture curves based on experi-
mental data determined in air.f The life fraction consumed, that is, 8760 h (the
number of hours in one year) was divided by the expected rupture time, to
obtain a life consumption fraction. The tube was deemed to have reached the
end of service life when the accumulated sum of the annual life fractions
consumed reached 1. The times to failure for tubes of different wall thickness
for different initial stresses were then plotted on the stress rupture diagram
(Fig. 10). The stress rupture curve for the 12CrlMoV steel, which if the Cr
content is above about 11.5% will exhibit excellent oxidation resistance in
simulated service atmospheres, is included in the figure.
The results clearly show that during the envisaged long term application of
a few hundred thousand hours, corrosion can lead to a significant decrease in
creep rupture strength of thin-walled 9% Cr steel tubes. Figure 10 shows that
for 9% Cr steel tubes with. wall thicknesses above about 8 mm, the effects of
oxidation on creep life may be disregarded for typical component lives of
300 000 h. The wall thickness at which tubes of high Cr 12CrlMo V steel
exposed at 600°C would begin to have a service life limiting effect based on
the observed oxidation rates in environments containing water vapour is
180~~~ ~ -+ ~
160r- ~~ _+------------~
140~----------~~~~~----_+------------~
ca
~ 100r- ~~~~~~~~~--~~----~
o
o
e
'0
1000 10000 100000 1000000

time to rupture, h
Fig. 10 Oxidation affected stress rupture life for P92 of different wall thickness in
simulated service environments
estimated to be about 0.5 mm. The oxidation behaviour of the stainless steel
316LN in simulated combustion gases with up to 12% water vapour content
was also excellent. However, in the model gas simulating pure steam, high
oxidation rates were observed with spalling of the oxide scales. The critical
wall thickness for service in steam may therefore be of the same order as that
of the 9% Cr steels.
Considering the very low corrosion rates of the 'high Cr' ferritic 12Cr steels
in both environments studied, for components of wall thickness of around
4 mm and service lives of 200 000 h, the 9% Cr steels do not show a significant
service life advantage over the 'high Cr' 12% Cr steel, even though the latter
possesses a significantly lower intrinsic creep strength than P92 or E911.
CONCLUSIONS
In steam and in simulated combustion gases the 9Cr steels P92, E911 and P91
show significantly higher corrosion rates than 12Cr steels provided that the
Cr contents of the latter are near the upper limit of the specification
(11.5-12.5 %
Fig. 4). Assuming spallation of the thick oxide scales occurs after
,
around one year exposure, the 9Cr steels show no significant advantage in
stress rupture strength over the 12Cr steels if components of around 2 mm
wall thickness are considered. The behaviour of the austenitic materials
strongly depends on exact composition and microstructure: in some cases a
behaviour similar to that of the 'high Cr' 12%Cr steels may be observed, in
other cases, especially in steam, much higher corrosion rates are found.
ACKNOWLEDGEMENTS
The authors acknowledge with gratitude the valuable contributions of M.

Thiele, E. Smaardijk, J. Ehlers and C. R. Williams to the work presented. Part
of the work was supported by RWE-Energie AG.
REFERENCES
1. V. K. Sikka, C. T. Ward and K. C. Thomas: in Proc. Con! Ferritic Steels for

High Temperature Applications, Warrendale, PA, USA, 6-18 October 1981;
ASM 1983, 65-84.
2. ASTM Specifications A335/A335M-91a (1986) and A213 (1985), ASTM, War-
rendale, PA.
3. Nippon Steel Corporation, Data Package for NF616 Ferritic Steel, January
1993, second edition March 1994.
4. C. Berger, R. B. Scarlin, K. H. Mayer, D. V. Thornton and S. M. Beech:
Materials for Advanced Power Engineering, D. Coutsouradis et al., eds.
Kluwer Academic Publishers, Dordrecht, Boston, New York, 1994, Part I,
47-72.
5. C. R. Williams, W. J. Quadakkers and D. B. Meadowcroft: COST 501/3 -
WP11, Assessment of steam oxidation and fireside corrosion of 9-12% Cr
steels, Report EUR-Contract No COST-CT-95-0099-DE, November
1996.
6. M. Thiele, H. Teichmann, W. Schwarz, W. J. Quadakkers and H. Nickel:
VGE Power Technology, 1997, 2, 129-134.
7. C. R. Williams, M. Thiele and W. J. Quadakkers: in Proc. EUROCORR 96,
24-26 September 1996, Nice, Vol III, 10/1-10/4.
8. O. Wachter and P. J. Ennis: VGB-Kraftwerkstechnik, 77, 1977, 77(a), 770-785.
Study of Corrosion Resistance of Newly
Developed 9-12%Cr Steels for
Advanced Units
K. NAKAGAWA*, I. KAJIGAYA*, T. YANAGISAWA*,
M. SATOt and M. ABEt
* Ishikawajima-Harima Heavy Ind. Co. Ltd., Toyosu Office 2-6 Toyosu,
3-Chome, Koto-ku, Tokyo, Japan 135
t Tohoku Electric Power Co., Inc.
ABSTRACT
The corrosion resistance against steam and coal ash between 600 to 700°C for the
newly developed high strength ferritic steels has been investigated. All the steels
tested have similar oxidation resistance at 600°C. However, 12%Cr steels have better
corrosion resistance than g%Cr steels at 650°C. The surface recessions of 12%Cr steels
are less than 50% of those for gO/oCrsteels after 500 h exposure. Coal ash corrosion of
steel in all cases was twice that of steam oxidation when alkaline sulphates were
present in the coal ash. The resistance against coal ash corrosion increases with
increasing Cr content in the steel. The corrosion rates of 12%Cr steels are about a half
of those for gO/oCrsteel. Coal ash corrosion induced by molten sulphates was noted to
occur in simulated combustion gases containing 502 at more than 0.05%.
1. INTRODUCTION
The conservation of energy and resources at thermal power plants is a major

consideration in Japan and throughout the world. Ultra supercritical pressure
steam power plants are currently under construction as one means to achieve
this purpose. In most ultra supercritical pressure steam power plants with
operating steam temperature of 593°C, the main steam pipes, superheater
tubes and reheater tubes are made of high strength ferritic steel, or modified
9CrlMo steel (T91/P91). Ferritic steels are presently under development for
application at thermal power plants that operate at higher steam tem-
peratures. These steels should be capable of withstanding high temperatures
than the modified 9CrlMo steel.'
Development is being directed to achieving greater creep strength at high
temperatures.v" The corrosion resistance of the new high strength heat
resisting ferritic steels has yet to be accurately evaluated and is considered
less than that of austenitic stainless alloys. Corrosion resistance in a steam
environment, that is, steam oxidation, and corrosion resistance in the pres-
ence of coal ash or resistance to coal ash corrosion, should be fully determined
468
CORROSION RESISTANCE OF NEWLY DEVELOPED 9-120/oCR STEELS 469
for the new steel to be used to manufacture main steam pipes and superheater
and reheater tubes of coal fired ultra supercritical pressure boilers. Thus,
corrosion resistance against steam and coal ash between 600 to 700°C for the
present high strength ferritic heat resisting steels were examined in the
present study.
2. EXPERIMENTAL
2.1 Corrosion in Combustion Gas Environment

The chemical compositions of steel samples in the present study are indicated
in Table 1.
Table 1 Chemical compositions of steels (wt.%)
Steel C Si Mn Cr Mo W V Nb Others
A 0.10 0.26 0.47 8.84 0.34 1.88 0.19 0.06

B 0.10 0.32 0.35 8.50 0.90 0 0 0.08
C 0.10 0.31 0.53 12.2 0.36 1.88 0.20 0.05 Cu:0.86
D 0.14 0.20 0.08 12.0 0.69 0.89 0.24 0.11 Cu:0.97
E 0.09 0.19 0.50 11.05 0.16 2.57 0.20 0.07 Co:1.49
347H 0.08 0.49 1.48 18.40 0.07 Ni:12.6
The equipment used for this determination appears in previous studies+

Rectangular test specimens (25mm X 15 mm X 3 mm) were prepared from
candidate steel tubes, whose surfaces were wet-polished with water and 600
grade polishing paper, followed by degreasing with acetone before composi-
tion determination.
Corrosion tests of 100 hours duration were conducted in simulated com-
bustion gas environment containing 4% O2, 15% CO2, 10% H20 and balance
N2. S02 in the environment was varied at 0, 0.01, 0.05, 0.1, and 0.25%. The test
specimens were coated by synthetic coal ash or not coated. Corrosion test
temperatures were 600, 650 and 700°C.
Synthetic coal ash for the coal ash corrosion test had the following % mass
composition: 5% mixed sulphate (Na2S04 and K2S04) and 95% mixed oxides
(33.3% A1203, 33.3% Si02, and 33.3% Fe203). The upper surface of each
specimen was coated with 40mg em"? of ash. Corrosion tests at 600 and
650°C in a simulated combustion gas environment containing S02 at 0.25%
were conducted for 50 and 200 hours in addition to the standard 100-hours for
evaluating the time dependence of corrosion. The specimens were then
chemically descaled. Specimen weight loss was measured for assessment of
corrosion resistance. Corrosion products on the surfaces were examined by
EPMA.
Fig. 1 Schematic of steamside test system
2.2 Corrosion in Steam Environment

Rectangular test specimens (25mm X 7.5 mm X 3 mm) were prepared in the
same manner as for the simulated combustion gas environments, using the
equipment shown in Fig. 1, a simulated boiler of the natural circulation type
with electric heaters. The test specimens were hung in a test loop in which
steam was adjusted to a specific temperature by an electrically heated furnace
for a maximum test time of 1000 hours. Test temperatures were 600 and
650°C. Weight gain and scale layer thickness were measured. Scale crystallo-
graphic structure were determined by EPMA and XRD.
3. EXPERIMENTAL RESULTS AND DISCUSSION
3.1 Corrosion in Simulated Combustion Gas

Corrosion results in the simulated gaseous environment containing S02 at
0.25% and temperatures of 600 and 650°C are shown in Figs 2 and 3,
Time (h)
Fig. 2 Weight losses of 9-12Cr steels exposed in simulated combustion gas

containing 0.25% 502 at 600°C
CORROSION RESISTANCE OF NEWLY DEVELOPED g-12%CR STEELS 471
~A 650CC, 0.25%S02
- &--B
~--C No Ash
- -~ - - D
••••~ ••- E
250
Time (h)
Fig. 3 Weight losses of 9-12Cr steels exposed in simulated combustion gas

containing 0.25% 502 at 650°C
Fig. 4 Metallographic cross-section of steels A and C after exposure for 200 h in

simulated combustion gas containing 0.25% 502 at 600°C
respectively. Parabolic increase in corrosion of specimens at these tem-

peratures with time is apparent from the figures. Figure 4 presents the
photographs of oxide scale cross-section microstructures of test specimens of
steels A and C heated at 600°C for 200 hours. The scales showed two-layered
structures consisting of outer and inner layers, the former consisting of iron
oxides as the main constituents. The inner layer consisted of mixed oxides of
chromium and iron. Both layers contained traced amounts of sulphide.
Corrosion in dry air atmosphere at 600 and 650°C is negligibly smalL The
corrosion of test specimens exposed to the simulated combustion gas environ-
ment may possibly have been due to steam in the environment. Parabolic
corrosion rate constants (Kp) determined from corrosion data at 600 and
650°C as chromium content are shown in Fig. 5. Corrosion resistance
"';"(I'J -3
~e
o
S -4
N
~
~~ -5
-6~~~----~~----~~~~
8 9 10 11 12 13
Cr Content (wt.%)
Fig. 5 Parabolic rate constants for oxidation of 9-12 Cr steels in simulated

combustion gas as a function of chromium content
x···········~············)(
~ __ ----C>
(1------
-5 '-
-6~~~'~~~'~~~'~~~
1 1.05 1.1 1.15 1.2
Iff x 1000(11K)
Fig. 6 Parabolic rate constants for oxidation of 9-12 Cr steels in simulated

combustion gas as a function of the reciprocal absolute temperature
increased with chromium content and for steel C containing chromium at 12.2
mass'zs, Kp was noted to decrease rapidly.
Arrhenius plots of parabolic rate constants (Kp) determined based on
weight change as elapsed time at various temperatures are shown in Fig. 6.
The corrosion of 9Cr steels A and B increases with temperature. For 12Cr
steels C, D and E, corrosion decreased with rise in temperature. Specimen
surface scale morphology for 12Cr steel in gaseous environment would thus
appear to change with temperature.
CORROSION RESISTANCE OF NEWLY DEVELOPED 9-12%CR STEELS 473
~A 600t,0.25%S02
-~ -B With Ash
--£]- - C
--~--D
••••)(•••- E
Time (h)
Fig. 7 Weight losses of 9-12 Cr steels coated with the synthetic ash at 600°C
~A 650'(:, 0.25%S02
-tr--B
Ne ---£J-
--~--D
- C
•••• )(---- E
With Ash
~ 100
g r-~--"'"
til
.s
til
~ 50
Fig. 8 Weight losses of 9-12 Cr steels coated with the synthetic ash at 650°C
3.2 Corrosion in the Case of Synthetic Ash Coating

Figures 7 and 8 show corrosion results in gaseous environment containing
0.25% 502 for specimens coated with synthetic ash at 600 and 650°C,
respectively. The corrosion of 9Cr steels A and B was quite different from that
of 12 Cr steels C, D and E, the extent being twice that of the latter.
Corrosion data for all grades of steel in Table 1 was observed to increase
parabolically with time. The corrosion of the synthetic ash-coated specimens
would appear to occur through controlled diffusion although corrosion is
considered due to the presence of molten sulphates. The slightly lower
corrosion at 650°C after 200 hours may possibly have been due to the
complete consumption of ash. Figure 9 shows Arrhenius plots of temperature
dependence of parabolic rate constants determined by corrosion weight loss
with time in simulated combustion gas environment containing 0.25% 502.
1 I I I
~25%S02
·2- ~ WithAsh_
.-4
.•."",-~
~
'(1.2 .~ ..~
'6
3-
..~ -
NO{)
s -4 r -
-P-- _ ~- - -......r
~
~
~ -5- -
---e--A - -~ - - D
6r ~ -B ••••~ ••- E -
- 8--C -t-- - 347H
-1I.
1.05 1.1 1.15 1.2
1/I' x 1000 (11K)
Fig. 9 Parabolic rate constants for ash corrosion of 9-12 Cr steels as a function of
reciprocal temperature
The plots were essentially linear, suggesting an identical rate-determining

step for all specimens at the temperatures tested. The different slopes of the
straight lines for 9Cr steels A and B and 12Cr steels C, D and E were
essentially different corrosion mechanisms to be operative for the two steel
groups.
Figure 10 shows the relationship between parabolic rate constants (Kp)
obtained at 600 and 650°C, and chromium contents. Kp of 347H steel
containing Cr at 18.4 mass': is shown for reference. The corrosion resistance
of steel C in the simulated combustion gas environment considerably
---e-- 600°C
····tr··-650°C
••••tr··~ •• -, With Ash
......
. ......
"
-..
-6--~~~~~~~~~~~
8 10 12 14 16 18 20
Cr Content (wt. %)
Fig. 10 Parabolic rate constants for ash corrosion of 9-12 Cr steels as a function of
reciprocal temperature at 600 and 650°C
CORROSION RESISTANCE OF NEWLY DEVELOPED 9-120/oCR 5TEELS 475
exceeded that of steels D and E. This resistance of steel C was essentially the
same as that of steels D and E previously coated with synthetic ash. For steel
containing chromium at more than 18 this parameter had considerably
%
,
improved. It follows then that higher chromium content may be required for
steel specimens to take on significantly greater corrosion resistance against
coal ash compared with that content requisite for the resistance achieved
toward combustion gas environment.
Coal ash corrosion is considered to occur through the action of low-melting
point sulphates formed by chemical reaction of alkaline sulphates with iron
oxides in coal and 503 in combustion gas, as follows:
3(Na,K)2(504) + Fe203 + 3503 ~ 2(Na,K)3Fe(504)3 (1)
A portion of 502 in combustion gas is oxidised to 503 as in eqn (2),
502 + O2 ~ 503 (2)
503 may possibly function as a cathodic reactant in molten sulphates, thus
accelerating the corrosion of steel specimens and accordingly, the effects of
502 in combustion gas on corrosion of steel were examined.
Figure 11 shows the effects of 502 on the corrosion of samples coated with
synthetic ash at 650°C. At 0.01% 502, the extent of corrosion was essentially
---e--A -·~·-D
- &- - B •...•)(--_.E
--EJ- - C
"0 0.05 0.1 0.15 0.2 0.25 0.3

SO 2 Content (vol. %)
Fig. 11 Effects of 502 content on the weight losses of 9-12%Cr steels coated with a
synthetic ash at 650°C
the same as in its absence. Figure 12 shows EPMA data for corrosion scales on
the steel A coated surface and in the simulated combustion gas environment
containing no S02. Scale formation was essentially the same under either
condition. Scale outer layer consisted mainly of iron oxide, and inner layer,
mainly of mixed oxides of iron and chromium. Sulphur was detected in trace
amounts in the scales. Corrosion in this environment may thus quite naturally
be considered due not to molten sulphates but the combustion gas itself. At
Fig. 12 Electron microprobe analysis of the scale formed on steel A after exposure
for 50 h in 502 free simulated gas at 650°C
0.05% 502, corrosion was noted to increase rapidly. At higher concentration,

only gradual increase was apparent. At more than 0.1 corrosion was
%,
saturated. Figure 13 shows EPMA data for corrosion scales of steel A at 650°C
in simulated combustion gas containing 0.05% 502. A large amount of
sulphides could be detected in the inner layer, indicating corrosion morphol-
ogy the same as that induced by molten sulphates. Mixed sulphate formation
(Na,K)3Fe(S04)3 may thus possibly be initiated at 502 between 0.01 and
0.050/0.
Fe-Ka
Fig. 13 Electron microprobe analysis of the scale formed on steel A coated with a
synthetic ash after exposure for 100h in simulated gas containing 0.05% 502 at
650°C
Fig. 14 Maximum thickness losses of 9-12%Cr steels exposed to 600°C steam
Fig. 15 Maximum thickness losses of 9-12%Cr steels exposed to 650°C steam
3.3 Steam Oxidation

Some scales on steel C as well as steel D specimen surfaces easily spalled off
following exposure to 650°C for 250 hours. Weight increase thus could not be
measured, and had to be determined based on inner layer thickness. Speci-
mens data at 600 and 650°C are shown in Figs 14 and IS, respectively. Scale
growth at 600°C was essentially that at 650°C, and parabolical with time.
Corrosion for all steel specimens at 600°C was the same. Figure 16 shows
microstructures of cross sections of steel A exposed to 600°C for 1000 hours.
The two scale layers were virtually of the same thickness. The outer layer
consisted mainly of Fe304 and inner layer, spinel type oxides containing Fe
and Cr. At the interface, an internal oxidation layer was present, which was
the same as the original surface of the steel specimen. The outer layer is thus
Fig. 16 Metallographic cross-section of steel A after exposure for lOOOhin steam at

600°C
considered to grow through outward diffusion of metallic elements, whereas

the inner layer, through inward diffusion of oxygen.
Corrosion at 650°C was found to depend primarily on specimen Cr content.
The corrosion of steel C of 12Cr steel is half that of steel A of 9Cr steel. Figure
17 shows EPMA results in the depth direction of scales formed on steels A
100 100
.-.80 ~ 80
~
f60
~
~
~ 60
0 .9
'ia ~
~ 40 ~ 40
0 0
0
~ ~
0
8 20 8 20
Fig. 17 Microprobe profile analysis of the scales formed on steels A and C after
exposure for 500 h in steam at 650°C
Fig. 18 Cracks in the inner scale formed on steel E after exposure for 500 h in steam
at 650°C
and C following exposure to 650°C for 500 hours. Two-layered scales could be
seen on the steel specimens. The layer rich in chromium at 35 mass" was
present at the interface between the base metal and inner layer of scales on
steel C having higher corrosion resistance but not for steel A of 9Cr steel. The
difference in corrosion resistance for steels C and A at 650°C may possibly
derive from the presence of this Cr-rich oxide layer.
Outer layer spalling from the surface subsequent to 650°C treatment for 250
hours was clearly noted for steels C, D and E of 12Cr steel. Figure 18 shows
the microstructure of a scale cross section on steel E exposed to 650°C for 500
hours. Many cracks in the inner layer were seen to run parallel along the
surface. No cracks would be seen for steels A and B of 9Cr steel. The spalling-
off may be induced primarily by these parallel cracks, through this awaits
confirmation.
3.4 General Discussion

Corrosion data for the steam and simulated combustion gas environments at
600 and 650°C after 500 hours are presented in Table 2. Corrosion values for
the latter were extrapolated based on data at 100 hours, assuming corrosion to
be parabolic in nature. Corrosion in steam at 600°C was essentially that for
simulated combustion gas at 600°C and accordingly, steam in combustion gas
would appear a major contributing factor. 12Cr steel corrosion at 650°C in
simulated combustion gas was too small for comparison with that in steam,
possibly due to the effects of this gas and oxygen.
Coal ash corrosion of steel in all cases was twice that of steam corrosion
when alkaline sulphates were present in the coal ash. Coal ash corrosion
should thus be considered a serious problem. This corrosion is induced in
superheater and reheater tubes of 9 to 12Cr steels of coal-fired boilers when
using coal of high sulphur content and alkali metals (Na and K).
Table 2 Corrosion rate in several environments (fJ-m/500 h)
Synthetic ash
Combustion gas (5wt. Alkali
%
(0.1 S02)
% Sulphates) Steam Oxidation
Steel 600°C 650°C 600°C 650°C 600°C 650°C
A 60 90 151 218 30 79
B 59 49 128 173 27 49
C 3 <1 57 79 26 32
D 21 <1 71 87 31 57
E 24 <1 69 84 30 34
347H <1 <1 3 4
4. SUMMARY
Examination was made of the corrosion of newly developed 9 to 12Cr steels in

steam and simulated combustion gas. The results obtained are presented as
follows:
1. The corrosion of 9Cr steel at 600°C in steam was essentially that of 12Cr
steel in the same gases. The corrosion of 12Cr steel at 650°C was much
less than that of 9Cr steel in these gases.
2. 9Cr steel corrosion in simulated combustion gas was nearly the same
as that of 9Cr steel in steam for all temperatures. The corrosion of
12Cr steel at 650°C was too small to permit comparison with that at
600°C.
3. Arrhenius relationships were found applicable to oxidation rate con-
stants and corrosion temperature for all steel specimens at 600 to
700°C.
4. Coal ash corrosion induced by molten sulphates was noted to occur in
the present new steel coated with synthetic ash in gaseous environments
containing S02 at more than 0.05%.
5. Corrosion of the present steel was noted to increase with time in
essentially a parabolic manner in steam and combustion gas.
REFERENCES
1. T. Fukita: The Thermal and Nuclear Power, 1991, 42, 1485.

2. Y. Sawaragi, K. Ogawa, F. Masuyama and T. Yokiyama: The EPRI/National
Conference, New Steel for Advanced Plants up to 620°C, London, UK, May
1995,45.
3. H. Naoi, H. Mimura, M. Ogami, H. Morimoto, T. Tanaka, Y. Yazaki and T.
Fujita: 'NF616 pipe production and welding consumable development',

ibid., 8.
4. W. S. Wolowodiuk, S. Kihara and K. Nakagawa: 'Laboratory Coal Ash
Corrosion Test', Topical Report GS-6449, Research Project 1403-19, EPRI,
Palo Alto, July 1989.
Development of aNew Heat Resistant
Austenitic Stainless Steel for High
Temperature Components of Power
Generation
Y. NISHIYAMA, Y. SAWARAGI, N. OTSUKA, H. HIRATA,
s. KIHARA* and I. KAJIGAYA*
Sumitomo Metal Industries, Ltd., Amagasaki, Hyogo 660-0891, Japan
* Ishikawajima-Harima Heavy Industries Co., Ltd., Tokyo 135-0061, Japan
ABSTRACT
New austenitic stainless steel, NAR-AH-4, which consists of 0.3 5i-23Cr-11.5Ni-
0.2N along with trace amounts of B and rare earth metals La and Ce has been
developed for the application of high temperature components (up to 1000°C)in
thermal power plants and chemical plants. The corrosion and erosion resistance for
the steel is better than AI51type 31055(25Cr-20Ni) and Alloy 800H (20Cr-32Ni-Al,
Ti). The creep rupture strength is considerably higher than that of Type 31055 and
Alloy 800H due to the addition of nitrogen and boron. The resistance to weld hot
cracking sensitivity for this steel is better than that for Type 31055 and high silicon
content austenitic stainless steels, due to decreasing silicon content (0.3%) and
optimum ratio of chromium equivalent to nickel equivalent. In addition, this steel
has an economic advantage over Type 31055 as well as Alloy 800H due to the
substitution of nitrogen for a part of the nickel. These results indicate that this steel is
expected to be widely utilised as a candidate material for high temperature
components.
INTRODUCTION
Recently, there is a strong demand for high efficiency power generation

plants which can better meet environmental regulations, conserving fuel at
the same time. Combined cycle power plants such as pressurised fluidised
bed combustion (PFBC) plants and integrated coal gasfication combined cycle
(IGCC) plants are examples of beneficial coal utilisation power plants in the
early 21st century+- as well as USC plant. It offers high total efficiency; low
NOx emissions; high sulphur retention; flexibility in choice of coal type; and
compact space to locate. These high efficiency power generation systems
require high temperature materials to be used in severe hot corrosion
(oxidation and sulphidation) and/or erosion environment. Thus the selection
of material presents some important problems. Conventional heat resistant
austenitic stainless steels such as AISI type 309, AISI type 310S5 and Alloy
482
NEW HEAT RESISTANTAUSTENITICSTAINLESSSTEEL 483
800H are widely applied to the areas for power plants, chemical plants,
industrial furnaces and automobile exhaust systems, but these are inferior in
corrosion and mechanical strength above 800°C.
In our work, a new austenitic stainless steel with superior high temperature
creep rupture strength to AI5I type 31055 and Alloy 800H and with excellent
corrosion and erosion resistance above 800oe, has been developed for high
temperature components, e.g. ducts, cyclone and attachment of thermal
power plant.v+ This steel was designed to ensure excellent weld ability, to
stabilise microstructure ageing long-term service, and to reduce material cost.
This paper describes the alloying elements design and the properties of the
new austenitic stainless steel, NAR-AH-4.
DEVELOPMENT OF NAR-AH-4
The chemical composition of the newly developed steel, NAR-AH-4, is listed

in Table 1. First, high temperature corrosion and erosion resistance are
Table 1 Chemical compositions of developed steel (mass'ze)
C Si Mn p S Cr Ni N La + Ce
Nominal value 0.07 0.3 1.00 Max 0.02 Max 0.030 Max 23 11.5 0.2 0.035
required for using components suffering from severe corrosive gases and/ or
deposits. Rare earth metals (REM) improve the corrosion resistance of alloys.
The most likely improvement mechanism proposes that REM's remove
sulphur from the oxide/matrix boundary, which reduces the adherence of the
protective oxide film.5,6 Figure 1 shows the effect of cerium content on the
oxidation resistance of 23Cr-llNi-0.2N based steels. As the cerium content
increases, the mass gain falls sharply, however, in high containing cerium its
effect is small. Thus the optimum value of cerium content is in the range
between 0.025 and 0.05mass /o and the developed steel contains about
O
0.03%La + Ce as misch metal. As shown in Fig. 2, the steel containing 0.03%

cerium exhibits particularly excellent oxidation resistance as compared with
the steel without cerium under cyclic heating and cooling test at 900 and
1000°C.
High temperature strength is another desirable property. Figure 3 shows
the effect of nitrogen on rupture time for 26.46MPa X 900°C and 9.8MPa X
1000°C. It indicates that time to rupture elongate in proportion to the nitrogen
content at both of test temperatures. We determined the optimum nitrogen
content as 0.2% in consideration of the microstructural phase balance.
Finally, investigations were made so as not to reduce the resistance to weld
hot cracking sensitivity. Figure 4 shows the result of Trans-Varestraint test
with 19-23%Cr-ll%Ni-0.2%N containing various amounts of silicon. It
30
For 200h in air
25
.-....
N
bb
e 20
""-'
.~ 15
eo
Ul
lOOO°C
~
5
o I
o 0.02 0.04 0.06 0.08 0.1 0.12 0.14
Ce content (mass%)
Fig. 1 Effect of Ce content on oxidation resistance of 23Cr-ll.SNi-O.2N steels for

200h in air
Number of Cycles
o 100 200 300 400
100
o
-100
N""-" -200
~""-' -300
o
§ 100 !:===========::::!
~
o
-100
-200 1000°C
-300 '--- --=-.1
(1cycle :25min heating - 5min cooling)
Fig. 2 Cyclic oxidation resistance of 23Cr-ll.SNi-O.2N steels at 900°C and IOOOoe

in air
reveals that silicon is a very harmful element for weld hot cracking sensitivity.
Thus the developed steel restricts the silicon content to approximately 0.3%.
Figure 5 shows the effects of nitrogen and nickel on weld hot cracking
sensitivity. Nitrogen does not affect it so much up to 0.20/0. On the contrary,
nickel is highly sensitive to hot weld cracking due to the microstructural
NEW HEAT RESISTANT AUSTENITIC STAINLESS STEEL 485
I 23%Cr-l1% Ni-O.3%Si- N I
lOOO°Cx 9.8MPa
1
0.8
900 °c x 26.46MPa
0.6
0.1 0.15 0.2 0.25
N content (mass%)
Fig. 3 Effect of N content on rupture strength
..-...
~~ 1.5
..s:::
on
c:
.£
~0 1.0
e0
e::s 0.5
.5
~
~ 0
0 2 3
Si content (mass%)
Fig. 4 Effect of Si content on hot cracking sensitivity. (Trans-Varestraint test)
phase balance. Therefore, we made an effort to design an optimum ratio of

chromium equivalent to nickel equivalent.
CHARACTERISTIC PROPERTIES
Chemical compositions
NAR-AH-4 was prepared by vacuum induction melting on a laboratory
scale. The ingot was forged, hot-rolled, cold-rolled and solution treated. Heat
1.5,------------- .
8' 23%Cr-Ni-O.3%Si-N I
S
.J:: f. =2%,n=2
~ 1.0
..2
~
~
ts
8 0.5
N
S
.~ o _D __\ __ ?. _
~ 0 o
8 10 12 14
Ni content (mass%)
I I
0.10 0.15 0.20 0.25
N content (mass%)
Fig. 5 Effects of Ni and N content on hot cracking sensitivity. (Trans-Varestraint
test)
Table 2 Chemical compositions of tested steels (mass'ze)
Steels C Si Mn Cr Ni Others
NAR-AH-4 0.07 0.3 0.8 23.3 11.2 0.2N, 0.035La + c-. 30 ppmB
AISI type 310SS 0.05 0.6 1.2 24.6 20.2
Alloy BOOH 0.07 0.5 0.9 21.0 32.4 Ti, Al
MA 0.07 1.4 0.7 21.0 10.8 N
SUS XM15J1 0.06 3.4 0.7 19.0 12.8
treatment was carried out at 1080 to 1160°C for appropriate time, water
quenched or air cooled. Chemical compositions of NAR-AH-4 and some
commercial base steels are given in Table 2.
Tensile properties and hardness at room temperature are shown in Table 3.
Tensile properties were tested on two types of specimen. These properties
satisfy the specifications.
High temperature corrosion and erosion

The results of isothermal heating test at 900 to 1100°C for 200hrs in air are
listed in Table 4. This indicates that the mass gain of NAR-AH-4 is equal to
NEW HEAT RESISTANTAUSTENITIC STAINLESSSTEEL 487
Table 3 Tensile properties and hardness of NAR-AH-4 at room temperature
Specimen Yield strength (Mpa) Tensile strength (Mpa) Elongation (%) HRB
JIS No. 14A (6 mmf') 309 690 60 86

JIS No. 13B (Lz mm') 391 730 48 89
Specifica tions ~280 ~600 ~40 ~95
Table 4 Mass gain of some steels for isothermal heating test at 900-1100°C for 200
hours in air (Mass gain (g/m2))
Tested temp.I''C) NAR-AH-4 Type 31055 Alloy 800H MA Type 30455
900 5.1 8.2 8.5 6.0 14.6

1000 12.4 20.7 22.1 13.3 >150
1050 22.4 31.0 42.6 21.2
1100 41.3 39.2 59.8 31.8
Number of cycles
o 100 200 300 400
~
N
e
~ -200 H-----I----+-----=~_4_~----=.F_I
~
]
u -400 I-+----+-------I----+-------+-~
til
~
:E
(lcycle is 25min. heating - 5min. air cooling)
Fig. 6 Results of cyclic oxidation test performed up to 400 cycles at IOOO°C
that of MA and SUS 5M15J1 which contain a high silicon content and is much
better than that of Type 310SS, Alloy 800H and Type 30455.
Figure 6 shows mass gain of some steels conducted by the cyclic oxidation
tests at lOOOoe in air. Tests were executed up to 400 cycles, which were done
in 25 min heating and 5 min of air-cooling. NAR-AH-4 exhibits excellent
oxidation resistance under conditions of severe thermal changes. This means
that the protective chromia oxide film formed on the surface is intact during
long-term exposure due to its relatively high chromium content and addition
of REM. High silicon content steels, MA and SUS XM15J1, which exhibit
excellent oxidation resistance in continuous heating test, are inferior to cyclic
oxidation resistance. This would suggest that silicon oxide is protective
against the diffusion of cation/anion ions, but it diminishes the adherence of
scale and base metal with thermal stress because the thermal coefficient of
expansion of silicon oxide is considerably different from that of the austenitic
structure.
2
(X 10 )
Alloys Mass Depth
6
••
til
til
NAR-AH-4
Type 310SS
0
~
]<.)
'On :E
~
S
'-' 4 ~0
~
til
til
.Q -a
(1)
til ""O~
~ S S
2 ~ :t
1]:
0
Time (h)
Fig. 7 Result of fluidised bed type erosion tests performed at 900°C up to 100h
Figure 7 shows the result of erosion test performed by fluidised bed type at
900°C up to 100 hrs. It shows that NAR-AH-4 is superior to Type 31055 is
both weight loss and maximum depth thickness loss.
Creep rupture properties

Figure 8 shows the results of creep rupture tests of NAR-AH-4 at 800 to
1000°C. Considerable data has been collected up to 25 000 hrs and some tests
are still in progress. Results show that the creep rupture properties of steels
containing nitrogen, boron additions and coarse grain size, are more stable in
terms of the rupture strength in high temperatures over 800°C.
The 104hrs rupture strength of NAR-AH-4 at 600 to 1000 e obtained from 0
the Larson-Miller parameter curve are higher than those of Type 31055, Alloy
800H and MA as shown in Fig. 9.
100 r-- '"""'- A

~INI.
F-.....IA
50 -.... ~
t--- ~ ""
~ r-.-. ~
"2' -"""r--....
·uat
~~
'T..-------
r--..
~ 20 .1-1"
~
til
til ~
--.. Indicates test in progress ~ ~ ~ r--.....
~ 10 ~~
A. A. ~
,)" .A ..•..•.
I--
r--.
c: V
~-.--
I-
800°C AF-..
~ 0
v ~
900°C r--
5
<> lOOO°C
~
103
Rupture time (h)
Fig. 8 Stress-rupture plot of developed steels at 800-1000°C
~ 500
~
~ 200
CI.l
CI.l
Q.)
b 100
CI.l
~ 50
i 20
~
10
5
600 700 800 900 1000
Temperature (OC)
Fig. 9 Comparison of stress to give rupture at 104 hrs for various alloys
Properties and microstructural observation after ageing

It is important to clarify the properties of the materials during long-term
exposure at high temperature. Results of Charpy impact tests at 20°C as
samples aged for 3000 hrs at 700 to 900°C are shown in Fig. 10. The impact
value of NAR-AH-4 exceeds 60J/cm2, and is superior to those of Type 31055
at all of the tested temperatures.
Identification of the precipitate phase was conducted by extracted residue
and X-ray analysis. Figure 11 shows the results of extracted residue analysis.
The main precipitate formed by ageing at 700 to 900°C is M23C6 (M == Fe,Cr)
5xl Omm,T-direction
2mm V-notch
(precipitate of
~__ -_-I_~=~hase)
,
..,,~
o------------~----~----~
700 800 900
Aging temperature ( t)
Fig. 10 Charpy impact properties at room temperature after aged for 3000 h
1.2
"'0
.!!,.....
~~ 0.8
IU ~
~S 0.6
§ ~
o:g 0.4
~e
0.2
0
As 300b 3000h 300b 3000h 300b 3000h
700°C 8000e 900°C
Fig. 11 Amount of extracted residues of the developed steel aged at 700-900°C
carbides. Brittle compounds such as sigma phase detected in Type 31055 and
phai phase? detected in high nitrogen and silicon content steels, have not been
observed in this steel.
Figure 12 shows the optical microstructure after ageing for 300 and 3000 hrs
at 700 to 900°C. Fine precipitates about 0.5-1 urn long are observed at grain
boundaries as well as the matrix. Thus it can be concluded that NAR-AH-4
possesses high microstructural phase stability and toughness, even after a
long time at high temperature.
Weldability
Weldability of NAR-AH-4 was evaluated by the hot cracking sensitivity tests
and welded joints test. Trans- Varestraint test and restrained test to clarify the
hot cracking sensitivity were examined as shown in Figs 13(a)(b). These
results show that hot crack sensitivity of this steel is less than that of Type
31055. Specimens of 60mm diameter were welded by TIG and coated
1---120j.Lm
Fig. 12 Microstructure of the developed steel after aged for 300 h and 3000 h at
700-900°C
(a)Trans- Varestraint test (n=2)

~<.)
13I
e::s
E =2%
.~~'-'fn 0.5
~]
,,-.... 0
?J. 15
'-'
~
g
$....t
<.) 10
~
0
no crack
0 5
.+==
~
0
1\
NAR-AH-4 Type 31088
Fig. 13 Hot cracking test result (a) Trans-Varestraint test (b) Resistrained test
492 ADVANCED HEAT RESISTANT 5TEELS FOR POWER GENERATION
50 I I I
- ..•
.......00 Data band ofNAR-AH-4-
...c... ......
r-,
/" base metal
r----QC -CD-Q v
~
-
900°C ~ ... ~
......... ... ... -
~ 20 •..
<, a...... ... .•.. ,---v;; •.....
.•.. ... .•.. .•..
rJ:l
rJ:l trJ~~ ...... .•.. .•.. .•..
! 10
IOOOoe EJ"'G
.•.. - _.•..
tiIr
~
......
- .•..
.•.. ....-"0.
•..
......
102 103 104

Rupture time (h)
Fig. 14 Creep rupture properties of welded joints
electrodes. Gas shielded TIG and MIG wire and coated electrodes with the
same compositions of base metals containing additional molybdenum to
improve the strength at joint, are already developed. Creep rupture proper-
ties of welded joints are shown in Figure 14. The creep rupture strength level
of welded joints are relatively within the data band of base metal.
CONCLUSIONS
1. A new steel has been developed with high chromium and trace amounts
of rare earth metals. The corrosion and erosion resistance for the steel
are superior to that of AI51 type 31055 and Alloy SOOH.NAR-AH-4
exhibits an excellent oxidation resistance up to 1000°C due to the
formation of a protective chromium oxide film.
2. The high creep rupture strength of the steel is due to the addition of
nitrogen and boron. The microstructural stability of NAR-AH-4 is
superior to that of AI51 type 31055. The main precipitates at grain
boundary and matrix of NAR-AH-4 after long-term ageing are M23C6
carbides, and the brittle compounds such as sigma and phai phase are
not observed.
3. The resistance to weld hot cracking sensitivity for this steel is better than
that of AI5I type 31055 and high silicon content austenitic stainless
steels, due to decreasing the silicon content (0.3%) and optimising the
chromium equivalent to nickel equivalent ratio. The creep rupture
strength level of welded joints are relatively within the data band of base
metal.
4. As described above, the new developed steel, NAR-AH-4, is a candi-
date material for high temperature components for thermal power

plants, chemical plants, industrial furnaces and automobile exhaust
systems.
REFERENCES
1. Y. Nakabayashi: Int. Clean Coal Technology Symposium on PFBC, (1994),

1.
2. H. Ishikawa et al.: The Thermal and Nuclear Power, 1990, 41 (4), 424.
3. H. Uno, T. Matsuda, S. Kihara and 1. Kajigaya: The Thermal and Nuclear
Power, 1996, 47 (2), 58.
4. Y. Nishiyama, Y. Sawaragi, T. Matsuda, S. Kihara and 1.Kajigaya: Sumitomo
Kinzoku, 1997, 49 (4), 50.
5. Y. Ikeda, K. Nii and K. Yoshihara: Trans. [pn. Inst. Met., 1983, 24, 207.
6. A. W. Funkenbusch, J. G. Smeggil and N. S. Bornstein: Met. Trans., 1985,
16A,l164.
7. M. Kikuchi, T. Sedita, S. Wakita and R. Tanaka: Tetsu-to-Hagane, 1978, 64,
440.
Development of the High Temperature
Materials for Ultra Super Critical
Boilers
A. TOHYAMA and Y. MINAMI
Materials and Processing Research Center, NKK Corporation, Kawasaki,
Japan
ABSTRACT
Technical data are presented on three new heat resisting stainless steels, which have
been developed by our company mainly for boiler tubing. The 0.1C-1BCr-10Ni-
Ti,Nb (TEMPALOYA-1) steel is an austenitic steel with considerable high tem-
perature strength derived from small additions of Ti and Nb to AISI type 304H
stainless steel. The 0.1C-1BCr-10Ni-3CuTi,Nb (TEMPALOYAA-1) steel has more
than 30% higher creep rupture strength at 600-700°C compared to TP347H. The
addition of 3wt.% Cu contributes to improve the creep rupture strength remarkably,
because of the fine Cu-rich phase which precipitates coherently in an austenitic
matrix during creep. And the precipitation of carbides (M23C6,MC) has improved the
creep rupture strength as same as TEMPALOY A-1. The 22Cr-15Ni-Nb-N-B
(TEMPALOY A-3) has higher high temperature strength and superior corrosion
resistance than those of conventional 1B-B stainless steels. The creep rupture
strength of this steel is 50°C higher than that of Alloy BOOH, and the corrosion
resistance of this steel is similar to Alloy 800H and Type 310 steel in coal ash
corrosion test. These newly developed steels are expected to be candidate materials
for ultra super critical boilers.
1. INTRODUCTION
In response to soaring oil prices accompanying the oil crises of the early 1970s,
studies of ways to increase the efficiency of thermal power plants were
conducted and the introduction of ultra super critical (USC) pressure power
generation was planned in the late 1970s and early 1980s. But the subsequent
drops and stabilization of oil prices slowed the process on USC plans. In
recent years, however, global environmental problems have restored the need
to develop and introduce USC plants, and USC plants with steam tem-
perature and pressure conditions in excess of 593°C and 24.1 MPa respectively
have been constructed.
In Japan the ultimate steam conditions are targeted at 650°C and 34.3 MPa,
but to achieve the goal, it is essential to obtain materials with improved high
temperature strength, superior resistance to oxidation, and resistance to high
temperature corrosion. It is also important that these new materials be easy to
494
MATERIALSFORULTRASUPERCRITICAL BOILERS 495
weld or process, that they can be used for a long time at high temperatures
without their material properties deteriorating, and that their cost must be
low enough for plant economy. With these circumstances taken into con-
sideration, we have developed several new heat resisting steels for boiler
tubing material comprising TEMPALOY series (A-1, AA-1, A-3). In this
paper, each of these new heat resisting steels shall be introduced including
their service performance.
2. TEMPALOY A-l
TEMPALOY A-1 is a steel made by adding small amounts of Ti and Nb to

AISI Type 304H for precipitation strengthening in order to improve its long-
term creep rupture strength. Its allowable stress at 650°C for 105 hours is 1.5
times that of conventional TP3211H and TP347H. It is suitable as material for
superheater tubes and reheater tubes in boilers. Because small amounts of Ti
and Nb are added, M23C6 carbides contributes to its creep rupture strength,
along with TiC and NbC. These fine precipitates remain uniformly dispersed
for a long time, without coarsening. In addition, the steel has less precipita-
tion of the (J" phase than either TP321H or TP347H, which also contributes to
its long-term creep rupture strength. Even after it has been used for 100 000
hours as tubing in a boiler, such properties as creep rupture strength and
toughness are still sufficient for practical use. This material is used in newly
constructed 1000 MW USC boiler.
2.1 Standard Chemical Composition and Mechanical Properties

The specified chemical composition and that of sample tube (45.0mm
diameter X 10.0tmm) are shown in Table 1. And mechanical properties are
shown in Table 2.
In the process of investigation of the creep rupture strength of austenitic
stainless steel, for example, 304H, 321H and 347H we paid attention to the fact
that the long term creep rupture strength at high temperature is closely
related to structural changes, particularly in the state of precipitation and
dispersion of carbides. Assuming that if a large amount of fine carbides
precipitate in service and that the condition of their uniform dispersion can be
maintained, such a material would have high strength at high temperature.
We studied the effect of alloying elements on the creep rupture strength of
austenitic stainless steels and the condition of dispersion of the carbides. As a
result of this study, it became known that through an addition of small
amounts of Ti and Nb, a uniform and fine dispersion of carbides can be
maintained in the grains at high temperature over a long period, so that a
material having high strength could be obtained.
Furthermore, to clarify the optimum amount of Ti and Nb, we conducted
N
<,
N
<,
Z II)
N
+ 0 I
E ~
rl
\0
0
C'rJ
rl ~0
Z 0 0
VII
\0 0
0 N
a a
~ VII
0
I.!)
0\
rl rl
I
< ~0
I
0
I.!)
~ J-f ex) -;
0 U rl rl
...J
<~ 0
~ 0
~ N
~ rl
~0 \0
t-, 0
I
rJ)
s::
Z 0\ 0
0\
.9
.~rJ)
\0 0
C'rJ
0
0 0 0
~0
a 0
sr: VII
u
~u
·s ao
N
0
~0
0
..c:
OJ ci 0
U ~ VII
~
aJ
.......c rl 0
,.Q ~ 0
~
E-c
rl N
~ VII
\0 0
\0 0
a ~
cr3 VII
~
rl
0
r-, t-,I
0 0
u ci 0
OJ~
,..QO
--•..
•..s:: ~rl
~x
OJ JB-e-
SOJ ~o
S . u
OJ
col.!)
~ rJ)~ ~
MATERIALS FOR ULTRA SUPER CRITICAL BOILERS 497
Table 2. Mechanical properties of TEMPALOY A-I
0.2% Proof stress Tensile strength Elongation Hardness

(Nmm=) (Nmm-2) (%) HRB
Sample Tube
284 608 77 83
(45.0 <p X 10.0 t)
Spec. ~205 ~520 ~35 ~90
creep rupture tests with large numbers of steels and it became clear that the
optimum value of weight percent ratio of (Ti + Nb/2)/C is in the range of 0.6
and 2.5.
2.2 High Temperature Strength and Allowable Stress

High temperature tensile test results carried out on the specimen tubes from
ambient temperature to 800 e
are schematically illustrated in Fig. 1.
D
NE 80.--~-----:'---:-----:---:---;--~-, - 800
E
~
~
0>
O~~~-~-+--+-~--~~- 0
c R~ductionof a~ea
"g 80 ------,
....----,.----
.. -*-.. ;---+.....--.~.. -.--.-j... ':'-'1: .-.-...
& l----~--------*-------,-------l------l-*--,---- •.--- ..s..
J~:::---_:::t::-::t::j~;;;~~~;t:J:~:t:o----
60
. 1 1 1 1 1 1 j
o~~~-~~-~~-~~
100 200 300 400 500 600 700 800
(212) (392) (572) (?52) (932) (1112)(1292) (1472)
Temperature 'C CF)
Fig. 1 High temperature tensile properties of TEMPALOY A-I
The results of creep rupture tests are shown in Fig. 2. As shown in the
figure, the longest rupture time of the creep rupture test has reached 100 000
hours.
Allowable tensile stress of TEMPALOY A-I are shown in Table 3.
500
400
300
l~
200
0>
~Z
100
SO en
en en
en
Q)
.b 60
~
(f)
U5
40
2 20
10 100 1000 10000 100000
Rupture time h
Fig. 2 Creep rupture strength of TEMPALOY A-I
Table 3 Allowable tensile stress of TEMP ALOY A-I
Temperature (OC) 500 525 550 575 600 625 650 675 700 725 750 775 800
Allowable stress
103 100 98 95 93 78 62 49 39 29 23 17 13
(Nmm=)
2.3 Discussion
The general characteristics of TEMPALOY A-I steel at high temperature is
equivalent to 18-8 austenitic stainless steel, but it is much higher in high
temperature strength. The amounts of extracted Ti and Nb decreased with
increasing solution treatment temperature. The atomic concentration of Ti
was found to be equal to that of Nb in extracted carbide, and the lattice
parameter of the carbide measured by X-ray diffraction was of an inter-
mediate between TiC and NbC. Therefore, the composition of Me may be
approximately (Tio.s,Nbo.s)C.Figure 3 shows the creep rupture strength at
650°C for 10 000 hours strength at 650°C for 10 000 hours as a function of the
content of dissolved Ti and Nb at solution treatment temperature. The closed
marks in this figure indicate the rupture strength of the materials solution
treated at 1150, 1200 and 1250°C without prior heat treatment at 1300°C. The
ASTM grain size number is 7.5 for 1150°C, 3.5 for 120QoCand 1.0 for 1250°C
solution treatment. The difference in the creep rupture strength was not
attributable to the grain size.
The creep rupture strength increases linearly with the increase in the
dissolved Ti and Nb. The amount of carbon precipitated as M23C6 during
creep was thought to be constant for the present solution treatment condition,
because the undissolved M23C6 was little even at the lowest solution treat-
E
~
0,
18
C
s:
c,
c
e
16
~/
C;;
e;:, 14
Vg/
C.
2
~
Y
0
12
/00
P 100
0 0.1 0.2 0.3
10
U)
Ti • Nb or C content as MC (at%)
o: Solution-treated after heat treatment at
• : Solution-treated without prior heat treatment

at 1300cC.
Fig. 3 Effect of MC carbide on the creep rupture strength
ment temperature. Therefore, the difference in creep rupture strength was

directly correlated with the dissolved Ti and Nb, which formed MC carbide
during creep.
The amount of carbon in the form of chromium carbide was calculated by
subtracting the amount of carbon forming MC carbide from the total carbon
content of steel. For titanium it was assumed that the formation of TiN
occurred preferentially and the rest of the Ti (if it existed) formed MC. This
calculation procedure is illustrated in Fig. 4. The strengthening effect per
TH-Nb at %-
Fig. 4 Schematic illustration of the calculation for MC and M23C6 carbides

Fig. 5 Precipitation of Me and M23C6 carbides in the matrix of the specimen creep-
ruptured at 700°C for 3640 hours
atomic carbon percentage is larger for MC carbide that M23C6• Figure 5 shows
the MC and M23C6 carbide precipitated in the specimen creep ruptured at
3640 hours at 700°C. The M23C6 type carbide was found to have cubic shape
and an average size of about 0.1 J-Lmin the matrix. On the other hand MC type
carbides were considerably finer, about 0.01 J-Lm,than M23C6 type carbide. It
is, therefore, suggested that the greater effect of MC type carbide on the creep
rupture strength than that of M23C6 carbide from this finer precipitation.
3. TEMPALOY AA-l
TEMPALOY AA-1 is a steel made by adding Cu to TEMPALOY A-I in order

to improve its long-term creep rupture strength through precipitation
strengthening by the Cu phase, and MC and M23C6 carbides. Its allowable
stress at 700°C for 105 hours is 1.4 and 1.2 times that of ASME SA213-TP347H
and TEMPALOY A-I respectively. It is suitable as a material for superheater
tubes and reheater tubes in boilers. Because 3% Cu and small amounts of Ti
and Nb are added. M23C6 carbide contributes to its creep rupture strength,
along with the coherent precipitation of the Cu single phase, TiC and NbC. As
in the case of TEMP ALOY A-I, the precipitates do not coagulate and coarsen,
contributing to the stability of its long-term creep rupture strength. It is a
material suitable for use in future USC boilers operating at pressures in excess
of 30 MPa and temperatures higher than 630°C.

