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NBSIR 77-1239

Workshop on Applications of

Phase Diagrams in Metallurgy

and Ceramics

L H. Bennett and G. C. Carter

Institute for Materials Research

National Bureau of Standards

Washington, D.C. 20234

April, 1977

Summary Report

Prepared for National Science Foundation

Defense Advanced Research Projects Agency

Office of Naval Research

National Aeronautics and Space Administration

ly Research and Development Administration

Army Research Office

100

.U56

77-1239

1977

NBSIR 77-1239

WORKSHOP ON APPLICATIONS OF

PHASE DIAGRAMS IN METALLURGY

AND CERAMICS

L. H. Bennett and G. C. Carter

Institute for Materials Research

National Bureau of Standards

Washington, D.C. 20234

April, 1977

Summary Report

Prepared for National Science Foundation

Defense Advanced Research Projects Agency

Office of Naval Research

National Aeronautics and Space Administration

Energy Research and Development Administration

U.S. Army Research Office

"•t.u of

U.S. DEPARTMENT OF COMMERCE, Juanita M. Kreps, Secretary

Dr. Sidney Harman, Under Secretary

Jordan J. Baruch, Assistant Secretary for Science and Technology

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Acting Director

PHASE DIAGRAMS IN METALLURGY AND CERAMICS

Table of Contents

1. Overview of the Workshop

1.1 Introduction ........... ..... 1

1.2 Goals .................. _ . X

1.3 Summary of the Program 2

1.4 Danonstrations and Films „ 3

1.5 Proceedings 4

2. Poster Board Design and Layout » 5

3. List of Registrants 8

4. Workshop Contents _ , 17

4.1 Program ............... 18

4.2 Abstracts ................... 37

4.3 Index to Abstracts ................... 225

5. Informal Program for Phase Diagram Data Center

Representatives ................ 227

6. Organizing Committee 229

1

PHASE DIAGRAMS IN METALLURGY AND CERAMICS

1. Overview of the Workshop

1.1 Introduction

A material's phase, depends on its temperature, composition, pressure, and

other thermodynamic variables. This relation is most commonly presented graphically in phase diagrams, which have become indispensable to metallurgists,

ceramists, geochemists, materials engineers and solid state chemists and

physicists. Knowledge of the structure of materials is important in understanding several industrially significant phenomena and applications such as aging, hardness, occurrence of brittle intermetallic compounds, magnetic

transition temperatures, high-temperature solubility of impurities, corrosion

resistance, solid electrolytes and non-crystalline solids. The study of a phase diagram appropriate to a particular material can often provide information

important to its scientific and technical application.

The list of the workshop registrants (section 3) exhibits wide participation

from industry, government, and universities. International participation was particularly successful among the data evaluation groups including important

presentations from the Soviet Union, Germany, France, the UK, Japan, and Canada.

Other countries were represented; experimentalists and theorists determining

phase diagrams were among the participants, as were a substantial fraction of

phase diagram users from industry.

The workshop was organized by the Alloy Data Center and the group compiling

"Phase Diagrams for Ceramists", and supported internally by the Institute for

Materials Research and the Office of Standard Reference Data, National Bureau

of Standards.

1.2 Goals

The workshop goals were:

1. to assess the current national and international status of phase diagram

determinations and evaluations for alloys, ceramics and semiconductors.
2

2. to determine the needs and priorities, especially technological, for phase

diagram determinations and evaluations , and

3. to estimate the resources being used and potentially available for phase

diagram evaluation.

Specific subjects of investigation were:

...to identify resources being expended that could be made more useful by

appropriate coordination,

...to recognize unnecessarily overlapping efforts in determining phase

diagrams

...to suggest areas of international cooperation,

...to gauge the relative importance of depth of coverage and range of

materials including factors such as a) high precision, b) metastable phases,

c) binary and higher order systems, d) magnetic, metal nonmetal and other

phase transitions, e) high pressure data, f) integration of collateral

information, and g) the role of impurities or trace additions,

...to determine current awareness needs,

...to review the strengths and limitations of various experimental techniques

for determining phase diagrams,

...to briefly survey the status and merits of various predictive methods

(CALPHAD, PHACOMP, psedupotential, etc.),

...to discuss diverse presentation methods, and

...to discuss effective and alternative means for dissemination of phase

diagram data.

1.3 Summary of Program

The workshop program (detailed in Section 4) was designed to stimulate

interactions between (i) phase diagram data providers and users, (ii) metallurgists,

geochemists, thermochemists , ceramists, solid state chemists, and physicists, and

other experimentalists, (iii) representatives from industry, government, and

the academia, (iv) phase diagram data centers from many countries (see section

5 for informal program held in addition for this latter group)

Plenary lectures introduced the subjects of present status of data availability

from reference books, data centers and computerized files, the status of experimental data and theory of alloy phases. A panel on computation and prediction gave

a more thorough introduction to that subject, and short reviews introduced the

subjects of phase diagram representations and methods of distribution. Poster

sessions followed these introductions, and extremely lively participation
3

by all ensued. The success of these interactive poster sessions was the result

of both the stimulating introductory sessions and a new design of poster board

arrangement (section 2) . Four on-line demonstrations of computer-data handling systems related to

phase diagrams were held in the poster session, while short instructional movies

were shown in the neighboring auditorium (see section 1.4 for listing) . Three

panels addressed the subjects of user's needs for phase diagram data, with strong

participation from the industrial sector. Discussion covered needs for multicomponent diagrams (up to 9 or 10 components) for industrial applications, as evident from the panel members, whereas voices from the audience emphasized

needs for less complex systems, down to binary equilibrium diagrams, for various

R&D programs.

1.4 Demonstrations and Films

Four demonstrations and a small film were held during the poster sessions in

the same lounge with the posters. Two series of short films were shown in the

auditorium, one during each poster session.

Summary of Demonstrations and Films

On-Line Computer Manipulations

J. Hilsenrath, B, B. Mo lino

Office of Standard Reference Data

National Bureau of Standards

Washington, D.C.

Alloy Data Center Graphical

Methods

R. A. Kirsch

Institute for Basic Standards

and

L. J. Swartzendurber

Institute for Materials Research

National Bureau of Standards

Washington, D.C.

MTDATA On-Line Thermochemical

Calculations

L . Kaufman

ManLabs, Inc.

Cambridge, MA

An On-Line Demonstration of a Computerized Canadian Thermodynamic

Data Bank

A. D. Pelton

Dept. de Genie Metallurgique

Ecole Polytechnique

Universite de Montreal

Montreal, Canada

and

(shown in conjunction with poster MPSI-7)

(shown in conjunction with poster MPSI-8)

(shown in conjunction with poster TPSI-11)

(shown in conjunction with poster TPSI-16)
4

W. T» Thompson

Dept. of Metallurgical and Mining

Engineering

McGill UniversityMontreal, Canada

A Short Film. Illustrating some Examples on the

Calculations of Phase Diagrams

I. Ansara

Thermochemical Data Center

Laboratoire de Thermodynamique

et Physico-Chimie Metallurgiques

Grenoble, France

Four Short Instructional Movies

Contributed by H. McKinstry

Materials Research Laboratory

Pennsylvania State University

University Park, PA

Produced at Pennsylvania State University; sponsored by NSF

Two Instructional Movies

Contributed by C.H.P. Lupis

Carnegie Mellon University

Produced at CMU, sponsored by NSF

1.5 Proceedings

A Proceedings of the workshop will be published as an NBS Special Publication

It will contain all the full papers presented, plus a number of comments and a summary of the workshop. The requisite number of copies will be forwarded

to the sponsoring organizations. Aditional copies will be available from the

Superintendent of Documents, U.S. Government Printing Office, Washington, D.C.

20402, under the title Proceedings of the Workshop on Applications of Phase

Diagrams in Metallurgy and Ceramics.
5

2. Poster Board Design and Layout

Poster "tripod" stations were designed to allow some shielding from neighboring

presentations. This basic idea was taken from poster sessions given at Uppsala,

Sweden at the 1976 "Solid Compounds of Transition Elements" conference, and

improved stations were designed at NBS (see Fig. 1), with large, high boards.

This layout allows for three poster presentations, isolated from each other,

per tripod center. Each such poster presentation can use two 4' x 5' boards

at an angle of 120* from each other, allowing ample space for the presentations.

A shelf was designed in front of the right panel, which hinges at the board and

a loose wooden stik to support the shelf if the author wishes to use it. This

shelf was designed somewhat higher than an ordinary table would be. This was useful to most, but maybe some would have preferred it a little lower.

The sessions were held in a carpeted lounge, which helped reduce noise

levels. Participation was larger than anticipated, allowing for only few chair

and table arrangements for additional discussions on the side. Several small

coffee centers were set in the lounge, during the poster sessions, obviously

adding to the liveliness of the sessions, and also helping to keep the group

from wandering off. Fig. 2 shows the layout of the lounge for Tuesday afternoon's

poster session.

After the first hour of each poster session we suggested that poster

authors could take a break and see some of the other posters, or to switch

coauthors at a poster where there are more than one author. This helps minimize

the problem that poster authors are not mobile to see other posters in their own

session.
6
7

EMPLOYEES LOUNGE

ENTRANCE ENTRANCE

POSTER SESSIONS

TUESDAY, JANUARY !l ,1977

3:30-6:00 p.m.

^DEMONSTRATION

Fig I 2, Layout of the poster tripod stations for the Tuesday afternoon (11 Jan)

poster session, indicating location of each poster paper. Small coffee

stations were placed along the walls.
8

3, List of Registrants

Nazir Ahmad

University of Birmingham

Birmingham, England

Frank Ajersch

Ecole Polytechnique

CP. 6079 Succ. "A"

Montreal, Quebec H2V-2W8

I. Aldinger

Max-Planck- Institut Flir Metallforschung

Busnauerstr. 175

D-7000 Stuttgart, W. Germany

Ernest Ambler

Office of the Director

National Bureau of Standards

Washington, DC 20234

Paul R. Ammann

Kennecott Copper Corp. , j Ledgemont Lab

128 Spring Street

Lexington, MA 02173

I. Ansara

Doraaine Universitaire

B.P. 44-38401

St. Martin-d'Heres, France

George T. Armstrong

Physical Chemistry Division

National Bureau of Standards

Washington, DC 20234

N. Ault

Norton Co.

