JO

AWARD PROGRAM REVISIONS: New Opportunities for Recognition

OCTOBER 2010 www.tms.org/jom.html

A publication of The Minerals, Metals & Materials Society

HIGH-TEMPERATURE MATERIALS Refractory Metals Nickel-based Superalloys

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TMS On Reserve An anthology of 12 newly-digitalized, library archive volumes of foundational documents and select conference proceedings from the American Institute of Mining, Metallurgy, and Petroleum Engineers (AIME). OneMine A collaborative effort among societies to create a single global resource for mining and minerals research. TMS members receive a special subscription rate.

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Member News

Updates on friends and colleagues in the materials community

Public & Governmental Affairs Director & Chair: Kevin J. Hemker, professor and chair of the Department of Mechanical Engineering at Johns Hopkins University, with joint appointments in the Departments of Materials Science and Engineering and Earth and Planetary Sciences. Publications Director & Chair: Carl M. Cady, technical staff member on the dynamic properties and constitutive modeling team within the Materials Science Division of Los Alamos National Laboratory. Electronic, Magnetic & Photonic Materials Division Director & Chair: Srinivas Chada, senior engineering manager for Global Electronic Interconnects Reliability, Whirlpool Corporation. Extraction & Processing Division Director & Chair: Adrian C. Deneys, business development manager for Praxair, Inc.

TMS Elects New Board Members

Seven newly elected members will ofcially take their seats on the Board of Directors at the TMS 2011 Annual Meeting & Exhibition, February 27 through March 3, in San Diego. Slotted to serve three-year terms, the new directors are: Vice President: Wolfgang A. Schneider, head of the research and development center at Hydro Aluminium and a professor of metallurgy at the Technical University of Berlin. Information Technology Director & Chair: William J. Jud Ready, adjunct professor in the School of Materials Science and Engineering at the Georgia Institute of Technology and senior research engineer on the research faculty of the Georgia Tech Research Institute. Professional Development Director: David A. Shier, program ofcer at the U.S. Department of the Navys Ofce of Naval Research.

A Tribute to Akira Yazawa

By Florian Kongoli
Akira Yazawa, a renowned leader in copper smelting technologies, passed away on August 14, 2010 at his home at the age of 84. He was a member of TMS since 1982, and was honored at the TMS 2003 Annual Meeting with the Yazawa International Symposium, which attracted 300 papers from authors in 37 countries. Professor Yazawa was recognized worldwide for his impact in the extractive metallurgy of copper, as well as Zn, Pb, Ni, Sn, Sb, Au, Hg, and Cd. His more than 300 publications dealt with a variety of subjects, such as slags, alloys, mattes, speiss, aqueous solutions, alcohols, and algae. He earned his bachelors and Ph.D. degrees at Tohoku University in Japan. He became a professor at Tohoku University, where he served as director of the Research Institute of Mineral Dressing and Metallurgy from 1981 to 1986. He was president of Miyagi National College of Technology, also in Japan, from 1989 to 1995. He was president of the Society of Calorimetry and Thermal Analysis, Japan, from 1987 to 1989, and president of the Mining and Materials Processing Institute of Japan from 1989 to 1990. Professor Yazawa has been recognized worldwide with many awards, prizes, and honors, including the TMS Extraction & Processing Division Distinguished Lecturer Award in 1979. He will be greatly missed by his colleagues and ex-students, but especially by his wife Kimi, his son, and two daughters.
Florian Kongoli is chief executive ofcer of FLOGEN Technologies Inc., Canada/ USA and a longtime colleague of Akira Yazawa. Additional information on Professor Yazawas many contributions is available at www.ogen.com/news.php?action=5.

Gregory Olson Awarded ASM Gold Medal

Gregory B. Olson, Walter P. Murphy Professor of Materials Science and Engineering at Northwestern University, will receive the ASM International Gold Medal during Materials Science & Technology 2010, October 1721 in Houston. The medal recognizes Olson for contributions to understanding the science of steel, application of thermodynamics to the design of steel with prescribed properties, and applications of this design concept to industry and education. He has been a TMS member since 1986.

George T. Rusty Gray III to Serve on NMAB Lightweighting Committee

George T. Rusty Gray III, laboratory fellow, Los Alamos National Laboratory, and 2010 TMS president, has been named to the National Materials Advisory Boards (NMAB) Committee on Benchmarking the Technology and Application of Lightweighting. Gray is one of 15 senior U.S. industry, national laboratory, and academic experts selected to assess the state of lightweighting implementation in military and civilian transportation platforms. The NMAB is the principal source of objective, independent, and informed scientic, technological, and policy assessments of materials, processes, and applications for use by U.S. industry, government agencies, and universities.

TMS Member Proles

TMS 2011 Symposium Honors Accomplishments of Carlos Tom
By Lynne Robinson
Editors Note: This is excerpted from an article that rst appeared on the Materials Technology @TMS site at http://materialstechnology.tms.org /EMT/article.aspx?articleID=3624

On muddy rugby elds in Argentina, Carlos Tom experienced how being open to an opportunity could yield a big benetand even a win. The perseverance, teamwork, and resourcefulness that he displayed for 20 years with his rugby club are also hallmarks of the scientic accomplishments he is being recognized for at Polycrystal Modeling with Experimental Integration: A Symposium Honoring Carlos Tom, taking place at the TMS 2011 Annual Meeting & Exhibition, February 27March 3, San Diego. I have been lucky to be often in the right place at the right time, which has given me the opportunity to get acquainted and work with very bright researchers, said Tom, technical staff member at Los Alamos National Laboratory. Each of them shared with me their knowledge, their passion, and their personal style of reasoning. This, plus the fact that I developed good friendships with most of them, has leveraged my scientic experience. Much of Toms work has focused on the analysis and simulation of the constitutive behavior of low symmetry metals, such as magnesium, zirconium, and uranium, as well as geologic materials, such as olivine and calcite. These materials deform via a complex combination of slip and twin modes and are characterized by a very anisotropic mechanical response, said Tom. As a consequence, more sophisticated and mechanism-based models and techniques are required than the ones used for understanding cubic materials. This search for understanding led Tom and his collaborators to develop sophisticated polycrystal modeling techniques and numerical codes that are now considered the gold standard of predictive tools for parameter identi-

cation, interpretation of experiments, and multiscale calculations. Carlos Tom is one of the pioneers of the self-consistent method for the modelling of the plastic deformation of polycrystalline materials. More in particular, he has been the rst to develop it for some of the materials which are

Carlos Tom: The linking of length scales and the description of mechanical response using probabilistic approaches are two exciting future possibilities in the eld of material simulation.

of interest in the nuclear sector, namely zirconium, said Paul Van Houtte, professor, Mechanical Metallurgy Section, Katholieke Universiteit Leuven, Belgium. In describing Tom as the leading scientist worldwide in multi-level modeling of the plastic deformation of HCP metals, Van Houtte also noted, Carlos is not working alone. He has done remarkable scientic work with the help of a series of students whom he has put on the path of science. Most of them have become excellent researchers and several of them already enjoy high esteem at the international level. Guiding junior scientists towards such excellence is indeed one of Carlos Toms most important achievements.

One such scientist is Ricardo Lebensohn, researcher in the Materials Science and Technology Division of Los Alamos National Laboratory, and organizer of Toms 2011 honorary symposium. Now a co-worker, Lebensohn was one of Toms undergraduate students at the National University of Rosario, Argentina. Later, Tom became his Ph.D. thesis supervisor, as well as a colleague and collaborator on a number of projects. Along his career, Carlos has pioneered the theoretical and numerical development of physically based modeling of mechanical behavior of polycrystals, with emphasis on the role played by texture and microstructure on the anisotropic properties of engineering materials, said Lebensohn. His many contributions have been critical to establishing a strong connection between models and experiments, and to bridge different scales in pursuit of robust multiscale formulations with experimental integration. Many of those presenting and attending the symposium note that Tom is admired as much for his generosity as his scientic accomplishments. As Rob Wagoner, George R. Smith Chair, Department of Materials Science and Engineering, Ohio State University, remarked, Like many others internationally, my group has used his codes with his unfailing assistance and without any kind of cost or obligation. I think it is this unselsh, caring attitude that sets Carlos apart from his peers, even more so than his tremendous technical achievements in creating and using his viscoplastic self-consistent (VPSC) code.
Each month, JOM proles a TMS member and his or her activities both in and out of the realm of materials science and engineering. To suggest a candidate for this feature, contact Maureen Byko, JOM editor, at mbyko@tms.org.

JO
C O N T E Volume 62, Number 10

HIGH-TEMPERATURE MATERIALS
N T S October 2010

REFRACTORY METALS 12: Refractory Metals An Exploration of Hightemperature Materials: S.K. Varma 13: Oxidation-resistant Coatings for Ultra-hightemperature Refractory Mo-based Alloys: J.H. Perepezko and R. Sakidja 20: The Microstructural Engineering of Mo-Si-B Alloys Produced by Reaction Synthesis: Michael R. Middlemas and Joe K. Cochran 25: A Multi-stage Hierarchical Approach to Alloy Design: P.K. Ray, T. Brammer, Y.Y. Ye, M. Akinc, and M.J. Kramer 30: Upscaling of the Investment Casting of the Intermetallic Alloy IC75: Simon Hollad and Andreas Bhrig-Polaczek

NICKEL-BASED SUPERALLOYS 35: The Thermodynamic Modeling of Preciousmetal-modied Nickel-based Superalloys: F. Zhang, J. Zhu, W. Cao, C. Zhang, and Y.A. Chang 41: Precious Metal Modied Nickel-based Superalloys: Motivation and Potential Industry Applications: A. Bolcavage and R.C. Helmink 45: The Use of Preciousmetal-Modied NickelBased Superalloys for Thin Gage Applications: Donna L. Ballard and Adam L. Pilchak 48: A Combined Mapping Process for the Development of Platinum-modied Ni-based Superalloys: A.J. Heidloff, Z. Tang, F. Zhang, and B. Gleeson

FEATURES 9: Your TMS Membership: Benets for You, Support for the Profession: George T. Rusty Gray III 10: Brimacombe, Cohen, and Smith: New TMS Awards Honor Materials Pioneers: Kelly Zappas ALSO IN THIS ISSUE insert: Member News 2: In the Final Analysis 3: News & Update 7: Your Member Connection 54: Meetings Calendar 55: Materials Resource Center: Jobs, Consultants, Marketplace 56: End Notes: Get Involved: Robert E. Hackenberg, Technical Committee Chair: Kelly Zappas

PAGE 3

PAGE 22

PAGE 51

About the Cover: A pure molybdenum coupon protected by an 80 m thick coating of Mo-Si-B is subjected to 1,700C oxidation. The image and details about the process used for this high-temperature treatment can be found in Oxidation-resistant Coatings for Ultra-hightemperature Refractory Mo-based Alloys by J.H. Perepezko and R. Sakidja, starting on page 13.

Vol. 62 No. 10 JOM

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In the Final Analysis

Have you seen that I was quoted in Rolling Stone?

Cyril Stanley Smith

*/
184 Thorn Hill Road, Warrendale, PA 15086, USA Telephone: (724) 776-9000 Fax: (724) 776-3770 Web: www.tms.org/jom.html E-Mail: jom@tms.org PUBLISHER James J. Robinson OCTOBER ADVISORS: Precious-metal-modied Nickel-based Superalloys Alloy Phases Committee Fan Zhang, CompuTherm, LLC Current Developments in Refractory Metals Refractory Metals Committee Shailendra K. Varma, University of Texas at El Paso EDITORIAL STAFF Maureen Byko, Editor Cheryl M. Geier, Senior Graphic Designer Shirley A. Litzinger, Production Editor Elizabeth Rossi, Web Developer CONTRIBUTING WRITERS Lynne Robinson Kelly Zappas PARTNER RELATIONS AND ADVERTISING STAFF Trudi Dunlap, Director Colleen Leary, Sales Representative JOM (ISSN 1047-4838) is published monthly by Springer Sciences & Business Media, LLC (Springer) 233 Spring St., New York, NY 10013 in cooperation with The Minerals, Metals & Materials Society (TMS). DISCLAIMER: The opinions and statements expressed in JOM are those of the authors only and are not necessarily those of TMS or the editorial staff. No conrmations or endorsements are intended or implied. SUBSCRIPTIONS, ORDERS, AND OTHER FULFILLMENT INQUIRIES: In the Americas, contact Journals Customer Service, P.O. Box 2485, Secaucus, NJ 07096, USA; telephone (800) 7774643 (in North America) or (212) 460-1500 (outside North America); e-mail journals-ny@springer.com. Outside the Americas, contact Journals Customer Service, Springer Distribution Center, Haberstr. 7, 69126 Heidelberg, Germany; telephone 49-6221345-4303; e-mail subscriptions@springer.com. TMS MEMBERS: Access this and back issues of JOM on-line at no charge via members.tms.org POSTMASTER: Send address changes to: JOM, Springer, 233 Spring Street, New York, NY 10013, USA. Periodicals postage paid at New York, NY, and additional mailing ofces.

While I am not 100% positive, Im reasonably certain that Cyril Stanley Smith might be the only member of TMS to be quoted in Rolling Stonea pop culture magazine dedicated primarily to rock-and-roll musicians and music. Now, many of us know that Smith was one of the materials elds coolest members, a man brilliant in every discipline that he explored, but how did he nd his way into Rolling Stone? Sure, he was known to work with heavy metal on occasion, but come on. Well, as recounted by Heather Lechtman in the Proceedings of the American Philosophical Society, Smith was quoted in the magazine by nuclear historian Richard Rhodes for observations that Smith made on the importance and inuence of boundaries: Quoting Rhodes who was quoting Smith: Everything in the universe consists of something organized surrounded by a boundary and . . . the conditions of the boundary determine whether or not the organism inside will thrive. . . . With amoebas and human beings, with stars and nation-states, boundary conditions are crucial. Is anyone surprised that a metallurgist would nd philosophical insight in boundary conditions? Lechtman tells us that Smith was quite pleased with his shout out in Rolling Stoneanother accomplishment in his large inventory of cross-cutting distinctions. For more background on Smith, see the honors and awards article on pages 10 and 11. The article by Kelly Zappas also tells us about procedural changes as to how TMS awards are being managed going forwardshorter review cycle, simplied nomination processes, . . . stuff that will surely be viewed as a mercy by nominators everywhere. More globally, the article details three new TMS awards that recognize distinction by todays professionals by invoking the names of late giants in the eld: Smith (a member of the rst class of TMS Fellows in 1963), Morris Cohen (another member of the rst class of TMS Fellows), and J. Keith Brimacombe (who became a TMS Fellow as a young man in 1989). A sidebar in the article acquaints us with the accomplishments of these gentlemen with both historical background and reminiscences from people who knew them. It is a great read. As you will learn, one set of awards serves to recognize capstone accomplishments in structure (the new Smith Award), processing (a renement of the existing Bruce Chalmers Award), and properties (the new Cohen Award). As a well-established nerd, I like to think of them as the TMS Materials Tetrahedron Awards. (We havent branded them that way yet; should we?) What an honor to be recognized as an exemplar of one of these materials greats. Beyond the TMS Materials Tetrahedron Awards, which go to individual recipients, the new Brimacombe Medal will be given to a group of recipients annually. Much like the rank of TMS Fellow, this award will be presented in classes each year. It is expected that the rst few classes may contain as many as ten medalists; in future years, the class size may go down to ve. Well see. The really neat thing about this award is that while the rank of TMS Fellow recognizes a lifetime of professional distinction, the Brimacombe Medal will recognize sustained excellence by someone at the midpoint of his or her career. What a great idea! Ill close by offering my compliments in advance to the individuals who will receive these new awards at the TMS 2012 Annual Meeting in Walt Disney World. They will certainly be individuals who have worked with their boundaries in a magnicent fashion.

James J. Robinson Publisher

2 www.tms.org/jom.html

JOM October 2010

News & Update

Items of Note from the Field, Profession, and Society

and professional life. His father was a founding member of ABM and, said Meyers, We never dreamt that ABM would one day be fully integrated with TMS in a meeting with scholars from around the globe. The recipient of the Acta Materialia Materials and Society Award (Figure 1), Meyers chose to accept this honor at the Congress, given his strong personal connection to the event. I belong to the rst generation of Brazilian metallurgists who left their universities to study abroad, he said. This is a group of highly talented and motivated individuals who have laid the foundations of modern materials research in Brazil. I accept this award with humility and the realization that it should reward that generation. While the seeds for the TMS-ABM Congress had been planted long ago, momentum to organize the meeting began in earnest in 2008 with the Alliance of the Americasa TMS initiative to seek out partnerships both to the south and north of the United States. This commitment led to TMSs signing a Memorandums of Understanding with both ABM and the Metallurgical Society of the Canadian Institute of Mining, Metallurgy, and Petroleum Engineers in 2009, with plans for the TMS-ABM Congress being developed almost immediately. The Congress far exceeded my expectations for our rst joint South American meeting, said 2009 TMS President Ray Peterson. The energy and enthusiasm of our organizers in persuading outstanding speakers to participate made for a high quality meeting. Like Peterson, Gray was impressed with the quality of the Congresss programming and viewed it as a solid foundation for future efforts. The joint symposia demonstrated the strong overlap in physical and extractive materials science and metallurgy that are central to both TMS and ABM, he said. Each societys strengths in bridging mineral processing to fundamental structure/ property relations in metals and alloys were well represented. The burgeoning opportunities that both organizations can bring to future collaborations, as well as exciting ways to expand interactions with other materials societies throughout South America, were also clearly demonstrated. As a next step, TMS and ABM ofcers and key staff are planning to meet at the TMS 2011 Annual Meeting to discuss future collaborative efforts. View additional photos and information from the rst TMS-ABM International Materials Congress in the Established Materials Technologies archive of Materials Technology@TMS, http://materialstechnology.tms.org/EST /home.aspx.

Successful TMS-ABM Congress Builds Bridges to Brazil

Amid the marble and stained glass splendor of the Rio de Janeiro Teatro Municipal, the curtain ofcially rose on a new chapter of collaborative learning at the welcoming event of the 65th Annual Congress of ABM (the Brazilian Metallurgical, Materials and Mining Association), held in conjunction with the rst TMS-ABM International Materials Congress, July 26 to 30, 2010. Noting in his remarks that the TMS-ABM Congress was a shared effort between two very similar professional societies that happen to be located on different continents, TMS President George T. Rusty Gray III reminded the audience of approximately 1,500 that the relationship between TMS and ABM actually stretched back to the 1940s, when the late Robert Franklin Mehl, a member of the rst class of TMS Fellows and recognized pioneer in materials science and engineering, participated in the formation of ABM. With all his education and research successes, this historic gure of our profession knew what could not be learned in a lab or classroom: that our best work is done through collaboration, said Gray. And he recognized, too, that professional societies present unmatched opportunities for organized collaboration. For Marc Meyers, TMS representative to ABM and international coordinator of the Congress, the event marked an emotional milestone in both his personal

TMS 2011 Expands Technical Programming

TMS announced that it is scheduling an additional half day of programming for its 140th Annual Meeting & Exhibition to accommodate the record number of abstracts submitted for the event. Taking place in San Diego, California, from February 27 to March 3, 2011, the meeting will now offer four full days of technical programming, instead of concluding at lunchtime of the nal day as it has in the past. Technical programming is organized within seven tracks: Aluminum and Magnesium; Advanced Characterization, Modeling and Materials Performance; High Performance Materials; Materials and Society: Energy and Sustainable Production; Materials Processing and Production; Nanoscale and Amorphous Materials; and Professional Development.
3

Figure 1. Marc Meyers (right) receives the Acta Materialia Materials and Society Award from Ted Massalski at the rst TMS-ABM International Materials Congress.

Vol. 62 No. 10 JOM

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TMS 1987: Were You There?

The 140th TMS Annual Meeting & Exhibition, set for February 27 through March 3, 2011 in San Diego, California, will mark the 25th anniversary of the rst exhibit, which debuted at the annual meeting held February 2427, 1987 in Denver, Colorado. To commemorate the anniversary, TMS is developing a 25th anniversary display for TMS 2011 and is asking JOM readers to dig through their personal archives for any photos or memorabilia, or to recount any past exhibit experiences that can be used for the project. The goal is to create a historical collage of materials science technology advancements that the TMS exhibit has showcased over the past two-and-half decades. Please submit photos in JPG or GIF format, as well as any written recollections, to Patti Dobranski, TMS communication specialist, at pdobranski@tms.org.

In addition, numerous special lectures and sessions are planned, including an aluminum plenary session focusing on the 125th anniversary of the Hall-Hroult electrolytic process for aluminum production. The epicenter for TMS 2011 is the San Diego Marriott Hotel & Marinajust steps away from the San Diego Convention Center, where among other events, the 25th anniversary of the Exhibition will be celebrated. As the headquarters hotel, the Marriott itself is the scene for TMS committee meetings and social functions. TMS has negotiated excellent rates with the Marriott so participants can get the most out of their experience by staying close to both formal and informal opportunities for learning and networking. Attendees are reminded to consider the expanded meeting sched-

ule when reserving their hotel rooms. Registration for TMS 2011 opens on October 15, 2011. Additional information, such as details about registration, student activities, networking receptions, and honorary symposia, is available at http://www.tms.org/meetings/annual-11 /AM11home.aspx.

Technical Working Groups Commence Roadmapping Process

Leading experts representing the spectrum of materials science and engineering convened in Pittsburgh, Pennsylvania, on September 16 and 17 as members of the Technical Working Groups (TWGs) established to address the recommendations made in Linking Transformational Materials and Processing for an EnergyEfcient and Low-Carbon Economy: Creating the Vision and Accelerating Realization. The Vision Report, as it is also known, was released in June 2010 as the culmination of the rst phase of a two-part study spearheaded by TMS in support of the U.S. Department of Energy (DOE) Industrial Technologies Program (ITP) and funded by Oak Ridge National Laboratory. To launch the projects second phase, a Technical Working Group was established for each of the cross-cutting themes delineated by the Vision Report. Each TWG is charged with developing technical roadmaps identifying and prioritizing breakthrough materials and manufacturing process opportunities. A nal report consolidating their recommendations and addressing interdependencies is due in late 2010. The Technical Working Groups and their members are as follows: Functional Surface Technology This TWG will examine functional surface innovations that can improve
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Get Energized at the TMS MS&T 2010 Member Lounge

Rest and recharge (literally) at the TMS Member Lounge at the Materials Science & Technology 2010 Conference & Exhibition (MS&T10), October 1721 in Houston, Texas. To underscore the lounges themeTMS: We Get Our Energy from Our Membersthe lounge will offer a free cell phone and laptop charging service, as well as an energizing mid-afternoon snack. Complimentary copies of the special September 2010 energy issue of JOM, as well as other publications focused on TMSs strategic commitment to energy materials, will also be available. TMS giveaways, comfortable seating, and a convenient conference area round out the lounges amenities.

renewable energy technologies, energy storage and distribution, transportation and industry efciency, and carbon management applications. Arvind Agarwal, Associate Professor, Mechanical and Materials Engineering, Florida International University Raghavan Ayer, Section Head, ExxonMobil Research & Engineering Clark Cooper, Director, Materials and Surface Engineering, National Science Foundation Michael T. Dugger, Distinguished Member, Technical Staff, Sandia National Laboratories Jonah Erlebacher, Associate Professor, Materials Science and Engineering, Johns Hopkins University Steven George, Professor of Chemical and Biological Engineering/ Professor of Chemistry and Biochemistry, University of Colorado at Boulder Jan F. Herbst, Principal Research Scientist, GM Research Brajendra Mishra (Chair), Professor and Associate Department Head, Metallurgical and Materials Engineering, Colorado School of Mines Yancy Riddle, Chief Technology Ofcer, UCT Coatings, Inc. Daniel Sordelet, Engineering Specialist, Caterpillar, Inc. Gtz Veser, Associate Professor and CNG Faculty Fellow, Chemical and Petroleum Engineering, University of Pittsburgh Zhenyu Zhang, Distinguished Research Staff Member, Oak Ridge National Laboratory Higher Performance Materials for Extreme Environments The focus of this TWG is on advancements in materials that can withstand the higher temperatures, corrosive chemicals, and intense radiation integral to the operating environments of many energy systems. William Brindley, Chief Technologist, Rolls-Royce Corporation Ivan Cornejo, Research Manager, Corning Incorporated Thomas Felter, Manager, Hydrogen and Metallurgical Science Department, Sandia National Laboratories
JOM October 2010

JOM READER POLL

To vote, go to www.tms.org/jomsurvey.html.

AWARD NOMINATION DEADLINE - April 1 Nominate a deserving individual for one of these new society awards
Bruce Chalmers Award - individual in materials processing. Cyril Stanley Smith Award - individual in materials structure. Morris Cohen Award - individual in materials properties. Brimacombe Medalist individuals in the middle portion of their career. Go to http://www.tms.org/society/tmsawards.aspx for all the details.

Last months question:

The Energy Materials Blue Ribbon Panel, whose Vision Report on materials technologies for an environmentally sustainable, energyefcient economy is inserted into the September issue of JOM, identied four broad areas for further study. This month JOM asks, which of those four cross-cutting themes are likely to have the greatest impact on a secure and sustainable energy future?

Last months answers:

Functional Surface Technology: including catalysts, nanomaterials and nano-level processing, coatings, electrochemical material systems, and thin lm technologies 30.77% Higher Performance Materials for Extreme Environments: including metallic materials, ceramics, engineered polymers, and electronic materials 38.46% Multi-materials Integration in Energy Systems: focusing on such technologies as joining processes, composite materials, thermal management materials and processes, and smart materials

When you add niobiumfrom

15.38%
Sustainable Manufacturing of Materials: including net-shape processing methods, industrial heating and waste heat utilization, and resource recovery and recycling 15.38%

Reference Metals
...you also add value

At Reference Metals, were all about valuethe value of our niobium products and the overall value we bring to our customers. These attributes have enabled us to successfully market the distinct advantages of niobium, as well as develop strong customer relationships. After more than 30 years, we remain on the leading edge of process/ production technology and metallurgy, combining the benets of niobium with its globally recognized technical expertise and support.

This months question:

TMS has established three new professional awards, named for some of the giants of materials science and engineering. (Read about the changes to the TMS Honors and Awards program on page 10 of the October issue.) This month, JOM asks, which of the award namesakes have had the greatest inuence on your professional pursuits? Remember, your comments and reminisces are also welcome.d.

Product qualityreliable customer service strong technical support. All reasons to choose Reference Metals as your value-added, strategic partner.
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This months answers:

Cyril Stanley Smith J. Keith Brimacombe Morris Cohen

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 Warren Garrison, Professor, Materials Science and Engineering, Carnegie Mellon University Brian Gleeson, Harry S. Tack Chair and Professor, Materials Science and Engineering/Director, Center for Energy, University of Pittsburgh Wayne King, Division Leader, Condensed Matter and Materials, Lawrence Livermore National Laboratory John J. Lewandowski, Professor, Materials Science and Engineering, Case Western Reserve University Xingbo Liu, Assistant Professor, Mechanical and Aerospace Engineering, West Virginia University George Spanos (Chair), Technical Director, TMS Peter F. Tortorelli, Deputy Division Director, Oak Ridge National Laboratory William Tredway, Group Leader for Ceramics; Deputy Department Leader, Physical Sciences Department, United Technologies Research Center Patrice Turchi, Scientic Capability and Group Leader, Lawrence Livermore National Laboratory Brian D. Wirth, Governors Chair and Professor, Computational Nuclear Engineering, University of Tennessee Christopher M. Wolverton, Professor, Materials Science and Engineering, Northwestern University Steve Zinkle, Director, Materials Science and Technology Division, Oak Ridge National Laboratory Multi-Materials Integration in Energy Systems The intent of this TWG is to optimize the efciency of energy technology systems, such as batteries, fuel cells, and solar cells, through effective integration of heterogeneous components. Glenn S. Daehn, Professor, Materials Science and Engineering, Ohio State University David M. Dietrich, Manufacturing Engineer/Direct Digital Manufacturing, Boeing Research and Technology Jerry E. Gould, Chief Engineer, Edison Welding Institute Darrell R. Herling, Chief Engineer, Pacic Northwest National Labora6

tory Warren H. Hunt, Jr. (Chair), Executive Director, TMS Robert W. Hyers, Associate Professor, Mechanical and Industrial Engineering, University of Massachusetts Bruce Kelley, Manager, Chemical and Biological Systems Department, Sandia National Laboratories Gerry Ludtka, Distinguished Research Staff, Oak Ridge National Laboratory Jaime Marian, Lawrence Livermore National Laboratory Angelo Mascarenhas, Materials Science Group Manager, National Renewable Energy Laboratory Mark Mathias, Technical Fellow and Director, Electrochemical Energy Research Laboratory, GM Research Michael Wixom, Senior Technical Director, A123Systems Carl Zweben, Zweben Consulting Sustainable Manufacturing of Materials This TWG encompasses methods and processes that minimize the loss of both energy and materials. John Barnes. Development Program Manager, Lockheed Martin Aeronautics Cynthia Belt, Senior Energy Engineer, Superior Industries Craig Blue, Group Leader, Materials Processing, Oak Ridge National Laboratory James W. Evans, P. Malozemoff Professor Emeritus/Professor of Metallurgy Emeritus, Materials Science and Engineering, University of California, Berkeley Randolph E. Kirchain, Associate Professor, Materials Science and Engineering, Massachusetts Institute of Technology Anantha Krishnan, Director, Research and Development/Section Leader, Meso-Micro-Nano Scale Technology, Lawrence Livermore National Laboratory Diana A. Lados, Assistant Professor, Mechanical Engineering, Worcester Polytechnic Institute Ray D. Peterson (Chair), Director of Technology, Aleris International, Inc.
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Ramana G. Reddy, ACIPCO Professor of Metallurgy/Professor of Metallurgical and Materials Engineering, University of Alabama Mark Smith, Technical Group Manager, Pacic Northwest National Laboratory Susan Smyth, Director, Manufacturing Systems Research, GM Research and Development David B. Spencer, Founder, Chairman, and Chief Technology Ofcer, wTe Corporation Ellen Stechel, Manager, Energy, Climate, and Carbon Management, Sandia National Laboratories Brian G. Thomas, C.J. Gauthier Professor/Director, Continuous Casting Consortium, University of Illinois at Urbana-Champaign The Transformational Energy Materials Project is a lead effort of TMS Energy, a strategic initiative of TMS to provide leadership, facilitation, and resources that generate and support effective energy solutions based on the innovative development and use of materials. For additional information, visit at http://energy.tms.org.

Abstract Deadline Approaches for ICME 2011

November 1, 2010 is the deadline for abstracts for the First World Congress on Integrated Computational Materials Engineering (ICME), to be held by TMS on July 1014, 2011, in Seven Springs, Pennsylvania. Interested authors should submit their abstracts via ProgramMaster at http://www.tms.org/Meetings /Specialty/ICME2011/techprog.aspx. Both computational- and experimental-based presentations representing the wide range of materials programs engaging an ICME approach are welcome. Specic topic areas include: Modeling processing-microstructure relationships Modeling microstructure-property relationships The role of ICME in graduate and undergraduate education Digital infrastructure ICME success stories The Congress will use the Gordon Research Conference model to offer a learning environment conducive to stimulating discussions and rich interactions.
JOM October 2010

YOUR MEMBER CONNECTION

Meet the TMS members who have contributed to or are featured in this issue of JOM. To join the TMS network, visit www.tms.org/Society/Membership.aspx. JOM AUTHORS AND ADVISORS Mut Akinc is a professor at Ames
Laboratory, Iowa State University, Ames, Iowa. He earned his Ph.D. in Ceramic Engineering from Iowa State University in 1977. A member of TMS since 1993, he is a member of the TMS Education Committee.

Travis M. Brammer is a graduate student at Iowa State University, Ames Iowa. He earned his B.S. in materials engineering from Iowa State in 2010. Page 25.

data. TMS has provided a forum for these developments and the bulk of the presentations and publications have been through TMS annual meetings and publications. Cochran joined TMS in 2001. Page 20.

Page 25. Donna L. Ballard is Senior Materials Research Engineer, Air Force Research Laboratory, Wright-Patterson Air Force Base, Ohio. She earned her M.S. in Materials Engineering from the University of Dayton, and has been a member of TMS since 2005. She currently serves as the secretary for the TMS High Temperature Alloys Committee and is the lead organizer for a TMS 2011 symposium. Page 45.