The specified chemical composition and that of sample tube (45.0mm x
9.0 tmm) are shown in Table 4. And mechanical properties are shown in Table
5. We had developed TEMPALOY A-I, which had superior high temperature
Table 4 Chemical compositions of TEMPALOY AA-l
Element C Si Mn P S Cu Ni Cr Ti Nb
Sample Tube 1.57

0.10 0.29 0.025 0.004 2.87 10.37 17.92 0.19 0.27
(45.0 <p X 9.0 t)
0.07 2.50 9.00 17.50

Spec.
-0.14 ~1.00 ~2.00 ~O.040 ~0.005 -3.50 -12.00 -19.50 ~0.25 ~0.40
Table 5 Mechanical properties of TEMPALOY AA-l
0.2% Proof stress Tensile strength Elongation Hardness

(Nmrrr=) (Nmrrr=) (%) HRB
Sample Tube
226 517 61 71
(45.0 <p X 9.0 t)
Spec. ~205 ~50O ~35 ~90
(\IE 80.----,--~--,----~--.,.---o----~---,- 800

E ""'" (\IE
~ 70 ---------r--------+-------+--------[---------r--------+-------+-------- - 700 ~
~ 60 ;·····-1-······+······+·······-1-······+······+······+- 600 ~
~-----t-------.L------~~~~~':-.~!:.:~~-~---j---------L-------
- 500
~~ 50
~~ * -r J, l I ~
~
~ : :::.::::L::::I:.::::t::::::t::::::::r:::::r::!:t::::,~ ::: ~
til .IB J ! i i •• ,
O.~% Proof stress ~
~ ·····-··r····t·······;·······*······-1-····l·~·l;··:~-
20 200 ~
* 10 --------+-----··+------·+---·-·-+-······+·--·-·-·r------..+--------1- 100 *
~ j j i j j j 1 ~
O~-+-~-~~--r--+-~-~~ o
.§ 80 _---~--------!------R~ducti~n-of--~rea---l---------t---------
:J : ~., , , 'I: III
& 60 ~-----r---------t---------r--------':---.----~------~-~-i--!-.
c?i< J;, i iElong,atlon iii ~)
.g 40 -·-··--~-··----f------t------CW----··-g-·------ES-------tt--~--I
~~ :::: ~ : € & (; a
~~ 20 ········t·········t········t·········I·········I······
..-r , .
O~~-~-~~----~~-~
100 200 300 400 500 600 700 800
(212) (392) (572) (752) (932) (1112)(1292)(1472)
Temperature 'C (OF)
Fig. 6 High temperature tensile properties of TEMPALOY AA-l

500
400
300
NE
N~ 200 E
<,
<,
0> z
~
100 en
en
en 80 Q)
en
b)
~ 6 ~~~~~~~~~~:t~~~~~~j~~~~t~~t~~t~t~tti~~~~~~~~~~~t~~~~~t~~~l~~t:t~t~~~l~l~~~
~~i~tttj:~~~:~::~~~~ 60
···········+·····+···+·+++·i-+i··········-+····+··+·++i··H+·········+····+·+·++·H·H···········+-····+···f·-+·++++i············
4 ...··.··.+·..·+.+·+++H+·....·····.r·.···+...t·.t·++tH···········
···········t······j····t·++t·H1···········+····+···j··++t-f-H· 40
···········r······trrt·Htj············\······r····i···nTrrl············:······t···r"l"-r-rfTr·········T····I···-rrItm··········
2~~~~~~--~~~~~--~~~~~--~~~~~~ 20
10 100 1000 10000 100000
Rupture time h
Fig. 7 Creep rupture strength of TEMP ALOY AA-1
Table 6 Allowable tensile stress of TEMP ALOY AA-1
Temperature (OC) 500 525 550 575 600 625 650 675 700 725 750
Allowable stress
114 112 110 108 105 100 81 66 51 42 35
(Nmm=-)
strength by the addition of Ti and Nb. And the effects of Cu addition in the
austenitic stainless steel had increased the creep rupture strength by 3%.
Therefore, the basic composition was determined to contain Ti,Nb and 3% Cu
in 18Cr-l0Ni austenitic stainless steel.

High temperature tensile test results carried out on the specimen tubes from
ambient temperature to 800°C are schematically illustrated in Fig. 6.
The results of creep rupture tests are shown in Fig. 7. As shown in the
figure, the longest rupture time of the creep rupture test has reached to 10 000
hours. Allowable tensile stress of TEMP ALOY A-I are shown in Table 3.
3.3 Discussion
The factors that contribute towards the improvement in creep rupture strength
can be given as high temperature solution treatment, precipitation strengthen-
ing by carbides and Cu rich phase. The quantitative relationship between (Ti +
Nb) and C contents is the same as TEMP ALOY A-I. Carbides are formed by (Ti
+ Nb) and C at an atomic ratio of 1 : 1. When the C content is higher than this
relationship, the surplus Cover (Ti + Nb) forms M23C6 carbide. This steel
Fig. 8 Microstructure of the Cu-rich phase
contains about 0.1 C, but the C content used for M23C6 is low. So this steel is
%
difficult to sensitise by high temperature use. On the other hand, Cu-rich phase
precipitates most rapidly at 7S0-800°C. Microstructure of the Cu-rich phase of
this steel is shown in Fig. 8. And the precipitation of Cu-rich phase was not
influenced by the carbides or other precipitates, therefore it is supported that
the effect of Cu-rich phase and the other strengthening methods can be utilised
independently for the improvement of creep strength.
TEMP ALOY A-3
TEMP ALOY A-3 is a steel with corrosion resistance equal to, and high
temperature strength greater than that of Incoloy 800H, and has superior
economic efficiency. It is suited for use in environments of 700°C or higher.
Other high Cr steels containing more than 20% Cr include TP309 and TP310,
but their high temperature strength is low. Its high temperature strength is
improved by Nb(C,N) and M23C6 formed by adding Nb and N to 22 Cr- %
1S /oNi.TP310 and other high Cr steels become brittle as large quantities of the
O
(J phase are precipitated during long use, but the (J phase precipitation of this
steel is equal to that of 18-8 type steel, providing it with suitable toughness
after long-term use. Its Ni content lower than that of TP310 and Incoloy 800H
provides superior economic benefits.

The specified chemical composition and that of sample tube (38.1 mm X
6.9tmm diameter) are shown in Table 7. And mechanical properties are
shown in Table 8. The effects of various alloying elements on the creep
rupture strength of high Cr austenitic stainless steel were examined. Incoloy
800H (21Cr-32Ni-Al-Ti) was considered as a prospective material, so the Cr
Table 7 Chemical compositions of TEMP ALOY A-3
Element C Si Mn P S Ni Cr Nb N B
Sample Tube 1.36

0.05 0.38 0.025 0.006 15.08 21.76 0.68 0.19 0.002
(38.1 <p X 6.9 t)
0.03 14.50 21.00 0.50 0.10
Spec.
-0.10 ~1.00 ~2.00 ~0.040 ~0.030 -16.50 -23.00 -0.80 -0.20 ~0.005
Table 8 Mechanical properties of TEMPALOY A-3
0.2% Proof stress Tensile strengt Elongation Hardness

(Nmm-2) (Nmm-2) (0/0) HRB
Sample Tube
256 660 43 83
(38.1 <p X 6.9 t)
Spec. ~235 ~590 ~35 ~95
200 N~
100
(J)
(J)
Q)
20
10 100 1000 10000 100000
Rupture time h
Fig. 9 Creep rupture strength of TEMP ALOY A-3
content of new steel was 22% the same as that of alloy 800H. Based on the
results of laboratory melted materials, 0.05C-22Cr-15Ni-0.7Nb-0.12N-
O.002Bwas selected as the alloy composition having acceptable ductility and
high creep rupture strength.

The results of creep rupture tests are shown in Fig. 9. Allowable tensile stress
of TEMPALOY A-3 are shown in Table 9.
Table 9 Allowable tensile stress of TEMPALOY A-3
Temperature (OC) 500 525 550 575 600 625 650 675 700 725 750 775 800
Allowable stress
120 116 113 109 106 85 67 54 44 34 27 21 17
(Nrrurr=)
140
120
ro0...
~ 100
en
en
e
+-'
80
en
~.0 60
~3:
0
40
<C
20
0
450 500 550 600 650 700 750 800 850
Temperature CC)
Fig. 10 Allowable stress of various grades of steel at high temperature
4.3 Discussion
The factors that contribute towards the improvement in creep rupture
strength can be given as high temperature solution treatment, strengthening
of solution of nitrogen and precipitation strengthening by carbides and
nitrides of niobium or other carbides and nitrides. Based on the state of
precipitation, it is considered that fine precipitation of nitrides of Nb4N3 and
carbides of M23C6 contribute to high creep rupture strength.
Comparison of allowable stress of steel under discussion, that is, TEMPA-
LOY A-I, AA-1 and A-3, and steel tubes in actual use is schematically
illustrated in Fig. 10. The figure shows that the allowable stress of TEMPA-
LOY series excels over the steel tubes in actual use.
5. CONCLUSION
This report describes those creep resistant and corrosion resistant steels for
use in thermal power plants. The TEMPALOY series far surpasses the 18-8
austenitic stainless steel in high temperature strength and corrosion resistance

at high temperatures. It is also considered to be economically viable since the
cost is the balancing of the high temperature strength and the content of alloy
element. These tubes can be used as single tubes in USC boilers at a pressure
of 32 MPa and temperature of 630°C.
Corrosion Testing of Superheater Steels
for 600°C Steam in Biomass/Co-Fired
Boilers
P. J. HENDERSON*, TH. ERIKSSONt, J. TOLLIN§ AND
T. ABYHAMMAR§
* Vattenfall AB, 162 87 Stockholm, Sweden
t Studsvik Material AB, 611 82 Nykoping, Sweden
§ Vattenfall Generation Services AB, 162 87 Stockholm, Sweden
ABSTRACT
Several commercially available stainless steels with sufficient creep strength for use
as heat exchangers with 600°C/200-300 bar steam have been exposed in a number of
probes placed in utility boilers operating with 100% biomass or co-firing with
biomass and coal. A conventional 10-12% Cr steel was also tested as a comparison.
The probes were heated by the flue gases and internally cooled with air and water to
give metal temperatures ranging from 640 to 670°C.The longest exposure time was
---3000hours. Chemical analyses were obtained for the fuel, ash and deposits. After
exposure the specimens were examined using light optical- and scanning electron
microscopy and energy dispersive X-ray analysis. Oxide thicknesses and internal
attack were measured.
Generally, the steels with the highest chromium content showed the lowest
corrosion rates, although there were some exceptions; a high manganese content
seemed to be beneficial. The corrosion rate increased with an increase in temperature
from 640 to 670°Cand the corrosion rates were generally higher in the 100%biomass
boiler compared with the co-fired boiler. The suitability of the tested steels for use in
superheaters in biomass fired boilers is discussed in terms of their creep strength and
corrosion resistance.
INTRODUCTION
Combined heat and power (CHP) Plants in Sweden currently operate with
maximum steam temperatures of 500 to 540°C and maximum pressures of
about 160 bar. In recent years there has been a move away from burning fossil
fuels to biomass or co-utilisation of biomass and coal in order to reduce CO2
emissions. Biomass is also a popular fuel in Finland, Denmark, Austria and
USA and is gaining increased interest in Holland, Germany and Portugal.
There are advantages to be gained in terms of electrical efficiency by
increasing the steam temperature and pressure, temperature having a greater
effect on the efficiency than pressure.' In order to build a biomass or co-fired
CHP plant with higher steam data, superheater materials have to be selected
507
SOB ADVANCED HEAT RESISTANT STEELS FOR POWER GENERATION
which have a combination of high creep strength and corrosion resistance.

Most corrosion testing of boiler tubes has been performed in coal-fired
environments. In comparison, there has been relatively little reported on
corrosion in biomass boilers at steam temperatures of 550°C or higher, which
was the motivation for the work reported here.
Burning of biomass causes widespread fouling of superheater tubes and
corrosion can occur rapidly under the sticky alkali deposits. This paper
reports the results of corrosion testing of several commercially available creep
resistant steels which were exposed in probes in a power plant and a hot
water boiler, operating at 100% biomass or co-firing with fossil fuels. The
probes were heated externally by the flue gases and cooled internally with
water and air to constant temperatures in the range 640-670°C.
EXPERIMENTAL
A number of austenitic stainless steels and one high chromium martensitic

steel were tested in four probes in two separate utility boilers during 1994/95.
The steels and their chemical compositions are given in Table 1. The steels
were tested in the form of rings with dimensions 33.4 mm OD X 3.4 thickness
X 30 mrn long which were welded together and mounted on to water and air-
cooled probes. The probes were then inserted into the boilers through
openings made in existing inspection doors. The rings occupied a total length
of about 300 mm along the probes starting at a position of 1.5-1.Bm from the
boiler wall and the temperature was monitored by 6 thermocouples in three
positions. The positioning of the rings and the thermocouples are also shown
in Table 1.
Before mounting, the outer and inner surfaces of the rings were turned to
give a surface roughness of Ra<0.4. This facilitates metal loss and corrosion
measurements, but a drawback is that the chromium reduced zone at the
surface might be removed and the corrosion resistance will probably be
slightly better than as-received tubing.
Three probes, Nl-3, were exposed in the boiler of Nassjo CHP station in the
southern part of Sweden. Nassjo consists of a 30 MW circulating fluidised bed
boiler which produces steam at BO bar /4BO°C and generates 9 MW electricity.
The heat is distributed in the town as district heating. During the time the
tests were running the fuel was 70% biomass (residual products from the
forestry industry) and 30% coal in terms of thermal energy produced. Since
1996 only biomass has been used.
One probe, J1, was exposed in Boiler 3 of Jordbro district heating station,
near Stockholm. Jordbro is a 70 MWth hot water boiler fired with 100%
biomass (pulverised wood). Details of exposure times and temperatures are
given in Table 2.
The wall thicknesses of the rings were measured at 8 points around the
CORROSION TESTING OF SUPERHEATER STEELS 509
Table 1 Chemical compositions in weight of the tested steels with their positions
%
along the probes and the temperatures and positions of the probe thermocouples.
The probes are called N1, N2, N3 and J1 and a temperature in bold type indicates a
control thermocouple. Thermocouples 1,3,5 were uppermost (the windward side)
Temp N1 Temp N2 Temp N3 Temp J1

Steel Cr Ni Mo Mn Other eC) eC) eC) eC)
Th 1 1 Position on probe nearest

ermocoup e boiler wall 605 620 575-625 640
Thermocouple 2 475-525 475-525 540-600 615
Si .46, Nb 1,
Esshete 1250 14.5 9.4 0.97 6.2 ~o~~<tos,
N .04
V 0.3, Si
X20 10.5 0.4 0.S3 0.7 ~~ .i9;2~,

.19
TP 321 17.2 10.1 - 1.4 Ti 0.4 7,

OSi5
0.36, C .0
Si 1.17, C
TP 310NbSi 25.4 21.2 0.22 1.7 ~:~~:~
0.67
Thermocouple 3 640 640 670 650
Thermocouple 4 500-550 540-575 600-625 610
Ti 0.93, C
Alloy 825 22.0 39.3 3.25 0.5 ~:~;: ~u
1.83
Ti 0.53, Al
Alloy 800H 20.3 30.2 - 0.6 0.5, Si 0.49,
CO.07
Si 0.4, Nb
HR3C* 25 20 0.25 1.1 0.5, NO.2,
C 0.06
AC 66*0 27 32 O.S 1.0 ~~8~C~.07
Th 1 5 Position on probe furthest from 605 640 640-660 600-650

erillocoup e boiler wall
Thermocouple 6 500-550 525-560 540-600 550-600
* Standard chemical analysis. 0 AC 66 was tested in only 2 of the 4 probes, N3 and J1.
Table 2 Details of the probes, exposure times, nominal temperatures and

percentage time at nominal temperature ±10°C
% time at set
Boiler name Fuel type Probe name Set Temp (OC) Exp. Time (h) temp ± 10°C
Nassjo Bio/coal Nl 640 3192 79

Nassjo Bio/coal N2 640 1416 97
Nassio Bio/coal N3 670 1776 64
Jordbro 3 100% bio Jl 650 1680 93
circumference before and after testing. Chemical analyses were obtained for
the fuel and the deposits. After testing the specimens were examined using
light optical- and scanning electron microscopy and energy dispersive X-ray
analysis.
RESULTS
Nlissjo - Co-Fired Boiler

For probes N1-N3 it was not possible to measure any metal loss after
exposure (metal loss == original wall thickness - wall thickness after expo-
sure). (N.B. This does not mean that metal loss did not occur.) Optical
microscopy was used to measure the oxide thickness and also showed that a
well formed oxide scale had grown nearest the metal interface, with a more
porous oxide on top at the surface. Total corrosion measurements defined as
oxide thickness plus internal oxidation are given in Table 3. At 640°C, X20
showed the largest amount of oxidation, followed by E 1250 and TP 321. At
670°C, X20 still exhibited the thickest oxide scale, closely followed by TP 321.
The maximum depth of corrosion on 800H was also relatively high. It was not
Table 3 Maximum total corrosion (measured in urn) on Probes N1, N2, N3
Cr content Total corrosion Total corrosion Total corrosion

Material (wt%) Nl (640°C) N2 (640°C) N3 (670°C)
Esshete 14.5 65 20 43
X20 10.5 120 30 105
TP321 17.2 50 20 90
TP310 25.4 3* 0 18*
825 22.0 8 0 12
800H 20.3 8 0 70
HR3C 25 25 0 21
AC66 27 not tested not tested 3
* Spalling had occurred

Table 4 Content in weight % of the main elements in the deposits, fuel and ash in
Nassjo power station
Sulphur Chlorine Calcium Potassium Sodium
Deposits 12-13 0.1-0.5 11-12 11-15 0.8-2.5

Coal (Dry) 0.44 0.01 2.72 0.64 0.1
Bio (dry) 0.04 0.01 0.36 0.05 0.01
Fly ash 2.1 0.31 9.5 2.84 0.67
possible to draw any conclusions about TP 310, because of oxide spalling. The
exposure time of probe N2 was too short to give any results for the alloys
containing more than 20% Cr.
X20, HR3C and Alloy 800H were chosen for more detailed analysis in the
SEM. In all the alloys a well formed oxide of chromium was found near the
metal interface, with a more porous layer of iron oxide on top at the surface.
The chromium oxide layer was enriched with sulphur and manganese. A
chromium and manganese depleted zone was detected in the metal directly
under the chromium oxide and manganese-rich sulphide particles were
detected in the metal close to the oxide. Additionally, the oxide layer in X20
was analysed for CI, Si, V, Mo and Ni, but none of these elements were
found.
Jordbro -100% Biomass Fired

A similar picture of oxidation emerged here, with a well formed oxide of
chromium near the metal interface and a more porous layer of iron oxide on
top at the surface. A chromium depleted layer in the metal directly under the
chromium oxide was detected, but unfortunately a Mn analysis was not
performed. 800H and HR3C were chosen for more detailed analysis in the
SEM. However, no sulphur could be detected. Results from [I are given in
Table 5. X20 showed the highest corrosion rate followed by TP 321.
Analysis of the deposits on the probes showed that there was more chlorine
and calcium in the deposits from the 1000/0biomass-fired boiler and more
sulphur in the deposits from the co-fired boiler, (see Tables 4 and 6).
DISCUSSION
Corrosion Resistance
The materials with the highest chromium content clearly showed the greatest
resistance to corrosion at 640-650°C (Tables 3 and 5). In spite of a lower
chromium content E 1250 showed similar corrosion resistance to TP 321 in the
co-fired boiler at 640°C and similar or better corrosion resistance to 321 and
Table 5 Corrosion results from Probe J1 (650°C). Measurements in p.m
Oxide scale Metal loss plus

Material thickness Inner corrosion Total corrosion Av. Metal loss corrosion
E 1250 <40 10 50 48 98
X20 100 0 100 47 147
TP 321 60* 10 70* 52 122*
TP310 <40 10* 50* 41 91*
825 35* 15 50* 40 90*
800H 30 15* 45* 61 106*
HR3C 20 10 30 23 53
AC66 <35 15 50 20 70
* Greater locally
Table 6 Content in weight % of the main elements in the deposits, fuel and ash in
Jordbro power station
Sulphur Chlorine Calcium Potassium Sodium
Deposits 4-7 0.2-0.8 17-23 8-17 0.5-1.4

Fuel (Dry) <0.01 0.01 0.08 0.04 0.01
Fly ash 0.94 0.31 5.49 2.85 0.6
800H at 670°C and in the biomass boiler at 650°C. This similarity has been
noticed before when it was difficult to distinguish between TP 310 (25 Cr), 347
(18 Cr), 316 (17 Cr) and E 1250 (14 Cr) in terms of corrosion after exposure in a
pulverised coal-fired boiler.?
The unexpectedly better corrosion resistance of E 1250 could be explained
by the alloy'S high manganese content. Tests on a series of experimental
stainless steels based on Alloy 800 ( i.e. containing 22% Cr and 30% Ni) but
with Mn contents ranging from 0.8% to g% showed that the depth of
corrosion after exposure at 800°C in sulphidising/ oxidising conditions
decreased rapidly with increasing Mn content up to 4% and remained
constant from 6 to 9%,3 as shown in Fig. 1. High levels of Mn were found in
the outer, normally Fe-rich scale, forming a Mn-Fe spinel and large numbers
of Mn-rich sulphides were formed under the surface.
The improved resistance to sulphidation/ oxidation was explained on the
basis that Mn-rich spinels are effective barriers for the inward transport of
sulphur through the oxide layer and that sulphur once in the base metal reacts
preferentially with internal manganese instead of chromium, so that more of
the chromium is available for the formation of a protective oxide scale."
However, a number of authors believe that Mn is deleterious, leading to an
increase in sulphidation, see for example Ref. 4. Mn has also been found to
increase the oxidation of binary Fe-Cr alloys by the formation of a less-
500
--.E 400 800 0
e 360 h
---.....:
:J.
300
0
o 200
cu.•..•
0 100
t-
O
0 2 4 6 8 10
Mn content (0/0)
Fig. 1 The effect of manganese content on the total corrosion (external scale plus
internal sulphidation) of Alloy 800H after 360h at 800°C in a sulphidising/
oxidising environment. Redrawn from information presented in Ref. 3
protective MnCr203 spinel rather than Cr203. Mn additions increased the

oxidation rate of a Fe-28Cr alloy when oxidised in dry flowing oxygen at 800
and 1000°C.5 However, the results of this investigation in sulphidising
conditions are in agreement with those from Ref. 3.
HR3C and AC 66 showed the best corrosion resistance in all the probes.
These alloys have the highest Cr content for general corrosion resistance
coupled with a high Ni content which improves resistance against chloride
attack." Corrosion testing of a number of stainless steels also showed that
HR3C had very good corrosion resistance in a coal-fired boiler." Chlorine was
not detected in the metal samples, although it was present in the deposits, fuel
and ash. It is known that chlorine has a high diffusivity and acts as a catalyst
for the oxidation processf
The total corrosion per 1000 h for the steels tested is shown in Fig. 2. The
steels are plotted in terms of increasing chromium content. This figure shows
that the corrosion rate is increased when the temperature is increased from
640 to 670°C and that burning 100% biomass causes more corrosion than a
mixture of biomass and coal. (N.B. The metal losses from probe J1 are not
included in Fig. 2. If these values are included the total corrosion rate will be
even greater.) That a maximum corrosion depth of ,....60J.Lm is reached in X20
probably indicates that spalling occurs in thicker oxide scales. E 1250
performed well in the 100% biomass boiler, considering its relatively low Cr
content, but obviously needs further testing along with AC 66 and HR3C.
Creep Strength
The corrosion resistance is not the only consideration in choosing a super-
heater material for higher stearn temperatures. The creep strength (or proof
60
50
E
a
.J: 40
0
0 .N1640°C
~
L. 30 f3N3670°C
(I)
C.
lmJ1650°C
-c 20
')(
0
'0
I- 10
0
X20 E 1250 TP 321 A 800 A825 HR3C AC 66
Steel name
Fig. 2 The total corrosion (oxide scale plus internal attack) per 1000h. Metal loss
values from J1 are not included. The steels are plotted in terms of increasing Cr
content on the x-axis. N1 and N3 are co-fired and J1 is 100% biomass
Table 7 The stress which causes creep failure in 100000 hours at different
temperatures, <1BI0h5in MPa. The 0.2% proof stress, <10.2,
is given instead if it is less
than <1BI0h5
600°C 650°C 670°C

Steel Cr Ni <1BI0h5 <1B105h <1B105hNotes
X20 10.5 0.4 59 23 X20 CrMoV 121

British Steel BS 3059 II
Esshete 1250 14.5 9.4 133<10.2%100 74
Stirling Tubes
X8CrNiTi 18 10,
TP 321 17.2 10.1 94 58 50
SS 2337
Alloy 825 22.0 39.3 Max temp 540°C - ASME boiler codes
Alloy 800H 20.3 30.2 95<10.2% 77 67 Low ductility 600-700°C
HR3C 25 20 158<10.2%113 96 Sumitomo
AC66 27 32 Werkstoff m. 1.4877

9OcrO.2%85cro.2%74
Mannesmann
stress) is also of prime importance. In order to keep tube thicknesses at

reasonable levels at 200-300 bar internal pressure, a creep strength of
90-100 MPa is desirable. The creep strengths of the tested steels are given in
Table 7. TP 310NbSi has a lower creep strength than TP 321.
X20, TP 321, 825 and 800H are not suitable for 600°C steam, where the metal
temperature will be 650, but 825 has been used as the outer component in co-
extruded tubes at lower temperatures," and could be used at higher tem-
peratures provided the inner component had sufficient creep strength. E 1250,
HR3C and AC 66 are all suitable for metal temperatures up to 650°C. HR3C
has the highest creep strength of all the materials tested, but has been found to
suffer from cracking because of low ductility caused by cold working.l?
Testing of E 1250, HR3C and AC 66 and other high chromium steels is
continuing in biomass and co-fired boilers.
CONCLUSIONS
• Results of corrosion testing of steels in a biomass/coal fired boiler at metal

temperatures of 640-670°C showed that the corrosion resistance of the
steels decreased in the order:
AC 66 > Alloy 825 > HR3C > Alloy 800H ~ Esshete 1250 ~ TP 321 > X 20.
• In a 100% biomass fired boiler with 650°C metal temperature the corrosion
resistance decreased in the order:
HR3C > AC 66 > Alloy 800H::= Alloy 825:=:;TP 310NbSi:=:;Esshete 1250 > TP
321 > X 20.
• In general the alloys with the highest chromium levels performed the best:
a high manganese content seemed to be beneficial. It is thought that if
sulphur diffuses into the base alloy it would react preferentially with
internal manganese instead of chromium, so that more of the chromium is
available for the formation of a protective oxide scale.
• In terms of creep strength, only three of the alloys are suitable for use at
metal temperatures of 650°C. The creep strength of these alloys decreased
in the order:
HR3C > Esshete 1250 > AC 66.
ACKNOWLEDGEMENTS
We thank Erik Haggblom (formerly Studsvik Material) and Jonas Rosen

(formerly Vattenfall Utveckling) for their invaluable help. This project was
entirely funded by Vattenfall Thermal Power (Vattenfall AB Viirmekraft).
REFERENCES
1. Scheffknecht et al.: A project to determine high temperature corrosion

I
characteristics of different steam generator materials', VCB Kraftwerk-

stechnic, 1996, 76, 768-792.
2. E. P. Latham, T. Flatley and C. W. Morris: 'Comparative performance of
superheated steam tube materials in pulverized fuel fired plant environ-
ments', Proc. Conf. Corrosion resistant materials for coal conversion systems,
D. B. Meadowcroft and M. I. Manning eds,. Appplied Science, London,
1983.
3. P. H. Wihelmsson: 'A new sulphidation resistant austenitic alloy for fossil-

fired systems', Proc. Conf. Stainless Steels '84, Institute of Metals, Lon-
don, 1985, 541-547.
4. F. Gesmundo: 'Materials corrosion in coal gasification - analysis of data
from COST 501 and other sources', Proc. Conf. High Temperature Materi-
als for Power engineering 1990', E. Bachelet et ale Eds, Kluwer Academic,
1990, 67-91.
5. F. H. Stott, F. I. Wei and C. A. Enahoro: 'The influence of Mn on the high
temperature oxidation of iron-chromium alloys', Werkstoffe und Korr.,
1989, 40, 198-205.
6. G. Sorell: 'The role of chlorine in high temperature corrosion in waste-to-
energy plants', Mater. At High Temp., 1997, 14 (3), 207-220.
7. J. L. Blough and G. J. Stanko: 'Fireside corrosion testing of candidate
superheater tube alloys, coatings and clad dings - phase II', Corrosion 97,
Paper 140, NACE, Houston, Texas, USA, 1997.
8. R. Riedl: 'Active oxidation in boiler tubes of a biomass district heating
power plant', VGB Kraftwerkstechnic, 1997, 77, 537-542.
9. A. Wilson, V. Forsberg and J. Noble: 'Experience of composite tubes in
municipal waste incinerators', Corrosion 97, Paper 153, NACE, Houston,
Texas, USA, 1997.
10. P. S. Chang: 'Lessons learned from reheater replacements in Gallatin fossil
plant units 1 and 2', Proc. 1996 EPRI fossil plant maintenance conf., EPRI,
Palo Alto, CA, USA, 1996.
Section 4:
FURTHER DEVELOPMENTS
US Developments in Advanced Steam
Turbine Materials
B. B. SETH
Westinghouse Power Generation, A Division of CBS Corporation, Orlando,
Florida, USA
ABSTRACT
Globalisation of the power industry has created intense competition in the market
place. The drive to produce power at the lowest possible cost has led to major
advances in efficiency, unit size, reliability, maintainability and cycle time. The
development of new materials and processes together with the understanding of
their behaviour have all played a key role in making these advances a reality. US
developments in these areas are reviewed and future needs described.
INTRODUCTION
Efficiency and unit size have been historic drivers for steam turbine advances.
Inlet temperature and pressure, reheat temperatures and unit size have
increased steadily since the beginning of the century as shown in Figs 1
and 2. The historic trend of a 10 e per year increase in inlet and reheat
0
temperatures culminated in the construction in 1960 of the world's highest

temperature (649°C) and pressure (34.5MPa) unit. Philadelphia Electric's
Eddystone unit 1 achieved a world record efficiency of 40%. Despite this
achievement, the trend towards higher temperature and pressure halted due
to concerns about the reliability of the boilers and high cost of austenitic steels
Eddystone
• Temperature
(OF)
1200
Eddystone. 1200°
1000
1000
Eddystone. 5000 PSI Max.
5
800
4
3
1
~e"~j,~~.---:r_u~e---,--_---,
600
1~r':."s~~~am
2 400
200
o~ __ ~=- ~ ~
1910 1920 1930 1940 1950 1960 1970 1980 1990 2000
Service Year
Fig. 1 History of temperature and pressure of steam turbines
519
1400
1200
1000
~
~ 800
cD
en
N
600
400
200
0
1900 1910 1920 1930 1940 1950 1960 1970 1980
Year
Fig. 2 Historic growth of steam turbine size
and superalloys. These economic considerations actually reversed the trend

and as a result, research on high temperature steam turbine materials
declined sharply.
Reliability concerns also halted the rapid rise in turbine size (output) of the
1950s and 60s. Reliability became the key concern. In the 1970s, the issue of
nuclear safety and the oil embargo shifted the industry's focus from the
addition of new units to life extension and improvement in the efficiency of
existing units. In-service inspection, repairs and remaining life prediction for
components became critical.
The 1980s were years of significant political and economic change in the
world. The breakup of the Soviet Union, opening of China to foreign trade
and industrialisation in India, Korea and other far eastern countries all had a
very positive influence in making the power industry truly global. The
intense world-wide competition directed attention once again to efficiency,
reliability, maintainability, cycle time and capital cost as all of them affect the
life cycle cost of power production.
The materials advances in the US have been directly influenced by these
historical events and trends. This paper reviews these advances in the context
of the key market drivers: efficiency, reliability, maintainability, size, cycle
time and capital cost. Future materials needs are discussed briefly.
ADVANCED MATERIALS DEVELOPMENTS IN THE US
Efficiency
The ever increasing steam turbine temperatures had resulted in the develop-
ment of ferritic materials for use up to 566°C. When the 325 MW Eddystone
unit was first conceived for operation at 649°C and 34.5 MPa, the development
of high temperature steam turbine materials was accelerated. 1 The steam
US DEVELOPMENTS IN ADVANCED STEAM TURBINE MATERIALS 521
Table 1 Materials for the Eddystone 1 Super Pressure Unit
Component Material
Rotor Discaloy
Rotating Blades K 42B, St. 422
Stationary Blades St. 316
Inner Cylinder St. 316
Inlet Features St. 316
Outer Cylinder 2~Cr-lMo-~V

Bolts W545
Main Steam Pipe St. 316
conditions, particularly for the super pressure (SP) element, presented serious
metallurgical challenges. Although most of the critical components were built
from austenitic stainless steels and superalloys used successfully in combus-
tion turbines, manufacturing processes for large sizes and long time test data
still needed to be developed. Table 1 summarises the materials used in this
unit.? The Eddystone unit established a world-record annual plant perform-
ance level of 9003 kJ/kWh.2
The Eddystone unit is still running today, albeit at slightly lower tem-
perature and pressure. All the turbine materials performed extremely well,
but reliability problems- were encountered with the boiler materials. These
problems, being temperature related, reduced the economic incentives to
continue raising temperatures and pressures. In fact, the trend towards higher
temperatures reversed and in the USA stabilised around 538°C and 27 MPa.
Recently, interest in higher efficiency machines has rekindled. The fuel cost,
concern about pollution and higher exhaust temperature of advanced com-
bustion turbines in combined cycle plants all demand higher temperature
steam turbines. The initial thrust is for 1100°F (593°C) machines but this is
expected to reach 1200 P (649°C). To overcome the cost obstacles encountered
0
with the Eddystone unit, the focus is to minimise the use of austenitic steels
and superalloys and extend the temperature capabilities of ferritic steels.
Many advances have been made throughout the world using 9-120/0 Cr
steels+I+ modified by the addition of alloying elements such as molybdenum,
vanadium, tungsten, cobalt, nitrogen, niobium and boron.
(a) Rotor steels

The development of 12% Cr type rotors started in the USA in the 1950s. The
St. 422 (12 CrMoWV) rotor was developed by Westinghouse2 and the
12CrMoVNbN by General Electric+ The chemical compositions of these
rotors is shown in Table 2.
While these rotors showed some improvement over the conventional 1%
Cr-MoV rotors, they were not considered adequate for 600°-650°C machines.
Table 2 Composition of Earlier US 10-12% Cr Steels
OEM C Si Mn Ni Cr Mo W V Nb N
Westinghouse- .23 .4 .8 .75 13 1 1 .25

GE - Orig.! .19 .3 .5 .6 10.5 1 .2 .085 0.06
GE-Mod.14 .14 .03 .59 .69 10 1 1 .18 .045 .041
T. Suda et al. have reported= the development of another composition with

higher tungsten and lower Nb and C. This alloy is claimed to be better than
the original version and capable of use up to 593°C.
Parallel work has been taking place in Europe under the COST 501 program
and in Japan by Mitsubishi Heavy Industries, Hitachi and Toshiba. The
Europeans have produced= five rotors to study the effects of B, N, W and Mo
and have generated stress rupture data extending to 50 000 hrs. The optimum
materials are capable of operation up to 600°C and are already in service.
Development work is continuing to extend the application of this family of
materials to 650°C. Mitsubishi Heavy Industries has developed-! three rotor
steels TRI100, TRl150 and TR1200 for use up to 593°, 621° and 640°C
respectively. Hitachi has developed= a rotor steel HR 1200. This alloy
contains W to improve creep strength, Co to prevent ferrite formation and B
to improve hardenability. Toshiba has developed= two improved rotor
materials TOS 107 and TOS 110. TOS 107 is a 10% Cr-I% Mo-l% W-V-Nb-
N alloy for 593°C application and TOS 110 is a 10% Cr-1.8% W-0.7% Mo-
V-3 %
Co-Nb-B alloy for application up to 630°C. The stress rupture
properties of US rotor compositions are summarised in Fig. 3.
1000
---- --~
---= =---
=-----
~ -----.....:
c,
~
--.G. E.M bd 12% Cr
enen 100
~ 12% Cr
~
en ....•.•.
1(:rMn\l
10
2.1 2.2 2.3 2.4 2.5 2.6 2.7
L.M.P = T (25 + Log (t)) x 10-3
Fig. 3 Stress rupture properties of various US rotor steels
(b) Blade materials

The primary high temperature blade material is St. 422. It has performed
extremely well in service over a long time. However, the rupture strength of
US DEVELOPMENTSIN ADVANCEDSTEAMTURBINEMATERIALS 523
this alloy above 550°C is limited. Some improvement is achieved by using St.
H46. Beyond about 570°C, Westinghouse has successfully used a Nickel-
Chromium-Cobalt based superalloy called Refractaloy 26 for blades and
bolts.
In an EPRI sponsored research project, RP 1403-15, Yamada et al.17
considered 16 different nickel based superalloys as potential high tem-
perature blading alloys. These alloys were compared for their physical
(thermal expansion coefficient and thermal conductivity) and mechanical
properties. Based on this comparison, the selection was narrowed to four
materials: M-252, Refractaloy 26, Nimonic 90 and Inconel 718. The key
features and problems of these four alloys are summarised in Table 3. M-252
Table 3 Features and Issues of Four Candidate Alloys
Superalloy Features and Problems
• Extensive service history as gas turbine buckets

• Good balance of strength and ductility
M-252
• Lower thermal expansion coefficient
• No tenon peening experience
• Experiences as advanced steam turbine buckets
Refractaloy 26 • Good balance of strength and ductility
• Tenon peening experience
• Good balance of strength and ductility
Nimonic 90 • Tenon peening is hopeful (no experience)
• Notch ductility behavior is not clear
• Extensive service history as gas turbine parts
Incone1718
• No tenon peening experience
was chosen as the primary alloy based on a vast amount of favorable gas
turbine experience. Refractaloy 26 was selected as the backup alloy because:
(1) it contains an alloy addition of iron and, therefore, represents an alternate
choice to the exclusively nickel-based superalloys, (2) it shows a good balance
of material properties, (3) it has a confirmed good peening capability, and (4)
although it does not have extensive service history, it has performed well in
the steam turbine buckets in the research and development of an advanced
steam turbine plant in Japan, which operated for about one year at 1200 P 0
(649°C).17
Contrary to the above statement by Yamada et al.)", Refractaloy 26 has been
used extensively and successfully in steam turbines over 30 years. Refractaloy
26 has been used not only for blades, but also for bolts and occasionally for
rotors. The excellent properties of this alloy cited by Yamada et al.'? and its
vast operating experience make it a most desirable high temperature material.
c
Q)
·0 15 _t_-__t_-___t--_t_-__t_--t----i=--+--____~
~o 252
~ S? 14
.~6
0-
13 _t_-__t_-___t--_t_-__t_--J---..,,~-+---+--____I
caT"""
o.x
~-12-t----t-----t----t---~~~~~~~~~----I
(ij
~ 11-t----t-~~~~-t----t---t---+---+------I
..c
~
100 200 300 400 500 600 700 800
Temperature °C
Fig. 4 Coefficient of thermal expansion of various blade materials
1000
-..;.:
r--.....
')f:r -:::::::: ~ <,
_...............
-.
~ t'"--- -, 'to <, <,
St422 =e: ~'"
" ~ ~ ~
~ f\-
100
'\
\.
18 20 22 24 26 28 30 32
L.M.P= T (25+ Log (t» x 10-3
Fig. 5 Stress rupture properties of various blade materials
Figures 4 and 5 compare the coefficient of thermal expansion and stress

rupture properties of key blade materials. When used in conjunction with the
modified 10-120/0 Cr rotor alloys discussed above, one drawback of nickel
based superalloys for blading applications is their higher coefficient of
thermal expansion. This difference needs to be accounted for in the design.
(c) Casing materials

The common high temperature casing materials are 1.25Cr-O.SMo and
2.25Cr-1Mo steels. St. 316 was used for the inner cylinder at Eddystone.
While St. 316 worked very well at Eddystone, the high thermal expansion and
cost are clear disadvantages. A cost effective ferritic steel initially developed
for boiler tubes has shown excellent promise for a steam turbine casing
material. Research conducted at the Oak Ridge National Laboratories of the
USA in the late 1970s and early 1980s produced a 9Cr-1Mo V, Nb alloy18-22
that has better stress rupture properties. The properties of this alloy in the cast
form has been evaluated by Westinghouse and found to be adequate for use
up to 593°C. The stress rupture properties of Mod. 9Cr-1Mo and 2.2SCr-1Mo
at 593°C are compared in Fig. 6.
en
en
~
Ci5
0-
Q)
Modified 9Cr-1 Mo Steel
~
o
"0
Q)
.~
CO
Eo
z
10° 101 102 103 104 105
Time to Rupture, HRS
Fig. 6 Stress rupture properties of modified 9Cr-lMo and 2.25Cr-lMo castings at

593°C
Similar observations were made'> in programs sponsored by EPRI and

COST. The EPRI program, which used the basic Mod. 9Cr-lMo steel, showed
the creep rupture strength to increase with increase in initial tensile yield
strength even up to extended test times of about 70 000 hours. In the COST
program, the material composition was altered. 1% W was added to raise the
creep strength relative to the tungsten-free alloy used in the EPR! program.
The chromium content was increased from 9% to 10% to increase the
solubility of the nitrogen and hence the creep strength. The nickel content was
raised to 0.7% to balance the tungsten in order to achieve martensitic
microstructure. Contrary to expectations, despite higher initial yield strength,
COST modified steel showed (Fig. 7) a lower creep rupture strength than the
base (EPRI) alloys (0.2% yield strength of > 499 MPa), especially for longer test
durations.
Retention of nitrogen in the castings is essential for maintaining high creep
ro
o,
~
ch
en
~
Ci5
100~------~~-------+----~~~~~--~
90~--------~-------+--------~~~~~
80+---------~-------+--------4_--~~~
70~~~~--~~~~-+~--~~4_~~~~
2.3 2.4 2.5 2.6 2.7
L.M.P =T (25 + Log (t)) X 10-3
Fig. 7 Creep rupture strength of COST and EPR! modified 9Cr-lMo Steels
Table 4 Chemical Composition of Modified 9Cr-1Mo Castings
Heat C Mn P 5 51 Cr Ni Mo V Cb N Al
1 0.10 0.5 0.018 0.003 0.40 8.9 0.3 0.95 0.23 0.08 0.01 0.015
2 0.11 0.5 0.016 0.001 0.45 8.7 0.3 0.96 0.19 0.09 0.05 0.021
800~--~~--~----~----~--~~--~----~
700~~==~~~-----r----+---~r----+----~
ctS
~ 600~~--~---+~~~~--+-----~---+----~
~ 500~C===F=~~=---~--~~~~~---+----~
c
~ 400+---~~---+----~~~~~~~~-+----~
t5 300+---~~---+----~----+---~~~~----~
200+---~~~~~~~~~+---~~---+~~~
100 200 300 400 500 600 700

Temperature °C
Fig. 8 Effect of Nitrogen on mechanical properties of modified 9Cr-1Mo Castings
200+-----+-~~~-----+------~----+-----~
ctS
a.
:2
en~
en
~
m 'OO+-----+-----~-----+--~~~~~+-----~
90+-----+-----~-----+--~~~~~&-----~
80+-----+-----~-----+----~~~--~~--~
70+-----+-----~----~~~~~~~+-----~
60+-----+-----~-----+------~----~~--~
50~~~+-~~~~~-+~~~~~~+-~~~
2.1 2.2 2.3 2.4 2.5 2.6 2.7
L.M.P = T (25 + Log (t)) x 10-3
Fig. 9 Effect of Nitrogen on creep rupture strengths of modified 9Cr-1Mo Castings
rupture strength. To evaluate the effect of nitrogen, two heats of composition

nominally similar except for different nitrogen levels were melted and cast.
The composition of the solidified castings is shown in Table 4.
The castings were given a standard normalising and tempering treatment
and tested for mechanical properties (Fig. 8) and creep rupture strength (Fig.
9). The yield and tensile strengths of the lower nitrogen casting were lower.
While the strength difference at elevated temperatures remained, it was
significantly reduced. Except for nitrogen content, the composition of both
heats was similar. Since both castings were given the same heat treatment, the
difference in mechanical properties can be attributed only to the difference in
nitrogen contents. The creep rupture strength was similarly lower in the
lower nitrogen casting. Whether the difference in creep rupture strength is
due solely to nitrogen content or to different yield strengths or to a combina-
tion thereof, cannot be established. It is clear, however, that the lower
nitrogen content affects creep rupture strength either on its own or by
affecting the yield strength. The beneficial effect of higher yield strength on
the creep rupture strength of modified 9Cr-1Mo steel had also been observed
in the EPRI Program.P
(d) Bolting materials

Like blade materials, bolting materials must possess high temperature
mechanical strength, creep rupture strength and a coefficient of thermal
expansion compatible with the casing materials. In addition, bolting materials
must have high resistance to stress relaxation. Many of the materials used for
blades are also used for bolting. For temperatures up to 566°C, the most
common materials used in the USA are St. 422 and H46. For temperatures
above 566°C, nickel based alloys have been used. Superalloys used by Wand
GE are Refractaloy 26 and Incoloy 901 respectively. W545 was used for the
Eddystone unit.
In an EPRI sponsored research project, K. H. Mayer-" investigated world-
wide experience on high temperature steam turbine bolt materials. The
chemical composition and service history of five superalloys are shown in
Tables 5 and 6 respectively. Based on this survey and other considerations,
Mayer concluded that Nimonic 80A is confirmed as a prospective candidate
for bolts up to 593°C. PER 2B and Refractaloy 26 were rated as promising
alloys. The approximately 15% failure rate of Incoloy 901 was considered very
Table 5 Chemical Composition of Superalloy Bolt Materials in Steam Turbines
Chemical composition in %
Alloy C Cr Ni Co Mo Ti Al B Fe
max. max. max. 0.010- Bal.