Worcester, MA

Donald M. Bailey

Iowa State University

130 Metallurgy Bldg.

Ames, LA 50011

Hugh Baker

American Society for Metals

Metals Park, OH 44073

Chris Bale

Ecole Polytechnique

CP. 6079

Montreal, Quebec H3C3A7

S. K. Banerji

Foote Mineral Company

Route 100

Exton, PA 19341

Ian R. Bartky

Institute for Materials Research

National Bureau of Standards

Washington, DC 20234

C J. Bechtoldt

Metallurgy Division

National Bureau of Standards

Washington, DC 20234

Larry H. Bennett

Metallurgy Division

National Bureau of Standards

Washington, DC 20234

Milton Blander

Argonne Nat'l Lab

9700 S. Cass Ave.

Argonne, IL 60439

John H. Blanks

Pennsylvania State University

271 Mat. Res. Lab.

University Park, PA 16802

Edward L. Brady

Office of Information Programs

National Bureau of Standards

Washington, DC 20234
9

Robert F. Brebrick

Marquette University

1515 W. Wisconsin Ave.

Milwaukee, WI 53233

Leo Brewer

Lawrence Berkeley Laboratory

Univ. of California

Berkeley, CA 94720

Jesse J. Brown, Jr.

VPI & SU

302 Holden Hall

Blacksburg, VA 24061

Daniel Butrymowicz

Metallurgy Division

National Bureau of Standards

Washington, DC 20234

J. W. Cahn

Metallurgy Division

National Bureau of Standards

Washington, DC 20234

Thomas B. Cameron

University of Connecticut

U - 136

Storrs, CT 06268

Cynthia Carter

Metallurgy Division

National Bureau of Standards

Washington, DC 20234

Forrest L. Carter

Naval Research Laboratory

Code 6132

Washington, DC 20034

Y. Austin Chang

College of Engineering

University of Wisconsin-Milwaukee

Milwaukee, WI 53201

James R. Chelikowsky

Bell Labs

600 Mountain Ave.

Murry Hill, NJ 07974

U. V. Choudary

College of Engineering

University of Wisconsin-Milwaukee

Milwaukee, WI 53201

G. W. Cleek

Consultant

5512 N. 24th St.

Arlington, VA 22205

W. Dale Compton

Ford Motor Company

20000 Rotunda Drive

Dearborn, MI 48124

Bruce R. Conard

INCO, Ltd.

Sheridan Park

Mississauga, Ontario, Canada

Lawrence P. Cook

Inorganic Materials Division

National Bureau of Standards

Room B214, Materials Building

Washington, DC 20234

S. R. Coriell

Metallurgy Division

National Bureau of Standards

Washington, DC 20234 .

Joseph Cox

Watervliet Arsenal

Watervliet, NY 12189

John R. Cuthill

Metallurgy Division

National Bureau of Standards

Washington, DC 20234

Amit DasGupta

Oak Ridge National Lab

Oak Ridge, IN 37830

Didier de Fontaine

University of California

6532 Boelter Hall

Los Angeles, CA 90024

Peter R. Debruyn

Industrial Liaison

National Bureau of Standards

Washington, DC 20234
10

Patrick K. Gallagher

Bell Laboratories

Rm. 6D - 311

Murray Hill, NJ 07974

Joseph E. Davison

Univ. of Dayton

300 'College Park

Dayton, OH 45469

R. C. Devries

General Electric

General Electric R&D Center K-1

Schenectady, NY 12345

R. L. Dreshfield

Materials Processing and Joining Section

NASA Lewis Research Center

Cleveland, OH

J. Elliott

Department of Metallurgy & Metals

MIT

Cambridge, MA 02139

S. G. Epstein

Aluminum Association

New York, NY

Maria-Luise Fiedler

North Carolina State University

Raleigh, NC 27607

H. Alan Fine

University of Arizona

Dept. of Met. Eng.

Tucson, AZ 85721

Gerhard R. Fischer

Corning Glass Works

SP, FR 1

Corning, NY 14830

I Julius Fister

Metals Research Laboratories

Olin Corp.

91 Shelton Ave.

New Haven, CT 06504

Sherman P. Fivozinsky

Office of Standard Reference Data

National Bureau of Standards

Washington, DC 20234

Rene Flukiger

Dept. Phys. Mat. Cond.

32, Bd. d'Yvoy

Geneva, Switzerland

Paul Fopiano

Watertown Arsenal

Arsenal Street

Watertown, MA 02172

B. C. Giessen

Department of Chemistry &

Mechanical Engineering

Northwestern University

Boston, MA

F. P. Glasser

University of Aberdeen

Old Aberdeen

Scotland, UK AB9 ZUE

Joseph I. Goldstein

Lehigh University

Bethlehem, PA 18015

J. Ronald Gonterman

Owens /Corning Fiberglas

Technical Center

Granville, OH 43023

Chuck Greskovich

General Electric Co.

K-1, 3C12, P.O. Box 8

Schenectady, NY 12301

John L. Haas, Jr.

U.S. Geological Survey

National Center, Stop 959

Reston, VA 22092

David Hansen

Ballistics Research Laboratory

Aberdeen, MD 21005

Ernst-Theo Henig

Max-Planck-Institut fiir Werkstof fwissensch

Buesnauerstr . 175

D-7000 Stuttgart-80, Germany

Keith A. Hill

Carpenter Technology Corporation

P.O. Box 662

Reading, PA 19603

K. A. Gschneidner, Jr.

Rare Earth Information Center

Iowa State University

Ames , lA
J. Hilsenrath

National Bureau of Standards

Washington, DC 20234

Michael Hoch

University of Cincinnati

Location 12

Cincinnati, OH 45221

John D. Holder

Oak Ridge National Laboratory

Box X, 4500S S280

Oak Ridge, TN 37830

Emanuel Horowitz

Institute for Materials Research

National Bureau of Standards

Washington, DC 20234

R. A. Howald

Chemistry Dept.

Montana State University

Bozeman, MT

Chen-Chao Hsu

Argonne National Laboratory

9700 S. Cass Ave.

Argonne, IL 60439

David Dew-Hughes

Brookhaven National Laboratory

Building 480

Upton, NY 11973

F. A. Hummel

Pennsylvania State University

Room 214 M.I. Bldg.

University Park, PA 16802

M. R. Jackson

General Electric Co.

CRD, K-1 223 Met

Schenectady, NY 12309

R. I. Jaffee

Electric Power Research Institute

Palo Alto, CA

Ronald B. Johnson

Institute for Materials Research

National Bureau of Standards

Washington, DC 20234

Daniel J. Kahan

Metallurgy Division

National Bureau of Standards

Washington, DC 20234

Larry Kaufman

Manlabs Inc.

21 Erie St.

Cambridge, MA 02146

B. H. Kear

' Pratt and Whitney

Materials Engineering &

Research Lab

E. Hartford, CT

S. E. Khalafalla

Dept. of the Interior

P.O. Box 1660

Twin Cities, MN 55111

R. Kikuchi

Hughes Research Laboratories

3011 Malibu Canyon Road

Malibu, CA 90265

R. Kirsch

Applied Mathematics Division

National Bureau of Standards

Washington, DC 20234

0. J. Kleppa

The James Franck Institute

University of Chicago

Chicago, IL

Michael J. Koczak

Drexel University

Dept. of Materials Engineering

Philadelphia, PA 19104

Tamara Kolesnikova

Academy of Sciences of the USSR

Baltijskaya ul., 14

Moscow, USSR

Ram Kossowsky

Westinghouse Research Laboratories

1310 Beulah Road

Pittsburgh, PA 15235
12

John Krc, Jr.

Parke, Davis & Company

Joseph Campau at the River

Detroit, MI 48232

Eric R. Kreidler

General Electric Co.

Nela Park

Cleveland, OH 44143

A. K. Kuriakose

Norton Research Corp. (Canada) Ltd.

8001 Daly St.

Niagara Falls, Ont., Canada

R. Laudise

Materials Research

Bell Telephone Labs

Murray Hill, NJ 07974

Y. E. Lee

Union Carbide Corp. Metals Div.

4625 Royal Ave.

Niagara Falls, NY 14302

David R. Lide, Jr.

Office of Standard Reference Data

National Bureau of Standards

Washington, DC 20234

James D. Livingston

General Electric Co.

Corp. Res. & Dev.

Schenectady, NY 12308

C. H. P. Lupis

Institute Fur Eisenhuttenkunde

Aachen , Germany

Lottie T. McClendon

Institute for Materials Research

National Bureau of Standards

Washington, DC 20234

Scott McCormick

Illinois Institute of Technology

Dept. of Metallurgical and Matls. Eng.

Chicago, IL 60616

H. McKinstry

Materials Research Lab

Pennsylvania State University

University Park, PA

R. McNally

Ceramic Research

Corning Glass Works

Coming, NY

Michael McNeil

National Bureau of Standards

Room A129, Technology Building

Washington, DC 20234

H. F. McMurdie

Inorganic Materials Division

National Bureau of Standards

Washington, DC 20234

Richard Magin

Nat'l Institutes of Health

9000 Rockville Pike

Bethesda, MD 20795

A. I. Malausky

Tyco Laboratories

Waltham, PA

John R. Manning

Metallurgy Division

National Bureau of Standards

Washington, DC 20234

Vincent C. Marco tte

IBM

D/45K B/300 -95

Hopewell Jen, NY 12533

Dennis Marshall

Globe-Union, Inc.