Y. Austin Chang is Wisconsin Distinguished professor in the Department of Materials Science and Engineering, University of Wisconsin, Madison, Wisconsin. He received his Ph.D. in metallurgy from the University of California at Berkeley. A member of TMS since 1962, he has received many honors and awards including the TMS William-Hume Rothery Award (1989), Educator Award (1990), Extraction & Processing Lecturer Award (1993), Champion H. Mathewson Medal (1996), ACTA Materialia Inc. Gold Medal Award (2009), and AIME Honorary Membership (2010). He is also a TMS Fellow and served as TMS president in 2000. Page 35. Joe K. Cochran is a professor in the
Materials Science and Engineering Department of Georgia Institute of Technology in Atlanta, Georgia. He earned his Ph.D. in Ceramic Engineering from Ohio State University in 1971. His background in ceramic processing was redirected to near-net shape, reactive processing of ceramic and metallic powders to produce metal alloys about 15 years ago. Recently, this has focused on microstructural engineering in refractory metal alloys and composites, particularly in molybdenum and tantalum based compositions. This processing has resulted in properties equivalent or superior to published
www.tms.org/jom.html

Brian Gleeson is the Harry S. Tack Chair professor of materials science and engineering at the University of Pittsburgh. He is also director of the Universitys Center for Energy. He has been a member of TMS for 21 years. Gleesons primary research focus is on the thermodynamics and kinetics of gas/solid and solid/solid reactions, with particular emphasis on the hightemperature degradation of metallic alloys and coatings. Pages 6, 48. Andrew Heidloff began his TMS involvement as an undergraduate by attending the TMS 2005 Annual Meeting and Materials Science & Technology (MS&T) 2005 and 2006 conferences. He was fund-raising chair of Iowa State Universitys Material Advantage Chapter in 200506. As a graduate student he presented at the TMS 2007 Annual Meeting and the MS&T07 conference. As a postdoctoral research assistant, he contributed to proceedings at the TMS 2010 Annual Meeting. Page 48.

Ann Bolcavage is Senior Specialist

in Coatings and Surface Engineering for Rolls-Royce Corporation, Indianapolis, Indiana. She earned her Ph.D. in Metallurgical Engineering in 1994 from The University of Wisconsin-Madison. Her current responsibilities at Rolls-Royce include the development of advanced coatings and repair techniques for combustor liners, turbine blades and vanes, and nickel superalloy disks. Bolcavage also recently served as the technical manager for the Air Force Research Laboratory Precious Metal Modied Superalloy Program. She has been a member of TMS since 2007. Page 41.
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Randolph C. Helmink is Staff Consultant: High Temperature Materials, for Rolls-Royce North American Technologies, Inc. in Indianapolis, Indiana. He earned his Ph.D in metallurgical engineering in 1977 from Case Western Reserve University, and has been a TMS member since 1982.
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He is a past member of the TMS Solidication and High Temperature Alloys Committees. Page 41.

Matthew J. Kramer is Senior Scientist and Associate Professor of Materials Science and Engineering at Ames Laboratory and Iowa State University, Ames Iowa. He earned his Ph.D. in Geology in 1988 from Iowa State University. A TMS member since 1990, he has been a member of both the Structural Materials and Electronic, Magnetic & Photonic Materials Divisions. Page 25.

chak is a member of the TMS Titanium Committee and serves as a reviewer for Metallurgical and Materials Transactions A, for which he is a frequent contributor. Page 45.

Michael R. Middlemas is a materials engineer with QinetiQ North America in Huntsville, Alabama. He has been a member of TMS through the Material Advantage program since 2007. Page 20.

Zhihong Tang received his Ph.D. in Materials Science & Engineering from Iowa State University in 2007, working on development of ultrahigh-temperature refractory-metal silicides. Currently, he is a Postdoctoral Research Fellow at Iowa State University, working on the high-temperature degradation of materials and coatings. His main area of expertise is in alloy development, metallic and ceramic coatings, and high-temperature corrosion. He has been an active TMS member since 2002. Page 48. Shailendra K. Varma is a Professor in the Department of Metallurgical and Materials Engineering at The University of Texas at El Paso. He earned his Ph.D. in metallurgy from the Georgia Institute of Technology in 1978. He serves as JOM advisor for the Refractory Metals Committee, and has participated in numerous other TMS activities, such as helping students make scientic presentations at TMS meetings, chairing sessions, and reviewing papers for publication in proceedings. Page 12.

John H. Perepezko is a Professor in

the University of Wisconsin-Madison Department of Materials Science and Engineering. He earned his Ph.D. in Metallurgy and Materials Science from CarnegieMellon University. A member of TMS since 1975, he has served on many TMS committees including the Solidication and Physical Metallurgy Committees. He has received numerous TMS honors, including the TMS Bruce Chalmers Award in Solidication (1997), TMS Fellow (2004), and the TMS William HumeRothery Award (2009). Page 13.

Fan Zhang is Principal Materials

Scientist with CompuTherm, LLC, Madison, Wisconsin. She became a TMS member in 1994 when she was a Ph.D. student at the University of Wisconsin-Madison. She attended her rst TMS meeting in 1995, and completed her Ph.D. in 1997. She has published several papers in JOM, and she is currently the chair of the TMS Alloy Phases Committee, for which she also serves as JOM advisor. Page 35.
www.tms.org/jom.html

Adam L. Pilchak is a research scientist with the Universal Technology Corporation in Dayton, Ohio. He earned his Ph.D. in Materials Science and Engineering in 2009 from Ohio State University, and has been a member of TMS since 2004. Pil8

OTHER MEMBERS FEATURED IN THIS ISSUE Arvind Agarwal, p. 4 Raghavan Ayer, p. 4 Cynthia Belt, p. 6 Carl M. Cady, Member News John W. Cahn, p. 11 Clark Cooper, p. 4 Srinivas Chada, Member News Glenn S. Daehn, p. 6 Adrian C. Deneys, Member News Michael T. Dugger, p. 4 James W. Evans, p. 6 Jonah Erlebacher p. 4 Warren Garrison p. 6 George T. Rusty Gray III, p. 9; Member News Robert E. Hackenberg, p. 56 Kevin J. Hemker, Member News Darrell R. Herling, p. 6 Warren H. Hunt, Jr., p. 6 Robert W. Hyers, p. 6 Randolph E. Kirchain, p. 6 Ricardo Lebensohn, Member News Ted Massalski, p. 3 Florian Kongoli, Member News Diana A. Lados, p. 6 John J. Lewandowski, p. 6 Xingbo Liu, p. 6 Gerry Ludtka, p. 6 Marc Meyers, p. 3 Brajendra Mishra, p. 4 Gregory B. Olson, Member News Ray D. Peterson, pp. 3, 6 William J. Jud Ready, Member News Ramana G. Reddy, p. 6 Yancy Riddle, p. 4 Indira Samarasekera, p. 10 Wolfgang A. Schneider, Member News David A. Shier, Member News George Spanos, p. 6 David B. Spencer, p. 6 Brian G. Thomas, p. 6 Carlos Tom, Member News Peter F. Tortorelli, p. 6 Patrice Turchi, p. 6 Paul Van Houtte, Member News Robert Wagoner, Member News Brian D. Wirth, p. 6 Christopher M. Wolverton, p. 6 Akira Yazawa, In Memorium, Member News Steve Zinkle, p. 6

JOM October 2010

Feature

Presidential Perspective

Your TMS Membership: Benets for You, Support for the Profession
George T. Rusty Gray III

Dear Colleague, As the President of The Minerals, Metals and Materials Society, I am writing to you today to ask you to renew your membership in our professional society. At the upcoming TMS 2011 Annual Meeting we will celebrate our 140th anniversary as the leading society serving the materials science and engineering community. This achievement would not have been possible without the support of members like you. Your membership not only provides resources to TMS in its efforts to support the profession of materials science and engineering, it also strongly benets you directly by providing you with tools needed to be informed and effective in your career. Some of the many tangible benets that you receive as a member of TMS include: Opportunities to shape the future

of TMS and the materials eld as well as earn professional recognition by participating in committee activities Access to both the print and electronic versions of JOM, TMS premiere technical journal that reports on academic, industrial, and government-sponsored work from around the world e-Subscriptions to the Journal of Electronic Materials, Metallurgical and Materials Transactions A and B, and 20 additional journals published by Springer Substantial discounts on TMS meeting registrations and publication purchases Access to professional development and mentoring resources developed by materials professionals for materials professionals Networking opportunities with colleagues from all over the world through TMS-sponsored meetings, short courses, webinars and podcasts. Full access to the online TMS

Membership Directory Your membership in TMS brings a great return on your investment. And, due to the fact that we continue to understand what impact the current state of the economy has on our members, we have held the line on membership dues at $115 for 2011 while continuing to provide enhanced services. I encourage you to respond swiftly and positively to the dues renewal messages that you will be receiving by mail. Responding electronically at www.tms. org will not only ensure that you do not experience an interruption in your benets, but will also favorably impact the environment by saving resources used for future mailings. Thank you in advance for your continued support. Sincerely yours,

George T. Rusty Gray III 2010 TMS President

Interested in adding value to your TMS membership?

Your Professional Partner for Career Advancement.

Discover the benets of joining TMS committees or engaging in other volunteer activities. Log in to our members only website http://members.tms.org click on the Get Involved tab, and then complete the volunteer interest form to receive more information! While youre logged in, take this opportunity to continue to grow with TMS by renewing your 2011 membership. Simply click on the Renew Membership tab and complete the online form. We look forward to continuing to serve your professional needs in 2011 and beyond.

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Feature

Professional Recognition

Brimacombe, Cohen, and Smith: New TMS Awards Honor Materials Pioneers
Kelly Zappas
Morris Cohen helped to create the discipline of materials science. Cyril Stanley Smith established one of the rst U.S. interdisciplinary research laboratories. J. Keith Brimacombe connected academic research to industrial application. All were inuential materials scientists and engineers. But what else do these three men have in common? Beginning in 2012, Brimacombe, Cohen, and Smith join the list of materials professionals recognized by the TMS Honors and Awards program. The Brimacombe Medalist, the Morris Cohen Award, and the Cyril Stanley Smith Award are three new TMS awards established to recognize excellence in materials science and engineering. For more on Brimacombe, Cohen, and Smith, see the sidebars. The new awards, which will rst be presented at the TMS 2012 Annual Meeting, are among many recent changes to the TMS Honors and Awards program that simplify, accelerate, and broaden the awards process.

BRIMACOMBE MEDALIST: A MID-CAREER HONOR To honor early-career professionals, TMS presents the Early Career Faculty Fellow and Robert Lansing Hardy awards. To honor a long and distinctive career in the materials eld, the society has the TMS Fellow award. But until now, TMS lacked an award to honor achievements in the middle portion of a professionals career. To remedy this, TMS has established the Brimacombe Medalist award,

J. Keith Brimacombe: Engineer and Mentor J. Keith Brimacombe was internationally recognized for his work in metallurgical process engineering at the University of British Columbia (UBC). He was well known for bridging the gap between research and industrial application of technology. But Indira Samarasekera, a former student and colleague of Brimacombe, thinks that he would most like to be remembered for his impact on the people that he mentored. He was very proud of his graduate students, but he was also proud of the thousands of undergrads he taught, colleagues he mentored in TMS and ISS [the former Iron and Steel Society], and his colleagues around the world, said Samarasekera, who is now president of the University of Alberta. His technical discoveries and innovations were very signicant, but I think he would be most proud of the people he mentored. Samarasekera counts herself as one of the people who beneted from his mentorship. Brimacombe served rst as her Ph.D. supervisor and then as her colleague at UBC. This is one of the reasons that the Brimacombe Medalist award, designed for a person in the middle of their career, is such a tting tribute to the former professor and researcher. He was very passionate about developing a persons human potential and working with people in the middle portion of their career, said Samarasekera. When he was TMS president, he actively engaged many who were just beginning to gure out how to engage with TMS. In 1970, Brimacombe joined the faculty at UBC, where he worked for 27 years. During his time at the university, he helped to create and then served as director of the Centre for Metallurgical Process Engineering. The purpose of the center was to strengthen

the interdisciplinary approach to metallurgical process research and to broaden the eld of application to materials other than metals. Often his research was conducted in collaboration with Canadian companies. He was a person who believed in doing cutting edge engineering science and then translating that into technology development that had commercial potential, said Samarasekera. He won awards for doing the best possible science. But he realized that if he just published it, it might be stillborn and never benet industry. Brimacombe achieved much success in a career that was cut short by his death in 1997 at the age of 54. He was an outstanding engineer who understood the complexities of materials and their benets to society, said Samarasekera. He was also a leader, across the breadth of disciplines. And to accomplish all of that in his brief life? That was amazing. Morris Cohen: From Metallurgy to Materials Morris Cohen grew up around metals. His familys business produced and rened lead-based alloys used in metal type and solders. When he enrolled at the Massachusetts Institute of Technology (MIT) in 1929, he expected to apply his metallurgy degree to the family business. Instead, he became an instructor at the school, earning the rank of Institute professor, the schools highest honor, in 1975. Although metals started his career, one of the achievements for which Cohen is best known is his role in expanding the eld of metallurgy into the discipline of materials science. In 1974, Cohen chaired the Committee on the Survey of Materials Science and Engineering, which produced the inuential National Academy of Science report Materials and Mans Needssometimes called the Cohen report. This report certainly played a key role in moving

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JOM October 2010

which recognizes the sustained excellence and achievement in business, technology, education, public policy, or science related to materials science and engineering. While there are no specic age requirements for the Brimacombe Medalist award, to be eligible, an individual must have been a professional member of TMS for at least ve consecutive years and must have a record of service to the society. SMITH, CHALMERS, AND COHEN: STRUCTURE, PROCESSING, AND PROPERTIES In reviewing its awards, TMS determined that the society should offer three separate honors for outstanding work in materials structure, processing, and properties. To make this possible, TMS established the new Cohen and Smith awards and repurposed the existing Bruce Chalmers award. To be eligible for each of the awards, an individual must have an established record of research, publications, and/or patents in the eld.

The new Cyril Stanley Smith Award will recognize an individual who has made outstanding contributions to the science and/or technology of materials structure. The Morris Cohen Award will recognize an individual who has made outstanding contributions to the science and/or technology of materials properties. The Bruce Chalmers Award, which previously recognized outstanding contributions in solidication processing, will now more generally recognize an individual who has made outstanding contributions to the science and/or technology of materials processing. A SIMPLIFIED NOMINATION PROCESS In addition to creating new awards, TMS has reworked its entire awards system to shorten the amount of time between nomination and presentation of honors. In previous years, nominations were submitted a year and a half before the honorees actually received their awards, and the timelines varied for division and society

awards. Now, the entire process takes less than a year, and all nominations, for both division and society awards, are due April 1. Award nomination packets are judged by committee members over the summer, and winners are determined by September 1. The TMS Board of Directors approves the society award winners at the Materials Science & Technology Conference in the fall; winners are notied in November. The awards are presented at the TMS Annual Meeting, in February or March. The inaugural Brimacombe, Cohen, and Smith awards will be presented at the TMS 2012 Annual Meeting, which will be held March 1115, 2012, in Orlando, Florida. Nominations for these and other TMS awards will be due April 1, 2011, with winners being notied in November 2011. On-line nomination forms for all TMS awards can be accessed through the TMS Professional Recognition web site at www.tms.org/society/tmsawards .aspx.
Kelly Zappas is a contributing writer for TMS.

academic departments from their metallurgy base to expand into ceramics, polymers, semiconductors, and compositesand the universal paradigm of structure-property-processing-performance relations that hold regardless of the particular type of material considered, said Edwin L. Thomas, current head of the Department of Materials Science and Engineering at MIT. Cohen made major contributions to the understanding of the structure of matter and the ways in which materials such as iron and steel can be processed. His work was central to the development of modern high-strength steels. The TMS Morris Cohen Award will recognize the achievements of individuals working with materials properties. Thomas, who also holds the title of Morris Cohen Professor of Materials Science and Engineering at MIT, understands what an honor it is to have his career linked to Cohens. Any materials scientist would be very, very highly honored to receive an award in Cohens name. When I would go to Japan 20 years ago and would be introduced as the Morris Cohen Professor for some seminaralways, always right after my talk, members of the audience would come up to me and greet me and want to pass their best regards and most sincere best wishes to me to take back to Morris, said Thomas. He was especially loved in Japan for his outstanding metallurgical contributions. In fact, Cohen was honored with Japans Kyoto Prize for Advanced Technology. He was the rst in the area of materials to receive the prize, according to Thomas. Cohen stayed at MIT throughout his career, retiring in 1987. He passed away in May 2005. Cyril Stanley Smith: The Structure of Everything The Cyril Stanley Smith Award was established to recognize achievements in materials structure. Smith was one of the most inno-

vative early physical metallurgists whose pioneering studies and ideas covered almost every aspect of our eld, said John Cahn, a former colleague of Smiths. His forte was the understanding and the elucidation of the signicant aspects of microstructures, how to measure them, and how microstructures evolved. He could look at a two-dimensional section of an opaque material and not only infer its three-dimensional structure, but also surmise how it came to be and how it would evolve with time, its fourth dimension. His pioneering research on the capillary and topological aspects of internal surfaces of solids, applied e.g. brilliantly to grain growth, have stood the test of time. Smith started his career as a research metallurgist at the American Brass Company in 1927 and later joined the Manhattan Project at Los Alamos. In 1946, he joined the University of Chicago, where he founded the Institute for the Study of Metals (ISM). ISM was the rst of what are now many interdisciplinary labs. Smiths ISM was a pioneering attempt to change the structure of our discipline, said Cahn. Smith had come from Los Alamos where he had his eyes opened by what physics, chemistry, and mathematics could do for metallurgy. Because of Smith, physics, chemistry and mathematics are today very much part of metallurgy and materials. But materials structure doesnt fully encompass Smiths interests, which included, in short, the structure of everything. Artists and craftsmens uses of structure were fascinating to him, whether ancient metallurgies, the art of Japanese swords and sword guards, or the structural play of M.C. Eschers work, said Anne Denman, Smiths daughter. In the 1930s, Smith began translating ancient texts on metallurgy, ancient technology, and archaeology. In 1961, MIT gave him the opportunity as an Institute professor to merge his interests. He established the Laboratory for Research on Archaeological Materials, which later led to the founding of the Center for Materials Research in Archaeology and Ethnology. (Photo courtesy of MIT.)

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Refractory Metalss

Commentary

Refractory MetalsAn Exploration of High-temperature Materials

S.K. Varma

The U.S. government is spending a signicant amount of human and nancial resources to develop high-temperature materials that can be used for turbine engines to elevate their service temperature capabilities as well as improve efciency. A promising class of materials with potential to address such issues is refractory metals. By denition, these metals have high melting points. Such research could have a positive impact on the U.S. economy and lead to the development of more operationally efcient and economical turbine engines. Historically, the role of high-temperature metallic materials has been dependent on nickel-based superalloys. However, these superalloys have limited service temperature because of the relatively low melting point of nickel, at 1,453C. On the other hand, niobium and molybdenum, candidates for nickel-based superalloys replacement, have melting points of 2,468 and 2,610C, respectively. Thus, weight may play a crucial role in the selection of materials for high-temperature applications. The Refractory Metals 2010 symposium held in Seattle, Washington, was sponsored by the TMS Refractory Metals Committee. Energy issues related to high-temperature materials, thermal stability, and their mechanical and oxidation properties were among the subjects of presentations made by various authors. The vast experience

and the noted expertise of these authors allowed the dissemination of state-ofthe-art technology. Their continued research promises a quick delivery of the actual material to be used in practices involving high temperatures. In this issue, J.H. Perepezko and R. Sakidjas paper examines the effect of surface coating of molybdenum-based alloys for ultra-high-temperature applications. In particular, the Mo-Si-B system was studied; typical borosilica oxidation scale was expected to provide a passive surface layer for enhanced oxidation resistance. The surface coating could reduce the thickness loss per unit area per unit time but thermodynamic compatibility between the substrate and the coating needs to be addressed. The authors stipulate that B/Si ratio can control the diffusion through the coating. The authors present their work on Mo-14.2Si-9.6B (at.%) ternary alloy and discuss the layered structure formation consisting of MoSi2 and T1 phase (Mo5Si3) with dispersoids of MoB. Next, Michael R. Middlemas and Joe K. Cochran deal with alloys from the Mo-Si-B system containing molybdenum solid solution phase and two Mo3Si and Mo5SiB2 (T2) silicides. Powders of molybdenum, Si3N, and BN, were used to synthesize an alloy through powder processing. The approach is to control the morphology of the three phases to tailor-make the properties. The processing has allowed the minimization of the clustering of the T2 phase through the control of BN addition. Oxidation resistance is derived from the molybdenum solid solution phase while other phases

can provide the mechanical properties through the control of their morphologies. The possibility of developing an alloy from the Mo-Ni-Al system up to 1,200 1,300C is explored by P.K. Ray et al. However, oxidation resistance is expected from the intermetallic NiAl through the formation of Al2O3 passivating scale. The compositional variation in molybdenum ranged from 1535 at.% while maintaining the atomic ratios of nickel and aluminum to be the same. The authors conclude that better oxidation resistance for up to 20 hours can be obtained by keeping the molybdenum concentration to less than 20 at.%. Finally, Simon Hollad and Andreas Bhrig-Polaczek used vacuum investment casting to produce 2590160 mm turbine blades by using 45 equiatomic percent of nickel and aluminum, 7.5%Cr, and 2.5%Ta. A shell mold free of SiO2 was produced for the investment casting of NiAl. There are two reasons for using an SiO2-free mold: silicon reacts with the NiAl melt and lowers the temperature capability of the mold and cannot be used for this alloy since it melts at 1,600C. The production of castings free of cracks uses a precise cooling rate control during the equiaxed process. A continuous production of turbine blades may be prepared following their experimental process subject to adaptation.
S.K. Varma, professor, is with the Department of Metallurgical and Materials Engineering, University of Texas at El Paso and is the advisor to JOM from the Refractory Metals Committee of the Structural Materials Division of TMS.

S.K. Varma is a TMS Member!

To read more about him, turn to page 7. To join TMS, visit www.tms.org/Society/Membership.aspx.

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JOM October 2010

Refractory Metals

Research Summary

Oxidation-resistant Coatings for Ultra-high-temperature Refractory Mo-based Alloys

J.H. Perepezko and R. Sakidja
The synthesis of robust coatings that provide protection against environmental attack at ultra-high temperatures is a difcult challenge. In order to achieve this goal for Mo-based alloys the fundamental concepts of reactive diffusion pathway analysis and kinetic biasing are used to design a multilayer coating with a phase sequencing that provides for structural and thermodynamic compatibility and an underlying diffusion barrier to maintain coating integrity. The coating structure evolution during high-temperature exposure facilitates a prolonged lifetime as well as a self-healing capability. Both borosilicide and aluminide coatings that can be synthesized by a pack cementation process are demonstrated to yield superior environmental resistance on Mo-based systems at temperatures up to 1,700C and can be adapted to apply to other refractory metal systems. INTRODUCTION In recognition of the need for increased operating temperatures in order to satisfy the demands for increased gas turbine engine performance and improved energy efciency that can not be satised by Ni-based superalloys, new ultra-high temperature structural materials in refractory metal systems and ceramic materials are under study.1 Within these efforts, alloys in the MoSi-B system have been identied with a number of attractive features based upon strength and creep resistance.25 For Morich Mo-Si-B alloys the phase equilibria has been established as shown in Figure 1, where the ternary intermetallic MoSiB2 (T2) phase is a key constituent in 5 the multiphase equilibria.6 Multiphase microstructures based upon (Mo + MoSi + T2) three-phase alloys appear to of3 fer an effective balance of high-temperVol. 62 No. 10 JOM

How would you

describe the overall signicance of this paper? This study examines the design and synthesis of protective borosilica and alumina coatings that have been applied to molybdenum based alloys by a pack cementation process. The multilayer coating structure provides an excellent oxidation resistance at ultra-high temperatures up to 1,700C for a prolonged exposure and offers a self-healing capability. describe this work to a materials science and engineering professional with no experience in your technical specialty? In this work, the diffusion path analysis and kinetic biasing strategy have been applied to design oxidation resistant multilayer coatings comprised of silicides, borosilicides and aluminides that are synthesized through a pack-cementation (CVD) process. The coatings were applied to molybdenum alloys. Oxidation tests in air at temperature up to 1,700C showed an excellent oxidation resistance of the coated samples with a very small recession rate and mass gain. The success can be attributed to the slow growth of a continuous borosilica or alumina layer on the surface and the evolution of the underlying oxidation resistant phases that also serve as a diffusion barrier between the coating and the substrate. describe this work to a layperson? Molybdenum-based alloys have a severe limitation in terms of operating temperature due to rapid oxidation despite the high melting temperature and signicant potential for high-temperature applications. This new coating technology enables a number of opportunities to use Mo-based alloys in oxidation environments at temperatures much higher than previously possible and beyond the capabilities of current advanced Ni-based superalloys.

ature performance.25 It is noteworthy that the relative atomic packing density in the T2 phase (75%) is higher than that in the Mo5Si3 (T1) phase (71%).7,8 This difference is also reected in a reduced diffusivity for Si, DSi in the T2 phase T2 T1 (DSi / DSi = 103) at elevated tempera9 ture. Three-phase alloys comprised of the Mo (solid solution (ss)), T2 (Mo5SiB2) and Mo3Si (A15) phases offer favorable combinations of high-temperature mechanical properties and oxidation resistance due to the formation of an adherent borosilica layer during hightemperature oxidation.1014 Similarly, a combination of mostly the Mo5Si3 (T1) phase with T2 and MoB phases shows an oxidation resistance comparable to that of MoSi2.15,16 For structural applications the requirements for high strength at high temperature along with environmental attack resistance are not usually satised concurrently for most materials. For example, the three-phase (Mo(ss)+ T2 + Mo3Si) alloys have attracted interest due to their excellent high-temperature strength. These alloys do develop a protective borosilica oxidation scale, but the alloy recession rate is too high for desired lifetimes.17 One effective strategy to address an enhanced resistance to environmental attack in highstrength materials is the application of oxidation-resistant coatings. While this strategy is attractive, the successful implementation of protective coatings over the entire operating temperature range requires the satisfaction of other requirements involving thermodynamic and mechanical compatibility between the coating and the alloy substrate and the robust stability of the coating in order to maintain the integrity of the environmental protection. For the development of a coating
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Mo3Si Gray Mo White T2 Dark a Figure 1. (a) BSE image of Mo-14.2Si-9.6B, (b) isothermal section of Mo-Si-B phase diagram10 at 1,600C with the composition marked as a triangle. b

design, the rst step is to identify the key compositional and kinetic factors controlling the oxidation response. In the current work this has been accomplished by analyzing the oxidation products and the reaction pathway as a basis for applying a novel kinetic biasing strategy to control the coating phase structure and sequencing and enhance the oxidation resistance. The approach for refractory metals is illustrated rst for Mo-Si-B alloys where the key components of the coating design are identied and then extended to other Mobased systems including pure Mo. See the sidebar for experimental details. OXIDATION OF MO-SI-B ALLOYS During initial contact with oxygen at elevated temperatures, Mo-Si-B alloys experience a transient oxidation stage characterized by rapid mass loss due to volatilization of MoO3. After some time, the borosilica originating from the Mo5SiB2 and Mo3Si phases extends to cover the sample surface, thereby reducing the inward oxygen diffusion. Further, it was also found that none of the alloys were passivated at lower temperatures, and all suffered from catastrophic oxidation between 700C and 800C. For example, bubbles were observed in the Mo-11Si-11B alloy scale at 800C, indicating that oxidation of molybdenum was occurring and that the MoO3 bubbles were moving through the scale.12 This behavior illustrates the ease with which material may be transported across the scale if the coating chemistry is not optimized. In addition, there is an issue with the high volatility of B2O3 at temperatures above 1,200C, which consequently impacts the metal
14

recession rate.1215 While several factors inuencing the oxidation resistance have been identied, it is clear that the B to Si ratio of the alloy is the dominant factor that controls the constitution, the viscosity and oxygen diffusivity24 of the in-situ SiO2-B2O3 passive layer upon oxidation. It is generally understood that lowering the B to Si ratio in the scale by means of increasing the silicon content in the Mo-Si-B alloys yields an increase in the high-temperature oxidation resistance due to the formation of the passive SiO2 rich layer. However, this response must be balanced by the result that excessive Si content will impact the oxidation resistance at low temperatures (i.e., 650750C) since the formation of a protective SiO2 layer in this temperature region is slow compared to the loss of Mo by the formation and volatilization of MoO3.2 Thus, coating designs are necessary to pro-

vide enhanced oxidation protection to the Mo-Si-B alloys. In order to provide a baseline for comparison, the development of oxide layer formation was analyzed in the uncoated alloy substrate. An Mo-14.2Si9.6B (at.%) (B/Si = 2/3) ternary alloy was selected based upon prior reports that alloys with B/Si 1 exhibited a superior oxidation resistance. A backscattered electron (BSE) image of an as-cast Mo-14.2Si-9.6B (at.%) sample and location of the nominal composition on the ternary isotherm at 1,600C are shown in Figure 1a and b. The as-cast microstructure is based on the Mo (ss) + T2 two-phase eutectic and a ne three-phase eutectic structure that shows no noticeable modication after annealing at 1,300C for 100 h in an Ar atmosphere. The amorphous layer was determined from electron probe micro-analysis (EPMA) measurements to contain mostly SiO2 with about 10 at.% B (or 17 mole% of B2O3) which is close to the liquidus25 and in the MoO2 layer the solubility of boron and silicon is negligible. From the layered product structure, the kinetic sequence involved in oxidation can be depicted in terms of the diffusion pathway26 that is represented in Figure 2a. The phase sequence in Figure 2 indicates that the borosilica layer is connected to MoO2 behind the initial pole between oxygen and the substrate composition.14 An examination of the pathway reveals that the composition of the borosilica

EXPERIMENTAL DETAILS Ingots of Mo-rich Mo-Si-B alloys with compositions of Mo-3Si-1B (wt.%) [Mo-8.9Si7.1B (at.%)] and Mo-14.2Si-9.6B (at.%) were prepared by repeated arc-melting in a Ti-gettered Ar atmosphere. Each ingot was sliced to a typical 3 mm thickness, polished through a 0.05 m Al2O3 slurry and cleaned with ethanol in an ultrasonic cleaner. Briey, the pack cementation process involves the elevated temperature deposition of Si or Si+B, carried by a volatile metal-halide vapor species to the substrate embedded in a mixed powder pack containing powder of the deposition element, a halide salt activator, and an inert ller.1820 The detailed procedure of pack-cementation process is well-dened elsewhere.2123 The powder mixture composed of 70 wt.% Al2O3, 25 wt.% total of Si and B powders, and 5 wt.% NaF was loaded in an alumina crucible together with the clean alloy pieces followed by sealing with Al2O3 slurry bond. The prepared crucible was annealed at 900C for 48 h in an Ar atmosphere. In the pack cementation, silicon uoride (SiF4) vapor synthesized from the reaction between NaF and silicon powders at elevated temperature reacts with the substrate to enrich the surface with Si. After high-temperature annealing, the samples were removed from the alumina crucible and ultrasonically cleaned. For Al pack processing, we used the NH4F as the halide activator (2 wt.%) with a similar procedure as that of Si+B pack cementation process.18 For oxidation testing, the alloys were annealed in air between 700 and 1,700C. Microstructural evaluation was performed by both optical and scanning electron microscopy (SEM) using either secondary or backscattered electron (BSE) imaging modes. Thermogravimetric analysis (TGA) was conducted in a Netzsch 409 instrument.