Incoloy 901(1) 11-14 40-45 5.0-7.0 2.0-3.0
0.10 1.0 0.35 0.020
max. 2.5-3.5 max. 0.001- Bal.
Refractaloy 26 16-20 35-39 1B-22 2.5-3.5
O.OB 0.25 0.01
max. Bal. (0.7-
Inconel X750(1) 14-17 2.25-2.75 0.4-1.0 5-9
O.OB 1.2 Nb)
PER2B(2) max. Bal. max.

19-23 13-20 - 1.6-3 1-2
0.15 10.0
max. Bal. max. max. max.
Nimonic BOA (3) 1B-21 1.B-2.7 1.0-1.B
0.10 2.0 O.OOB 3.0
(1) trade name of INCO (2) trade name of Aubert & Duval (3) trade name of Wiggins
Alloys
Table 6 Failure of Superalloy Bolt Materials in Steam Turbines
Bolt material No. of units No. of bolts No. of failure cases Percentage of failed bolts
Incoloy 901 49 434 15 14.9

Refractaloy 26 250 abt. 50000 ? abt. 0.03
PER2B 6 1470 0 0
Nimonic80A 231 20291 24 0.37
Inconel X750 3 28 1 3.5
high and experience on X-7S0 was too limited. Incoloy 901 also suffered from
negative relaxation behaviour.
It is rather curious that despite the facts (Table 6) that Refractaloy 26 has
been used in more units, for more bolts and has experienced less than one
tenth the failure rate of Nimonic 80A, Mayer-" concluded Nimonic 80A to be
the alloy of preference. It is possible that Nimonic 80A was preferred because
it is more familiar to Europeans and because the following remedial steps
have been taken to minimise cracking:
• Elimination of sulphur and lead bearing lubricants.
• Design measures to eliminate deposition of stagnating steam con-
densate.
• Melting with lowest possible trace elements e.g. <20 ppm phosphorous.
• Provision of thermo-elastic bolted joints with low stress concentration.
• Selecting and strictly maintaining a preload matched to the bolt tem-
perature.
It is obvious from the above countermeasures that the alloy is inherently
not the best, but its use can be finessed by careful design, processing and
operation. It should be noted that the excellent performance of Refractaloy 26
is without the benefit of any such remedial measures.
Reliability and Maintainability

The most critical consideration in introducing a new material is its reliable
performance in the operating environment over a long period of time. Rapid
inspection and repair procedures are critical to maintaining high reliability
and availability. SOIDeof the recent work in these areas is discussed below.
(a) Materials behavior

To ensure the reliable long-term performance of steam turbines, rational
extrapolation techniques for the materials behaviour must be developed.
Temper embrittlement, stress corrosion and creep rupture are critical time
dependent phenomena. Considerable work has been done on temper embrit-
tlement and knowledge about temper embrittlement in low temperature rotor
materials is quite extensive. The role of residual elements is well understood

and steelmaking techniques exist to produce virtually temper embrittlement
free low pressure rotor and disc materials.
The stress corrosion cracking of low alloy steels has been an area of ongoing
research since the famous Hinkley Point incident= in 1969. Studies on field
experience, controlled laboratory tests and basic mechanisms have continued.
CEGB in the UK, EPRI in the USA and virtually all OEM have been involved
in this research. As a result, our understanding of the key variables affecting
crack initiation= and propagation= is quite extensive. However, there are
several fundamental aspects of stress corrosion cracking in operating steam
turbines that are still not fully understood so that cracking remains a
probabilistic event. The inspection intervals, especially for steeples, are
therefore approached in a probabilistic manner.V
The creep behaviour, especially of the family of 9-12% Cr steels discussed
earlier, is critical. Small changes in composition and processing can have a
large effect on creep rupture and creep rate behavior. Figure 10 shows a
10
8
.~c
Ci5 6
"'0
Q)
.~ Pa
(ij 4
E 8
0
z 2
o 1 5 10 15
Normalised Time
Fig. 10 Creep rate of two nominally identical heats of St. 422
drastic difference in the creep behaviour of bar stock from two different heats
of St. 422 material. The composition, heat treatment, hardness and micro-
structure were all within expected ranges. After detailed structural character-
isation, it was concluded that the difference in creep behaviour resulted from
the imbalance of residual aluminum and nitrogen. To verify this effect, two
laboratory heats were melted: one with low aluminum and high nitrogen and
the other with high aluminum and low nitrogen (Table 7).
The heats were forged, rolled and given the standard heat treatment. The
hardness and microstructures after heat treatment were normal. Samples
were cut from each heat and creep tests performed at two temperature-stress
combinations. The results are shown in Fig. 11. Under both testing conditions,
heat 1 had much lower creep rate than heat 2 suggesting that small differences
in residual Al and N have a pronounced effect on creep behaviour. A similar
effect of Al and N was previously explained by Foldyna et al.28 on the basis of
Table 7 Composition of Laboratory Heats of St. 422
Heat C Mn P S Si Ni Cr Mo V Al N
1 .19 .63 .020 .009 .24 .83 11.9 1.1 .21 .006 .044
2 .22 .93 .005 .004 <.01 .76 12.0 1.1 .24 .029 .007
25 --
-- ~
20 -
rfl.
15
: 7 • 0
.•.,,0. 590°C - 275 MPa
540°C - 340 MPa f--
C Open points - Heat 1

.~
~ I I Closed points - Heat 2
U
Ci5 10
5
¢
..to..
~~
.A. .A
0
o 200 400 600 800 1000
Time, hours
Fig. 11 Creep rate of laboratory heats of St. 422
residual free nitrogen. The higher Al content ties the N, thereby lowering the
free N necessary for higher creep strength.
(b) Solid particle erosion

Erosion by iron-chromium oxide particles is a common concern in the
operation of steam turbines. Exfoliated oxide particles in the super-heated
steam from steam generating boilers impinge at a high velocity on the nozzle
blocks, rotating blades and stationary vanes. The incessant impingement
causes erosion on the leading edge, upper fillet radius and trailing edge (Fig.
12). This is expected to get worse as the inlet temperature increases. Various
coating systems have been developed to combat erosion. The effect of
chromium carbide and boride coating on relative erosion under laboratory
conditions is shown in Fig. 13. The coated components have now been in
service for many years and results are somewhat mixed. Although a sig-
nificant variation in improvement has been observed, the relatively low cost
of coating makes it an attractive treatment.
(c) Nondestructive examination

Inspection techniques for rotors and discs have steadily improved. Also,
advanced systems have been developed for in-service ultrasonic inspection of
rotor bores. The bore keyway cracking of shrunk-on discs necessitated the
development of sophisticated ultrasonic techniques-" using computer model-
ling.
The remote eddy current inspection technique was developed-v " to detect
Fig. 12 Solid particle erosion of steam turbine control stage blade row
120
i<
<1>
"§ 100
c
o
.~ 80
CD
"0
.~ 60
«;
E
~ 40
20
o
42288 Boride Cr3C2
Systems
Fig. 13 Relative erosion resistance of coatings
cracks before they cause blade failure and forced outage. This technique
permits blade inspection much as inspection ports and fiber optics enable
inspection of high temperature components during a very short outage and
without disassembly of the unit.
Several attempts have been made to develop ultrasonic inspection tech-
niques for steeples without the need to remove blades. This is desired since
stress corrosion cracks can initiate in the interior surfaces of the steeples.
Various techniques have emerged, but their reliability and accuracy are still
questionable.
(d) Repair welding

The repair welding of steam turbine stationary parts such as cylinders, valves,
nozzle chambers, vanes etc. has been common. However, the repair welding
of rotating components such as rotors and blades is generally approached
with caution because of their greater duty requirements and the more serious
consequences of failures resulting from weld repairs. Advances in weld
consumables, welding process and heat treatments together with the
increased confidence gained from experience have demonstrated31-33 that
repair welding can produce properties similar to or better than those of the
base material. The repair welding of rotor blade attachment areas has now
become routine.
Since the commercial introduction of repair welding by Westinghouse in
1979, over 300 rows of LP rotors and discs have been successfully welded.
Since 1988, 70 rows covering 34 HP, HP lIP rotors have undergone control
stage repair. This technology has been extended to combustion turbine discs
and non-Westinghouse rotors. Repairs have been made on all compositions
covered by ASTM A470 for rotors manufactured since 1948. Rotor bores, discs
bores, coupling holes, journals, locking slots and control stages are examples
of many components that have been successfully repaired.
Steeples or blade attachments represent the most common areas of repair.
These have included side entry configurations such as straight, skewed and
curved. The most common steeple repair has been the entire row (360° build
up), but individual steeples (from one to eight) have also been repaired. For
the past 25 years, Westinghouse has been aggressively evaluating all phases
of processes, equipment and materials for rotor welding.P
To further increase the margin against stress corrosion cracking of low
pressure steeples, Westinghouse has recently qualified-" steeple weld build-
up using 12% Cr stainless steel. The Ni-Cr-Mo-V rebuilt steeples have now
run well beyond the time for cracking experienced in the original steeples
demonstrating that weld build-up behaves as well as or better than the
original material. The 12% Cr steeples are expected to provide even greater
resistance to stress corrosion cracking.
Development and Manufacturing Cycle Time

The total time for development and manufacturing is becoming a significant
driver. The utilities and independent power producers are pushing for the
shortest duration from the placement of the order to start up of the plant.
Woodford= has developed an approach to predict long term creep defor-
500
400
ro
n,
~ 300
(J)
(J)
~
Ci5 200
100
0
.01 .1 10 100 1000 10000
Predicted Time hr.
Fig. 14 Creep prediction using SRT method, Woodford-+
mation and creep rupture using short time stress relaxation tests (SRT).Using
a single specimen and testing at four different temperatures, a curve of stress
vs. strain-rate covering over 12 orders of magnitude in strain-rate can be
generated in a matter of few hours. Woodford and Iijima''? have compared the
predictions for Cr-Mo-V steel using these accelerated tests with those from
conventional long term tests. Figure 14 shows the predicted time vs. actual
time for 0.5 and 1.0% strain at 600°C. The agreement between the two
methods is quite encouraging. If this approach can be validated, it has the
potential of significantly reducing the test duration and hence development
time for new alloys. The approach may also be applicable for in-service
components where remaining life estimates require measuring the creep
behaviour of service exposed material. Further research is required to fully
evaluate this approach.
Capital Cost
The need to reduce capital cost led to the development of large single element
turbines operating in either Rankine cycle or combined cycle with combustion
turbines. Rotors in such turbines must possess high creep strength, with low
susceptibility to temper embrittlement on the hot end and high yield strength
with good toughness in the cold end. Dual heat treated and welded rotor
concepts have been developed.
Long last row blades are also attractive because of their increased annulus
area which allows passage of a correspondingly greater volume of steam.
Conceptually, this approach extends the MW output of single LPs thereby
lowering the system cost. The development of longer last row blades requires
the use of titanium blade material. US approaches to single case rotor and
titanium blades are discussed below.
(a) Dual heat treated rotor

Mitsubishi Heavy Industries= and Westinghouse have developed a rotor
alloy composition of 2.25 Cr IMo .25V with strict limits on P, S and Si as well
as on Sn, As and Sb. The rotor is refined using the VCD process and dual heat
treated after forging. The LP end is austentised at 900°C, water quenched and
tempered at 635°C. The HP end is austentised at higher temperature (955°C),
blast cooled and tempered also at a higher temperature (665°C). The transition
Austentising Temperature
~---------------------
Partition
LP
Blast Cooling Water Spray
Fig. 15 Concept of dual heat treated single case rotor
500
400 ----~
co
o,
:E
300
en~ 200
~-
r-. ~ ..
"<
en
~ ~
U5 1 CrMoV
2.25Crt-v oV~
100
90
80
70
19 20 21 22 23 24 25 26
L.M.P = T (25+ Log (t)) x 10-3
Fig. 16 Creep rupture strength of 2.25 CrMo V rotor
en 100 125
Q)
LP
"S
~ 90 +--I---:~-~---+--+-----1f-------b~-+---+---+---+ 100 ~
~ 0
~ co
~ 80+--~~--~~4-~+-~f--~~-+----+----+---+ 75 ~
w
..c: ~
~ 70+---~~--~----+-~~~f---+---+----+----+---+ 50 m
z 15
:> "E
~ 60 25 Q)
«1
~
..c: a..
Q)
o 50~~~~~~~~~~~~~~~~4-~~~ 0
-100 -80 -60 -40 -20 0 20 40 60 80 100 120
Temperature °C
Fig. 17 Charpy V-Notch tests on 2.25 erMo V rotor bore material

from HP to LP is carefully controlled. The basic concept of the dual heat

treated rotor is shown in Fig. 15.
Many rotors have been tested and show the desired mechanical properties.
The creep rupture strength of the HP end (Fig. 16) is similar to that of
conventional lCrMoV rotors. Typical bore impact properties corresponding
to LP and HP are shown in Fig. 17 and represent FATT of 30°F (-1°C) and
65°F (18°C) respectively.
(b) Welded rotor

An alternate approach to a dual tempered rotor is to weld together the
CrMoV HP section and the NiCrMoV LP section. Our extensive experience
base on repair welding these materials provided a solid foundation for
developing a rotor welding process. Laboratory tests on dissimilar pieces
were used to optimise the weld consumables and welding process. Following
successful welding trials, a mock-up simulating a full sized rotor was welded
and it shows excellent NDE quality.
(c) Long last row blade

Titanium is suitable for long last row blades because its lower density lowers
steady stresses in blades as well as in blade attachment areas. This precludes
the need for very high strength blade and rotor materials. In some applica-
tions, longer last row blades can also improve efficiency'? by providing
greater annulus area and reduced leaving losses. An increase in L-O blade
length from 851 mm to 1016 mm has been estimated'? to increase thermal
efficiency by 1.60/0.Experience exists in the US on 23 in. last row blades.v The
23 in. blades were installed without any erosion shield and have been running
successfully for over 25 years.
Westinghouse has independently developed a 1067mm titanium last row
blade with an exhaust annulus area of 9.0 square meters for operation at
3600 rpm. The blade is forged from a Ti-6AI-4V alloy with bi-modal
microstructure. This interlocked blade was first applied to large single flow
axial exhaust turbines in reheat combined cycle plants.
Interlocked blades feature a 'Z' type shroud which provides continuous
coupling of all blades in a row at operating speed. Continuous coupling
improves the strength to stress ratio and has the added operational benefits of
greater off-frequency bandwidth and higher exhaust pressure capability.
Product development of a companion 1280mm interlocked last row blade
operating at 3000 rpm is underway.
Extensive testing has been carried out to characterise the microstructure
and mechanical properties. Samples were taken at various locations along the
length of the blade in both the longitudinal and transverse directions. The
typical microstructure is shown in Fig. 18. The tensile properties are shown in
Table 8.
Edge 200X Edge 500X
cent re 200X Centre 500X
Fig. 18 Microstructures of 42 in. Titanium blade at mid-airfoil location
Table 8 Tensile Properties of 42 in. Titanium Blades
Root Mid-Foil Tip

Property Long. Trans. Long. Trans. Long.
Yield Strength, KSI 131.7 135.7 138.2 129.0 136.5

Tensile Strength, KSI 142.1 145.1 147.8 140.0 146.2
Elongation, % 16.8 16.8 16.8 15.9 16.6
Reduction of Area, % 45.6 45.9 45.9 43.2 43.5
Future Materials Needs

The intense competition in this industry will continue to demand higher
temperature, cost effective materials on a compressed development cycle.
Deregulation of the power industry requires a better assessment of remaining
life and risk. Continued emphasis must also be placed on cost effective
processes. The key areas for future research are outlined below:
(a) 10-12% Cr steels

Considerable progress has already been made in extending the temperature
capability of 9-12% Cr steels, but there is still need to develop reliable, stable
materials capable of operation up to 650°C. The efforts in Japan and funda-
mental work being carried out in Europe on structural stability combined
with the Woodford= approach to predicting long time creep behavior, will all
play an important role.
(b) Materials and process modelling

In the past, development of materials and processes has been an empirical
process, dependent on the experience of the developer and 'trial and error'
experimentation. It could take a long time to bring a new material to the
marketplace. Over the last decade, however, increased availability of comput-
ing power has allowed accurate modelling of alloy phase diagrams and
processes such as melting, casting, forging, welding and heat treating.
Modelling is also being used to predict alloy properties from compositional
data. This total modelling capability potentially allows alloy designers to
predict the behaviour of a material in the final component from its composi-
tion and proposed processing routes. This will eliminate much of the
experimentation currently necessary to develop a new alloy system. The
integrated modelling approach is shown schematically in Fig. 19. Well
Manufacturing Component
requirement behavior
!
requirement
Process
+
Component
models behavior
models
Fig. 19 Materials and process modelling
developed models for welding power plant materials currently allow predic-
tion of consumable compositions, weld metal microstructures and process
parameters.
(c) Damage detection by NDE

So far, nondestructive techniques have been unable to allow detection of
accumulated fatigue damage in components until after the cracks have
reached a macro size. The assessment of fatigue damage is a critical aspect of
15
410Cb
E
~
~ 10
c
o
~:::J
c
~5~ •
•
O+---~----~----~----
Fatigue Level (Cycle) Fatigue Level (Cycle)
:§
~ 1.54E+06
en 12000
E
Q) 1.53E+06
z:::J
E
~
:::J 1.52E+06
~
Cti
10000
en a:::
g
rd
~
Q)
8000
1.51E+06
z-
's
Q)
:::J
C'"
t5:::J 1.50E+06 ~ 6000

"C
c t5
1.49E+06
'o*
0
o 4000
n; c
.~0 1.48E+06 rd
t5
Q)
Q) ~ 2000
m 1.47E+06 .9
~ en
~~
Q)
1.46E+06 13
>-
0 20 40 60 80 100
o
10000 20000 30000 40000 50000
Percent of Total Fatigue Life Cycles to Failure (N1)
Fig. 20 Fatigue damage detection by NDE techniques42,43,44
remaining life estimation. Advanced NDE techniques are being explored for
this purpose. Chou and Earthman= have demonstrated the feasibility of
using laser light scanning to characterise low cycle fatigue damage in Inconel
718. Goldfine and Clark have reported=' an excellent correlation between the
Meandering Winding Magnetometer conductivity measurements and percent
of total fatigue life of St. 304. Jeong K. Na et al.44 have studied the acoustic
emissions, longitudinal velocity and non linearity parameters and observed a
linear correlation with log cycles in high cycle fatigue tests on St. 410Cb
material. The results from these NDE techniques are shown in Fig. 20. These
promising approaches need to be pursued further with a view to developing
them into application tools.
SUMMARY
1. Efficiency, reliability, maintainability, cycle time and capital cost are key
market drivers for advancing steam turbines.
2. The highest temperature (649°C) and pressure (34.5MPa) unit was
placed in operation in the USA in 1960. The unit is still operating. The
construction of this unit led to the development of many austenitic steels
and superalloys for steam turbine components.
3. 9-12% Cr steels have been developed to extend the useful application
temperature of ferritic steels to 593°C. Both castings and forgings have
been produced successfully.
4. Small variations in Al and N are demonstrated to have a pronounced
effect on the creep behavior of 9-12% Cr steels.
5. Refractaloy 26 has demonstrated long, successful performance for bolts
and blades.
6. Maintainability has been improved through remote inspection tech-
niques, solid particle erosion resistant coatings and repair welding
techniques.
7. Single case rotors have been produced successfully either by dual heat
treating or by welding.
8. A 42 in. last row titanium blade is currently under development.
Successful forgings have been produced.
9. Continued development of 9-12% Cr steels, materials/process model-
ling and NDE techniques for fatigue damage detection have been
identified as areas for future research.
REFERENCES
1. J. H. Harlow: 'Engineering the Eddystone Plant for 5000 lb. 1200°F Steam',
Trans. ASME, Aug. 1957, 79, 1410.
2. W. E. Trampler et al.: 'Development Associated with the Superpressure
Turbine for Eddystone Station Unit No.1', Trans. ASME, Oct. 1960, 82,
286.
3. H. G. Chamberlin: The Eddystone Experience-An Overview of Experience in the
First Twenty-Four Years, EPR! Advanced Pulverized Coal Power Plant
Utility Advisory Committee, Washington, USA, July 1983.
4. D. L. Newhouse et al.: A Modified 12% Chromium Steel for Large High
Temperature Steam Turbine Rotors, Presented at ASTM 68th Annual
Meeting, June 1965.
5. Y. Nakashayashi et al.: 'Japanese Developments in High Temperature Steam
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Engineering, Liege, Belgium, 24-27 September 1990.
6. Y. Nakabayashi et al.: 'Development of Advanced Steam Plants in Japan',
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Zurich, 13-14 October 1992.
7. C. Berger et al.: 'Improved Ferritic Rotor and Cast Steels for Advanced
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International EPR! Conference on Improved Coal Fired Power Plants,

Washington, USA, 1-4 March 1993.
8. C. Berger et al.: 'Steam Turbine Materials: High Temperature Forgings',
COST 501 Conference on Materials for Advanced Power Engineering, Liege,
9. R. B. Scarlin et al.: 'Steam Turbine Materials: High Temperature Castings',
Ibid.
10. C. Berger C et al.: High Temperature Rotor Forgings of High Strength 10%
CrMoV Steels, 12th International Forgemasters Conference, Chicago,
USA, 11-17 September 1994.
11. T. Fujita: 'Advanced High Chromium Ferritic Steel for High Temperature',
Met. Prog., 1986, 8, 33.
12. K. Hikada et al.: 'Development of 12 Cr Steel for 650°C USC Steam Turbine
Rotors', Proc. COST 501, Materials for Advanced Power Engineering, Liege,
13. P. J. Uggowitzer et al.: 'Development of Nitrogen Alloyed 120/0Chromium
Steels', Advances in Materials Technology for Fossil Fuel Power Plants, R.
Viswanathan and R. I. Jaffee (eds), ASM, 1987, 181.
14. Y. Tsuda et al.: 'Advanced 120/0Cr Steel for High Temperature Rotors',
Third International Conference on Improved Coal-Fired Power Plants, EPR!
Proc. TR-100848, Aug. 1992, 25-1.
15. D. V. Thornton and K. H. Mayer: 'New Materials for Advanced Steam
Turbines', Advances in Turbine Materials, Design and Manufacturing, The
Institute of Materials, London, 1997, 203
16. Y. Tsuda et al.: 'Development of High Temperature Materials for Steam
Turbine', Ibid, 283.
17. M. Yamada et al.: 'New Materials for Advanced Steam Turbines', Vol. 1:
Evaluation of Superalloys in Turbine Buckets for Advanced Power Plants,
TR100979, Vol. 1, Sept. 1992.
18. Advanced Alloy Technology Program Semiannual Progress Report for Period
Ending September 30, 1980, ORNL/MSP /1.7-80/3, February 1981.
19. V. K. Sikka et al.: Ferritic Steels for High Temperature Applications, American
Society for Metals, Metals Park, Ohio, 1982, 65-84.
20. Modified 9 Cr-l Mo Steel Technical Program and Data Packagefor Use in ASME
Sections I and VIII Design Analyses, ORNL Technology Transfer Meeting:
A New Chromium-Molybdenum Steel for Commercial Applications,
Knoxville, Tennessee, 6-8 April 1982.
21. V. K. Sikka and P. Patriarca: Data Package for Modified 9 Cr-1Mo Steel, Oak
Ridge National Laboratory, Oak Ridge, Tennessee, December 1983.
22. Advanced Alloy Technology Program Semiannual Progress Report for Period
Ending September 3D, 1984, ORNL/MSP /1.7-84/1, January 1985.
23. K. H. Mayer: 'New Materials for Advanced Steam Turbines', Vol. 5: Survey
of Superalloy Bolt Failures in High Temperature Service, TR100979 Vol. 5,
Sept. 1992.
24. D. Kalderon: 'Steam Turbine Failure at Hinkley Point A', Proc. Inst. Mech.
Engrs., 1972, 186, 341.
25. S. Cheruvu and B. B. Seth: Key Variables Affecting the Susceptibility of
Shrunk-on Disks to Stress Corrosion Cracking, IJPGC, Pwr. 21, ASME,
1993.
26. W. Clark et al.: 'Procedures for Estimating the Probability of Steam Turbine
Disk Rupture from Stress Corrosion Cracking', ASME Paper, Power
Generation Conference, 81-JPGC-PWR-31, 1981.
27. J. R. McCracken and W. R. Brose: Risk Assessment Method for LP Disc
Attachments with Stress Corrosion Cracking, ASME, IJPGC, Power 2 1997,
383.
28. A. Foldyna et al.: 'Effect of Structural Factors on the Creep Properties of
Modified Chromium Steels', Steel Research, 1991, 62 (10), 453.
29. D. O. Willaman et al.: 'Remote Eddy Current Inspection of Turbine Blades',
Proc. Fossil Plant Inspection Conf., EPR! CS-5320, 1987, 19.
30. M. J. Metala and D. O. Willaman: Field Experience with Remote Turbine Blade
Eddy Current Inspection System, ASME, JPGC, Philadelphia, PA, USA,
1988.
31. R. E. Clark et al.: Weld Repair of Low Pressure Rotors for Increased Availability,
JPGC, Toronto, Canada, 30 Sept.--4 Oct. 1984.
32. R. E. Clark et al.: Experience with Weld Repair of Low Pressure Steam Turbine
Rotors, Amer. Pwr. Conf. Chicago, USA, 22-24 April 1985.
33. R. E. Clark et al.: 'Development of the Techniques for High Pressure Rotor
Weld Repair', EPRI Workshop on Weld Repair of High Pressure and
Intermediate Pressure Rotors for Life Extension, Palo Alto, USA, 1-2 Dec.
1987.
34. D. R. Amos and K. W. Beddon: 'Improved Properties for Welding Low
Pressure Steam Turbine Rotors', Materials Engineering in Turbines and
Compressors, The Institute of Metals, 1995.
35. D. R. Amos et al.: 'Qualification of Welding Rotors with 12 Cr Stainless
Steel to Improve SCC Resistance', EPR! Conf. on Steam Turbine Stress
Corrosion Cracking, Baltimore, USA, 19-20 March 1997.
36. D. A. Woodford, 'Test Methods for Accelerated Development, Design and
Life Assessment of High Temperature Materials', Materials and Design,
1993, 14(4), 231.
37. D. A. Woodford and Iijima: 'Creep Strength Evaluation, Design and Life
Management of Cr-Mo-V Rotor Steel Using Stress Relaxation Testing',
Advances in Turbine Materials, Design and Manufacturing, The Institute of
Materials, London, 1997, 613.
38. I. Kitagawa et al.: 'Manufacture of 2.25 CrMoV Steel HP-LP Type Steam
Turbine Forgings', 11th International Forgemasters Conference, Terni, Italy,
11-14 June 1991.
39. W. G. Steltz, Turbine Cycle Performance Improvement Through Titanium LP
Blades, EPR! AF-903, Sept. 1978.
40. Y. Ishiki et al.: 'Development of 40 Inch Long Blade of Titanium Alloy for
Low Pressure Last Stage of Steam Turbines', EPRI Workshop on Titanium
Steam Turbine Blading, R. 1. Jaffee ed., Pergamon Press, 1990, 62.
41. T. M. Rust et al.: 'Operating Experience of Titanium Steam Turbine Blades',
Amer. Power Conference, Chicago, USA, 24-26 April 1978.
42. K. J. C. Chou and J. C. Earthman: 'Characterization of Low Cycle Fatigue
Damage in Ineonel 718 by Laser Light Scanning',]. Mater. Res. 1997, 12
(8),2048.
43. N. Goldfine and D. Clark: 'Materials Characterization Using Model Based
Meandering Winding Eddy Current Testing', EPRI Topical Workshop:
Electro-Magnetic NDE Applications in Electric Power Industry, Charlotte,
USA, 21-23 Aug. 1995.
44. Jeong K. Na et al.: 'Linear and Nonlinear Ultrasonic Properties of Fatigue
410Cb Stainless Steel', Review of Progress in Quantitative Nondestructive
Evaluation Vol. 15, D. O. Thompson and D. E. Chimenti eds. Plenum
Press, New York, 1996, 1347.
Development of Ultra-Super Critical
Plant in Japan
K. MURAMATSU
Electric Power Development Co., Ltd. (EPDC), 6-15-1 Ginza, Chuo-ku,
Tokyo, 104, Japan
1. INTRODUCTION
Since the Oil Crises, Japan's approach to the building of thermal power plants
has been to give definite preference to coal-fired thermal power plants from
the viewpoint of such considerations as the assurance of energy supply
stability as well as economic performance and operational characteristics. In
terms of global environmental issues, efforts have been made to upgrade
efficiency in order to reduce the burden on the environment.
In Japan, a variety of power generating technologies have been developed
with a view to improving the efficiency of coal-fired thermal power plants.
This includes the pressurised fluidised-bed combustion (PFBC) and inte-
grated gasification combined cycle (IGCe) technologies. In most recent years,
advances have also been made in the development of a high efficiency
generation technology with a promising realisation potential which employs
ultra-super critical steam conditions (USC). This entails the use of much
higher steam temperatures and pressures for the conventional thermal power
plants that the conventional super critical steam conditions (SC) to achieve a
significant improvement in efficiency (up 4-6% in relative terms).
Efforts to develop this USC technology was first made in 1980 when the
saving of resources was a key issue in the wake of the Oil Crises of the 1970s.
Development work on this technology has been continued until the present.
The technical development has been spearheaded by The Electric Power
Development Co., Ltd. (EPDC) with the support of the Ministry of Inter-
national Trade and Industry (MITI) and in collaboration with boiler and
turbine manufacturers.
This paper presents fuller details of the EPDC-Ied development of this USC
technology in Japan.
2. DEVELOPMENT PROCESS
Research and development on the USC technology has been carried out since
1980, with the overall development process divided into two phases. Phase-I
543
Table 1 USC Development Process

Ve. iseo 1985 1990 1995 Implement-tion system
Test item I
1. Phue-I
(1)
(2)
(3)
Preliminarytests
Boiler element tests
Turbine rotdin.lt tests

~ 1593~ 1 EPDe MHI
EPDe Toshiba Hitachi
(4) Ult,.-hith temperature

turbine demonstration tests
EPDe
(5) Analysis and overall evaluation
2. Phase-II
630"C
(1) Boilerelementtests EPDe MHI IHI Hitachi
630'C
(2) Turbina rotatint tests
(3) Analysis and overall evaluation

I II
covers the period until 1994 and phase-II the subsequent period from 1994
through to 2001. Table 1 gives an overview of the development process.
The most important issue in the development of a USC plant is the develop-
ment of materials that are resistant to the high temperature and pressure
conditions associated with this technology and the assurance of the reliability of
the high-temperature and high-pressure materials. To verify the reliability of
the materials, demonstration test runs performed on commercial plant inevita-
bly plays a major role, seeing that it is difficult, if not impossible, to reproduce
the complex operating conditions of a thermal power plant in laboratory-scale
or even pilot plant scale tests. Apart from the demonstration test runs, a variety
of tests were also performed on the boiler and turbine peripherals.
3. OBJECTIVES OF DEVELOPMENT
Phase-I of the research and development process from 1980 took place in two
steps. The target steam temperature for Step-I (ferritic steel materials) was
593°C and that for Step-II (austenitic steel material) 649°C. In the second
phase starting from 1994, ferritic steel materials have been used to the
maximum possible extent because of their economy and operational flex-
ibility and studies are still in progress with a view to the early introduction of
a USC plant. The target steam temperature of phase-II is 630°C. While this
temperature region is in excess of the 600°C limit that has been considered the
maximum allowable temperature for ferritic steels attempts are made to
achieve this high target temperature through the positive use of the recently
developed high-temperature resistant ferritic steel materials.
Table 2 shows the development targets, the extent to which efficiency has
DEVELOPMENT OF ULTRA-SUPER CRITICAL PLANT IN JAPAN 545
Table 2 USC Development Targets
Development targets
Phase-1 Phase-2
Conventional
system Step 1 Step 2
Main materials used Ferritic steel Ferritic steel Austenitic steel Ferritic steel
Steam pressure
24.1 31.4 34.3 30.0
(MPa)
Steam temperature
538/566 593/593/593 650/593/593 630/630
eC)
Design gross
thermal efficiency 42.1 44.2 44.9 44.16
(0/0)*)
Improvement in 6.5
Base 5 4.8
efficiency (%) **)
Annual coal savings
Base 105 134 95
(ton)
Reduction in annual
CO2 emissions Base 124 158 112
(106Nm3)
*) Unit equivalent to 1000 MW

**) Relative value
538!S3~
..•..
200 250 300 350

Steam Pressure (atg)
Fig. 1Steam Conditions vs. Heat Rate

been improved and the results obtained from this. Figure 1 presents the
relationship between the steam conditions and the heat rate.
The use of high-temperature and high-pressure steam conditions offers a
potential improvement in the design gross thermal efficiency amounting to
5% (Step-I) and 6.5% (Step-2) in phase-I and to 4.8% in phase-II. This not only
permits annual coal savings of 105 000 tons, 130 000 tons and 95 000 tons,
respectively, but also helps to reduce carbon dioxide emission levels to an
extent commensurate with the amounts of coal saved.
4. PREVIOUSLY IMPLEMENTED USC TECHNOLOGY

DEVELOPMENT (PHASE-I: 1980-1994)
The Phase-I development targets were defined on a two-stage basis as Step-I

and Step-2. While the most advanced ferritic steel material available at that
time was used in Step-l the configuration of the ferritic plant, Step-2 was
pursued primarily with the use of a completely novel high-temperature
resistant austenitic steel material.
4.1 Elemental Tests on a Boiler Plant

The tests on the boiler system were conducted in order to assess the properties
of the new high-temperature resistant materials that had been selected as the
USC materials. For this purpose, a test stem generating panel was installed at
the EPDC Takasago Thermal Power Plant to carry out' elemental tests' on the
boiler plant so as to determine the corrosion behaviour (resistance) of the
high-temperature resistant boiler materials, their steam oxidation character-
istics and their mechanical strength properties. At the EPDC Matsushima
Thermal Power Plant, corrosion tests were performed in order to determine
the corrosion resistance of the boiler materials at the high temperature
occurring in the boiler fired on overseas coal. Table 3 details the test materials
used for the test runs at the Takasago Thermal Power Plant. It can be
concluded from the test results that neither the ferritic nor the austenitic steel
materials showed any corrosion or steam oxidation problems and that they
did not exhibit any deterioration in their mechanical strength properties in the
temperature region corresponding to the target steam conditions of phase-I
and under the anticipated exhaust gas conditions.
4.2 Turbine Rotating Tests

For testing the turbine rotor system, model turbine rotating tests were
performed using ultra high-temperature steam generated with the above
steam generator. These tests demonstrated the practical usefulness of the high-
Table 3 Test Materials Used for the Phase-I Elemental Tests
Classifica tion Material Nominal Composition Temp.
CrMo steel STBA24 2.25Cr-Mo at 593°C

HCM9M(STBA27) 9Cr-2Mo
9-12Cr steel Super9Cr(ASME
9Cr-lMo- V- Nb
SA213T91)
SUS347HTB(MITI) IBCr-I0Ni-Nb
" chromised IBCr-I0Ni-Nb
SUS32IHTB(MITI) IBCr-I0Ni-Ti
" fine grained IBCr-I0Ni-Ti
" chromised IBCr-I0Ni-Ti
IBCr-BNi steel
SA2I3TP347(ASME) IBCr-I0Ni-Nb at 593 & 649°C
" fine grained IBCr-I0Ni-Nb at 649°C
" chromised IBCr-I0Ni-Nb
Tempaloy A-I IBCr-I0Ni-Ti-Nb
" chromised IBCr-I0Ni- Ti-Nb
I5Cr-15Ni steel I7-I4CuMo I7Cr-14Ni-Cu-Mo

" chromised I7Cr-14Ni-Cu-Mo
HighCr- HighNi NCFBOOHTB 2ICr-32Ni-AI- Ti
steel HR3C 25Cr-20Ni-Nb-Ti
SA2I3TP347HI
IBCr-I0Ni-Nb/25Cr-20Ni
SUS3I0
Tempaloy A-II
Co-extruded IBCr-l0Ni-Ti-Nb/25Cr-20Ni
SUS310
17-14CrMol
17Cr-14Ni-Cu-Mo/25Cr-20N "
SUS310
temperature resistant turbine materials and helped to establish the design

technology for a 1000MW output turbine.
The test program included rotating tests using the 593°C target-tem-
perature test rotor of Step-1 that are identical in size and construction to the
1000MW output SP turbines and the 649°C target temperature test rotor of
Step-2. Table 4 shows the materials of major components used for the rotating
tests.
In Step-1, continuous operation was maintained for 4818 hours in order to
verify the reduction of the service life due to creep. In Step-2, continuous
operation was maintained for 2161 hours with 151 start and stop cycles in
order to verify the reduction of their service life due to low-cycle failure under
DDS (daily start and stop) conditions. The tests demonstrated that the results
in terms of the structure of the materials, the deterioration of their mechanical
properties (ageing) and the percentage of their service life were within the
allowable range for commercial plant operation.
Table 4 Test Materials Used for Phase-I Rotating Test
Test conditions
STEP-l STEP-2
Rotor 12Cr forged steel A286 forged steel

HP Inner casing 12Cr cast steel SUS 316H forged steel
IP Inner casing 12Cr cast steel
Outer casing 2.2SCr- Mo cast steel
MSV SUS 316H forged steel
Main steam pipe SUS316TP
4.3 Demonstration Tests

The test program in Phase-I consisted of demonstration tests on 50 MW
generator plant under ultra high-temperature conditions at the EPDC Waka-
matsu Coal Utilization Research Center. The HP-IP turbine that had been
used until then on the plant were replaced by ultra high-temperature turbines
and operated for a cumulative 14302 hours in Step-1 and 5130 hours in Step-2
in order to establish the design data for the practical turbines and to
substantiate their increased efficiency and reliability.
Tests were carried out in Steps-1 and -2 in order to establish, in particular,
the manufacturing characteristics of the rotors, their mechanical strength
under the ultra high temperatures and cooling structure. The results obtained
from these tests have indicated that it is technically possible to achieve a large
USC turbine in practice. The Step-2 austenitic steel material aimed at what
was the world's highest temperature condition at that time did, however,
exhibit some properties such as a large coefficient of linear expansion and a
small heat transfer rate that appeared to suggest some practical limitations on
the operating conditions. They also showed a significant reduction in service
life due to start and stop operation and presented difficulties also in terms of
their economic performance characteristics due to the cost of the material. In
view of these considerations it was concluded that a suitable lead-time would
be required for the practical application in commercial plant.
4.4 Application of the Phase-I Results to Commercial Plant

Phase-I ended in 1994. The results on high-temperature resistant materials
have been reflected in the development of the EPDC Matsuura Thermal
Power Plant's No.2 Unit and in the construction of the most recent state-of-
the-art coal-fired power plants.
Table 5 shows the major large-scale coal fired power plants built in recent
years and due to be built. It can be seen that plants using the so-called USC
Table 5 Most Recent Large-Scale Coal-Fired Power Plants in Japan
Rated Main Steam Steam

Electric Power Output Pressure Temperature
Power Plant Company MW MPa °C Commissioning
Kyusyu Electric
Reihoku #1 700 24.1 566/566 Jul-95
Power Co.
Tohoku Electric
Haranomachi #1 1000 24.5 566/593 Jul-97
Power Co.
Matsuura #2 EPDC 1000 24.1 593/593 Jul-97
Hokuriku Electric
Nanao-Ohta #2 740 24.1 593/593 Jul-98
Power Co.
Tohoku Electric
Haranomachi #2 1000 24.5 600/600 Jul-98
Power Co.
Tyugoku Electric
Misumi#l 1000 24.5 600/600 JuI-98
Power Co.
Kyusyu Electric
Tachibana-wan 700 24.1 566/593 Jul-OO
Power Co.
Tachibana-wan
EPDC 1050 25 600/610 Jul-OO
#1
Hokuriku Electric
Tsuruga #2 700 24.1 593/593 Oct-OO
Power Co.
Kyusyu Electric
Reihoku #2 700 24.1 593/593 JuI-01
Power Co.
Tachibana-wan
EPDC 1050 25 600/610 JuI-01
#2
high-temperature steam conditions of 593°C or over are successively being

put into operation or scheduled for commissioning.
5. CURRENT USC TECHNOLOGY DEVELOPMENT (PHASE-II)
The current Phase-II of the technology development program was initiated in

1994 and is due to take until the year 2001. The boiler tests are taking place on
a quadripartite joint research basis involving the Electric Power Development
Co., Ltd. (EPDC), Babcock-Hitachi K.K, Ishikawashima Harima Heavy Indus-
tries Co., Ltd. and Mitsubishi Heavy Industries, Ltd. The turbine tests are
being conducted on the basis of a tripartite joint research arrangement in
which the Electric Power Development Co., Ltd. (EPDC), Hitachi, Ltd. and
Toshiba Corporation co-operate with each other.
The objective of Phase-II is the development of a USC plant capable of
being put into practical use in the very near future, in other words, a plant
that can reasonably be expected to have a higher efficiency than that of Step-l
of Phase-I which is already practically feasible, and also a plant with superior
economic operating performance as compared to the system of Step-2 of
Phase-I which uses austenitic steel materials. It would therefore be best to use
ferritic steel materials to the greatest possible extent, and recent development
is producing favourable results with the emergence of new ferritic materials
providing a high mechanical strength also in the high-temperature range in
excess of 600°C and up to 650°C.
The steam conditions of 630°C and 30 MPa were determined by taking into
account the maximum allowable temperature for the materials and the most
practicable pressure range for the plant.
These new high-temperature resistant materials have been selected as
candidate materials and a range of tests is carried out to verify their reliability
and practicability. The following sections present fuller details of the boiler
and turbine candidate materials and the methods used for testing them.
5.1 Candidate Materials for Boiler

Apart from the high-temperature pressure-resistant parts such as the super-
heater and re-heater, high-strength materials with mechanical strength char-
acteristics exceeding the current ones as also used, in the phase-II boiler, for
the low-temperature parts such as the economiser and the medium-tem-
perature parts such as the water walls. Their use reflects an effort to minimise
the increase in the thickness of the pipes associated with the higher pressures
and to reduce boiler weight. Table 6 gives an overview of the candidate
materials tested in Phase-II and their main components.
As there are limits to which the mechanical strength of carbon steels as the
materials for the economiser can be increased, the candidate steel materials
that were selected were WT780C and TEMPALOY HT 780. These are steel
alloys with minor additions of Cr, Mo, and Cu. In Europe, attempts are made
to use a 9-12% Cr steel for the water walls. In view of the operating
temperature, however, it is more economical to use a steel material with 1-2%
Cr to impart a high mechanical strength. For this reason, three types of steels
were selected as candidates for the medium-temperature parts: NF1H and
HCMV3 with 1.25% Cr addition and 2% TEMPALOY F-2W.
The most important condition to assure the success of Phase-II was the
development of a heat-resistant ferritic steel capable of being used for the
large-diameter pipes in the high-temperature zones such as the outlet pipe
connector of the final super-heater and the main steam pipe. In this context
the candidate materials that were selected were a range of high-strength steels
which are currently being developed by the steel producers. These comprised
the steel varieties NF616, HCM12A and TEMP ALOY F-12M in which part of
the Mo of the currently used heat-resistant ferritic steel STPA28 (P91) with the
DEVELOPMENTOFULTRA-SUPERCRITICAL PLANT IN JAPAN 551
Table 6 Candidate Materials for Phase-II Boiler
Steel Grade Main components Manufacturers
Economiser Tube
WT780C O.8CrO.5MoCu Nippon Steel Co.
TEMPALOY HT780 O.6CrO.3MoCu NKK
Water Wall Tube
NFIH 1.25CrlMo VNb Nippon Steel Co.
HCMV3 1.25CrlMoV Sumitomo Metal Industries, Ltd.
TEMPALOY F-2W 2CrO.5MoWVTi NKK
Superheater Tube
Ferritic steel
NF616 9CrO.5Mol.8WVNb Nippon Steel Co.
HCM12A 12CrO.4Mo2WCuVNb Sumitomo Metal Industries, Ltd.
TEMPALOY F-12M 12CrO.7MoO.7WCuVNb NKK
SAVE12 l1Cr3WCoVNbTa Sumitomo Metal Industries, Ltd.
NF12 lICr2.6WMoCoVNb Nippon Steel Co.
Austenitic steel
SUPER304H 18Cr9Ni3CuNbN Sumitomo Metal Industries, Ltd.
TEMPALOY AA-l 18Crl0Ni3CuNbTiN NKK
NF709 20Cr25NiMoNbTiN Nippon Steel Co.
SAVE25 23CrI9Ni3.5Cul.5WNbN Sumitomo Metal Industries, Ltd.
Header IMain Steam Pipe
NF616 9CrO.5MOl.8WVNb Nippon Steel Co.
HCM12A 11CrO.4MoO.7WCuVNb Sumitomo Metal Industries, Ltd.
TEMPALOY F-12M 12CrO.7MoO.7WCuVNb NKK
NF12 l1Cr2.6WMoCoVNb Nippon Steel Co.
highest mechanical strength has been replaced by W, as well as the NF13

containing Co additions to upgrade its high-temperature strength.
The candidate materials chosen for the high-temperature heat-transfer
pipes, including the final super-heater and re-heater were identical to the
materials selected for the large-diameter pipes. SAVE 12 is a. high-strength
steel with Co additions similar to NF12. Austenitic type heat transfer pipes
are required not only to have a high-temperature strength but also to have a
corrosion resistance against coal ash and an oxidation resistance against
steam. For this reason, four candidate steel materials were selected, namely,
SUPER304H, TEMP ALOY AA-1, NF709 and SAVE25. These steels chromium
contents in the range of 18-23%, seeing that Cr has a major effect on the steel's
corrosion resistance.
5.1.2 Material properties

The following sections present the characteristics of the candidate materials in
accordance with the test results available until the present.
250 Material for low- Material for med- Material for High-
temp. zone
[Ferritic steel] [Austenitic steel]

> 200 [NEW ~
~Q)
0-
i
CD 150
(/)
r-+
.,
CD
(/) 100
,-......
(/)
3!:
-0
Q) ,--------------- ..
'-' 50 : Current :
.----------
:----~~~--j
..
~OO 300 400 500 600 700 800

Temperature (OC) *) forthennal power plant
Fig. 2 Allowable Stresses for USC Boiler High-Strength Materials
(a) High-temperature strength behaviour

Figure 2 compares the allowable stresses for the USC boiler's high-strength
materials with those applicable to the current materials. These values for the
allowable stresses of the candidate materials were calculated on the basis of
the tensile, creep shear and creep test results. It can be seen that the candidate
materials have allowable stress values approximately 1.3 times those of the
currently used materials for the entire temperature region from low to high
temperatures.
: Model ash:l.5MNaSOr1.5MK~SOrlMFe~03
- - - - - - - - - - -:- - - - - - - - - - Temperature:650 C
~ 140
oen
Time:20h
120 -----------i----o------;------------:------------:------------
o
::J : : 0: :
•m 100 --------o-~-_o---------:- ----------;------------:------------
: 0: : :
CD
3'
80 -------O-~---------:------O- --!------------(---------
CC
- - - - - - - - - - ~- - - - - - - - - - - - ~- - - - - - - - - - -0- --- -----; 502·
<,
() 60 -----
~ : : : 0.5%
~
40 ----------
I I
------------i------------:------------:---_._------ I I
I I I
-- .•. _l i _
20
I
: [ ~roz=
o
5 10 15 20 25 30
Cr content(%)
Fig. 3 Cr Content of Candidate Material vs. Corrosive Wear due to Coal Ash
(b) Corrosion resistance

Another problem to take into consideration when selecting materials is the
wear of high-temperature heat-transfer pipes due to corrosion caused by the
sulphur components of the coal. Figure 3 shows the relationship between
the corrosive wear due to the imitative coal ash and the Cr content of the
candidate as well as the currently used steel materials. When the S02
concentration is 0.1% (corresponding to a sulphur content of the coal of
approximately 1%), the corrosive wear does not change significantly for
austenitic steel materials with a Cr content of 18% or more and even a lower
Cr content presents no problem. When the sulphur content of the coal is
around 5% (with a S02 concentration of 0.5%) and the materials are exposed
to intensely corrosive conditions, however, it will be necessary to use a high-
Cr austenitic steel material with a Cr content of, or in excess of, 20%.
(c) Steam oxidation behaviour

Figure 4 shows the relationship between the logarithmic rate of scale growth
Kp on the candidate materials and the reciprocal value of the temperature. Kp
has been introduced here on the assumption that the rate of growth of the
steam oxidation scale is proportional to 1/2 square of the time. The ferritic
steel materials presented in Fig. 4(a) have a superior resistance to oxidation
due to steam. Although these steels have roughly the same Kp in the
temperature range of up to 600°C the difference comes at higher tem-
peratures. When this rises above 600°C, it can be seen that the materials with a
higher Cr content have a smaller Kp.
It can also be seen that the austenitic steel materials presented in Fig. 4(b)
T CO)
4
0
cc 3 0
~
"C
't: -1
3~
<,
2: -2
0 -3
-1 -4
0.0009 0.001 O.0011 0.0012 0.0013 0.0009 0.001 0.0011 0.0012 0.0013
liT (K-l ) 1 IT (K·1 )
(a) Ferritic steel materials (b) Austenitic steel material
Fig. 4 Steam Oxidation Scale Growth Rate Kp of Candidate Materials vs.