5757 N. Greenbay Ave.

Milwaukee, WI 53201

Robert F. Martin

Institute for Materials Research

National Bureau of Standards

Washington, DC 20234
13

Thadeus B. Massalski

Carnegie-Mellon University

Schenley Park

Pittsburgh, PA 15213

Leo Merrill

High Pressure Data Center

5093 HBLL, Brigham Young University

Prove, UT

Peter J. Meschter

Univ. of Tennessee

Dept. Chem. & Met. Eng.

Knoxville, TN 37919

Alan D. Mighell

Inorganic Materials Division

National Bureau of Standards

Washington, DC 20234

D. B. Minor

Inorganic Materials Division

National Bureau of Standards

Washington, DC 20234

A. P. Miodownik

University of Surrey

Guildford, UK GU2 5XH

W. G. Moffatt

General Electric Co.

1 River Road P.O. Box 8

Schenectady, NY 12301

B. J. Molino

Office of Standard Reference Data

National Bureau of Standards

Washington, DC 20234

L, F. Mondolfo

Syracuse University

Syracuse, NY 13210

John E. Morral

University of Connecticut

U-136

Storrs, CT 06268

Arnulf Muan

Penn State Univ.

118 H. S. Bldg.

University Park, PA 16802

A. Navrotsky

Chemistry Division

National Science Foundation

Washington, DC

Taki Negas

Inorganic Materials Division

National Bureau of Standards

Washington, DC 20234

T. 'Nishizawa

Dept. of Metallurgy, Materials

Science & Metal Processing

Tohoku University

Japan

E. F. Osborn

Carnegie Institution of Washington

2801 Upton St. , NW

Washington, DC 20008

Robert L. Parker

Metallurgy Division

National Bureau of Standards

Washington, DC 20234

P. Parish

U.S. Army Research Office

Box 12211

Research Triangle Park, NC 27709

Elio Passaglia

Institute for Materials Research

National Bureau of Standards

Washington, DC 20234

David D. Pearson

United Technologies Research Center

Silver Lane

East Hartford, CT 06108

W. B. Pearson

Faculty of Science

University of Waterloo

Waterloo, Canada

Arthur Pelton

Ecole Polytechnique

CP, 6079

Montreal, Quebec H3C3A7

Guenter Petzow

Met-Planck-Inst. Metallforschung

Buesnauerstr 175

7000 Stuttgart 80, W. Germany
14

Sri Prakash

Union Carbide Corporation

P.O. Box 5928

Greenville, SC 29606

Svante Prochazka

GE CR & D

P.O. Box 8

Schenectady, NY 11301

Alan Prince

Hirst Research Centre

East Lane, Wembly

Middlesex HA9 7PP, England

Schrade F. Radtke

International Lead-Zinc Research Org.

292 Madison Ave.

New York, NY

Dennis Readey

Division of Physical Research

ERDA

Washington, DC 20545

Curt W. Reimann

Institute for Materials Research

National Bureau of Standards

Washington, DC 20234

R. C. Reno

Dept. of Physics

University of Maryland

Baltimore, MD

Robert J. Reynik

National Science Foundation

1800 G St. , NW

Washington, DC 20550

Frederick N. Rhines

University of Florida

Dept. of Mat-Sci. & Eng.

Gainesville, FL 32611

A, D. Romig

Lehigh University

Whitaker Lab. #5

Bethlehem, PA 18015

Barry H. Rosof

Technology Division, Cabot Corp.

1020 Park Avenue

Kokomo, IN 46901

W. Rostoker

University of Illinois

Chicago Circle, P.O. Box 4348

Chicago, IL 60680

Robert S. Roth

Inorganic Materials Division

Room B214, Materials Building

Washington, DC 20234

William Ruff

Metallurgy Division

National Bureau of Standards

Washington, DC 20234

M. L. Saboungi

Argonne National Lab

Chemical Engineering Div.

Argonne, IL 60439

Saed Safai

Materials Sci. Dept.

SUNY at Stony Brock

Stony Brook, L. I. , NY 11794

E. Salkovitz

Office of Naval Research

Arlington, VA

Gary Sandrock

International Nickel Co^

Sterling Forest

Suffern, NY 10901

L. M. Schetky

International Copper Research Assoc.

825 Third Ave.

New York, NY 10022

Coulson M. Scheuermann

NASA Lewis Research Center

21000 Brookpark Road

Cleveland, OH 44135

Fred C. Schwerer

U. S. Steel Research, MS //98

Monroeville, PA 15146

J. E. Selle

Metals and Ceramics Div.

Oak Ridge National Lab

Oak Ridge, TN 37830
15

M. Semchyshen

Research Laboratory

Climax Molybdenum Corp.

1600 Huron Pkwy.

Ann Arbor, MI 48105

Charles E. Semler

Ohio State Univ.

Refractories Research Center

2041 College Rd.

Columbus, OH 43210

Gertrude B. Sherwood

Office of Standard Reference Data

National Bureau of Standards

Washington, DC 20234

John Shyne

NSF

1800 G St., NW

Washington, DC 20550

W. C. Simmons

AFOSR

Bldg. 410

Boiling AFB, DC 20332

Satish P. Singhal

State University of New York

Materials Science Dept.

Stony Brook, NY 11794

P. Slick

Bell Telephone Laboratories

Murray Hill, NJ

J. F. Smith

Iowa State University

Ames, lA 50010

J . E . Smugeresky

Sandia Labs

Div. 8312

Livermore, CA 94550

Shigeyuki Somiya

Tokyo Institute of Technology

Ookayama, Meguro, Tokyo, 152

Tokoyo, Japan

Charles A. Sorrell

Dept. of Ceramic Engineering

Univ. of Missouri

Rolla, MI 65401

Karl E. Spear

Pennsylvania State University

Materials Research Laboratory

University Park, PA 16802

G. R. Speich

U. S. Steel, Research Labs

Monroeville, PA

G. Springer

Falconbridge Nickel Mines Ltd.

8810 Yonge Street, P.O. Box 900

Thornhill, Ontario

Judith K. Stalick

Inorganic Materials Division

National Bureau of Standards

Washington, DC 20234

Kurt H. Stern

Naval Research Laboratory

Code 6130

Washington, DC 20375

C. P. Stroble

Allegheny Ludlum Steel Corp.

Research Center

Brackenridge, PA 15065

Lydon J. Swartzendruber

Metallurgy Division

National Bureau of Standards

Washington, DC 20234

J. Swisher

Energy Research & Development Admin.

Washington, DC

R. E. Thoma

Union Carbide Corporation

P.O. Box X

Oak Ridge, TN 37830

Marshall K. Thomas, Jr.

Naval Air Devel. Center (30231)

Warminster, PA 18974

William Thompson

McGill University

Montreal, Quebec

C . Thurmond

Bell Telephone Labs

Murray Hill, NJ 07974
16

H. van Olphen

Numerical Data Advisory Board

National Research Council

2101 Constitution Avenue

Washington, DC 20418

E. C. van Reuth

DARPA

1400 Wilson Blvd.

Arlington, VA 22209

Chester J. Van Tyne

Lehigh University

Whitaker Laboratory #5

Bethlehem, PA 18015

Francis L. Ver Snyder

Pratt & Whitney Aircraft Group

400 Main Street

East Hartford, CT 06108

Walter E. Wahnsiedler

Alcoa Laboratories

Alcoa Technical Center

Alcoa Center, PA 15069

J. Waldman

Frankford Arsenal

Bridge & Tacony Streets

Philadelphia, PA 19137

Chang-F. Wan

Pennsylvania State University

271 Materials Res. Lab

University Park, PA 16802

Frederick E. Wang

NSWC

Silver Spring, MD

Richard M. Waterstrat

Polymers Division

National Bureau of Standards

Washington, DC 20234

George Wei

ORNL

P. 0. Box X

Oak Ridge,. TN 37830

J. H. Westbrook

General Electric Co. Bldg. 5-327

1 River Road

Schenectady, NY 12345

Howard J. White, Jr.

National Bureau of Standards

Office of Standard Reference Data

Washington, DC 20234

William B. White

The Pennsylvania State University

Materials Research Laboratory

University Park, PA 16802

Calvin S. Williams

Union Carbide Corporation

P.O. Box 5928

Greenville, SC 29606

Ray Woodriff

Roberts Hall

Montana State University

Bozeman, MT 59715

L. Richard Woodyatt

Bethlehem Steel Corp.

Homer Research Labs

Bethlehem, PA 18015

Han-Il Yoo

Inorganic Materials Division

Room B214, Materials Bldg.

Washington, DC 20234

William Vincent Youdelis

Dept. Engineering Materials

University of Windsor

Windsor, Ontario N9B 3P4

R. E. Watson

Brookhaven National Laboratory

Upton, NY 11973

Alan Webb

Naval Research Laboratory

Code 6434

Washington, DC 20375
4. Workshop Contents

9:00 -

10:00 -

MONDAY

January 10, 1977

REGISTRATION

INTRODUCTIONS

REVIEWS 1. Ceramics

2. Semiconductors

COFFEE

REVIEWS 3. Metals - General

4. Metals - USSR

5. High Pressure

LUNCH

TUESDAY

January 11, 1977

REVIEW

1. Theory of Alloy Phases

COFFEE

PANEL I COMPUTATION AND

PREDICTION

OF

PHASE DIAGRAMS

LUNCH

WEDNESDAY

January 12. 1977

PANEL II USER NEEDS

PRIMARY METALS

PRODUCTION

COFFEE

PANEL 111 USER NEEDS

MATERIALS PROCESSING

LUNCH

- 9:00

- 10:00

- 11:00

- 12.00

1:00

2:00 -

3:00 -

6:00 -

REVIEWS

6. Computer Data Banks

7. Experimental Methods

FORMAT AND DISTRIBUTION

2. Representation of Pnase Equil.

3. User's View

4. Dfstritjutor's View

5. Producer's View

Buses leave NBS for Hotel Buses leave NBS for Hotel

4:00 - COFFEE AND COFFEE AND

POSTER SESSION POSTER SESSION

Phase Diagrams Experimental Computational Format

5:00 - Compilations Techniques Techniques and

Activities Distribution

PANEL IV

USER NEEDS

PRODUCT APPLICATIONS

COFFEE

SUMMARY

- Buses leave for Hotel, Airports

- 2:00

- 3.00

- 4:00

- 5:00

- 6:00

7:00 - 11:00 informal Discussions at Hotel - Gallery Room

Reception at Hotel (7 PM)

Banquet at Hotel (8 PM)

7:00-11:00
18

4.1 Program

The program includes surveys given

by rapporteurs, and panel, tutorial, and

poster presentations. There will be ample

time for informal discussions among the

workshop attendees.