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a b c Figure 2. (a) Schematic illustration of the diffusion pathways indicating the phase evolution upon oxidation of the Mo-Si-B alloy located in the Mo-Mo3Si-T2 three-phase eld (virtual nominal diffusion pathway between borosilicate and MoO2 is also indicated). (The numbers indicate (1) Mo(ss) body-centered cubic phase with internal silica precipitates, (2) MoO2, and (3) borosilicate layer. The region below (1) in (a) is the alloy substrate). (b) The cross section SEM-BSE image of Mo-14.2Si-9.6B (at.%) alloy oxidized at 1,200C for 100 h in air. (c) Schematic of the oxide structure in the Mo-Si-B alloy in (b).

layer directs the initial phase development and inuences the composition of the nal product phases. For example, the formation of MoO2 rather than MoO3 conrms that the coating does restrict oxygen transport since it reduces the oxygen activity. Moreover, the identication of product phases can be inversely applied as a guideline for operating conditions. For example, by enriching the SiO2 content of the outer borosilica layer, the equilibrium can be shifted from (borosilica + MoO2) to (SiO2 + Mo) with a consequent drop in the oxygen activity (i.e., Po2) and the transport of oxygen to react with the alloy substrate. From the current observations as well as from prior reports, the oxidation reaction commences with a transient stage which is accompanied by mass loss due to the evaporation of MoO3 as well as boron oxide. The oxidation process then evolves into a steady state which is signied by the development of borosilica layer at the outermost portion of the oxide structure. Following oxidation in air, the (SiO2 + B2O3) layer produced is naturally protective, but it does not completely block O2 transport so that with continued exposure, the thickness of the oxide increases along with a recession of the alloy base. The initial onset temperature for the steady state oxidation is highly dependent on the composition of the Mo-Si-B substrate alloys. Furthermore, the B/Si ratio in the substrate and that develops in the oxide scale controls the nature of the transient stage. The signicance of the B/Si ratio opens up opportunities in
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coating design to alter the oxygen diffusion pathways, the oxygen mobility and consequently the overall oxidation resistance. DESIGN OF OXIDATIONRESISTANT BOROSILICA COATINGS To control the B/Si ratio a pack cementation process was adapted for coating synthesis. During the Si pack
MoSi2 T1

cementation process coating process, a steep chemical potential gradient of Si across the vapor-substrate interface produces a ux of Si into the substrate that uniformly enriches the local Si concentration and results in the synthesis of a MoSi2 coating layer.2123 A BSE image of an as-Si packed sample is shown in Figure 3a. Underneath the MoSi2 layer, there is a Mo-rich silicide layer of Mo5Si3 (T1) phase and dispersoids of the MoB phase.18 There is a limited amount of boron in the substrate and consequently it is not possible to establish a continuous layer of MoB. The presence of MoB phase can be understood from the diagram of composition trajectories of the Si-pack cementation process into this alloy as shown in Figure 3b. In this case, due to the relatively low temperature of the pack process (900C), any preferential mass loss of the elements (Mo,Si,B) on the surface due to evaporation should be negligible. Thus, as Si diffuses into the Mo-Si-B alloy, the composition trajectory of the process should follow the line connecting the Si source to the composition of the substrate (Mo-3Si-

MoB

2 m a Figure 3. (a) Si pack-cementated Mo3Si-1B (wt.%), (b) composition trajectory of the Si-pack cementation process on Mo-3Si-1B (wt.%) alloy depicted in the Mo-Si-B phase diagram. MoSi2 MoB b

2 m a Figure 4. (a) Pack-cementated Mo-3Si1B (wt.%) with a partial substitution of Si with B (1:20 B to Si weight ratio), (b) composition trajectory of Si + B pack cementation process on Mo-3Si-1B (wt.%) alloys depicted in the Mo-Si-B phase diagram. A full development of the boride phase underneath the silicide phase is observed with the partial substitution.

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1B wt.%). From the tie line between MoB and MoSi2 in Figure 3b, it is clear that only a limited amount of MoB can be created as the MoSi2 layer starts to develop on the surface. Enrichment of only Si via pack cementation does not provide the amount of boron needed to stabilize a continuous layer of borosilicide and/or boride phases in Mo-rich Mo-Si-B alloys. Therefore, it is important to pursue a simultaneous or co-deposition of B and Si onto the Mo-rich Mo-Si-B alloys followed by annealing treatments at 1,2001,400C.19,20 Indeed, as exemplied in Figure 4a, by partly substituting Si with B in the pack powder mixture, a continuous layer of MoB can be stabilized underneath the silicide layer coating onto the Mo-3Si-1B wt.% substrate. As illustrated in Figure 4b, the nominal composition path for the co-deposition processes can be represented by rotation about the substrate nominal composition whereby the initial vapor source moves from the pure Si to a mixed Si/B source. During oxidation tests of the (B+Si)pack alloys, the initial MoSi2 outer layer is consumed by formation of the T1 phase as one consequence of the transient composition trajectory. With continued elevated temperature exposure during oxidation, the outer T1 phase layer would eventually be consumed by dissolution into the substrate. However, part of the initial transient stage of

reaction that yields the T1 phase from the inward ux of Si and B also leads to the development of the T2 borosilicide and/or boride phase layer. The relative amounts of the T2 and MoB phases below the T1 phase region depend on the B/Si ratio of the powder sources as illustrated in the composition trajectories in Figure 4b. The T1 phase is always in contact with the MoB or T2 borosilicide phase, which guarantees B saturation in the T1 phase. Furthermore, since the T1 phase that is saturated with B has excellent oxidation resistance27 and the loss of Si is blocked by the underlying diffusion barrier (i.e., the borosilicide and boride phases), the T1 layer thickness change can be arrested.19,20 Further, any damage to the outer T1 layer can be recovered from the underlying T2 + MoB layer. In effect, the in-situ reaction that yields the T2 + MoB layer also provides a kinetic bias28 that allows for the continued existence of the outer T1 layer and also yields a self-healing characteristic of the coating. Oxidation tests performed at 1,400C show the benets of the coatings to provide an effective oxidation protection. As shown in Figure 5, with uncoated samples, oxidation of Mo-3Si1B (wt.%) alloys results in a large mass loss as evident by the thickness reduction of the originally 333 mm3 cube samples. The scanning electron microscopy (SEM) cross section of the oxide scales shows that even though there is
Thick Borosilica Glass ~100125 m Intermediate Region Glass + Substrate, depleted of Si and B Mo-3Si-1B (wt. %) Substrate Borosilica Glass ~1015 m Silicide (MoSi2) Silicide (B-Doped Mo5Si3) B Enriched Region Mo-3Si-1B (wt. %) Substrate

b 13 mm Figure 6. (a) Pure molybdenum coupon protected by an 80 m-thick borosilicide coating being subjected to 1,700C oxidation in air. (b) The same Mo coupon sample after 1,700C/25 h oxidation test with a minimal mass change of less than 2 mg/cm2.

Figure 5. SEM image of uncoated Mo-Si-B sample after an oxidation test at 1,400C for 30 h showing the extensive recession rate even though a continuous borosilicate layer develops on the surface as shown in the BSE-SEM image in (b). In contrast, with the same oxidation condition the coated sample in (c) exhibits a minimal mass loss due to the borosilicade coating protection. (d) SEM-BSE cross section image of the coating showing the development of B-saturated T1 phase and the diffusion barrier underneath the silicide phase that is comprised of T2 and boride phases.

a thick and continuous borosilicate layer on the surface, the high evaporation rate of B2O3 at this temperature results in a relatively large mass loss during the transient oxidation. In contrast, the coated sample shows the thickness retention of the sample and furthermore a very limited growth of the borosilicate layer on top of the coating (less than 15 m after 30 h exposure). The Si and B co-deposition treatment can also be applied to pure Mo to provide a robust oxidation protection at ultra-high temperatures as high as 1,700C as exemplied in Figure 6a. The pure Mo coupons (2.5 cm diameter with thickness of 6.5 mm) were initially coated by 7580 m thick of Mo-Si-B coating through a pack cementation process at 1,000C for 50 h. The initial coating was comprised of MoSi2 and MoB phases. The MoB phase forms both as dispersoids in the MoSi2 layer as well as a continuous layer underneath the disilicide layer. The Mo coupons were then exposed to a range of ultrahigh temperatures (1,6001,700C) in air and despite the relatively thin borosilicide coating, the integrity of the Mo coupons was retained with minimal mass gains (see Table I). After oxidation the samples were completely covered by silica-base glass as shown in Figure 6b and the SEM images in Figure 7.
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Oxygen Partial Pressure (atm) dM (mg/cm2)

Table I. The Mass Changes of the MoSiB-coated Mo Coupons after Ultra-high Temperature Exposures in Air
Oxidation Tests 1,700C/25 h 1,675C/25 h 1,650C/100 h 1,650C/25 h Mass Change (mg/cm2) +1.7 +1.9 +2.26 +2.21

mal mass change enables us to examine the maximum partial pressure of oxygen allowed at the silica/coating interface. There are a number of possible oxidation reactions at the interface: MoSi2 +7/2O2 => 1/3(MoO3)3 (g) + 2SiO2(s) (1) MoSi2 + 7/2O2 => MoO3(g) + 2SiO2(s) (2) MoSi2 + 2O2 => MoO2(s) + SiO2(s) (3) MoSi2 + O2 =>Mo(s) + SiO2(s) (4)

10 12 14 16 18 20 22 24 26 1,000 1,100 1,200 1,300 1,400 1,500 1,600 1,700 Temperature (C) Figure 8. The maximum oxygen partial pressure for formation of MoO2(s), Mo(s) or Mo5Si3(s) from MoSi2 oxidation. 50 0 50 100 150 200 250 300 350 400 450

ANALYSIS OF COATING REACTIONS The key to an effective oxidation protection is the restriction of the partial pressure of oxygen at the coating interface due to the continuous formation of the glassy scale. There are a number of possible oxidation reactions that one can consider during this hightemperature exposure. For simplicity, we consider the oxidation reactions that pertain only to the MoSi2 as the overall mole fraction of MoB is relatively small and there is even a much smaller portion of MoB phase as dispersoids within the MoSi2 layer. Nevertheless, the MoB phase does play an important role in supplying the silica glass with a necessary boron dopant. Underneath the borosilica glass, there is a Mo5Si3 (T1) layer as the initial part of the eventual conversion into the T1+T2 coating. The presence of the T1 phase layer at the MoSi2/SiO2 interface and the mini-

MoSi2 + 7/5O2 => 1/5Mo5Si3(s) + 7/5SiO2(s) (5) Reactions 1 and 2 may have proceeded during the transient stage of oxidation which would have resulted in a signicant net mass loss due to the evaporation of Mo oxides. However this was not observed in the experiments. The three remaining reactions would have yielded a mass gain attributed to the growth of the SiO2 oxide thickness and MoO2(s) for Reaction 3. Since the Reaction 5 is the dominant reaction as observed in the oxidation experiments, one can compare the maximum partial pressure required for Reactions 35 where each will produce mass gain for the temperature range of 1,0001,750C. The mass change suggests that the oxidation takes place mostly following Reaction 5. The preferred reactions can be further understood from the required PO2 thermodynamically required to stabilize these reactions. With the assumption of the chemical activity of the possible solid products of the reactions (SiO2, Mo5Si3, Mo and MoO2) is equal to 1, then the PO2 required for Reactions 35 for a range of temperature of 1,0001,700C is graphed in Figure 8. The plot shows that for a given temperature, the PO2 required to stabilize Mo5Si3 is always lower than that for MoO2 and Mo. Since there is only the Mo5Si3 (T1) phase that was observed below the silica at hightemperature oxidation, the partial pressure of oxygen must have been signicantly reduced by the silica glass layer (e.g., at 1,700C, PO2 109 Pa). This is again a testament to the effectiveness of the present coating in preventing oxidation even at such a high temperature. With a suppression of the PO2 within the
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20 30 40 50 Time (h) Figure 9. DTA results25 from pack aluminized and uncoated Mo-3Si-1B (wt.%) samples oxidized for 50 h between 7321,300C. Due to its signicant mass loss, the run for the uncoated sample at 1,300C was stopped after 2.5 h.

10

borosilica glass layer, the oxidation process can be biased to yield Reaction 5. It is also worthwhile to emphasize here that the converted T1+T2 coating is actually thicker than the original MoSi2+MoB coating even after the ultra-high oxidation exposure. This can be understood from the fact that during the conversion of the MoSi2 and MoB coating into a T1+T2 coating, the MoSi2 and MoB phases react with Mo substrate following the reaction: aMoSi2 + bMoB +cMo dMo5Si3 + eMo5SiB2 (6)

b Figure 7. Backscattered cross section SEM of the MoSiB coating after oxidation tests at (a) 1,675C and (b) 1,700C for 25 h. Insets are the samples after the tests. The coating is comprised of T1 and T2 phases with a small fraction of A15 phase at the silica glass/coating interface.

The total volume of the initial coating phases can be estimated from (a.MWMoSi2/MoSi2) + (b.MWMoB/MoB) is where MW is the molecular weight and is the weight density of each species. Then, the volume ratio, rv, of the converted coating products to the initial coating is: rV = [(d.MWMo5Si3/Mo5Si3) + (e.MWMo5SiB2/Mo5SiB2)] : [(a.MWMoSi2/ MoSi2) + (b.MWMoB/ MoB)]

(7)

The amount of the Mo that reacted to

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1 2

Table II. Estimated Conversion of Coating Volume from Typical Si+B Pack Powder Sources Following the Conversion into T1+T2 and into A15+T2
Si:B wt. Ratio 25:1 35:1 40:1 MoSi2:MoB Mole Ratio 4.83:1 6.75:1 7.72:1 Coating Volume Ratio for T1+T2 Conversion 1.84:1 1.86:1 1.86:1 Coating Volume Ratio for A15+T2 Conversion 2.74:1 2.79:1 2.80:1

60 m

1 2 3

60 m

Figure 10. SEM-BSE cross section of aluminized Mo-3Si-1B (wt.%) sample after oxidation at (a) 732C and (b) 1,372C for 50 h depicting (1) alumina layer, (2) Mo3Al8 phase, (3) Mo3(Si,Al) /A15 phase, and (4) Mo-Si-B substrate. Note that the A15 phase grows both from the alumina/Mo3Al8 interface as well as the Mo3Al8/ substrate.

the initial coating (c) in this case is dependent upon the B/Si ratio which subsequently determines the ratio of MoSi2 and MoB phases (i.e., a/b). In the MoSi-B coating process where the weight ratio of B to Si powders is in the range of (2540):1, the resulting volume ratio of the converted coating phases to the initial coating will be about 1.85 as listed in Table II (for coatings with a Si: B ratio of 35:1, the equivalent mole ration of MoSi2 to MoB is approximately 6.75). The almost doubling (8586% increase) of the coating volume enables the lifetime of the coating to be extended further beyond the completion of the conversion process since both T1 and T2 phases posses excellent high-temperature oxidation resistance and more importantly the T2 phase allows for a much slower mobility of Si and B from the coating into the pure Mo substrate. The converted T1+T2 coating will eventually transform into an A15+T2 coating structure following a net reaction: aMoSi2+bMoB +cMo dMo3Si + eMo5SiB2 (8)

175% which will almost triple the coating thickness assuming that the coating cross sectional area remains fairly constant and the diffusion mostly moves inward (one directional) following the chemical potential gradient of Si and B. Since A15+T2 two-phase alloys still exhibit a relatively a good oxidation resistance27,29,30 and the growth rate of A15 is typically the slowest amongst the silicide phases, particularly at high temperatures,31,32 the lifetime of the coating can be signicantly increased by these coating conversions. The growth of the coating thickness, however, will have to be partly counterbalanced by the growth of the silica on the surface which will consume the MoSi2 layer and later the Mo5Si3 layer at the SiO2/ coating interface. Nevertheless, with the relatively low growth rate of silica and the thickening effect of conversion process from MoSi2+MoB into T1+T2 and then into A15+T2 phases, the MoSiB coating clearly offers an enabling coating technology to increase the utility of Mo alloys at much higher temperatures. Moreover, since Mo is soluble and coma
A15 Layer A15 T2

patible with other refractory metals, the present coating strategy can be applied to refractory metal systems that are coated with a Mo surface layer. DEVELOPMENT OF ALUMINIDE COATINGS The coating strategy for oxidation protection of refractory metals that has been applied to the borosilicide coatings can also be applied to an aluminidebased coating when a water vapor environment is a concern. The pack aluminizing process on Mo-Si-B alloys yields a primary product of the Mo3Al8 phase with dispersions of ternary MoAlB, Mo3(Al,Si) and T2 phases underneath the Mo3Al8 layer. Similar to the borosilicide coatings, aluminide coatings offer exceptional resistance to oxidation primarily due to (1) the formation of continuous alumina on the surface and (2) relatively slow growth rate of the alumina during exposure. Figure 9 exemplies the TGA data from the oxidation of an aluminized Mo-3Si-1B (wt.%) alloy19 where the mass change is signicantly smaller than that from the

Substrate

20 m

b
A15 Layer A15 T2

20 m

Substrate Composition (Mo-Al-B Phase Lines in Mo-Al-B Phase Diagram Diagram) Lines in Mo-Si-B Phase Diagram Pack Powder Composition (Al-12Si at %) Lines in Mo-Al-Si Phase Diagram Lines in Mo-Al-B=Si Quaternary Phase Diagram

As shown in Table II, the estimate of the total conversion into a A15+T2 coating for a typical Si+B co-pack cementation process will correspond to a total increase of the coating volume by
18

Figure 11. (a) BSE SEM micrograph of Al-pack and (b) Al+B pack after 1,300C/50 h oxidation test. The A15 layer is composed of a Mo3(Al,Si) matrix and of the T2 phase. A semi-continuous T2 phase starts to develop into the A15 layer (b) and can be used to limit the inward diffusion of Al into the substrate. The composition trajectories for Al and Al+B pack treatments are illustrated in (c). Inset in (c) shows a detailed view of trajectories of paths A and B near the substrate.

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Substrate

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Mo-Si-B base alloy substrate. The oxidation reaction is mainly governed by the oxidation of Mo3Al8 through: Mo3Al8(s) +5.5O2(g) Mo3Al(s) +3.5Al2O3(s) (9)

which yields a small mass gain from the alumina growth. The cross section of the oxidized coating is depicted in Figure 10 after an oxidation test at 1,372C for 100 h showing the protective alumina layer on the surface. A lifetime estimate of the coating can be evaluated based on the growth rate of the alumina and the A15 phase from the oxidation Reaction 9.33 The key for prolonging the lifetime of the coating in this case is the retention of a high enough Al concentration supplied to the surface from the coating. This also means that the Al inward diffusion into the substrate must be prevented. One approach to achieve this goal is to increase the mole fraction of the T2 phase in the A15+T2 layer as the T2 phase has a limited solubility of Al and the mobility of metalloids within the T2 phase is sluggish.10 In this case, a sequential pack processing (B-pack cementation + Alpack cementation) was employed where the rst process enriches the surface initially by the borosilicide (T2) phase due to the increased boron content and then the Al pack process proceeds to form the aluminide coating on the surface. By this approach, the volume fraction of the T2 phase underneath the Mo3Al8 layer is increased and the amount of Al diffusion into the A15+T2 layer is reduced as exemplied in Figure 11.19 CONCLUSIONS The synthesis of robust coatings that provide protection against environmental attack at ultrahigh temperatures is a difcult challenge. However, the experience with the oxidation response of alloys in the Mo-Si-B system highlights the important role of the B/Si ratio as a key element in coating design strategies for Mo-based alloys. In order to achieve compatibility, a multilayer coat-

ing structure is an effective approach. In this way, compatibility can be assured and a diffusion barrier provided to limit transport. The use of kinetic biasing has been demonstrated to be effective to alter the B/Si ratio and control the coating diffusion pathway. Silica biasing effectively limits oxygen transport through the coating while silicide biasing alters the phase sequencing to incorporate an oxidation resistant T1 layer in the diffusion path and silicide and boride biasing shifts the pathway to include a diffusion barrier underlying the T1 phase. The high-temperature protection originates from the formation of continuous borosilica on the surface and the stability and integrity of the coating is assured by incorporation of an underlying diffusion barrier. The coating performance conrms the utility of the diffusion path trajectory and kinetic bias analysis to design the layer formation and to enhance the oxidation resistance. The experience with the Al-based pack cementation process shows that a similar biasing approach can be employed to further extend the lifetime of the coating by producing an effective diffusion barrier. ACKNOWLEDGEMENTS The support from the Ofce of Naval Research (N00014-10-1-0913, Dr. David A. Shier, program manager) is most gratefully acknowledged. The continued interest and encouragement from Dr. Steven G. Fishman is appreciated.
References
1. J.-C. Zhao and J.H. Westbrook, MRS Bulletin, 28 (9) (2003), pp. 622627. 2. D.M. Dimiduk and J.H. Perepezko, MRS Bulletin, 28 (9) (2003), pp. 639645. 3. J.H. Perepezko, R. Sakidja, and K.S. Kumar, in Advanced Structural Materials: Properties, Design Optimization, and Applications, ed. W. Soboyejo (Boca Raton, FL: CRC Press, 2007), pp. 437473. 4. J.H. Schneibel, R.O. Ritchie, J.J. Kruzic, and P.F. Tortorelli, Metall. Mater. Trans., 36A (2005), pp. 525 531. 5. A.P. Alur, N. Chollacoop, and K.S. Kumar, Acta Materialia, 52 (2004), pp. 55715587. 6. J.H. Perepezko, R. Sakidja, S. Kim, Z. Dong, and J.S. Park, in Third International Symposium on Structural Intermetallics (ISSI-3), ed. Kevin J. Hemker and

Dennis M. Dimiduk (Warrendale, PA: TMS, 2002), pp. 505514. 7. R. Sakidja and J.H. Perepezko, J. Nuclear Mater., 366 (2007), pp. 407416. 8. R. Sakidja, J.H. Perepezko, S. Kim, and N. Sekido, Acta Mater., 56 (2008), pp. 52235244. 9. S. Kim and J.H. Perepezko, J. Phase Equilibria and Diffusion, 27 (6) (2006), pp. 605613. 10. M.G. Mendiratta, T.A. Parthasarathy, and D.M. Dimiduk, Intermetallics, 10 (2002), pp. 225232. 11. V. Supatarawanich, D.R. Johnson, and C.T. Liu, Mater. Sci. Eng. A, 344 (2003), pp. 328339. 12. D.M. Berczik, U.S. patents 5,595,616 (1997) and 5,693,156 (1997). 13. J.S. Park, R. Sakidja, and J.H. Perepezko, Scripta Mater., 46 (2002), pp. 765770. 14. D.A. Helmick, G.H. Meier, and F.S. Petit, Metall. and Mater. Trans., 36A (2005), pp. 33713383. 15. K. Yoshimi, S. Nakatani, T. Suda, S. Hanada, and H. Habazaki, Intermetallics, 10 (2002), pp. 407414. 16. K. Yoshimi, S. Nakatani, N. Nomura, and S. Hanada, Intermetallics, 11 (2003), pp. 787794. 17. D.M. Shah, D. Berczik, D.L. Anton, and R. Hecht, Mater. Sci. Eng. A, 155 (1992), pp. 4557. 18. R. Sakidja, J.S. Park, J. Hamann, and J.H. Perepezko, Scripta Mater., 53 (2005), pp. 723728. 19. R. Sakidja, F. Rioult, J. Werner, and J.H. Perepezko, Scripta Mater., 55 (2006), pp. 903906. 20. J.H. Perepezko, J.S. Park, and R. Sakidja, U.S. patent 7,005,191 (2006). 21. S.R. Levine and R.M. Caves, J. Electrochem. Soc., 121 (1974), pp. 10511064. 22. A. Mueller, G. Wang, R.A. Rapp, E.L. Courtright, and T.A. Kircher, Mater. Sci. Eng., A155 (1992), pp. 199207. 23. B.V. Cockram and R.A. Rapp, Metall. Mater. Trans., 26A (1995), pp. 777791. 24. N.P. Bansal and R.H. Doremus, editors, Handbook of Glass Properties (Orlando, FL: Academic Press, 1986). 25. A.E. McHale and R.S. Roth, Phase Equilibria Diagrams, 12 (1996), pp. 1112. 26. J.S. Kirkaldy and D.J. Young, Diffusion in the Condensed State (London: Institute of Metals, 1987). 27. M.K. Meyer, A.J. Thom, and M. Akinc, Intermetallics, 7 (1999), pp. 153162. 28. J.H. Perepezko, M.H. da Silva Bassani, J.S. Park, A.S. Edelstein, and R.K. Everett, Mater. Sci. Eng. A, 195 (1995), pp. 111. 29. M. Meyer, M.J. Kramer, and M. Akinc, Intermetallics, 4 (4) (1996), pp. 273281. 30. M. Akinc, M.K. Meyer, M.J. Kramer, A.J. Thom, J.J. Huebsch and B. Cook, Intermetallics, A261 (1999), pp. 1623. 31. P.C. Tortorici and M.A. Dayananda, Scripta Mater., 38 (1998), pp. 18631869. 32. J-K. Yoon, J-K. Lee, K-H. Lee, J-Y. Byun, G-Ho Kim, and K-T. Honga, Intermetallics, 11 (7) (2003), pp. 687696. 33. F. Rioult, N. Sekido, R. Sakidja, and J.H. Perepezko, J. Electrochemical Society, 154 (11) (2007), pp. C692C701. J.H. Perepezko, professor, and R. Sakidja, assistant scientist, are with the Department of Materials Science and Engineering, University of WisconsinMadison, 1509 University Ave., Madison, WI 53706 USA. Dr. Perepezko can be reached at perepezk@ engr.wisc.edu.

John Perepezko is a member of TMS!

To read more about him, turn to page 7. To join TMS, visit www.tms.org/Society/Membership.aspx.

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Refractory Metals

Research Summary

The Microstructural Engineering of Mo-Si-B Alloys Produced by Reaction Synthesis

Michael R. Middlemas and Joe K. Cochran
Mo-Si-B alloys are candidate materials for next-generation jet engine turbine blades and have the potential to increase the service temperature of the base metals 200C higher than nickel superalloys. These refractory alloys form a composite microstructure of molybdenum solid solution (Moss) and two intermetallic phases, Mo3Si and Mo5SiB2, where the Moss phase enhances toughness and the intermetallic phases provide oxidation resistance. The properties of the alloys are highly dependent on the morphology of the microstructure. A powder processing approach has been developed to synthesize the three-phase alloys through the reaction of molybdenum, Si3N4, and BN powders. Electron backscatter diffraction imaging has been used to map the location of individual phases and provide a method for quantifying the cluster size distribution of a secondary phase to examine the effect of BN reactant powders on the dispersion of the intermetallic phases. INTRODUCTION The performance and efciency of jet turbine engines are dependent on the highest temperatures achieved in the engine. The progression of the maximum operating temperature for the nickel superalloys used in jet engines is plotted chronologically in Figure 1. The reduced creep rates of directionally solidied (DS) and later single-crystal (SX) blades have allowed for increases to temperatures approaching 85% of the melting point of the base material.1 Despite these advances it is evident that the development of nickel superalloys is approaching a limit and there is a need for a new class of high-temperature structural materials for the continued advancement of jet engines. The increases that could be gained
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from the use of refractory metal (RM)based alloys are also indicated in Figure 1, with potential increases of 200C over the nickel superalloys. Molybdenum is of particular interest due to its low coefcient of thermal expansion and high thermal conductivity, which impart good thermal shock and fatigue resistance.2 The main limitation of molybdenum is How would you
describe the overall signicance of this paper? Mo-Si-B alloys are a candidate for next generation jet turbine engine blades with potential operating temperatures 200C higher than nickel superalloys. The processing method presented creates a ne-grained microstructure with a molybdenum matrix phase, which is necessary for high strength and toughness. Reduction of manufacturing cost is a key objective of the powder metallurgy approach. describe this work to a materials science and engineering professional with no experience in your technical specialty? Mo-Si-B alloys have a microstructure of molybdenum solid solution and two intermetallic phases. Using powder metallurgy, molybdenum is reacted with silicon and boron nitrides to form a ne dispersion of intermetallics in a molybdenum matrix. Boron nitride size and morphology controlled dispersion of intermetallic phases. Large BN particle size and agglomeration resulted in clustering of intermetallics while well dispersed, isotropic BN signicantly reduced clustering. describe this work to a layperson? Successful molybdenum-silicon-boron alloys should signicantly increase operating temperatures of jet engines to improve performance in both fuel efciency and power. This research presents potential improvements gained by using unique processing and raw materials during the fabrication of the alloys.

a lack of oxidation resistance. Molybdenum oxide evaporates at low temperatures and does not form a barrier to further oxidation. The molybdenum silicides, on the other hand, have excellent oxidation resistance due to the formation of a silicon dioxide surface layer, but have poor mechanical properties. Alloys in the Mo-Si-B system are under investigation to combine the mechanical properties of molybdenum and the oxidation resistance of molybdenum silicides. The compositions of interest are in the highlighted region of the phase diagram (Figure 2) and form a three-phase mixture of a molybdenum solid solution (Moss) and two intermetallics, Mo3Si (A15) and Mo5SiB2 (T2). All three phases have melting points above 2,000C, are thermodynamically stable, and exhibit signicant resistance to coarsening at elevated temperatures, making these alloys excellent candidates for high temperature use. The oxidation resistance of Mo-Si-B alloys is due to the formation of a protective glass layer. The addition of boron results in a lower viscosity borosilicate glass that is able to ow over the otherwise unprotected molybdenum regions. Fracture toughness of the alloys is improved by crack bridging and entrapment by the more ductile Moss phase. One of the obstacles in the development of Mo-Si-B alloys is balancing the conicting requirements for the alloys; toughness increases with higher volume fractions of the molybdenum phase, but at the expense of oxidation resistance. The composition Mo-3Si-1B wt.% (Mo8.9Si-7.7B at.%) is thought to strike an adequate compromise between these competing properties and has been the subject of investigation by a number of research groups. The microstructural morphology of
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Mo-Si-B alloys has a dramatic effect on properties. Molybdenum should be present as a continuous matrix to maximize toughening and a ne dispersion of intermetallic particles has been shown to result in faster formation of a protective glass layer.3,4 Many studies have produced samples by melt-based processes, but this typically results in segregation and non-equilibrium phases. Long heat treatments are required to equilibrate the alloys due to the slow diffusion rates in the Mo-Si-B system.5 Furthermore, molybdenum has the highest melting point in the Mo-A15-T2 phase eld, which leads to primary solidication during cooling and a microstructure with molybdenum dendrites surrounded by a brittle intermetallic matrix.6 Unlike many alloys, this system is not amenable to microstructural improvement by heat treating. The system has been likened to a ceramic in that the initial synthesis methods largely dictate the nal microstructure.7 Hot working by extrusion or forging has been successfully used to break up the intermetallic matrix, but the required working temperature of 1,760C makes these techniques difcult and costly.8,9 REACTION SYNTHESIS METHOD Fabrication of Mo-Si-B alloys by powder metallurgy eliminates many of the problems associated with melt-based processing, but early efforts resulted in alloys with coarse microstructures or high oxygen impurity contents.1012 In a process developed at the Georgia Institute of Technology, molybdenum, silicon nitride (Si3N4), and boron nitride (BN) powders are reacted to synthesize a ne dispersion of the intermetallic phases in an Moss matrix.13 The intermetallics phases are formed by the reactions: 3Mo + 1/3Si3N4 Mo3Si + 2/3N2 5Mo + 1/3Si3N4 + 2BN Mo5SiB2 + 5/3N2 (1)

(2)

Unlike elemental silicon and boron, the covalent nitrides are stable in oxidizing environments up to 1,000C, which allow for ne particle processing without the formation of silicon and boron oxides. Oxygen impurities for the reaction synthesis alloys are low compared to
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other powder processing methods, typically in the range of 300400 ppm. Submicrometer powders are used to lower the sintering temperature and to retain ne grain size after heat treatment. The reactions to form the intermetallics can be completed as low as 1,300C and densities of 95% of theoretical are achieved after ring at 1,600C.14 The resulting microstructure is a ne dispersion of the intermetallic phases in a molybdenum matrix, as illustrated by an electronbackscatter diffraction (EBSD) image in Figure 3. This process results in negrained alloys, with average grain sizes of only 2 m for the A15 and T2 phases, and 4 m for molybdenum. Previous studies of the reaction synthesis alloy have demonstrated a combination of oxidation resistance and strength.1517 Stress-strain curves for tensile tests conducted between 900C and 1,300C are plotted in Figure 4. It can be seen that the reaction synthesis method produces a high strength alloy, with an ultimate tensile strength of 740 MPa at 1,100C, as compared to less than 200 MPa for a modern nickel superalloy material.8 High strength is also maintained far above the maximum use temperature of nickel superalloys, with an ultimate tensile strength of 440 MPa at 1,300C. One of the most signicant impediments to the implementation of Mo-SiB alloys is a lack of low temperature ductility. Zero ductility was measured for the reaction synthesis alloy below 1,100C and the samples fractured in a brittle, intergranular manner. The poor ductility increases the aw sensitivity of the material and leads to brittle fracture at low loads, as observed for the sample tested at 900C. Jhanno et al. have demonstrated dramatic improvements in strength and ductility of an Mo-3Si-1B wt.% alloy as the result of improvements in microstructural morphology.9,18 In their research, an alloy was initially prepared by consolidation of gas atomized powders, which resulted in a microstructure with a coarse dispersion of molybdenum in an intermetallic matrix. Subsequent extrusion at 1,760C was used to break up the intermetallic matrix and create a molybdenum matrix, which resulted in a 150C decrease in the ductileto-brittle transition temperature (DBTT) and over a 50% increase in strength at 1,100C. A key advantage of the reacwww.tms.org/jom.html

tion synthesis method is that changes in the microstructure can be made through changes in the raw materials and processing conditions without resorting to costly and difcult measures such as hot-working. The objective of this research is to investigate the ability to produce a ner, better dispersed distribution of intermetallics through changes in the reaction synthesis method. MICROSTRUCTURAL ENGINEERING Despite the relatively ne distribution of intermetallics produced by the reaction synthesis method, clustering is evident in Figure 3, particularly for the T2 phase. The clustering is better illustrated by a T2 phase map for an alloy sintered at 1,300C, where lower diffusion rates limited coarsening of the T2 phase (Figure 5). The alloys in Figures 3 and 5 were produced using hexagonal boron nitride (hBN) powder. While the molybdenum and silicon nitride powders used are both isotropic, submicrometer powders, the hBN powder is in the form of large akes approximately 0.25 m thick and 10 m across. Examination of the green powder compacts revealed the large akes remain intact after milling, creating an inhomogeneous distribution of the boron reactant. It is proposed that the distribution of the intermetallic phases is controlled by the initial dispersion of the nitride reactants in the powder compacts. The relationship between the dispersion of the BN and the T2 phase should be pronounced because boron diffuses slowly in molybdenum and the T2 phase has a growth rate constant of only 91016 m2/s at 1,600C, as compared to 3.81014 m2/s for the A15 phase.19 The effect of the BN powder on the distribution of the T2 phase was examined by comparing a sample prepared with hBN to three samples produced using different sizes of cubic boron nitride (cBN). The cBN powders have isotropic particle morphologies and size distributions more closely matched to the molybdenum and silicon nitride powders, which should result in a ner, more dispersed T2 phase in the sintered alloys. See the sidebar for experimental methods. MICROSTRUCTURE COMPARISON Enlarged portions of the EBSD phase
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1,400 Temperature of Base Metal in Gas Turbine (C)

1,200

1,000

800 1940 1960 1980 Year 2000 2020

Figure 2. Isothermal section of the Mo-Si-B phase diagram at 1,600C with the composition examined in this work indicated. Mo3Si-1B wt.% contains approximately 57% Moss, 16% A15, and 27% T2 by volume.7

Figure 1. The progression of the maximum service temperature of nickel-based superalloys used in gas turbines, including the directionally solidied (DS) and single crystal (SX) blades. The potential increases that could be gained from the use of refractory metal (RM) alloys are indicated.21

Figure 3. EBSD phase map of the Mo-3Si-1B wt.% alloy processed with hBN powder and sintered at 1,600C, with the grain boundaries plotted.