Temperature
have an improved steam oxidation resistance, with the Kp becoming the

smaller the higher the Cr content of the material. The dotted line gives the Kp
of a shot-blast finished 18% Cr SUPER304H steel. It can be seen that the
resistance of austenitic steels to steam oxidation can be improved by shot-
blasting. In the case of boilers using low-sulphur coals, it is therefore possible
to configure the super-heater of the USC boiler by means of high-strength 18%
Cr stainless steel pipes that have been shot-blast on their inner surfaces.
Since the thickness of the steam oxidation scale can be estimated on the
basis of Kp it is possible to select the material in such a manner that the
maximum permissible scale thickness at which it begins to peel off will not be
reached at the operating temperatures.
5.2 Candidate Materials for Turbines

The general practice is to use CrMoV steels for the high- and medium-
pressure rotor materials in steam temperatures of 538°C or 566°C. The
currently used rotor materials are known to have a 100 000 hour creep
rupture strength at 566°C of approximately 10kg mm='. It is therefore
necessary that the phase-II rotor candidate materials should also have a creep
rapture strength in the same order of magnitude at 630°C. While the 12Cr
steel developed in Phase-I has a more favorable creep rupture strength in the
high-temperature range than the currently employed CrMoV steels, it lacks
strength in the near-630°C temperature region. It is therefore essential that
some new materials offering adequate strength at 630°C range should be
developed. At present, turbine manufacturers are engaged in the develop-
ment of a new 12Cr steels that are capable of withstanding temperatures in
the range of 630°C. From these, two rotor steels (candidate steel A and B) with
a sufficient creep rupture strength were selected as candidate materials. Table
7 gives an overview of the available chemical analysis data of the candidate
steels.
Both these steel materials have an increased Wand decreased Mo content
and contain Co and B as new alloying constituents in order to improve their
creep rupture strength. The constituent additions differ on a subtle scale.
These difference reflect certain gaps in the perception of the designers as to
Table 7 Chemical Composition (%) of Rotor Candidate Steels
C Si Mn Ni Cr Mo V Nb W N Co B
0.14 0.50 1.00 O.BO 0.12 0.03 0.04

CRMoV steel 0.40> ,.., 0.60> ,..,
(Current steel) 1.00 1.20 1.20 0.25 0.12
0.23 O.OB
Candidate steel 'A' 0.09 0.03 0.49 0.50 10.B9 0.17 0.20 0.60 2.61 0.0195 2.52 0.011
Candidate steel'B' 0.11 O.OB 0.1 0.2 10.0 0.65 0.2 0.05 1.B 0.02 3.0 0.01
the way in which the minor constituents influence the strength of the
material.
Steel A has a stable precipitation strengthening at high temperatures so that
Mo has been replaced by W with the Mo equivalent (= Mo + 1/2W)
remaining equal so as to improve the dispersion strengthening by increasing
the W content. The object is to suppress the reduction in strength due to the
long-time exposure to high temperatures and at the same time achieve greater
solid solution strengthening.
Steel B has been developed in order to upgrade creep rupture strength by
seeking a further reduction in Mn and Ni contents. In both these materials, the
Cr equivalent (= Cr + 6Si + 4Mo + IlV + 5Nb + 1.SW -(40C + 2Mn + 4Ni
+ 2Co + 30N)) has been controlled to a value equal to, or below, the specified
level in order to prevent the formation of delta ferrite which is responsible for
decline in mechanical strength. Figure 5 compares the creep rupture strength
data of the candidate material A, the currently used steel and the 600°C range-
resistant material.
Table 8 shows the chemical analysis of the candidate materials for the
moving blade. Table 9 gives the main constituents of the candidate materials
for the auxiliary turbine equipment (including the main steam flanges,
casings, and main steam valves).
400
350
m
~300
'::E'
~250
+J
e
Cf) 200
l...
Q)
:J
~150
'"
0::
~ 100
LI")
CrMoV steel(Current)
o
50
450 500 550 600 650
Ternperaturef'C)
Fig. 5 Creep Rupture Strength Data for Turbine Rotor Candidate Material
Table 8 Chemical Composition (%) of Candidate Materials for the Moving Blades
C Si Mn Ni Cr Mo V Nb W N Co B Re
Candidate steel'C' 0.11 0.04 0.51 0.5 11.02 0.15 0.19 0.08 2.61 0.029 2.89 0.014 -
Candidate steel'D' 0.11 0.05 0.5 0.6 10.5 0.10 0.2 0.10 2.5 0.03 1.0 0.01 0.2
Table 9 Candidate Materials for Auxiliary Equipment of Turbines
Parts Material
Body High-strength 9Cr forged steel

Main steam flange Volt Ni based alloy
Nut
Casing New 12Cr forged steel
Main steam valve flange Volt Ni based alloy
Nut 19Cr-12Ni-3W steel
Body High-strength 9Cr forged steel
Casing
Volt High-strength 12Cr forged steel
Casing New 12Cr forged steel
MSV
Valve bar 40Ni-13Cr-Ti-Mo-Fe(Bal.) steel
5.3 Experimental Procedure

5.3.1 Boiler test
(a) mock-up model test
For the tests, a mock-up model was fabricated. Its dimensions were equiva-
lent to the economiser, water wall, super-heater, header and main steam pipe
dimensions of a 1000MW range output coal-fired USC boiler to the Phase-II
steam conditions. Tests were carried out to determine their strength and
corrosion resistance so as to corroborate the technical soundness of the
fabrication engineering technique and of the pressure-resistant part. By way
of example, Table 10 shows the dimensions of the header and the main steam
pipe model.
Table 10 Mock-up Model (NF616) Dimensions

Design pressure: 30 MPa; Design temp.: 630°C
Header Nozzle stub Main steam pipe
Outer diameter mm 520.7 45 584.2

Wall thickness mm 134 12.8 116
Length mm 2040 1000*80pcs 5300
(d) Commercial boiler demonstration tests

Demonstration tests on a commercially operational boiler were performed for
a maximum of four years by incorporating the candidate materials into the
economiser, water wall and super-heater of the No.1 Unit of the EPDC
Takehara Thermal Power Plant. After the tests had been completed, the
candidate materials were investigated to examine the changes in their
Table 11 Main Specifications of Takehara Thermal

Power Plant No.1 Unit Boiler
Item Description
Evaporation 810t/h
Output 250MW
Super-heater outlet pressure 17.2 MPa(176kg cm-2)
Fuel Coal
NF616
HCM1'lA
TEWALOY F-12M
SAVE12
NF12
SlPER304H
TEWALOY M-1
NF709
Design Temperature:592°C
Design Pressure:19.2MPa
mao
IDPALOY HT780
l
Water Wall Design Temperature:316°C
Design Pressure:19.2MPa
III: in-situ position of test pieces

Fig. 6 Positions for Test Pieces in the Commercial Boiler Demonstration Tests
structure, strength properties and corrosion condition as a function of time

and thus to substantiate their practical application potential. Table 11 presents
the main specifications of the boiler used for the tests and Fig. 6 shows the
positions in which the candidate materials were installed for the commercial
boiler tests.
5.3.2 Turbine test
(a) Turbine rotating tests

The turbine rotating tests were carried out at the same temperature and rated
rotor speed (rpm) conditions as those of a commercial plant. The purpose of
Heater
Fig. 7 Turbine Rotating Test Apparatus
the tests was to corroborate the ability to use the candidate materials for
fabricating the rotor, the stationary blades and moving blade materials and
the blades connecting structure. At the same time, the tests provided basic
data on the turbine design. The high-pressure and the medium-pressure
initial-stage blades installed in the experimental rotors had the same shape as
those on the 1000MW steam turbine. The plan for these tests was that the
rotating test time should be 500 hours and the test temperature 650°C in order
to allow for sufficient time for the initial creep strain. Figure 7 shows the
rotating test apparatus.
(b) Elemental test

Model specimens of the ancillary turbine parts, including the turbine casing,
flanges, bolts and valves were fabricated and tested under the Phase-II steam
1) Hig,-teq>erature flange model test unit i Loop 8 system i

_ -- -----------------------------------------------------~....... 2HISV model test unit
Test steen:
•....•3(IIPa. 650"C
approx. 2t/h
a) IIa in Steam f lanQt' c) Turbine casillJ ,
~
, Loop A: 30MPa.635°C< I'
( Loop A system I
. Loop 8: 19MPa. approx. 600°C
I 3) Valve IJK)del test unit
Fig. 8 Elemental Test Apparatus

conditions (630°C, 30 MPa). The purpose of these tests was to substantiate the
reliability of the flanges and valve slides in terms of the fatigue strength and
sealing properties under the high-temperature and high-pressure conditions
of the tests. The test schedule allows for 500 hours in order to ensure sufficient
time for the initial creep strain. Figure 8 shows the elemental test apparatus.
CONCLUSION
At The Third Session of the Conference of the Parties to the United Nations
Framework Convention on Climate Change (COP3) held in Kyoto in Decem-
ber 1997, the targets for the reduction of carbon dioxide (C02) emissions were
fixed in order to prevent global warning. Demands for further efforts to
enhance the efficiency of energy utilisation were also placed on Japan. On the
other hand, however, deregulatory moves in the electricity sector have led to
the approval of Independent Power Producers (IPP) to join the electricity
market. For the power producers, it is therefore essential to assure high
efficiency and to achieve further cost reductions. The development of the USC
technology that is the subject-matter of this publication is designed to assure a
higher efficiency for the conventional coal-fired power plants. Compared with
other technologies, this technology has the advantage that there are few
development factors and that is can be introduced at an early stage. It can
therefore make a very substantial contribution to society. At present, phase-II
is in progress and further efforts will be sustained in a commitment to
bringing this development to a successful conclusion. The full thrust of our
development effort will therefore be concentrated on the practical realisation
of a USC plant with superior economic performance, reliability and operating
characteristics.
ACKNOWLEDGEMENTS
In concluding, the authors express their sincere thanks to Hitachi Works,

Babcock-Hitachi K.K, Mitsubishi Heavy Industries, Ishikawashima Harima
Heavy Industries Co., Ltd. and Toshiba Corporation for their co-operation in
this joint Phase-II project.
REFERENCES
1. T. Hanada: 'EPDC's Atmospheric Fluidized-Bed Combustion and Ultra-

Supercritical R&D - A Progress Report', The Second International Con-
ference on Improved Coal-Fired Power Plant, Palo Alto, CA, Nov. 2, 1988.
2. Tetsuo Kikuchi, Hiroyuki Nakada, Kiyotaka Muramatsu and Takeo Hirai:
Japan Mech. Soc., No.5 Dynamics & Energy Technology Symposium '96,
Proceedings of Lectures, 7, 1996.
Production and Properties of Modified
9Cr-1Mo Steel Forging (F91) for Valve
Bodies
Y. YAMAMOTO, s. SEa and J. MATSUMOTO
Pacific Steel Mfg. Co., Ltd., Toyama, Japan
Y. KADOYA, T. NISHIMURA and R. MAGOSHI
Mitsubishi Heavy Industries, Ltd., Takasago, Japan
ABSTRACT
In order to conserve the energy resources and to reduce dependence on oil, a large
coal fired power plant which has improved heat efficiency has been developed. A
very effective method of improving the heat efficiency of a steam power plant is to
improve the steam conditions. It is important to develop a high temperature turbine
valve forging which is a major structural material of such a steam power plant.
Modified 9Cr-1Mo (Grade 91) steel has been used in the parts of boilers in thermal
plants due to its excellent properties at high temperatures. In recent years, this steel
has also been applied to the parts of turbines in ultra super critical pressure plants.
Previous experience with a process for manufacturing forged valves of low alloy
steel in thermal power plants have enabled the application of F91 steel for forging
valves. A 25 ton ingot was produced by a basic electric furnace and was molded into
valve bodies by a combination of forging and shaping with gas. The manufacture of
a trial valve with F91 steel was successfully carried out. They exhibited high quality,
good creep rupture properties and excellent toughness.
1. INTRODUCTION
The coal fired ultra super critical pressure (USC) power generation plant is
drawing attention as a possible way to meet the parallel demands for greater
economy and reduction of environmental pollution (C02-emissions, etc.).
Current fossil power turbines inlet steam temperature is 538°C or 566°C in
most cases. By elevating this steam temperature to the 600°C class or higher, a
substantial improvement in the thermal efficiency can be expected compared
to that of conventional plants.'
Therefore, the steam temperatures have been being increased and currently
600°C class power generation plants in Japan have started to operate at super
critical pressures.s ' Modified 9Cr-lMo steel, which is high in strength at
elevated temperatures has been adopted for the main stop valve located at the
high-pressure turbine inlet and reheat stop valve located at the intermediate-
pressure turbine inlet of these 600°C class power generation plants.2,3
560
MODIFIED 9CR-1Mo STEEL FORGING (F91) FOR VALVE BODIES 561
Modified 9Cr-lMo was developed by the Oak Ridge National Laboratory

(ORNL)4 as a material mainly to substitute for the austenite stainless steel of
FBR pressure vessels and their piping. Because its characteristics at elevated
temperatures are excellent, it has been put into practical use as the steel pipe
material for the boilers of fossil power generation plants with many fruitful
resultsf
When modified 9Cr-lMo is adopted for the above-mentioned large valves,
however, because it would be a large forged steel and pass through some
special processes, these valves must be manufactured at high quality with
differences in material characteristics at each location and mass effects
sufficiently taken into consideration and the characteristics of the materials of
the modified 9Cr-lMo forged steel valves must be verified."
In order to increase the reliability of large forged steel products, the full size
trial valves of modified 9Cr-lMo steel were manufactured using a combina-
tion of special forging with gas shaping, and the quality and material
characteristics of the trial valves were evaluated.
2. FORGING OF MODIFIED 9CR-IMO STEEL
Because products such as forged valves may reach 400 to 500 mm in thickness
during heat treatment, depending on their form, it is uncertain that uniform
characteristics can be obtained throughout. The weight of the ingot to be used
may exceed 40 ton. The engineering problems on the actual production of
forged valves that must be solved are as follows.
1. Making of large steel ingots by electric furnace.
Until now, many modified 9Cr-IMo steel ingots of commercial base
were formed from 10 ton class steel ingots. The AOD (argon oxygen
decarburisation) process and AODjESR (electro slag remelting) process
were chosen as the ingot making methods. In recent years, however, the
LF (ladle furnace) Process by electric furnace (EF) has become used due
to the increasing size of steel ingots. However, the production experi-
ences of those large steel ingots exceeding 20 ton which were manu-
factured by this process are poor and, therefore, 40 ton class large steel
ingots must be manufactured using this process and then verified.
2. Free from ferrite at the center of thick walls and understanding the
effects of the cooling rate at normalisation on the mechanical proper-
ties.
Though the effects of cooling rates on pipes and sheets has been
studied rather in detail, the data on thick wall members near the ferrite
deposit area where the cooling rate is slow is less detailed and, therefore,
it must be studied further.
3. Understanding the effects of the expected temper holding times for thick
wall members.
Because forged products have a large in wall thickness, their temper

holding time is 10 hours or longer, assuming that the temper rate is 1
inch/hour which is the standard for forged products. The data on
materials in which a temper holding time exceeds 10 hours is scarce and,
therefore, must be studied further.
A preliminary study on items (2) and (3) was performed by the
following method. An extra part was provided at the short pipe section
of a forged valve made from a 30 ton steel ingot and various tests were
performed by on-site simulation of the actual heat treatment.
3. EVALUATION OF THE MANUFACTURABILITY
Figure 1 shows the CCT diagram of modified 9Cr-1Mo steel during normal-
isation at 1050°C.
1000
800
~ 600
.a
~
a
E
~ 400
200
Time (5) 1 2 3 6 12 24 1 2 3 6 12 24
min hour
Fig. 1 CCT Curve Diagram of the Modified 9Cr-lMo Steel
The Ms point indicating about 420°C does not reach the ferrite nose until a
cooling rate of 1.SoC/min is reached, and thus an approximately constant
normalised hardness of Hv = 400 can be obtained. In addition, the cooling
rate at the centre of an ingot of 300 to 400 mm in thickness is 1.5 to 2°C/min
during air cool treatment. In this case, the precipitation of any ferrite cannot
be recognised, and a martensite structure can be obtained. In the structural
observation after normalisation, finely distributed MX carbo-nitrides were
observed. The presence of this carbide is considered to suppress the grains
from becoming coarse.
In connection with its toughness, a normalising temperature of 1040 to
1060°C was considered to be appropriate.
MODIFIED 9CR-IMo STEEL FORGING (F91) FOR VALVE BODIES 563
~
!l.c
700
6 ---
~
.",.. •.. .... ------..

U)
U)
600 t';S 100

~ ~ Reduction in area (600·C)
c.... t';S
-- ---
CI)
~ .S --
ec..
0
500 0.2% Proof stress (23 ·C) c:
.8
~
Reduction in area (23"C)
~N t)
:::s
400 "0
0
~
(1)
-5 50
Oll
.J:~sg.e_ ~tg~~_ ~~:~6 C 8 Elongation (23·C)
c 300 ,, .52
E 0' •. --e- -.• ---- - - --- .• ~ee ---a--~---~---u----. g
CI)
'/0.2% Proof stress (600 C) c:
•
D
Elongation (600·C)
200 0
~c &3
~
(1)
100 0
0.1 10 100 0.1 10 100
Cooling rate CC/min:800·C-300°C) Cooling rate rC/min:800°C-300°C)

Tempering temperature: 760°C
Tempering time: 10h
Fig. 2 Effect of the Cooling Rate on the Tensile Strength at Room Temperature and
600°C
Figure 2 shows the effects of the cooling rate on the tensile strength at room
temperature and at 600°C for normalisation at 1050°C.
The tempering conditions were set at 10 hours and 760°C. At a cooling rate
of 1°C/min or higher, no difference in the strength or ductility could be
noticed. In addition, all actual characteristics at room temperature exceeded
specifications. A reduction of strength was noticed only in materials cooled at
a cooling rate of O.SoC/min in which ferrite precipitated and the strength of it
at room temperature was below specifications. This characteristic tendency
was also observed in the impact characteristics and when ferrite is precipi-
tated, the impact characteristics worsen remarkably.
Figure 3 shows the tempered hardness curves at 730, 760, and 780°C. The
normalising conditions are a temperature of 10S0°C and the cooling rate of
2°C/min in the estimated centre part of a 200 to 300mm thick ingot. At each
temperature, the hardness is reduced with an increase of the holding time.
However a difference was also observed in softening behaviour by tempering.
Namely, at the temperature of 730°C, the hardness was much lower and
stayed low until a tempering time of 20 hours was passed. Beyond that time, a
stable hardness could be obtained. At 760°C, the dependency of the hardness
on the tempering temperature was small and a stable hardness could be
obtained over a wide range. At 780°C, the hardness began to drop remarkably
after a tempering time of 20 hours was passed.
Figure 4 shows a TEM thin-foil micrographs for each tempering tem-
perature. The martensite lath width becomes wider as the tempering tem-
perature increases and the transition density in the lath introduced by the
martensite transformation is small. At a tempering temperature of 730°C, a
Normalizing temperature: l050·C

Cooling rate: 2-C/min
--c=
Q)
al 150
100 ~~~~~~~~~~~~
0.1 10 100
Tempering time (h)
Fig. 3 Tempered Hardness Curves for 730, 760 and 780°C
Fig. 4 TEM Thin-Foil Micrographs showing Martensite Structure at each Tempering

Temperature: (a) 730°C-l0h, (b) 760°C-20h and (c) 7BO°C-20h
clear martensite lath structure could be observed also in those materials

tempered for 10 hours. In the structure, most carbide was precipitated finely
in the grain boundaries, and less coarse carbide could be observed. At a
tempering temperature of 760°C, coarse carbide could be observed in the
grain boundaries, but the configuration of the lath structure remained as it
was. This configuration was almost un-changed even after 10 hours was
passed and, therefore, it can be judged that the structure is stable. At a
tempering temperature of 780°C, the recovery of lath and coarse boundary
carbide could be observed as very clear structural changes.
In particular, a tendency to equiaxial ferrite low in transition density which
is caused by the recovery and softening of the lath could be noticed in those
areas where the time exceeded 10 hours. A difference in these structures is
considered to influence the hardness and softening behaviour.
Figure 5 shows the effect of the tempering temperature on the impact
properties at three different cooling rates in the center of the wall as estimated
by various dimensions, which was arranged by the Larson-Miller parameter.
300
o : l·C/min
5 o : 2·C/min
~ A :4·C/min
e!l
0
t:
0
"'0 0
-e0
0
200
CI)
.I:J
-c ~8~" .'
/S:..".,.........
Tempering time : lOb

100
20 21 22 23
P=(T+273) • (logt+20)X 10-3
Fig. 5 Effect of the Tempering Temperature on the Impact Properties
The tempering time was set at 10 hours for the three temperatures. At each
cooling rate, the impact value was increased as the tempering temperature
rose. In addition, the difference in the absorbed energy according to the
cooling rate was decreased as the tempering temperature rose. This is because
the configuration of the martensite structure generated by normalisation
varies with cooling rates, and thus the recovery behavior of the toughness
caused by the tempering softening varies.
Figure 6 shows the creep rupture properties at 500 to 600°C obtained when
the cooling rate at normalisation and tempering temperature were varied
--- ..
300 ~ .. ....
.._ .._
......
_ .... _------ASTM,/
0
.•.
data band
"
.......... " .•.
--~
p...
200
<. "" ~ """"~&
6en
CI)
Q)
.b 100
CI) r---------- ..
-'
•• ~,~
I'C/min 2'C/min 4'C/min ~~
730·C 0 0 e
17 18 19 20 21
P=(T +273) • (logt+20) x 10-3
Fig. 6 Creep Rupture Strength at 500 to 600°C obtained when the Cooling Rate and
Tempering Temperature are Varied
respectively, and are ordered by their Larson-Miller parameters. Though no

remarkable effect on the cooling rates could be noticed, the effect of the
tempering temperature on the rupture time could be noticed. The tendency
was different according to the test temperatures and, as the creep test
temperature rises, the difference in the rupture time according to tempering
temperature was reduced. This tendency appeared remarkably clearly in the
higher temperature and longer time cases.
It is believed that when the tempering temperature is increased, the
dislocations introduced by the stable carbide and martensite transformation
are recovered to a more stable structure.
Based on the results thus obtained, the following points could be verified.
1. A normalisation to obtain martensite structure can provide excellent
characteristics.
2. Even thick wall forged products can meet the specifications by air
cooling treatment.
3. Tempering is performed desirably at approx. 760°C with the tensile and
impact properties and the stability of the creep rupture strength taken
into account.
4. MANUFACTURE OF A TRIAL VALVE
A trial valve was made from a 25 ton steel ingot which was melted by the EF
process using a 50 ton basic electric furnace. Table 1 shows the chemical
Table 1. Chemical Composition of the Manufactured Trial Valve (wt%)
Valve Process C Si Mn P S Ni Cr Mo V Nb Al N
Trial-A EF 0.09 0.32 0.39 0.009 0.006 0.09 8.76 0.95 0.20 0.076 0.013 0.046
0.08 0.20 0.30 8.00 0.85 0.18 0.060 0.030
SFV AF28
Specification
0.12 0.50 0.60 0.020 0.010 0.40 9.50 1.05 0.25 0.100 0.040 0.070
composition of the trial valve, while Fig. 7 shows the shape and dimensions of
the trial valve. A reheat stop valve was then planned on trial as a full scale
unit.
Figure 8 shows the manufacturing process of the trial valve. The 25 ton steel
ingot was solid-forged and upset repeatedly by a 4300 ton press so that the
forging coefficient of the overall steel ingot is 3 to 4 or higher. Because the trial
valve was formed in a bag shape internally (stopped midway), the oval hole
was provided to the intermediate depth by punching. The lateral short hole
was provided and its diameter was enlarged. Through these special forgings
Fig. 7 The Shape and Dimensions of the Trial Valve and the Test Specimen
Sampling Position
Erectric Arc Furnace

tngot weight: 25 ton
Normalizing: 1050°C x 12HR AC

Tempering : 760°C x 20HR FC
Stress Relieving Annealing
Fig. 8 The Manufacturing Process of the Trial Valve and Test Specimens
and forging processes, the trial valve was formed to a specified shape and
then preliminarily heat-treated.
Then, to form the fork pipe to a specified shape it was drilled, the reference
plane was set up by machining, and gas shaping and machining were
partially repeated. After that, the final heat treatments such as normalisation
and tempering were applied to the valve. To perform the normalisation of the
valve, it was held at l050°C for 12 hours and to perform the tempering, it was
held at 760°C for 20 hours, and then cooled in the furnace.
After the final heat treatment the trial valve was cut off and test specimens
were sampled from each position. In addition, only the sampled test speci-
mens were annealed for stress relieving at a temperature of 745°C for 15 hours
because they are expected to be heat treated after welding. Figure 9 shows the
appearance of the trial valve after cutting.
Fig. 9 The Appearance of the Trial Valve After Cutting
Figure 7 also shows the test specimen sampling position. As mentioned

above, because the forged valve is complicated in shape and formed through
some special forging processes, its forging coefficient and polarity become
extremely non-uniform.
To sample the test specimen, therefore, some locations on the forged valve
where the effects of the forging and forging coefficient are difficult to be
calculated were selected.
No.1: This is equivalent to the underside of the steel ingot and the largest in
wall thickness. Because the holes are enlarged, however, the forging is
effective. The forging coefficient was estimated to be about 7. It is difficult to

provide a head as ingot for this position.
No.2: This is equivalent to the top side of the steel ingot at the cross section
of the main body with the pipe section. Forging is liable to be effective, and
the forging coefficient was estimated to be about 10. This position has rather
fewer defects.
No.3: This is equivalent to the bottom side of the steel ingot at the crossed
section of the fork pipes. It is the most difficult place to forge. The forging
coefficient of this part was estimated to be about 5. It is difficult to provide a
head as ingot for this position and, therefore, shrinkage cavities are liable to
occur here.
No.4: This is equivalent to the middle of the steel ingot, where forging is
sufficiently effective. The forging coefficient is about 10.
5. EVALVA TION OF THE TRIAL VALVE
5.1 Chemical Compositions

Table 2 shows the analysed values obtained by the checking of the trial valve
at each location. No segregation of components could be noticed at any
Table 2 Variations in the Chemical Composition of the Manufactured Trial Valve

(wt%)
C Si Mn P S Cu Ni Cr Mo V Nb N
Ladle 0.09 0.32 0.39 0.009 0.006 0.06 0.09 8.76 0.95 0.20 0.076 0.046
No.1 0.09 0.32 0.39 0.010 0.006 0.07 0.10 8.80 0.94 0.20 0.075 0.046
No.2 0.09 0.32 0.38 0.010 0.006 0.07 0.10 8.75 0.94 0.20 0.075 0.046
No.3 0.09 0.32 0.39 0.010 0.006 0.07 0.10 8.75 0.94 0.20 0.076 0.045
No.4 0.09 0.32 0.38 0.010 0.006 0.07 0.10 8.75 0.94 0.20 0.074 0.044
location. In the trial valve, a fine structure could be obtained over the entire
area, and no defect could be noticed. The microstructure was fine tempered
martensite in which no ferrite was segregated at any location.
Figure 10 shows the TEM thin-foil micrographs of the trial valve at the
maximum wall thickness section (position (1)). It shows a uniform martensite
lath structure.
5.2 Mechanical Properties

Figure 11 shows the mechanical properties of the trial valve at each location. It
presents excellent strength and ductility at each location, and no non-
Fig. 10 TEM Thin-Foil Micrographs at Three Locations on Position (1) of the Trial
Valve
T.S. : 629 MPa T.S. : 614 MPa T.S. : 614 MPa

v.s, : 458MPa Y.S. : 442 MPa v.s. : 443 MPa
EI. : 29.4 % EI. : 29.2 % EI. : 30.2 0/0
R.A. : 72.1 R.A. : 71.3 % A.A. : 71.7 0/0
~rl®~
%
FAn : -12°C FAn : -1°C FAn :3°C

Energy: 204 J Energy: 191 J Energy : 185 J
@[ I
\
T.S. : 630 MPa
'-
T.S.
»>
@~
: 634 MPa T.S.

\
: 634 MPa
Y.S. : 478 MPa Y.S. : 468 MPa Y.S. : 466 MPa
EI. : 28.4 0/0 EI. : 29.0 0/0 EI. : 29.0 %
A.A. :72.1 % A.A. : 70.4 % R.A. : 70.4 %
FATT :O°C FATT : -4°C FATT :-4°C
Energy: 138 J Energy : 142 J Energy: 142 J
Fig. 11 Mechanical Properties of the Trial Valve at each Location
uniformity can be observed. In addition, it meets the requirements of ASME

F91 at any location. The impact transition temperature was excellent around
O°C at the center of the thick wall section. The absorbed energy of 130 J or
more at O°Cwas also excellent.
800 100
••
~~
::s ~
'-"~
~ ~=
(o;S
80
t
~~ 600
.S
.•.. ~
e
0
.~0o 60
0..
~N 400 ='
"C
~
Q)
0 a 40
.:f .S
~co
~
b.O
200 ~0
~~ fij
20
~
aQ) 0 0
E-t 0 100 200 300 400 500 600 700
0 100 200 300 400 500 600 700
Testing Temperaturef'C) Testing Temperaturef'C)
Fig. 12 Tensile Properties of the Trial Valve at High Temperatures
Figure 12 shows the high temperature tensile properties of the trial valve. In
the figure, the solid lines represent the ORNL4 minimum lines. Both the
strength and ductility surpass the minimum lines.
5.3 Creep Properties

The current status of the creep tests of the trial valve is shown in Fig. 13.
Specimens from positions (1) to (4) are being tested at 500, 550, 600 and 650°C.
Regardless of the test conditions, the rupture ductility was 25% or higher in
300
=-~ 200
~
o
80
500°C •
550°C •
60
600°C •
650°C • Mod.9Cr-lMo(F91)
40 ~~~~~--~~~~--~~~~--~~~~
10 100 1000 10000 100000
Time to rupture tr (h)
Fig. 13 Creep Rupture Strength of the Trial Valve at the Temperatures of 500,550,
600 and 650°C
elongation and 85% or higher in reduction of area at any location. The test
data for long periods of up to 30 thousand hours was obtained. It has a creep
strength stable even under high temperatures, and the 100 thousand hour
creep rupture strength estimated from the test data meets the requirements
for both the average and minimum rupture strength which are required by
the allowable tensile stress of ASME F91.
In addition, the high temperature fatigue characteristics of the trial valve
were investigated, and it was found that no particular problem was present."
CONCLUSION
In order to increase the reliability of large forged steel products, full scale
valves were manufactured from 25 ton steel ingots and the quality and
material properties of the valves were evaluated. The results obtained are as
follows.
1. Melting and manufacturability
By the adoption of the modified 9Cr-1Mo steel, large steel ingots can
be manufactured using the EF process in a 50 ton basic electric furnace.
In addition, no cracking could be detected even after those processes
which included a special forging method in which a measure to bring
the shape of the ingot to that of the product was taken and gas reshaping
was completed, and excellent production quality was provided.
2. Mechanical properties of steel forging for valve bodies
The mechanical properties of the trial valve, even at the center of its
wall thickness, meet ASME F91 requirements with respect to both
strength and ductility even if the valve is subjected to heating to the
temperature of 745°C for 15 hours which is equivalent to post-weld heat
treatment. The impact characteristics of it are excellent with an absorbed
energy of 130 J or more at DoCwhen the fracture appearance transition
temperature at the center of the wall thickness is about DoC.As for the
creep properties, excellent characteristics including long period test data
were obtained for both strength and ductility.
3. Wall thickness susceptibility
The full scale forged valves formed by the repetition of special
forgings were found to have no differences in quality depending on the
sampled location or testing direction, and had remarkably excellent
uniformity as compared with cast steel products.
REFERENCES
1. K. Kougami and H. Isaka: Tetsu to Hagane, 1990, 76, 1043.

2. M. Kishimoto, Y. Minami, K. Takayanagi, M. Umaya and H. Obara:
Mitsubishi Juko Giho, 1994, 31, 21.
3. 1. Obara, T. Yamamoto and Y. Tanaka: Mitsubishi Juko Giho, 1995, 32, 8.

4. V. K. Sikka, C. T. Ward and K. C. Thomas: Proc. ASM Int. Con! Production,
Fabrication, Properties and Application of Ferritic Steels for High Temperature
Applications, Warren, P. A. (Oct. 1981).
5. H. Haneda, F. Masuyama, S. Kaneko and T. Toyota: The International
Conference on Advances in Material Technology for Fossil Power Plants,
Chicago, Illinois, Sep. 1987.
6. Y. Yamamoto and S. Seo: The Thermal and Nuclear Power (Karyoku Genshir-
yoku Hatsuden), 1995, 46, 488.
7. Y. Yamamoto, S. Seo, K. Shiozawa, S. Nishino and K. Takahashi: The
Thermal and Nuclear Power (Karyoku Genshiryoku Haisuden), 1997, 48,
1102.
Advanced Heat Resistant Steels for
Steam Turbines
M. MIYAZAKI, M. YAMADA, Y. TSUDA and R. ISHII
Toshiba Corporation, 2-4 Suehirocho, Tsurumi, Yokohama, 230 Japan
ABSTRACT
Recently, ultra super critical steam turbines with 593-610°C inlet steam tem-
peratures have been constructed in Japan. 9-120/0Cr heat resistant steels for high
temperature components contribute greatly to the construction due to their good
properties. This paper summarises the current status of the advanced heat resistant
steels in the Toshiba Corporation.
INTRODUCTION
The higher efficiency of thermal power plants become extremely important

for the economical consumption of fossil fuels and the preservation of the
global environment, such as the suppression of CO2 emissions. As shown in
Fig. 1, Toshiba has been leading the design and manufacture of advanced
steam turbines such as in the Kawagoe #1 unit, 700 MW, 31MPa,
566/566/566°C which went into service in 1989. During the 1990s, the high
efficiency in large steam turbines has been achieved by further increases in
steam temperatures up to 593-610°C in Japan. The resultant relative
efficiency is approximately 3-4% in increase using 538-566°C reheat turbines
as the base case. To achieve such steam conditions, it was necessary to
•••••Siioiii3ioiii8/IIIIiioiS6iiiiooii6•••••••••••••••••••• 0 .
output: SOO-lS00MW
Year in service
Fig. 1 Trend of steam temperature in large rating units in Japan
574
ADVANCED HEAT RESISTANT STEELS FOR STEAM TURBINES 575
develop advanced compositions and manufacturing processes for heat resist-

ant steels with higher creep rupture strength. We developed 12% Cr rotor
steel for 566°C turbines and have verified its integrity through long term
service since 1973. Based on such experiences, various kinds of advanced
9-12% Cr alloy steels have been developed for high temperature compo-
nents.
EXPERIENCE AND CURRENT STATUS OF MATERIAL

DEVELOPMENT
To cope with expensive fuel cost after oil crises in the world, the feasibility
studies on advanced steam cycles were carried out in the USA and Japan in
the late 1970s. The results were reported in 1981,1-3 and then led the
verification studies of advanced steam cycles started from the beginning of
1980s, which are represented by USC (ultra super critical)-project supported
by EPDC (Electric Power Development Company), ICPP (Improved Coal-
fired Power Plant)-project supported by EPR! and COST 501 in European
countries.
As for advanced steam turbines, Toshiba has promoted the EPDC, TEPCO
(Tokyo Electric Power Company) and EPRI-projects as shown in Table 1. In
Table 1 Toshiba participation in advanced steam turbine projects
Year Projects Remarks
'82-88 EPDC -phase-l Turbine rotating test at 593 & 649°C

'82-84 TEPCO Development of turbine rotor steels for 593°C
'86-90 EPRI-RP1403-15 Material development of key parts for 11000P
'95-99 EPDC- Phase- 2 Accelerated turbine rotating test at 650°C
EPDC-projecti phase-I, the operational integrity of modified 12% Cr rotor /

bucket steels was verified through the rotating test at Takasago for 4818 hrs at
593°C. Successively, aiming at more advanced steam conditions in future, the
same rotating test at 649°C using A286 austenitic alloy rotor was also carried
out. TEPCO-project5 was to validate the producibility and the properties of
three kinds of modified 9-12% Cr steel rotors- developed in Japan, thereby
supporting EPDC project phase-I. In EPR! project," we were engaged in key
material tasks for advanced steam turbines with 31 MPa, 593/593/593°C
(4500psi, 1100/1100/1100 P) in steam conditions. And the properties of
0
modified 12% Cr rotor/bucket steels and superclean 3.5% NiCrMoV rotor

forgings were verified. Now EPDC project phase-2 is in progress to develop
more advanced steam turbines with 630°C in steam temperature.
Table 2 shows the first use of our developed materials for advanced steam
Table 2 First use of new materials developed by Toshiba for advanced steam
turbines
First use units and utilities Year

New materials (designation) Parts in service
Kudamatsu#2 (375MW, 16.6MPa, 566/538°C), Chugoku E.P.C. 1973

120/0Cr rotor (TOS101) HP-IP rotor
Kawagoe #1 (700 MW, 31.0 MPa, 566/566/566°C), Chubu E.P.C. 1989
120/0Cr casting (TOS301) VHP-HP turbine casing,
nozzle box, MSV & CV bodies
9% Cr- 20/0Mopiping Main steam lead pipes
Superclean 3.50/0NiCrMoV rotor LP rotors
Tsuruga#l (500MW, 24.1 MPa, 566/566°C), Hokuriku E.P.C. 1991
Modified 12% Cr rotor (TOSI07) HP-IP rotor
Modified 12% Cr forging (TOS202) Buckets & bolts
Haramachi#l (1000MW, 24.5MPa, 566/593°C), Tohoku E.P.C. 1997
Modified 120/0Cr casting (TOS302) HP inner casing
Nanao-ohta#2 (700 MW, 24.1 MPa, 593/593°C), Hokuriku E.P.C. 1998
Super g% Cr forging; MSV & CV bodies
New 120/0Cr forging (TOS203) Buckets
Tachibanawan#l (1050MW, 25 MPa, 600/610°C), EPDC 2000
New 12% Cr casting (TOS303) CRY bodies
25~------------------------------------------
20
~
e
~o
15
1 10
~
.-..--
Z Modified 12% Cr rotors!--
5 (TOSlO?) ,_•• :
._---.!j'-----
Year in service
Fig. 2 Application experience of 9-12% Cr rotor steels (Toshiba)
turbines. As mentioned above, 12% Cr rotor steel had been developed and
was used for Kudamatsu #2 in 1973. Since then, many of the steel rotors have
been applied to advanced steam turbines with 566°C in steam temperature as
shown in Fig. 2. In addition to the excellent rotor experiences, the wide
application of 9-12% Cr alloy steels enabled the construction of the Kawagoe
#1 unit? in 1989. In short, the unit is characterised by using new 9-12% Cr

alloy steels even for turbine casings, nozzle boxes, valve bodies and steam
pipes of high pressure/temperature components as well as for rotors. The
superclean 3.5%NiCrMoV steel developed in EPRI project was also used for
LP rotors for Kawagoe #1. Modified 12% Cr steels were applied to high
temperature rotors, buckets/bolts and casings for advanced turbines, and
also the other advanced materials will be applied as shown in Table 2.
During this decade, there has been a remarkable advance in 9-12% Cr
steels in the world, represented by materials development reported by
Pujita.v? Based on the same concepts we also developed more heat resistant
ferritic steels with optimised alloy chemistry adding W, Co, Band Re, whose
material designations are TOS110 for rotors, TOS203 for buckets and TOS303
for castings. Though long term tests have continued until now, some of them
are applicable to the critical components for higher temperature units.
HIGH TEMPERATURE ROTOR MATERIALS
Three kinds of 12% Cr rotor steels were developed for the turbines with above
566°C in steam temperature. The typical chemical composition and the creep
rupture strength of the steels are shown in Table 3(a) and Fig. 3, respec-
tively.
Table 3 Typical chemical composition of advanced heat resistant steels (mass'zs)
(a) Rotor forging C Cr Mo V Ni Nb N W Co B Re

12% Cr (TOS101) 0.18 11 1 0.2 0.4 0.07 (Ta) 0.05 -
Mod. 120/0Cr (TOS107) 0.14 10 1 0.2 0.7 0.05 0.05 1
New 12% Cr (TOS110) 0.11 10 0.7 0.2 0.2 0.05 0.02 1.8 3 0.01
(b) Bucket bar
Mod. 120/0Cr (TOS202) 0.16 11 1 0.2 0.7 0.2 0.05 1.1 -
New 12% Cr (TOS203) 0.11 10.5 0.1 0.2 0.6 0.1 0.03 2.5 1 0.01 0.2
(c) Casting
12% Cr (TOS301) 0.14 10 1 0.2 0.5 0.1 0.05 -
Mod. 120/0Cr (TOS301) 0.12 10 1 0.2 1 0.1 0.05 0.8 -
New 12% Cr (TOS303) 0.12 10 0.7 0.2 0.2 0.05 0.02 1.8 3 0.006 -
12% Cr Rotor Steel (TOS101)
120/0 Cr rotor steel was improved fro H46 alloy steel for gas turbines. To
accomplish target properties for steam turbines, extensive studies were
conducted in alloy chemistry, heat treatment and manufacturing processes.
From a metallurgical viewpoint, in addition to its good hardenability and
toughness, the steel is characterised by precipitation strengthening with Nb /
,, ,
";' '<0
0,,°,. ,~"O
li~
~
300
'........
OS;~
~<,
oq.~, " , .•.. ,.•.. ,
.£j I!£~
bO
c:
or), .•..
~
200
"~. " ",
00
e:s .. "
" , ,",
~
~ .., ,",,,
..c: 150 {C=20 for l%CrMoV .., ,,
~
120
C=25 for TOSI0l, 107, 110
in Larson-Miller parameter ,
450 500 550 600 650
Temperature (OC)
Fig. 3 Rupture strength of rotor steels
Ta carbo-nitride adding to M23C6 and VC carbides in tempered martensite,

thereby giving high temperature strength enough to HP-IP or IP double flow
turbines with 566°C in reheat steam temperature. The producibility of large
ingots was improved by lowering the Nb content to avoid heavy segregation.
Additionally, the application of VCD (vacuum carbon deoxidisation) process
is beneficial to the improvement of ingot homogeneity. To prevent a bearing
problem called 'shaft galling' inherent in 12% Cr steels, sleeves of low alloy
steel were shrunk on journal at the beginning of application, and recently
overlay welding is done on journal shafts.
Since 1973, a lot of 12% Cr steel rotors have accomplished a satisfactory
performance. Except for cracking caused by fretting fatigue on shrunk-on
couplings at the beginning, there is no problem such as a gradual increase in
critical vibration due to creep deformation and low cycle fatigue cracking
which can be experienced in traditional 10/oCrMoVlow alloy steel rotors.
Basically, 9-12% Cr steels are good in physical and mechanical properties
such as thermal expansion/conductivity, yield strength and the resultant
thermal deformation. Accordingly, it is clear that the higher creep strength
and the good thermal stability of the steel contribute greatly to the excellent
performance of the rotors.
Modified 12% Cr Rotor Steel (TOSI07)

Aiming at raising a steam temperature to 593°C, the development of modified
12% Cr rotor steel was required, of which the target creep rupture strength
was above 98 MPa at 593°C in 105 hours. From the results of numerous
laboratory heats, it was concluded that the high temperature strength of
conventional 120/0Cr steel significantly increased with the following chem-
istry; (a) lower carbon and addition of 1% tungsten for high temperature
ADVANCEDHEAT RESISTANTSTEELSFOR STEAMTURBINES 579
strength, (b) increase nickel to improve toughness and for obtaining a

balanced alloy design to prevent the formation of delta ferrite.
Starting in 1982 after the completion of fundamental studies on alloy
chemistry, the verification of modified 12% Cr rotor steel (TOS107) were
conducted with different objectives through TEPCO, EPDC and EPRI projects
as previously shown in Table 1. To verify the producibility, quality and
properties of the steel, the sample forging estimating product-size was
produced as the most promising steel in the TEPCO project, which was
manufactured from 70 tons ingot using the VCD process. The extensive tests
and their excellent results as well as creep rupture strength are described in
Iiterature.f In the EPDC project, the operational integrity of the steel rotor was
confirmed through rotating tests at 593°C. In the EPRI project, ESR process
and heat treatment were studied to evaluate the potential properties and
quality of the steel. Since the first use in 1991, the application of the TOS107
rotor steel has been followed by more advanced turbines with above 593°C in
steam temperature as shown in Fig. 2.
There are some different views on the role of tungsten in W-bearing alloy
steels. The microstructure observation of creep ruptured specimens made it
clear that the growth of sub-grains and the recovery of dislocation during
creep delayed in modified 120/0Cr steel with 0.92% W more than W-free steel
as shown in Fig. 4. Also Fig. 5 summarises the chemical analysis of residue
extracted from as heat-treated 100/oCrMoVNbN steels with different W
contents. The amount of residues, most of which were estimated to consist of
carbides and carbo-nitrides, was almost equal to each heat regardless of
different W contents. Though Cr, Mo and V were found in both precipitates
Heat-treated
Rupture tested
at 640°C, 147MPa
W free: 352.3h )
( 0.92% W: 1970.4h
Fig. 4 Dislocation structure of lO%Cr-Mo-V-Nb-N steels

Wfree 0.46% W 0.92% W 1.24% W
e
---. 1.0
~ 0.5 Ladl~ .
analysis Conte~t m
O------~~~~------~~~~ the residue
Fig. 5 Content of alloy elements in residue extracted from lO%Cr-Mo-V-Nb-N

steels
and the matrix, most of the tungsten existed in the matrix and the addition of
tungsten predominantly resulted in the increase of tungsten content in the
respective matrix. These results indicate that the improved creep rupture
strength of TOS107 depends on the solid solution strengthening effect of
tungsten.
During creep and thermal ageing, the formation of Laves phase were found
in the steel. But longer term ageing tests demonstrated that the decrease in
impact toughness and the shift of FATT (fracture appearance transition
temperature) were observed only at the initial stage, which became saturated
in the long term. Though the embrittlement in toughness probably corre-
sponded to the formation of Laves phase, the toughness and FATT of the steel
were established to be good enough for long term operation.
New 12% Cr Rotor Steel (TOS110)

A new 120/0 Cr rotor steel!" with super heat resistance was recently developed
for turbine rotors of above 630°C in steam temperature. Compared with the
TOS107 steel, the characteristic of the alloy chemistry is as follows; (a) lower
carbon, manganese and nickel contents, (b) higher tungsten and lower
molybdenum contents, (c) addition of cobalt and boron.
Figure 6 summarises the influence of typical alloying elements on tough-
ness and creep rupture strength. As well as with carbon, the decrease in
:I:/
120
0.IC-0.2Ni-l.8W-
100
6
~
~ 80
~~
60
180
~-
..d~
~~ 170
fI).,..-C
160
M~
Q.. •••.•
150
2u
~g
"",\.0
140
u~
130
0.11 0.13 0.16 0.2 0.6 o 0.005 0.011
C(%) Ni(%) B (%)
:::L
120
0.IC-0.2Ni-I.8W-
100
6
e.....
~ 80
~~
60
0.1 C-O.2Ni-3Co-0.0IB <>----,-0----0
0.1 C-0.2Ni-1.8W -0. 7Mo
180
~-
..d~
i~ 170
fI),;P
eo
2-;;
160 ~
0.. .••.•
150
2u
&g
e\.O 140
u~
130
1.0-1.0 1.8-0.7 2.2-0.4 2.6-0.4 o 2 4
W-Mo(%) Co(%)
Fig. 6 Effects of alloy elements on toughness and creep rupture strength
manganese and nickel is beneficial to creep rupture strength. On condition

that the molybdenum equivalent is 1.5 times the tungsten content is beneficial
to increasing the creep rupture strength. But exceeding 1.8% tungsten, a rapid
shift of FATT was revealed. Therefore, the combination of 1.8% tungsten and
0.7% molybdenum contents were optimised in our investigation. There was a
tendency toward increasing chromium equivalent and accelerating the forma-
tion of delta ferrite in the chemistry modifications. To offset such a potential
problem, an addition of cobalt was required. Moreover, it was revealed that
the increase in cobalt up to 3% was beneficial to creep rupture strength. It is
known that an addition of boron improves extensively the creep rupture
strength but reduces the toughness. In view of forgeability, the boron content
is preferable to be less than 150 ppm.
To verify the producibility and properties of the alloy steel rotors, a

medium size of 20 tons and a product-size of 80 tons ingots were manu-
factured. The ladle refining/Vf'D and ESR processes were applied to make
ingots clean and homogeneous. Trial rotor forgings made from the ingots
were oil-quenched at 1070°C and double tempered at 570/680-690°C, and
then were subjected to evaluation of their quality and properties. Extensive
tests for evaluation demonstrated that the rotor forgings were acceptable for
the specification and significantly improved on creep rupture strength at
630°C as shown in Fig. 3.
HIGH TEMPERATURE BUCKET MATERIALS
Traditional bucket steels operating up to 566°C are 120/0Cr1°loMo1 % WV and

11°loCr1 MoVNbN
%
steels. For the same purpose to raise temperature, mod-
ified and new 12°10 Cr bucket steels were developed, which were based on the
similar concept of alloy chemistry to the advanced rotor steels. Typical
chemical composition and creep rupture strength are shown in Table 3(b) and
Fig. 7.
400~----------------------------------------
, ,,
, ,
C=25 in Larson-Miller parameter
100
450 500 550 600 650
Temperature eC)
Fig. 7 Rupture strength of bucket steels
Because of the much smaller product size compared with rotors, modified
12°10 Cr bucket steel (TOS202) was allowable to be improved as follows; (a)
higher niobium content in addition to above 1°10 tungsten, (b) higher quench
temperature. Thereby the bucket steel shows the excellent creep rupture
strength more than the rotor steel of similar alloy chemistry.
The characteristics of the new 12 Cr bucket steel (TOS203)11are higher
%
ADVANCEDHEAT RESISTANTSTEELSFORSTEAMTURBINES 583
tungsten, lower molybdenum contents and an addition of rhenium, compar-

ing with TOSII0 rotor steel. During creep or thermal ageing, it was estab-
lished that high tungsten increased the amount of Laves phase precipitates,
and which spread all over grain boundaries and martensitic lath interfaces as
shown in Fig. 8. Therefore it is considered that the recovery of dislocation
Fig. 8 Microstructure of 12%Cr-V-Nb-N steels crept at 650°C, 176MPa (arrow

mark: identified Laves phase)
structure in the high tungsten bearing steel was suppressed by continuous

and wide formation of Laves phase and M23C6 carbides, thereby giving higher
creep strength.
Another important factor in alloy chemistry of TOS203 bucket steel is the
addition of rhenium. As shown in Fig. 9, rhenium does not only act as a solid
solution element, but also has an effect to maintain the sufficient amount of
solute tungsten in the matrix during creep or thermal ageing. Thus it was
presumed that the amount of solute tungsten in rhenium bearing steel was
about twice as much as rhenium free steel at the same creep time, by which
the additional solid solution strengthening effect was brought to increase
creep strength.
Bucket bars were manufactured by VSR (Vacuum ESR) process. The
application of VSR process was very useful to the production of clean and
homogeneous ingots.
3~---------------------------------------
10.5%Cr-2.6%W-V-Nb-N-Co-B Steel
<> : Steel containing

0.2-0.8 mass% Re
o :Re free steel
O~----~~~~--~~~--~~~~~~~~
As-tempered
Creep I Aging time (h)
Fig. 9 Change of amount of solute tungsten in creep and ageing
HIGH TEMPERATURE CASTINGS
The application of traditional cast steels such as 1.25%CrMo V and 2.2S%Cr-

Mo steels to advanced steam turbines must increase the wall thickness of
castings. Particularly the resultant thermal stress during cyclic operation
would become severer to the thicker walls. To prevent such disadvantages,
12% Cr heat resistant cast steel (T05301) was used for VHP-HP turbine casing
et ale of Kawagoe #1. Based on such experience and the concept of improve-
ment of rotor steels, the alloy chemistry of T05302 and T05303 cast steels
were modified as shown in Table 3(c), in which weldability as well as heat
resistance were taken into consideration. On the other hand, there were some
specific requirements for castings, such as gas cutting of riser, gouging of
padding, repair weld and welding with pipes. Extensive tests were conducted
to establish such thermal handling, welding techniques and to evaluate the
properties of welded joints. Completing the final verification through the
manufacture of product-size castings and welding with pipes, T05302 and
T05303 castings with sufficient heat resistance to the application at 600 and
630°C are coming into practical use as shown in Table 2.
SUMMARY AND ACKNOWLEDGEMENT
The current status of our advanced ferritic steels has been described here. It is
expected that the use of such steels would result in significantly improved
efficiency of advanced steam turbines due to higher operating temperature of
630°C or above. During the next decade, a greater effort should be made still
on material development aiming at 650°C. Finally the authors would like to
express our gratitude to all those who supported the R&D efforts and the
application of advanced steels in utilities, R&D institutes and steel makers.
REFERENCES
1. EPR! CS-2223, Project 1403-1, Final Report, Jan. 1982.