All technical sessions will be held

in the NBS Green Auditorium except the

poster sessions, which will be conducted

in the Employee's Lounge. Evening activities

will be held at the Holiday Inn of Bethesda.

Sunday, January 9, 1977

7:00 p.m. Reception and Registration at

the Holiday Inn

Monday, January 10, 1977

8:00 a.m. Buses leave hotel for NBS

8:30 a.m. Registration

9:15 a.m. Wetaome and Intvoduation

(Green Auditorium)

Eo Ambler, Acting Director

National Bureau of Standards

Washington, DC

D. R. Lide, Jr.

Office of Standard Reference

Data

National Bureau of Standards

Washington, DC

L. H. Bennett

Alloy Physics Section

Institute for Materials Research

National Bureau of Standards

Washington, DC

H. van Olphen

Numerical Data Advisory Board

National Academy of Sciences

Washington, DC
19

MONDAY, JANUARY 10, 1976

Morning Session ' (Continued)

10:00 a.m. Present Status of Phase Diagram

Compilation Activities

Chairman T. B. Massalski

Dept. of Metallurgy and Materials

Sciences

Carnegie-Mellon University

Pittsburgh, PA

,^ Phase Diagram Comp ilaf-f ot. 10:00 a.m. Activities in Ceramics

R. S. Roth

Solid State Chemistry Section

Institute for Materials Research

National Bureau of Standards

Washington, DC

M-2

10:30 a.m. Semiconductor Phase Diagrams

C. Thurmond

Bell Telephone Laboratories

Murray Hill, NJ

11:00 a.m. COFFEE

11:20 a.m. Present Status of Phase diagram

Compilation Activities ( Continued)

M-3 Phase Diagrams Compilations for

11:20 a.m. Metallic Systems - an Assessment

of Ongoing Activities

G. C. Carter

Alloy Data Center

Institute for Materials Research

National Bureau of Standards

Washington, DC

M-4 Organization of Phase Diagram

11:50 a.m. Information in the Soviet Union

N. V. Ageev, D. L. Ageeva, T. P.

Kolesnikova, and L. A. Petrova

Baikov Institute of Metallurgy, and

Institute for Scientific Information

Academy of Sciences of the USSR

Moscow, USSR
20

MONDAY, JMUARY 10, 1977

Afternoon Session (Continued)

M-5 Phase Diagrams of Materials at

12:10 p.m. High Pressure

L, Merrill

High Pressure Data Center

Brigham Young University

Provo, UT

12:30 p.m. LUNCE

2:00 p.m. Fvesent Status of Phase diagvdm

CompiZat'Con Aativzties (Continued)

Chairman K. A. Gschneidner , Jr.

Rare Earth Information Center

Iowa State University

Ames , lA

M-6 Phase Diagram Information

2:00 p.m. from Computer Banks

I. Ansara

Laboratoire de Thermodynamique

et Physico-Chimie Metallurgiques

Institut National Polytechnique

Grenoble, France

M-7 Experimental Techniques in

2:30 p.m. Phase Diagram Determination

- an overview -

F. N. Rhines

Dept. of Materials Science

and Engineering

University of Florida

Gainesville, FL

3:30 p.m. POSTER SESSION

(Employee's Lounge)

Coffee will be availabe during

the session

Two topics will be addressed

in the session.
21

MONDAY, JANUARY 10, 1977

Poster Session (Continued)

I. Phase Diagvam Compilation

and Data Evaluation Activities

MPSI-1 Proposal for a Comprehensive

Handbook on "Ternary Phase Diagrams

of Metals"

F. Aldinger, E.-Th. Henig,

H. L. Lukas, and G. Petzow

Max Planck Inst, fur Metallforschung

Institxit fur Werkstoffurissenschaften

Stuttgart, Germany

MPSI-2 WO^-Containing Binary Oxide Systems

L. Y» Chang

Department of Geology

Miami University

Oxford, OH

MPSI-3 RIC in Phase with Rare-Earth

Constitutional Diagrams

K. A. Gschneidner, Jr., M. E. Verkade,

and R. L. Evans

Rare Earth Information Center

Iowa State University

Ames , lA

MPS 1-4 Phase Diagrams and Thermodynamic

Properties of Ternary Copper AJ.loy

Systems

Y. A. Chang, Joachim P. Neuman,

and U. V. Choudary

Materials Department

College of Engineering and Applied

Science

University of Wisconsion - Milwaukee

Milwaukee, WI

MPSI-5 Phase Equilibria in Variable Valence

Oxide Systems

W. B. White

Materials Research Laboratory

Department of Geosciences

Pennsylvania State University

University Park, PA
22

MONDAY, JANUARY 10, 1977

Poster Session (Continued)

MPSI-6 Phase Diagrams for Ceramists

L. P. Cook, R. S. Roth, T. Negas,

and G. W. Cleek

Institute for Materials Research

National Bureau of Standards

Washington, D.C.

MPSI-7 NBS Crystal - Data Center

A.. Mighell, H. Ondik, J. Stalick,

and R. Boreni

Institute for Materials Research

National Bureau of Standards

Washington, D.C.

MPSI-8 The NBS Allov Data Center

G. C. Carter, D. J. Kahan,

and L. H. Bennett

Institute for Materials Research

National Bureau of Standards

Washington, D.C.

MPSI-9 Phase Equilibria in Cryolite Systems

J. J. Brown, Jr.

Department of Materials Engineering

College of Engineering

Virginia Polytechnic Institute

and State University

Blacksburg, VA

MPSI-10 Methods of Compiling and Editing

"Handbook of Binary Metallic Systems"

A. E. Vol and E. K. Kagan

Leningrad, USSR

„. JJ. Esrpernmental Techniques in

Phase diagram Determinations

MPSII-1 The Determination of Phase Diagrams

for Liquid Oxides and Metallurgical

Slags by Hot-Wire Microscopy

H. A. Fine

Dept of Metallurgical Engineering

University of Arizona

Tucson, AZ
23

MONDAY, JANUARY 10, 1977

Poster Session (Continued)

MPSII-2 Experimental Techniques in Phase

Diagram Determinations of

Superconducting Compounds Containing Volatile Components at

Temperature up to 2200 "C

R. Flukiger and J.-L. Jorda

Dept. de Physique de la Matiere

Condensee

University of Geneva

Geneva, Switzerland

MPSII-3 Experimental Techniques in Phase

Diagram Determinations : Applications

to Silicate Systems

F. P. Glasser

Dept. of Chemistry

University of Aberdeen

Aberdeen, Scotland

MPSII-4 Protective Coatings for Superalloys

and the Use of Phase Diagrams

M. R. Jackson, J. R. Rairden

Research and Development Center

General Electric Co.

Schenectady, NY

MPSII-5 Application of the Scanning Electron

Microscope (SEM) to the Study of High

Temperature Oxide Phase Equilibria

L. P. Cook and D. B. Minor

Institute for Materials Research

National Bureau of Standards

Washington, D.C.

MPSII-6 Nuclear Hyperfine Techniques

in the Determination of Phase

Diagrams

R. C. Reno

Dept. of Physics

University of Maryland, Baltimore

County

Baltimore, MD

and

L. J. Swartzendruber , G. C. Carter,

and L. H. Bennett

Institute for Materials Research

National Bureau of Standards

Washington, D.C.
24

MONDAY, JANUARY 10, 1977

Poster Session (Continued)

MPSII~7 Experimental Determination of Phase

Diagrams with the Electron Microprobe and Scanning Transmission

Electron Microscope

A. D. Romig, Jr., and J. I. Goldstein

Dept.. of Metallurgy and Materials

Science

Lehigh University

Bethlehem, PA

MPSII-8 Interrelations between Phase Diagrams

and Hydriding Properties for Alloys

based on the Intermetallic Compound FeTi

G. D. Sandrock

Paul D. Merica Research Laboratory

International Nickel Co., Inc.

Suffem, NY

and

J. J. Reilly, and J. R. Johnson

Dept. of Applied Science

Brookhaven National Laboratory

Upton, NY

MPSII-9 Phase Equilibria in the System

MgO-RCl (R-Li, Na, and K) Solution

under Hydrothermal Conditions by

Means of a Capsul Bursting Method

S. Somiya, K. Nakamura, S.-I. Hirano,

and S. Saito

Research Laboratory of Engineering

Materials

Tokyo Institute of Technology

Tokyo , Japan

MPSII-10 Use of High Energy Ion Beams in

Phase Diagram Determination

J. E. Smugeresky

Metallurgy and Electroplating

Division

and

S. M. Myers

Ion-Solid Interactions Division

Sandia Laboratories

Livermore, CA
MONDAY, JANUARY 10, 1977

Poster Session (Continued)

MPSII-11 Phase Equilibrluin Diagrams in terms

of Electronic Structure

F. E. Wang

Materials Division

Naval Surface Weapons Center

White Oak, MD

MPSII-12 Use of Segregation Phenomena

in Solid Solutions as a Method for

Determining Solidification Diagrams

Application to some SC2O3 - Ln203

bys terns

T. M, Badie

Laboratoire des Ultra-Refractaires

Centre National de la Recherche

Scientifique

Odeillo, France

MPSII-13 Studies of the Fe-C-B Phase Diagram

by Autoradiography

T. B. Cameron and J. E. Morral

Dept. of Metallurgy and Inst, of

Materials Science

University of Connecticut

Storrs, CT

MPSII-14 Industrial Needs

P. J. Fopiano

Army Materials and Mechanics Research

Center

Watertown, MA

3:30 p.m. Demonstrations

(Employee's Lounge)

Demonstration Video Tape

I. Ansara

Thermo chemical Data Center

Laboratoire de Thermodynamique et

Physico-Chimie Metallurgiques

Grenoble, France
MONDAY, JANUARY 10, 1977

Poster Session (Continued)

knd demonstrations In Con.iimction With

MPSI-7 On-Line Computer Manipulations

J. Hilsenrath, B. B. Mo lino

Office of Standard Reference Data

National Bureau of Standards

Washington, D.C

MPSI-8 Allov Data Center Graphical Methods

R. A. Kirsch

Institute for Basic Standards

and

L. J. Swartzendruber

Institute for Materials Research

National Bureau of Standards

Washington, D.C.