Figure 4. Stress-strain curves as a function of temperature for a Mo-3Si-1B wt.% alloy prepared by reaction synthesis alloy, measured at an initial strain rate of 104 s1.

Figure 5. EBSD phase map of the T2 phase in a Mo-3Si-1B wt.% alloy processed with hBN powder and sintered at 1,300C.

Figure 6. EBSD maps for Mo-3Si-1B wt.% alloys processed with (a) hBN, (b) 1 m cBN, (c) 0.5 m cBN, and (d) 0.123 m cBN.

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Figure 7. The cumulative grain and cluster size distributions of the T2 phase, measured for Mo-3Si-1B wt.% alloys prepared with different BN reactant powders.

Figure 8. The cumulative grain and cluster size distributions of the A15 phase, measured for Mo-3Si-1B wt.% alloys prepared with different BN reactant powders.

EXPERIMENTAL METHODS remove any oxygen impurities or moisture present in the inlet gas. The reactant powders used are listed in Table A. The powders seThe samples were hot-isostatically pressed at 1,500C and 30 ksi lected have high purity, low oxygen content, and are obtainable in for 6 hours to remove remaining porosity. commercial quantities. The particle size of the hBN powder was erScanning electron microscopy (SEM) images lack the phase roneously reported by the manufacturer to be less than 1 m, likely contrast necessary to differentiate between the A15 and T2 phases. based on surface area measurements. As previously noted, the hBN There is also little contrast between the molybdenum and intermepowder has a thin, plate-like morphology with radial dimensions tallic phases, which prevents automated analysis of the images. The of up to 10 m, which prevents a simple description of the aversample microstructures were imaged using a combination of elecage particle size. The other powders have isotropic morphologies tron backscatter diffraction (EBSD) imaging and energy-dispersive that are more accurately described by the manufacturers reported spectroscopy (EDS). The EBSD technique uses the electron difparticle sizes. fraction pattern to determine the phase and orientation at a given The reaction synthesis method uses powder processing techpoint in the microstructure, while the EDS data used help differenniques common to the powder metallurgy and ceramics industries. tiate the cubic molybdenum and A15 phases. Scans were taken over The reactant powders are mixed in acetone with 3 wt.% of a low a 300 m square region using a 0.30 m step size. The EBSD data molecular weight poly-methyl methacrylate (Elvacite 2008, Lucite creates high-quality microstructure phase maps suitable for autoInternational) added as a dispersant and binder. The Elvacite resin mated image analysis and also determines the volume fractions and depolymerizes between 300400C and evaporates, leading to low grain size distributions for each of the phases in the samples. residual carbon levels. The mixtures were milled with Al2O3 media The EBSD analysis provides the grain size distributions of the for 30 minutes on a commercial paint shaker to break up agglomerindividual phases, but in most cases the intermetallic grains are ates and improve dispersion. To maintain homogenous dispersions grouped into interconnected clusters. A method to quantify the of the reactants, the slurries were spray dried using a laboratory cluster size distribution of a secondary phase was developed in scale spray dryer (BCHI Model 190). The spray-dried powders order to examine the effect of the BN powder selection. Individual were screened to separate the spherical granules which give a more phase maps were created for the A15 and T2 phases and the reuniform ll and reduce density gradients in dry pressing operagions of continuous interconnected intermetallics were dened as tions. Powder compacts were uniaxially pressed at 70 ksi in a 1/2 clusters. The areas of individual clusters were measured using the die. The samples were red in a sealed atmosphere tube furnace image analysis software ImageJ and converted to equivalent diat 3C/min. to 1,600C with a 6 h hold. A reducing atmosphere ameters for the purpose of comparing the sizes, as illustrated in of Ar-10% H2 was used to eliminate surface oxidation on the moFigure A.20 lybdenum. In addition, a titanium gettering furnace was used to

Table A. Properties of the Raw Materials Used in the Reaction Synthesis Method
Raw Material Grade Puritya 99.95% 99% 99.5% Particle Sizea 100500nm 0.5 m (d50) 0.73 m (Fisher) 0.13 m (d50) 0.54 m (d50) 0.83 m (d50) Surface Area (m2/g) 2.4 4.0 6.7 45.7 26.5 11.3 Oxygenb Content 1.02 wt.% 0.82 wt.% 0.92 wt.%

Mo (Climax) Ultrane SN-E03 Si3N4 (UBE) hBN (Cerac) B-1084 cBN (Advanced Abrasives) #0.125 #0.5 #1

a = value supplied by the manufacturer b = measured by Dirats Laboratories (Westeld, MA)

Figure A. Schematic illustrating the denition of the intermetallic cluster size. The area of the intermetallic phase was measured and converted to an equivalent diameter.

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maps are compared in Figure 6 for samples prepared using the four different BN reactant powders. The grain boundaries have been omitted in these images to better illustrate the distribution of the intermetallic phases. Comparing the microstructures qualitatively, it can be seen that the clustering of the T2 phase changes with the different BN reactant powders. The alloys prepared with the 0.5 m and 1 m cBN powder have more uniform dispersions of T2 than the hBN based sample, as was predicted from the ner sized reactant powder, but there is signicant clustering in the sample prepared with the 0.125 m cBN powder. These observations are reected in the T2 cluster size distributions of the four samples (Figure 7). Although the selection of BN powder has little effect on the grain size distribution of the T2 phase, a signicant change is observed in the cumulative size distribution of the clusters. The size of the T2 clusters in the sample prepared with 0.125 m cBN powder deviates from the assumption that the cluster size would be proportional to the size of the nitride reactant. This discrepancy is likely the result of agglomeration of the BN powder during processing. For ne, high surface area powders, the van der Waals force becomes the predominant force acting on the particles and makes fully dispersing the powder difcult. It is possible that higher energy milling or sonication of the slurry prior to spray drying would improve this problem. The grain and cluster size distributions for the A15 phase are compared in Figure 8. As with the T2 phase, the grain size is independent of the BN powder used. The trend in the cluster sizes for the A15 phase appears to match that observed for the T2 phase, which is unexpected because the same Si3N4 powder was used for all four samples, but a comparison of the average grain and cluster sizes measured for the samples reveals the differences in the A15 average cluster sizes are small compared to the T2 phase (Table I). Further research needs to be completed to evaluate the

Table I. Average Intermetallic Grain and Cluster Sizes for Mo-3Si-1B wt.% Alloys Produced with Different BN Reactant Powders
Intermetallic Size Distributions Grain Size (d50) (m) BN Powder hBN 1 m cBN 0.5 m cBN 0.125 m cBN A15 2.3 2.1 2.2 2.3 T2 1.6 1.7 1.7 2.1 Cluster Size (d50) (m) A15 4.5 3.8 3.9 4.2 T2 7.0 4.0 3.9 5.7

effect of the Si3N4 reactant powder on the intermetallic distributions. CONCLUSIONS As the traditional jet turbine engine blade technologies approach their engineering limits, the continued improvement of jet engine performance will require a major advancement in high-temperature structural materials. Mo-Si-B alloys are a leading candidate, but their implementation is dependent on nding a favorable compromise between mechanical properties and oxidation resistance. The reaction synthesis method presents an opportunity to optimize microstructural parameters for a given composition. The research presented demonstrates that changes in the BN reactant powder can be used to minimize clustering of the T2 phase. Based on these ndings, the further study of the reaction synthesis process has been modied to use the 0.5 m cBN powder. ACKNOWLEDGEMENTS This work has been supported by the Ofce of Naval Research (contract no. N00014-08-1-0507) and the Naval Air Systems Command (contract no. N00421-05-1-0002) and monitored by Dave Shier and Rob Kowalik. Much help has been provided by Doug Berczik of Pratt & Whitney (East Hartford, CT).
References
1. J.C. Zhao and J.H. Westbrook, MRS Bulletin, 28 (9) (2003), pp. 622630. 2. J.A. Shields and E.L. Baker, Advanced Materials & Processes, 155 (1999), pp. 6166. 3. J.J. Kruzic, J.H. Schneibel, and R.O. Ritchie, Scripta Materialia, 50 (2004), pp. 459464. 4. F.A. Rioult, S.D. Imhoff, R. Sakidja, and J.H. Perepe-

zko, Acta Materialia, 57 (2009), pp. 46004613. 5. R. Sakidja, G. Wilde, H. Sieber, and J.H. Perepezko, MRS Symposium Proceedings, 552 (1999), p. KK6.3. 6. C.A. Nunes et al., Intermetallics, 8 (4) (2000), pp. 327337. 7. J.H. Perepezko and D.M. Dimiduk, MRS Bulletin, 28 (9) (2003), pp. 639645. 8. D.M. Berczik, Method for Enhancing the Oxidation Resistance of a Molybdenum Alloy, and a Method of Making a Molybdenum Alloy, U.S. patent 5,595,616 (21 January 1997). 9. P. Jhanno, M. Heilmaier, H. Kestler, M. Bning, A. Venskutonis, B. Bewlay, and M. Jackson, Metallurgical and Materials Transactions, 36A (2005), pp. 515523. 10. J.H. Schneibel, M.J. Kramer, . nal, and R.N. Wright, Intermetallics, 9 (2001), pp. 2531. 11. J.H. Schneibel, M.J. Kramer, and D.S. Easton, Scripta Materialia, 46 (2002), pp. 217221. 12. T.G. Nieh, J.G. Wang, and C.T. Liu, Intermetallics, 9 (2001), pp. 7379. 13. M.R. Middlemas and J.K. Cochran, Advanced Metallic Composites and Alloys for High Performance Applications, ed. A. Pandey, K.L. Kendig, and J.J. Lewandowski (Warrendale, PA: TMS, 2007), pp. 6372. 14. M.R. Middlemas and J.K. Cochran, JOM, 60 (7) (2008), pp. 1924. 15. C. Rockett, M.R. Middlemas, and J.K. Cochran, Advanced Metallic Composites and Alloys for High Performance Applications, ed. A. Pandey, K.L. Kendig, and J.J. Lewandowski (Warrendale, PA: TMS, 2007), pp. 95104. 16. M.R. Middlemas and J.K. Cochran, Supplemental Proceedings Volume 1: TMS2009Materials Processing and Properties (Warrendale, PA TMS, 2009), pp. 177183. 17. M.R. Middlemas, J.K. Cochran, P. Jain, and K.S. Kumar, Supplemental Proceedings Volume I: TMS2010 Materials Processing and Properties (Warrendale, PA: TMS, 2010), pp. 859866. 18. P. Jhanno, M. Heilmaier, and H. Kestler, Intermetallics, 12 (2004), pp. 10051009. 19. J.H. Perepezko, R. Sakidja, S. Kim, Z. Dong, and J.S. Park, in Structural Intermetallics 2001: Proceedings of the Third Symposium, ed. Kevin J. Hemker and Dennis M. Dimiduk (Warrendale, PA: TMS, 2001), pp. 505514. 20. W. Rasband, ImageJ, version 1.38x (Research Services Branch, National Institutes of Health, Bethesda, MD), rsb.info.nih.gov/ij/. 21. P. Jhanno, Results of R&D Program Take Off (accessed 01/27/09), www.ffg.at/getdownload. php?id=1477. Michael R. Middlemas and Joe K. Cochran are with the Materials Science and Engineering Department, Georgia Institute of Technology, Atlanta, GA 303320245. Dr. Cochran can be reached at joe.cochran@ mse.gatech.edu.

Michael R. Middlemas is a student member and Joe K. Cochran is a full member of TMS!
To read more about them, turn to page 7. To join TMS, visit www.tms.org/Society/Membership.aspx.

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Refractory Metals

Research Summary

A Multi-stage Hierarchical Approach to Alloy Design

P.K. Ray, T. Brammer, Y.Y. Ye, M. Akinc, and M.J. Kramer

A multi-stage hierarchical sieving approach based on a combination of semiempirical and ab initio calculations along with selected experimental studies was used to down-select potential alloy systems for ultra-high-temperature applications. This approach indicates that the Mo-Ni-Al system has potential for applications at the target temperatures of 1,2001,300C. The Mo was selected for its high melting temperature, room temperature toughness, and creep resistance while the NiAl is a reservoir for the Al2O3 passivating scale. Microstructures based on casting and powder processing of the Mo-Ni-Al alloys were studied. Oxidation behavior of the Mo-Ni-Al alloys at 1,100 and 1,200C in dry air was determined and those alloys with 20 at.% Mo were shown to be superior to the T2 (Mo5SiB2). Furthermore, the calculations predicted that small amounts of platinum group metals Pd, Ir, and Rh additions would increase the melting temperature without forming detrimental intermetallic phases, which results in improved oxidation stability of the NiAl phase. INTRODUCTION Superalloys are the workhorse materials for land-based gas turbine blades, which are required to operate under extremely harsh combustion environments while retaining their mechanical integrity. Operating temperatures for Ni-based superalloys have been greatly increased by application of the thermal barrier coating along with a suitable Ni-Al-based bond coat. Commercial turbine blades are routinely operated at temperatures up to 1,150C.1 Even higher efciencies such as envisioned in the U.S. Department of Energy (DOE) National Energy Technology Laboratorys FutureGen gas turbine program will
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describe the overall signicance of this paper? Discovery of new alloys that can operate at temperatures well above Ni-based superalloys requires new and more efcient means of sifting through prospective phase space. We present a semi-empirical approach combined with more accurate computational materials design, density functional theory, to rapidly identify a prospective alloy for ultrahigh-temperature applications. describe this work to a materials science and engineering professional with no experience in your technical specialty? Traditional materials discovery involves researchers basic materials: knowledge, intuition and a lot of trial and error. The semiempirical approach used here allows us to estimate formation enthalpies as a rapid screening method to identify regions in ternary systems that have high melting temperatures. In this way we can screen thousands of combinations in a short time. We then use more accurate ab initio methods to rene our search. describe this work to a layperson? The maximum operating temperature of current commercial Ni-based superalloys is ~1,150C. However, the objectives of the FutureGen project require alloys that can function at about 1,350C. Such large increases in operating temperatures will require new materials. An Edisonian approach to the discovery of new materials is tedious and we lack the numerical tools to efciently predict new phases. For instance, a fourcomponent Ni-based system, with all elements selected from the transition metals, leads to 3,654 possible combinations, while Ni-based superalloys may have eight elements or more. A rapid means of sieving through possible combinations of elements is presented.

require alloys that can function at temperatures above the melting point of todays commercial alloys. Hence, design of ultra-high-temperature alloys will require a major breakthrough. Refractory metal silicides in the metal-T2-A15 phase eld region can operate at high temperatures and retain their strength.25 However, the oxidation resistance of these alloys is signicantly reduced. Alloys in the T1-T2-A15 or disilicides of refractory metals offer improved oxidation resistance.6 However, the presence of only brittle intermetallics in the phase assemblage renders them unusable in practice. A signicant increase in operating temperatures is not likely to be achieved by tweaking current Ni-based alloy compositions. A trial-and-error based approach toward the discovery of new materials is tedious, yet we lack the numerical tools to efciently and accurately predict new phases and their properties. Potential phase space is enormous. For instance, a four-component Ni-based system, with all the elements selected from the transition metal elements, yields 3,654 possible combinations, and adding only one more constituent expands the number of combinations to 23,751. Considering that many commercial high-temperature alloys can have in excess of eight constituents, a systematic investigation of even a fraction of the potential phase space through computational thermodynamics or ab initio methods is unrealistic. Hence using rapid sieving techniques in an alloy design project is essential. Faster but lower accuracy approaches to quickly screen out the least favorable combinations followed by more rigorous methods to narrow the potential phase space offers an efcient alloy design approach.
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their potential as a high temperature (T ~ 1,300C), oxidation and fracture resistant material. Select alloy compositions predicted by the computational tools were then synthesized, characterized, and tested for their high-temperature oxidative stability as the rst goalpost in the alloy development process. THEORETICAL CALCULATIONS
Figure 1. Interrupted owing air oxidation of liquid phase sintered alloys of different Mo content at 1,100C.

Fortunately, we do have a few clues to pursue for developing fast screening methods. For instance, the melting temperature of a material can be taken as one of the guidelines for a prospective high-temperature alloy. The melting temperature of a compound, in turn, correlates well with the interatomic bond strength and its formation enthalpy.79 It has been demonstrated that the formation enthalpy of a multicomponent system can be estimated with a reasonable degree of accuracy and extremely low computational cost using an extended Miedema approach.10 However, melting temperature is not the only requirement; only certain elements are known to promote the formation of protective oxide scales, most notably, Al, Cr, and Si. Therefore, additional screening criteria include developing alloys comprised of a phase that will promote the formation of a slow-growing protective oxide scale. Due to the low stability of chromia at the target operating temperatures, 1,350C, and susceptibility of silica-based scales to moisture in coal combustion byproducts, we are left with an alumina-forming alloy.11 Alloys based on a mix of refractory metals (RM) and NiAl are believed to be the best candidates. The RM forms the backbone of the alloy, providing toughness at low temperatures and creep resistance at high temperatures. The -NiAl (B2 structure, SG 221), in turn, acts as a reservoir for the passivating alumina scale. However, alloying additions to the NiAl are required in order to boost its melting temperature (Tm = 1,640C). The primary focus of this study was to evaluate a series of alloy combinations narrowed down by the guidelines mentioned above, using semi-empirical, as well as ab initio calculations for
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The initial cut through the prospective phase space was performed using semi-empirical calculations based on an extended Miedema approach.10 Briey, this approach is based on using an energy minimization scheme by optimizing the compositions of the constituent binary systems under appropriate mass balance constraints. Our modied Miedema model was used for estimating the difference in formation enthalpies between NiAl and TM-Al (TM = transition metal). Twenty-six elements from the transition metal block were tested over the entire composition range of their ternaries with Ni and Al. Three considerations were given for the selection of the TM: high formation enthalpy, absence of intermetallics with Ni or Al over a signicant composition range, and a cubic crystal form to insure some ductility at lower temperatures. Using these criteria, Mo was clearly the best candidate. Molybdenum retains its body-centered cubic (bcc) structure up to its melting temperature and has a limited solubility with Al or Ni. While not possessing good oxidation stability of itself, its low diffusivity and low solubility with NiAl suggests that a graded microstructure can be designed to minimize susceptibility for oxidation. The next step in alloy design was to search for ternary addition to the NiAl to boost its melting temperature. As mentioned above, the ternary additions to the NiAl should not only raise the melting temperature but should be retained in solid solution with the NiAl. Again we used our modied Miedema model to down-select the most promising candidates based on their formation enthalpies. Of the late-transition elements, only Hf, Y, Zr, Nb, Pd, Rh, and Ir showed the highest formation enthalpies with NiAl and a smaller afnity for Mo. It is critical that the ternary addition to NiAl does not exhibit high heat of mixwww.tms.org/jom.html

ing with Mo. At this point, more accurate calculations were required. Ab initio methods are preferred at this stage. Unlike embedded atom methods, interatomic potentials do not have to be developed or in the case of computational thermodynamics, developing databases are not necessary. The disadvantage of ab initio methods is in instances where the crystal structure and its atomic decoration are not known so that a large number of prospective structures must be calculated. It should be stressed that unless specically determined, ab initio provides only the most enthalpically stable structure (0 K). Entropically stable structures or highly complex low symmetry systems are very difcult to identify with this approach. In this particular system we suspected that the small platinum group metal (PGM) additions will not result in degeneracy of the -NiAl, which was readily conrmed experimentally. Therefore the number of calculations required was small. The ab initio calculations were carried out using the Vienna ab initio Sim-

Base Alloy

Oxide Scale Cu Plating

200 m

Base Alloy

Oxide Scale Cu Plating 10 m

Figure 2. (a) Low magnication image of the oxidized alloy. The alumina scale appears to have formed continuously on the surface. (b) Higher magnication image of the oxidized alloy showing the non-uniformity of scale thickness primarily as a result of presence of Mo phase at the surface. Mo gets oxidized and the resultant MoO3 volatilizes allowing oxygen to penetrate relatively larger distances into the alloy.

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ulation Package (VASP)1214 to get the thermodynamically stable structure of B2 phase in the Ni1xAlTMx and NiAl1 TMx systems using a 54-atom supercell, x where TM represents the transition metal element selected by the Miedemas model. The density functional calculations are performed using a plane-wave pseudo-potential representation, with ultra-soft pseudo-potentials13 for all species and with a plane-wave energy cutoff of 300 eV. The k-point sampling was chosen to converge all of the total energies to an accuracy of 2 meV/atom. The k-point grid used for structural relaxation was 666, chosen according to the Monkhorst-Pack scheme,15 and symmetry reduced to the irreducible Brillouin zone. See the sidebar for experimental methods. RESULTS AND DISCUSSION Oxidation Behavior of the Mo-Ni-Al Alloys Samples processed by liquid phase sintering showed the inuence of alloy composition on the oxidation behavior. Alloys under 20 at.% Mo, with equiatomic NiAl showed fairly good oxidation resistance, while the alloys with a higher volume fraction of Mo (e.g. Mo35Ni32.5Al32.5) failed to form a passivating oxide layer (Figure 1). The strong composition dependence of oxidation is due to Mos deleterious effect on the oxidation resistance. Minimizing the interconnected Mo network is required. Continuity of Mo phase depends on its volume fraction and the size of the Mo grains. The higher the volume fraction of the Mo phase and larger the grain size, the larger is the probability of connectivity, resulting in poorer oxidation resistance. Figure 2a shows a low-magnication microstructure of the oxidized Mo20Ni40Al40 cast alloy at 1,200C. It can be seen that the alloy has developed a continuous alumina scale of about 5 m thickness, albeit not uniform, across the length of the sample. A look at the oxide scale at higher magnication (Figure 2b) shows that the scale thickness uctuation is due to the presence of long Mo dendrites growing into the alloy. It has been widely observed in Nibased alloys that the initial oxidation
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EXPERIMENTAL METHODS Based on our calculations, the Mo-Ni-Al system was selected as a viable candidate for the base alloy. A number of compositions in this system were tested for their resistance to high temperature oxidation. The testing temperatures were restricted to 1,200C due to massive scale spallation at higher temperatures. This pointed to a need for improving the NiAl phase with selected transition metal additions as indicated by the calculations above. Mo-Ni-Al Alloys Mo-Ni-Al alloys are known to exhibit a two-phase (bcc Mo + -NiAl) microstructure over a limited range of compositions.16 All the experiments in the present study were carried out in this phase eld. Higher phase fraction of molybdenum would be detrimental to the oxidation resistance; hence the phase fraction of Mo was kept below 35 at.% in all cases. The alloys were synthesized using powder metallurgical techniques as well as casting. The powder metallurgy involved mixing the pure metal powders (~10 m) in a mixer/shaker (SPEX 8000, SPEX CertiPrep Inc, Metuchen, NJ) for 10 min. followed by compaction of the powders by dry pressing at a pressure of 24 MPa. The cylindrical pellets thus produced had a diameter of 10 mm and a height of 20 mm. The pellets were then sintered at 1,750C for 45 min. The pellets synthesized by this route had nominal compositions of Mo = 15, 20, 25, and 35 at.%, with the balance in each case being equiatomic NiAl. Oxidation coupons having a diameter of 10 mm and a thickness of 1 mm were cut from the cylindrical samples and subjected to interrupted oxidation tests at 1,100C which is the maximum temperature that current superalloys are exposed to in practice. Oxidation tests with multiple compositions allowed us to study the effect of Mo phase fraction and determine an appropriate composition range where the oxidation resistance was reasonably optimized. The composition of the drop-cast alloy (Mo20Ni40Al40) was decided based on the oxidation behavior of the sintered alloys. Drop-cast samples were prepared from pelletized elemental powder mixture of Mo (Alfa Aesar, 99.5% purity), Ni (MPC, 99.6% purity) and Al (Alfa Aesar, 99.8% purity) which were arc-melted. The alloys were re-melted thrice to achieve a greater degree of homogenization followed by drop-casting in order to obtain a cylindrical rod. The drop-cast alloy was subject to interrupted oxidation tests over a range of temperatures from 1,000C to 1,200C. In this test, the samples were exposed to the target temperatures for a total of 20 h with occasional interruptions for mass measurements at ambient temperature. The testing temperatures were deliberately kept at 1,200C or lower since our work on oxidation of pure nickel aluminides at temperatures above 1,200C (discussed below) has shown massive scale spallation. Microstructures of the as-prepared alloys as well as the oxidized coupons were studied using a JEOL 5910LV scanning electron microscope (JEOL, Tokyo, Japan) at an accelerating voltage of 20 kV. Nickel Aluminides with TM Additions The Ni-Al-TM alloys were produced from pieces cut from pure bulk metal sheets obtained from the Materials Preparation Center at Ames Laboratory, having a purity of 99.7% or more. Pure Ni and Al were rst arc-melted together in an argon atmosphere to form -NiAl. The ab initio calculations suggested that the transition metals have a preference for the Ni site in the B2 structure. Alloys with compositions Ni50xAl50TMx, (x = 3, 6, and 9) were then arc-melted in an argon atmosphere. The samples were re-melted thrice to achieve better homogenization before drop-casting. The rods were annealed at 1,300C in an argon atmosphere for 6 h to ensure homogeneity. Scanning electron microscopy was used to characterize the microstructure while phase analysis was done using x-ray diffraction (XRD) on a Philips PANalytical x-ray diffractometer (Panalytical, Almelo, Netherlands) with a BraggBrentano geometry and Cu K1 radiation ( = 1.54056 ). The x-ray data was Rietveld rened using GSAS software to estimate the lattice parameters of the phases as well as determine site preference for different elements.17 Of the transition metals studied, alloys with platinum group metal (PGM) modications formed single phase alloys while the other alloys showed a eutectic microstructure. Hence, further studies were carried out only on the PGM modied alloys. Oxidation coupons were prepared as described above, but more aggressive testing conditions, 1,300C for two hours and ambient for 30 min, were employed to determine if the PGM improved the oxidation stability of NiAl reservoir phase.

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Figure 3. Interrupted owing air oxidation of an arc-melted and drop cast alloy (Mo20Ni40Al40) at 1,200C.

product of NiAl is the formation of NiO.18 Subsequently, NiO is reduced by Al resulting in the formation of Ni and Al2O3. Typically such a reduction results in linear rather than parabolic kinetics. Aluminum can also react with atmospheric oxygen to form Al2O3 which should exhibit parabolic oxidation kinetics. Additionally, NiO and Al2O3 can react to form an NiAl2O4 spinel.19 All the reactions involving Ni and Al result in a slow mass gain, whereas the oxidation of Mo and the subsequent volatilization of MoO3 results in a rapid mass loss.4 Consequently, the overall oxidation rate is a sum of mass gain due to oxidation of Ni and Al and loss due to volatilization of MoO3. Figure 3 shows the oxidation kinetics during the interrupted oxidation process for the Mo20Ni40Al40 alloy at 1,200C. As a baseline comparison, the steady state mass loss value for the T2-Mo5SiB2 compound is shown on the same gure for comparison. The preliminary data indicates that the oxidation behavior of Mo-Ni-Al alloy is comparable to the refractory metal silicides at fairly elevated temperatures. Oxidation studies were limited to a temperature of 1,200C because the alumina scale formed on nickel aluminides is prone to spallation above 1,200C. Oxidation Behavior of the Nickel Aluminide X-ray diffraction studies on the nickel aluminides with Zr, Y, Hf, and Nb additions indicated a two phase mixture. The PGM additions were shown to form a single phase with the same crystal system as the -NiAl. A monotonic and approximately linear increase in the lattice parameter was observed with increasing PGM additions. Sub28

sequent Rietveld renement conrmed that PGM substitutions preferred the Ni site, which is in accordance with the ab initio calculations (Figure 4). Figure 4 shows the variation of formation enthalpy of PGM substituted -NiAl. It can be seen that substitution of PGM elements for Ni is energetically favorable. Also, controlled additions result in a monotonic change in formation enthalpy. This suggests that these PGM additions might be benecial for obtaining an increase in the melting temperature of the nickel aluminide. The other transition metals that showed large negative formation enthalpies with the nickel aluminide included Hf, Y, Zr, and Nb. All of these additions were experimentally found to produce deep eutectics. A high formation enthalpy can indicate high stability of both the solid and the liquid phase. The phase selection is decided by the relative stability of these two phases. Miedemas model is a structureless model; hence it cant be used to predict which of these two phases will be more stable. Formation of a eutectic suggests that the liquid phase is relatively more stable compared to a single phase intermetallic with the same composition in case of these alloying additions. Hence, further oxidation studies were carried out with only the PGM additions, since they were readily soluble in the -NiAl. Figure 5 shows the oxidation kinetics for the three PGM substitutions (all 6 at.%) to the -NiAl compared against undoped -NiAl as a benchmark. It can clearly be seen that the Pd substitution performed worse than the -NiAl during oxidation testing at 1,300C. The oxide spallation of the Pd sample was

noticeable early on during the test. The spallation akes were large and discernable with the naked eye, just like the -NiAl spallation. The Rh sample performed better than the base alloy NiAl, but worse than the alloy doped with Ir. The sample with Rh showed an adherent oxide scale initially, but after ve hours oxide spallation was observed. From the oxidation resistance point of view, Ir substitution to -NiAl appears to be superior. No sign of spallation was evident at times shorter than 20 h for alloys with 9 at.% substitution. In all cases it should be noted that the best performing alloy at the end of 20 h was always the alloy with the highest fraction of the ternary substitution for all of the elements tested. Figure 6ad shows the oxidation microstructures of the baseline NiAl along with each ternary substitution set at 6 at.%. These samples were oxidized for 24 h at 1,300C and then examined to better assess the evolution of the oxide scale formation. Figure 5 clearly displays that neither the benchmark NiAl alloy nor the -NiAl doped with Pd additions show an adherent oxide layer. Since both alloys had relatively signicant mass loss, the surface would be devoid of a continuous oxide scale. The Rh doped -NiAl showed an overall mass gain as well as signs of spallation. Looking at the oxide microstructure, it can be seen that the oxide layer is fairly continuous with a thickness of approximately 10 m. The Ir addition showed an almost continuous oxide scale with a thickness of 8 m. The only discontinuities were observed at the corners of the specimen where stresses in the oxide layer would be highest.