2. EPR! CS-2555, Project 1403-2, Final Report, Aug. 1982.
3. T. Suzuki: Proc. of EPRI Heat Rate Improvement Conference, Charlotte, NC,
EPR! CS-2180, Dec. 1981.
4. K. Miyashita: IMechE Conference Transactions 1997-2, Advanced Steam
Plants, C522/029, 1997, 17.
5. F. Ito, K. Kuwabara and M. Miyazaki et al.: 86-JPGC-Pwr-3, Oct. 1986.
6. G. P. Wozney, M. Akiba, G. L. Touchton, R. I. Jaffee and S. J. Woodcock:
APC, 1986.
7. M. Miyazaki and O. Watanabe: IMechE 1990, C386/003, 1990, 75.
8. T. Fujita: Metal Progress, 1986, 130 (2), 33.
9. T. Fujita: Proc. of 3rd International Charles Parsons Turbine Conference, 1995,
493.
10. Y. Tsuda, M. Yamada, R. Ishii, Y. Tanaka, T. Azuma and Y. Ikeda: Proc. of
13th Forgemasters Meeting, Vol. 1, 1997, 417.
11. R. Ishii, Y. Tsuda and M. Yamada: 'ASTM STP1259', Steel Forgings Vol. 2,
1997, 317.
Development of a High-Strength
Martensitic CrNiMo VNb Steel with
10.5% Cr and 0.11% C (OPTIMAR Type)
M. SCHIRRA and K. EHRLICH
Forschungszentrum Karlsruhe, Institut flir Materialforschung I, D-76021
Karlsruhe, Germany
INTRODUCTION
Worldwide efforts to develop steels for use at temperatures exceeding 600°C

have focussed on advanced 9-120/0 Cr steels. This is considered an inter-
mediate step on the way to achieving a 105 hi 600°C creep strength of
~100 MPa or better than the well-known austenitic stainless steel AISI 304.1-3
The development of the T91/P91 originally began at the Oak Ridge
National Labs (ORNL) and resulted in the T91/P91 (9% Cr-modified) steel
which has become well known in the meantime as a result of supplementary
European and Japanese work. With respect to creep rupture strength up to
600°C, it barely meets the original requirements of Rm10~/600°~ 100 MPa and
better than AISI 304, respectively. Its relatively low chromium content of 9%
has raised some doubt about its corrosion resistance in long-term use at and
above 600°C.4,S
Parallel developmental work carried out at FZK/IMF (Fig. 1) within the
framework of various projects among others led to a CrNiMoVNb steel with
10.50/0 Cr and 0.11 C labeled OPTIMAR. This material has a high creep
strength up to 650°C and good impact bending strength.v? The steel composi-
tion was based on findings relating to Nb effects in stabilisation, the
appropriate NI Al and N/C relation as well as the B-Ferrite and 02-influence
on mechanical properties developed during the development of 9-12% Cr
steels.
TEST MATERIAL
SAARSCHMIEDE- Volklingen produced four experimental heats as 25 kg

batches by the SV-3 process, i.e. melting in a vacuum induction furnace and
forging the ingot to bars of 25 mm X 25 mm cross section. The chemical
composition is provided in Table 1. The C998 and 699 batches are parallel
586
HIGH-STRENGTHMARTENSITICCRNIMoVNB STEEL 587
Development work of 9-12% Cr-steels at

Forschungszentrum Karlsruhe
Institut fur Materialforschung I
Starting point I X22CrMoV 12

( 1.4922/23)
'1 Nb-free
lli.Q.! i
Optimization of higher
I )('8C,MoVNb 12 ,]
··
fracture toughness (1.4914)
Nb-stabilization
·
N-, C-reduction
Fast-Breeder Technology
Technology for
1
coldforming
lliP..!!
Balance between
toughness and creep-
fracture
I X11CrMoVNb 1111 ~ (
(MANET)
OPTIMAR
(1.4914-X1)
···
strength
N/C-variations
Fusion Technology Conventional
N/AI-relation Technology
1
6-ferrite influence (Cr)
Step'"
Optimization of low-
activation
variants
and high purity
for the fusion I OPT/FER
I
·
technology
Substitution of Nb,
Mo, Ni byTa, W, Ge
·
etc.
low concentration of
tramp elements: Ag,
Tb, Ho, Eu etc.
Fig. 1 Development program
batches with the same analytical results. Batch 700 has a low cerium content,
while batch 701 contains 0.87% tungsten. Compared to the specification of
T91/P91 steel, first of all the higher chromium content of 10.5% must be
mentioned which, in our opinion, is required to ensure higher oxidation
resistance under long-term stress at T ~ 550°C. The slightly higher Mn fraction
eliminates sulphur so that the difference between longitudinal and transverse
specimens is clearly reduced in notched bar impact tests. It also counteracts
the formation of 8-ferrite. The higher Nb content ensures fine grains.
TEST RESULTS
Quenching and Annealing Tests

Hardening experiments in the temperature range of 850-112SoC indicated
that maximum hardness is achieved between 1000 and 1125°C with grain
Table 1 Chemical composition [w.%]
OPTIMAR (1.4914-Xl)
heat T91/P91
C998 699 700 701 specifica tion
C 0.11 0.11 0.10 0.12 0.08-0.12

Si 0.31 0.31 0.38 0.37 0.20-0.50
Mn 1.10 1.22 1.19 1.16 0.30-0.60
P 0.002 0.004 0.004 0.004 max. 0.02
S 0.003 0.003 0.003 0.004 max. 0.01
Cr 10.5 10.5 10.65 10.75 8-9.5
Ni 0.66 0.60 0.58 0.58 max. 0.40
Mo 0.60 0.63 0.64 0.62 0.85-1.05
V 0.22 0.21 0.21 0.21 0.18-0.25
Nb 0.21 0.21 0.21 0.22 0.06-0.10
B 0.0076 0.0072 0.0081 0.007
Co 0.005 0.003 0.005 0.005
Ce 0.06
W 0.87
N 0.034 0.033 0.036 0.027 0.030-0.070
Al 0.015 0.014 0.016 0.015 max. 0.04
02 0.0036 0.0161 0.0170 0.0135
8.5-9 7.5 8 7.5 Grain size ASTM
, .,
sizes between 10 and 15 urn, i.e., the material is very fine grained. All heats are
free from delta ferrite and residual austenite. 1075°C was defined as the
reference hardening temperature, also on the basis of experience from earlier
work."
Annealing experiments after hardening at 1075°C resulted in the reference
annealing temperature being fixed at 700°C. As an option for optimum
toughness properties, also 730°C could be used, which would show a
sufficient margin to the Ac-, temperature (onset of (X-"Y transformation) of
760-770°C.
Transformation Behaviour
For heats C998 and 701, one CCT diagram (continuous cooling) each was
plotted with 1075°C as the austenitising temperature. Figures 2a-c shows
them compared with the CCT diagram of T91jP91 steel for the austenitising
temperatures of 1030-1050°C. This comparison shows, first of all, that the
OPTIMAR variant without tungsten (heat C998) is clearly less active in
transformation, and pearlite formation does not begin until a cooling rate of
HIGH-STRENGTH MARTENSITIC CRNIMoVNB STEEL 589
AC1e
(O.I.O/min)
AC1b
C1J
~ 500
o
:ua. LOO
E
C1J
I-
Hardness
a.=-l...J....L..J.---L.---1-~----L----L...Jw..l.--L--W....l...!---L--L.t::C1.....-L-LLJ.J HV
sec.-10 103 104 105 106
1 min. 30 1 hours 10 1 days 10
(a)
sec.-10
1 min. 1 hours 10 1 days 10
(b)
AC1e
(O.4°/min)
AC1b
~
:;
C1J
~a.
E
C1J
I-
Hardness
.~~~~~~~~~~~~~-ll~~~~HV
sec.-10 103 106
1 min. 30 1 hours 10 1 days 10
(c)
Fig. 2a-c CCT-diagrams (continuous cooling)"

0.5°/min has been reached. For cooling in air, this corresponds to a full-
martensitic transformation up to dimensions of 1600 mm dia., as against only
220mm dia. (= SO/min) for T91/P91. The OPTIMAR variant with 0.87% of
tungsten exhibits a transformation behavior in the pearlite stage which is
delayed even further.
This clear difference in transformation behavior between OPTlMAR and
T91/P91 is due not only to the difference in one single alloying constituent
(e.g. chromium), but to the entire chemical composition."
Tensile Tests
Tensile tests were carried out in the temperature range RT up to 700°C on
specimens with 1075°C hardening temperature and annealing temperatures
of 600-750°C. By way of example, Figs 3a + b shows the 0.2% yield strength
and tensile strength levels for the OPTIMAR variant without tungsten.
Evidently, the decrease of both parameters is moderate in the annealing
temperature range of 600-700°C. Only an annealing temperature of 750°C
causes both parameters to decrease more strongly. The OPTIMAR versions
200
RPQ,2
N/mm2
1ZOO---
1.00
Fig. 3a Yield strength RpO,2 vs. annealing - and test temperature (OPTIMAR
1075°30'/ air, Heat: e998 + 699)
Fig. 3b Ultimate tensile strength Rm vs. annealing - and test temperature

(OPTIMAR 1075°30'/ air, Heat: e998 + 699)
containing cerium and tungsten (heats 700 + 701), respectively, attain the
same strength levels. The three OPTIMAR versions also achieve almost
identical levels of ductility parameters. Over the range of test temperatures,
RT, up to 700°C, the levels of total elongation (A) are 8 and 15 those of
%
,
uniform elongation (Ag), are between 6 and 1 and of area reduction (Z),
%
,
between 63 and 86%.
Creep and Creep-rupture Tests

The creep rupture tests conducted on the OPTIMAR versions were carried out
in the temperature range of 550-700°C with, at present, some 20000 hours of
maximum test time. All experiments were run in single-specimen test units
with continuous elongation measurement, thus always resulting in a com-
plete creep curve, from which the technically important yield limits (e.g.
500.-r-r-------r-------~------~------~------~----~
4 OPTIMAR 1075°30'/air
+ 700 2h/air 0
&
~
-100~--------
(/)
------
~ 8
L-
V; 6
700 A +Ce
701- +W
4
30~~~~~~~~~~~~~~~~W-~~~ll-~~-L-L~~~
24 25 26 27 28
P=TK.(25+log tr) 10-3
Fig. 4 Master curve (Larson-Miller parameter)
0.1-100/0) can also be determined. Temperature measurements and controls

are conducted by means of 3Pt/Rh-Pt thermocouples.
The creep rupture levels so far attained for the reference condition are
shown in Fig. 4 as a function of the test stress in a master curve. The time to
rupture and the test temperature in this case are combined as a parameter of
the form, P = c + log tr (according to Larson-Miller). Within a limited
framework, this plot allows an estimate to be made to times to rupture not yet
attained experimentally. For comparison, a hatched creep-rupture strength
scatterband is indicated for T91/P91 steel resulting from experiments con-
ducted by various authors in the temperature range 538-650°C.4, 5, 9, 10
The experimental levels of test temperatures, 550-650°C, obtained in
tungsten-free heats are clearly above the band for T91/P91 up to P == 25;
above that level, they are close to its upper bound. The variants additionally
alloyed with cerium and tungsten, respectively, produced levels even slightly
better. Only the specimens tested at 700°C showed a clear decrease of creep-
rupture strength, with levels in the range of the P91/T91 values.
The ductility parameters, ultimate elongation, Au, and area reduction, Zu,
are largely independent of the time to rupture, and lie between 12-25% and
60-85%, respectively, for 550-650°C test temperatures.
The notch impact toughness behaviour of OPTIMAR steel is excellent as a
consequence of its fine grain. However, there are clear differences in the heats
studied which are due to the different oxygen contents (Fig. 5). Heat e998,
with 02 = 36 ppm, has clearly better Av and FATT values than are shown by
the other heats with O2 contents > 100 ppm. This adverse influence was
observed also in another group of martensitic steel grades containing 8-12%
Cr.11
200
180 __ - --0
160
~120
~
Q)
C:::l00
C!J
\)
~80
Q
V)
~60
1.0
ISO - V-specimen
20
FATT:
DC998 -15°C
• 699 ll.°C
• 700 33°C
& 701 25°C
~ 60
'0 1.0
fit
C!J
.s 20
~
.~
C°L-:l:-~-:-I:.--1--~~~~----J....~---'--.....L...---'--..,..L- ..L.-~--'-~
100 120
Fig. 5 Fracture toughness diagram
Metallurgical Aspects
Some metallurgical aspects are particularly important for the further develop-
ment of martensitic 12% Cr steel grades.
• (The N / Al concentration must be stoichiometrically positive, in accord-
ance with recommendation CN - 100 ~ 0.52 CAl. This prevents the so-
called s-slope in the creep rupture strength curve, frequently observed as
a conseq~ence of coarsening of M23C6 carbides, and favours boride
formation. 12, 13
• For carbonitride formation and fine grain production, the niobium
fraction should not be below 0.150/0.Niobium stabilisation also improves
the ageing characteristics.v 14, 15
• Carbon can be substituted by nitrogen within a narrow boundary, the
impact of this substitution on creep rupture strength or tensile strength
being different at room temperature and at DBTT (ductile-brittle transi-

tion temperature) with respect to notch impact toughness. Reducing the
C content from 0.2% to 0.1% and raising the N content from 0.025% to
0.125% (1:1 ratio) resulted in the same creep rupture strength data.
Identical tensile strengths at room temperature and identical ductile-
brittle transition temperatures (DBTT) in the notch impact test require
substitution in the relationship of 3N = 1C.6,16
• The composition must be harmonized in such a way that the material is
free from 8-ferrite so as to avoid negative impacts on the mechanical
properties. 17-23
• The chromium content should not undergo 10% so as to ensure sufficient
oxidation stability.24,25
CONCLUSIONS
The CrNiMoVNb type of steel referred to as OPTIMAR is a full-martensitic

10.5% Cr steel whose creep rupture strength levels are clearly above those of
P91/T91 steel. These properties are combined with good toughness character-
istics due to the fine-grained structure (FATT: -15°C). Optimised chemical
composition results in high structural stability and extremely delayed trans-
formation into the pearlite stage under continuous cooling (beginning at
0.5°/min). For cooling in air, this means all-martensitic hardening through to
a dia. of 1600 mm. Moreover, the structure is free from 8-ferrite, and a
chromium content of 10-11% ensures good oxidation stability.
REFERENCES
1. P. Patriarca, E. E. Hofman and G. W. Cunningham: ASME-Sect. I + III, April

1982.
2. R. Blum, J. Hald, W. Bendick, A. Rosselet and J. C Vaillant: VGB-
Kraftwerkstechnik, 1994, 74 (8), 641-652.
3. K. Solbeck: Stahl und Eisen, 1994, 114 (10), 49-57.
4. ECSC-Info-Day, 5.11.92 Dusseldorf, Proceedings volume.
5. F. BrUhl, K. Haarmann, G. Kalwa, H. Weber and M. Zschau: VGB-
Kraftwerkstechnik, 1989, 69 (12), 1214-1231.
6. K. Ehrlich and M. Schirra: 6.11.92-Dusseldorf-VDEh, Proceedings volume.
7. K. Ehrlich: http: hbksun17.fzk.de:8080/imf/stahl.jpg
8. M. Schirra and H. Finkler: FZKA-report 5607, Sept. 1995.
9. H. Finkler and K. David: priv. com.
10. V. K. Sikka, C. T. Ward and K. C. Thomas: Proc. ASM-Conf, Warren-Pens.,
Oct. 1987.
11. H. J. Bargel and G. Schulze: VDI-Verlag Dusseldorf, 1988 and unpublished
results.
12. M. Schirra and K. Anderko: steel research, 1990, 6, 242-252.

13. E. Materna-Morris, M. Schirra, 19.11.91 Diisseldorf-VDEh, Proc. volume
and Praktische Metallografie, Sonderband 25, 1994.
14. K. J. Irvine, D. J. Crowe and F. B. Pickering: Journ. of 151, Aug. 1960,
386-405.
15. T. Fujita and N. Takahashi: Trans. ISIS, 1978, 18, 269-278.
16. B. Anthamatten: Dissertation ETH Zurich, Nr. 9047, 1990.
17. M. Schirra: KfK-report 5080 Feb. 1994.
J
18. W. Wessling: Journal Sie und Wir, Siegen, 1976, 17, 4-14.
19. A. K. Khare: Proc. of ASM-Conf., Warren, Pens., Oct. 1981.
20. E. Materna-Morris: Scanning Micr., 1990, 4 (2), 287-296.
21. K. Anderko, L. Schafer and E. Materna-Morris: Journ. of Nucl. Mat., 1991,
179/181, 492-495.
22. M. Schirra: Stahl und Eisen, 1992, 112 (10), 117-120.
23. J. Bald: steel research, 1996, 67 (9), 369-374.
24. T. Fujita, K. Assakura and H. Miyake: Trans. ISIS, 1982, 22, 13-21.
25. K. J. Irvine and F. B. Pickering: lSI-Spec. Rep. 86, MG-Conf., 12/64.
Creep Modeling and Strengthening
Mechanism of Tungsten Alloyed 9-12%
Cr Steels for Power Applications
KYU SEOP PARK*, FUJIMITSU MASUYAMAt and
TAKAOENDO§
* Graduate Student, Yokohama National University
t Nagasaki Research and Development Center, Mitsubishi Heavy Industries,
Ltd., 5-717-1, Fukahori-machi, Nagasaki 851-0392, Japan
§ Faculty of Engineering, Yokohama National University, 79-5, Tokiwadai,
Hodogaya-ku, Yokohama 240-8501, Japan
ABSTRACT
Recently, high strength, tungsten (W) alloyed steels have been developed for use in
power plants with higher steam conditions resulting in improved thermal efficiency,
lower fuel costs, and lower emissions.
In order to establish a creep modeling of high strength martensitic steel and to .
understand the basic role of W in tungsten alloyed 9-12Cr steels, the conventional
martensitic steels (X20CrMoV121,X20CrMoWV121 and Mod.9Cr-1Mo) and tung-
sten alloyed steels (NF616 and HCM12A) were subjected to creep tests and the data
were analysed by the n method.' The proposed creep model, which takes into
account both primary and tertiary creep, satisfactorily described the creep curves
and accurately predicted creep life, as martensitic steel undergoes a relatively large
amount of primary creep of up to approximately 300/0over normal life. The tungsten
alloyed steels exhibited a smaller minimum creep rate and a larger stress exponent
compared with the conventional steels. Also, in tungsten alloyed steel the n value
features strong stress dependence such that creep life is prolonged at lower stresses
due to high n values. The importance of the n value from the standpoint of creep
strengthening in primary and tertiary creep is discussed.
INTRODUCTION
Recent years have seen increasing social demands for energy saving and
environmental protection by further raising the efficiency of power plants,
leading to increasing temperature and pressure in terms of steam conditions.
Accordingly, efforts aimed at the development of heat-resistant steels have
been taken up in various countries. Such newly developed heat-resistant steels
have shown high creep strengths by adding small amounts of Wand reducing
the Mo content in the basic compositions of conventional 9-12Cr steels. How-
ever, the creep strengthening mechanism due to the addition of W remains
596
TUNGSTEN ALLOYED CR STEELS FOR POWER ApPLICATIONS 597
unclear and various studies are currently being made with regard to this. The
objectives of the work presented here are to formulate the creep behaviour of
recently developed martensitic heat-resistant steels using certain parameters in
order to clarify the correlations between those parameters and creep life and
creep rate. Also work has been conducted to clarify which parameters are
influenced by W by comparing creep behaviour between tungsten alloyed
steels and tungsten-free steels in order to investigate tungsten strengthening.
MATERIALS AND EXPERIMENTAL PROCEDURES
Test materials were Mod.9Cr-1Mo(T91, 9CrlMoVNb), X20CrMoV121(12Cr-

1MoV), X20CrMoWV121(12Cr-lMo-0.5WV), NF616(T92, 9Cr-0.4Mo-
1.8WVNb) and HCM12A(T122, 12Cr-0.4Mo-2WCuVNb), all consisting of
single phase tempered martensite. Their chemical compositions are listed in
Table 1.
Table 1 Chemical composition of steels tested (mass % )
Mod.9Cr-lMo NF616 X20CrMoV121 X20CrMoWV121 HCM12A
C 0.10 0.10 0.23 0.22 0.12

Si 0.25 0.04 0.42 0.37 0.04
Mn 0.40 0.46 0.62 0.62 0.63
P 0.016 0.008 0.016 0.015 0.013
S 0.005 0.001 0.004 0.005 0.001
Ni 0.04 0.72 0.73 0.28
Cu 0.90
Cr 8.39 8.96 11.30 11.15 10.75
Mo 0.90 0.47 0.80 0.88 0.39
W 1.84 0.46 1.92
V 0.20 0.20 0.22 0.24 0.21
Nb 0.07 0.068 0.04
N 0.042 0.051 0.062
The creep test specimens had a diameter of 6 mm and a gauge length of

30 mm. The test temperature was 873 to 923 K, using the constant load creep
test and the initial stress of 107.9 to 235.3 MPa.
CREEP MODELING OF MARTENSITIC STEELS
Figure 1 schematically illustrates the relationship between the logarithmic

strain rate and the true strain. The dotted line shows this relationship, which
is the foundation for the n. method." and can be expressed by the following
equation:
e*
eo~~ ~ __ ~
fr(tr)
Creep strain, E
Fig. 1 Schematic illustration of logarithm of creep rate plotted against creep strain
InE E = In Eo + fie (1)

Where Eo is the imaginary initial strain rate in a tertiary creep model with n or
a gradient of eqn (1). When the primary creep region is small, Eo is very close
to the minimum creep rate (Em), but in tempered martensitic steel Em differs
widely from Eo because the change of strain rate during primary creep is large
and, in addition, the strain prior to reaching the minimum creep rate is also
great.
Figure 2 shows the relationship between the strain rate and the true strain
-
.!.
~
Q. 10-7
~ 873K
o
cro (MPa) n
10-8 • 196.1 56
• 176.5 57
• 166.7 68
6. 147.1 83
10-9
0 0.05 0.1
Creep strain
Fig. 2 Relationship between creep rate and creep strain at various stresses for
Mod.9Cr-lMo
in Mod.9Cr-1Mo at 873 K. From Fig. 2, it is seen that the value of n increases

with decreasing stress. Although the figure is omitted here, the value of n is
found to increase slightly with decreasing temperature. Meanwhile, the
imaginary initial strain rate increases with increasing stress and temperature,
and can be described by the following constitutive equation:
Eo = Aoaoo exp(-Qo/RT) (2)
where Ao is a constant, no is a stress exponent and Qo is apparent activation
energy. These values are, respectively, 1.08 X 108 s-I, 13.2 ± 0.2 and 751 ±
5KJ / mol. aD is the initial stress. The relationship between the value of Eo
normalised by temperature; i.e. Eo exp(Qo/RT) and the value of ao shown in
Fig. 3 confirms that Eocan be described by eqn (2).
Temp. (K)
\l 923
6 913
o 898
o 883
o 873
100 150 200

Stress (MPa)
Fig. 3 Temperature compensated Eo versus initial stress
Like the imaginary initial strain rate, the temperature and stress depend-
encies of n can be expressed by:
n = Anaonn exp(Qn/RT) (3)
where An is a constant, nu is the stress exponent of 0 and Qn is a value
indicating the temperature dependence of O. These values are, respectively,
0.15s-1, 1.46 ± 0.1 and 98 ± 3kJ/mol. Figure 4 which shows the relationship
between the vaue of n normalised by stress, i.e. n·aonn and the value of T:),
verifies the appropriateness of eqn (3) describing O.
When the duration of primary creep is short enough for substantial
description of the creep curve using eqn (I), the creep life can be expressed by
the following equation.l--
0.00108 0.00110
.1 0.00112
(K-1)
0.00114
Fig. 4 Effect of temperature on the magnitude of stress-compensated n value
103
en
~
CD
M
~
:m
Q.
CD
CD
a.. 102
(,)
"C
s
tU
:;
o
"iii
0
101
Measured creep life ex 3.6ks)

Fig. 5 Comparison of calculated creep life with measured creep life
tr = 1/(0 Eo) (4)
Figure 5 shows the relationship between the creep life calculated according
to eqn (4) and the measured creep life of Mod.9Cr-1Mo. Figure 5 shows that
the measured creep life is always shorter than the calculated creep life. This is
because the primary creep of this steel accounts for a large share of the total
TUNGSTEN ALLOYED Cn STEELS FOR POWER ApPLICATIONS 601
creep life. Primary creep must therefore be taken into account in order to
improve the accuracy of approximation.
In this study, the following equation for logarithmic creep was used for
formulation of primary creep.
E == (1/0*) In(O*Eo*t + 1) (5)
Where EO* is the initial strain rate and 0* is the gradient of the dotted line in
Fig. 1. Differentiation of both sides based on time fractions yields:
E ==In EO* - O*E (6)
Because relatively good correlations are seen between EO* and EO and between
n* and n as expressed by eqns (7) and (8), the contribution of primary creep
in the total creep life can be deemed a function of 0 and EO.
EO* = 0.138 EOO.725 (7)
!1*/n = An*;n·aonn*m·exp(Qn*/niRn (8)
where An*/n is temperature and stress independent constant, nsr ni is the
stress exponent of 0* / 0, and Qn* /n is the temperature-dependent parameter
of n*/0,. They are, respectively, 2.82 X 103 s-l, 2.0 and 21 ± 2 kJ/mol.
Comparison of the measured life and the calculated life taking into account
the extent of primary creep is shown in Fig. 6 according to this method. From
Fig. 6, it is seen that creep life can be described by the two parameters 0 and
EO, even when primary creep is large.
103
en
JIll:
CD
M
~
:=e,
Q)
102
'Q)
!
u
"C
.!
co
"S
u
as
0
101
Measured creep life (x 3.6kS)
Fig. 6 Comparison of calculated creep life with measured creep life

CREEP BEHAVIOUR OF TUNGSTEN ALLOYED STEELS
As discussed above, n
and the imaginary initial strain rate are important
parameters in describing the characteristics of not only tertiary creep but also
primary creep, and extension of the strain region in tertiary creep is desirable
for accurate determination of the imaginary initial strain rate. This is because
even a small amount of error in the n.. value can greatly affect Eo when the
value of n.. is relatively large. It was therefore decided to measure minimum
creep rates, which are relatively easier to measure than Eo values, and then
compare minimum creep rates with the values of n.. in various steels in order
to investigate the creep behaviour of tungsten alloyed steels.
Figure 7 compares the minimum creep rate of Mod.9Cr-1Mo with that of
10-5 Mod.9Cr-1 Mo
o 923K 11.4
0 913K 11.7
.!.
o 898K 12.9 /
/
s
~
10-6 6 883K 14.2
\l 873K 14.3 -I-
Co /
~
M
(J
10-7
f
/
E
:s /
E
'E
~ /
f
10-8 /
/
10-9
70 80 90100 200 300
Stress (MPa)
Fig. 7 Relationship between minimum creep rate and initial stress
NF616. Figure 7 shows three characteristic trends, i.e., (a) in both steels the
stress exponent tends to increase with decreasing temperature, (b) compari-
son at the same stress and temperature shows that the minimum creep rate of
NF616 is more than one order smaller than that of Mod.9Cr-1Mo, and (c) the
stress exponent is slightly larger with NF616.
Figure 8 shows the stress dependence of the minimum creep rate in
X20CrMoV121, X20CrMoWV121 and HCM12A. From Fig. 8, it can be
observed that the minimum creep rate for X20CrMoV121 is not greatly
different from that of X20CrMoWV121. The feature in Fig. 8 is that the stress
exponent of the minimum creep rate of HCM12A within the measured stress
range is larger than those of the former two, leading to a marked difference in
X20CrMoV121
10-4 • 923K 8.0
X 898K 10.0
+ 873K 9.4
~
.! X20CrMoWV121
e0. 10-6
<> 923K 7.9
/
o 898K 9.0 /
~o o 873K 8.6 ~
~
E
:s
E j. /
'c /
~ 10-8 /
HCM12A
~ 923K 15.2
.• 873K 18.0
1
10- °80 90 100 200 300
Stress (M Pal
Fig. 8 Relationship between minimum creep rate and initial stress
the creep rate in the low stress region. Clear stress dependence of n was
observed in Mod.9Cr-1Mo, NF616 and HCM12A. Stress dependencies of n in
those steels are shown in Fig. 9. As seen from Fig. 9, the stress dependence of
n is high in steels containing much W, suggesting that increases in the low n
stress region. Because n for heat-resistant steels containing much W depends
100
90
80 .•
.•
.•,
.•.. -,
50 '«
40 Mod.9Cr-1 Mo 0" \
c <> 923K -1.43

• 873K -1.49
30
NF616
0 923K -2.94
20
• 873K -3.07
HCM12A
~ 923K -2.09
• 837K -2.13
10
60 70 80 90100 200 300
Stress (MPal
Fig. 9 Relationship between n and initial stress

on stress more strongly than n for Mod.9Cr-1Mo not containing W, n for

tungsten alloyed steels becomes greater than that of Mod.9Cr-1Mo without
W content at all temperatures in the low stress region. When creep life is
considered, based on eqn (4), the correlation between n and Eo must also be
considered, since Eo decreases with an increasing value of n as illustrated in
Fig. 1. The relationship between the value of 0 and Eo is further discussed
below.
Since Eo and n are functions of the initial stress and temperature as shown
by eqns (2) and (3), elimination of (To from the two equations would yield the
following:
Eo = AoAn(no/nn)O-(no/nn)exp[-{Qo - (no/nn)Qn}/Rl1 (9)
Equation (9) shows that Eo decreases with increasing ll. From eqn (9), it is
found that the value of (Eo· n) is proportional to n{1-(no/nn)}. If the creep life tr
is given by eqn (4), it is found that the creep life is proportional to n{(no/l1n)-l}.
Because no = 13 and na = 1.45 if Mod.9Cr-1Mo is cited as an example, the
creep life is proportional to the eighth power of o.
Change of creep strain over time can be expressed by integrating eqn (1):
E = (1/0) In[l/(l - OEot)] (10)

Because the value of Eo is represented by 0, creep strain at time t can also be
expressed using 0, and it is found that strain time t becomes smaller with
increasing O.
As can be understood from the foregoing discussion, 0 is a structural factor
governing the creep rate, the creep life, and the profiles of primary and
tertiary creep curves. As noted above, the relevant feature of tungsten alloyed
steels is that both 0 and the stress dependence of 0 are large, and the time to
creep rupture is therefore long.
CREEP STRENGTHENING IN TUNGSTEN ALLOYED STEELS
The characteristic of the creep curve in tempered martensite steels is that the
time period of primary creep is long. Because primary creep is characterised
by a decrease in the rate of strain, it can be deemed a work hardening or a
decreasing process of moving dislocation density. If the former presumption
is corrent, the internal stress would increase along with strain during creep. If
the latter is correct, it is inferred that the cell structure of lath-martensite
introduced in the tempering process would rearrange, assisted by tem-
perature and stress, leading to a coarsening of the lath-martensitic structure.
In fact, coarsening of the lath-martensitic structure has been confirmed in
creep-interrupted testing of tungsten alloyed steels.' If the primary creep
region can be described by the logarithmic creep, then, the logarithmic creep
can be understood as a decrease in moving dislocation density." It must
TUNGSTENALLOYEDCR STEELSFORPOWERApPLICATIONS 605
therefore be clarified whether the change of strain rate during primary creep
is caused by change moving dislocation density or by change in the internal
stress accompanied by strain, i.e., decrease in dislocation velocity. It must also
be determined how the addition of W influences such changes.
In single phase materials, the constitutive equation of the steady-state creep
rate takes a form similar to eqn (2), but, in general, the stress exponents of
heat-resistant steels are markedly greater than the stress exponent (less than
5) of single phase materials. For example, the stress exponent of the minimum
creep rate of 2.25Cr-lMo steel changes slightly according to temperature and
stress, whereas the stress exponent of the imaginary initial strain rate is
independent of temperature and stress and is about 9.7 ± 0.2.5 The stress
exponents of the materials tested in this work were also high, and the stress
exponents of steels containing much W tended to be higher than those of
steels without W. Also, the stress exponents of X20CrMoV121 and
X20CrMoWV121 are lower than those of the other steels, and this may be
related to the fact that these steels alone contain a relatively high level of
carbon without containing Nb, In other words, there is a possibility that, in
the case of these steels, M23C6and V4C3 carbides are relatively coarse, not
contributing to an increase in internal stress like an MX precipitate.
The stress exponent and internal stress of 9Cr-3W -3Co steel without
precipitates were recently measured at 923 K to 1023K.6The results show that
the stress exponent is n = 27 at 923 K, n = 16 at 973 K and n = 10 at 1023K,
and that the internal stress is about 95% of the applied stress. It has been
reported that internal stress decreases with increasing strain as well as with
rearrangement of the lath-martensitic structure, whereas the effective stress is
nearly constant over the entire strain." Although it was conventionally
inferred that the high stress exponent of heat-resistant steels is due to the
presence of precipitates, it is noteworthy that in steels containing much W,
even without the aforementioned precipitates, creep progresses while main-
taining a high internal stress.
When the internal stress within flow stress is high, the relationship between
the apparent stress exponent (n) and the stress exponent (m*)of the moving
dislocation is as follows:
aInpm) (alnu*)
n-
- ( --aInu r +m*-- oln« r
(11)
where Pm is the moving dislocation density and o" is the effective stress within
flow stress.
Many heat-resistant steels contain high levels of chromium, and the
chromium atom does not contribute to dragging stress because of the small
difference in the atomic diameter between the solute Cr atom and the Fe atom
in the matrix. However, because chemical interaction between the Cr atom
and interstitial atoms such as carbon and nitrogen is strong, and the Cr atom
is likely to form a cluster, dislocation may be moving while dragging this
cluster. Also, because the difference in atomic diameter is large between Mo

and W solute atoms and the Fe atom, it is inferred that dislocation may be
dragging the solute atmosphere of Mo and W atoms, and hence m* is deemed
to be 1. Because the first term of the right side in eqn (11) is about 2, the value
of (aIna* / aIna) is about 5 to 18. Because it is now known that the stress
exponent of tungsten alloyed steel containing no precipitates is high, the
reason for the large value of (aIna* / aIna) requires additional investigation in
a further study of the solution strengthening due to Wand the effects of W on
the rearrangement process of tempered martensitic structure. Also, because
the stress dependence of n is large in tungsten alloyed steels, it is inferred that
a increases in the low stress region, extending the time before it reaches Eo,
i.e., the primary creep time. In contrast, when stress increases, n tends to
decrease, and it is thus inferred that, even if a rise in local stress has occurred
due to reduction of the cross section or by local softening recovery in the
tertiary creep region, the increase in the strain rate would be too small to
produce strain, which means that strain softening is inhibited since a
becomes smaller.
Figure 10 compares the creep rupture strengths of test materials used for
300
200
(i
e,
~
fn 100
fn
~ 90
en 80
70
60 6. Mod.9Cr-1 Mo
A NF616
50 0 X20CrMoV121
40 • X20CrMoWV121
0 HCM12A
30
30 31 32 33 34 35 37
T(35+log t) x 10-3
Fig. 10 Comparison of creep rupture strength of steels tested
this study, and the following can be said when this figure is observed, based
on the foregoing discussion. Although no difference in the stress exponent of
the minimum creep rate was observed between X20CrMoV121 and
X20CrMoWV121, the creep rupture strength rises slightly due to the addition
of O.s%W, and this increment is nearly equal over the entire range of the
Larson-Miller Parameter. It is therefore inferred that although the creep
behaviour per se in this case shows no large difference, a rise in strength

corresponding to a rise in modulus due to the addition of W was observed.
Meanwhile, in Mod.9Cr-1Mo, free from W but having MX precipitate, the
time to rupture is extended longer on the low stress side, whereas in NF616
and HCM12A containing large amounts of Wand also having MX precipitate,
the time to creep rupture is further extended on the low stress side, increasing
the creep strength. This tendency agrees well with the small minimum creep
rate, the large stress exponent, and the degree of stress dependence of 0.
CONCLUSIONS
In this work, creep curves have been analysed using the n method to clarify
factors which govern the creep rate and the creep life of recently developed
high-strength, heat-resistant, martensitic steels. The parameters that are
influenced by W as an alloying element have been identified. The results
obtained are as follows:
High-strength heat-resistant steels having a martensitic structure show an
extended duration of the primary creep region, accounting for nearly 30% of
the total life. Therefore, the life predicted using creep modeling of the tertiary
creep region alone would extend beyond the measured results. Accordingly, a
method to describe the primary creep region using the same parameter has
been proposed in this paper. When such creep modeling taking into account
the primary creep region is used, it is clear that the predicted life agrees well
with the measured value.
When stress dependence of the minimum creep rate and n in tungsten
alloyed steels are checked, it has been found that the minimum creep rate is
markedly smaller than that of steels free from Wand the stress exponent is
large. It has also been found that stress dependence of n is large, showing a
marked increase of n in the low stress region, which can improve the creep
rupture life.
REFERENCES
I. M. Prager: Trans. ASME, J. Pressure Vessel Technology, 1995, 117, 95.