Fi Zms

(Green Auditorium)

Four Short Instructional Movies

Contributed by H. McKins tryMaterials Research Laboratory

Pennsylvania State University

University Park, PA

Produced at Pennsylvania State University

6:00 p.m. Buses leave NBS for hotel

7:00 p.m. Informal discussion at hotel

Tuesday, January 11, 1977

8:15 a.m. Buses leave hotel for NBS

Methods of Phase Diagram Calculations

T-1 Theory of Allov Phases

9:00 a.m.

R. E. Watson

Brookhaven National Laboratory

Upton, NY

H. Ehrenreich

Harvard University

Cambridge, K\

and

L. H. Bennett

Institute for Materials Research

National Bureau of Standards

Washington, D.C.
26

TUESDAY, JANUARY 11, 1977

Morning Session (Continued)

10:00 a.m. COFFEE

10:30 a.m. Computation and Prediction of Phase

Diagrams (Panel)

Moderator: 0. J. Kleppa

The James Franck Institute

University of Chicago

Chicago, IL

Panel Members: L. Brewer

Inorganic Materials Research Div.

Lawrence Berkeley Laboratories

University of California

Berkeley, CA

D. de Fontaine

Materials Department

University of California

Los Angeles, CA

R. L. Dreshfield

Materials Processing and

Joining Section

NASA Lewis Research Center

Cleveland, OH

B. C. Giessen

Dept. of Chemistry and

Mechanical Engineering

Northeastern University

Boston, MA

L . Kaufman

ManLabs, Inc.

Cambridge, MA

A. Navrotsky

Chemistry Department

Arizona State University

Tempe, AZ

12:30 p.m. LUNCH

2:00 p.m. Review of Phase D-iagvam Representations:,

FormatJ and Distribution

Chairman: J. W. Cahn

Dept. of Materials Science & Engineering

M.I.T.

Cambridge, MA
27

TUESDAY, JANUARY 11, 1977

Afternoon Session (Continued)

T-2 The Representation of Phase Equilibria

2:00 p.m.

A. Prince

Hirst Research Centre

• -r--';- General Electric, Ltd.

Wembley, Middlesex England

T-3 Phase Diagram Format and Distribution - 2:45 p.m. User's View

J. Livingston

Research and Development Center

. General Electric, Ltd.

Schenectady, NY

T-4 Some Thoughts on the Distribution

3:05 p.m. of Reference Data

H. J. White, Jr.

Office of Standards Reference Data

National Bureau of Standards

Washington, D.C.

T-5 Remarks on Producing and Publishing

3:20 p.m. Critically Evaluated Data

W. B. Pearson

Faculty of Science

University of Waterloo

Waterloo, Canada

3:30 p.m. POSTER SESSION

(Employee's Lounge)

Coffee will be available during the

session.

Two topics will be addressed in this

session.

r J. Computational Teohniques for

Phase Diagram Constvuation

TPSI-1 Computerized Characterization of the

Al-Cu-Ni and Al-Cu-Ag Ternary Phase

Diagrams

M. L. Boyle, C. J. Van Tyne,

and S. K. Tarby

Dept. of Metallurgy and Materials

Science

Lehigh University

Bethlehem, PA
28

TUESDAY, JANUARY 11, 1977

Poster Session (Continued)

TPSI-2 Correlations and Predictions of

Metal-Boron Phase Equilibria

K. Spear

Materials Research Laboratory

Pennsylvania State Unversity

University Park, PA

TPSI-3 A Valence Bond Test for the V-alidity

of Intermetallic and Semiconducting

Structures

F. L. Carter

Chemistry Division

Naval Research Laboratory

Washington, D.C.

TPSI-4 Computation of the Comnonent Activities

from Ternary Miscibility Gap Data : Cu-Ag-S (Se)

U. V. Choudary and Y. A. Chang

Materials Department

College of Engineering and Applied

Science

University of Wisconsin-Wilwaukee

Milwaukee, Wisconsin

TPSI-5 The Mathematical Representation of

Activity Data in Three Component

Systems and its Use for the Computation

of Multiphase Equilibria

I. Eliezer and R. A. Howald

Chemistry Department

Montana State University

Bozeman, MT

TPSI-6 A Program for Binary Phase Equilibria

Using the Redlick-Kister Equations

E. Eliezer and R. A. Howald

Chemistry Department

Montana State University

Bozeman, MT
29

^ TUESDAY, JANUARY 11, 1977

Poster Session (Continued)

TPSI-7 Polynomial Representation of the Excess

Free Energy of Multicomponent Systems

and Their Use in Phase Diagram Calculations

H. Gaye

IRSID - PCM 57

Maizieres - les - Metz

France

and

C. H. P. Lupis

Department of Metallurgy and Materials

Science

Carnegie - Mellon University

Schenley Park, Pittsburgh, PA

TPSI-8 Thermodynamic Data for the Fe-0 System

Evaluated Using a New Computer-Aided

Strategy .

J. L. Haas, and J. R. Fisher

National Center for the Thermodynamic Data of Minerals

Geological Survey

Res ton, VA

TPSI-9 Analysis and Synthesis of Phase

Diagrams of Fe-Cr-Ni, Fe-Cu-Mn and

Fe-Cu-Ni Systems

M. Hasebe and T. Nishizawa

Department of Materials Science

Faculty of Engineering

Tohoku University, Sendai, Japan

TPSI-10 Optimization of Phase Diagrams by

a Least Squares Method Using

Simultaneously Different Data

E.-Th. Henig, H. L. Lukas, and B. Petzow

Max Planck Institute fur Metallforschung

Institut fur Werkstoffwissenschaften

Stuttgart, Germany

TPSI-11 Application of Data Bank Methods to

Calculation of the Thermochemistry

and Phase Diagram of Metal and Ceramic

Systems

L . Kaufman

ManLabs , Inc.

Cambridge, MA
30

TUESDAY, JANUARY 11, 1977

Poster Session (Continued)

TPSI-12 a. Theoretical Calculation of Phase

Diagrams Using the Cluster Variation

(CV) Method

b. Fundamental Caluclations of Coherent

Phase Diagrams

R. Kikuchi and D. de Fontaine

Dept. of Engineering and Applied

Science

University of California

Los Angeles , CA

TPSI-13 Evaluation of Free Energy Functions for

the Prediction of Phase Equilibria in

Multicomponent Systems: The Fe-Cu

System as an Example

0. Kubaschewski

Institute fur Kembrenstoff e und

Theoretische Huttenkunde

Technische Hochschule

Aachen, Germany

and

J. F. Smith and D. M. Bailey

Ames Laboratory USERDA

Iowa State University

Ames , Iowa

TPSI-14 Characteristics and Calculation of

Stability Diagrams

S. McCormick and Y. Bilimoria

Illinois Institute of Technology

Chicago, IL

TPSI-15 Effect of Irradiation on Phase

Stability

P. A. Miodownik

Metallurgy and Materials Technology

Department

University of Surrey, U.K.
31

TUESDAY, JANUARY 11, 1977

Poster Session (Continued)

TPSI-16 Facility for the Analysis of Chemical

Thermodynamics - (A computerized

Canadian Thermodynamic Data Bank)

A. D. Pelton, and C. W. Bale

Dept. de Genie Metallurgique, Ecole

Polytechnique

Universite de Montreal

Montreal, Canada

and

W.. T. Thompson

McGill University

Dept. of Metallurgical and Mineral

Engineering

Montreal , Canada

TPSI-17 The Calculation of Pourbaix Diagrams

Using a Modified Linear Programming

Technique

B. H. Rosof

Technology Division

Cabot Corporation

Kokomo , Indiana

TPSI-18 Theoretical Concepts Useful in the

Calculation or Storage of Phase

Diagrams of Ionic Systems

M.-L. Saboungi, and M. Blander

Chemical Engineering Division

Argonne National Laboratory

Argonne, IL

TPSI-19 Estimation of Isothermal Sections of

Ternary Phase Diagrams of Lithium -

.. Containing Systems: The Li-Al-Mg

System

M. L. Saboungi, and C. C. Hsu

Chemical Engineering Division

Argonne National Laboratory

Argonne , IL
32

TUESDAY, JANUARY 11, 1977

Poster Session (Continued)

TPSI~20 Cybernetic Prediction of the Formation

of Chemical Compounds in Uninvestigated

Systems

E. M. Savitsky, V. B. Gribulya,

and N. N. Kiseleva

Baikov Institute of Metallurgy

Academy of Sciences of the USSR

Moscow, USSR

TPSI-21 The Determination and Representation

of Metastable Phase Diagram Features

and Some Kinetic Characteristics of

Alloys

G. C. Giessen

Institute of Chemical Analysis,

Applications and Forensic Science, and

Department of Chemistry

Northeastern University

Boston, Mass.
33

TUESDAY, JANUARY 11, 1977

Poster Session (Continued)

II, Format and Distr-Chution of

Phase Diagram Data

TPSII-1 Tables of Contents and Ctimulative

Subject Index for "Phase Diagrams

of Metallic Systems", N. V. Ageev

editor. Volumes 1-19

C. M. Scheuermann

Alloys Section

NASA Lewis Research Center

Cleveland, OH

TPSII-2 Graphical Summary of Binary Diagrams

J. E» Selle

Metals and Ceramics Division

Oak Ridge National Laboratory

Oak Ridge, TN

TPSII-3 Standards for Publication of Phase

Equilibrium Data

E. R. Kreidler

Lamp Business Division

Lamp Materials Research Lab #1361

General Electric Co.