Figure 4. Variation of formation enthalpy of -NiAl with PGM additions.

Figure 5. Cyclic oxidation of -NiAl with and without PGM substitutions at 1,300C.

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50 m

tract no. DEAC02-07CH11358 through Iowa State University.

References
1. R.C. Reed, The Superalloys: Fundamentals and Applications (Cambridge, U.K.: Cambridge University Press, 2006). 2. M. Meyer, M. Kramer, and M. Akinc, Adv. Mater., 8 (1996), pp. 8588. 3. M.K. Meyer, M.J. Kramer, and M. Akinc, Intermetallics, 4 (1996), pp. 273281. 4. M.K. Meyer and M. Akinc, J. Amer. Cer. Soc., 79 (1996), pp. 938944. 5. J.R. Nicholls, MRS Bulletin, 28 (2003), pp. 659 670. 6. A.J. Thom, E. Summers, and M. Akinc, Intermetallics, 10 (2002), pp. 555570. 7. J.H. Rose, J. Ferrante, and J.R. Smith, Phys. Rev. Lett., 47 (1981), p. 675. 8. C. Li and P. Wu, Chem. of Mater., 14 (2002), pp. 48334836. 9. C. Li, J. Lim Hoe, and P. Wu, J. Phys. and Chem. of Solids, 64 (2003), pp. 201212. 10. P.K. Ray, M. Akinc, and M.J. Kramer, J. Alloys and Comp., 489 (2010), pp. 357361. 11. J.E. Croll and G.R. Wallwork, Oxidation of Metals, 4 (1972), pp. 121140. 12. G. Kresse and J. Furthmller, Phys. Rev. B, 54 (1996), p. 11169. 13. G. Kresse and J. Furthmller, Computational Mater. Sci., 6 (1996), pp. 1550. 14. G. Kresse and J. Hafner, Phys. Rev. B, 47 (1993), p. 558. 15. H.J. Monkhorst and J.D. Pack, Phys. Rev. B, 13 (1976), p. 5188. 16. X. Lu, Y. Cui, and Z. Jin, Metal. and Mater. Trans. A, 30 (1999), pp. 17851795. 17. B.H. Toby, J. Appl. Cryst., 34 (2001), pp. 210213. 18. G.R. Wallwork, Reports on Progress in Physics, 39 (1976), pp. 401485. 19. X. Zhao, I.P. Shapiro, and P. Xiao, Surface and Coatings Technology, 202 (2008), pp. 29052916. P.K. Ray, T. Brammer, Y.Y. Ye, M. Akinc, and M.J. Kramer are with Ames Laboratory and Department of Materials Science and Engineering, Iowa State University, Ames, IA 50011. Dr. Kramer can be reached at mjkramer@ameslab.gov.

Figure 6. Microstructures of oxidized alloys after oxidation at 1,300C for 24 h. (a) NiAl and -NiAl with 6 at.%, (b) Rh, i.e. Ni44Al50Rh6, (c) Ir, i.e. Ni44Al50Ir6, (d) Pd, i.e. Ni44Al50Pd6.

CONCLUSIONS We have shown that a hierarchical approach to alloy design starting with a less accurate but fast tool, followed by a more accurate but time consuming computational tool can be an efcient and effective means of down-selecting high-temperature alloys. Our modied Miedema model is particularly effective in identifying regions of high (negative) formation enthalpies, indicative of high melting temperatures. Using the criteria of refractory base metal as the backbone of the alloy and identifying the NiAl as the most promising reservoir compound for alumina scale former, we demonstrated that Mo-Ni-Al-(PGM) shows good promise as a high-temperature alloy. To further stabilize the reservoir compound, the most enthalpically stable

ternary additions were determined. The most promising of the Ni-Al-(PGM) alloys based on ab initio calculations were synthesized and their oxidation behavior was studied. It was found that a few alloys in this system had enough potential to warrant further investigation of these materials for ultra-high-temperature applications. The Mo phase fraction and its grain size play a critical role in the oxidation behavior of these alloys. Future work would be focused on developing PGM substituted Mo-Ni-Al alloys in the two phase bcc-Mo(ss) + -NiAl phase elds. ACKNOWLEDGEMENT This work was supported by the Department of Energy-Fossil Energy (Atmospheric Radiation Measurement program) through Ames Laboratory con-

M. Akinc and M.J. Kramer are full TMS Members and T. Brammer is a student member!
To read more about them, turn to page 7. To join TMS, visit www.tms.org/Society/Membership.aspx.

Superalloy 718 and Derivatives

Edited by E. A. Ott, J.R. Groh, A. Banik, I. Dempster, T.P. Gabb, R. Helmink, X. Liu, A. Mitchell, G.P. Sjberg, and A. Wusatowska-Sarnek Over the past 20 years, a series of six symposia devoted to Superalloy 718 and derivative alloys 625 and 706 have been organized and published by TMS. The proceedings of this seventh symposium maintains an international technical forum for the communication and discussion of recent innovations in material processing and understanding of the general class of superalloys including Alloy 718 and various related compositions. The scope of the proceedings of the Superalloy 718 and Derivatives symposium includes all aspects of alloy and process development, production, process improvements, products, trends, and the application of advanced modeling tools to industry challenges. There are a total of 75 papers that are included in these proceedings. Specic topic areas of continuing technical interest include: 5. Novel product forms technology and applications 1. Raw material developments in ingot metallurgy, melt 6. Field applications and trends (energy, aero, chemical, etc.) processing, supply chain expansion, and new capability 7. Microstructure, properties, and advanced characterization 2. Casting technology and developments 8. Corrosion, coatings, and environmental effects 3. Wrought processing technology and developments 4. Fabrication technology and developments

For more information visit: http://knowledge.tms.org/books.aspx.

Refractory Metals

Research Summary

Upscaling of the Investment Casting of the Intermetallic Alloy IC75

Simon Hollad and Andreas Bhrig-Polaczek

This research work is based on a specially developed SiO2-free shell mold system for the investment casting of NiAl alloys. Hitherto, this shell system has only been used for scientic work on small, laboratory scale samples made of IC75 alloy. The main focus of the research is to examine the feasibility of upscaling of the shell mold system for production scale samples. For this reason, 200 mm long dummy turbine blades were cast. Non-destructive analysis of the castings by visual examination of the blades surface quality, computed tomography scans of their internal structures and three-dimensional measurements showed very good results for the shell mold system. In particular, the good dimensional stability of the shell mold with average deviations of +0.3 mm and a local maximum deviation of 0.73 mm are excellent for a watersoluble shell mold system. The results of this work demonstrate that the investigated mold system is suitable for large samples and melt weights of up to 5 kg and is thus adaptable for the production process of NiAl components. INTRODUCTION The intermetallic alloy IC75, having the composition (in atomic percent) 45Ni-45Al-7.5Cr-2.5Ta, has already been investigated in detail within the research project15 of which this research is part. The alloy is characterized by its high melting point of 1,600C and, after the solidication of the NiAl, a typical brittle-ductile transition between 1,000 and 800C.6 It is also worth mentioning that the alloy has a low density of 6.3 g/cm, which is about two-thirds of comparable Ni-base alloys, and has a four-to-eight times higher thermal conductivity, which guarantees a more uniform temperature distribution in the
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turbine blade.7,8 The fundamental challenges to the casting of the NiAl alloy have already been examined within this research project. A feasible shell mold system, a suitable core technology, and cored-cast, ber-reinforced NiAl-investment casting samples were reproducibly fabricated on the laboratory-scale.15 The next logical step is to transfer these How would you
describe the overall signicance of this paper? For the manufacture of NiAl turbine blades on an industrial scale, it is necessary to revert to the investment casting process. The use of an SiO2-free shell mold system enables production of parts with good quality. The casting series was combined through the use of nondestructive testing methods to cover the entire industrial process chain. describe this work to a materials science and engineering professional with no experience in your technical specialty? For the manufacture of NiAl turbine blades on an industrial scale, it is necessary to revert to the investment casting process. The use of a chemically inert and temperaturestable SiO2-free shell mold system is necessary to produce parts with good quality. The main challenge is the development of a suitable shell mold to minimize internal stress during and below the ductile to brittle transition of the intermetallic phase NiAl which could lead to cracking of the casting parts. describe this work to a layperson? Investment casting is used to manufacture turbine blades made of refractory metals. The use of chemically-inert ceramic shell molds enables production of parts from these refractory metals. The quality of the casting was determined by nondestructive testing methods.

techniques to the industrial scale by upscaling component geometries and by focusing on the casting of turbine blades. The fact that components made of IC75 can already be cast on this scale was shown in 2003 by Palm et al. although, in their case, they produced combustor liners for gas turbines.9 The focus of this research is on the casting of dummy turbine blades on the production scale. In contrast to the previous research, this involves a signicantly increased demand on the complexity of the geometry. The basic requirement for the shell mold system is to exclude SiO2 in order to avoid chemical reactions with the very reactive melt since even small amounts of silicon inuence the properties of IC75.7 Furthermore, the already mentioned high melting temperature of the NiAl melt of 1,600C and above inhibits the use of SiO2-bonded shell systems because the operating temperatures of common SiO2-based shell molds are signicantly exceeded.10 The examined SiO2-free shell mold system has demonstrated its usability for investment casting of samples on the laboratory scale in recent years.1,2 The peculiarities of the shell mold system are the inert front layers, compressible intermediate layers and stabilizing backup layers. The special front layers are essential, as the NiAl melt is chemically very reactive and the high casting temperature also demands special ceramic materials. In addition to the inert front layers, the intermediate layers are of crucial importance since they prevent the metal from cracking during the solidication and during the ductile-brittle transition. These soft intermediate layers also provide the greatest benet to the upscaling process of NiAl-casting. In order to guarantee a sufcient stability of the shell mold system, supportive
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backup layers are dipped and sanded with commercial slurry.1 See the sidebar for experimental procedures. RESULTS AND DISCUSSION Visual Examination Although the investigation of the shell mold system was the main focus of this research work, resulting sample quality also played an important role. The properties of the castings allow direct conclusions about the suitability of the shell mold system for industrial component sizes. The samples dimensional quality, which is directly inuenced by the shell mold system, was investigated. As the two turbine blades shown in Figure 1 demonstrate, all the samples cast in this series are crack-free and provide good surface quality. The compressible intermediate layers in the shell mold guarantee crack avoidance during the ductile-brittle transition owing to their tension-degrading function. The crackresistant effect of the shell mold has already been demonstrated in several preliminary works1,2,11,13 and is not the focus of this research work. This work
1,000 m Figure 3. Longitudinal micrograph taken from the center axis of the blade. No casting defect can be observed. The micro-section from left to right shows the main axis of the component from the shroud up.

1,000 m Figure 4. The micrograph shows the microstructure perpendicular to the components axis. The constitution of microstructure shows no deviations regarding the microstructure in longitudinal direction.

is especially important in the upscaling capability of the shell mold systems. It is evident that the process parameters  were optimally THeater, TCasting, and T controlled for dimensional stable cast parts. Computer Tomography Examination In addition to the visual examination

10 cm Figure 1. Two faultless equiaxed cast NiAl turbine blades, with and without feeder.

Pore Gray Scale Value 1 Figure 2. The CT images show (a) an equiaxed sample with a massive shrinkage cavity in the head which was cast without a feeder and (b) a dense microstructure in the blade area as well as in the massive root. This sample was cast with the nal feeder design. The CT scan shows a dense microstructure containing no casting defects. The black area at the bottom is the CTs clamp. Gray Scale Value 1

Shrinkage Cavity

of the components, a study of the casting quality has been carried out using computed tomography (CT) scanning. The measurement of the CT generates a gray scale spectrum of 64 bits. To display the image on the computer, only 16 bits can be used, therefore thick- and thin-walled component areas are represented by different shades of the gray scale spectrum, whereas the cathode voltage of the CT remains the same. The CT images in Figure 2 also conrmed previous visual observations of the components to be crack-free. Figure 2a shows an equiaxed turbine blade with a massive cavity in the massive root area and a pore of approximately 2.5 mm diameter in the blade. This component was one of the rst casting samples, with which the effectiveness of the feeder was optimized. The dummy blade in Figure 2b was also equiaxed cast and was part of a fourcluster with optimized feeders. The image shows a marked improvement in the quality of the sample; the blade is porefree and the shrinkage hole in the root area of the blade has been eliminated. The controlled solidication sequence in Figure D (seen in the sidebar) results in a nearly homogeneous heat distribution in the components which permit a uniform solidication. However, the solidication starts from the bottom toward the feeder because the wall thickness increases from the blade to the root area. A hot spot is formed inside the feeder, so that the bulky root area is densely fed. Through further investigations of the microstructure, it could be
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demonstrated that there was no porosity, mold material inclusions, or micro cracks present. On the basis of micrographs in the transverse and the longitudinal direction of the component, the microstructure could be analyzed, as shown in Figures 3 and 4.

3-D-SCANNING AND ANALYZING Finally, the cast blades were investigated with regard to their dimensional accuracy since these are directly determined by the stability of the shell mold.
EXPERIMENTAL PROCEDURES

For this, the 3-D scan of the wax model was superimposed with the 3-D scans of the NiAl turbine blades. In this manner, it was possible to determine the positive and negative shape deviations. As example of all equiaxed cast blades, Figures 5 and 6 show the surface scan

Conguration of Shell Molds All the castings in this work had an idealized turbine blade geometry. This blade does not exhibit the typical aerofoil shape but was chosen because of its size which is related to its potential scope of manufacture. A series of 16 dummy turbine blades was produced by equiaxed casting. The dimensions of the blade, shown in Figure A, are 35 mm 90 mm with a blade length of 160 mm and an overall length of 195 mm. Initially, clusters with two blades were cast in order to optimize the process parameters for the vacuum investment casting. Furthermore, these clusters were used to dimension the form and the size of the feeder. In order to enlarge the upscaling process, clusters with four blades were cast to increase the shell mold size/geometry by a further dimension. Figure B shows the nished shell mold for the equiaxed process. It should also be noted that mold variants with and without a feeder and also several feeder volumes and geometries have been cast (Figure C). To produce the intended crack-free components on an industrial scale, equiaxed solidication was chosen because the shell molds can maintain the thermal loading. Shell Mold Production The ceramic shell molds are built up by repeated dipping and sanding with different slurries and alumina sands. The following introduces the specially developed shell mold system for casting NiAl alloys. The two front layers are built up from the inert surface coat slurry and ne-grained (0.120.25 mm diameter) high-purity alumina sand. The sand used is ne enough to achieve the desired surface quality. The surface coat slurry is based on three different alumina powders with average particle sizes of 1 m, 4 m, and 50 m. The different grain size fractions ensure a high packing density, which results in a strong agglomeration during the ring process. Also, the slurry is characterized by the SiO2-free binder. Reactions between ceramics and liquid metal are avoided by a combination of various grain size fractions and the absence of SiO2. For the fol-

lowing, compressible interlayers also used an SiO2-free slurry. This slurry is based on two alumina powders. The two grain size fractions averaging 4 m and 50 m offer a lower packing density and therefore lower sintering after ring. Due to the different particle size distribution of ceramic powders in the slurry, the cushioning of these layers is achieved. To guarantee a sufcient reduction of residual stresses in the IC75 during solidication, ve layers with the cushioning slurry are effective. The sand used in these layers is again high-purity alumina with a grain size of 0.25 to 0.5 mm (used only for the third layer to obtain a good bond) and 0.51.0 mm. The gradual increase of the grain diameter of the stucco material allows good bonding between the different types of layers. The nal three layers, for stabilizing the shell mold system, are based on a commercial SiO2-based slurry and are sanded with coarse alumina sand. The SiO2 stabilizes the mold by forming mullite together with Al2O3 during the ring process. After drying the shell molds, the wax is rapidly melted in the steam autoclave at 6 bar pressure and 160C steam temperature. The full dewaxing process should take no longer than 90 s since the SiO2-free layers of the shell mold are water soluble. For longer periods in the autoclave, the shell mold becomes soft, leading to the molds complete destruction. The dewaxing process is one cause of the molds geometric deviation since the mold only possesses green strength at this step of the process chain. The ultimate strength of the shell mold is achieved by a multi-step ring process. The process starts with ramp of 150 K/h up to 600C. A rst dwell of 30 min. at 600C removes the intercrystalline water. Following a second ramp of 100 K/min., the shell mold is heated to 1,200C. The ne alumina powder is sintered at 1,200C for 60 min. Furthermore, inside the outer layers, the SiO2 starts to transform into cristobalite. With a third ramp of 100 K/h, the maximum ring temperature is reached after 150 min. The ring temperature of 1,450C for 60 min. ensures that the shell mold obtains its ultimate strength. During this step, the coarse stucco material and SiO2 of the SiO2based slurry (in the backup layers) sinter and form mullite (3 Al2O3

Figure A. Schematic sketch of the dummy turbine blade showing the main dimensions and the positions for the thermocouples (black dots).

Figure B. Finished shell mold of a fourblade cluster.

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of the front and rear of equiaxed blades. It is clearly recognizable that the shape of the shell mold expanded minimally in the massive root. The front scan in Figure 6 shows an expansion on the lower end of the blade to a maximum of 0.67 mm. Besides this, deviations

of the component are about 0.2 mm. On the basis of the 3-D scans shown in Figure 6, the above described results are conrmed regarding the shape deviation. The equiaxed blade in Figure 6 shows that over the entire component volume, slightly bigger variations in

shape occur than those of the turbine blade shown in Figure 5. The only dimensional variation occurs in the middle of the rear side. Here, a specic maximum deviation of +0.73 mm occurs, which is caused by a softening or bulging of the shell mold. The front

2 SiO2).11 To avoid cracks during the multi-step ring process, the heating rates were kept relatively uniform. The temperature measurement inside the casting is realized by introducing an Al2O3 sheath into the wax model. The capillary tubes are injected into the wax model and protrude about 15 mm from the wax surface. Owing to the dipping and sanding process, the external part of the sheath is enclosed by the shell mold and results in a stable connection with the ceramic mold. After the ring process, the external ends of the sheaths are cut and allow the shell mold to be instrumented with thermocouples. Casting Series All casting experiments were carried out in an industrial Bridgman furnace with a melting chamber volume of approximately 4 m. Further specications of the plant include an induction crucible unit up to 1,750C, which can be tilted, and resistance heating of the shell mold up to 1,700C. Furthermore, the facility offers the opportunity of controlled cooling of the heaters and directional solidication by withdrawing the shell mold. During the casting experiments, a protective atmosphere of 300 mbar argon pressure was charged in the vacuum furnace. For the equiaxed experiments, the ceramic shell mold was preheated with the resistance heater up to 1,450C and held for 15 min. at this temperature. With the tilt-able crucible unit, the liquid IC75 was cast at 1,650C into the shell mold. The weights of the castings ranged from 3 to 5.5 kg for the clusters with two and four blades, respectively, with a single blade weight of about 1 kg. Afterwards, the mold was control cooled at a high cooling rate of 12C/min. to 1,100C. From 1,100C to 600C, the cooling rate was reduced to 2.5C/min. so that cracks below the ductile-brittle-transition-temperature (DBTT) were avoided. The positive inuence on crack avoidance using these special casting parameters by means of changing the cooling rate to 2.5 K/min. at temperatures above the DBTT has already been published by Scheppe et al. in 2002.12 Figure D shows the temperature curve of the resistance heater together with the cooling conditions inside the blade. The temperatures

were monitored by means of the three thermocouples distributed along the full length of the component. It is clear that the cooling conditions for a crack-free solidication are optimally controlled by using the resistance heaters. Analysis and Testing By means of visually inspecting the components, a rst assessment of the quality of the casting parts can be made. Surface defects that are due to reactions with the mold material, shrinkage cavities in the massive root area, pores as well as cracks in the component can be directly detected as a preliminary selection of the turbine blade. The high-precision analysis of the casting quality is performed using an industrial computer tomograph XT H 320 LC, made by the company XTEC. This uses an x-ray source with 320 kV accelerating voltage and the option of a rotating target. The precise ve-axis manipulator, designed for heavy samples, can accommodate test samples up to a weight of 50 kg and dimensions of 0.6 m (height) to 0.6 m (width). Due to the high resolution, an accurate identication of the casting quality is possible. The nondestructive detection of pores, cracks, and mold material inclusions is standard for the testing of turbine blades. The most important studies of this scientic work are based on the determination of the shell mold systems dimensional stability. By using the three-dimensional (3-D) scanner Comet IV, made by the company Steinbichler, a 3-D solid model of every casting part is generated. The system operates using a white light fringe projection technique and provides accuracy in the lower two-digit micrometer range. Following this, these models are superimposed with the solid model of the original wax component. Since it was not possible to access the original computer assisted design data of the wax die, the wax model had been used as a reference. Since lled wax was used for the wax parts, shrinkage only appears between the wax model and the casting. This method allows even the slightest deviations in the lower micrometer range to be represented.

c Figure D. The temperature curves of the heater elements depict the used cooling conditions, allowing the production of crack-free components despite the alloys ductile-brittle transition.

Figure C. Three different wax patterns for the equiaxed process. (a) A dummy blade with the in-gate, (b) a blade with a cylindrical feeder (diameter of 35 mm and a length of 60 mm), and (c) the nal design with feeder on the top of the blade.

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33

side scan of the blade shows variations in shape of less than 0.2 mm and thus is clearly within the range of the required tolerances. Deviations in symmetry between the front and rear sides of the dummy blades are due to the radiation heating during the casting process. Owing to the mold geometry, the two sides of the blade are not evenly heated by the radiation heater. The reason for the positive and negative deviations of the molds is caused in both cases by softening of the shell mold during the casting process. These tight tolerances were conrmed by almost all the equiaxed solidied samples (exceptions to this: rst two castings used for the process optimization). Since no blade shows large dimensional deviations, the shells also conrm stability without huge deformations. These results suggest that the shell mold system with inert front layers, compressible middle layer and stabilizing backup layers is working correctly. With average deviations ranging from 0.2 mm to a maximum of 0.73 mm, these are also very satisfying results for production scale samples using a mold whose dimensions are 350 mm high and 250 mm in diameter. CONCLUSION In this research work, equiaxed dummy turbine blades of medium size were successfully produced from the NiAl

Front Side

Rear Side

Figure 6. Equiaxed cast turbine blade with a small shape deviation on the front side.

alloy IC75. The developed shell mold system was found to be suitable for the manufacture of NiAl turbine blades on production scales. During the equiaxed process, the cooling rates at different stages were optimally controlled to ensure a crack-free solidied structure. By optimizing the feeder, cavity formation could be avoided. ACKNOWLEDGEMENT Financial support by the German Research Foundation is gratefully acknowledged.

References
1. M. Klaassen, I. Wagner, and P.R. Sahm, Incast, 14 (3) (2001), pp. 2832. 2. M. Klaassen, I. Wagner, and P.R. Sahm, Giessereiforschung, 54 (1) (2002), pp. 18. 3. M. Rosefort, C. Dahmen, and A. Bhrig-Polaczek, Paper presented at the 14th Annual International Conference on Composites/Nano Engineering, July 28, 2006, Boulder, Colorado. 4. M. Rosefort, C. Dahmen, A. Bhrig-Polaczek, W. Hu, H.C.Y. Zhong, G. Gottstein, D. Hajas, and J.M. Schneider, Advanced Engineering Materials, 8 (8) (2006), pp. 730735. 5. S. Hollad, C. Dahmen, and A. Bhrig-Polaczek, Superalloys 2008, ed. R.C. Reed et al. (Warrendale, PA: TMS, 2008), pp. 229239. 6. M. Rosefort, C. Dahmen, and A. BhrigPolaczek, Feinguss effusionsgekhlter NiAlGasturbinenschaufeln: Prozessentwicklung mittels numerischer Simulation (Paper presented at Werkstoffwoche 2004, Mnchen, Germany). 7. R.D. Noebe and W.S. Waltson, Structural Intermetallics 1997, ed. M.V. Nathal et al. (Warrendale, PA: TMS, 1997), pp. 573584. 8. R. Darolia, JOM, 43 (3) (1991), pp. 4449. 9. M. Palm, J. Preuhs, and G. Sauthoff, J. Materials Processing Technology, 136 (1-3) (2003), pp. 105 113. 10. K.O. Yu, J.A. Oti, and W.S. Walston, JOM, 45 (5) (1993), pp. 4951. 11. M. Klaassen, Development of a Cast Shell System for the Application of High Temperatures for FineCasting Technical Production Substantial and Hollow NiAl Construction Units (Aachen, Germany: Shaker Publishing House Aachen, 2003), Ph.D. dissertation. 12. F. Scheppe, P.R. Sahm, W. Hermann, U. Paul, and J. Preuhs, Material Science and Engineering A, 329331 (2002), pp. 596601. 13. F. Scheppe and P.R. Sahm, Investment Casting of NiAl Basis Alloys, Foundry Research, 53 (3) (2003). Simon Hollad, head of the Investment Casting/ Molding Materials Group, and Andreas BhrigPolaczek, head of the Foundry Institute, are with the Foundry Institute, RWTH Aachen University, and can be reached at s.hollad@gi.rwth-aachen.de and sekretariat@gi.rwth-aachen.de, respectively.

Front Side

Rear Side

Figure 5. This equiaxed cast turbine blade shows an average shape deviation of 0.2 mm.

34

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JOM October 2010

Nickel-based Superalloys

Research Summary

The Thermodynamic Modeling of Precious-metal-modied Nickelbased Superalloys

F. Zhang, J. Zhu, W. Cao, C. Zhang, and Y.A. Chang
mechanical properties, such as creep strength. The high-temperature strength of modern superalloys depends heavily on the use of refractory alloying elements. However, the composition of superalloys must be carefully controlled since the refractory alloying elements promote the formation of topological closed packed (TCP) phases which are detrimental to the mechanical properties. On the other hand, while focusing on the superior mechanical properties, the environmental stability of these alloys, such as oxidation and corrosion resistance, must be addressed due to the harsh operating environment of gas turbine engines. It is therefore desirable to develop nickel-based superalloys, which are inherently strong, and at the same time possess good oxidation and corrosion properties. This is challenging since optimal alloying compositions for strength often contradict those needed for oxidation and corrosion resistance. This leads to the inevitable use of environmental barrier coatings (EBCs) and thermal barrier coatings (TBCs) for high-temperature applications. It was found in the 1970s that platinum and the other platinum-group metals (PGMs) can be used as major alloying constituents in nickel-based superalloys to promote enhanced resistance to both oxidation and corrosion at elevated temperature in various aggressive environments, especially the cyclic oxidation resistance.2 This makes them attractive for the development of innovative TBCs for nickel-based superalloys. In recent years, the technology of depositing platinum onto nickel-based superalloys followed by treatments to produce an aluminum-rich layer has been used to produce improved protection at elevated temperature as compared to the conventional aluminide coating.
35

Enhanced for the Web

This article appears on the JOM web site (www.tms.org/jom.html) in html format and includes links to additional on-line resources.

How would you

describe the overall signicance of this paper? This paper discusses for the rst time the effects of precious metalsPt, Ir, and Ruon the properties of multicomponent nickel alloys from a thermodynamic point of view. The phase equilibrium related properties calculated in this paper, such as phase transformation temperatures and phase fractions, provide guidance for the selection of alloy chemistry to develop materials with desired properties. describe this work to a materials science and engineering professional with no experience in your technical specialty? It was found that platinum and precious group metals can be used as major alloying elements for Nibased superalloys to promote their oxidation and corrosion resistance. On the other hand, the platinum group metals are also very effective solid solution strengtheners to Nibased superalloys, which allows for the development of inherently strong superalloys. This paper discusses the effects of this group of elements on the phase equilibrium properties of nickel alloys using the CALPHAD approach. describe this work to a layperson? Platinum and precious group metals are found to have the abilities to improve the properties of nickel-based superalloys from several different aspects. In order to understand this, it is important to know how they change phase equilibria of multicomponent nickel alloys. Phase diagrams are road maps for materials scientists to understand this issue. In this study, the CALPHAD approach is used to calculate phase equilibrium and related properties of nickel alloys when precious group metals are added to nickel alloy systems.

Thermodynamic modeling of precious-metal-modied Ni-based superalloys (PMMS) was performed in this study using the CALPHAD approach. With this approach, the effects of platinum-group metals (PGMs) such as platinum, iridium, and ruthenium on the properties of nickel-based superalloys and their interplay with other alloying elements were understood from a thermodynamic and phase equilibrium point of view. Thermodynamic database containing PGMs was developed on the basis of the PanNi1 database for multicomponent nickel alloys. The database was rst validated with available experimental data. It was then used to understand phase stability and phase transformation temperatures, such as liquidus, solidus, and precipitation temperature, of PGM modied nickelbased superalloys. The effects of alloying elements on the formation of strengthening precipitate and their partitioning in and were also discussed. INTRODUCTION As structural materials, nickel-based superalloys possess outstanding properties at elevated temperatures and play an important role for high-temperature applications, especially in the development of gas turbine engine components. The continual demand for improved performance of jet engines has pushed the usage of these alloys to even higher temperatures, which requires better
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0.7 0.6 0.5 Fraction of 0.4 0.3 0.2 0.1 0 600 700 800 900 1,000 1,100 1,200 Temperature (C) Fraction of
Calculated Experimentally Determined

0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 600 700 800 900 1,000 1,100 1,200 Temperature (C)
Calculated Experimentally Determined

Figure 1. Comparison of the calculated and experimentally determined13 fraction of the phase for the Ni-15Al-5Cr-0.1Hf-2.5Pt (at.%) alloy.

Figure 2. Comparison of the calculated and experimentally determined13 fraction of the phase for the Ni-15Al-5Cr-0.1Hf-2.5Ir (at.%) alloy.