2. T. Endo and J. Shi: Strength of Materials, Oikawa, et a1., eds., Japan Inst.
Metals, 1994, 665.
3. N. Nishimura and F. Masuyama: Materials for Advanced Power Engineering,
Part I, Coutsouradis, et al., eds, Kluwer Academic Publishers, 1994, 351.
4. J. C. M. Li: Acta Met., 1963, 11, 1269.
5. J. Shi, K. Tai and T. Endo: Tetsu-to-Hagane, 1995, 81, 839.
6. F. Yoshida, H. Nakao and H. Nakashima: Abstracts of the 122 Meeting of
Japan Inst. Metals, 1998, 246.
Section 5:
WELDING
Behaviour of Advanced 9-12 Cr Steels
and its Weldments in Short and Long
Term Tests
H. CERJAK and E. LETOFSKY
Graz University of Technology, Kopernikusgasse 24, A8010 Graz, Austria
ABSTRACT
There are strong environmental and economic pressures to increase the thermal
efficiency of fossil fuel fired power stations, and this has led to a steady increase in
steam temperatures and pressures resulting in world wide plans for ultra super-
critical power plants. Basic investigations on the weldability of advanced 9-12%Cr
steels which are either currently in use or which are intended to fulfil this
requirement were performed on pipes of P91, NF616, E911, and a tungsten
containing cast steel G-X 12 CrMoWVNbN 10.1.1, (G-X12). Gleeble simulations
representing the manual metal arc welding process were applied to produce HAZ
simulated microstructures. After different post-weld heat treatments they were
tested using hardness tests, metallographic investigations, constant strain rate tests,
and creep tests. Particular attention was given to the softening effect in the HAZ and
its influence on the creep resistance of the welded material. This decrease shown by
simulated and manufacturing welded samples, seems to be less pronounced of the
tungsten modified versions than observed at P91 material.
INTRODUCTION
There is a substantial and growing interest in operating thermal power plants

at relatively high temperatures and/ or pressures for improving thermal
efficiency and reducing CO2 emissions. Materials with ferritic/martensitic
microstructures are preferred, because of their favourable physical properties,
such as good thermal conductivity and low coefficient of thermal expansion,
coupled with higher resistance to thermal shock.l-? These are some of their
advantages over austenitic stainless steels. For these reasons, there has been a
growing demand for high strength, high chromium ferritic steel, which has
resulted in the development and application of several kinds of 9 to 12%
chromium steels. The development of these materials as a function of the
100 000 h creep rupture strength at 600°C can be seen from Fig. 1.3 The main
steps in the development are different in various countries, such as in the
USA, the European nations and Japan. In Europe, particularly in Germany the
gap between the application range of the ferritic steel P22, German desig-
nation 10 CrMo 9.10, and the austenitic stainless steels regarding their creep
611
100000 h Creep Rupture Strength at 600°C
35MPa 60-80MPa 80-100 MPa 120-140 MPa

(Expected)
@1/4cr-IMo 1oo-i Mo-l WVNbN

G-X 12 CrMoWVNbN 10 1 1
9Cr-IMo 9Cr-IMo-1 WVNb

E911
,9Cr-lMoVNb 9Cr-0.5Mo-l.8WVNb
F9 NF616
12Cr-0.5Mo-l.8WVNbNi
-Mo TB12M
+W
r-------, +Cu
12Cr-IMo-l WVNb 12Cr-0.5Mo-2WVNbCu
X20CrMoV12 1 HCM12 HCM12A
Fig. 1 Development progress of 9-12%Cr creep resistant steels"
resistance was successfully bridged in the past by using the 12% chromium
steel X20 CrMoV 12.1.4 Since 1975 a new modified 90/0chromium steel has
been developed in the US under the leadership of ORNL and standardised i.e.
as P91 in ASTM A335, (German designation X10 CrMoVNb 9.1) in the early
1980s. These developments led to the application of tungsten containing
9-12% chromium steels, which showed higher creep resistance, compared to
the type P91. After extensive research, Nippon Steel Corporation developed a
9Cr-O,5Mo-1,8W-Nb-V - ferritic steel, designated NF616.5
Within the framework of the European COST 501 programme" a cast
version of a tungsten modified 100/oCr-steel for castings and a 9%Cr version
for pipes and forging, called E911, was designed to fulfil the increased
400
..-. r--
MPa
300
,1
55JoC
I - -- --.~ -:.:
-~ r:-
It_ -- -;-
600°C ...•.
200
.•t'---••
•..
....•.•....
~
i -..... r-......
r---....
<,
0 i"'--
-,
••...
I'--.r-...
e
~100 n
.•.•.•.•......•.•.•.
,...
00 80
""
r'\.
60
' ..
40 0+
- : parent material P91

30 - • ••••
o.0
: rupture in parent material
: rupture in HAZ
20 I I I I I I I
1()O 2 5 101 2 5 102 2 5 103 2 5 104 2 h 105
Time--.
Fig. 2 Creep rupture strength of parent material P91 and crossweld specimens?
BEHAVIOUR OF ADVANCED 9-12CR STEELS 613
demands on the creep strength for advanced design values for fossil fired
power plants.
For a successful service application and acceptance in practice, the welda-
bility and the long time behaviour of the newly developed materials is one of
the most important aspects. In Fig. 2 the creep rupture strengths of the parent
material P91 at different temperatures are compared to the creep rupture
strengths of crossweld specimens? It can be observed that the creep rupture
strength of crossweld samples is at higher temperature significantly lower
than that of the base material.
Materials Investigated
As for the material P91, the investigations for the study were performed on a
seamless pipe produced by the pilgermill rolling process, dimension 149 mm
o.d. and 20 mm wall thickness. Investigations for material NF616 were
performed on a hot extruded tube. The dimension are 54 mm in o.d. and
12mm wall thickness. The newly developed COST steel E911, heat no. 3
comes from Mannesmannrohren-Werken, Germany. The tests were realised
on a seamless pipe with 336 mm o.d. and 62 mm wall thickness. The
manufacturing weld was carried out by Austrian Energy & Environment, in
the framework of COST 501 Round III. As for the welding rod, MTS 911 stick
electrodes produced by Thyssen SchweifStechnik GmbH., were used. For the
casting material G-X12, the material investigated comes from the valve body
trail casting produced by Georg Fischer Schaffhausen, Switzerland. Table 1
shows the chemical composition of the materials investigated.
Table 1 Chemical composition in wt_% of materials investigated
Material C Si Mn Cr Ni Mo W V Nb N
P91 0.099 0.385 0.40 8.75 0.128 0.96 0.03 0.204 0.07 0.058
NF616 0.124 0.02 0.47 9.07 0.06 0.46 1.78 0.19 0.063 0.043
E 911 0.11 0.18 0.40 8.61 0.21 0.92 0.99 0.19 0.089 0.065
MTS 911 0.092 0.34 0.65 9.20 0.78 0.91 0.84 0.22 0.045 0.041
G-X12 0.12 0.29 0.62 10.5 0.93 0.99 0.99 0.22 0.08 0.048
Heat Affected Zone Simulation

The different microstructures appearing in the heat affected zone (HAZ) of
fusion welds show different properties, depending on their thermal history.f
The simulation of weld thermal cycles is a powerful method for investigation

of HAZ microstructures. Compared to the HAZ microstructure of real joints,
simulated microstructures can be produced in relatively large volumes. This
leads to a transparent variation of welding parameters and helps to reduce
scatter in testing results which is caused by inhomogeneities in real welded
microstructures. Effects of local gradients in microstructure, properties and
residual stresses are not taken into account when using the HAZ simulation
technique.
For simulation a Gleeble 1500 machine was used. The weld thermal cycles
which are needed as input for the simulation process were calculated from
Rosenthal's solution of Fourier's heat conduction equation in a simplified
version derived by Rykalin.? These equations allow the representation of the
weld thermal cycles by the cooling times between two temperatures (respec-
tively the cooling time between 800°C and 500°C - ts/s), the peak temperature
(Tp), the preheat temperature, and the plate thickness. For this investigation
the thermal cycles applied were selected to represent a manual shielded metal
arc welding process with heat input of 25.2 kJcm-1 and a preheat temperature
of 22SoC for the material P91, NF616 and G-X12. These conditions led to a
corresponding cooling time between 800°C and SOO°Cof 21.6 s, see Fig. 3. For
the material E911 a heat input of 9.Sk]em"! and a preheat temperature of 180°C
was applied. This condition led to a corresponding cooling time of 7.55 s.
1400
1200
1000
o
o
:;ar 800
Gj
Q)
a.
E
Q) 600
~
.x:
ct'J
Q)
a..
400
To =
t8/5 = 21,6 s _._ .. _--
2°:1 d = 30,0 mm
I
--
0 £5 10 15 20 25 30 35 4b 45 50
Time, s
Fig. 3 Thermal cycles calculated for various peak temperatures between 1300 e and 0
760°C. SE, heat input; To, preheat temperature; ts/s, cooling time between BOOoe
and SOO°C;d, wall thickness, (Ref. 10)
Investigations of HAZ Simulated and Welded Materials

Using real welds of P91, E911, and G-XI2, metallographic investigations,
hardness tests, and creep rupture tests were performed. The results of P91
investigation were presented in Ref. I, the results of cast steel investigation
were summarised in Ref. 6. Concerning Gleeble HAZ simulated samples from
P91, NF616, E911, and G-X12 special attention was given to the evaluation of
the soft zones in the HAZ by metallographic investigations, using light
microscopy and TEM, hardness tests, and constant strain rate tests. Addition-
ally, creep rupture tests were performed to investigate the creep strength
behaviour of the soft zone at the HAZ region.
Hardness
In hardness tests across a weld seam of material P91, it was noted that this
type of steel shows a tendency to form a soft zone in the fine grain HAZ after
post-weld heat treatment (PWHT) (Fig. 4). The hardness in the zones was
450
400 P91, 750°Cl2h

S -+- E911, 760°C/2h
>
::c: 350
~ 300
Q)
$::l
"0
~ 250
::c:
200
Base Material HAZ Weld Metal
150 +-------t----I-----t---~·-+__-______t_--~-_+__-_______t--___I
o 10 20 30 40
Distance, mm
Fig. 4 Hardness of weld seam in as welded condition and after various post-weld
heat treatments of P91 and E911, (Ref. 1)
found to be z20 HV(10 kg) lower than that of the unaffected base material. The
hardness profile across weld seam of E911 show a similar curve to that of P91
(Fig. 4). To define the zone in which maximum softening occurs, specimens
were subjected to HAZ simulation at different peak temperatures in the range
between 760 and 950°C according to Fig. 3. The hardness was tested in the as
welded, simulated, and in the simulated and tempered condition. The
tempering conditions after welding were 760°C/2h air cooled for P91,
740°C/4h for NF616, 760°C/2h for E911, and 730°C/12h for G-X12.
425-r-------------------
•.•••.• G-X 12CrMoWVNbN 10 11, simulated thermal cycle
400 __ G-X 12 CrMoWVNbN 10 1 I, simulated thermal cycle+730°c/12h
S 375 -+- P91, simulated thermal cycle
:> ! - P91, simulated thermal cycle+ 760°C12h

::r: 350: -0- E9 I I, simulated thermal cycle
~
~
~
325
300 j
+
275........
-+- E91 I, simulated thermal cycle+ 760°C/2h
-0- NF616,
NF616,
simulated
simulated
thermal cycle
thermal cycle+ 740°C/4h
250t bas~ material
225) : ~
200
175 t --~~----4--~~.------
750 800 850 900 950
Peak Temperature, °C
Fig. 5 Results of hardness measurements on specimens of P91, NF616, E911, and

G- X12 subjected to weld thermal cycle simulation treatments (softening behaviour
ofHAZ)
The results of the hardness tests performed on the weld simulated micro-
structures of the investigated materials are presented in Fig. 5 as a function of
the peak temperature for both the tempered and as welded conditions. The
hardness of the base materials tested is shown on the left side of Fig. 5. It is not
influenced by thermal cycles with peak temperatures up to about 850°C. The
beginning (XI v-trensformation as a function of heat cycles can be observed by
the increase of hardness in the as welded condition. After stress relieving, the
hardening effect disappears in the materials as can be observed from Fig. 5. In
the range of peak temperatures between 850 and 950°C in the materials, a
minimum hardness can be observed. The hardness here is about 10 HV(10 kg)
lower than the remaining values.
Constant Strain Rate Tests on HAZ Simulated Materials

Constant strain rate tests at 600°C using an constant strain rate of E = 10-5 S-1
were applied on specimens which have been subjected to HAZ simulation
and subsequent tempering to investigate the principal influence of the HAZ
softening effect on the creep resistance. This test method was first applied on
this type of steel in Ref. (11). The maximum stress gives no indication of the
creep resistance of the microstructures tested. The results of these tests,
performed at 600°C on microstructures produced by weld simulation with
different peak temperatures, are shown in Fig. 6. For the unaffected base
material P91 a maximum stress of 280MNm-2, for NF616 a stress of
320MNm-2, for E911 a stress of 290MNm-2, and for G-XI2 a stress of
260 MNm -2 was measured. For peak temperatures in the range of 850-950°C,
there is a significant decrease in the maximum stress, analogous with the
decrease in hardness. The minimum in the stress versus peak temperature
curve is for P91 at 250 MNm-2 and 920°C, for NF616 at 286 MNm-2 and
375~-~--~---------------------,
...•.• G-X 12CrMoWVNbN 101 1, simulatedthermalcycle+730°C/12h
-+- P 91, simulatedthermalcyc1e+760°C/2h
350
-0-
E911, simulatedthermalcycle+760°C/2h
NF616, simulatedthermalcycle+740°C/4h
c = 10 -5 S -1
en 325
T = 600°C
Vl
~
(/.)
300
S
§
.~
~ 275
250
242MPa
225 +------1---f---I-----+--L-----f---t---t---
750 800 850 900 950 1000
Peak Temperature, °C
Fig. 6 Results of constant strain rate tests on specimens of P91, NF616, E911, and
G-X12 subjected to weld thermal cycle simulation treatment followed by tempering
(HAZ-softening)
900°C, for E911 at 275 MNm-2 and 925°C, and for G-X12 at 240 MNm-2 and
875°C. The measured minimum of stress is about 10% lower than that
measured for the unaffected base material.
Creep Rupture Tests on HAZ Simulated Materials

Creep rupture tests on samples which were designed to represent material
containing microstructures caused by a peak temperature of 920°C (HAZ
simulated) were performed. The results are shown in Fig. 7 and are compared
with results obtained on creep samples made from uninfluenced base
material and welded joints. As can be seen from Fig. 7 the creep resistance of
plain HAZ simulated materials falls for all investigated materials at high
stress levels, significantly below the creep resistance of that of the unin-
fluenced base material and of welded joints. Comparing the behaviour of
HAZ simulated material P91 to HAZ simulated materials NF616, E911 and
G-X12 it can be seen that the softening effect in the tungsten modified material
on the creep behaviour, at high stress levels, is lower than that of material P91.
Creep tests performed on original welded and stress relieved samples of the
cast steel show similar behaviour. At high stress levels the creep resistance of
HAZ simulated samples lay below that of the base material. The creep
rupture strength of welded joints lay, as a result of the restraining effect in the
HAZ region, at the same level as that of the base material. At lower stress
levels HAZ simulated materials and welded joints shows the same creep
resistance.
, .... -.
;:
~_L • P 91, base material, 760°Cl2h, (600°C) .•. GX-12, weld joint, SMA W, 730°Cl12h, (600°C)
f-i- ..•.. GX-12, base material, 730°C/12h, (600°C) NF616, base material, 740°C/4h, (600°C)
+ E91l, base material, 750°Cl2h, (600°C) t.< NF616, simulated (fp=900°C), 740°C/4h. (600°C)
• P 91, simulated (Tp=920°C), 760°Cl2h, (600°C) A NF616, weld joint. SMAW, 740°Cl4h, (600°C)
• GX-12, simulated (fp=920°C), 730°CI12h. (600°C) ." E911, simulated (Tp=925°C), 760°Cl2h, (600°C)
A E911, welded joint, SMA W, 770°Cl2h, (600°C)
10--~~-----------------------------------------------
1 10 100 1000 10000 100000
Time, h
Fig. 7 Results of creep rupture tests of P91, NF616, E911, and G-X12 base material,
welded joint (Refs. 5, 6) and soft zone HAZ simulated materials
Creep Rupture Tests on Crossweld Samples

The current status of the creep tests at 600°C with a testing time of 30 000
hours is shown in Fig. 7. The cast steel G-X12 and pipe versions E911 and
NF616 appears to have a creep strength which is at least as high as that of
modified 9 CrMo steel P91. Crossweld samples of the repair weld (code E) of
%
the pilot valve body was tested,"

The current status of creep tests at 650°C with a testing time of 12 000 hours
is shown in Fig. 8. At high stress levels the fracture is located in the base
material. As the applied stress decreases and the rupture time increases, the
1000
:1
..
I 0 E911, SMAW-v, 770°Cflh, (650°C)
~ j
-:I
;-;~-- 'j
~ !
E911, base material, (650°C)
.,.-
i
!-----._,
,
~ i I I !
,
:: i i
I i I i
~on
,
I'
i
u
r
I, I
i
s:::::
r---
i
H-~~-
I
I
\ !
~en
1~~ M-' j
~ 100
II
II
1--+-,
l
i
~~ I ~~L
+tH26f
~- '-- +- --=.-t--c
-,~ '-.. ,-
Bc,
~-=--m 1~-~
I I I
-I--- ('f -.....;;;;:
i-t--
II I I II~ f-'- -',
..•
~-
I
.".~
2 I I
I I I
i
:
I ~.~
k-~
i---
e, I I :
i-I ~~
,---,
i
j
<U I I ! :
~
t
U I Ii i - .:~-.- .~ .. ,--_ ..
! i I
I :
I
10
I I I I i i i !
1 10 100 1000 }0000 }0000

Time, h
Fig. 8 Results of creep rupture tests of E911 base material and welded joint at 650°C
Base Material HAZ Weld Metal
CI)
CI)
Q)
r:::
~~
:::c
175 --+-----+------f------j-t--+--+------+--+--L--+---+--~__+__'___+-_+__+___+____1
o 10 20 30 40 50 60 70 80 90
Length of Specimen [mm]
Fig. 9 Fracture location and hardness profile at crossweld sample: specimen no. 26,
(E 911/MTS 911 [SMAW-vertical], 650°C, 117MNm-2, 217h)
Base Material Ad Intercritical Zone Ac3 FG-Zone CG-Zone FL WM
400llm
Fig. 10 HAZ at crossweld sample: specimen no. 28, (E 911/MTS 911 [SMAW-
vertical], 650°C, 70 MNm -2, 4.295 h)
fracture location shifts from the base material (Fig. 9) into the intercritical
zone in the HAZ (Fig. 11). Results of microstructural investigation and
hardness tests of broken creep rupture samples are shown in Figs 9 and 11.
The microstructure of the HAZ, given in Fig. 10, shows cavities and micro
cracks located in the intercritical zone it was also detected in Fig. 6.
BM HAZ Weld Metal HAZ
:: ~ No. 29; SMAW-V'60MPa'6~~~r==.:::=-[ _

__ 245
r -- ~Q)
-~i
i
-
~
§-------/-------
:
o 2351 "Ci) --t-- "<n----l----".

; ~ .2 I 2~ I
:r: 1 I ~ __
i-E 215j--
2251
/J-I \Jlil
---I....---_
n~ _
1 l~ I i -=
-+-~-jl~--
205 p ~
~ 195 " I I_T' i
-
r
185 ---+----+-{i
175t--~~==:=,:!====;___r~,,_t1i;::rr.::::;::;~:;:=~~-_____r--
165j_-----+---------,-----+--~___+____~-AZ---"---ll ~~~I_~ -,-1 ~ .

o 10 20 30 40 50 60 70 80 90
Length of Specimen [mm]
Fig. 11 Fracture location and hardness profile at crossweld sample: specimen no.
29, (E 911/MTS 911 [SMAW-vertical], 650°C, 60MNm-2, 7.302 h)
CONCLUSIONS
Previous investigations (Refs. I, 9) have shown that the weldability of the heat
resistant material P91 can be described as very satisfactory. Although, in the
HAZ a drop in the creep resistance can be observed. Compared to the base
material a loss of creep resistance measured in crossweld samples of welded
P91 material of about 20-25% have to be taken into account. Basic investiga-
tions using mainly the Gleeble HAZ simulation technique revealed that this
drop in the creep resistance occurred in the fine grained area of the HAZ,
where the peak temperature reached a level of about 850-950°C. The aim of
this study was to investigate whether newly developed tungsten containing
materials, with higher creep resistance than P91 material, show similar
behaviour in the welded condition. The results obtained revealed that the
behaviour of the tungsten modified chromium steels NF616, E911, and G-XI2
shows similar behaviour regarding the creep resistance in the HAZ to P91.
Hardness tests, constant strain rate tests, and short time creep tests on HAZ
simulated microstructures showed that also in tungsten modified 9-100/oCr
creep resistant steels a drop of the creep strengths in the welded area have to
be taken into account. The first results of HAZ simulated short time creep
tests showed that this drop is less than observed in P91 pipe material. At
stresses lower than 150 MNm-2, the fracture location shifts from the base
material into the softened intercritical zone of the HAZ. At 600°C and more
than 10 000 h, the data points of the weldments are below those of the base
material by more than 25%. In the design of welded components made from
this type of materials, this effect must be taken into account.
ACKNOWLEDGEMENTS
This work is a part of the European Action COST 501, Round II and III and
was supported by the Austrian Research Funds (FFF) which is gratefully
acknow ledged.
REFERENCES
1. W. Bendick, H. Cerjak, K. Niederhoff, G. Wellnitz and M. Zschau: Proc. Int.

Conf. on Trends in welding science and technology', ASM, 1992.
2. R. Blum, J. Hald and E. Lund: in Proc. VGB-TB, Int. Conf. on Werkstoffe in
der Schweifltechnik im Kraftwerk, Paper No.9, 1991.
3. F. Masuyama: in Proc. 123rd ISIJ Annual Meeting, April 1992, Vol. 5, 811.
Cited in: Blum et al., in Proc. VGB-TB 140, Int. Conf. on Fossil-fired power
plants with advanced design parameters, Vol. V2, 1993.
4. M. K. Booker et al.: in Proc., Int. Conf. on Production, fabrication, properties
and application offerritic steels for high temperature applications, ASM, 1981.
5. H. Naoi, H. Mimura, M. Ohgami, M. Sakakibara, S. Araki, Y. Sogoh, T.
Ogawa, H. Sakurai and T. Fujita: 'Development of tubes and pipes for
ultra-supercritical thermal power plant boilers', Nippon Steel Technical
Report No. 57, 1993.
6. D. Coutsouradis et al.: Int. Conf. on Materials for advanced power engineering,
1994.
7. W. Bendik, K. Haarmann, G. Wellnitz and M. Zschau: 'Eigenschaften der 9-
bis 12-0/o-Chromstahle und ihr Verhalten unter Zeitstandbeanspru-
chung', VGB Kraftwerkstechnik 1993, 73, Heft 1.
8. K. Easterling: Introduction to the physical metallurgy of welding, Butterworths
Monographs in Metals, 1983.
9. N. N. Rykalin: Berechnung der Wiirmevorgiinge beim Schweij3en, VEB Verlag
Technik Berlin, 1957.
10. B. Buchmayr: Schweiflen Schneiden 1989, 46 (2).
11. F. Bruhl: 'Verhalten des 9%-Chromstahles XI0 CrMoVNb 9.1 und seiner
SchweifSverbindungen im Kurz- und Langzeitversuch', Doctoral Thesis,
TU-Graz, 1989.
High Alloy Ferritic Steel: Mechanical
and Creep Properties and its
Microstructural Evolution
A. Di GIANFRANCESCO, O. TASSA, S. MATERA
and G. CUMINO
Centro Sviluppo Materiali S.p.A. Rome Italy, Dalmine Plants S.p.A.,
Dalmine (BG) Italy
ABSTRACT
The development of new high chromium ferritic steels E911 for boilers for super-
critical power plants was investigated during the European 501 COST Program.
Within the scope of the project, Dalmine fabricated the ingots produced by United
Engineering Steel of UK into boiler tubes and header pipes. Centro Sviluppo
Materiali carried out qualification tests. Results pertaining to the chemical composi-
tion, creep properties, mechanical properties and longtime ageing effects on micro-
structural evolution and mechanical property degradation are presented here.
Results obtained on base metal have been compared with those of weldments. The
Grade 911 shows highest performance a Grade 91 and their microstructural evolu-
tion has a low influence on ductility-
1. INTRODUCTION
High temperature steels for boilers and headers of advanced power plant are
subjected to increasingly severe requirements on strength, corrosion, creep
rupture properties and thermal stability for long time service exposure. To
meet these requirements, several steels have been developed.v- In the
framework of the programme COST 501 Round III WPll, CSM and Dalmine
developed components made by a new steel called E911 derived from the
Grade 91 (9Cr1MoNb VN) with the addition of 1 W. The aim of this paper is
%
to present work carried out by CSM and Dalmine in this program to qualify
E911 in term of mechanical properties and microstructure evolutions.
2. MATERIAL PRODUCTION AND PROPERTIES
In agreement with the COST 501 work distribution, ingots of about 2.5 tons,
made by UES (United Engineering Steel, UK), have been fabricated by
Dalmine in pipes and tubes. The chemical composition is shown in Table 1.
The pipes (285 X 55 mm) have been made by with the following process route:
622
HIGH ALLOY FERRITIC STEEL 623
Table 1 Chemical composition of UES industrial cast B2516
Element C Si Mn P S Cr Mo Ni Nb V Al W N
% wt 0.105 0.2 0.35 0.007 0.003 9.16 1.1 0.23 0.068 0.23 0.007 1.0 0.072
• ingot heating at 1300°C

• partially boring at horizontal press
• piercing at Mannesmann mill
• pilger mill
• heat treatment (normalising 1060°C/air + tempering 760°C)
• finishing operations
• machining
In case of tube (48.3 X 7.2 mm) bars have been hot rolled in a continuous mill
and heat treated in the same temperature conditions. The welded joint has
been made by Submerged Arc Welding of pipes (Baldon Welding).
2.1 Mechanical Testing on as received materials

The E911 transformation temperatures have been evaluated and these are
higher than reference steel P91, as show in Table 2.
Table 2 Transformation temperature
Material
P91 815 865

E911 841 948
Tensile tests
The room temperature mechanical properties of the products are shown in
Table 3: the values are very homogeneous on the thickness and on the
orientation of the pipe; obviously the tube shows higher properties due to the
different process route.
The tensile properties from room temperature up to 700°Care shown in Fig. 1.
Table 3 Room temperature mechanical properties of tubes and pipes
Y.S. U.T.S. Elong. Red. Area FATT Hardness