Cleveland, OH

TPSII-4 Formatting and Distributing Evaluated

Reference Data by the Office of

Standard Reference Data at the

National Bureau of Standards

S. P. Fivozinsky and G. B. Sherwood

Office of Standard Reference Data

National Bureau of Standards

Washington, D.C.

3:30 p.m. Demons traiions

(Employee's Lounge)

Demonstrations in Conjimation with

TPSI-11 MTDATA On-Line Thermochemical

Calculations

L . Kaufman

Manlabs, Inc.

Cambridge, MA
34

TUESDAY, JANUARY 11, 1977

Demonstrations (Continued)

TPSI-16 An On-Line Demonstration of a Computerized Canadian Thermod^mamic

Data Bank

A. D. Pelton

D^pt, de Genie Metallurgique

Ecole Polytechnique

Universite de Montreal

Montreal Canada

6:00 p.m. Buses leave NBS for hotel

7:00 p.m. Reception at hotel

8:00 p.m. Banquet at hotel

Keynote Speaker:

W, Dale Compton

Vice President, Scientific Research

Ford Motor Company

Dearborn, MI

Wednesday, January 12, 1977

8:15 a.m. Buses leave hotel for NBS

Usev Needs for Phase Diagram

Information

9:00 a.m. Primary Production

(Panel)

Moderator: J. F. Elliott

Dept. of Materials Science

and Engineering

M.I.T.

Cambridge, MA

Panel Members P . Amman

Ledgemont Laboratory

Kennecott Copper Corporation

Lexington, MA

H. Larson

American Smelting and Refining

Company

Plainfield, NJ
35

WEDNESDAY, JANUARY 12, 1977

Morning Session (Continued)

R. D. Pehlke

Metallurgy Division

University of Michigan

Ann Arbor, MI

10:40 a.m. COFFEE

11:00 a.m. Materials Processing

(fabricating, machinging, heat

treating, etc.)

(Panel)

Moderator: W. Rostoker

Dept. of Materials

Engineering

University of Illinois

Chicago , IL

Panel Members E. R. Kreidler

Lamp Business Division

General Electric Co.

Cleveland, OH

R. McNally

Ceramics Research

Coming Glass Works

Coming, NY

L. Mondolfo

Consultant

Clinton, NY

S. Prochazka

Ceramics Branch

Physical Chemistry Laboratory

General Electric Co.

Schenectady, NY

G. R. Speich

Research Laboratories

United States Steel

Monroeville, PA

12:30 p.m. LUNCE

2:00 p.m. Product Applications

(Panel)

Moderator: F. L. VerSnyder

Materials Engineering and Research

Pratt and Whitney Aircraft, U.T.C.

E. Hartford, CT
36

WEDNESDAY, JANUARY 12, 1977

Panel Members: C. Greskovich

Research and Development Center

General Electric Co.

Schenectady, NY

R. I. Jaffee

Fossil Fuel & Advance Systems

Division

Electric Power Research Institute

Palo Alto, CA

B. H. Kear

Materials Engineering and

Research Laboratory

Pratt and Whitney Aircraft, U.T.C.

Middletown, CT

A. I. Mlavsky

Sr. Vice President of Technology

Tyco Laboratories, Inc.

Waltham, MA

P. Slick

Bell Telephone Laboratories

Allentown, PA

3:30 p.m. CCFFEE

4:00 p.m. Svirmary

J. Elliott

Dept. of Materials Science and

Engineering

M.I.T.

Cambridge, MA

5:00 p.m. Buses leave NBS for hotel, airports
37

^.2 Abstracts

MONDAY. 10 JANUARY. 19

10:00 AM - 12:30 PM

REVIEWS OF THE PRESENT

STATUS OF

PHASE DIAGRAM CO^PIU\TION ACTIVITIES
38

M - 1

PHASE DIAGRAM COMPILATION ACTIVITIES IN CERAMICS

R.S. Roth, L.P. Cook, T. Negas , G.W. Cleek, and J.B. Wachtman

National Bureau of Standards

Washington, D.C. 20234

Phase diagrams play an important role in the development of ceramic

materials. Phase equilibria data are essential in meeting the expanding

needs for refractories, electronic components, non-crystalline solids, and

various other applications of interest to ceramic scientists and engineers.

Compilation of ceramic phase diagrams began in 1933, when the American

Ceramic Society published 178 diagrams, compiled by Hall and Insley. The

effort has been continued through the years by compilers at the National

Bureau of Standards. In 1964, a revised edition of "Phase Diagrams for

Ceramists" was published containing 2066 diagrams. This was followed in

1969 by a supplement containing an additional 2183 diagrams . A third

supplement, published in 1975, contains another 850 diagrams - this latest

supplement includes a discussion of the methods, data and interpretations

made in the construction of each diagram. Since the death of E.M. Levin

in 1974, this effort is being continued by a team of scientists actively

engaged in phase equilibria studies in ceramic research centers around the

country and abroad. This group is led by researchers at NBS who are assuming

the responsibility for collecting data from the literature, distributing it

among the group for evaluation, and coordinating preparation of the publication,

as well as preparing evaluations of systems in their own area of expertise.

This effort is being supported in part by the Office of Standard Reference Data.

There are some duplications of compilation activity in the ceramic sciences.

This is largely an international problem: the principal compilations in addition to "Phase Diagrams for Ceramists" are Russian. Such duplication is not

necessarily wasteful, since any publication would have to be made available

in both languages. Also, the two groups of publications, which are partly

independent, can be cross-checked for inclusion of otherwise missed obscure

references. A more complete review of other partial compilations in this field

will be presented.

A questionnaire was ' distributed by the American Ceramic Society in July

1976 to purchasers of the 1975 supplement requesting information from users

of this service. A 40% response allows a determination of user needs in phase

equilibria with a reasonably statistical probability of success. The major

categories covered in the questionnaire include a description of the respondent,

his uses of phase equilibria data and principles, evaluation of "Phase Diagrams

for Ceramists" as a publication of the American Ceramic Society and the users

needs for experimental and/or theoretical work not now being done. The statistical results of this questionnaire will be presented along with specific

examples illustrating user oriented problems.
39

M - 2

SEiMICONDUCTOR PHASE DIAGRAMS

by

CD. Thurmond

Bell Laboratories

Murray Hill, New Jersey 0797-^

. -The largest group of semiconductors for which

extensive phase studies have been made are the tetrahedrally

coordinated semiconductors with ^ valence electrons per atom.

The prototypes are the group IV diamond structure elemental

semiconductors C (diamond). Si and Ge . The binary zincblende

semiconductors, III-V and II-VI compounds, are members of

this class as are the ternary chalcopyrite semiconductors,

II-IV-V2 and I-III-Vl2^.-

-

. The range of properties of these semiconductors is

greatly extended by the occurrence of solid solutions of wide

composition range. For example, III-V compound solid solutions

of great practical interest are Ga., Al As and GaAs, ^P^.

Many other pseudobinary semiconductor solid solutigns have

been studied as h?.ve the associated ternaries.

The interest in this class of semiconductors lies

in the ability to alter their electrical and optical properties

with the addition of small amounts of donors or acceptors.

The donor (acceptor) - semiconductor phase diagrams represent

a la.rge portion of the phase equilibria of interest.
40

M - 2

The principal sources of reviews of evaluated phase

diagrams of the tetrahedrally coordinated semiconductors are

the following:

The Hansen^ Elliot and Shunk volum.es -"^^ which

contain many T-x binary diagrams for which Si or C-e is one

of the ccmiponents . A number of III-V and ll-'^n binary

(2 ) diagram.s are also given. ?. A. Kroger^ ^ whc has included

the phase diagrams of a nujnber of semiconductors in his bock.

Particular emphasis is given by Kroger to the Brcuwer diagram.

M. B. Panish and M. Ilegems who have critically evaluated

and presented a number of important ternary III-V system.s.

J. L, Shay and J. H. Wernicke who have included a critical

evaluation of a large number of chalcopyrites, I-III-V"Tp and

Il-IV-Vg compounds^ and solid solutions. M. Ilegems and C-. L.

Pearson^^ who ha.ve reviewed phase equilibria in IIi-V, ii-Vi.

and IV-VI compound sem.iconduc tor alloy system.s.

Other sources of information will also be considered

Of broader interest are electronic materials of whicl

semiconductors are a part. Some comm.ents will be made about

phase diagrams of other electronic materials.
41

1. M. Hansen, Constitution of Binary Alloys , 2nd Ed.,

prepared in cooperation with K. Anderko, McGraw Hill,

1958; R. P. Elliott, First Supplement , I965; F. A.

Shunk, Second Supplement , 1969.

2. F. A. Kroger, The Chemistry of Imperfect Crystals , Vol. 1, Preparation, Purification, Crystal Growth and

Phase Theory , and Vol. 2, Imperfection Chemistry of

Crystalline Solids , 2nd revised edition, 197^.

3. M. B. Panish and M. Ilegems, Phase Equilibria in Ternary

III-V Systems , in Progress in Solid State Chemistry , eds.,

H. Reiss and J. 0. McCaldin (Pergamon Press, New York) 1972,

Vol. 7, p. 39-83.

4.. J. L. Shay and J. H. Wernick, Ternary Chalcopyrite

Semiconduc tors ; Growth, Electronic Properties and Applicati ons

Pergamon Press, 1975.