Gleeson et al.3 showed that platinum plus hafnium modied + coatings may be viable superior alternatives to current B2 type bond coatings. On the other hand, the PGMs are also very effective solid solution strengtheners to nickel-based superalloys comparable to the refractory metals,2 which allows for the development of inherently strong nickel-based superalloys. The purpose of this paper is to understand the properties of PGM-modied nickel-based superalloys from a thermodynamic point of view. Phase diagrams, which provide insight into phase stability, are road maps for alloy design and development. Traditionally, phase diagrams have been determined purely by experimentation, which is costly and time consuming. While an experimental approach is feasible for the determination of binary and simple ternary phase diagrams, it is less efcient for the complicated ternaries, and becomes practically impossible for higher order systems over a wide range of composition and temperature. On the other hand, commercial nickel-based superalloys are mostly multi-components in nature, and a more efcient approach is therefore needed to understand the phase equilibria when PGMs are used as alloying elements. The CALPHAD (i.e., CALculation of PHAse Diagram) approach will be adopted in this study. This approach has been used to understand binary, ternary, and even quaternary phase equilibria of nickel-based superalloys including PGMs.47 In this study, it will be used to understand the thermodynamics and phase equilibria of PGM-modied multi-component nickel-based superalloys.
36

In this paper, we will rst give a brief introduction to the CALPHAD approach and the use of this approach in the development of a multi-component thermodynamic database for nickel alloys containing PGMs. The developed database will then be used to calculate phase transformation temperatures, phase fractions, and other properties for the multi-component nickel alloys containing PGMs and will be validated by the experimental data. Finally, the validated database is used to understand the effects of alloying elements, such as Al, Cr, Pt, Ir, and Ta, and their interplay on the properties of nickelbased superalloys. THERMODYNAMIC DATABASE DEVELOPMENT The CALPHAD approach, which has been discussed a great deal in the past several decades,811 is a phenomenological approach. The essence of

this approach is to obtain self-consistent thermodynamic descriptions of the lower order systemsbinaries and ternariesin terms of known thermodynamic data measured experimentally and/or calculated theoretically, as well as the measured phase equilibria. The advantage of this method is that the separately measured phase diagrams and thermodynamic properties can be represented by the same thermodynamic description of a materials system in question. More importantly, on the basis of the known descriptions of the constituent lower order systems, a reliable description of a higher order system can be obtained via an extrapolation method.12 This description enables us to calculate phase diagrams of the multi-component systems that are experimentally unavailable. Development of a thermodynamic description (usually called thermodynamic database or database) of a multi-component system therefore starts with the development of the descriptions for all the constituent binaries and ternaries. For example, a quaternary system consists of six binaries and four ternaries and the database for the quaternary can be built up by combining the descriptions of these six binaries and four ternaries using a geometric model. It is found that the binary interactions are strong, the ternary interactions are less strong, and the quaternary and higher order interactions are several orders of magnitude smaller than those of the binaries. It is for this reason that a multicomponent system can be well predict-

Table I. Comparison of the Calculated and Experimental Determined Phase Composition for Ni-15Al-5Cr-0.1Hf Base Alloys with 2.5Ir and 2.5Pt (at.%) at 1,000C
Composition (at.%) Alloy 2.5Ir Phase (exp) (exp) Partition (/) (exp) (exp) Partition (/) Ni 79.13 (79.320.13) 73.74 (75.030.10) 1.073 (1.057) 79.57 (80.360.16) 73.13 (74.030.11) 1.088 (1.086) Al 12.98 (12.350.12) 19.26 (18.280.14) 0.674 (0.675) 12.31 (11.790.07) 20.30 (18.560.02) 0.606 (0.635) Cr 5.25 (5.860.03) 4.48 (4.260.05) 1.172 (1.376) 6.05 (5.970.05) 2.93 (4.150.09) 2.065 (1.438) Hf 0.01 (0.060.01) 0.29 (0.210.02) 0.034 (0.291) 0.01 (0.050.02) 0.27 (0.190.01) 0.037 (0.242) Ir 2.63 (2.410.04) 2.23 (2.220.06) 1.179 (1.086) Pt 2.06 (1.840.11) 3.37 (3.070.01) 0.611 (0.600)

2.5Pt

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Table II. Compositions of Four Groups of Alloys Studied in This Work

Group I II III IV Ni Bal Bal Bal Bal Al 15 15 13 14 Pt 2.55 2.55 2.5 2.5 Ir 02.5 2.5 02.5 0 Cr 2.55 5 510 10 Re 1 1 12 1 Ta 0-2 2 2 2 Ru 0 12 12 2 W 0 1-2 12 1 Hf 0.1 0.1 0.1 0.1 Si 0 0 0 0.5

tionship for the PGM-modied nickelbased superalloys with special focus on these three phases. In particular, we will use this database to calculate liquidus, solidus, -solvus, phase fraction and phase composition of and , and other properties for a variety of nickel alloys containing PGMs. PHASE EQUILIBRIA AND RELATED PROPERTIES The database was rst applied to the Ni-15Al-5Cr-0.1Hf-2.5Pt (at.%) and the Ni-15Al-5Cr-0.1Hf-2.5Ir (at.%) alloys. The fraction of as a function of temperature is calculated for these two alloys and compared with the experimental data13 as shown in Figures 1 and 2. The calculated phase composition of and and the partition coefcients for these two alloys at 1,000C are listed in Table I and compared with the experimental data13 (in parentheses). As can be seen from these two gures and the table, the calculated phase fractions of agree with the experimental data very well for both alloys, while the calculated phase compositions are also in
1,400

ed when the thermodynamic descriptions for the constituent binaries and ternaries are well developed. However, a 20-component system consists of 190 binaries and 1,140 ternaries. Not only are the assessments of so many binaries and ternaries not realistic, the lack of experimental data for some of these subsystems has made the development of a complete 20-component thermodynamic database impossible. As a result, a reasonable alternative is to focus on some key systems that are important for industrial applications and have abundant experimental information. Nickel-based superalloys are very complex, and typically contain ten or more components in the system. The alloying elements usually belong to one of the three groups according to their effects. The rst group of elements comprises those which partition to the matrix and impart solid solution strengthening, such as Co, Cr, Fe, Mo, and W. The second group consists of those which partition to the precipitate and promote precipitation strengthening, such as Al, Ti, Nb, and Ta. The last group of elements comprises those which segregate to grain boundaries and aid ductility, such as boron and zirconium. Previously, we developed a database for nickel alloys, PanNi,1 which has 19 components and includes elements from all three groups. In this work, we add Pt, Ru, and Ir into this database to study the properties of PGMmodied nickel-based superalloys. To thoroughly understand the interaction of these three elements with all the 19 components currently included in the PanNi database would involve development of thermodynamic descriptions for 60 binaries and 571 ternaries, which is not a realistic task. In this study, we have focused on the Ni-Al-Cr-(Pt, Ru, Ir) system due to key roles played by Al and Cr in the Ni-based superalloys. The key binaries and ternaries for this subset are: Ni-Pt, Ni-Ru, Ni-Ir, Al-Pt, Al-Ru, Al-Ir, Cr-Pt, Cr-Ru, Cr-Ir, NiVol. 62 No. 10 JOM

Al-Pt, Ni-Al-Ru, Ni-Al-Ir, Ni-Cr-Pt, Ni-Cr-Ru, and Ni-Cr-Ir. Thermodynamic descriptions for these systems have been developed and published by the authors of this work.47 Readers are referred to these papers for details on the phase equilibrium and thermodynamic properties of these key subsystems. In addition to the thermodynamic database for the Ni-Al-Cr-(Pt, Ir, Ru) system, interactions of the PGMs with other elements, such as Re, Ta, W, and Hf, need to be considered as well in order to understand the PGM-modied nickel-based superalloys. In this study, such interactions were developed only for the key phases, such as liquid, , and . The database thus developed was then used to study the phase rela1,460 1,440 Calculated (C) 1,420 1,400 1,380 1,360 1,340 1,340 1,360 1,380 1,400 1,420 1,440 1,460 Determined (C)
Liquidus Solidus Diagonal 20C Band 20C Band

1,350 Calculated (C) 1,300 1,250 1,200 1,150

Solvus Diagonal 20C Band 20C Band

1,100 1,100 1,150 1,200 1,250 1,300 1,350 1,400 Determined (C)

Figure 3. Comparison of the calculated and measured14,15 liquidus and solidus for Group I alloys listed in Table II.
1,440

Figure 4. Comparison of the calculated and measured14,15 solvus temperatures for Group I alloys listed in Table II.
70

Calculated (%)

1,420 Calculated (C) 1,400 1,380 1,360 1,340

Liquidus Solidus Diagonal 20C Band 20C Band

65 60 55 50 45 40 35 35 40

Percentage of Gamma_Prime Diagonal

1,320 1,320 1,340 1,360 1,380 1,400 1,420 1,440 Determined (C) Figure 5. Comparison of the calculated and measured14,15 liquidus and solidus for Group II-IV alloys listed in Table II.

45

50 55 60 Determined (%)

65

70

Figure 6. Comparison of the calculated and measured14,15 percentage of the phase for Group II-IV alloys listed in Table II.

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37

Table III. Effect of Cr on the Phase Relations of the Ni-15Al-5Pt-0.1Hf (at.%) Based Alloys
Cr content (at.%) 0 2.5 5 10 15 20 Liquidus (C) 1430 1419 1409 1388 1369 1352 Solidus (C) 1415 1401 1387 1361 1337 1314 Solvus (C) 1159 1171 1175 1168 1146 1119 HTW* (C) 256 230 212 193 191 195 (%) at 1,000C 23.0 28.1 33.1 38.3 32.3 21.6

HTW*: Heat Treatment Window = Solidus Solvus

reasonable accord with the experimental data. The calculated hafnium composition in the phase is too low for both alloys, which leads to the strong partitioning of hafnium to the phase. This is because the overall concentration of hafnium is very low and a small variation in either calculation or experimentation will lead to a big difference. For the Ni-15Al-5Cr-0.1Hf-2.5Pt alloy, the measured chromium concentration in the phase is more than 1 at.% higher than that calculated, while the measured chromium concentration in the phase agrees with that calculated value very well. The measured chromium concentration in the phase is believed to be too high when mass balance is applied. As can be seen from Figure 1, the calculated and measured phase fraction for the phase match each other perfectly (0.34) at 1,000C. The overall concentration of chromium is then calculated by the following equation:
x Cr x Cr f x Cr f

(1)

By taking the experimental measured concentration of chromium in the two phases into the above equation, we get the overall composition of chromium to be 5.35 at.% which is higher than its nominal composition of 5 at.%. On the other hand, the calculated phase composition meets the mass balance and gives the perfect overall composition of 5 at.% Cr. The database is then applied to alloys containing Re, Ta, Ru, and W. The compositions of the four groups of alloys studied in this work are listed in Table II. The purpose is to understand the effects of a variety of elements on the phase transformation temperatures, the amount of , and the partitioning of elements in the and phases. Group I alloys are based on Ni-15Al-1Re-0.1Hf (at.%) with Pt varying from 2.5 to 5
38

at.%, Ir 0 to 2.5 at.%, Cr 2.5 to 5 at.%, and Ta 0 to 2 at.%. Figure 3 shows the comparison between the calculated and measured14,15 liquidus and solidus for this group of alloys, and Figure 4 compares that of the solvus for the same group of alloys. It is seen that the calculated liquidus temperatures agree with the experimental measured values very well. The calculated solidus temperatures for this group of alloys tend to be higher than those measured experimentally, while the difference is less than 20C for the majority of these alloys. Group II alloys are based on Ni-15Al-2.5Ir5Cr-1Re-2Ta-0.1Hf (at.%) with Pt varying between 2.5 and 5 at.%, Ru between 1 and 2 at.%, and W between 1 and 2 at.%. The major difference between Group II and Group I is the use of Ru and W in Group II. Group III and IV alloys reduce the Al content while increase the Cr content as compare to Group II. Figure 5 compares the calculated and measured14,15 liquidus and solidus for Group II-IV alloys. It is interesting to see that the calculated solidus are lower than those experimentally determined values for Group II-IV alloys, which is contrary to the Group I alloys. Yet, the agreement between the calculated and

measured phase transformation temperatures for all these alloys is in general quite satisfactory. A similar plot for the solvus was not shown for Group II-IV alloys due to the lack of experimental data. Figure 6 compares the calculated and the measured14 percentage of the phase for several alloys from Group II-IV. While Figures 1 to 6 serve as a validation of the database, the ultimate goal of this study is to predict the effects of a variety of elements on the phase relations of multi-component nickel alloys containing PGMs. In particular, it would be interesting to see which elements enhance the precipitation (i.e., increase the fraction of the phase) and how the phase transformation temperatures vary with the alloy composition. Heat treatment window (HTW), which is dened as the temperature range between the solidus and the solvus, plays a key role in the selection of heat treatment temperature. A very narrow HTW will certainly lead to the difculties in solutionizing the alloy. It is therefore of great help if the effect of different elements on the HTW can be predicted. The rst example is to study the effect of the chromium content on the properties of the Ni-15Al-5Pt-0.1HfxCr based alloy. As listed in Table III, the liquidus, solidus, solvus, heat treatment window, and the amount of at 1,000C are calculated for this alloy with different amounts of chromium. Both liquidus and solidus decrease with the increase of the chromium content, while solvus increases to the maximum at ~5 at.% Cr, then starts to decrease with higher chromium content. The heat treatment window decreases at
1,600 89Hon
x(Al) = 0.17 x(Al) = 0.15 x(Al) = 0.13 x(Al) = 0.11 x(Al) = 0.09

1,500 1,400 Temperature (C) 1,300 1,200 1,100 1,000 + 10 15 x% (Cr) 20 25 Liquid + Liquidus Temperature (K) Liquid

1,500 1,400 1,300 1,200 1,100

Solidus Solvus

0 5 Ni-15Al-5Pt-0.1Hf

Figure 7. Calculated isopleth of Ni-15Al5Pt-0.1Hf-xCr (at.%).

1,000 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 Mol. Fracn. Cr Figure 8. Dependence of solvus on the Cr concentration for Ni-Al-Cr alloys at different levels of Al contents; experimental data are from Reference 16.

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Table IV. Effect of Ruthenium and Tungsten on the Phase Relations of the Ni-15Al-5Cr-0.1Hf-2.5Ir-2.5Pt-1Re (at.%) Based Alloys
Ru and W Content (at.%) 0 1Ru 1W 1Ru+1W 2Ru 2W 2Ru+2W Liquidus (oC) 1403 1408 1404 1408 1414 1403 1411 Solidus (oC) 1367 1364 1362 1358 1359 1357 1345 Solvus (oC) 1312 1312 1310 1310 1312 1309 1305 HTW* (oC) 55 52 52 48 47 48 40 (%) at 1000 oC 63.8 63.4 65.1 64.8 63.4 65.9 65.9

HTW*: Heat Treatment Window = Solidus Solvus

rst, and stays at almost constant value with chromium content greater than 10 at.%. The amount of reaches the maximum at ~10 at.% Cr, and starts to decrease as more chromium is added. The trend can also be illustrated by the phase diagram shown in Figure 7. As is seen in this gure, the liquidus and solidus keep going down as more chromium is added to the Ni-15Al-5Pt-0.1Hf-based alloy, while the solvus reaches the maximum at ~5 at.% Cr. A similar trend is also observed for the Ni-Al-Cr alloys as shown in Figure 8, which compares the calculated and experimental measured16 solvus lines for a variety of Ni-Al-Cr ternary alloys. The effect of small amounts of Pt and Ir on the liquidus and solidus of the Ni15Al-0.1Hf-xCr based alloys is shown in Figure 9. It is seen that 2.5 at.% Pt slightly increases the liquidus but marginally decreases the solidus of the Ni15Al-0.1Hf-xCr based alloy, while 2.5 at.% Ir increases both the liquidus and solidus of the Ni-15Al-0.1Hf-xCr-based alloy. In general, depending on the concentration of chromium, the liquidus is ~520C higher when 2.5 at.% Ir is
1,450 Liquidus 1,420 T (C) 1,390 Solidus 1,360 1,330 Ni-15Al-0.1Hf-2.5Pt-xCr 1,300 0 5 10 x % (Cr) 15 20 Ni-15Al-0.1Hf-xCr Ni-15Al-0.1Hf-2.5Ir-xCr

used rather than platinum. Tantalum has a signicant effect on the precipitate of nickel-based superalloys. One example is shown in Figure 10 for the Ni-15Al-5Cr-0.1Hf-2.5Ir2.5Pt-1Re alloy. It is seen that 2 at.% of tantalum greatly enhanced the precipitation of , which is benecial in view of materials strength. On the other hand, 2 at.% Ta decreases the liquidus and solidus of the above alloy by ~20C, while increasing the solvus by ~150C. This dramatically decreases the heat treatment window, which imposes a practical heat treatment challenge. Aluminum is found to have an effect similar to tantalum. It is seen from Figure 11 that reducing Al content by 2 at.% for the Ni-15Al-5Cr-0.1Hf-2.5Ir2.5Pt-1Re-2Ta alloy increases the liquidus and solidus by ~20C, while decreasing the solvus by ~50C. This opens up the heat treatment window by ~70C, but the strengthening phase is reduced by more than 15% in the temperature range shown in this gure. The effects of Ru and W on the thermodynamic properties of the Ni-15Al5Cr-0.1Hf-2.5Ir-2.5Pt-1Re-based alloys
1 f()-No Ta Solidus 0.9 f()-No Ta f()-2Ta f()-2Ta 0.8 0.7 0.6 0.5 0.4 0.3 0.2 Solvus Liquidus 0.1 0 700 800 900 1,000 1,100 1,200 1,300 1,400 1,500 Temperature (C)

are listed in Table IV. It is seen that 12 at.% Ru increases the liquidus slightly, but decreases the solidus slightly; it has almost no effect on the solvus and the fraction of . On the other hand, 12 at.% W does not change the liquidus, but somewhat decreases both the solidus and the solvus. Tungsten does increase the fraction of a little. Overall, a small amount of ruthenium and tungsten has a minimal effect on the phase transformation temperatures and phase amount for the Ni-15Al-5Cr-0.1Hf2.5Ir-2.5Pt-1Re-based alloys. Elemental partitioning, which affects the shape of precipitate and the coherence between and , plays an important role in determining the mechanical properties of nickel-based superalloys. It is therefore interesting to see how the elemental partitioning is affected by a variety of factors, such as temperature and other alloying elements. Figure 12 demonstrates two examples of such calculations. Figure 12a shows the temperature effect on the elemental partitioning of every element in alloy Ni-15Al-5Cr0.1Hf-5Pt. It indicates that temperature has signicant effect on the partitioning of chromium for this alloy, while its effect on that of nickel is very small. Figure 12b shows the effects of chromium and tantalum on the partitioning of platinum for the Ni-15Al-5Pt-based alloy. It is seen that 5 at.% Cr has a marginal effect on the partitioning behavior of platinum, while tantalum reduces the partitioning tendency of platinum to the precipitate. CONCLUSIONS The traditional development cycle of nickel-based superalloys using a trial1 f()-15Al 0.9 f()-15 Al Solidus f()-13 Al 0.8 f()-13 Al 0.7 0.6 0.5 0.4 0.3 0.2 0.1 Solvus Liquidus 0 700 800 900 1,000 1,100 1,200 1,300 1,400 1,500 Temperature (C)

Phase Fraction

Figure 9. Effect of Pt and Ir on the liquidus and solidus of the Ni-15Al-0.1Hf-xCr (at.%) alloys.

Figure 10. Effect of Ta on the phase transformation temperatures and amount for the Ni-15Al-5Cr-0.1Hf-2.5Ir-2.5Pt-1Re based alloy.

Phase Fraction

Figure 11. Effect of Al on the phase transformation temperatures and amount for the Ni-5Cr-0.1Hf-2.5Ir-2.5Pt-1Re-2Ta based alloy.

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1.0 4.0 Partitioning of Elements (FCC/L12) 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 500 a 600 700 800 900 1,000 1,100 Temperature (C) Partitioning of PT (FCC/L12)
AL CR HF NI PT

0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 500 b

Ni-15Al-5Pt Ni-15Al-5Pt-5Cr Ni-15Al-5Pt-2Ta

R. Helmink (Rolls-Royce) for technical discussions.

References
1. PanNiThermodynamic Database for Multicomponent Nickel Alloys (CompuTherm, LLC: Madison, WI, 2000). 2. C.W. Corti, D.R. Coupland, and G.L. Selman, Platinum Metals Rev., 24 (1) (1980), pp. 211. 3. B. Gleeson et al., Materials Science Forum, 461-464 (2004), pp. 213222. 4. C. Zhang et al., Acta Materialia, 56 (2008), pp. 25762584. 5. J. Zhu, Thermodynamic Description of Multicomponent Ni-Base Superalloys Containing Al, Cr, Ru, and Pt: A Computational Thermodynamic Approach Coupled with Experiments (Ph.D. thesis, University of Wisconsin-Madison, 2008). 6. C. Zhang et al., Calphad, 33 (2) (2009), pp. 420 424. 7. J. Zhu et al., Acta Materialia, 57 (2009), pp. 202 212. 8. Y.A. Chang et al., Progress in Materials Science, 49 (2004), pp. 313345. 9. M. Hillert, NATO ASI Ser., Ser. E, 276 (1994), pp. 113124. 10. L. Kaufman, Computer Calculation of Phase Diagrams (New York: Academic Press, 1970). 11. N. Saunders and A.P. Miodownik, CALPHAD: A Comprehensive Guide, ed. R.W. Cahn (New York: Pergamon Materials Series, 1998). 12. K.-C. Chou and Y.A. Chang, Ber. Bunsenges, Phys. Chem., 93 (1989), p. 735. 13. A.J. Heidloff et al., Metallurgical and Materials Trans. A, 40 (2009), pp. 15291540. 14. J.S. Van Sluytman and T.M. Pollock, Private Communication (University of Michigan at Ann-Arbor, 2009). 15. J.S. Van Sluytman et al., Acta Materialia, 58 (2010), pp. 19521962. 16. Y.M. Hong et al., ISIJ Int., 29 (1) (1989), pp. 7884. F. Zhang and W. Cao are with CompuTherm, LLC, Madison, WI; J. Zhu is with the Department of Materials Science and Engineering, University of Michigan, Ann Arbor, MI; and C. Zhang and Y.A. Chang are with the Department of Materials Science and Engineering, University of Wisconsin, Madison, WI. Dr. F. Zhang can be reached at fan.zhang@computherm.com.

600

700 800 900 1,000 1,100 Temperature (C)

Figure 12. Partitioning of elements () as a function of temperature: (a) Element partitions for alloy Ni-15Al-5Cr-0.1Hf-5Pt, (b) effect of Cr and Ta on the partition behavior of Pt.

and-error experimental approach may last for many years due to the difculty of nding the optimum alloy composition with desired mechanical properties and material stability. Modern material design inevitably involves a computational approach which provides guidance for the selection of alloy chemistry and processing conditions. In this study, thermodynamic calculation is used to understand the phase stability and thermodynamic properties of multi-component nickel alloys containing PGMs, in particular, the calculated liquidus, solidus, and solvus provide the temperature windows for processing. The calculated fraction of precipitate as a function of alloy compositions helps to identify the alloys that have potential for high strength, and the partitioning of elements is used to understand the / mist. These calculations are therefore used to guide the selection of optimum chemistry with balanced

properties. For example, alloy chemistry needs to be carefully adjusted so that a high volume fraction of precipitate is obtained for high strength, while a reasonable heat treatment window is maintained. Thermodynamic calculation in combination with key experiments shows great potential for accelerating the process of materials development and optimization. ACKNOWLEDGEMENTS A portion of this work was conducted due to the PMMS project sponsored by the Air Force Research Laboratory (AFRL) in collaboration with RollsRoyce, University of Michigan, and Iowa State University. The authors acknowledge D. Ballard (AFRL), B. Gleeson (University of Pittsburgh), A. Heidloff (Iowa State University), T. Pollock (University of California at Santa Barbara), J. Van Sluytman (University of Michigan), A. Bolcavage and

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The Superalloys: Fundamentals and Applications

by Roger C. Reed
Superalloys are unique high temperature materials used in gas turbine engines, which display excellent resistance to mechanical and chemical degradation. This book presents the underlying metallurgical principles which have guided their development and practical aspects of component design and fabrication from an engineering standpoint. The topics of alloy design, process development, component engineering, lifetime estimation and materials behavior are described, with emphasis on critical components such as turbine blading and discs. The rst introductory text on this class of materials, the book will provide a strong grounding for those studying physical metallurgy at the advanced level, as well as practicing engineers. Included at the end of each chapter are exercises designed to test the readers understanding of the underlying principles presented.

Contents:
1. 2. 3. 4. 5. Environmental degradation: the role of coatings Introduction 6. Summary and future trends The physical metallurgy of nickel and its alloys This book contains a foreword by Dr. Mike Hicks of Rolls-Royce Plc. Single crystal superalloys for blade applications Superalloys for turbine disc applications For more information visit: http://knowledge.tms.org/books.aspx.

Nickel-based Superalloys

Overview

Precious-metal-modied Nickelbased Superalloys: Motivation and Potential Industry Applications

A. Bolcavage and R.C. Helmink
Nickel-based superalloys are extensively used in the hot sections of gas turbine engines and other propulsive power machines because they possess an excellent combination of high-temperature strength and resistance to oxidation and hot corrosion degradation. The - microstructure inherent in nickel-based superalloys is designed with respect to composition and morphology so as to achieve a balance of strength versus environmental resistance. Often, aluminide and platinum-modied aluminide coatings are applied to the component surface to further improve the resistance to environmental degradation by supporting the formation of a protective aluminum oxide scale. The potential exists to utilize alloying concepts from novel platinum and hafnium-modied - diffusion coatings so as to create in-situ a new class of superalloy that combines enhanced environmental resistance while maintaining sufcient strength at high temperatures. This paper describes how precious-metal-modied superalloys can offer advantages for structural applications in gas turbine engines. Several examples that illustrate component performance benets are also presented. INTRODUCTION Structural nickel-based superalloys are used extensively in the hot sections of gas turbine engines and other propulsive power machines because they possess an excellent combination of high-temperature strength and resistance to environmental attack.1 The basic structure of these superalloys consists of coherent, ordered Ni3Al gamma prime ( ) precipitates in a matrix of solid solution-nickel gamma (), with refractory metal strengthening of both
Vol. 62 No. 10 JOM

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describe the overall signicance of this paper? This paper describes the potential of modifying nickel-based superalloys with platinum-group metals (PGM) to create a new class of superalloy with unparalleled environmental resistance and sufcient strength at elevated temperature. These PGM-modied superalloys are potentially promising for structural applications in gas turbine engines. Several examples where PGMmodied superalloys offer component performance benets are presented. describe this work to a materials science and engineering professional with no experience in your technical specialty? The - microstructure inherent in nickel-based superalloys is designed to achieve a balance of strength versus environmental resistance. Often, protective aluminide and platinum-modied aluminide coatings are applied to the component surface to further improve the resistance to environmental degradation by supporting the formation of a protective aluminum oxide scale. The potential exists to utilize alloying concepts from novel platinum and hafnium-modied - diffusion coatings to create a new class of superalloy that combines enhanced environmental resistance with strength at high temperatures. describe this work to a layperson? Nickel-based superalloys are extensively used in the hot sections of gas turbine engines because they possess an excellent combination of high temperature strength and resistance to oxidation and hot corrosion degradation. The potential exists to redesign superalloys using platinum and other precious metal group elements via alloying to create in-situ a new class of superalloy with enhanced environmental resistance for structural applications.

phases and grain boundary strengthening additions, mainly carbon, boron, and zirconium. The aluminum in the phase is generally partially replaced by titanium, tantalum, and niobium. The volume fraction of ranges from about 25% to 70%, with higher volume fractions present in cast alloys, particularly single-crystal castings. Most superalloys rely on the formation of a continuous and adherent thermally grown oxide (TGO) scale of alumina for extended resistance to degradation in the high-temperature environment of a gas turbine engine.2 As operating temperatures continue to increase in the hot section, nickelbased superalloy components require additional protection against oxidation and hot corrosion since there is not sufcient aluminum in the alloy at the near surface to prevent the eventual spallation of the protective Al2O3 layer. However, the optimal alloying compositions for strength are often contradictory to those needed for oxidation and hot corrosion resistance. Compromises are made to achieve various balances of strength versus environmental resistance and the materials are often protected with thermal and/or environmental barrier coatings for harsher applications. Diffusion nickel-aluminide (NiAl) coatings, typically applied using chemical vapor deposition (CVD) processing, are used to increase the aluminum content at the gas/metal interface and thus improve the ability of the component to form and maintain a thin Al2O3 scale on the surface for longer periods of time.3 This protective scale grows slowly, separating the component from the oxidizing environment. The primary requirements of diffusion -NiAl coatings, acting in conjunction
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with the substrate alloy, include chemical and microstructural stability, sufcient creep strength, low coefcient of thermal expansion (CTE) mismatch, and sufcient ductility to resist thermomechanical fatigue cracking. If a thermal barrier coating (TBC) is applied to reduce metal-side surface temperatures, the ability of the TGO to bond the TBC to the coated component and avoid spallation takes on even greater importance.4 State-of-the art aluminide coatings are modied with platinum in order to further improve the Al2O3 scale adhesion and thus enhance high-temperature oxidation resistance.5 The precise role of platinum is still being investigated, and several possible mechanisms have been proposed to explain how the presence of platinum in diffusion aluminide coatings aids retention of the Al2O3 scale.68 Commercially used versions typically have microstructures consisting of single-phase -(Ni,Pt)Al, twophase -(Ni,Pt)Al + PtAl2, or, more recently, two-phase -Ni + -Ni3Al with high volume fractions of . Coatings based upon + microstructures are particularly viewed as advantageous with respect to their mechanical properties. These coatings exhibit better high-temperature strength and superior stress relaxation resistance versus the -NiAl and -(Pt,Ni)Al systems.9 There is also a closer match of the coating CTE to that of the substrate, as both contain the same phase constitu-

ents. Therefore, + based coatings exhibit a much reduced propensity for rumpling, especially in the absence of a constraining TBC layer. PMMS: A NEW CLASS OF SUPERALLOY Recent work has shown that certain unique alloy compositions encompassing platinum-modied -Ni+Ni3Al systems with reactive element additions also provide environmental coatings with a signicant increase in the durability of the protective Al2O3 scale.10,11 It has also been shown that -Ni+-Ni3Al-based alloys modied with 5 to 20 at.% platinum and up to 2 at.% hafnium form highly adherent, slow-growing Al2O3 scale during both isothermal and cyclic oxidation at high temperature. The oxidation kinetics of these alloys are up to an order of magnitude slower than conventional -NiAl(Pt) alloys. Additions of chromium and silicon provide a further boost to the dual needs of oxidation and hot corrosion resistance, especially in alloys containing lower amounts of platinum.12 The similarity of this new class of coating to conventional structural superalloys led to speculation that the alloying strategy employed for nickelbased superalloys could be extended to the hafnium-modied + based coating compositions to create a new class of superalloy with sufcient strength at elevated temperature. These alloys,

called precious-metal-modied superalloys (PMMS) or platinum-group metal (PGM) modied superalloys, were considered to be potentially promising for supported or stand-alone structural applications with unparalleled environmental resistance. The experimentally determined 1,150C isothermal section from the equilibrium phase diagram for the Ni-Al-Pt system is shown in Figure 1.13 This diagram, determined by Gleeson and colleagues, shows that the composition space for + equilibrium in this system is fairly large. As a consequence, it is quite practicable to control the phase proportions and to select quaternary and higher-order additions for the purpose of modifying microstructure and strengthening the alloys. Furthermore, the phase diagram can be used to select compositions to use as the starting point for study of this new class of superalloys. Researchers within the Air Force Materials Laboratory, Rolls-Royce, Iowa State University, and the University of Michigan collaborated on a program to systematically explore the phasal thermodynamics, physical metallurgy, environmental resistance, and creep strength of PGM-modied (platinum and iridium) compositions in the + two phase eld.14 Strengthening additions typically used for superalloys, including Cr, Co, Ti, Ta, W, Mo, Re, Ru, C, and Si, were also incorporated into the base Ni-Al-(Pt/Ir)-Hf compositions. The work focused on approximately 50-50 + alloys for strength and ductility considerations while trying to minimize precious metal content to control raw material cost without undue loss in environmental resistance. COMPONENT REQUIREMENTS AND POTENTIAL APPLICATIONS Some of the potential applications for PGM-modied alloys in gas turbine engines include: Environmental barrier and TBC bond coatings for advanced singlecrystal superalloy airfoils Suldation and hot corrosionresistant coatings for blade stalks and attachments Airfoil segments with advanced construction techniques Single-piece or multi-piece turbine
JOM October 2010

Figure 1. Experimentally determined 1,150C section of the equilibrium Ni-Al-Pt phase diagram.