Product Position (MPa) (MPa) (%) (%) YS/UTS (OC) (HB)
Pipe long. ext 543 728 25.4 66.4 0.74 -10 224
Pipe long. into 536 716 25 66.8 0.75 -10 222
Pipe trans. 545 722 23 59.8 0.75 -2
Tube long. 656 824 24.5 0.79 259 Hv 30
I.. . __
I'"
~
~
'-'
800 I
700111
600
Ilia
•
I
• YS
A 80ng.
••••UTS
•• Red. Area .- •• --+
• •• 100
90
80 ~
70 f
~ 500 --~--- -.----~------.---- '!I~--m- ~ 60 ~
~ 400 ••• ._ETI 50 ~
"--=~ 40
r-t __~_~_=_ t~~~
~ 300 :
~~~~
I I ---------------- - .---:-
~_A_
o I I 0
o 100 200 300 400 500 600 700
Temperature ee)
Fig. 1 Tensile properties of the E911 pipe versus temperature
Creep tests
Creep tests have been carried out on pipe and tube material, and on a welded
joint. Isothermal tests were performed at 575, 600, 625 and 650°C. Creep
rupture tests have now reached 20 000 hours and continue. Figure 2 shows
Isothermal curves
1000
10
1000 10000 100000
Time to rupture (bours)
Fig. 2 Isothermal curves of pipe, tube and welded pipe at 600°C (open points are
test running)
the isothermal curves of pipe, tube and welded pipe at 60QoC.Figures 3 and 4
show a comparison between the behaviour of E911 and P91 pipes at 600°C
and 650°C respectively. Figure 5 shows the ductility in term of reduction of
area and elongation of the brocked specimens.
The ductility of the E911 decreases just a little after 15 000 hours for the
specimens tested at higher temperature, but in any case, up to now the
elongation to rupture is still more than 17% and the reduction of area is more
than 500/0.The lowest values of the reduction of area concern the highest test
temperature (650°C).
IsotherIllal curves
1000
I 2 tests
100
____ i.E911_,_+ __ ---j·_-_+----+f------t---_tf-_+-f-+++__ +------j, 3 tests
I----t--~I C p9 1 it-t----t-----t---I -t--+---t-+-+-Hf-----+-----+----t----+---t-t--+-H
i-TIlT
10
100 • 1000 ).0000 100000
TI.Ille 1:0rupture ~nours)
Fig. 3 Isothermal curves of E911 and P91at 600°C (arrows indicate test running)
Isothernnalcurves
1000
-
I
~
~
~'-" .•..
-
-
100
tlL. -n: ---111111_ ~I
fI.l
fI.l ~'--
:[ ]-'
~ JC:l~
---
.E911 I
~ CP91 ••....
'-'-.J I
1-
1 test 1---
10 I I
10 100 1000 10000 100000

'T'Ijme to rupture (bours)
Fig. 4 Comparison of E911 and P91 creep behaviour at 650°C (arrow indicates test
running)
Ductility in creep tests

-
-.-
100
~
=
~~
80 •• II
II
II. IIi IiII1
--
l"
1m III
~! III !JiI -.. -II
F'''I II~III
--I--f-
-- ~19
~I!I
-e 60 _~.Elongation
•
I
--=~ BRed. of Areal 650°C

~
~
40
"'I~ .•
~l "'~
.•... ...~
~ 1IIl10llllt"
I"•
-- ~...-....••~
III••••••••
=
ci> 20 ~4
1
0
S 0
10 100 1000 10000 100000
'T'Jrrre to rupture (bours)
Fig. 5 Ductility of E911 creep specimens (all the temperature 575, 600, 625, 650°C)
2.2 Mechanical Testing of aged materials

Grade 911 and 91 materials have been subjected to a long-term exposure in
order to evaluate the variation in tensile and impact properties at room
temperature after an isothermal exposure at 625 and 650°C up to 1000, 3000
and 10000 hours. The exposures were carried out in an electrical laboratory
furnace showing a maximum temperature deviation in the chamber of + 4°C.
The results of the tests are summarised in figures 6-9.
The results of the long-term exposure show:
- a 10% maximum reduction of the tensile properties after 1000 hours (Fig.
6),
- a constant values of ductility (Fig. 7),
- a strong reduction of the impact properties during the first 3000 hours of
exposure (Fig.B) with an increase of of brittle fracture (Fig. 9). These
%
behaviours are maintained practically constant for longer time.
Tensile properties
800
h-a-Ie
i
700 I
l600 I I I
i
I U
I.
I
I
~ 500 6 I
I
I
I h
I
~ 400 I
~
en 300 I I
I
I -
i
:
r- .UTS E911/625 OUTS E911/650
I1 •
i
200 IlYS E911/650
YS E911/625
100 .UTS P91/625 [JUTS P91/650 :1
_ ~625 _~~S P91/65~ ____ 1
o
o 2000 4000 6000 8000 10000
Exposure time (hours)
Fig. 6 Effect of exposure time on tensile properties of E911 and P91
Tensile Properties
80
_ 70
~e..... 60
ns
••
~~
0
!
•
••
4- ''I
••
e 50
<t
-g 40
e; 30
C)
.~J-JJ II
5
iii
20
10
r. Elon. E911/625
lllElon. RA./650
OElon. E911/650
.Elon. P91./625
--
.R.A. E911/625
[JElon. P91/650
o ,.RA.PB1/625 QRA.P91/650 ____ _ _
o 2000 4000 6000 8000 10000

Fig. 7 Effect of exposure time on ductility of E911 and P91

Impact test
.,
- 300
[J J .E911/625 <>E911/650 I
;: 250
II I [J J .P91/625 [JP91/650
•
~
CI)
200
I~
5i
•
EJ
150 ~~-
~ 100
II
E 50 ~~8
- 0
•9 ~,
o 2000 4000 6000 8000 10000
Fig. 8 Effect of exposure time on absorbed energy of E911 and P91
~,
Impact test
~:::l 100
+J
(J <>
A. c~
80
~ "V'
E
..:
CI)
60
-3 .•..
...•.
-
•-
.ll 40 ~~-
H
'to-
0
20 ~, I.E911/625 OE9111650 ~I
~
-- .-
0
I·P911625 []P91 1650
0 ...
o 2000 4000 6000 8000 10000
Fig. 9 Effect of exposure time on brittle fracture of E911 and P91
After the same long-time exposure, steel 91 shows a similar trend in term of
tensile properties, but impact properties are better (open and full square in
Figures 6-9), compared to grade E911 steel.
2.3 Microstructural evolution

STEM investigations on thin foils have been performed on both steels i.e. E911
and P91, in the as received and aged conditions, for charactering the evolution
of the tempered martensite and determining the different types of second
phases. In order to measure the dimensional distribution of different type of
precipitates and their composition evolution with ageing treatment, quantita-
tive analysis on extraction replicas have been carried out by automatic image
analysis system, X-Ray diffraction and EDS microanalysis.
The recovery process is observed because subgrains with a reduction of the
dislocation density replace the original martensite laths gradually. At 625°C
the rate of recovery process is quite similar for both the steels. At 650°C the
evolution is faster for E911 steel, in which the transformations of martensite
laths in sub grain is complete after 1000 hours.
The retained high dislocation density is connected with a stable micro-

structure also in the more aged structures.
In all the samples the MX type carbide or carbo-nitride are observed inside
the subgrains; these precipitates remained quite stable in terms of composi-
tion and size increasing ageing time. M23C6 particles are observed predomi-
nantly on sub grain boundaries and a tendency to a coarsening with ageing
was detected.
The most relevant microstructure change was the precipitation of the
intermetallic Laves phase during ageing, that was also localised at the
subgrain boundaries and often these precipitates are associated with carbides.
At 625°C the nucleation of the Laves phase is observed just in the first 1000
hours in both the steels. The rate of coarsening of this phase was very high
and these particles grow up to dimensions of approximately 1 urn after an
ageing time of 10 000 hours. At 650°C the Laves phase precipitation occurred
during the first 1000 hours for E911, where in the P91 steel was observed only
after 3000 hours. After 10 000 ageing hours the Laves phase in both the steels
reached micron sizes. Also carbides size have been grown reaching a
maximum size of 400nm after 10 000 hours of ageing at 650°C (Fig. 10).
The extensive quantitative analysis on precipitated phase shows an increase
of Cr content in M23C6 with ageing time. The chemical composition of Laves
phase doesn't substantially change with the ageing treatments.
70
60
~
~CJ
50
c 40 18 M23C6
CI)
:::s 30 ,.
~_Laves
C"
...
CI)
20
LL.
10 I
0 I I m I -
200 300 400 500
d(nm)
(a)
60
50
~
~
CJ
c
CI)
:::s
40
30
20
l:~23C6·
aves I
e
C"
LL 10
0 III . ..
0 300 600 900
d (nm)
(b)
Fig. 10 Size distribution of particles precipitated in the steel E911 during ageing at
650°C (a) after 1000 hours (b) after 10 000 hours
Table 4 Composition of M23C6 and Laves phase on E911 and P91 steels(wt%)
M23C6 Phase Laves

Mat/Temp. /Time
CC) (h) Dim (nm) Cr Fe W Mo Dim (nm) Cr Fe W Mo
E911 base 132 46 35 14 4

E911/625/1000 110 52 28 11 9 100 13 32 28 27
E911/625/3000 68 53 31 11 4 137 6 35 41 18
E/911/625/10 000 145 59 24 8 9 353 8 33 29 31
E911/650/1000 90 58 25 9 9 139 7 33 33 27
E911/650/3000 150 59 23 8 9 636 7 30 28 34
E911/650/10 000 183 61 21 9 9 732 8 32 29 31
P91/625/1000 104 56 31 3 10 110 10 42 4 44
P91/625/3000 87 59 29 1 10 349 7 54 0 39
P91/625/10 000 160 62 26 0 11 353 16 37 0 46
P91/650/1000 130 63 27 0 11
P91/650/3000 131 55 35 1 10
P91/650/10 000 169 66 22 0 12 820 7 35 0 58
3. DISCUSSION
Due to the fact that the E911 in each isothermal curve is always at the upper
band of the P91, a preliminary extrapolation of the base material creep results
with the data at this moment available seems show at 600°C a stress of
100-105 MPa to have the rupture in 105hours, instead of 94 MPa for the P91,
with a possible increase of about 10 MPa and probably at higher temperature
this difference could be increased.
The higher resistance of E911 steel is obviously due to the addition of W,
which is completely in solid solution in the ferrite only for short time tests.
The high Wand Mo contents of Laves phase that produces a loss of these
elements in the ferrite is normally connected with a loss of creep strength due
to the precipitation of these intermetallic phase. The creep results for E911 at
625°C and 650°C and after 1000 when the Laves phase is just precipitated,
show a higher creep resistance of this steel with respect to the P91 steel. As
suggested by Hald.v" the highest creep resistance cannot be associated with
the solution strengthening of W but it's due to the beneficial effect of the
precipitation of Laves phase that increase the total volume fraction of
secondary phases and can contribute to the precipitation strengthening. The
loss of ductility observed after time to rupture of 15 000 hours particularly at
650°C, can be associated at the increased size of these precipitates that grow
up to micrometric dimensions.
The coarsening process for both the precipitates phases Laves and M23C6 is
described by means of the equation proposed by Wagner> and Lifshitz:"
d3 = do3 - Kt
Table 5 Second phases coarsening constant for P91 and E911
Material Temperature eC) K Laves (m3/h) K M23C6 (rn3/h)
P91 625 9.88 X 10-28 1.03 X 10-28

P91 650 8.67 X 10-29
E911 625 1.41 X 10-27 6.75 X 10-29
E911 650 1.03 X 10-25 1.52 X 10-28
where do is the initial dimension of the precipitates, K is the coarsening

constant and t is the time.
The coarsening constant of M23C6 and Laves phases were calculated at
650°C for the E911 steel and shown in Table 5. The most relevant difference is
the highest Laves phases coarsening constant for both the steels. For P91 has
not evaluated because the Laves phases appears only after 10 000 hours. For
both steels the coarsening kinetics of the intermetallics phase is highest than
in the M23C6 carbides, taking into account that it has been supposed a linear
relationship of the coarsening of these phases.
The equilibrium composition of M23C6 and Laves phase were calculated by
THERMOCALC and measured by EDS in aged samples. In Table 5 the
calculated composition of the M23C6 and Laves phases are compared with
composition after 10000 hours aging at 625 and 650°C for the E911 steel. The
agreement between the calculated and measured composition is quite good
specially for chromium in the carbides and chromium and iron in the Laves
phases,"
The most relevant difference in terms of chemical composition was
revealed in the highest calculated Mo content in the M23C6 carbides and in the
highest W content in the Laves phases instead of measured contents. These
discrepancies are related to the fact that THERMOCALC does not predict
correctly the presence of the Laves in the chromium steels and also because
'Table 6 Comparison of calculated and measured composition of M23C6 and Laves

phases (wt 0/0)
M23C6 M23C6 Laves Laves

Temperature eC) Element (calcula ted) (measured) (calculated) (measured)
Mo 20.5 9 12.9 31
Cr 68 59 6.6 8
625
Fe 3 24 35.4 33
W 0.1 7 45 28
Mo 20 9 14 31
Cr 67 61 6 8
650
Fe 4 21 35 32
W 0.5 9 45 29
7.E+06
II E911625·C
• 'E9116S0·C
6.E+06 __
A P9162S·C
Lineare (,E911 6S0·C) _ •
_
'P916S0·C
Lineare ('P91 6S0·C) •
- _ - Lineare (P91 62S·C) _ - - - Lineare (E911 62S·C)
5.E+06
M
< 4.E+06
E
S 3.E+06
M
<
"C
2.E+06
1.E+06
•
O.E+OO
2000 4000 6000 8000 10000 12000

Exposure time (h)
(a)
6.E+08
•• •
l1li E91162S·C 'E9116S0·C
&. P9162S·C 'P91650·C
5.E+08 __ Lineare (,E911 650·C) _ _ Lineare (P91 62S·C)
_ •• •• • Lineare (E911 62S·C)
4.E+08
M
<
E 3.E+08
.E-
M
< 2.E+08
"
1.E+08
O.E+OO
2000 4000 6000 8000 10000 12000
Exposure time (h)
(b)
Fig. 11 Time dependence of the mean particle diameter (a) Carbides (b) Laves
phase
a 50000 100000
Ageing Time (h)
Fig. 12 Cr content in the M23C6 as function of ageing temperature

the ageing time and temperature are not equivalent to the equilibrium
conditions.
The values of Cr content in M23C6 carbides measured at increasing ageing
times show an enrichment in the Cr content, toward the equilibrium level of
Cr at the ageing temperature, which is higher respect to the equilibrium Cr
content of carbides precipitates at the tempering temperature (Fig. 11).
4. CONCLUSIONS
The mechanical properties such as tensile, hardness toughness and creep

rupture strength have been discussed for the new steel Grade E911, in
comparison with the Grade P91.
The tensile and creep rupture properties appears to be higher than the
values measured on the reference material. A limited loss of ductility for
creep test at 650°C after time to rupture of 15 000 hours can be associated with
the coarsening of Laves phase, as suggested by the results of the micro-
structure analysis. By considering that this steel has been developed for
applications temperature of 600°C, where the constant coarsening are expec-
ted to be lower than the values measured at 650°C, the microstructure stability
of these steel can be guaranteed in terms of precipitation state.
REFERENCES
1. H. Naoi, H. Mimura, M. Oghami, H. Morimoto, T. Tanaka, Y. Yazaki and T.

Fujita: Proc. New Steels for Advanced Plant up to 620°C, E. Metcalfe, ed.
London, May 1995, EPRI, USA, 1995, 8.
2. Y. Sawarahi, K. Ogawa, F. Masuyama and T. Yokoyama: Proc. New Steels for
Advanced Plant up to 620°C E. Metcalfe ed., London, May 1995, EPRI,
USA, 1995, 45.
3. J. Hald: New Steels for Advanced Plant up to 620°C E. Metcalfe ed., London,
May 1995, EPRI, USA, 1995, 152.
4. J. Hald: Steel Research 1996, 67, 369.
5. C. Wagner: Z. Elektrocem. 1961, 65, 581.
6. J. M. Lifshiz and V. V. Sloyzov: J. Phys. Chern. Solids, 1961, 14, 35.
7. V. Foldina: COST Report Microstructural stability of 9-12 % chromium steels.
Delta Ferrite Formation in 9-12%
Chromium Steel Weldments
E. AYALA*, M. A. ROMAN*, J. VEGAt, x. GOMEZt,
T. GOMEZ-ACEBOt and J. ECHEBERRIAt
* Babcock Wilcox Espanola (BWE), 48510 Galindo, Vizcaya, Spain
t Centro de Estudios e Investigaciones Tecnicas de Gipuzkoa (CElT), P"
Manuel de Lardizabal, 15, 20009 San Sebastian, Spain
ABSTRACT
Although the 9-12% Cr steels normally have fully martensitic microstructures, they
have some tendency to the formation of delta ferrite, mainly during the welding
process. It is well-known that B-ferritehas several detrimental effects on such proper-
ties as creep ductility and toughness. Thus it is important to avoid its formation.
The formation of delta ferrite has been studied in several steels belonging to the
9-120/0 Cr family through (a) the microstructural characterisation of different welds,
(b) the determination of the chromium equivalent Creq, and the Kaltenhauser ferrite
factor, FF., and (c) the phase diagrams obtained with the Thermo-Calc program.
Through the phase diagrams determined by the Thermo-Calc program the
evolution of different phases with temperature can be ascertained. Besides, it can be
used to determine the necessary heat treatment to transform the delta ferrite, formed
during welding, into austenite.
The EM12 steel (9% Cr 20/0 Mo Nb V) with a ferrite/martensite microstructure,
although presently substituted by the modified T91, has been used as a reference in
this work, since its composition is inside the ferrite + martensite stability range.
1. INTRODUCTION
High chromium 9-12%Cr ferritic steels, like T91 and X20CrMoV12 1 (abbre-
viated as X20), constitute an important family of steels used in power
generation, and in general they are extensively used in industrial applications
at high temperatures. They are favoured as opposed to, standard 9% Cr-l %
Mo and T22 steels, since they enable achievement of higher operation
efficiency in the energy generating plants, because of their higher strength
and improved creep properties at elevated temperatures. Besides, these steels
can be used with thinner cross-sections, resulting in considerable weight
saving in the boilers, and hence cost reduction of as much as 300/0.
Although these steels have fully martensitic microstructures, their chemical
compositions, in the Schaeffler diagram;' are close to the martensite +
S-ferrite area.2,3 Therefore, in welds, subjected to elevated temperatures,
depending on the procedure used, small amounts of 8-ferrite can be formed.
633
The potential for B-ferrite formation can be estimated by different routes, (a)
the determination of the chromium equivalent Creq (and Nieq) used to
represent the composition of the steel in the Schaeffler diagram.' (b) the
Kaltenhauser ferrite factor FF,3,4 and (c) the analysis of phase diagrams
obtained with thermodynamic calculations.v"
The present work describes the microstructures developed during similar
and dissimilar welding of 9-12% Cr steels, and the estimates carried out to
know the tendency for the formation of B-ferrite. The phase diagrams used to
know the evolution of the different phases, especially B-ferrite, with the
temperature have been obtained using the Thermo-Calc system."
The chemical composition of the different steels (tubes or pipes) used in the
present work is given in Table 1. As shown in this table, except for 2.25CrlMo
Table 1 Chemical composition of steels used, wt-S
Material T22 P22 T91 (*) P91 X20 EM12
C 0.05-0.15 0.11 0.10 0.12 0.20 0.06

Mn 0.3-0.6 0.44 0.50 0.45 0.63 1.08
Si 0.31 0.29 0.33
Cr 1.9-2.6 2.04 8.51 8.78 10.4 8.88
Mo 0.87-1.13 0.94 0.90 0.97 0.85 1.82
V 0.22 0.18 0.26 0.28
Ni 0.10 0.11 0.49 0.30
Nb 0.081 0.072 0.38
N 0.041 0.050
(*) Tube manufactured by Tubos Reunidos (Basque Country Company) in the context of a
research project with BWE, Iberdrola and CElT.
(T22/P22), the rest of materials correspond to steels that belong to the 9-12%
Cr steel family, i.e., modified 9CrlMo (T91/P91), X20CrMoVI2 1 (X20) and
9Cr2MoNbV (EMI2).
Different combinations of these materials have been used to study the
delta-ferrite formation during distinct welding procedures. These combina-
tions are: T91-T91, P91-P22; X20-X20, X20-EM12, EMI2-EMI2 and EMI2-
T22. The welding procedures, carried out in BWE, are outlined in Table 2. In
this table postwelding heating treatments (PWHT) are also included. The
specimens from Al and EI procedures, in Table 2, have also been analysed in
the as-welded condition.
Longitudinal sections were cut from the AW and the PWHT samples and
prepared using conventional techniques for optical metallography. The quan-
DELTA FERRITE FORMATION 635
Table 2 Welding procedures
Code Materials Consumables Type PWHT
AW;
Al T91-T91 SG-XIOCrMoVNb91 AGTAW (Fixed-Head)
760°C/30'
A2 P91-P22 ER90SB3-E9015B3L GTAW + SMAW 720°C/IH
Xl X20-X20 SGCrMoWVl2 - ECrMoWVl2 GTAW+SMAW 760°C/3H
X2 X20-EM12 UPS2CrMoWV12 GTAW +SAW 760°C/3H
AW;
EI EMI2-EMI2 SG-XIOCrMoVNb91 AGTAW (Orbital)
740°C/IH
E2 EM12-T22 SGCrMo2 AGTAW (Fixed-Head) 760°C/30'
E3 EM12-T22 SGCrMo2 - E9015B3 GTAW + SMAW 760°C/30'
SAW = submerged arc weld (automatic); SMAW = shielded metal arc weld (manual);
GTAW = gas tungsten arc weld; AGTAW = Automatic gas tungsten arc welding; AW =
as-welded; PWHT = post-weld heat treatment.
titative analysis of 8-ferrite in the EM12 steel was determined, in the HAZ
zone and in the unaffected base material, by point counting. In the same way,
microhardness cross sections were carried out with a Leco microhardness
tester using a 1 Kg load. In the case of EM12 specimens a load of 25 g was used
to differentiate the hardness of 8-ferrite and martensite grains.
The formulas employed (for 9-12% Cr steels) to calculate the Creq and Nieq
in order to be included in the Schaeffler diagram, and the Kaltenhauser ferrite
factor, FF, are:
Creq = a/oCr + 2%Si + l.s%Mo + SO/oV+ 1.75%Nb + l.s%Ti + O.7S%W (1)
Nieq = + %Co + O.5%Mn + O.3%Cu + 25%N + 300/oC
%Ni (2)
FF = a/oCr + 6%Si + gO/oTi+ 4%Mo + 2%AI + 4%Nb - 2%Mn
- 4%Ni - 400/o(C + N) (3)
Finally, the thermodynamic approach has been done using the CALPHAD
method, in which each phase is described by its Gibbs energy as a function of
composition, temperature and pressure. The calculations have been per-
formed using the Thermo-Calc system," a computer software program for the
phase diagram and complex equilibrium calculations. The thermodynamic
data used in this calculations are those existing in the SGTE (Scientific Group
Thermodata Europe) database." exactly the SSOL database.
3. RESULTS AND DISCUSSION
3.1 Base Materials

In Table 3 the Creqf Nieq, and FF values are shown as obtained by calculations
from the formulas (1-3). The two first values are used to locate the composi-
Table 3 Creql Nieql and Ferrite Factor for the 9-12% Cr Steels.
T91 P91 )(20 EM12
Creq 11.7 11.5 13.6 14.3

Nieq 4.3 4.7 6.8 2.8
FF 7.7 6.8 4.4 13.8
25
20
15 .EM12
d-
Q) oT91
Z .X20
10 zP91
0
0 5 10 15 20 25 30
Creq.
Fig. 1 Schaeffler diagram showing the location of the composition of the 9-12% Cr
steels
tion of the different 9-120/0 Cr steels in the Schaeffler diagram (Fig. 1). As it
can be verified in the figure, except for the EM12 material, which is inside the
matensite + ferrite (M + F) stability range, the remaining steels are localised
inside the martensite stability field (M), very close, specially )(20 alloy, to the
borderline of delta ferrite formation. This means that, although these steels
have fully martensitic microstructures at room temperature, they have a high
potential for o-ferrite formation.
The microstructural analysis made over base materials agree with these
estimations, since as it can be shown in the Fig. 2, only the EM12 steel presents
a o-ferrite-martensite duplex microstructure. The ferrite grains, in light
contrast, maintain the texture after rolling, indicating that they have not
transformed to austenite during the heat treatment. Point counting showed
the average ferrite content to be 36%. The rest of materials presents a fully
martensitic microstructure.
With respect to the ferrite factor, several authorsvv" indicate that a ferrite
factor less than 8 gives rise to a fully matensitic microstructure, whilst FF
higher than 11 results in the formation of significant amounts of o-ferrite. In
line with these arguments, EM12 has an FF higher than 11 and has a duplex
Fig. 2 Micrographs showing the microstructure of base materials
structure, where as T91 (and P91) and X20 have FF<8 and there is no 8-ferrite
formation. However, since X20 has the lowest FF, it is the material with the
lowest potential for the ferrite formation. Moreover, in Schaeffler diagram,
X20 steel is slightly nearer to the borderline between M and M + F regions,
therefore, its tendency for the ferrite formation is practically the same as the
T91. Additionally, in the same line the 36% of 8-ferrite measured by point
counting in EM12 base material and, the 52% in HAZ in a region close to the
weld metal, as will see afterwards, turns out to be noticeably higher than the
28% calculated form the extrapolation made from the ferrite factor estima-
tions carried out by Panton-Kentvf in weld metal. Therefore the Creq and Nieq
values used in Schaeffler diagram apparently gives a relatively better predic-
tion of the 8-ferrite potential formation than FF.
Although both Schaeffler diagram and Ferrite Factor indicate that only
8-ferrite should appear in EM12 material, there is some disagreement as has
been noted before in the determination of the ferrite formation potential of
T91 and X20 steels. Besides/ they do not provide any information about the
variation of the different phases with temperature. Thus, with the aid of the
Thermo-Calc system we have obtained the phase diagrams as a function of
composition and temperature for these steels. Although, equilibrium phase
diagrams do not show martensite, these phase diagrams provide an impor-
(a) T91 (b) X20

1600 1600 -t--"------'---'---;--L----L--+
L
1500 1500 1=::::::::::--_-:-L-=-~ __1
1400 1400
1300 1300
o U
ai 1200 1200
:;
/1'-
~
~ 1100 ~ 1100
E 1000
(J) (J)
E 1000
~ 900 ~ 900
800 800 r----!.---.:..-.~---__I

700 700
600 -t--.-----,---r---'---r--~-+
0.05 0.10 0.15 0.20 0.25 0.30 0 0.05 0.10 0.15 0.20 0.25 0.30
Weight percent C Weight percent C
(C) EM12
15001::::::=--;---- --1 L Liquid

a., 0 Ferrite
1400
'Y Austenite
1300 Cl M23C6
o
Pi 1200 C2 Me
~ 1100
E 1000
(J)
~ 900
800
700
0.05 0.10 0.15 0.20 0.25 0.30

Weight percent C
Fig. 3 Section of the Fe-C phase diagram for (a) T91, (b) X20 and (c) EM12
tant tool to know the temperature dependant evolution of phases, especially

at high temperatures.
Figure 3 shows sections of the Fe-C phase diagrams as a function of
temperature for T91 (P91 are very similar), X20 and EM12. In these diagrams,
in addition to ferrite (ex) and austenite ('Y), the carbides: M23C6 (Cl)-MC(C2)
are included. In order to know the evolution of these phases with tem-
perature, a line with the corresponding wt-O/oC for every material has been
drawn. Analysing this figure a big difference is found between diagrams
corresponding to T91 and )(20 materials, and the EM12 diagram. Particularly
for T91 and X20 steels there exists a wide range of temperatures (800-1200°C)
in which they have a fully austenitic structure, and therefore after an
austenisiting treatment, fully martensitic microstructure is obtained on air
cooling. Moreover, if the specimen has been subjected to temperatures higher
than 1200°C, for instance during welding, the austenite will partially trans-
form to B-ferrite and this phase, after a relatively fast cooling, could be
maintained at room temperature.
On the other hand ferrite is stable in EM12 steel (Fig. 3c), for this particular
carbon content, at all temperatures, without the presence of a complete
transformation to austenite as shown in the other steels. Therefore, a fraction
of the ferrite formed at high temperatures will still be stable at room
temperature, independently of the heat treatment carried out. In accordance
with this phase diagram, depending on the temperature and the cooling rate
it is possible to modify the ferrite-austenite (and the martensite) phases
relationship. In this way, as an example, as seen afterwards, during welding
the fraction of delta ferrite can increase.
3.2 Effects of Welding on Microstructure and Hardness

EM12-EM12 (E1); EM12-T22 (E2, E3)
The microstructure of the HAZ on the side of EM12 is very similar in all cases.
Although the microstructure of the as-welded E1 sample is not very clear, it
has been observed that the ferrite grains close to the weld metal have grown.
The post-weld heat treatment (PWHT) reveals a HAZ band of ,..;7mm (Fig.
4a). Two zones can be distinguished inside the HAZ. From the unaffected
base material (zone III) to the weld metal there is a first zone (zone II) in
which there is an apparently continuous increase in the amount and size of
8-ferrite. Near the weld metal it appears a second zone (zone I), with a
thickness of more than 1 mm, in which the grains of 8-ferrite have grown
considerably and have taken a equiaxed morphology. Figure 4b shows a
detail of zones I and II.
As observed from the EM12 phase diagram shown in Fig. 3c, regions in the
HAZ that had been at temperatures higher than 1000°C will produce an
increase of the 8-ferrite content. Therefore as shown in zone II, from base-
material to weld metal the fraction of ferrite is increasing gradually. Besides,
at 1300°C there is a complete austcnite-s-S-ferrite transformation. Thus at
these temperatures because of the size of B-ferrite grains in zone I the
austenite-sferrite transformation should take place on the ferrite-austenite
boundaries and ferrite grains grow consuming the austenite grains. Since
cooling in welding is fast the ferrite can not transform to austenite, at room
temperature, as confirmed in Fig. 4, is observed, particularly the zone I, a
region with a large fraction of 8-ferrite. The average ferrite content measured
by point counting is 52%. Hardness measurements carried out on HAZ
indicates that due to the increased 8-ferrite content in zone I there is a
reduction of the hardness and therefore give rise to lower tensile properties.
Finally, it is worth emphasising that the Fe-C phase diagram allows to
determine the best heat treatment to reduce the content of ferrite in the zones
I and II of the HAZ. In austenitising at temperatures between 950-1000°C the
maximum amount of austenite is obtained, because at these temperatures the
line marked in the phase diagram is found close to the nose of the austenite
stability field. On cooling the austenite formed at this temperatures reverts to
Fig. 4 (a) Microstructure of EM12-EM12 PWHT welding. (b) Detail of zones I and II
Figure 5 Microstructure of HAZ (zone I) after heat treatment to reduce the 8-ferrite
content
martensite. Figure 5 shows an optical micrograph of HAZ after austenitising

at 950°C, 4 hrs, air cooling, and tempering for 30 min at 750°C. The large
8-ferrite grains have disappeared and the HAZ microstructure is similar to
the base-material.
T9l-T91 (Al) and P91-P22 (A2)

Nor Al neither A2 welding procedures lead to the formation of 8-ferrite in
HAZ. As shown in the phase diagram of Fig. 3a, only in the regions in HAZ
that have been at temperatures higher than 1200°C, will give rise to 8-ferrite.
But on cooling this ferrite can transform to austenite, since there is a large
range of temperatures (1200-850°C) in which the only stable phase is
austenite (in addition to the MC carbides). Therefore with these types of
welding procedures the cooling rate must be slow enough to allow the
ferrite-austenite transformation.
Fig. 6 Optical micrograph of HAZ of PWHT Al welding procedure (T9I-T91)
In these weldings the microstructure of the HAZ has the characteristic

morphology, the grain growth region close to the weld interface, and the
grain-refined region farther away from the weld interface.
X20-X20 (Xl) and X20-EM12 (X2)

In X2 welding, the microstructure and hardness of EMI2 side are not
considered, because it presents the same pattern as the other procedures seen
before.
The characteristics of the welded specimen are very similar to that corre-
sponding to T91 specimens, As sh.own in Fig. 7, the grain size of martensite
grains in the growth region close to the weld interface is larger in X2 sample.
This difference must be caused by differences in heat input during welding.
The SMAW weld (Xl) was made with the lowest heat input and therefore, the
zone that has been at temperatures high enough to produce grain growth has
Fig. 7 Microstructure of HAZ in X20-X20 welding specimens
Fig. 8 Weld metal in (a) Xl procedure: GTAW + SMAW; (b) X2:GTAW + SAW
to be at a lower temperature. Another feature related with heat input during

welding is the dependence of this with the a-ferrite content. Several studies
have carried out in this sense. While Edmons et al.9 have found to be
independent of welding conditions, Panton-Kent'' has found that higher heat
input gives rise to increased 8-ferrite content, whereas others-? reported that
the 8-ferrite content in HAZ decreased as heat input increased. In this work,
although there has no found 8-ferrite in HAZ, it has found in weld metal. As
shown in Fig. 8, according to Panton-Kenf' the percentage of a-ferrite
increases as heat input increases.
4. CONCLUDING REMARKS
Although the Schaeffler diagram provides a better prediction of a-ferrite

formation with respect to Kaltenhauser ferrite factor, neither of them provide
any information about the variation of the different phases with temperature.
Therefore, phase diagrams obtained from the Thermo-Calc system is a very
useful tool to make a true estimation of 8-ferrite formation during welding.
There is an important increase of 8-ferrite percentage in EM12 HAZ after
welding, because, as predicted by the phase diagram, in zones where the
temperature was higher than 1000°C, there was an austenite-s-ferrite trans-
formation. The ferrite formed at these temperatures can not transform on
cooling because of the absence of ferrite free stability range. In T91 and X20
the content of 8-ferrite formed in the weld metal increases with the heat
input.
ACKNOWLEDGEMENT
The authors gratefully acknowledge financial support from the Departamento

de Industria del Gobierno Vasco.
REFERENCES
1. L. Pryce and K. W. Andrews: ISIJ, 1960, 415.

2. F. B. Pickering and A. D. Vassiliou: Metals Tech, 1980,409.
3. R. Panton-Kent: Welding Institute Members Report, 404/1989, 3.
4. R. H. Kaltenhause: Met Eng Quarterly, 1971, 41.
5. A. Iseda, Y. Sawaragy, K. Ogawa, M. Kubota and Y. Hayase: The Sumitomo
Search, Jan. 1992.
6. B. Sundman, B. Jansson and. J. O. Anderson: Calphad, 1985, 153.
7. 1. Ansara and B. Sundman: 'Computer Handling and Dissemination of
Data', P. S. Glaeser ed., Proc. Xth Codata Conf., Ottawa, July 1986, Elsevier
Sci. Pub., 1986.
8. R. Panton-Kent: Bulletin, 1991, 15.
9. D. P. Edmons and B. Chew: CEGB.TPRD/M/1258jN82, 1982.
10. N. Abe et al.: Nippon Kokan Steel Research Center, Kawasaki, Japan.
Optimisation of Dissimilar Metal Weld
Procedures for High Temperature
Design
M. A. ROMAN*, v. BICEGOt, G. FEDELI§, B. BROWN<JI,
H. VAN WORTELt, N. TAYLOR** and E. AYALA*
* Babcock & Wilcox Espanola, S. A. Bilbao, Spain
t Cise Spa, Milan, Italy
§ ENEL Spa, Piacenza, Italy
Yl Mitsui Babcock Energy Ltd., Renfrew, UK
t TNO, Apeldoorn, The Netherlands
** Cise Spa, Milan, Italy, presently at IRe Petten, The Netherlands
ABSTRACT
This paper is concerned with the evaluation of different alternative welding

procedures using different weld processes and filler materials for two types of
dissimilar metal joints of an austenitic-ferritic Esshete 1250-P91 joint and a ferritic-
ferritic P91- P22 joint both relevant to advanced thermal power plants.
The pipes dimensions were 168mm. of diameter and 25mm. thickness for the
three types of materials. Type IV regions were evidenced by conventional hardness
tests. The rupture strengths at typical service conditions were evaluated through
crossweld creep and low cycle fatigue specimens. Metallographic studies involving
carbon and chromium profiles through the fusion line were carried out and a weld
procedure ranking was performed according to the average creep strength reduction
factor (SRF)and cyclic life reduction factor (CLRF)obtained in each case.
Of the four welding procedures studied for the dissimilar ferritic joints, P91- P22,
the TIG & SMAW proved to be the most economical and frequently used in the
workshop. The second and the most used when the automation is possible was the
TIG + SMAW + SAW process. The other two more sophisticated options studied
involved either a 9Cr or a SCr butter layer on P91 and resulted in lower high
temperature performance. They are therefore not recommended. Regarding dissim-
ilar ferritic-austenitic joints, P91-E1250, a comparison between two welding pro-
cesses SMAW and SAW and filler materials of different chemical composition gave
slighly better crossweld properties at 650°C in the manual welded joints in both
creep and LCF tests than the automatic welded joints.
1. INTRODUCTION
Dissimilar metal welds failures were treated in the past as maintenance

problems, but the designer can improve the service life eliminating dissimilar
644
OPTIMISATION OF DISSIMILAR METAL WELD PROCEDURES 645
metal welds, wherever possible and the manufacturer can also optimise the
service behaviour by developing the best welding procedures.
Weldments are weak points due to the following reasons:
- Stress concentrations arise because of the mismatch of mechanical
properties among the several materials involved. Often named metallur-
gical notch effect.'
- Specific microstructural changes occur, like HAZ tempering phenom-
enon during welding, postwelded with heat treatment and long term
ageing in service. In ferritic-austenitic joints the strain is concentrated in
the softened region that more often than not is in the carbon depleted
region of the HAZ of the low alloy ferritic side.2,3,4 This is one of the
main reasons for introducing the P91 in many high temperature super-
heaters, replacing the stainless steels, besides reducing the dependence
on the strategic elements chromium and nickel.
- Self induced thermal stresses are set up, arising from thermal dilatation
differences and enhanced by the mismatching of the three materials
involved in the joint."
Two dissimilar metal combinations representative of the newer joints being
used in Power Plants were selected in this study, 2.25CrlMo to 9CrMoVNb
and 9CrMoVNb to Esshete 1250.
A ranking of different welding procedures is carried out based on the creep
and low cycle fatigue tests on crossweld specimens besides additional
metallographic and room temperature mechanical characterisation.
2. MATERIALS AND WELD TYPES
2.1 Base Materials

The base materials used were the 2.25Cr-1Mo (SA335 P22) and 9Cr-1Mo VNb
(SA 335P91) in the ferritic-ferritic joints and 9Cr-1MoVNb and ESSHETE
1250 in the ferritic-austenitic joints. The pipe dimensions were 168mm. of
diameter and 25 mm. thickness with the chemical compositions and mechan-
ical properties meeting the code requirements.
2.2 Welded Joints Types

Different alternatives of filler materials and welding processes were con-
sidered in the two following joints types studied; i.e. ferritic-ferritic, P91- P22
and ferritic-austenitic P91-ESSHETE1250. These are described below:
High alloy jerritic-low alloy jerritic joints (P91-P22)

For the high alloy ferritic to low alloy ferritic joints four different weld types
B1 to B4 were designed involving the combination of a number of options like
choice of the filler material, possible use of buttering layer, weld process and
Table 1 Welding Procedures of P91-P22

Procedure Depo." main element.(,,-)
Proce •• Joint PWHT H.I. (KVorn)
C:O.04; Or:2,33 7~~~/ln

81 Mo: 1,2; 81:0,3~
TIG+
SMAW
P9~\l P22
~C/h 11-14
2'~Cr 1Mo 30 -e
o: 0,09; Or. 2, ~ 1 TlG + 720~ 15-C/1 h
82 Mo:0,97; 8':0,22 SMAW P9i::s:\1 P22
~O-C/" 10-12
+ SAW 2%Cr 1Mo 300-C see-e
765: 15°C/1 h
0:0.06 SMAW P91~9Cr ~.C/" 9-11
~oo.e
83 Cr:8,158
Mo:O,98
300·C
720:
IHT
15°C/1 h
81:0,46 T/G + P9~22
SMAW ~O.C/" 15-17
9Cr 300·C PWHT eee-e
C:O,04; Cr:~,07
Mo: O,~7; 81:0,62
SMAW P91~5cr No IHT 7-8
84
o: 0,04; Or. 2,33 T/G + P9~22 7~h
Mo:1,2; 81:0,3~ SMAW 70-C '" 7O·C/h 15-17
2%Cr1MO eee-e PWHT eee-e
Interpass temperature 200°C-2500C
type of Postweld Heat Treatment as shown in Table 1. In welding 2,25 Cr-

1Mo steel (P22) to Modified 9Cr-1Mo (P91) the filler materials chosen in the
procedures B1, B2 and B4 were 2,25 Cr-1Mo and traditional 9Cr in procedure
B3. Welding processes and parameters and the chemical compositions of the
weld deposits, including the butterings on P91 side, of the four procedures are
detailed in the above mentioned table. These butterings on P91 were ger in
procedure B3 and SCr in procedure B4.
The role of buttering in DMW's is normally twofold. Firstly it has the
funtion of barrier against atoms migration, essentially the carbon which is
driven by the chemical potential gradient between the two dissimilar alloys.
Secondly it provides the possibility to apply different PWHT optimised for
the two sides of the weld.
Ferritic-austenitic joints (P91- Esshete 1250)

In this second ferritic-austenitic materials combination the two solutions
explored are mainly differentiated by the welding processes, TIG+ SMAW for
B5 weld and TIG + SMAW + SAW for B6 weld as it is detailed in Table 2. As
it can be seen in this table the chemical composition of weld deposits, Inconel
Table 2 Welding procedures of P91- Esshete 1250

Proceaure Oepo.it mSln e'ement8(%) Procee. .Joint PWHT H.I.(Kj/cm)
Mn:6.38; Cr:1!5,96 7ffi±1SOC/1 h

TlG +
85 Nb:1,84;
rest NI
Fe:6,38
SMAW
P9~;:E ~O-Ofh 7-10
INCONEL 82/182 500·0 300-0
Mn:3.'1; Cr:20,84 TlG + 7ffi±1SOC/1 h

P9~ETE
B6 Nb:1 ,9'; Fe:4,!57 SMAW ~O-O/h 7-10
reet NI + SAW INCONEL 82 300"0 300-0
nterpass temperature 2000C - 2500 cI *Esshete 1250: C:O,1: Mn:S,3: Cr:15: : Mo:1 : NI:11 : Nb:0.9
82 and 182, are very similar and were chosen because of its intermediate
thermal conductivity and expansion properties between the two parent
metals besides its low affinity for carbon reducing its diffusion."
3. RESULTS AND DISSCUSSION
3.1 Ferritic-ferritic Joints (P91-P22)

Code requirements
Tension, bend and Charpy tests were performed at ambient temperature on
specimens from each weld type. All the four procedures (BI-B4) met the
requirements specified by the European standard and comparable with those
of the parent metals. The adequate ductility of the weld was demonstrated by
the fact that the four side bends were acceptable and that rupture occured in
the parent metal part of the crossweld tensile specimens.
High temperature strengths at 600°C

Uniaxial creep and low cycle fatigue tests on the parent materials, filler and
especially on crossweld specimens centred on the 'assumed' weak fusion
Fig. 1 LCF and creep results for the P22-P91 welds and base materials
lines7,8 were carried out on the various weld types. For the P22-P91
combination, the creep properties of the Bl and B2 weld are similar, with a
SRF of ~O.92; while at high stress the failure is located in the P22 base material,
at low stresses, typical of service, the failure occurred in the HAZ as was
presumed. The other two alternatives, B3 and B4 welds gave inferior creep
values with a mean SRF of 0.86.
In contrast with other weld types that broke in the P22 side, the B4 weld
broke in the lower creep strength of the SCr butter layer at the P91 FL.
Therefore we do not recommend the use of the SCr butter layer to reduce the
long time carbon depletion by reducing the difference in the Cr-content
because the lower Mo content causes lower creep properties than P22.
Regarding LCF tests, the crossweld tests results were similar for the four
weld types, Fig. 1, the failure being located in the P22 base material close to
HAZ obtaining the average cyclic life reduction factor of 2.22 with respect to
P22 base line curve due to the metallurgical notch effect.
Type IV area
The determination of the softened area in the HAZ through the hardness test
and the carbon migration were two points of interest. In the failure type IV9,lO
inferior creep properties can not be assessed by standard tensile test at room
temperature because the work hardening effect experimented, but can be
detected by hardness testing. A softening is experimented in the outer
extremity of the HAZ due to overtempering at temperatures below the lower
critical or due to microstructural changes in the intercritical temperature
range.11,12 In the procedure Bl observed in Fig. 2 a hardness reduction of
10-15 HV1 in a region of 2 rom from (3.5 mm in horizontal) of the HAZ of P91
and in the HAZ of P22, weakest side of the joint, was also observed some
softening, about SHYl, at 3.5-4.5 mm minimum distance from the F.L. There
is a gradient of hardness in the butterings of 9Cr, procedure B3, and SCr,
procedure B4, due to the influence of dilution with base material, P91 that
produces higher hardness in this side than in the weld metal side.
Room temperature impact properties

The lowest Charpy values were always higher than 50 Joules and were
located in the heat affected zone P91 side of B1 and B2 welds because of the
low the PWHT temperature, 720°C, required by P22 material or in the HAZ of
9Cr butter layer of B3 weld for the same reason than above.
Carbon migration
Carbon migration on both P22 and P91 sides of the joint during PWHT were
studied in procedures B1 and B2 and the results in the weak area of the joint,
Fig. 3, show that carbon has been diffused from HAZ of P22 into the weld
metal reducing from 0.1 to 0.07% and increasing to about 0.1% in the weld
metal reaching contents up to 0.16%. In the P91 side the carbon increased
~V1
280 -Una I
* Una II
a Una III Una II
230 Una III
P91 P 22 -t
180 HAZ P22 MATERIAL
2 3 4 5 6 7 8 Q 10 11 12 13
Fusion line minimum distances (mm)
~V1
280
HAZ P91 MATERIAL
230
180
130~--------------------------------------------
o 2 3 4 5 6 7 8 Q 10 11 12 13
Fusion line minimum distances (rnrn)
Fig. 2 Hardness profile in the heat affected zones of procedure Bl
P22-Weld Bl (SMAW) P91-Weld Bl (SMAW)
10
1'22....... :
12"'T·······························T···················
-+ . . ...•.............. 1 . . . . . . . ..
I
P22.........'
. ...................•
-G.l4
~ 0.20
. _10
!
It
.-+- ··········· .. ··········I · · · tQ.I, i !
a I u- o•
·1 '~
I C~):
.• i I·
-:\A : ; ·.. · · ·tQ.I1.1
I·r·.-~i.·w.···;-:'\0. I .w~L~··:·~~~,,;t §•
H
:r:~·\·:;:::'·-dJ::" ! ·····:..-~·~:::::-:~1
•••• 8
• . 0.00
IlDD uoo
Fig. 3 Distribution of C and Cr across the weld/HAZ interface of weld Bl
from 0.09 to 0.17 while a slight reduction was experienced in the weld metal.
However, these zones did no affect the behaviour of these two welded joints.
In the uniaxial creep and LCF tests fracture always took place outside these
zones. The crossweld creep specimens centred on the FL of P22 side of weld
B3 failed on the weak decarburised zone adjacent to the P22 fusion line giving
a consistent SRF of ~0.75.
Weld ranking
Basing on the overall result described above a ranking of the welds is as
below:
1st. B1, B2 (SMAW and SAW respectively)

2nd. B4 (SMAW with 5Cr buttering)
3rd. B3 (SMAW with 9Cr buttering)
3.2 Ferritic-austenitic Joints (P91-Esshete 1250)

Code requirements
Tensile, bend and Charpy V tests were performed at ambient temperature on
specimens taken from the two welds and the results met the European code
requirements. The adequate strength and ductility of the joints were checked
through the tensile and bend tests obtaining the results.
High temperature strength at 650°C

In this type of joint the failure at 650°C in creep and low cycle fatigue (LCF)
testing, see the results of the tests in Fig. 4, occurred in the P91 HAZ with
650·C, 1E-5 l/s
.: iI~P91 rwfer,nc8
curve
W 11( _ ./
*-
~
I
-J
o P91
- B5 -; crossweld: crossweld:
* B6 Il P91Ii~:ion
P91 fUsion
line
O·1 L.... ---.::..=.....----1.-'-00-O
----1--'0.000 l?OO
0 O 1.000 10.000 100.000
Cyclic Ufe, Nf lime to rupture, hours
Fig. 4 LCXF and creep results for the P91 Esshete 1250 welds and base material
similar creep strength reduction factor in both welds of aproximately 0.665

and similar cyclic reduction factors around 4 with a pronounced further
softening effect in the region type IV due to LCF testing.
Type IV area
Similary to the welded joints mentioned before it was joint found a softened
HAZ region in P91 of about 8 HVl between 2 and 4 mm from the fusion line
as it is illustrated in Fig. 5.
HV1
I ...•..Surface
I
235h * Center
i •
215
195
1~~----------------------~
o 2345678
Fusion line minimum distcnces (mm)
Fig. 5 Hardness profile in the heat affected zone of P91 of the procedure BS
'k : :...........
.24i·················~·············································rO~
I P9t bale ~ lac 82/182. wetd meW i
~ 20~···· ......•.••• ~•••• 0.» ~
!
~
t6~·················1····
j
.. -:.~':::.:~.c:~~~ UI o
j
5 124 0.12 ~
s . \
0• ••• • •••••••••••••••••••••••••••• 00.0 ••• o· 0 0 •••••
8C
-
8. ~... I
. o.GI 8
8 : ~.~~~) ............•••
.. -
I
,-
I
ctiIIaDce (pm)
Fig. 6 Carbon and chromium profiles across FL of P91 side of the procedure B6
Room temperature toughness

The toughness in the HAZ of P91 were higher than 125 J because the optimum
PWHT temperature, 765°C, for P91 was used.
Carbon migration
It was observed after PWHT in the weak side of the joints some decarburation
in the HAZ of P91 from 0.09-0.08 to 0.06-0.04%, Fig. 6, but no carbon
increase was found in the Ni base weld metal. The presence of the de-
carburised zone did not affect the uniaxial and creep behaviour, and the
failure was located outside of this zone.
Weld ranking
As discussed above there is little difference in the performance of the B5
(SMA W) and B6 (SAW) welds in favour of B5.
4. CONCLUSIONS
The conclusions below cited are based on weld cooling times typical of piping
manufacturing, that are lower than typical of tubing welding.
A Regarding dissimilar ferritic joints between P91- P22 there is evidence
of the following:
Al All the welds were succesfully qualified for microstuctural, tensile,
bend and impact properties meeting the requirements specified by the
European Standard EN 288.
A2 The creep strengths of welds Bl and B2 were similar, SRF ~O.92,with
failure occuring in the HAZ of P22 material, outside of the carburised/
decarburised regions at stresses lower than 93 Mpa.
The rupture strength of welds B3 and B4 was inferior to that of Bl
and B2.
A3 Concerning to LCF tests the results indicates that:
- Failure occurs predominantly in the P22 base material outside of the
HAZ.
- No significant differences in the behaviour of the 4 welds.
- It was obtained a cyclic life reduction factor of 2.2 with respect to the
P22 reference curve for these test conditions; this is explained by
metallurgical notch effect i.e. strain is concentrated in the softer
material.
A4 It is not recommended to use a butter layer of SCr-O.SMo because there
is a loss of creep properties and on the other hand the other alternative
of using a buttering of ger gave even lower values.
AS The carbon migration after PWHT provoked a slight decarburation in
the P22 side of FL together with a carburation in W.M. next to FL that it
is accentuated during service and could be an alternative failure focus
to the softened area found in the HAZ of P22 at 3-4 mm from FL.
The decarburisation of weld metal after PWHT near to FL of P91 united to a
noticeable carburation on the other side of the FL is another weak area in
service.
B In connection with the ferritic-austenitic joints between P91 and Esshete
1250.
Bl The two base materials have been welded succesfully by TIG + SMAW
and TIG + SMAW + SAW meeting also the requirements of the
European Code.
B2 All P91-E12S0 welds failed in creep tests on the P91 HAZ side of
specimen. A stress reduction factor of 0.665 with respect to the P91 base
material was noted.
B3 LCF tests showed that the failure cracking occurs in the P91 HAZ
without significative differences in Nf values for the two welds with a
cyclic life reduction factor of ~4 with respect to the P91 reference

curve.
B4 The weak area of the joint located in the P91 heat affected zone,
presents a wider softening region than in dissimilar ferritic-ferritic
joints.
This is also the weakest zone both for creep and LCF service.
ACKNOWLEDGEMENTS
The authors gratefully acknowledge the European Commission's support for

the DISMEW Brite Euram Project. Morever the partners wish to express their
gratitude to Jan Heerings, originally at TNO and presently at the Netherlands
Institute of Welding (NIL) who took a great part in DISMEW during the first
year of the program.
REFERENCES
1. V. Bicego: Low Cycle Fatigue Investigation of a Dissimilar Weld IIWWG, Creep,

Amhem 18-19 June 1992.
2. B. Buchmayr, H. Cerjak, M. Witwer and J. S. Kirkaldy: 'Carbon diffusion
and microstructure in dissimilar Cr-Mo-V welds and their influence on
the mechanical properties' Proceedings of Second International Con-
ferences on Trends on Welding Research, Gatlinburg, Tennesse, May 89.
3. J. Bardford and K. S. Probert: 'International Effects in Dissimilar Steel
Joints', International Conference on Welding Research related to Power
Plant, University of Southampton, 17-21 Sep. 1972.
4. H. K. D. H. Bhadesia: Bainite in Steels, Institute of Materials, 1992.
5. J. D. Parker: 'High temperature failure of thick-section, low alloy steel to
stainless steel transition welds', Materials at high temperatures, 1995, 12
(1).
6. J. A. Williams and J. J. Parker: 'Effect of thermal cycling on creep behaviour
of 2.25Cr-1Mo/type 316 steel dissimilar metal welds', Materials Science
and Technology, 1994, 10 (10).
7. P. Roy and T. Lauritzen: The relative Strength of Base Metal and Heat Affected
Zone in 2,25 Cr lMo Weldments - A Microstructural Evaluation.
8. M. De Witte and C. Coussement: Behaviour of 2.25Cr-1Mo Base Material
(Repair) Weldments at High Temperature, Proceedings of the Fifth
International Conference on Creep of Materials, Lake Buena Vista, Florida,
May 1992.
9. C. J. Middleton: 'An assessment of the relative susceptibilities to Type IV
cracking of high and low chromium ferritic steel pipework Systems',
Proc. Conf. Steam Plant for the 65, London, I Mech E, April 1990.
10. V. Bicego, B. Brown, G. Fedeli, M. A. Roman, N. Taylor and H. Van Wortel:

'Life Optimisation on Dissimilar Metal Welds For Temperature Compo-
nents', International Conference on Creep and Fracture of Engineering
Materials and Structures V', California, Irvine, 10-15 August.
11. F. Bruhl, H. Cerjak, H. Mush, K. Niederhoff and M. Zschan: 'Behaviour of
the 9% chromium steel P91', Mannesmann Report 12-1989.
12 D. A. Wojnowski and J. E. Indacochea: HAZ Tempering Phenomena of
Multipass Welds in Bainitic HP Rotor Steels, International Trends in
Welding Science and Technology. Proceedings, TN, 15 June 1992.
Creep Properties of Heat Affected Zone
of Weld in W Containing 9-12%
Chromium Creep Resistant Martensitic
Steels at Elevated Temperature
Y. HASEGAWA*, M. OHGAMI* and Y. OKAMURAt
* Nippon Steel Corporation, 20-1 Sintomi, 293-8511 Futtsu-shi, Chiba-ken,
Japan
t Casting and Forging Corporation
1. INTRODUCTION
Ferritic heat resistant steels have the advantage of low thermal expansion, high
thermal conductivity and good steam corrosion resistance over austenitic heat
resistant materials. These advantages allow the main steam pipes, headers and
other components in fossil power generation plant to be operated at a higher
steam temperature than 600°C and steam pressures greater than 300 bar. The
increase of high temperature creep resistance developed for ASME T91 /P91 or
ASME T92/P92 with tempered full martensitic structure extends the applica-
bility possibility compared with conventional ferritic steel.
The transformation point at around BOO°C, ACl, for ferritic steels introduces
considerable dislocation in the lath structure by quenching after austenitising.
But the fine grained heat affected zone has lower strength than the base
material. Even a short heating cycle whose peak temperature exceeds AC3 and
cooling after the heat cycle causes a decrease in the strength of the fine
grained zone. Therefore, the strength (hardness) profile across a weld is not
flat. Figure 1 shows an example of a heat affected zone failure after creep
exposure. Many creep voids at the fine grained zone link up and grow into
large cracks.
Such creep damage deteriorates the creep rupture strength at the weld
relative to the base metal. Figure 2 indicates the creep rupture strength
deterioration of HAZ in both T91 and T92 at 600°C. Table 1 gives typical
chemical compositions for T91 and T92 steels.
But during the actual application of ferritic steels in boilers, the HAZ exists
parallel to the circumferential weld joint of pipe. Only the hoop creep stress
damages the HAZ of the weld. But analysis of the creep rupture strength
deterioration mechanism at the HAZ avoids the local weak weld joint of
ferritic heat resistant steel and completes the homogeneous boiler compo-
nent.
655
Weld metal
Base material
HAZ
Fig. 1 Weld joint failure induced by HAZ creep rupture strength deterioration
1000
- .- I
-. i
~--..
'V
J--
t- 1"---
~~
> t-
'-
~ leNF616 Parent material 0 NF616 HAZ
i-
• T91 Parent material <> T91 HAZ
F ~
"I
!
10
11111 IIIII 11111 11111 I
1 10 100 1000 10000 100000
Rupture Time (h)
Fig. 2 Comparison of the creep rupture strength with HAZ creep rupture test
results for NF616 and for T91
Table 1 Chemical compositions for latest 9°1o chromium steels (mass'zs)
C Si Mn Cr Mo W Nb v N
T91/P91 0.10 0.30 0.50 9.00 1.00 0.05 0.20 0.05

T92/P92 0.08 0.25 0.50 9.00 0.50 1.80 0.07 0.20 0.05
CREEP PROPERTIES OF HEAT AFFECTED ZONE OF WELD IN W 657
Therefore, quantitative investigations of the creep behaviour at the heat

affected zone of ferritic steels has led to the development of new steels that
can resist heat affected zone creep rupture strength deterioration.
2. POSSIBLE HYPOTHESES FOR HAZ CREEP RUPTURE STRENGTH

DETERIORATION
Heat affected zone softening often occurs also in conventional low carbon
bainitic or martensitic steels. A part of the heat affected zone that is reheated
to a temperature higher than A3 rapidly transforms into the austenite phase
and is then cooled again gradually. The reheated part to just above the A3
point, for a short time, recrystallises into fine grained austenite, and the
hardenability decreases compared with that of the parent material. The
cooling rate is also not enough to cause supercooling for bainite or martensite
transformation of the fine austenite grain structure.
But such conventional understanding does not explain the creep rupture
strength deterioration in ferritic heat resistant steel because of the complicated
creep mechanism at elevated temperature.
Three different types of hypotheses are expected to clarify the creep rupture
strength deterioration mechanism at HAZ. Namely;
1. Owing to the stress concentration at the weakest part of the HAZ, this is
almost the same mechanism as the HAZ softening mentioned above.
2. Through the plastic deformation along the prior austenite grain bound-
ary. This mechanism implies dynamic recrystallisation at the increased
grain boundary in the fine grained zone.!
3. Coagulation and coarsening of precipitates during the HAZ heat cycle.
Fine carbide and nitride resolve rapidly into the austenite matrix
because of its high carbon and nitrogen solubility. Large size precip-
itates do not resolve completely and remain mainly at the grain
boundary and lath boundary. Resolved elements precipitate on the
remaining precipitates and on the both and lath grain boundaries during
the post weld heat treatment (PWHT) with larger size.
The HAZ creep rupture strength deterioration mechanism must be discussed
based on these three hypotheses during the other mechanism will be
declared.
3.1 Material Preparation

9 Cr-l.8 W-O.5 Mo
% % %
steel ASMET92/P92, whose commercial name is
NF616, is the parent weld material. A vacuum induction furnace produced
the 300 kg ingot and 10 ton ingot. The specimen ingot was hot rolled from
1150°C into 15mm thick plate. It was normalised at 1070°C for 1 hour and
tempered at 780°C for 1 hour to attain the full martensitic structure and well
balanced mechanical properties at room temperature.
3.2 Welding
A 15mm thick weld joint specimen with a 45 degree V shape groove was
welded by the tungsten inert gas arc welding method, the heat input was
15000 J/ em- in an Ar gas atmosphere.
The welding consumable is a similar metal to NF616. Table 2 shows the
Table 2 Chemical composition of welding consumable for GTAW (mass%)
C Si Mn Cr Mo W Ni Nb v N
0.065 0.20 1.00 9.00 0.50 1.60 0.35 0.040 0.10 0.030
representative chemical composition. A PWHT of 1 hour decreased the

hardness of bond and recovered the amount of precipitation.
3.3 Simulated Heat Affected Zone Heat Cycle Test

3.3.1 Simulated HAZ heat cycle condition
In order to determine the heat cycle condition, the HAZ temperature was
measured during the actual welding by using thermocouples every 2 m.m
from the welding bond, as indicated in Fig. 3. Figure 4 shows the simulated
heat cycle pattern which substitutes that of actual welding. The simulated
HAZ specimen was used for chemical analyses, transmission electron micro-
scope analysis for thin foil and replica, and evaluation of the various
mechanical properties including creep properties.
IV--Qoove IFine grain zone
Thermo couples
Fig. 3 Investigation of fine grained zone heat cycle

13sec.
Fig. 4 Simulated HAZ heat cycle pattern
4. INVESTIGATION OF HAZ CREEP RUPTURE STRENGTH

DETERIORATION MECHANISMS
4.1 Inhomogeneous Strength Profile and Stress Concentration at HAZ

Figure 5 shows the hardness distribution at the weld joint both at room
temperature and at 600°C. The hardness deteriorates markedly at just above
the A3 transformation temperature in spite of the room temperature measure-
ment result. But, a high temperature hardness profile does not indicate the
distinguishable low hardness zone around the transformation temperature .
• Measured at R T
300
280
o Measured at 600°C /u
V·
(J)260
(J)
~240
"EC'a 220
:c
Al.A;j.
• • I
.• -, . l.
"'v
• I
~. -
-:
(J) 200
·1
180
..x
·
a~
• I
II ~)
:; 160
:I
I 0
0 <>
140
120 C)
·· ......
./
:'" "'pI"
o~
00 o
100