5. M. Ilegems and G. L. Pearson, Phase Studies in III-V, II -VI

and IV-VI Com.pound Semiconductor Alloy Systems, Annual

Review of Material Science, Vol. 5. 1975^ p. 3^5-371.
42

M-3

Phase Diagram Compilations for Metallic Systems - an Assessment of Ongoing Activities

G. C. Carter, L. H. Bennett, and D. J. Kahan

Alloy Data Center

Metallurgy Division

Institute for Materials Research

National Bureau of Standards, Washington, D.C. 20234

Alloy phase diagrams provide a basis for solving many industrial problems. It is

(therefore not surprising to find critical phase diagram data compilation

activities generally concentrated in the more industrialized countries. Among

Ithese are extensive compilation projects in Germany ^-^-^

, France^^\ and the

USSR^"^-^ , all three well-established, outstanding centers. Numerous smaller

Bprojects, also of reputable quality, exist in England and other western European

countries, the USA Japan, and elsewhere.

Methods of preparing critical phase diagram compilations have undergone

f4') substantial changes since large products such as the USA's "Hansen" series was "produced. The reason is that in the past there existed an ample, though not

^excessive, amount of classical metallurgical data on the one hand, while, on the

other hand, theoretical models and computerized methods to obtain phase diagrams

from thermodynamic data were not yet adequate.

At the present time, the available phase diagram data have become so diverse and

numerous that a single, concise condensation for all binary alloys has become

impracticable for a single evaluation project to be carried out. This problem

becomes amplified for ternaries and other multi component alloys. The alternate

route, which applies improved computer facilities and increasingly sophisticated

Jmodels has therefore received greatly increased attention in recent years. These

methods either integrate existing experimental data with evaluated thermodynamic

data, from which equilibrium diagrams can be calculated, or simply use the

"thermodynamic data to predict equilibrium diagrams. This latter method becomes

—invaluable for alloys for which classical phase diagram determination experiments

are cumbersome, difficult, and lengthy (and often expensive). This is often the
43

M-3

case for multicomponent alloys utilized in industrial applications. Especially

for these alloys, specific groups of phase diagrams only in certain ranges of

composition need to be evaluated, and comprehensive phase diagram compilations are

not always a desired product for such specific needs. For instance, the PHACOMP

method was developed to determine phase diagrams of quaternary and other Ni -based

alloys in which certain hard intermetallic phases tend to precipitate after

solidification ^^-^

As a result of these computational developments, a large number of small projects

are now underway in various countries . Several o each other, forming larger groups such as CALPHADare now underway in various countries. Several of these projects collaborate with

(6)

The ADC will have available at the workshop, a comprehensive list of all existing

r7"l phase diagram compilations^ ^

, a comprehensive list of currently on-going phase

diagram compilation centers^ , and a list of the related phase diagram

calculation and evaluation projects briefly described above. Availability of

phase diagram data from these compilations, calculations, automated data banks,

and translations, will be reviewed, as well as programs of the other data centers.

(1) A major center is under 0. Kubaschewski , P. J. Spencer, and collaborators,

Inst, fur Theoretische Huttenkunde, R.-W, Technische Hochschule, Aachen.

(2) I. Ansara, C. Barnard, and collaborators, Laboratoire de Thermodynamique

et Physico-Chimie Metallurgique, Domaine Universitaire de Grenoble.

(3) N. V. Ageev, 0. S. Ivanov, and collaborators. Institute of Metallurgy,

Baikov Institute, Moscow.

(4) "Constitution of Binary Alloys", M. Hansen and K. Anderko, McGraw-Hill

(1958); Supplement I, R. P. Elliott (1965); Supplement II, F. A. Shunk

(1969) .

(5) L. R. Woodyatt, C. T. Sims, and H. J. Beatte, Trans AIME 218 , 277 (1960),

and W. J. Boesch and J. S. Slaney, Met. Prog. 86_, 109 (1964).

(6) CALPHAD - an international group on "Calculations of Phase Diagrams"

meetings are held about once a year to discuss progress and problems

in calculations and predictions of phase diagrams from thermodynamic

data.
44

M-3

This will be an update of the compilation in "Alloy Phase Diagram Data",

Lo H. Bennett, D. J. Kahan, and G. C. Carter, Mat. Sci. and Eng. 2£, 1 (1976)

.

In addition to the three major data centers in refs. (1) to (3), there

are a large number of other centers, which will be reviewed at the

Workshop. These are compiled in Appendix A (CALPHAD members) and

Appendix B (other data centers) of Reference 9, which will be updated

for the workshop. An abbreviated, ammended list, selecting some more

prominent centers of appendix B not listed above:

•L. Brewer et al., Inorganic Materials Research Div.

University of California, Berkeley, CA 94720

(prediction of high-temperature' mult i component alloy equilibria presented

in two-dimensional Brewer projection diagrams: review of Mo binary alloy

phase diagrams in preparation)

.

• Y. A. Chang et al.. Materials Department

University of Wisconsin, Milwaukee, WI 53211

(ternary copper alloy phase diagrams are being critically evaluated)

,

• K. Gschneidner, Rare Earth Information Center

Iowa State University, Ames lA 50010

(the Center's bibliographic files include phase equilibria, crystallographic

and thermodynamic data of rare earth alloys; phase diagram evaluations published)

.

• L. Kaufman, ManLabs, Inc., Cambridge, Mass, 02139

(ManLabs-National Physical Laboratory (U.K.) Data Bank- a computer -stored

numerical data file of thermodynamic data made available commercially),

• L. Merrill, High Pressure Data Center

Brigham Young University, Provo, UT 84602

(the Center's bibliographic files include phase transformations under pressure).

• W, Moffatt, Metallurgy and Ceramics Laboratory

General Electric Research & Development Lab., Schenectady, NY 12301

(compilations of unevaluated binary phase diagrams, for diagrams not encountered

in "Hansen"-Elliott-Shunk series, (ref . 4) )

• G. Petzow, et al., Max-Planck-Inst itut fi'r Metallf or schung

Institut fifr Werkstof f wissenschaf ten, Stuttgart-80, Busnauerstr. 175, Germany

(handbook on ternary phase diagrams: bibliography completed; comprehensive

handbook of data proposed) ,
45

4

I

A, Prince, Hirst Research Centre. General Electric Co. Ltd,

East Lane, Wembley, Middlesex, HA9 7PP, England

(critical evaluation of phase diagram data on Au -based alloys is in progress)

G. Raynor, Dept. of Physical Metallurgy and Science of Materials

University of Birmingham, Birmingham. B15 2TT, England

I

(in progress: critical evaluation of ternary phase diagram data on Au -based allo^i

compilation of a bibliography on mult icomponent alloy constitution)

•» E. Rudy, Materials Science Department, Oregon Graduate Center, Beaverton, OR 977(J

(evaluated phase diagrams of refractory carbide and boride systsns)

• K.- E. Spear, Materials Research Laboratory, Pennsylvania State University, I

University Park, PA 16802

(Evaluation of metal -boron phase equilibria; predictions of undiscovered phases

using electronic structure considerations) ,

(9) L. H. Bennett, G. C. Carter, and D. J. Kahan, CODATA Conference, Boulder,

{||

Colo, , June 1976.

I

I

II

[I

B

II

n

I

I
46

A paragraph taken from the submitted paper. ^ ^

ORGMISATION OF PHASE DIAGRAM IIIFORMATION lU THE

SOVIET UNION

N. V. Ageev, D. L. Ageeva, T. P. Kolesniitova , and L. A. Petrcva

Baikov Institute of Metallurgy

USSR Academy of Sciences

Institute of Scientific Information

Moscow

A critical overrieTT of the phase diagram information in

the Soviet Union suggests that:

(1) ixLformation on phase diagrams covers not just "binary

but also ternary and more complex systems;

(2) handbooks reproduce phase diagrams from original

publications without any modification;

(3) regular published infoimation on pliaae diagrams of

metal and oxide systems is produced;

(4) primary publications dealing with studies of phase

diagrams are not concentrated in any singls source, but scatte

red over several journals and serials;

(5) times spent on bringing infoi^aticn to user's notice

are: through VHTITI's abstract journal - for Soviet publications, 3 to 5 months; for foreign publications, 4 to 8 months;

throu{-h VIITITI's handbooks, three years;

(6) no '.Torks on critical review of experimental data,

such ac the handbook of U. Hansen et al, , are available;

(7) those handbooks that are being published are sold ou

too soon; and

(8) despite definite phase diagram description forma-s

sanctioned by practice, there are strict standard requirements

so that publications often lack essential data for a judgement

about reliability and quality of the phase diagrams
47

' Ll-4

Prom data covered by handbooks, one can conclude (see

Pigure) that the Soviet Union holda a major place in studie

of metal systems' piiase diagrams*

Uf3 usc-^ GO cnca — u-5 coctj ca — c^j i^o ^

05 o^o^ Q-j cncD o:) crs o^c^ cn c-j cncn cn cri cn years

years
48

Phase Diagrams of Materials at High Pressure

Leo Merrill

High Pressure Data Center

Brigham Young University

Provo, Utah 84601

A survey of polymorphic phase diagrams as a function of temperature and

pressure is presented for the elements and simple inorganic compounds. All

materials included in this survey are those for which cryst alio graphic data

are available. Phase studies of materials include the following formula

types: elements (69), AB (87), AB2 (78), AB^ (8), ABO^ (11), A^B, (67),

ABO^ (54) , and miscellaneous types (58) mainly of mineral systems or mineral

analogs. The number in parentheses is the number of materials which have

been tabulated in each formula type.