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Cooling Airow
Figure 2. Advanced multi-wall cooling concept with predominantly internal heat transfer enhancements. This makes it less susceptible to uncertainty in the external environment than highly lm cooled systems.

blades and vanes Oxidation, suldation, and hot corrosion-resistant coatings for disk ow path and attachment surfaces Nonstructural sheet metal fabrications, such as thermal protection tiles for exhaust or space reentry vehicles Structural sheet metal fabrications, such as combustor liners The primary requirements for environmental barriers and TBC bond coatings are oxidation resistance, chemical and microstructural stability with the substrate, sufcient creep strength to resist rumpling, and sufcient ductility to resist thermo-mechanical fatigue cracking. This use of PGM-modied superalloys for bond coatings on single-crystal superalloy airfoils represents the nearest-term application. Potential compositions with high contents have been identied and work is ongoing. Thermally grown oxide scale spallation resistance and chemical and microstructural stability superior to existing bond coating systems have also been demonstrated. Solid solution and second phase strengthening to balance the often-conicting requirements of strength, ductility, and environmental resistance could further optimize these compositions. More work would be required to adapt these materials to advanced airfoil materials, including long time phasal and microstructural evolution studies at high temperatures, as well as the development of effective diffusion barriers. All aerospace manufacturers of large
Vol. 62 No. 10 JOM

gas turbine engines have observed Type II hot corrosion on the platform, stalk, attachment, and internal surfaces of single-crystal turbine blades and, to a lesser extent, on disk areas exposed to the ow path. This material degradation mechanism likely will become much more pervasive for future engines as disk temperatures reach 700 to 750C. In addition to the requirement of hot corrosion resistance, effective coatings or surface treatments will require adequate ductility, strength, and thermal expansion matching to minimize or eliminate low cycle fatigue (LCF) debits. These requirements will be particularly arduous for disks, since thermal and mechanical stresses in the blade attachment region are quite high and disks are the most fracture critical components in gas turbine engines. Rolls-Royce North American Technologies, Inc. (LibertyWorks) has been a leader in the design and fabrication of turbine components in nearstoichiometric hot gas environments and has developed a number of concepts for efcient use of materials in these demanding applications. A number of these concepts revolve around advanced multi-wall cooling congurations with predominately internal heat transfer enhancements as shown schematically in Figure 2. These advanced cooling concepts have been applied to combustor liners, similar sheet metal ow path structural com1.0 0.9 0.8 0.7 Relative Cooling 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0.0 1.0

ponents, and static and rotating airfoil components. The benets of these advanced cooling technologies versus more conventional airfoil cooling techniques are shown in Figure 3. For airfoil components, a PGM-modied superalloy could form the ow-path surface layer or a portion thereof. These designs would take advantage of the outstanding environmental resistance of the PGM-modied superalloy, while minimizing the component cost penalty. It is anticipated that the requirements for creep, rupture, and LCF strength of the PGM-modied superalloy material will be more stringent than for the aforementioned coating applications. Highly oxidation-resistant sheet metals used to fabricate structural and nonstructural components may offer performance benets over current materials. The primary challenge is to enhance hot workability and formability through microstructural control and atomic bonding optimization while minimizing the platinum content. Lower cost precious metal additions, such as palladium, iridium, and ruthenium, may be substituted for platinum. Another possibility is to employ bimetallic constructions in which the more expensive alloys are used selectively in only the harshest locations. Examples of this would be graded compositions for thermal protection tiles and lower cost cold-side material for multi-wall

2.0 3.0 4.0 Cooling Airow Parameter

5.0

6.0

Figure 3. Advanced multi-wall airfoil cooling technology approaches ideal transpirational cooling capability.

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10,000 Platinum Raw Material Cost ($ per Component lb.)

1,000

100

10

1 0 5 10 15 Platinum Concentration in Coating/Cover Skins/Alloy (wt.%) 20

Figure 4. Economic trade study illustrating the estimated required raw material cost of platinum per component unit weight (lb.) versus the concentration of platinum in a component alloy or coating manufactured from PGM-modied alloys.

wrought alloys. For reference, the approximate raw material cost of equiaxed and single crystal superalloy materials is also shown in this chart. It is evident that platinum content in a coating, while signicant, is not prohibitive, since a coating contributes only several tenths of a percent to the overall component weight. For bimetallic constructions, for which the PMMS material can represent a few percent to about ten percent of the component weight, the platinum content can easily double the raw material cost of the component. This would restrict its use to applications for which alternative, lower cost solutions are not available. For bulk alloy applications, the cost of platinum would be prohibitive except for highly specialized cases such as thermal protection tiles.
References

constructions. Single crystal PGM-modied superalloy blades and vanes potentially offer high performance benets, but also are burdened with the most demanding requirements and constraints. The creep, rupture, and fatigue strength requirements at high temperature will be greater in addition to these requirements at low and intermediate temperatures with correspondingly higher stresses. As with sheet metal applications, raw material cost would also be a major factor and could potentially prohibit economic exploitation of this technology. It is clear that a range of compositions and microstructures of PGMmodied superalloys would be required to satisfy all of these potential applications and would likely include: Equiaxed and single-crystal grain structures Gamma prime volume fractions ranging from less than 50% to nearly 100% Platinum content from 5 wt.% or less to around 20% Strengthening, ductility enhancement, and hot corrosion protection

alloying additions so as to meet a wide range of requirements COST COMPARISON OF PLATINUM-GROUP METAL MODIFIED SUPERALLOYS From the beginning of the PMMS program, it was recognized that production of most components using alloys with a high PGM content would be prohibitively expensive. The design challenge ultimately presented is how to exploit the outstanding oxidation resistance of these materials in the demanding environment of gas turbine engines and access-to-space vehicles while minimizing utilization so as to offset the inherently high raw material cost. Figure 4 shows the results from an economic trade study illustrating the estimated required raw material cost of platinum per component unit weight (lb.) versus the concentration of platinum in a component alloy or coating manufactured from PGM-modied alloys, based on May 2010 prices.15 Cost ranges are presented for application scenarios including coatings, surface layers or bimetallic sheets, and bulk cast and

1. R.C. Reed, The Superalloys, Fundamentals and Applications (Cambridge, U.K.: Cambridge Univ. Press, 2006). 2. J.R. Nicholls, MRS Bulletin, 28 (9) (2003), p. 659. 3. G.W. Goward, Surf. Coat. Technol., 108109 (1998), p. 73. 4. C.G. Levi, Current Opinion in Solid State and Mat. Sci., 8 (2004), p. 77. 5. A.L. Purvis and B.W. Warnes, Surf. Coat. Technol., 146-147 (2001), p. 1. 6. W.T. Wu, A. Rahmel, and M. Schorr, Oxid. Met., 22 (1984), p. 59. 7. K.A. Marino and E.A. Carter, Acta Materialia, 58 (2010), p. 2726. 8. J. Angenete, K. Stiller, and V. Langer, Oxid. Met., 60 (2003), p. 47. 9. X. Wang, R.T. Wu, and A. Atkinson, Surf. Coat. Technol., 205 (2010), p. 2472. 10. T. Izumi, N. Mu, L. Zhang, and B. Gleeson, Surf. Coat. Technol., 202 (2007), p. 628. 11. Y. Zhang, B.A. Pint, J.A. Haynes, and I.G. Wright, Surf. Coat. Technol., 200 (2005), p. 1259. 12. B. Gleeson and D. Sordelet, U.S. patent app. 20,090,324,993 (31 December 2009). 13. T. Izumi and B. Gleeson, Acta Materialia, 53 (2005), p. 3319. 14. AFRL contract no. FA8650-05-C-5220. 15. Precious Metal Prices Index (Chard Ltd., 521 Lytham Road, Blackpool, Lancashire FY4 1RJ, U.K.), www.taxfreegold.co.uk/preciousmetalpricesindx .html. A. Bolcavage is with Rolls-Royce Corporation, P.O. Box 420, Speed Code W-08, Indianapolis, IN, 46206, and R.C. Helmink is with Rolls-Royce North American Technologies, Inc., Indianapolis, IN. Dr. Bolcavage can be reached at ann.bolcavage@ rolls-royce.com.

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Nickel-based Superalloys

Overview

The Use of Precious-metal-modied Nickel-based Superalloys for Thin Gage Applications

Donna L. Ballard and Adam L. Pilchak
Precious-metal-modified nickelbased superalloys are being investigated for use in thin gage applications, such as thermal protection systems or heat exchangers, due to their strength and inherent oxidation resistance at temperatures in excess of 1,050C. This overview paper summarizes the Air Force Research Laboratory (AFRL) interest in experimental two-phase -Ni + -Ni3Al superalloys. The AFRL is interested in alloys with a based composition of Ni15Al-5Cr (at.%) with carbon, boron, and zirconium additions for grain-boundary renement and strengthening. The alloys currently being evaluated also contain 45 at.% of platinum-group metals, in this case platinum and iridium. The feasibility of hot rolling these alloys to a nal thickness of 0.120.25 mm and obtaining a nearly fully recrystallized microstructure was demonstrated. INTRODUCTION Nickel-based superalloys having densities exceeding 8 g/cm2 may not initially be thought of as viable materials for acreage thermal protection systems (TPS) on hypersonic or space vehicles. Indeed, as the only reusable spacecraft currently in operation, the space shuttle utilizes many types of nonmetallic TPS materials, in both tile and blanket form. In many cases, these nonmetallic materials are the only option under extreme environments (in terms of temperature, stress, etc.) which demand properties exceeding those of metallic thermal protection systems (MTPS).1 However, shuttle refurbishment between ights has been reported to require more than 17,000 labor hours2 with a total inspection and refurbishment time exceeding 40,000 hours.3 This level of maintenance is unacceptable for U.S. Air Force applications, where the turn-around
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describe the overall signicance of this paper? This overview paper describes development of nickel-based superalloys with precious metal additions which have better strength and oxidation resistance at higher temperatures than commercially available nickel-based superalloys. These alloys can be processed to sheet or foil gage, and have the potential to be used for niche applications in thermal protection systems of high speed vehicles. describe this work to a materials science and engineering professional with no experience in your technical specialty? Inherent oxidation resistance and strength at temperatures exceeding 1,050C are key considerations for manufacturing metallic honeycomb panels. Dependence on oxidationresistant coatings is undesirable since post-coating performance can be degraded. The goals of this research are to develop the basic materials knowledge required to successfully produce oxidation-resistant sheet and foil and understand the microstructureproperty evolution under representative service conditions. describe this work to a layperson? A beehive is a honeycomb structure that is very strong while minimizing weight. The nickel alloys being developed withstand temperatures over 1,050C but are also heavy, requiring a vehicle to use more fuel and carry a lighter payload. This requires rolling the metal very thin (imagine rolling metal dough to the thickness of aluminum foil) then test it to determine how long it will last, or its life. Using a beehive as an example, we take the foil and form it into honeycomb then sandwich it between thicker sheets of the same alloy to make a honeycomb panel.

time goal is hours to days rather than weeks to months. As a result, thin gage metallic sheet and foil may become an acreage option because the time to complete inspections can be signicantly reduced, durability is improved, waterproong between ights is not required, and replacement time is shortened because MTPS panels are mechanically attached rather than adhesively bonded. Sandwich construction MTPS (outer surfaceIN617 nickel-based superalloy honeycomb core and face sheets; inner surface titanium alloy honeycomb core and face sheets) was evaluated (Figure 1) and was considered to be a leading candidate for a signicant portion of the lower surface of the NASA X-33 vehicle,2 a wedged-shaped subscale prototype of a reusable launch vehicle4 designed by Lockheed Martin. PLATINUM-GROUPMETAL-MODIFIED NICKEL-BASED SUPERALLOYS Weight is critical in vehicle design because total vehicle weight will impact performance.3 In both current and proposed systems, the TPS is parasitic and not designed to carry signicant structural load regardless of material selection.5 Because of the increase in density of MTPS, materials under consideration must be very thin, 0.170.25 mm for a typical face sheet and 0.050.10 mm for the honeycomb core. One experimental class of alloys being evaluated for MTPS applications is platinum-groupmetal (PGM)-modied nickel-based superalloys where one substitutes one or more PGMs, in this case platinum and iridium, for nickel. Table I identies several of the alloys that have been evaluated at the Air Force Research Laboratory (AFRL) as well as a base45

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Table I. Platinum-group-metal-modied Nickel-based Superalloys Tested (at.%)

Heat Number Pt-modied 5A 5B 5C 8A 10A 10B 10C 10D 10E Ni 35.0 79.4 74.4 74.4 75.6 75.6 79.6 74.4 79.4 75.6 Cr 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Al 50.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 Hf 0.30 0.30 0.30 0.15 0.15 0.15 0.30 0.30 0.10 C 0.25 0.25 0.25 0.12 0.12 0.12 0.25 0.25 0.12 B 0.04 0.04 0.04 0.08 0.08 0.08 0.04 0.04 0.08 Zr 0.04 0.04 0.04 0.03 0.03 0.03 0.04 0.04 0.03 Pt 15.0 5.0 3.0 2.0 2.0 3.0 2.0 Ir 2.0 2.0 2.0 2.0 2.0

line example of a platinum-modied nickel aluminide-NiAl(Pt) composition (e.g., Ni-50Al-15Pt) used in the turbine-engine industry for airfoil

coatings because of its oxidation resistance.69 However, using -NiAl(Pt) for a monolithic application is not practical because it is brittle, difcult to process,

Outer Inconel 617 Honeycomb Sandwich Fastener Access Cover Structure

Inconel 617 Beaded Side Walls

Felt/RTV Seal Fastener Access Tube Assembly Inner Honeycomb Sandwich Cutout Safl Insulation Inner Titanium Honeycomb Sandwich Mechanical Fastener

Figure 1. A proposed option for the X-33 metallic thermal protection system.

Figure 2. Oxidation performance of -NiAl(Pt), PGM-modied nickel-based superalloys and commercial nickel-based superalloys (PGM alloys tested at 1 h cycles, Alloy 617 and H230 at 24 h cycles). Note that the candidate PGM-containing alloys outperform both Alloy 617 and Haynes 230, even though the testing for the candidate alloys is at a higher temperature (1,150C versus 1,000C and 1,100C) than the commercial alloys. However, the oxidation resistance of -NiAl(Pt) is better than either of the candidate alloys.

and does not perform well across the entire service temperature range, particularly below 600C.10,11 Recent results on PGM-modied Ni + Ni3Al ( + ) compositions for bond coats8,12,13 suggest that these -Ni + -Ni3Al compositions may be suitable thin gage candidates due to the formation of an adherent, protective -alumina scale which provides increased environmental resistance over a larger service temperature range.14 In addition, results reported in the late 1970s and early 1980s by Corti et al.1517 concluded that platinum had the best overall performance in both oxidizing and suldizing environments. Cyclic oxidation testing was performed at Iowa State University and the test procedures are described in Reference 13, with the only differences being the oxidation cycle time and the test temperature. The NiAl(Pt) samples and the experimental alloys were tested at 1,150C at 1 hour cycles and the commercial alloys were tested at 1,000C and 1,100C and cycled every 24 hours (Figure 2). The data indicate that although the performance of the experimental alloys, designated 5C and 8A, does not equal that of NiAl(Pt), the oxidation resistance is better than either Alloy 617 or Haynes 230, commercial alloys under consideration for use in MTPS applications. Although there is no added benet to environmental resistance, iridium is added to the candidate alloys because it partitions almost equally to both and there is a slight preference for the phaseand it reduces the lattice mismatch.18,19 Corti et al. also documented1517 that platinum provided the best strength at temperatures in excess of 1,000C because it partitions to and strengthens the precipitate phase.20,21 A high volume fraction of the precipitate phase is desirable for reasonable high temperature strength and adequate creep resistance, which are important MTPS design considerations and may allow the use of thinner foils than is possible with conventional nickle-based superalloys. Figure 3 compares the tensile strength of commercial alloys to a PGM-modied experimental alloy at room temperature and at 900C (IN617 was tested at 871C). Figure 3b is an enlargement of the low strain portion of Figure 3a in order to more clearly identify the IN617 test data. At both test temperatures, the
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1,500 Engineering Stress (MPa) 1,200 900 600 300 0 0.0

IN 617 y = 395 MPa UTS = 423 MPa f = 0.007

PGM 5C y = 732 MPa UTS = 1327 MPa f = 0.24 Haynes 230 y = 378 MPa UTS = 844 MPa f = 0.535
0.6

a
1,000 Engineering Stress (MPa) 800 600

0.1 0.2 0.3 0.4 0.5 Engineering Strain (mm/mm)

PGM 5C

IN 617
400 200 0 0.00

Haynes 230

b
500 Engineering Stress (MPa) 400 300 200 100 0 0.00

0.01 0.02 0.03 0.04 Engineering Strain (mm/mm)

0.05

PGM 5C (900C) y = 346 MPa UTS = 412 MPa f = 0.087

IN 617 (871C) y = 146 MPa UTS = 152 MPa f = 0.006

Haynes 230 (900C) y = 255 MPa UTS = 259 MPa f ~ 1

0.02 0.04 0.06 0.08 Engineering Strain (mm/mm)

0.10

Figure 3. Tensile property comparison of an experimental alloy (5C) to commercial Ni-based superalloys IN617 and Haynes 230 at (a) RT and (c) 871C or 900C. (b) is an enlargement of the early region of (a).

strength at elevated temperatures may justify this high cost if the alloy does not require additional environmental or thermal barrier coating (E/TBC) prior to service. Introduction of an E/TBC to either the face sheets or the core dramatically increases system complexity and expense. Also, these high-cost alloys may not make up the entire sandwich structure, but instead be used for the most demanding environmental applications. This assumes thin gage sheet and foil of a candidate alloy can be produced by conventional hot working processes, further manufactured into honeycomb core, and subsequently joined to fabricate MTPS panels. However, processing of superalloys, let alone PGM-modied superalloys, into the desired thin gages can be challenging. At present, most of the experience with PGM-modied nickel-based superalloys has been in the area of casting; relatively little has been reported on wrought processing.19,22 The processing, manufacturing and joining issues identied above are a consideration for this application as well. Research results to date include evaluating the hot working characteristics of and establishing the feasibility of near-conventional processes for producing sheet and foil products of experimental PGMmodied nickel-based superalloy compositions. Published results on one of the experimental alloys (5C) are available.23 ACKNOWLEDGEMENTS A portion of this work was conducted as part of the in-house research activities of the Metals Branch of the Air Force Research Laboratorys Materials and Manufacturing Directorate, Ceramics and NDE Division. One of the authors (ALP) was supported through Air Force Contract FA8650-07-D-5800. The support and encouragement of AFRL management and the Air Force Ofce of Scientic Research (Dr. Ali Sayir, program manager) are gratefully acknowledged. The assistance of T. Brown, J. Brown, T. Goff, A. Rosenberger, and Z. Tang with the experimental work and data analysis is much appreciated. The invaluable

mentoring and guidance provided by Lee Semiatin is acknowledged and always appreciated.
References
1. E.A. Avallone, T. Baumeister III, and A.M. Sadegh, editors, Standard Handbook for Mechanical Engineers (New York: McGraw-Hill, 2007), pp. 11104108. 2. M.L. Blosser, NASA-TM-110296 (1996), ntrs.nasa. gov/archive/nasa/casi.ntrs.nasa.gov/19970005361_ 1997005055.pdf. 3. David E. Myers, Carl J. Martin, and Max L. Blosser, AIAA Paper, 99-3459 (1999), ntrs.nasa.gov/archive/ nasa/casi.ntrs.nasa.gov/20040086853_2004091432. pdf. 4. Reusable Launch Vehicle Program Fact Sheet NASA website (September 1997), www.hq.nasa.gov/ofce/ pao/History/x-33/rlv_facts.htm. 5. Ravi C. Penmetsa, Ramana V. Grandhi, and Mark Haney, AIAA, 44 (11) (2006), pp. 26632671. 6. C.T. Sims, N.S. Stoloff, and W.C. Hagel, Superalloys II (New York: John Wiley and Sons, 1987), pp. 301310. 7. C.T. Sims, N.S. Stoloff, and W.C. Hagel, Superalloys II (New York: John Wiley and Sons, 1987), pp. 368369. 8. B. Gleeson et al., Mater. Sci. Forum, 461-464 (2004), pp. 213222. 9. S. Hayashi et al., Acta Mater., 53 (2005), pp. 3319 3328. 10. D. Pan et al., Acta Mater., 51(8) (2003), pp. 2205 2217. 11. M.P. Taylor et al., Acta Mater., 51(8) (2003), pp. 32413252. 12. T. Izumi and B. Gleeson, Mater. Sci. Forum, 522-523 (2006), pp. 221228. 13. S. Hayashi, T. Narita, and B. Gleeson, Mater. Sci. Forum, 522-523 (2006), pp. 229238. 14. G.J. Tatlock, T.J. Hurd, and J.S. Punni, Platinum Metals Rev., 31 (1987), pp. 2631. 15. D.R. Coupland, C.W. Corti, and G.L. Selman, in: Proceedings of the Petten Intl Conf. on the Behaviour of High Temperature Alloys in Aggressive Environments, ed. I. Kirman et al. (London: The Metals Society, 1980), pp. 525536. 16. C.W. Corti, D.R. Coupland, and G.L. Selman, Platinum Metals Rev., 24 (1980), pp. 211. 17. D.R. Coupland, C.W. Hall, and I.R. McGill, Platinum Metals Rev., 26 (1982), pp. 146157. 18. H. Murakami et al., Superalloys, ed. K.A. Green, T.M. Pollock, and R.D. Kissinger (Warrendale, PA: TMS, 2000), pp. 747756. 19. A.J. Heidloff et al., Metall. Mater. Trans. A, 40A (2009), pp. 15291540. 20. Platinum Today (Johnson Matthey, 40-42 Hatton Garden, London EC1N 8EE, U.K.), www.platinum. matthey.com. 21. H. Borodianska et al., Intermetallics, 10 (2002), pp. 255262. 22. H. Chang and I. Baker, Mater. Sci. Eng. A, 476 (2008), pp. 4659. 23. D.L. Ballard et al., J. Eur. Ceram. Soc., 30 (11) (2010), pp. 23052312. Donna L. Ballard, senior materials research engineer, is with the Air Force Research Laboratory, Materials and Manufacturing Directorate, AFRL/RXLM, 2230 10th Street, Wright-Patterson Air Force Base, OH 45433-7817. Adam L. Pilchak, visiting scientist at AFRL/RXLM, is a Research Scientist with Universal Technology Corporation, Dayton Ohio. Donna Ballard can be reached at (937) 255-4003; fax (937) 255-0445; e-mail donna.ballard@wpafb.af.mil.

data illustrate the higher strength of the experimental alloy than either of the commercial alloys and also indicate higher ductility than IN617. However, the PGM-modied alloy demonstrated lower ductility than Haynes 230 under both conditions. Platinum prices uctuate substantially18 with a high in early-mid 2008 at over $2,200/troy oz. and an average price for April 2010 at $1,720/troy oz. Because some of the candidate compositions being evaluated at AFRL contain a platinum content of 23 atomic percent, the material cost is not trivial. However, the inherent environmental resistance and

Donna L. Ballard and Adam L. Pilchak are TMS Members!

To read more about them, turn to page 7. To join TMS, visit www.tms.org/Society/Membership.aspx.

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Nickel-based Superalloys

Research Summary

A Combined Mapping Process for the Development of Platinummodied Ni-based Superalloys

A.J. Heidloff, Z. Tang, F. Zhang, and B. Gleeson
Heat-resistant Ni-based alloys have been used extensively for components in turbine engines for the past 50 years. Platinum group metal (PGM) alloying additions (i.e., platinum and iridium) have been found in past studies to increase the oxidation and the hot corrosion performance of Ni-based alloys. The basis for this investigation was to develop a PGM-modied superalloy having high-temperature strength, thermal stability, and excellent oxidation/ hot corrosion performance. INTRODUCTION Heat-resistant Ni-based alloys have been used extensively for components in turbine engines for the past 50 years. Components such as turbine blades and vanes have received the most attention due to the extremely harsh environments in which they operate.15 The primary approach to improve the high-temperature capability of Ni-based alloys has been to create a strong, mechanically sound alloy, with an emphasis on hightemperature creep resistance. As a result, the operating temperatures of turbine engines have increased from about 800C to 1,250C, over this period of 50 years, and the thrust of turbine engines has increased about 80 fold.4 Improvements have been accomplished through a variety of compositional, microstructural, and processing modications (e.g., single-crystal).4,5 Concomitant with the increase in mechanical properties has been a continuous increase in refractory metal content (i.e., Mo, W, Nb, Ta, Re, Ru) and an associated decrease in Cr content.3 Such changes have typically been to the detriment of oxidation resistance. Early alloy-development efforts focused on the Ni-Al-Cr-based system and showed that creep strength is direct48

ly proportional to volume fraction of the -Ni3Al precipitate phase. Accordingly, Al content was maximized within the constraint of the alloy being heat-treatable. The corresponding increase in Al content caused the thermally grown oxide (TGO) that formed on these alloys to change from being primarily Cr2O3 to being primarily Al2O3. However, subsequent increases in refractory-metal contents for the purpose of further strengthening have tended to diminish the oxidation and hot corrosion performance of Ni-based superalloys.6 The engineering solution to being able to use advanced Ni-based superHow would you
describe the overall signicance of this paper? A heat-treatable Ni-based alloy is developed that uniquely exhibits excellent resistance to both hightemperature oxidation and saltinduced hot corrosion. describe this work to a materials science and engineering professional with no experience in your technical specialty? This paper describes an efcient graphical approach that combines both experimental and computed results to arrive at an optimum composition range. describe this work to a layperson? The design of a high-temperature alloy is a complex process that typically requires a signicant amount of time and effort owing to the fact that many interrelated variables must be considered. In this study, a graphical approach is used that combines experimental results with computed predictions to efciently arrive at an alloy composition range that has an optimized set of desired hightemperature properties.

alloys has been to deposit Al-enriched coatings that are capable of forming a protective TGO of Al2O3. Such coatings typically have -NiAl as the main constituent phase.1 However, as turbine engine temperatures increase the thermal stability of the coatings becomes a primary concern.7 Moreover, -based coatings have been shown to have a lack of compatibility with the newer generation superalloys.8 Degradation of the protective coating can lead to accelerated failure of the underlying Ni-based superalloy.9 In light of these shortcomings, it would be advantageous to produce a strong base material that is intrinsically oxidation-resistant. Furthermore, applications exist where the base material cannot be coated and in these instances an alloy with mechanical strength and oxidation resistance is needed. However, further alloy development must be made in order to produce an Ni-based superalloy that best fullls the unique combination of properties required for coatingless applications. Platinum group metal (PGM) alloying additions of platinum (Pt) and iridium (Ir) have been found in past studies to increase the oxidation and the hot corrosion performance of Ni-based alloys.1016 There are undoubtedly increased costs associated with producing an alloy containing such elements; however, the omission of processing steps, in this instance the application of an oxidation-resistant coating, may counter the high cost associated with the use of a PGM. Past studies that considered PGM modication of existing Ni-based alloys focused primarily on oxidation and hot corrosion behavior with little regard to alloy microstructure and stability. Only recently have the effects of Pt and Ir alJOM October 2010

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loying additions on -Ni3Al precipitate microstructure been reported.1719 The data that exist indicate that modication of existing state-of-the-art alloys with an element like Pt can seriously affect the microstructure in detrimental ways. Indeed, accounting for the presence of a PGM during the early stages of alloy development allows for judicious alloying to tailor the microstructure and associated thermal stability. The basis for this investigation was to develop a PGM-modied superalloy having high-temperature strength, thermal stability, and excellent oxidation/ hot corrosion performance. This paper will distill the important aspects stemming from this investigation. It became apparent during the course of this investigation that two alloying elements in particular, Pt and Cr, were responsible for most of the changes observed in both the surface (i.e., oxidation and hot corrosion) and microstructure (i.e., heat-treatability and phase stability) aspects of the alloy development. As a result, Pt vs. Cr composition space will be used to encompass, describe, and summarize the key performance areas of a fully alloyed Nibased superalloy having the base composition Ni-13Al-1Re-2Ta-2W-2Ru0.1Hf, which will be used throughout. All compositions stated herein will be given in atomic percent. RESULTS Oxidation It was found in this investigation that additions of Re, W, and Ru were all detrimental in promoting the formation of an exclusive thermally grown Al2O3 scale. This has also been reported by other investigators.2023 Such a negative effect is believed to arise for multiple reasons, including: reduced Al diffusion through cross-term interactions; increased oxygen permeability of the alloy; and non-protective oxide formation. It was also found in this investigation that Ta tends to be less detrimental compared to Re, W, and Ru. In fact, Ta appeared to be benecial in reducing the oxidation rate when exclusive Al2O3 formation was able to occur. In order to negate these refractory-element effects it was determined that a critical Cr content was necessary to faVol. 62 No. 10 JOM

cilitate formation of an exclusive Al2O3 scale. Two alloys of the base composition with 2.5 at.%Pt (Ni-13Al-2.5Pt1Re-2Ta-2W-2Ru-0.1Hf) and either 5 or 10 at.% Cr were isothermally oxidized at 1,000C for 100 h. The resulting cross-sectional images in Figure 1 clearly show that, even with 2.5 at.% Pt in the alloy, a critical amount of Cr was necessary to suppress non-protective oxide scale formation. To elucidate, if Pt is necessary if sufcient Cr is present in the alloy, two alloys of the base composition with 10 at.% Cr and either 0 or 2.5 at.% Pt were cyclically oxidized at 1,000, 1,150, and 1,200C for 750 cycles. Each cycle consisted of 1 h at temperature and 0.5 h at about 70C. The measured weightchange kinetics summarized in Figure 2 show the benets of Pt addition in reducing scale spallation, which is manifested as a weight loss. Hou et al.24 recently reported the benets of Pt addition in improving Al2O3-scale adhesion on Hf-modied -Ni + -Ni3Al model alloys. This improvement is apparently additive with what can be provided by Hf, which is known to aid in scale adhesion.25 Thus, the ways in which Pt and Cr affected oxidation behavior of the base alloy were found to be quite different. The addition of Cr aided the short-term oxidation behavior by facilitating the establishment of a continuous Al2O3 scale, while the Pt primarily served to maintain the scale during thermal cycling. Hot Corrosion Hot corrosion is a molten-salt induced attack whereby acidic or basic uxing of the protective oxide scale occurs, depending on the salt chemistry. Hot corrosion is an extremely aggressive mode of attack and has become of increasing concern as the operating temperatures of turbine engines increase. So-called Type I hot corrosion tests were performed at 900C for a total of 100 h, with Na2SO4 applied to the alloy coupons every 20 h. The test atmosphere was a continuous ow of O2+0.1 vol.% SO2 that passed through a platinized honeycomb catalyst to give an equilibrium partial pressure of SO3. Similar to the oxidation tests, two alloys of a base composition (Ni-13Al10Cr-1Re-2Ta-2W-2Ru-0.1Hf) and eiwww.tms.org/jom.html

b Figure 1. Cross-section BSE SEM images of isothermal oxidation at 1,000C for 100 h for base composition Ni-13Al2.5Pt-1Re-2Ta-2W-2Ru-0.1Hf with (a) 5Cr and (b) 10Cr showing the dramatically increased oxidation resistance with increased Cr content.

ther 0 or 2.5 at.% Pt addition were tested. The results are presented in Figure 3, where it is seen that the benecial effect of Pt addition is quite dramatic. This is true even though both alloys contained 10 at.% Cr, an element that is well known for increasing hot corrosion resistance. This result gives a clear indication that the presence in Pt is profound for imparting Type I hot corrosion resistance to the alloy. The mechanism by which Pt improves hot-corrosion resistance is currently not completely understood. Pt and Cr Composition Space for Oxidation and Hot Corrosion Base alloys containing 2.5 at.% Pt and 10 at.% Cr were found to have good resistance to cyclic oxidation up to 1,200C and Type I hot corrosion resistance. The addition of 10 at.% Cr facilitated the early formation of an exclusive Al2O3 scale, while the presence of Pt maintained the scale during thermal cycling. Additionally, the presence of Pt resulted in signicantly improved resistance to Type I hot corrosion. These and other results allowed for the mapping of oxidation and hot corrosion resistances in Pt vs. Cr composition space, as shown in Figure 4. The shaded regions in this
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gure correspond to good resistance to a given mode of degradation. Solutionizing Heat-Treatment Window One of the most difcult hurdles during the alloy design process proved to be the heat-treatment window size when considering a Pt-modied superalloy. The heat-treatment window is dened as the temperature range between the -Ni3Al solvus and the -Ni solidus where the alloy can be single-phase solutionized. As discussed elsewhere,19 Pt can radically change the morphology by changing the lattice parameter. But just as importantly, Pt has also been shown to decrease the -Ni solidus, while at the same time, stabilizing the -Ni3Al solvus to higher temperatures.26 These trends can result in large changes in the heat-treatment window. Considering the melting temperatures of stoichiometric Ni3Al (1,372C)27 and Pt3Al (1,556C),28 an increase in the -Ni3Al stability temperature with increasing Pt content is plausible. The thermodynamic software package PANDAT29 was used in this study to predict the shifts in the relevant phase-boundaries with increasing Pt and Cr contents. The base composition of Ni-13Al-1Re-2Ta-2W-2Ru-0.1Hf was used to construct an array of Cr and Pt compositions ranging from 010 at.%, with increments of 2 at.%, for each element. The temperature difference between the -Ni solidus and the -Ni3Al solvus (i.e., heat-treatment window) from each PANDAT prediction was then used to create the contour plot

shown in Figure 5. The contours shown in Figure 5 are increments of 10C. The regions of purple and blue have heat-treatment windows greater than 50C, which is the value selected as being the minimum that is acceptable from the standpoint of commercial practice. Heat-treatment window values below this minimum are deemed too narrow to allow for variations in the furnace temperatures and would result in either insufcient solutionizing or incipient melting. The area outlined in red incorporates the preferred region of heat-treatment windows. It is readily seen by the predictions summarized in Figure 5 that the use of Cr did not signicantly change the heat-treatment window, as the contours run relatively parallel with increasing Cr content. However, Pt was shown to greatly reduce the heat-treatment window at ~10C/at.% Pt added. This is in excellent agreement with heattreatment window measurements determined by DTA on two model alloys in which it was found that the addition of 2.5 at.% Pt (from 2.5 to 5 at.%) decreased the heat-treatment window by 23C, or 9.2C/at.% Pt added.19 This signicant effect of Pt is a reason why Pt modication of existing alloys is problematic. -Ni3Al Volume Fraction and Phase Stability Other than the heat-treatment window, a major obstacle to overcome in developing a Pt-modied superalloy is reducing the lattice mist through decreasing the -Ni3Al lattice parameter. Platinum greatly expands the -Ni3Al

lattice parameter due to its substitution on the Ni sublattice, and the strong partitioning of Pt to the -Ni3Al phase only exacerbated this effect. At the same time, Pt-modication was not found to greatly inuence the partitioning of other elements present in the system. Elements such as Cr, Re, W, Ru, and Ta all showed partitioning trends similar to those in PGM-free superalloys. From an alloy development standpoint, this enabled the use of pre-existing databases for PGM-modied superalloys. Figure 6 summarizes the PANDATpredicted variation in volume fraction at 1,050C with varying amounts of Pt and Cr in the base composition.

b Figure 3. Cross-section BSE SEM of Type I hot corrosion under O2-0.1SO2 (vol.%) for 100 hours for Ni-13Al-10Cr1Re-2Ta-2W-2Ru-0.1Hf (a) without and (b) with 2.5Pt. 10 8 Cr Content (at. %) 6 4 2 0 0 2 Hot Corrosion Oxidation

Figure 2. Cyclic oxidation weight gains at 1,000, 1,150, and 1,200C for a base composition Ni-13Al10Cr-1Re-2Ta-2W-2Ru0.1Hf with and without 2.5Pt showing the increased spallation resistance with the addition of Pt.