800 900 1000 11 00
HAZ Peak Temp er aturef''C)
Fig. 5 Hardness profile for weld joint at various temperatures

The very small change of hardness might exist supposedly, but this hardness
difference at the fine grain zone does not seem to severely affect the creep
rupture strength at the HAZ of the weld. The dominant factor for HAZ creep
rupture strength deterioration must be discussed from another point of
view.
Even small differences cause the stress concentration, but the hardness
difference between parent material and HAZ fine grained zone decreases at
high temperature. Figure 6 shows the HAZ creep behaviour at 650°C for
1000
.• NF616 Pcrent rreterial
~ NF616 HAl
..~ ~ ~- ~
--
;J
r---
~ ....
~
~'
~
10 100 1000 10000 10CXJ00

~ure Tirre (I,)
Fig. 6 Example of HAZ creep rupture deterioration for NF616 exposed at 650°C
NF616 compared with that of the parent material. The HAZ creep rupture
strength deterioration at 650°C is larger than that at 600°C, as indicated in Fig.
2. Small differences of hardness in the fine grained zone at high temperature
do not explain this tendency.
4.2 Prior Austenite Grain Size Effect

The fine grained zone is the weakest part of the HAZ. The prior austenite
grain diameter is obviously decreased through the HAZ heat cycle. Research
shows that the creep properties of austenitic steels strongly depend on the
grain size.? The austenitic material has a stable and strong intragranular
structure. Therefore, the plastic deformation during the creep concentrates at
the grain boundary. Grain boundary crack and sliding has been reported.
But in the case of ferritic steels, only in Ref. 3 has this been disclosed and
discussed. But at the early stage of creep exposure, there is the possibility that
the high strength ferritic steel with strong intragranular structure also
deforms at the grain boundary, namely dynamic recrystalisation.
In order to confirm this contribution, the following investigation was
CREEP PROPERTIESOFHEAT AFFECTEDZONE OFWELD IN W 661
1
"E
cu
.•... 0.5
~ 0
o
o -0.5
CD
~ -1
c::
Co -1.5
Q)
~ -2
o
E -2.5
Ec -3
~ -3.5
-4
o 2 4 6
Log(Rupture Time) (h)
Fig. 7 Monkman-Grant Plot for NF616
carried out. Six bar specimens for heat cycle testing with a 12 mm square
cross-section were divided into 2 groups, the first three specimens being
heated up to 950, 1000 and 1050°C each and held 10 minutes and then cooled
down to 950°C for a hold time of 50 minutes. The other three specimens were
also heated up to 950, 1000 and 1050°C, but held only 10 seconds and cooled
down to 950°C for a hold time of 50 seconds. The precipitation condition was
uniform, at least for each specimen group, but the prior austenite grain size is
different. These specimens extract the prior austenite grain size effect to the
mechanical properties with little influence of precipitation.
Figure 7 confirms the Monkman-Grant rule for NF616 as per eqn (1).
tr . EY == K (1)
Here, tr is the rupture time (h), E is the minimum creep rate constant, and Y
and K are constants. According to Fig. 6, Y == 0.862 for NF616. Figure 7 shows
the relationship between and prior austenite grain size.
Figure 8 shows us that E is roughly proportional to the prior austenite grain
size,
E = A/d (2)
Here, A is a constant. The HAZ and the parent material basically consist of the
same materiaL Therefore eqns (1) and (2) lead to eqn (3)
E (HAZ)/E (BASE) == (A/d-HAZ)(A/d-BASE) = d-BASE/d-HAZ (3)
d-HAZ stands for the austenite grain diameter at the HAZ fine grain zone,
and d-BASE stands for that of the parent materiaL Austenite grain size ratio
between the parent NF616 and the fine grained zone is 5:1 according to the
comparison in Fig. 9. Therefore,
+"
c
ca '-----
-,
+" '- "- .6S00C -
en
c:
o -, r--
-
o o 700°C
u 0.1
+"
ca
a:::
c.
- "-
-,
,...
-
""
u -o'\.
ou
0.01 •
E -, <, - ~ -,
-,
-,
""'!'
:::s
E
.c: <, --
"
~ 0.001 •
o 20 40 60 80 100
Prior Austenite Grain Size( J.1. m)
Fig. 8 Influence of the prior austenite grain size on minimum creep rate constant
Base material (d :=; 50 urn) HAZ fine grain zone (d =::;: 10 urn)
20~m
Fig. 9 Comparison of the microstructure of NF616 parent material and its HAZ
E (HAZ) IE (BASE) = 5 (4)
Thus, the rupture time ratio between parent material and fine grain zone is
tr (HAZ)/tr (BASE) = E (BASE)I E (HAZ) = 0.25 (5)
Therefore, the rupture life of the fine grained zone is 114 of that of NF616.
This reduction of rupture life means about a 15 MPa creep strength
deterioration at 6000e for 100 000 hours (an 11 deterioration). %
4.3 Loss of Precipitation Strengthening Through the HAZ Heat Cycle

Figure 10 indicates the precipitation behaviour after the HAZ heat cycle and
after PWHT at a peak temperature every 100e from 850 to 10000e in order to
1.00
go.90
~ 0.80
:l
~ 0.70
c(
Q) 0.60
:::s
~ 0.50
Q)
0:: 0.40
"0
Q)
"0 0.30
~
S 0.20
0.10
0.00
850 900 950 1000
Peak Temperature during HAl cycle(OC)
Fig. 10 Precipitation amount change during the creep

••.•.• as HAZ Heat Cycle 00,6,0 as PWHT
simulate the fine grained zone. The specimens were held at each peak
temperature for 12 seconds based on the simulated HAZ heat cycle condition.
Chromium and iron resolve into the austenite phase rapidly owing to the
high solubility limit for carbon and nitrogen. A M23C6 type carbide was easy
to resolve because of its relatively low chemical affinity with carbon at high
temperature. On the other hand, Nb and V do not resolve into the austenite
matrix during the short heat cycle.
But the coherency of all precipitates will be lost owing to the phase
transformation, and the dislocation will also be released immediately.
The amount of precipitation recovers after the PWHT. Analysis of the
extracted residue confirmed this phenomenon, but the heat cycle with
transformation changes precipitation morphology. Figure 11 shows the rep-
lica image of precipitates just after the HAZ heat cycle and after PWHT.
Selected peak temperatures are Al + 30 e (a) and (d), A3 + 30°C (b) and (e)
0
and 1000 e (c) and (f). An increase of peak temperature decreases the
0
precipitation density, but PWHT recovers the amount of precipitates, as can

be seen Fig. II(d), (e) and (f). The mean precipitation size increases and the
mean precipitation distance also increases. Therefore, the precipitation
strengthening effect decreases even if the coherency to the matrix of the
precipitates is maintained.
Fine precipitates affect the creep rupture strength, but they resolve rela-
tively easily during the HAZ heat cycle. The large size precipitates remain
during this heat cycle. Resolved elements precipitate again, but on the
remaining precipitates and at the grain and lath boundaries. Figure II(d), (e)
and (f) indicate this precipitation coarsening during the heat cycle clearly.
Fig. 11 Transmission microimage of extracted replica of precipitates at fine grain

zone ofHAZ
Namely, the HAZ heat cycle accelerates the precipitation morphology change
as if it were exposed at an elevated temperature.
Orowan stresses can be estimated through eqn (6) as4,5
(T = MbE [In(h/5b) + 0.7]/(4'IT(1 + v)) (6)
where the Taylor factor, M = 2.5, Burgers vector, b = O.247nm, the elastic
modulus, E = 170 GPa, h is the harmonic average, h. is the average particle
distance and v is Poisson's ratio.
The estimated Orowan stress at the coarse grain zone of the HAZ is about
13.1 MPa before creep exposure and the stress at the fine grained zone is about
9.7MPa based on the accurate analyses carried out through thin foil TEM
observation. Therefore, a 3.4 MPa deterioration through the HAZ heat cycle
was estimated according to the simulated HAZ heat cycle test.
5. CONTRIBUTION RATIO OF CREEP RUPTURE STRENGTH

DETERIORATION FACTORS
Sections 3 and 4 conclude the contribution ratio 15 MPa to 3.4 MPa from both
creep rupture strength deterioration factors: (A) fine prior austenite grain
effect at the HAZ, and (B) precipitation coarsening and coagulation through
the heat cycle. There must be a small contribution from the stress concentra-
tion, but fine grain and loss of precipitation at the HAZ result in a low
strength area at the HAZ and leads the stress concentration. Therefore, a
decrease in the prior austenite grain size and precipitation coarsening are the
most important factors for the HAZ creep rupture strength deterioration. The
estimated creep rupture strength deterioration at 600°C for 100 000 hours in
the HAZ fine grained zone for NF616 is approximately 25 MPa according to
the Larson-Miller extrapolation. Therefore, the rest of the creep rupture
strength decrease, 6.6 MPa, is apparently derived from precipitation coarsen-
ing and ripening at the prior austenite grain boundary during the creep
exposure in the HAZ. In order to confirm this hypothesis, further investiga-
tions are necessary of the precipitation behaviour at the HAZ which was also
creep exposed for at least 10 000 hours through TEM and Orowan stress
estimations.
6. EFFECT OF THE ADDITIONAL ELEMENT PRECIPITATING AT THE

GRAIN BOUNDARY
Decrease of the prior austenite grain size affects the creep properties through
the decrease of hardenability and possible grain boundary deformation. This
idea implies that the grain boundary precipitation also affects the creep
properties. For example, copper is well known to precipitate at the grain and
lath boundaries because of its very low solubility in the ferrite phase.
Therefore, copper containing stee16 exhibits different properties at the grain
boundary at the fine grained zone in the HAZ compared with ordinary ferritic
steels. Therefore the evaluation of creep properties for copper containing steel
confirms this possibility and proves the effect of grain boundary on the HAZ
creep rupture strength deterioration in ferritic steels.
The trial melt in the vacuum induction furnace was carried out in order to
elucidate the grain boundary role in HAZ creep behaviour. Hot rolled 15 mm
thick plate specimens revealed that the creep of the weld joint with a 45
degree groqve. The material preparation procedure completely follows the
sample NF616 in this report.
Table 3 shows the chemical composition of the 3% copper containing 11%Cr
steel with a tempered full martensitic microstructure.
Figure 12 shows the creep rupture strength of both parent steel and weld
joint. The weld joint always ruptured at the HAZ fine grained zone, i.e. this
Table 3 Chemical composition of 11%Cr-W-Cu containing trial melt (mass'ze)
C Si Mn Cr Mo W Cu Nb v N
0.12 0.18 0.48 10.76 0.48 2.21 3.0 0.055 0.20 0.0472
en
a,
6
c
0 50
~
0
.~
45
40 .-----------~--~-~-- --
CD 35
"C
..c 30
0,
c 25
~
en 20
(l)
15
~
C. 10
2 5
C-
(l)
O
I 1
(l)
0 T92/P92 T91/P91 11 Cr-3Cu
Fig. 12 Difference of creep rupture strength between HAZ and parent material at
600°C for 10 000 hours
copper containing steel has a lower HAZ creep rupture deterioration resist-
ance. Grain boundary precipitated copper apparently decreases the resistiv-
ity, but an accurate quantitative analysis is necessary to decide the limit for
copper content in such ferritic materials.
7. CONCLUSION
Investigation of creep properties, precipitation analysis and structural obser-

vation through optical and transmission electron microscopy evaluated the
heat affected zone of the weld for the latest 9 to 120/0 chromium containing
tempered martensitic steels.
Instead of the conventional stress concentration mechanism, the possibility
of the fine prior austenite grain effect and the coarsening of precipitates
explain the creep rupture strength deterioration.
The estimated quantitative contribution ratio of fine prior austenite grain
and precipitation coarsening is 50:50%. A possible absolute deterioration
strength value is 12.5 MPa each.
From the viewpoint of the prior austenite grain role in creep behaviour,
grain boundary precipitating element, for example copper, apparently affects

the creep rupture strength of HAZ.
REFERENCES
1. G. Eggler, J. C. Earthman, N. Nilsvang and B. Ilschner: Acta metall., 1989,

37 (1), 49.
2. F. Garfalo, W. F. Domis and F. Gemmingen: Trans. Metall. Soc. AIME, 1964,
230, 1460.
3. Y. Kadoya and T. Goto: Tetsu-to-Hagane, 1992, 78, 1601.
4. R. o. Scattergood and D. J. Bacon: Phil Mag., 1975, 31, 179.
5. R. o. Scattergood: Acta Metall., 1982, 30, 1665.
6. Y. Hasegawa, N. Mizuhashi, H. Naoi and H. Sakurai: CAMP ISI!, 1991, 6,
884.
The Effect of Submerged-ARC Welding
and PWHT on Creep Damage
Occurrence in Long-Seam Welded
Cr-Mo High Energy Piping
CARL D. LUNDIN and GANG ZHOU
The University of Tennessee, Materials Science and Engineering,
434 Dougherty Engineering Building, Knoxville, TN 37996, USA
ABSTRACT
A series of failures, leaks and cracks in Cr-Mo high energy steam piping in the US
has created widespread utility concern for the integrity and serviceability of these
piping systems. The concerns rose to a high level after the catastrophic failures of hot
reheat piping at the Mohave and Monroe power stations as well as main steam
piping failures at the Mt. Storm station. In the evaluation of the failed piping, it was
determined that the damage and cracking in seam welded steam piping initiates and
propagates by creep-related mechanisms. The damage occurrence is often directly
related to the procedures used to fabricate long seam submerged-arc (SA) welded
piping. In general, for SA welds which have been normalised and tempered (N&T)
prior to service, cavities are predominant in weld metal segregation bands adjacent
to the fusion boundary and are associated with grain boundary particles (inclusions
and carbides). However, in the case of SA welds which have been subcritically
PWHT prior to service, cavities preferentially initiate in the fine-grained region in
either the base metal HAZ or weld metal overlap HAZ's and are related to grain
boundary triple points and inclusion particles.
It was also found that the type of flux used in the SA welds has a significant
influence on segregation band formation in the weld metal and on the inclusion
density and distribution in the segregation bands. As a result, the welding flux has a
significant influence on the creep behavior of the long-seam welded Cr- Mo piping.
The results of evaluations and studies on damaged piping have lead to optimisation
of SA welding procedures for enhanced performance of long-seam welded Cr-Mo
high energy piping.
1. INTRODUCTION
It is estimated that, in the US, approximately 70% of electric power is

produced by fossil energy. Fossil energy power plants are, and will continue
to be, the mainstay of electric power production for the foreseeable future.l-?
However, over 75% of the fossil power plants in the US are more than 25 years
old, and many of them are now being relegated to cyclic duty.s A significant
amount of plate-formed and long-seam SA welded high energy piping has
668
THE EFFECTOFSUBMERGED-ARCWELDINGANDPWHT 669
been used in the US. Thus, the performance of these SA welds is often the key
life limiting factor.
Since 1979, a series of failures, leaks and cracks in Cr-Mo high energy
piping throughout the US has created widespread utility concern for the
integrity and future serviceability of plate-formed piping with extended
service exposure. In particular, all significant failures were associated with the
long-seam welded pipe spools, which were fabricated using SA welding.v+ In
the last 10 years, more than 500 feet of creep damaged high energy piping
(both main steam and hot reheat piping) from more than 30 fossil power
plants throughout the US has been characterised at The University of
Tennessee using advanced metallographic techniques and a 'Cryo-Cracking'
fractographic method+:" It has been found that the damage and cracking in
high energy piping is directly associated with the long seam SA weld. The
root cause for the damage and cracking in seam-welded steam piping is
constrained creep cavitation. In addition, the welding procedures and post-
weld heat treatment (PWHT) employed during fabrication have a significant
influence on damage level and the features of the creep damage.v l? This
paper reviews and summarises the major results of the evaluation studies on
creep damaged high energy piping in an attempt to provide understanding of
the effect of SA welding and PWHT on creep damage occurrence in long-
seam welded Cr- Mo piping.
2. FABRICATION OF HIGH ENERGY PIPING
Welding has been the basic process for fabrication of high energy piping in
the US. The SA welding process, with its high heat input and high deposition
rate, has been extensively employed in production due to substantial econ-
omic benefits. In general, the SA welds were deposited in a multipass
sequence using a double IV' groove preparation for hot reheat piping and a
narrow 'U' groove preparation for main steam piping. Both acid and neutral
welding fluxes were used for fabrication of high energy piping due to their
efficiency in enhanced penetration, deposition rate and tolerance of pipe
surface condition and effect on weld surface contour. As a result, the flux
ingredients produced a high oxygen content (600-1000 ppm) in the SA weld
metal of long-seam welded piping, and thus a high weld metal inclusion
content. Acid flux was extensively used in deposition of the ID bead in the
long-seamed hot reheat piping." 10-12
Two postweld heat treatments were normally used in fabrication of the long-
seam welded high ellergy piping.v 11 Weldments subcritically heat treated
show a distinct heat-affected zone (HAZ) upon metallographic etching. As a
result, the fine-grained/intercritical HAZ (FG/ICHAZ) region with low creep
strength remained in the piping in both the base metal along the fusion
boundary and the weld metal in the pass overlap regions. In weldments which
were N&T or annealed, the HAZs in both the base metal and weld metal are
effectively 'erased', and a uniform microstructure and grain size are present
throughout the entire weldment. During the microstructural alteration upon
N&T or annealing, a coincidence of inclusions and grain boundaries occurs by
grain boundary movement and inclusion pining (during austenisation and
subsequent transformation). As a result, a high inclusion level is generated
along the grain boundaries. These grain boundary inclusions act as prefer-
ential cavity initiation locations due to the incoherent interface between the
inclusion and the matrix. Thus, differences in PWHT result in a clear distinc-
tion in creep damage distribution for differently treated pipe spools.
3. CHARACTERISTICS OF CREEP DAMAGE IN HIGH ENERGY

PIPING
It has been determined that creep damage initiates heterogenerously in the

form of cavities at subsurface locations either in the weld metal or in the
HAZs at preferential locations, which are related to weld geometry and
PWHT. A damage gradient is often observed, extending from a subsurface
preferential damage location toward the outer surfaces. Creep damage is
rarely found at the weld surface and thus in-situ replication is of no value for
damage determination. Only state-of-the-art ultrasonic methodologies, such
as time of flight (TOFD) and focused beam, and advanced metallographic
techniques are suitable for detecting and defining the level of creep damage.
However, current ultrasonic techniques have their greatest technical difficulty
in detectin.g creep damage early in life (isolated cavitation), and advanced
metallographic techniques require significant skill in specimen preparation
and characterisation. Artifacts of specimen preparation can lead to a mis-
understanding of damage level and thus an incorrect assessment of the
integrity of the piping. Therefore, a new fractographic methodology called
'Cryo-Cracking' was developed at The University of Tennessee for character-
isation and quantification of creep damage. The 'Cryo-Cracking" method does
not depend on an individuals metallographic skills and is thus considered
less sensitive to misinterpretation due to specimen preparation techniques.v?
3.1 Characteristics of Creep Damage in High Energy Piping Which Has Been N&T
Prior to Service
For the majority of the US long-seam welded hot reheat piping (20"-32" OD
with 3/4" to 1-1/2" wall thickness), a N&T treatment was employed after
welding (prior to service). Two weld geometries are common in the long-
seam welded hot reheat piping:
• Type I: Double IV' groove weld geometry with similarly sized OD and
ID weld deposits as shown in Fig. 1.
THE EFFECT OF SUBMERGED-ARC WELDING AND PWHT 671
• Type II: Double 'V' groove weld geometry with the OD deposit sig-
nificant larger than ID deposit, and a wide OD cap bead as shown in Fig. 2.
The preferential damage location for N&T SA welds depends significantly on

weld geometry. In general, creep damage predominantly occurs in the weld
metal adjacent to the fusion boundary within weld metal segregation bands.
The segregation bands are high in inclusion content. These bands are oriented
primarily parallel to the fusion boundary and spaced 'more closely' along the
fusion boundary than at other locations in the weld metal. For hot reheat
piping with a Type Iweld geometry, the preferential damage location is in the
weld metal 'cusp' region adjacent to the fusion boundary (Fig. 1). In this case,
creep damage will progress from the' cusp' along either or both of the OD and
ID fusion lines in the weld metal. For hot reheat piping with a Type II weld
geometry, the preferential damage location is in the weld metal adjacent to
the fusion boundary just below the cap pass bead (Fig. 2). In this case, creep
damage will be distributed in the weld metal along the fusion line toward the
ID.
Constrained cavitation is the basic mechanism of creep damage in long-
seam welded high energy piping. For N&T SA welds, cavities preferentially
initiate at grain boundary inclusions in the weld metal due to the incoherent
interface between the inclusion and the matrix. Figure 3 shows a typical
example of constrained cavitation in N&T SA weld metal both optically and
on the fracture surface produced by 'Cryo-Cracking'. It is evident that cavities
initiate on grain boundaries and are normally associated with grain boundary
inclusions. With progressive nucleation of cavities from grain boundary
particles and continuous growth of cavities, link-up between the cavities will
occur and progress to a microcrack stage. Macrocracks are subsequently
formed by link-up of microcracks. Final failure (leakage or rupture) occurs by
link-up of macro cracks to a critically unstable size along the fusion boundary
through the wall of the long-seam welded piping.
The welding flux has a significant effect on amount of inclusions in the SA
weld metal through the interaction between the flux and molten weld pooL
During SA welding, the maximum extent of periodic segregation occurs near
the fusion boundary. As a result, more extensive and more closely spaced
segregation bands, rich in inclusions, are formed adjacent to the fusion
boundary compared to the other locations in the weld metal. Table 1 shows
Table 1 Areal inclusion density for acid and basic flux SA welds
Location in SA Weld Acid Flux SA Weld Basic Flux SA Weld
In segregation band (#/mm2) 19000-37000 6000-9000

At center of Weld Metal (#/mm2) 10000-16000 5000-8000
Oxygen Content in Weld Metal 1200 ppm 190 ppm
2.0x
Weld Geometry
SOx
Preferential Damage Location
Fig. 1 Type I weld geometry and preferential damage location for hot reheat piping
with a N&T PWHT
2.0X
Weld Geometry
50X
Preferential Damage Location
Fig. 2 Type II weld geometry and preferential damage location for hot reheat
piping with a N&T PWHT
1000x
Optical Metallography
1000x
Cryo-Cracking Fractography
Fig. 3 Typical morphology of cavities in the weld metal adjacent to the fusion
boundary for a Cr-Mo SA weld with a N&T PWHT
THE EFFECTOFSUBMERGED-ARCWELDINGANDPWHT 675
the areal inclusion density in Cr-Mo SA welds as function of flux type and
location within the weld metal.
It is evident that the inclusion density for acid flux SA welds is significantly
greater than that of basic flux welds. The inclusion level is consistent with the
weld metal oxygen content. After a N&T treatment, the number of inclusions
residing on grain boundaries increases as a result of grain boundary move-
ment and, grain boundary pining by inclusions during austenisation and
subsequent transformation. Table 2 presents an example of grain boundary
Table 2 Grain boundary linear inclusion density

before and after N&T treatment for an acid flux SA
weld
As-welded N&T
Linear Density (#/mm) 130 170
linear inclusion density before and after N&T treatment for an acid flux SA
weld.
The grain boundary inclusions in the weld metal segregation bands play
the primary role in initiation of creep cavities. In addition, a significant stress
concentration along the fusion boundary is caused by a mismatch in the creep
rate between the weld metal and the base metal. This unique distribution of
metallurgical factors, in terms of a significant level of grain boundary
inclusions and a stress concentration along the fusion boundary, results in the
weld metal adjacent to the fusion boundary becoming the preferential
damage location. The correlation between the preferential damage location,
weld geometry and PWHT reflects the influence of the microstructure and
stress/ constraint on cavitation.
3.2 Characteristics of Creep Damage in High Energy Piping which has been
Subcritically PWHT
For the majority of the long-seam welded main steam piping (16"-20" OD
with 2-3/4/1 to 3-3/8/1 wall thickness), a sub critical PWHT was employed
during fabrication. The SA welds in main steam piping normally have a
narrow 'U' groove weld geometry with a small side wall angle. A typical
cross section of long-seam welded main steam piping with a subcritical
PWHT is shown in Fig. 4. In general, two passes per layer are deposited from
the OD throughout the pipe wall thickness. Thus, a continuous, radially
oriented, FG/ICHAZ region is created at the center of the weld metal between
the two fill passes in the double pass per layer deposit. In addition, the
significant overlap between the small SA passes produces an essentially
x
o
LO
E--4
:r::
~
c ~
~
0
ca
o .~
0
.....J .~ $-01
U
Q) ,..0
Cl ::l
ctS C/)
E cO
ctS
Cl o:S
(ij .~
E 0.0
~ s::
Q)
.~
a: 's..
Q5
s cO
Q)
"'-'en
s::
'a
S
$-01
0
'1."-1
s::
.9
"'-'cO
u
X r9
0
C\i OJ
0.0
cO
S
cO
"'0
ca:c
c
Q)
$-01
~OJ
c, $-01
"'d
s::
cO
e-, $-01
~ "'-'Q)
Q) S
E 0
Q)
0
Q) 0.0
o "'d
"'0
Q)
QJ
~ ~
~
eb
~
1000x
Optical Metallography
1000x
Cryo-Cracking Fractography
Fig. 5 Typical morphology of cavities in the base metal FG /ICHAZ region for a Cr-
Mo SA weld with a subcritical PWHT
continuous base metal FG /ICHAZ through almost the entire wall thickness.
A sub critical PWHT does not alter the HAZ grain size distribution induced
during welding.
For sub critically PWHT SA welds, creep damage predominantly forms in
the FG /ICHAZ region in either the weld metal HAZ or the base metal HAZ
due to the creep strength/ grain size effect in the FG/ICHAZ region. It is
believed that the lower creep strength of the FG/ICHAZ is due to the fine
grain structure plus coarse carbides produced during the welding thermal
cycle and subsequent subcritical PWHT as well as service exposure. A typical
example of creep damage, in the form of cracking, in the base metal FG /
ICHAZ is presented in Fig. 4.
Cavitation is the principal mechanism for creep damage in the main steam
piping subjected to a sub critical PWHT. Figure S shows a typical example of
cavitation in the base metal FG/ICHAZ region with optical metallography in
Fig. Sa and 'Cryo-Cracking' fractography in Fig. Sb. It is evident that cavities
in the base metal FG/ICHAZ initiate primarily at grain boundary triple
points. The base metal contains significantly lower oxygen content and thus a
lower oxide inclusion level compared to the SA weld metal. However, when
the inclusions reside on the grain boundaries, they do participate in the base
metal HAZ cavity initiation. In the case where damage occurs in the weld
metal HAZ's, the significant number of weld metal inclusions have a
combined and synergetic effect and thus they can exacerbate creep damage
occurrence.
In summary, it can be concluded that, for enhanced performance of long-
seam welded Cr-Mo high energy piping, the optimum SA welding pro-
cedures include the use of a basic flux during welding to reduce the oxygen
content and inclusion level in the weld metal and the application of an N&T
treatment after welding (prior to service) to eliminate the FG/ICHAZ region
in both the base metal and the weld metal.
4. CONCLUSIONS
1. Submerged-arc welding procedures and PWHT conditions have a sig-

nificant influence on creep damage occurrence in long-seam welded Cr-
Mo high energy piping.
2. There is a preferential creep damage location in high energy piping
depending on weld geometry, weld metal characteristics and PWHT.
2a. For SA welds with a N&T PWHT prior to service, cavities preferentially
form in the weld metal segregation bands which are located adjacent and
parallel to the fusion boundary. For a Type I weld geometry, the
preferential damage location is in the weld metal adjacent to the fusion
boundary in the 'cusp' region. For a Type II weld geometry, the prefer-
THE EFFECTOFSUBMERGED-ARCWELDING ANDPWHT 679
ential damage location is in weld metal adjacent to the fusion boundary

just below the cap pass.
2b. For SA welds with a sub critical PWHT prior to service, cavities preferen-
tially form in the FG/ICHAZ region in either the base metal HAZ or the
weld metal·HAZ's.
3. Type of flux used during SA welding has a significant effect on the
oxygen content and inclusion level in the weld metal. Acid flux results in
a high oxygen content and thus a high inclusion level.
4. For enhanced performance of long-seam welded Cr-Mo high energy
piping, the optimum SA welding procedures include the use of a basic
flux during welding and the application of an N&T treatment after
welding (prior to service).
REFERENCES
1. R. Viswanathan: Damage Mechanisms and Life Assessment of High- Temperature

Components, ASM International, Metals Park, Ohio, 1989.
2. DOE, 'Inventory of Power Plants in The United States 1988', DOE/EIA-0095
(88), Distribution Category UC-98, US DOE Washington, DC 20585,
August 1989.
3. S. Bangs: 'When a Weld Fails ... ,' Weld Design and Fabrication, March 1986,
79-82.
4. F. L. Becker, S. M. Walker and R. B. Dooly: 'Industry Experience and
Review of Steam Pipe Activities,' Proceeding of EPR! Conference on Life
Extension and Assessment of Fossil Power Plants, 1987, Electric Power
Research Institute, Palo Alto. CA, USA.
5. C. D. Lundin, K. K. Khan, D. Yang, S. Hilton and W. Zielke: 'Failure
Analysis of A Service-Exposed Hot Reheat Steam Line in A Utility Steam
Plant,' WRC Bulletin 354, June 1990.
6. G. Zhou: 'Metallurgical Causes for the Occurrence of Creep Damage in
Longitudinally Seam-Welded Cr-Mo High Energy Piping,' Dissertation
for the Doctor of Philosophy Degree, The University of Tennessee, Knoxville
Tennessee, USA, August 1997.
7. C. D. Lundin, G. Zhou, W. Liu, and P. Liu: 'Evaluation of 1996 Main Steam
Piping Failure, Mt. Storm Unit 1,' Technical Report to The Materials
Properties Council, February 1997.
8. C. D. Lundin, G. Zhou, C. Y. P. Qiao and P. Liu: 'Metallurgical Character-
ization Studies,' HEP-15, The Materials Properties Council, April 1996.
9. C. D. Lundin, G. Zhou and M. Prager: 'Cryo-Cracking', A New Technique
for Creep Damage Assessment in High Temperature Components,'
Proceeding of the International 'HIDA' Conference on Creep and Fatigue
Crack Growth in High Temperature Plant, 15-17 April 1998, Saclay,
France.
10. J. F. Hennry, F. V. Ellis and C. D. Lundin: 'The Influence of Flux

Comnposition on the Elevated Temperature Properties of Cr-Mo Sub-
merged-Arc Weldments,' WRC Bulletin 354, June 1990.
11. T. M. Cullen, F. V. Ellis and J. R. Henry: 'Examination and Testing of
Longitudinal Seam Welded Hot Reheat Piping,' Proceeding of EPRI
Conference on Life Extension and Assessment of Fossil Power Palnis, 1987,
Electric Power Research Institute, Palo Alto. CA.
12. F. V. Ellis, M. P. Borden and P. Skute: 'Creep Rupture and Crack Growth
in Longitudinal Seam Weldments,' Life Assessment and Life Extension of
Power Plant Components, Proceeding of ASME Pressure Vessels and
Piping conference, PVP-Vol. 138, Pittsburgh, Pennsylvania, July 1988,
78-97.
Summary of Papers
J. NUTTING
The Conference was attended by 135 delegates from 17 countries. In all some
57 papers were presented, with the authors coming from 11 countries. This
was, therefore, an international meeting and the proceedings were of major
significance.
The scene was admirably set by the first two papers in which the new
driving forces for the power generators were clearly outlined. Seldom has a
conference on Power Generation received such clear guidelines in relation
to:
1. The political philosophy with regard to deregulation.
2. The economic factors linked with deregulation.
3. The environmental factors linked with the production of CO2, S02 and
Nox•
In order to meet these requirements it is clear that higher service tem-
peratures are needed, thus giving rise to greater efficiency. It is hoped that
from this greater efficiency generation costs can be reduced. However, to
meet these targets new materials are required.
It is perhaps useful to assess first the likely price stability with regard to the
alloying elements (chromium, molybdenum, tungsten and nickel) required in
these new materials. The factors would seem to be as follows:
CHROMIUM
The chief source of chromium is the southern hemisphere. With the political
changes which have occurred in South Africa stability seems to have been
established - therefore price volatility is unlikely. Other chromium sources in
the former USSR are now being opened up and again this will lead to price
stability.
MOLYBDENUM
The chief sources of molybdenum are as a by-product from the refining of

copper. If the copper demand goes down, the production of molybdenum
decreases and the price goes up. After a period of great volatility in the price
of molybdenum, it is now believed that stability will be achieved for the next
few years.
681
TUNGSTEN
Tungsten is widely distributed throughout the world and, therefore, the price
is not sensitive to political turmoil. China, as the world's major tungsten
supplier, needs to maintain a steady market for tungsten and this again will
lead to price stability.
NICKEL
Nickel prices have been steady and low for the last few years and are likely to
remain so. Nickel is widely distributed, but the chief sources of supply are in
the Western hemisphere and again political stability leads to price stability.
CONVENTIONAL BOILER STEELS AND ROTOR STEELS
It would seem that the end of the road has been reached with the develop-
ment of conventional Ni-Cr-Mo-V and Cr-Mo-V steels. Little can be done
to increase the service temperatures of these steels. The factors leading to their
structural stability during service were well established by the 1970s.
Although there was a flurry of interest in super clean developments which
came during the period 1980-1995 this now seems to be over. Steels can be
produced which are virtually free from overheating during forging, temper
embrittlement during service and from sulphide particle creep embrittlement
and the cost penalty is not great «20%).
THE NEW STEELS
Following the last EPR! Conference in 1995, it became clear that emphasis
should be placed on assessing the development of 9-12% chromium steels for
both boiler and rotor applications. From the papers presented at this meeting,
it has now become clear that we have a thorough understanding of the
metallurgy of these materials. Perhaps there have been arguments as to
whether tungsten is a good or bad addition, but generally the evidence
favours the addition of tungsten to the steels.
The techniques for determining the microstructures of 9-12% chromium
steels are now readily available and the microstructural characterisation
would appear to be complete. The precipitation of carbides, the formation of
nitride phases, the precipitation of the laves phase and the changes of the
dislocation densities during tempering and during service have been well
documented and surprising unanimity has been achieved.
Microanalysis would appear to have achieved its ultimate limit insofar as
SUMMARY OF PAPERS 683
by a combination of field-ion microscopy and mass spectroscopy, individual

atoms can be identified and their location in the original microstructure
established.
A number of papers have been presented devoted to the modelling of
microstructural development. If accurate modelling can be achieved, it is a
much cheaper method of assessing microstructural stability than that nor-
mally used, namely electron microscopy of the structural changes occurring
as a function of time. If modelling is accurate, we can find out in a few
minutes what will happen after 20 years in service, but it is important that the
modelling is accurate. The papers presented show that, although progress has
been achieved, much further work is required.
Just as it would appear that we have reached the end of the road with the
development of low alloy rotor, boiler and tube steels, we now appear to have
reached the limit with what can be achieved by the use of 9-12% chromium
steels by conventional metallurgy. The equilibrium diagrams we require for
assessing the possible heat treatments can now be determined by modelling
and using thermo-calc programmes. The conventional steel making tech-
niques require the full melting of the alloy constituents and their dispersion in
the liquid state. It is then hoped that all the alloying elements are kept in solid
solution whilst the steel is heat treated in the austenitic stage and that the
precipitation of carbides and inter-metallic phases can be achieved when the
steel is quenched and then tempered in the ferritic state. The conventional
equilibrium diagrams enable us to understand what can be achieved by this
route. There are, however, other possibilities and one paper was presented
showing how the limitations of the equilibrium diagram can be overcome by
the direct addition of carbides to the melt. A similar paper was offered to the
Conference on the direct addition of oxides, but unfortunately this was not
presented. It is hoped that the paper could be incorporated with the final
proceedings.
An alternative method of achieving suitable volume fractions of strongly
alloyed carbides could be to raise the temperature in the steel making furnace
within the range 1700-1800°C and saturating the liquid steel with carbon, on
cooling alloy carbides would precipitate from the liquid phase and remain
stable during solidification and give the appropriate strengthening in the
solid state. The steel making problems are great and there looks to be many
advantages in following the direct carbide addition route.
In retrospect it seems likely that the present Conference will be looked
upon as the definitive meeting at which the properties of 9-12% chromium
steels were firmly established in relation to their use as boiler materials, as
tubes and as rotors. Wh.ere service temperatures in excess of 600°C are
required, the materials of construction would now seem to be readily
available - their mechanical properties are understood and we have a good
working knowledge of their long term thermal stability.
It is hoped that a hardback edition of the present Conference proceedings
will be published by The Institute of Materials and that the edition will
include some of the papers which unfortunately could not be presented at the
Conference. A copy of the hardback proceedings will be made available to all
who attended the Conference and the hardback edition will be available for
general sale from The Institute of Materials.
Author Index
Abe, F., 84 Fedeli, G., 644
Abe, M., 298, 468 Filip, M., 322
Abe, T., 365, 408 Foldyna, V., 322
Abyhammar, T., 507 Fujita, M., 298
Agren, J., 270 Fujita, N., 223
Andren, H.-O., 199 Fujita, T., 259, 418
Angeliu, T., 234 Fujitsuna, N., 84
Armor, A.F., 1 Fukui, Y., 418
Ayala, E., 445, 633, 644
Azuma, T., 332, 397 Goecmen, A., 430
G6mez, X., 445, 633
Bakker, W.T., 435 G6mez-Acebo, T., 633
Bates, P., 309 Goodwin, C.C., 212
Baumhoff, V., 157 Granacher, J., 288
Bendick, W., 133 Gustafson, A., 270
Berger, C., 288
Berroeta, J.A., 445 Haarmann, K., 133
Bhadeshia, H.K.D.H., 223 Hahn, B., 157
Bicego, V., 644 Hales, R., 212
Blaes, N., 386 Hall, E.L., 234
Bontempi, P., 247 Hasegawa, Y., 259, 655
Brown, B., 644 Hashizume, R., 332
Buchanan, L.W., 65 Hattestrand, M., 199
Hayashi, K., 51
Cerjak, H., 611 Henderson, P.J., 507
Cerri, E., 247 Hidaka, K., 418
Cumino, G., 622 Hirano, K., 119
Hirata, H., 482
De Luis, J., 445 Hoglund, L., 270
Deshayes, F., 133 Holmes, P., 430
Di Gianfrancesco, A., 622 Honda, T., 119, 184
Echeberria, J., 445, 633 Igarashi, M., 84

Ehrlich, K., 586 Ikeda, Y., 397
Endo, T., 596 Ishiguro, T., 332, 397
Ennis, P.J., 457 Ishihara, 1., 96
Eriksson, Th., 507 Ishii, R., 277, 574
Ernst, P., 430 Ishiyama, 0., 365, 408
Evangelista, E., 247
Everson, H., 65 [akobova, A., 322
Faulkner, R.G., 212 Kadoya, Y., 560
685
Kajigaya, I., 172,468, 482 Nutting, J., 12, 681

Kaneko, R., 418
Kihara, S., 482 Ohgami, M., 259, 655
Kimura, H., 298 Okada, H., 96
Kimura, K., 84 Okamura, Y., 655
Kojima, T., 51 Ono, S., 397
Komai, N., 96, 144 Orr, J., 65
Korcak, A., 322 Osada, T., 119
Kusano, T., 119 Otsuka, N., 482
Langner, K., 386 Park, K.S., 596

Larsen, M., 234 Price, S., 109, 309
Letofsky, E., 611
Linsebigler, A., 234 Quadakkers, W.J., 457
Lundin, C.D., 668
Roman, M.A., 445,633,644
Magoshi, R., 560
Maile, K., 288 Sakuma, T., 184
Masuyama, F., 33, 96, 144,596 Sato, M., 298, 468
Matera, S., 622 Sawaragi, Y., 96, 144, 482
Matsumoto, J., 560 Schellenberg, G., 288
Matsumoto, 0., 365, 408 Schirra, M., 586
Maurischat, M., 386 Schonfeld, K.-H., 375
Mayer, K.H., 349 Schwind, M., 199
Meade, D., 212 Seo, S., 560
Mimura, H., 259 Seth, B.B., 519
Minami, Y., 51, 494 Shudo, Y., 397
Miyakawa, M., 365 Spigarelli, S., 247
Miyata, K., 96, 144 Spindler, M.W., 212
Miyazaki, M., 277, 574
Morinaga, M., 332 Takaku, H., 184
Mukira, C., 234 Takemoto, K., 119
Muneki, S., 84 Tanaka, Y., 332, 397, 418
Muramatsu, K., 543 Tassa, 0., 622
Murata, Y., 332 Taylor, N., 644
Thornton, D.V., 349
Nakada, T., 365 Toennes, C., 430
Nakagawa, K., 468 Tohyama, A., 494
Nakamura, S., 418 Tollin, J., 507
Nakashima, H., 365 Tramer, M., 288
Nakayama, G., 172 Tsuchiyama, T., 365, 408
Naoi, H., 259 Tsuda, Y., 277, 574
Nishimura, T., 560
Nishiyama, Y., 482 Vaillant, J.-C., 133
AUTHOR INDEX 687
Valle, J., 445 Yamamoto, K., 172

Van Wartel, H., 644 Yamamoto, S., 144
Vega, J., 633 Yamamoto, Y., 560
Vodarek, V., 322 Yamauchi, M., 298
Yanagisawa, T., 468
Wagner, H., 375, 386 Yasumoto, Y., 408
Walsh, M.A., 109, 309 Yokoyama, T., 96, 144
Wouters, Y., 457 Yuuki, M., 172
Yamada, M., 277, 574 Zhou, G., 668

Yamadera, Y., 96 Zschau, M., 157
Subject Index
Alloy 800H, 42, 43, 45 hot workability, 57-8
Alpha prime & embrittlement, 243-4 Bucket steel development, 582-3
Aluminium, 311, 529-30
Antimony impurities, 338 Capacity factor of power plants, 7-8
Arsenic impurities, 338 Carbide powder additions, 29-30,
Ash corrosion, see Coal ash 311
corrosion FeWTiC, 312-20
Asset management, 8-9 Carbide precipitation, 25
Atom probe field ion microscopy, alloy content, 19-25, 29, 345
200-2 carbon steels (plain), 13-14
Austenitic steel development, 42-7, tempering temperature, 22-4
482-93, see also specific steels Carbo-nitride coarsening models,
bimetallic tubes, 445-56 270-6
grain boundary precipitation Carbon additions, 400
modelling, 212-22 Carbon dioxide emissions, 3, 111-12,
ultra-super critical boilers, 179-82, 349
494-506 Carbon steel (plain), tempering,
weld strength, 180-2 13-19
Casing materials, 524-7, 556
Bimetallic tubes, 445-56 Cast steel development, 119-29,
bending, 453 359-61,584
heat treatment, 452-3, 455 Cerium & oxidation resistance, 483
interface microstructure, 447-51 Chromium content
service performance, 454-5 corrosion resistance, 180, 459-62,
welding, 454 463-4,466,471-2,475,478-9,
Biomass boilers, 507-16 511-12,513,515,553
Blade materials, 522-4, 555 creep strength, 339, 341, 342, 400
titanium, 535-6 sources of, 681
Blades, long last row, 533, 535-6 tempering behaviour, 19-21, 400
Blowholes & silicon content, 120, 128 toughness, 56, 337, 400
Boiler steel development, 176-7, transformation temperature, 337
435-44,494-506,550-4,682-3, Coal ash corrosion, 179-80, 436, 468,
see also specific steels 469,473-0479-80,553
austenitic steel, 42-7 chromium content, 180,475,553
ferritic steels, 35-42, 84-95 coal type, 439-41
historical background, 34-5 Coal plants, see Fossil plants
Bolting materials, 527-8 Coal type & corrosion, 439-41
Bond order, 332 Coarsening models, 270-6
Boron additions, 311, 386-96, 581 Coatings, erosion resistant, 530
ageing behaviour, 204, 207-8, 209 Cobalt additions, 41, 311, 420, 581
creep strength, 53-4, 355, 384, Copper additions
419-20,421 creep strength, 45, 500, 502, 503
689
heat affected zone creep cobalt content, 420

properties, 665-6 manganese content, 56
precipitation during ageing, 200, predicting, 54, 56, 634, 635-9,
205,206-7,209 642-3
Corrosion tungsten content, 55
chromium content, 180,459-62, in welds, 121, 633-43
463-4,466,471-2,475,478-9, DICTRA, 270-6
511-12,513,515,553 Double austenitising, 324-5, 328-30
coal ash, 179-80, 436, 468, 469, Dual heat treated rotors, 534-5
473-7,479-80,553
chromium content, 180,475,553 E911, 65-83, 134, 137-42, 437,
coal type, 439-41 612-13,622-32
manganese content, 512-13, 515 ageing, 626-7, 628-9
service lifetime effects, 464-6 cold bending, 74, 81
steam oxidation, 463-4, 468, 470, creep behaviour, 72, 73, 624, 629
477-9,553-4 hot isostatic pressing, 75-6, 81
water vapour, 462-3 mechanical properties, 623
of waterwalls, 436, 442-3 microstructural stability, 76-80,
COST E steel, 375-85 627-9
CR30A, 43, 46 oxidation, 457-66
Cr equivalent, 54-6, 121, 128, 129, strength, 71, 73, 623
634,635-7 stress corrosion cracking, 75
Creep behaviour transformation temperature, 623
alloy element content, 26-7, 39-42, welding, 72, 74, 81, 139-40,
53-4,332-5,339-46,354-6, 611-21,624
399-400, see also specific alloy Economic factors, 3-5, 6-7, 437-8
elements EM12, 36, 37, 134
carbide forming elements, 345 welding, 633-43
grain size, 26 Embrittlement, 234-46
inherent creep strength, 87, 279 alpha prime, 243-4
latent creep resistance, 208 impurities, 234-5, 238-42, 244
microstructure, 26-8, 247, 251-7, second phase precipitation, 234,
280-1,283,342-1,355-6 242-4
modelling, 596-607 Energy production trends, 109-10
temperature effect, 343-5 Environmental issues, 3, 111-12, 349
Creep-fatigue, 298-308 Erosion resistant coatings, 530
Creep-fatigue cracking, 288-97 Esshete 1250, 43
Creep resistance, latent, 208 dissimilar metal welding, 644-54
Creep strength, inherent, 87, 279
Cryo-Cracking,669,670 Fatigue damage assessment, 537-8
Ferrite factor, 634, 635-7, 642-3
d-orbital energy level (Md), 54-6, Ferritic steel development, 35-42,
332 84-95, see also specific steels
delta ferrite formation, 121, 128, 129 FeWTiC, 312-20
SUBJECT INDEX 691
Field ion microscopy, 200-1 creep strength, 39,40-1, 602-3

Fossil plants, Ill, 361, see also Power service exposure, 149-55
plants creep strength, 152-3, 155
carbon dioxide emissions, 3, mechanical properties, 151-2,
111-12,349 155
efficiency, 112, 349-50 steam oxidation, 153-4, 155
environmental issues, 3, 111-12, steam oxidation, 153-4, 155, 553
349 ultra-super critical boiler
repowering, 6-7 applications, 177-9, 550, 551,
in USA, 1-11 553
Fractography, 239-40 welding, 149
Fracture appearance transition HCMV3, 550, 551, 552
temperature (FATT), 235, 238-9 Heat affected zone simulation,
trace element content, 335-8 613-14
Fuel types, 110 creep properties, 655-67
Heat treatment parameters, 322-31
Grade 91 steel, see P91
cooling rate, 323-4, 328
Grade 92 steel, see P92 double austenitising, 324-5,
Greenhouse gas emissions, 3,
328-30
111-12,349 normalising temperature, 324, 328,
Hall-Petch relationship, 14 330
HC~2S,36,37,41-2, 144-5, 147 tempering temperature, 327, 328,
ageing properties, 148 330
allowable stresses, 146 Hot isostatic pressing, 75-6, 81
bent metal properties, 104-7 Hot workability & alloy content,
creep-fatigue, 298-307 57-8
creep strength, 41-2, 300 HR3C, 42,43,45, 46
pipes/tubes, 96-108, 144-56 HR6W, 43, 46
service exposure, 149-55 HT9, 36, 37,40-1
creep strength, 152-3, 155 HT91, 36, 37, 38,40-1
mechanical properties, 151-2,
Impurities
155 embrittlement, 234-5, 238-42, 244
steam oxidation, 153-4, 155
toughness, 338
waterwalls, 441
transformation temperature, 338
welding, 99-104, 149
Incoloy 901, 527-8
HC~9M, 36, 37
Inconel 718, 523
HC~12,36,37,38,40-1 Inconel X750, 527, 528
HC~12A, 36, 37, 38-9, 86, 134, 137,
Inherent creep strength, 87, 279
144-6,147,597
Intergranular corrosion of stellite
ageing properties, 148-9
weldments, 184-96
microstructural changes, 200,
Iridium additions, 90, 92-4
202-10
allowable stresses, 146 Japanese power plant development,
creep-fatigue, 298-307 84-5,543-59
Kaltenhauser ferrite factor, 634, welding, 611-21

635-7, 642-3 heat affected zone creep
properties, 655-67
Laser light scanning, 538 NF709, 42, 43,45,46, 551,552,553
Latent creep resistance, 208 Nickel additions
M-252, 523, 524 carbide precipitation, 24
Manganese additions creep strength, 340, 341, 399, 400,
corrosion resistance, 512-13, 515 424-5
creep strength, 53, 399-400 sources of, 682
delta ferrite formation, 56 stacking fault energy, 27
stacking fault energy, 27 temper resistance, 400
temper resistance, 400 toughness, 337-8, 399, 400
toughness, 399, 400 transformation temperature, 337,
transformation temperature, 338 338
Maraging steel, 206 weld hot cracking, 484-5
Martensite formation, 13 Nimonic 80A, 527, 528
Md (d-orbital energy level), 54-6, Nimonic 90, 523
332 Niobium additions
Meandering winding magnetometry, austenitic grain size control, 311
538 carbide precipitation, 22-5,495
Modelling, 537 creep strength, 39-40, 45, 400, 419,
carbo-nitride coarsening, 270-6 495,497,498-9
creep, 596-607 interaction with vanadium
precipitation, 212-22, 223-33 additions, 40, 310-11
Molybdenum additions temper resistance, 400
creep strength, 39-40, 285-6, 355, toughness, 67, 400
400,419 Nitrogen additions
sources of, 681 creep strength, 339, 341, 342,400,
tempering behaviour, 20-1, 400 421-2,483,525-7,529-30
toughness, 400 precipitation characteristics, 310
tempering characteristics, 310, 400,
NAR-AH-4, 482-93 430-1
Neodymium additions, 41 toughness, 337,400
NF1H, 550, 551 transformation temperature, 337
NF12, 36,37,41,551,552, 553 weld hot cracking, 484
NF616, 36, 37, 86, 127-8, 597, 612 see Nondestructive inspection, 530-2,
also P92 537-8,670
casting, 119-29
creep-fatigue, 298-307 n (omega) values, 597-601
creep properties, 37, 602 OPTIMAR, 586-95
steam oxidation, 553 Ostwald ripening, 14-17
ultra-super critical boiler modelling, 270-6
applications, 177-9, 550, 551, Overheating, 27-8
553 Oxidation, 457-67, see also Corrosion
SUBJECT INDEX 693
P91, 36,37, 134-7, 138,437,612' embrittlement, 26

ageing,626-7, 628-9 transformation temperature, 338
bending, 160, 161 Piping failures, 668-80
continuous cooling Platinum additions, 90
transformation, 159-60, 325-7 Power plants, see also Fossil plants
creep & microstructural changes, capacity factor, 7-8
247-58 economic factors, 3-5, 6-7, 437-8
creep strength, 135, 160 efficiency, 112, 546
double austenitising, 324-5, fuel types available, 110
328-30 independent system operators, 1
heat treatment, 322-31 repowering, 6-7
cooling rate, 323-4, 328 Precipitation modelling, 212-22,
double austenitising, 324-5, 223-33
328-30
normalising temperature, 324, Refractaloy 26, 523, 524, 527, 528
328,330 Remote eddy current inspection,
tempering temperature, 324, 530-1
327,328,330 Repair welding, 532
oxidation, 457-66 Retrofitting material choice, 166-71
retrofitting,166-71 Rhenium additions, 42, 284, 286, 338,
tempering, 160 340,341,583
precipitation during, 247, 251, Rhodium additions, 90, 94
327-8 Rotors / rotor steel, 309-10, 354-9,
temperature, 324, 327, 328, 330 386-96,408-17,418-29,430-1,
transformation temperature, 623 521-2,554-5,557-8,575-82,
valve forging, 560-73 682-3
welding, 160, 162-6, 611-21 COST E steel, 375-85
delta ferrite formation, 633-43 creep & structural changes, 28-9
dissimilar metal, 163-6, 633-43, dual heat treatment, 534-5
644-54 high pressure-low pressure
heat affected zone creep combined, 365-74, 397-407
properties, 655 welding, 532, 535
P92, 134, 137-42, 437, see also NF616
ageing microstructure, 200, 202-4, SAVE12,36, 37,41, 551,553
207, 208, 209 SAVE25, 43, 46-7, 551, 553
creep strength, 464-6 Schaeffler diagrams & delta ferrite
forging, 113-18 prediction, 634, 636-7, 642-3
oxidation, 457-66 Sensitisation phenomenon, 185
welding, 139-40 Silicon additions
P122, see HCM12A blowhole development, 120, 128
Palladium additions, 90, 94 creep strength, 399-400
PER 2B, 527, 528 oxidation resistance, 89, 488
Phosphorus traces stacking fault energy, 27
ageing behaviour, 204, 207 temper resistance, 400
toughness, 122-3, 400 Titanium additions

transformation temperature, 338 carbide precipitation, 22-5,495
weld hot cracking, 483-4 creep strength, 45, 340, 342, 495,
Smith-Zener relationship, 17-18 497,498-9
Stacking fault energy, 27 toughness, 337
Steam oxidation, 463-4, 468, 470, transformation temperature, 337
477-9,553-4 Titanium blades, 535-6
shot-blasting, 554 TMK1 & TMK2, 408-17
Stellite weldments, 184-96 Toughness & alloy element content,
Stress corrosion cracking, 529 399-400, see also specific alloy
Stress relaxa tion tests, 533 elements
Submerged-arc welding & creep TP304H,43
damage, 668-80 TP310,43
Sulphide precipitation, 27-8 TP316H,43
Super 304lI,42, 43, 45, 551, 553, 554 TP321lI,43
Super clean steels, 28 TP347H,43
Superheater tubing, 438-41 TP347HFG, 42,43,45
Transformation temperature & trace
T9, 36, 37 element content, 335-8
TIl bimetallic tubes, 445-56 Tube failures, 5
T22, 36, 37 Tungsten additions, 137-42, 259-69
T23, see HCM2S ageing
T91, see P91 extracted residue content, 266
T92, see P92 martensite precipitation, 264-5
Tantalum additions, 41, 337, 340, tungsten precipitation, 266-8
342,345 carbide precipitation, 22-5, 29
TB12,37 creep strength, 39-40, 53, 90-2, 94,
Tempaloy A-I, 42, 43, 45, 494, 138,261,268,277-87,354,419,
495-500 43~579-80,596-7,602-7
Tempaloy A-3, 42, 43, 45, 46, 494, delta ferrite formation, 55
503-5 solid solution strengthening,
Tempaloy AA-1, 494, 500-3, 551 278-80,286
Tempaloy F-2W, 550, 551 sources of, 682
Tempaloy F-9, 36, 37 strength, 262, 268
Tempaloy F-12M, 51-2, 58-64, 550, toughness, 56,262-4,268,581
551
Tempaloy HT780, 550, 551 Ultrasonic inspection, 530, 531-2,
Tempering 538,670
alloy element content, 19-21, 400, Ultra-super critical plants, 51, 112-13
430-1 alloy development, 179-82,
plain carbon steel, 13-19 435-44,494-506,574-85
temperature & carbide efficiency, 112, 546
precipitation, 22-4 in Japan, 84-5,543-59
Tin impurities, 338 Under stabilising, 45
SUBJECT INDEX 695
United States of America power Weld hot cracking & alloy content,
plants, 1-11 483-5
materials development, 519-42 Welding
Upper shelf energy & trace element creep damage, 668-80
content, 335-8 delta ferrite formation, 121, 633-43
dissimilar metals, 163-6, 633-43,
Valves 644-54
manufacture, 119-29, 560-73 heat affected zone creep
stellite cladding, 184-96 propertie~655-67
Vanadium additions repairs, 532
creep strength, 39-40, 400, 419 simulation, 613-14
interaction with niobium VVT780C,550,551, 552
additions, 40, 310-11
tempering behaviour, 20-1, 400, XI0 steel, see P91
430-1 X20 steel, 134
toughness, 400 welding, 633-43
Water vapour & oxidation, 462-3 Zirconium additions, 337, 340, 342,
Waterwalls, 436, 441-3 345
MICROSTRUCTURAL
DEVELOPMENT AND
STABILITY IN HIGH
CHROMIUM FERRITIC
POWER PLANT STEELS
Edited by
A. Strang & D.]. Gooch
Contents: Historical development and microstructure of high chromium ferritic steels for
high temperature applications; Precipitation processes in martensitic 12CrMo VNb steels during
high temperature creep; The development of 9% CrMo steels from steel 91 to E911;
Development of advanced high chromium ferritic steels; Microstructural development in
advanced 9-12% Cr creep resisting steels - a collaborative investigation in cost 501/3 WP11;
Evolution of microstructure and properties of 10% Cr steel castings; Microstructural
development and stability in new high strength steels for thick section applications at up to
620°C; Microstructure of advanced high chromium power plant steels; Thermodynamic
prediction of microstructure; Modelling the developments of microstructure in power plant
steels; List of delegates; Subject index.
Book 667 ISBN 1 861250215 Hardback

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MICROSTRUCTURAL
STABILITY OF CREEP
RESISTANT ALLOYS FOR
HIGH TEMPERATURE
PLANT APPLICATIONS
Edited by
A. Strang, J. Cawley & G. W. Greenwood
These are the proceedings of the second in a series of specialist international
conferences aimed at focusing attention on the microstructural changes occurring in
high temperature materials during service exposure and identifying the processes
and mechanisms leading to the observed degradation of their mechanical properties.
Once more the papers presented at this conference, which was held at Sheffield
Hallam University in March 1997 and attracted over 80 delegates from 15 countries,
have highlighted the work currently in progress on the development of improved
high temperature materials designed to be more resistant to microstructural
degradation in service.
Book 682 ISBN 1 86125045 2 Hardback
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Advanced Heat

Resistant Steels for

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

© 10M Communications Ltd

10M Communications Ltd

ISBN 1 86125 079 7

EPRI Report Number TR-111571

Printed and bound in the UK at

Overview of the Power Generation Business in the United States 1

The Long Term Structural Stability of Power Generation

New Developments in Steels for Power Generation Boilers 33

Section 1A: Steel Developments 49

Development of 12% Cr Heat Resistant Steel Plate

The Commercial Development and Evaluation of E911, a Strong

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

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

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

Section lB: Service Experience 131

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

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

Service Experience with the Application of Advanced Materials in Improved

Effects of Microstructure on Intergranular Corrosion of Weldments of

Section 2: Microstructures 197

Microanalysis of9-12% Chromium Steels P92 and P122 199

Forecasting Microstructural Change in Austenitic Steels for

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

Ageing Embrittlement of Fe-12Cr Steels 234

Microstructure and Creep of a T91 Steel 247

Effects of Tungsten on Mechanical Properties and Microstructure in

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

Creep Fatigue Crack Behaviour of Two Power Plant Steels 288

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

Properties of a 12% CrMo V High Temperature Turbine Steel

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

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

Section 3A: Turbines 347

European High Temperature Materials Development for

Manufacturing and Properties of 2%Cr Family Steels for a

Experience in Manufacturing and Mechanical Properties of Turbine Rotor

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

Development and Manufacturing of Advanced 12%Cr Rotor Forgings for

Development of Heat Resistant l2%CrWCoB Steel Rotor for

Development of High Strength Corrosion Resistant Ferritic Steels for

Section 3B: Oxidation 433

Materials for Advanced Boilers 435

Development of a New Heat Resistant Austenitic Stainless Steel for

Development of the High Temperature Materials for Ultra

Corrosion Testing of Superheater Steels for 600°C Steam in

Section 4: Further Developments 517

US Developments in Advanced Turbine Materials 519

Development of Ultra-Super Critical Plant in Japan 543

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

Advanced Heat Resistant Steels for Steam Turbines 574

Development of a High-Strength Martensitic CrNiMo VNb Steel with

Creep Modelling and Strengthening Mechanism of Tungsten Alloyed

Section 5: Welding 609

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

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

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

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

Summary of Papers 681

Subject Index 689

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