4 6 8 10 Pt Content (at. %) Figure 4. Regions of high resistance to cyclic oxidation (up to 1,200C) and hot corrosion (Type I) for varying amounts of Pt and Cr for a base composition of Ni13Al-1Re-2Ta-2W-2Ru-0.1Hf.

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The composition space selected is the same as that used for the prediction of the heat-treatment windows (Figure 5). The color contours in Figure 6 represent ~1.0 vol.% changes in volume fraction. Such a sensitive plot was made because it is known that creep rupture life is extremely sensitive to volume fraction.30 The plot shows that, for a xed Pt content, the volume fraction increases with increasing Cr content up to approximately 8 at.%. A maximum volume fraction is observed at this level and further additions of Cr result in a decrease in volume fraction due to new phase formation (i.e., -NiAl and the TCP - and -phases). This change in phase constitution with increased Cr is well documented in MCrAlY-type coatings, which at high temperature have a + microstructure as a result of the high Cr content.31 Also, the Cr content was observed to have a large effect on the presence of TCP phases,
10

Cr Content (at.%)

which is in accordance with the newer generation superalloys having relatively low Cr contents to avoid TCP phase formation.32 The region of optimum volume fraction and equilibrium phase stability, outlined in orange on Figure 6, was determined by the need to avoid the presence of detrimental phases (e.g., lower Cr) and to minimize the -Ni3Al lattice parameter expansion (e.g., lower Pt). This allows for a stable + two-phase microstructure with long-term stability. Therefore, high Cr alloys (10 at.% Cr) should be used with caution since longterm phase stability may be an issue. Despite these cautions, superior oxidation and hot corrosion resistance is still being pursued with the use of high-Cr superalloys with careful alloying.33 Experimental Observations In order to conrm the PANDAT predictions in Figure 6 the bulk struc-

10 8 Cr Content (at.%) 6 4 2 0 0 2 Phase Stability

4 6 8 10 Pt Content (at.%) Figure 7. Shaded region showing what the PANDAT software predicts as a high volume fraction with no TCP phase formation. Markers indicate experimental alloys within the Pt and Cr composition space. 10 8 6 4 2 0 0 2 Phase Stability

8 Cr Content (at.%)

Cr Content (at.%)

90C 80C 70C 60C 50C 40C 30C 20C 10C

4 6 8 10 Pt Content (at.%) Figure 8. Change in + phase stability region with experimental results suggesting that the addition of Pt suppresses the formation of TCP phases at 1,000C. 10 8 6 4 Heat-Treatability 2 0 0 2 Phase Stability

4 Figure 5. PANDAT predicted heat-treatment windows for an array of Pt and Cr compositions with a base composition of Ni-13Al-1Re-2Ta-2W2Ru-0.1Hf. 0 10
53% 52% 51% 50% 49% 48% 47% 46% 45% 44%

0 2 4 6 Pt Content (at. %) 8 10

4 6 8 10 Pt Content (at.%) Figure 9. Region of optimum heat-treatability (>50C) and large volume fraction of with high phase stability with varying amounts of Pt and Cr for a base composition of Ni-13Al-1Re-2Ta-2W-2Ru-0.1Hf. 10 Cr Content (at.%) 8 6 4 Heat-Treatability 2 4 6 8 10 Pt Content (at.%) Figure 10. Region outlined in yellow with a composition space of ~24 at.% Pt and ~810 at.% Cr where all required properties are present for a base composition of Ni-13Al-1Re-2Ta-2W-2Ru-0.1Hf. 0 0 2 Phase Stability Hot Corrosion Oxidation

8 Cr Content (at.%)

0 0 2 4 6 Pt Content (at.%) 8 10

Figure 6. Plot of changes in the volume fraction with respect to Pt and Cr content. Contours represent 1.0 vol.% .

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Figure 11. SEM BSE micrograph of Ni-13Al-2.5Pt-10Cr-1Re-2Ta-2W-2Ru0.1Hf as heat-treated showing typical two-phase + microstructure.

tures of the two experimental alloys of the base composition (Ni-13Al-1Re2Ta-2W-2Ru-0.1Hf) having 10Cr and 10Cr-2.5Pt were analyzed after longterm exposures at 1,000, 1,150, and 1,200C. The results are shown as yellow dots on Figure 7. At 1,000C the 2.5Pt alloy showed small amounts of TCP formation along grain boundaries after 750 hours. The precipitates were unidentied, but through semi-quantitative analysis, were believed to be the P or R phase. Calculations also predict phase at temperatures of less than about 1,000C.34 The precipitates were blocky in morphology and their presence on the grain boundaries is in agreement with Wang et al.,36 who found the same morphology of Re and Cr-rich TCP on the grain boundaries after 20 hours. The Pt-free alloy showed signicantly more TCP phase formation than the Pt-containing alloy when exposed to 1,000C. There were two distinct TCP phases in the Pt-free alloy. The same P or R phase was present at the grain boundaries in an irregular blocky shape and in higher concentration than the 2.5Pt alloy. In addition there was a signicant amount of needle- or plate-like TCP phase throughout the interior of the grains. The needle- or plate-like precipitates had a composition of around Ni-12Cr11Hf-8Re-3Ru. The lower Cr and Re contents suggest the -phase, however, would be in disagreement with Rae et al.,34 who reported that the TCP phases do not contain any measurable level of Hf. At 1,200C, the 2.5Pt alloy showed no signs of TCP phase formation within the grains or at the grain boundaries. This was not surprising, as the time-temperature-transition curves developed for
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TCP formation indicate that at temperatures near or above 1,200C the formation of TCP is sluggish due to a higher solubility of the refractories.34,36 The Ptfree alloy showed signs of secondaryphase formation at 1,200C. The phase present at 1,200C was morphologically different from those found at 1,000C, as they were not present at the grain boundaries and were uniformly distributed throughout the + microstructure having a blocky morphology and a composition near Ni-80Hf-2Cr. These results suggest that the addition of Pt stabilizes the + microstructure at 10 at.% Cr over long-term thermal aging at temperatures associated with the precipitation of TCP phases. Figure 8 shows the change in + phase stability region with variations in Pt and Cr contents and with the experimental results of Pt-free (red data point) and 2.5 at.% Pt (green data point) as a guide for determining the phase stability boundary. The use of the experimentally modied phase stability region overlaid with the PANDAT-assisted heat-treatment window assessment allows one to nd a composition range of Pt-modied superalloys where both structural stability and heat-treatability are within the realm of being practically viable. This region is established in Figure 9. As mentioned in the Introduction, this project was aimed at developing an alloy with both microstructural and mechanical properties similar to those of traditional Ni-based superalloys, while also possessing excellent oxidation and hot corrosion properties. Since nearly all superalloy developments have focused on the mechanical aspects and Pt-modication studies have focused on oxidation and hot corrosion aspects, much of this investigation was focused on opposing aspects to nd suitable compositions for all metrics. By utilizing the empirically determined oxidation/hot corrosion Pt vs. Cr plots and overlapping them with the empirical/predicted microstructural Pt vs. Cr plots, a region where all metrics overlap would dene a composition space where the microstructural stability is suitable for Ni-based superalloys with increased oxidation and hot corrosion resistance. This nal plot is shown in Figure 10, where a region of 24 at.% Pt and 710 at.% Cr is deemed
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optimum. This region of composition space, as mentioned, was for a base composition of Ni-13Al-1Re-2Ta-2W2Ru-0.1Hf. This allows for tailoring the microstructure through additions of strengthening elements to result in the proper lattice mist and phase stability while maintaining the oxidation and hot corrosion resistances of a protective coating. The star indicating a composition of Ni-13Al-2.5Pt-10Cr-1Re-2Ta2W-2Ru-0.1Hf has been tested and has been found to meet or exceed predicted performance.19 These performances are its ability to be an Al2O3 former (Figure 1) with high cyclic spallation resistance (Figure 2) and excellent Type I hot corrosion resistance (Figure 3). In addition, it has sufcient heat-treatability and phase stability (Figure 9) along with a typical + microstructure (Figure 11). CONCLUSIONS The development of PGM-modied Ni-based superalloys with respect to enhancing the oxidation and hot-corrosion performance, while maintaining the microstructural properties consistent with commercial Ni-based superalloys, has been summarized. While the mechanical properties of the PGM-modied alloys were not directly measured in this investigation, a wealth of knowledge concerning the relationship between the oxidation/hot corrosion and microstructure properties of Ni-based superalloys have been attained. During the course of this investigation, two elements in particular were found to have the most profound impact on both the oxidation/hot corrosion and microstructure. These two elements were Pt and Cr. As strengthening elements detrimental to oxidation were increased in quantity, the overall amount of Cr needed for exclusive Al2O3 formation was determined to be ~10 at.%. 2.5 at.% Pt was determined to be sufcient for increasing the oxide scale adherence and increasing the hot corrosion resistance. The regions of optimum resistance to hot corrosion and cyclic oxidation are shown in Figure 4. From a microstructural perspective, Pt was found to be detrimental by reducing the heat-treatment window available for single-phase solutionizing treatments by both increasing the -Ni3Al solvus temperature and decreasing the
JOM October 2010

-Ni solidus temperature. The volume fraction did not increase with increasing Pt content. Cr did not drastically change the heat-treatment window but could lead to the precipitation of TCP phases. Pt also was found to suppress the precipitation of a previously unobserved Hf-rich, high-aspect-ratio TCP phase at 1,000C for 10 at.% Cr (higher order) compositions. Another TCP phase was present in both Pt-containing and Ptfree alloys at the grain boundaries, but in reduced quantities for the Pt-containing alloy. At 1,200C the Pt prevented all TCP phases while the Pt-free alloy contained an Hf-based precipitate. The optimum heat-treatment window and volume fraction/phase stability regions were combined, as shown in Figure 9. Combining all of the mapped data (Figure 10) denes the optimum Pt-Cr composition space that can be utilized for a complex Ni-based superalloy to have the combination of desired properties including oxidation (Figure 1), thermal cycling resistance (Figure 2), hot corrosion resistance (Figure 3), heattreatability (Figure 5), and two phase + stability (Figure 8 and Figure 11) as shown throughout. ACKNOWLEDGEMENTS Thanks are given to D. Ballard of Wright-Patterson Air Force Base (WPAFB) and A. Bolcavage and R. Helmink of Rolls-Royce Corporation for their input and comments. This work was supported through the Versatile Advanced Air Turbine Engine (VAATE)

program of Liberty-Works in conjunction with WPAFB.

References
1. M. McLean, Phil. Trans. R. Soc. A., 351 (1995), pp. 419433. 2. T.M. Pollock and S. Tin, J. Propulsion and Power, 22 (2006), pp. 361374. 3. R.C. Reed, The Superalloys Fundamentals and Applications (Cambridge, U.K.: Cambridge University Press, 2006). 4. C.T. Sims, N.S. Stoloff, and W.C. Hagel, Superalloys II (New York: John Wiley & Sons, 1987). 5. M.J. Donachie and S.J. Donachie, Superalloys A Technical Guide (Materials Park, OH: ASM International, 2002). 6. R. Darolia, Advanced Oxidation Resistant Superalloy Workshop (Dayton, OH: Wright-Patterson AFB, 2006). 7. T. Narita, K.Z. Thosin, L. Fengqun, S. Hayashi, H. Murakami, B. Gleeson, and D. Young, Materials and Corrosion, 56 (2006), pp. 923929. 8. J.D. Nystrom, T.M. Pollock, W.H. Murphy, and A. Garg, Metall. Mater. Trans. A, 28A (1997), pp. 24432452. 9. B. Gleeson, J. Propulsion and Power, 22 (2006), pp. 375383. 10. E.J. Felten, Oxidation of Metals, 10 (1976), pp. 2328. 11. C.W. Corti, D.R. Coupland, and G.L. Selman, Platinum Metals Review, 24 (1980), pp. 211. 12. D.R. Coupland, C.W. Hall, and I.R. McGill, Platinum Metals Review, 26 (1982), pp. 146157. 13. G.J. Tatlock and T.J. Hurd, Oxidation of Metals, 22 (1984), pp. 201226. 14. G.J. Tatlock, T.J. Hurd, and J.S. Punni, Platnium Metals Review, 31 (1987), pp. 2631. 15. G.J. Tatlock and T.J. Hurd, Werkstoffe und Korrosion, 41 (1990), pp. 710715. 16. B. Gleeson, W. Wang, S. Hayashi, and D. Sordelet, Materials Science Forum, 461-464 (2004), pp. 213 222. 17. A.J. Heidloff, T. Izumi, and B.M. Gleeson, Metallurgical and Materials Transactions A, 40 (2009), pp. 15291540. 18. J.S. Van Sluytman, A. Suzuki, A. Bolcavage, R.C. Helmink, D.L. Ballard, and T.M. Pollock, Superalloys 2008, ed. R.C. Reed et al. (Warrendale, PA: TMS, 2008), pp. 499508. 19. A.J. Heidloff. Development of Pt-modied -Ni+Ni3Al-based Alloys for High-temperature Applications (Ph.D. Thesis. Iowa State University, 2009). 20. M. Moniruzzaman, M. Maeda, Y. Murata, and M.

Moringa, ISIJ International, 43 (2003), p. 386. 21. L. Huang, X.F. Sun, H.R. Guan, and Z.Q. Hu, Surface and Coatings Technology, 200 (2006), p. 6863. 22. K. Kawagishi, A. Sato, T. Kobayashi, and H. Harada, Materials Science Forum, 522-523 (2006) pp. 317 322. 23. Q. Feng, B. Tryon, L.J. Carroll, and T.M. Pollock, Materials Science and Engineering A, A458 (2007), pp. 184194. 24. P.Y. Hou, T. Izumi, and B. Gleeson, Oxidation of Metals, 72 (2009), pp. 109124. 25. B.A. Pint, Surface Coatings and Technology, 188189 (2004), pp. 7178. 26. H. Murakami, T. Honma, Y. Koizumi, and H. Harada, Superalloys 2000, ed. K.A. Green, T.M. Pollock, and R.D. Kissinger (Warrendale, PA: TMS, 2000), pp. 747756. 27. H. Okamoto, J. Phase Equilibrium, 14 (1993), p. 257. 28. Y. Oya, Y. Mishima, and T. Suzuki, Z. Metallkd., 78 (1987), p. 485. 29. CompuTherm LLC. PanNickel Database (2009), www.computherm.com. 30. H. Harada, M. Yamazaki, Y. Koizumi, N. Sakuma, N. Furuya, and H. Kamiya, High Temperature Alloys for Gas Turbines 1982 (Jluch, Germany: Forschungszentrum Jluch, 1982). 31. G.W. Goward, Materials Science and Technology, 2 (1986), pp. 194200.. 32. R. Darolia, D.F. Lahrman, R.D. Field, and R. Sisson, Superalloys 1988, ed. D.N. Duhl et al. (Warrendale, PA: TMS, 1988), pp. 255264. 33. Y. Murata, R. Hashizume, A. Yoshinari, N. Aoki, M. Morinaga, and Y. Fukui, in Ref. 26, pp. 285294. 34. C.M. Rae, M.S. Karunaratne, C.J. Small, R.W. Broomeld, C.N. Jones, and R.C. Reed, in Ref. 26, pp. 767776. 35. W.B. Wang, Q. Feng, L.J. Carroll, Y.L. Wang, G.L. Chen, and T.M. Pollock, Materials Science Forum, 546549 (2007) pp. 12071210 36. R. Darolia, D.F. Lahrman, and R.D. Field, in Superalloys 1988, ed. S. Reichman et al. (Warrendale, PA: TMS, 1988), pp. 255264. A.J. Heidloff and Z. Tang are with the Department of Materials Science and Engineering, Iowa State University, Ames, IA; F. Zhang is with CompuTherm, LLC, Madison, WI; and B. Gleeson is with the Department of Mechanical Engineering and Materials Science, University of Pittsburgh, Pittsburgh, PA. Dr. Heidloff can be reached at aheidloff@gmail. com.

A.J. Heidloff is a student member and F. Zhang and B. Gleeson are full members of TMS!
To read more about them, turn to page 7. To join TMS, visit www.tms.org/Society/Membership.aspx.

Modeling of Casting, Welding, and Advanced Solidication Processes XII (MCWASP XII)
by Steve L. Cockcroft and Daan M. Maijer These proceedings encapsulate the progress made in modeling casting processes and liquid-solid phase transformations over the years. The papers presented provide a clear picture of the modeling activities for processes involving solidication, covering continuous casting, welding, remelting, semi-solid, and shape and ingot casting processes. Other topics related to casting technologies, such as liquid metal treatment and casting tools (e.g., mold manufacturing and life time), are also examined. These proceedings bring together leading academic research that brings up to date information from the industry. Classical studies of structure and segregation formed upon solidication as well as new in-situ observation techniques are addressed. A collection of papers from the 12th International Conference held in Vancouver, British Columbia June 7th-14th, 2009.

For more information visit: http://knowledge.tms.org/books.aspx.

Meetings Calendar

Presenting upcoming meetings and calls for papers

Symposia Proposals and Abstract Submissions: For TMS-sponsored meetings, symposia proposals and abstracts must be submitted through ProgramMaster, the on-line TMS conference and proceedings management system. The system can be accessed at www.tms.org. Using the Meetings & Events pulldown menu, select the Upcoming TMS Meeting for which you wish to submit a symposia proposal or an abstract, and follow the on-line instructions. The society especially encourages the submission of hot-topic symposia or special-session proposals on timely or developing subjects. To advance an idea, use the symposium creation form in ProgramMaster. Additional information can be acquired from the TMS Technical Support Services Department, 184 Thorn Hill Road, Warrendale, PA 15086; (724) 776-9000, ext. 212; fax (724) 776-3770.

MS&T 2010
October 1721, 2010 Houston, Texas The Materials Science & Technology (MS&T) annual conferences are hosted by four leading materials societies: ACerS, AIST, ASM, and TMS. This partnership brings together scientists, engineers, students, and suppliers to discuss current research and applications, and to shape the future of materials science and technology. Since corrosion has become a very relevant topic to materials, NACE International will cosponsor MS&T10. Papers presented will address structure, properties, processing and performance across the materials community. MS&T10 addresses eight diverse themes to cover the breadth of materials science and engineering: Biomaterial Technology, Ceramic and Glass Materials, Corrosion Control and Sustainability, Electronic and Magnetic Materials, Environmental and Energy Issues, Fundamentals and Characterization, Iron and Steel, Materials Performance, Nanotechnology, Processing and Product Manufacturing, and Special Topics. A plenary session will feature Energy, Infrastructure, Policy and Security by Terry Michalske, Director of Savannah River Nuclear Solutions, LLC. Michalske and Robert T. McGrath, Deputy Laboratory Director, Science and Technology, at National Renewable Energy Lab, will be available for discussion after Michalskes lecture. Contact: TMS Meeting Services, TMS, 184 Thorn Hill Road, Warrendale, PA 15086; (724) 776-9000, ext. 243; e-mail: mtgserv@tms.org; matscitech.org/.

Structures (ISUGS), and the International Conference on Advanced Structural Steels (ICASS). The scope of the conference will promote the development of advanced steels and cover almost every aspect of steel, including physical metallurgy, steel and alloy products, steel processing and fabrication, steel design and modeling, performance of steels, and applications of steel products. Contact: Su Liu, Central Iron and Steel Research Institute, 76 Xue Yuan Nan Lu, Beijing 100081, China; 86-10-6218-5204; email: icas2010@nercast.com; www.nercast .com/icas2010/home.html.

TMS 2011 Annual Meeting

February 27March 3, 2011 San Diego, California Materials science and engineering professionals hailing from more than 68 countries will gather February 27 to March 3 in San Diego to network, present research, share industrial applications, and introduce innovation. This blend of academic, technical, business, and social elements creates the perfect synergy to move research and development forward to produce applications that fuel global solutions. Technical themes for the 140th TMS Annual Meeting include advanced characterization, modeling, and materials performance; aluminum and magnesium; high performance materials; materials and society: energy and sustainable production; materials and processing; nanoscale and amorphous materials; and professional development. Complementing the technical program will be: over 70 unique symposia hosting 3,000 presentations; symposia-specic networking sessions; a dynamic selection of student events and programming; 200 special lectures, keynotes, invited and plenary talks; world-class TMS 2011 Exhibition; and more than 300 posters on display. Also featured will be short courses, tutorial lectures, award presentations, receptions and division luncheons. Celebrating the 25th Anniversary of the TMS Annual Meeting Exhibition, the 2011 event will bring together nearly 4,000 industry leaders, buyers, engineers, scientists, and researchers who are eager to explore new technology, emerging trends, and the latest products and services in the materials technology industry. Contact: TMS Meeting Services, 184 Thorn Hill Road, Warrendale, PA 15086; (724) 776-9000, ext. 243; e-mail: mtgserv@ tms.org; www.tms.org/meetings/annual-11 /AM11home.aspx.

Arctic Technology Conference (ATC)

February 79, 2011 Houston, Texas The Houston-based Offshore Technology Conference is adding a new conference to its portfolio of events. The OTC model, which brings together a dozen professional societies and associations to create a comprehensive technical conference, will serve as the basis for the new event. OTCs new Arctic Technology Conference is managed by the American Association of Petroleum Geologists. Program highlights include: a plenary session Addressing Arctic Aspirations and Rejuvenating Arctic Exploration: Less Ice, More Hydrocarbons; 130 oral sessions from a dozen countries with topics including pipelines, geohazards, icebreaking and shipping, vessels, ice loads, regulatory topics, and more; 17 posters; 2 topical breakfasts, 4 topical luncheons, and a lunch in the Exhibit Hall; and an exhibition featuring suppliers and the latest technologies available for the Arctic. Contact: Terri Duncan, American Association of Petroleum Geologists, 1444 South Boulder Avenue, Tulsa, OK 741193604; (918) 560-2641; e-mail: tduncan@ aapg.org; www.arctictechnologyconference .org/index.cfm.

International Conference on Advanced Steels 2010 (ICAS 2010)

November 911, 2010 Guilin City, Guangxi, China ICAS 2010 is the merging of the International Symposium on Ultrane Grained

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JOM October 2010

MATERIALS RESOURCE CENTER: Positions Available

TENURE-TRACK FACULTY POSITION
School of Materials Science and Engineering Clemson University, Clemson, S. C. 29634
The School of Materials Science and Engineering at Clemson University is seeking an outstanding candidate to ll a tenure-track position at the Assistant Professor level. It is expected that the candidate will be capable of establishing a high quality research program that coincides with one or more of the following areas: metallurgy, ceramics, optical/electronic materials, and computational materials science. However, the School will also consider exceptional candidates whose research aligns with Clemson Universitys strategic emphasis areas which include energy and automotive innovation. Candidates must hold a doctoral degree in Materials Science and Engineering or a related discipline, have demonstrated a record of prior research accomplishments and shown the potential to educate and mentor students. Successful candidates will be expected to attract signicant external funding, lead nationally recognized research programs, and be able to collaborate with current faculty both within MSE and the University as a whole. In addition, the candidate must demonstrate the potential to teach both undergraduate and graduate courses, particularly those focused on aspects of metallurgy and ceramics. All applications should be submitted electronically. Qualied applicants should provide: 1) a current CV; 2) research statement describing a minimum of two externally fundable research programs and also highlighting complimentary capabilities to existing faculty and programs (2-6 pages; for current faculty research areas, please refer to http://www.clemson.edu/mse/People/Faculty. htm); 3) a description of teaching philosophy including undergraduate and graduate course competencies and how they would t into the present academic programs (1-2 pages); and 4) names and contact information for three references. The application package should be combined into a single PDF le and emailed to: msesearch@clemson.edu. Questions can be sent via email to Dr. Jian Luo, Chair of the MSE Search and Screening Committee (jianluo@clemson.edu; no phone calls please). Review of applications will commence November 1st, 2010 with full consideration being assured to applications received by this date. Screening will continue until the position is lled. Women and minorities are especially encouraged to apply.
Clemson University is an Afrmative Action/Equal Opportunity employer and does not discriminate against any individual or group of individuals on the basis of age, color, disability, gender, national origin, race, religion, sexual orientation, veteran status or genetic information.

Another TMS Member Benet: Materials Technology@TMS

www.materialstechnology. tms.org/TECpage.asp Your resource for technology overviews, news stories, downloadable resources, and links.
IVE SPECIALIZED FOR 31 YEARS
in the placement of Metallurgical, Materials, and Welding Engineers in the areas of R&D, Q.C. Production, Sales & Marketing, nationwide. My background as a Met. Eng. can help you! Salaries to $190K. Fees paid by Co. Call/Send/E-mail Resume: Michael Heineman, Meta-Find, Inc.; P.O. Box 610525, Bayside, NY, 11361; Phone (212) 867-8100; E-mail mikeh@meta-ndny.com; Web: www.meta-ndny.com

Meetings and Workshops

FRAY INTERNATIONAL SYMPOSIUM
December 4-7, 2011 * Cancun, Mexico

Incorporating three international symposia: Advanced Sustainable Iron and Steel Making Sustainable Non-Ferrous Smelting in 21st Century Molten Salts and Ionic Liquids 2011 Visit www.flogen.com/FraySymposium for additional details.

and Derivatives
625 718 706
PWA 1472 Ren 220 C263 718 Plus

Attend the 7th International Symposium on Superalloy 718 & Derivatives, October 10-13, 2010, Pittsburgh, Pennsylvania. Save $100 off on-site registration by joining TMS! Visit www.tms.org/Meetings/ Specialty/Superalloys2010 to learn more.
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725

625 Plus
Waspaloy Ren 41

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Join the ultimate discussion on all aspects of alloy and process development.
Vol. 62 No. 10 JOM

End Notes

Materials science and engineering in our community

Get Involved: Robert E. Hackenberg, Technical Committee Chair

Kelly Zappas
Get Involved is a recurring End Notes feature that spotlights the work of TMS volunteers and shows the wide range of activities available through TMS. This month, Robert E. Hackenberg, R&D scientist at Los Alamos National Laboratory and chair of the TMS Phase Transformations Committee, discusses his role as a TMS technical committee chair. Q. What was your rst volunteer role with TMS? How did you get involved? A. Early in my career, I was asked to be a symposium session chair at several TMS Annual Meetings. I learned that this was a good opportunity to network, especially at Authors Coffee, which helped me put names to faces. Q. How did you become involved in the Phase Transformations Committee (PTC)? Did you have to work your way up to serving as committee chair? A. My mentor invited me to join the PTC just after I started my postdoctoral work at Los Alamos National Laboratory in 2001. I was aware of the PTC since its members had organized and published several key symposia that I had gotten to know while doing literature searches in graduate school. In fact, I presented and published my rst major paper at a PTC-sponsored symposium. Once on the PTC, I served as the lead organizer for a symposium held in 2004. Since conference programming is the major activity of the PTC, this experience helped lead to my election as vice-chair (2006) and then chair (2008). Q. What kind of work is involved in chairing a TMS technical committee? A. The organizational work involves preparing for and chairing the twiceyearly PTC meetings, and periodically reminding people of action items, deadlines, new opportunities, etc. The technical aspect involves working with committee members to nucleate and grow new ideas (for symposia, etc.) and see them through to maturation. As the chair, you are always on the lookout to make connections and realize synergies between different ideas, technical committees, communities of interest, etc. Bringing in new committee members and helping them ourish has been one of the most rewarding aspects of this leadership role. Q. How much time do you commit to your activities as a committee chair? Is it difcult to balance your work and your volunteer responsibilities? A. The total effort required is not large, but it is needed in short, concentrated spurts right before and after our meetings. My two years spent as vice-chair gave me a good feel for the yearly rhythm of committee activity, so once I became chair I did not have much of a problem balancing my daily work and
If you want to get involved with a TMS technical committee, visit members.tms.org /admin.html and click on the Committee Home Pages link to nd the TMS technical committee that best suits your interests. Log in to the site for information on how to contact committee members and inquire about upcoming events and activities. If you know of a TMS member who should be featured in a future Get Involved column, contact Kelly Zappas at kzappas@tms.org.

these volunteer responsibilities. Q. Do you do any other volunteer work with TMS? A. I am a Key Reader for Metallurgical and Materials Transactions A. This is a rewarding activity that helps me keep informed of developments in the eld. Q. How has volunteering with TMS helped you professionally? A. Being in the thick of things as PTC chair has helped me stay abreast of the latest advances in my own specialty, phase transformations. My exposure to a wider range of technical ideas and a broader community of scientists has had positive impacts for my job and longer-term career goals. Q. What advice would you give to a new TMS member who was hoping to become more involved in society activities? A. You should identify a TMS committee that interests you. One shortcut is to nd the sponsoring committee for symposia that have particularly interested you; this is usually listed in the conference program. Or go to the committee homepages on the TMS website; if you log in as a TMS member, you can view the roster, view past meeting minutes, and contact the committee chair.
Kelly Zappas is a contributing writer for TMS.

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JOM October 2010

REWAS 2008: Global Symposium on Recycling, Waste Treatment and Clean Technology
by B. Mishra, C. Ludwig, and S. Das, editors
The 2008 Global Symposium on Recycling, Waste Treatment and Clean Technology (REWAS 2008) is the third in a series of international conferences to address the continuing globalization of environment protection through progress in recycling technology, re-engineering of the production system, and clean technologies. The conference incorporates the Fifth International Symposium on Recycling of Metals and Engineered Materials and R08 - the World Congress on the Recovery of Materials and Energy for Resource Efciency. Technical topics covered in the conference proceedings include:

Aluminum By-product Recovery and Secondary Production Automotive Recycling Case Studies in the Development of Waste Treatment Technologies Clean Technology and Re-engineering of Current Processes Composite Materials Design and Engineering of Waste Treatment Plants Economic Evaluation of Waste Treatment Strategies Electronic Waste Environmental Issues Related to Waste Storage and Recycling

Ferrous Metals General Recycling and Solid Waste Processing Heavy-Metal Containing Waste Nonferrous Metals Precious and Rare Metals Radioactive Waste Refractory Metals Remediation of Contaminated Soil and Industrial Sites Resources, Monitoring and Characterization of Waste Treatment of Liquid and Gaseous Efuents Waste Conversion and Reutilization

For more information about REWAS 2008: Global Symposium on Recycling, Waste Treatment and Clean Technology and other TMS titles, visit: http://knowledge.tms.org/books.aspx.