The preparation of high pressure phases falls into two principal

categories; (1) pressure and temperature induced structural transformations,

and (2) inorganic synthesis in which the product can be recovered either

stably or metastably. In general, in the case of pressure induced

polymorphic transformations, materials proceed to structures with higher

densities and higher cation coordination. The characteristic measurements

are the determinations of pressure and temperature behavior of the

liquid-solid and solid-solid phase boundaries. Occasionally some of these

phases may be retained metastably at atmospheric pressure. Many new

compounds and polymorphs have been prepared by inorganic synthesis. In a class of compounds it is often observed that a certain structural type is

found to exist up to a certain empirical radius ratio. Beyond this region,

the particular structure can not be prepared under normal synthesis

procedures. Due to the differential compressibilities of the component

elements of the compound, it has been shown that the range of a particular

structure type can be extended by high pressure synthesis. This has been

repeatedly demonstrated with compounds of the rare-earth series.
49

The study of high pressure phases has played an important role in the

basic understanding of solids. If one expands the free energy as a function

of temperature and volume, it can be shown to a first approximation that the

total energy of a system can be altered by the heat term which changes the

population of the energy levels, or by the work term which relates a change

in volume to a shift in the energy levels. The significance of pressure,

then, is that it serves as a convenient method to study the volume

dependence of physical properties. Pressure also has been a most important

parameter in the search for new materials, notably, synthetic diamond and

cubic boron nitride. The study of phases of geologic minerals with their

associated physical properties have made significant contributions to the

understanding of the structure of the earth's interior. Tables of

cryst alio graphic data for many of the high pressure phases are also

presented. .
50

MONDAY. 10 JANUARY. 1977

2:00 ?n - 3:30 PM

REVIEWS OF THE PRESENT STATUS OF PHASE

DIAGRAM COMPI!J\TION ACTIVITIES (CONTINUED)

AND

REVIEW OF EXPERMNTAL PHASE DIAGRAM

DETERMINATION METHODS
51

I PHASE DIAGRAM INFORMATION FROM COMPUTER BANKS

I. ANSARA

LABORATOIRE DE THERMODYNAMIQUE ET PHYSICO-CHIMIE METALLURGIQUES (L.A. 29) - E .N.S .E .E .G.

B.P. 44 - Domaine Universitaire - 3840] - SAINT MARTIN D'HERES - CFRANCE)

.

storage purposes arises from a nxmber of major pratical considerations. Firstly, since

the volume of information is extremely great, whether phase diagrams or the thermodynamic

properties of materials are concerned, computers provide a simple means of handling the

data. Secondly, modem technology requires that information be provided rapidly on the _ equilibrium phase stability of the materials that it uses. The computer enables such |

data to be calculated for the operating conditions of interest. Thirdly, the problem

of achieving consistency of all the available information for a particular system I

often requires tedious calculation procedures.

For these reasons, a certain nxamber of data centres have already established

computer programs for the storage, retrieval, and application of phase diagram information!

The centres currently involved in such work and their particular areas of interest will

be briefly mentioned. The basic differences in these data banks lie in the manner in

which the phase diagram is reproduced. The phase boundaries themselves may be mathematically described or they may be calculated from stored thermodynamic values. Examples of « both techniques applied to binary systems will be given as well as the structure of the I

data file. The thermodynamic approach to the calculation of phase diagrams of multicomponen

systems is mainly carried out using the properties of the limiting binary systems. The I

numerical aspects will be discussed and illustrated for two ternary systems.

The need to develop computer techniques for phase diagram calculation and

I

I

I

I
52

M - 7

Expevmental Techniques -in Phase D-iagram Determination

~ An Overview -

F. N. Rhines

Department of Materials Science and Engineering

University of Florida

Gainsville^ Fla. 32611

In his hooky "Phase Diagrams in Metallurgy" Professor Rhines

introduces his chaigter "Determination of Phase Diagrams" with the following

paragraph:

The modest collection of phase diagrams of metal systems that is now- available to us is the product of the painstaking labor of a very large

number of skillful investigators working in all parts of the world during

the past three-quarters of a century. It is a constantly growing body of literature, improving both in the extent of its coverage and in the precision of its content. Few, if any, diagrams may be considered complete

and final. Repeated investigation, with refinements in apparatus and

techniques, leads to their frequent revision. Much of this refinement has

been achieved through the modification and adaptation of a few basic

research methods to fit the special requirements of specific alloy systems.

It is not feasible, therefore, to present a collection of the "best" methods

of investigation (no method is " best " for all systems), nor is it feasible to give a standardized procedure for any one method. It is possible, however,

to outline the basic methods from which most of the specialized techniques are derived and to state those principles of investigation which are common to all cases.* For detailed guidance the investigator must, of necessity, turn to the research Uterature, because the specialized problems met in constitutional studies are almost as numerous as are the

alloy systems themselves.

"

^ A detailed outline of experimental procedures is given by W. Hume-Rothery,

J. W. Christian, and W. B. Pearson, "Metallurgical Equilibrium Diagrams," The

Institute of Physics, London, 1952. Some helpful experimental techniques are also described by A. U. Seybolt and J. E. Burke, "Experimental Metallurgy," John Wiley

& Sons, Inc., New York, 1953.

Professor Rhines will review the basic classical methods and several

refinementsJ as well as some new approaches to experimental phase diagram

determinations in his tutorial talk.

(1) F.N, Rhinesf "Phase Diagrmas in Metallurgy j Their Development and Application"

Metallurgy amd Metallurgical Engineering Series, R.F. Mehl ed. . McGraw-Hill,

N.Y.^ p. 290 (1956).
53

MONDAY. 10 JANUARY. 19

3:30 PM - 6:00 PM

PAPERS GIVEN BY POSTER

TOPIC I

PHASE DIAGRAM COMPIU\TION ACTIVITIES
54

MPSI - 1

Proposal for a Comprehensive Handbook on "Ternary Phase Diagrams

of Metals"

F. Aldinger, E.-Th. Henig, H.L. Lukas and G. Petzow,

Max-Planck-Institut fiir Metallforschung,

Institut fiir Werkstoffwissenschaften,

D7-Stuttgart-80, Biisnauerstr. 175

Today, constitutional data of ternary systems are available on a

large scale, but they are scattered over a large number of different reports, journals and books. In order to use this enormous amount of knowledge more extensively, our Institute together

with the Gmelin Institute has proposed to publish a comprehensive handbook on ternary phase diagrams.

For a proposal on this subject we prepared a literature survey

covering constitutional work carried out before 1974. This preliminary index comprises about 4000 references on about 1500 ternary systems of metals.

A rough estimate shows that about 400 systems are fully investigated, and about 600 are covered fairly well. Of the remaining

500 systems constitutional data are available only on a rather

limited scale. According to our concept the book will extend

to about 6000 pages 1 We are not going into details of organization and costs of this

project, but we will discuss the content of the handbook as well

as the kind of presentation of the systems and diverse nomenclatures. The content of the handbook includes a brief presentation of fundamentals of the heterogeneous phase equilibria together with a proper nomenclature, enabling to "read" the ternary phase diagrams which will be presented in the alphabetical

order of the chemical symbols. In addition to this the binaries

which provide the basis for the ternary diagrams should be listed

in an appendix. For this appendix a critical evaluation of the

available data is necessary to derive definite diagrams. That

means mainly to summarize data of the well-known books of Hansen

and Anderko as well as of the two supplements of Elliott and Shunk.
55

MPSI - 1

In order to discuss the format of presentation of the ternaries

we prepared three examples each representing one of the three

classes of systems mentioned above. The list of contents includes

1. A brief critical review of the work which has been published

in the literature

2. Ternary intermetallic phases

3 . Invarient equilibria

4 • Liquid surface

5* Isothermal sections

6.. Solid solutions

7. Miscellaneous (e.g. ordering, isopleths, etc.).

For this comprehensive work we wish to solicitate the cooperation of other institutes and organizations with experience in special groups of alloys. These institutions should

contribute to the publication by critically reviewing special

phase diagram data.
56

MPSI - 2

WO 3 -Containing Binary Oxide Systems

Luke L. Y. Chang

Department of Geology, Miami University, Oxford, Ohio

The purpose of this review is to summarize phase relations in WO 3 -containing systems and to present the compilation of phase diagrams according to the types of chemical compounds. Fourteen tungstate groups are selected for discussion

and their phase relations are presented.

For the alkali tungstates , in addition to the 1:1

and 1:2 (oxide/W03 ratio) compounds, which are common to all

systems, 1:3 and 1:6 compounds exist in the systems of K, Rb,

and Cs , and the 1:4 compound is stable in the systems of Li,

Na, and K. There is a tendency in their crystal structures

for the polyhedral WO6/WO4 ratio to increase from 1:1 to 1:6

compounds . In the alkaline earth oxide - WO3 systems , the

number of tungstates formed increases with the increase in the

size of the divalent cation. The Be system is a simple eutectic, the Mg system has a 1:1 compound with the wolframite-type

structure, and Ca , Sr, and Ba systems have both 1:1 and 1:3

compounds with, respectively, the scheelite-type and (NH4)3FeF6

type structures.

All rare earth oxide systems have 1:1 and 1:3^ tungstates. In the systems of large rare earths (La - Sm) , tungstates of other ratios also exist. The 1:3 compounds have

crystal structures closely related to the scheelite-type. The

actinide oxide - WO3 systems are represented by the formation

of a 1:2 compound in the Th system and a 1:1 compound in the

U system.

A 1:2 compound characterizes both Zr02-W0 3 and Hf02-

WO3 systems, and its crystal structure is related to the wolfra

mite-type. No titanium tungstates have been reported.

In the V2O5-WO3 system, only a 1:1 compound has been

reported, but a great number of compounds are known in the systems of Nb205 and Ta205. These are 30:1, 6:1, 7:3, 8:5, 9:8,

4:9, 2:7, 6:11, 1:11, 1:15 in the Nb system, and 41:4, 15:2,

41:8, 67:14, 89:22, 37:10, 59:18, 81:26, 11:4, 1:1 in the Ta

system.

The formation of a 1:1 compound has been reported in

the M0O3-WO3 system, but its existence is definitely in question. No study has been made for the system Cr03-W03, but a
57

MPSI - 2

1:1 compound forms between Cr203 and WO3 and has a tri-rutile

structure.

Phase relations of WO3 with FeO, MnO , NiO , and CoO

are characterized by the formation of the wolframite-type

(1:1) compound. In addition, a 1:1 compound is also present

in the Fe203-WD3 system. In the CUO-WO3 system, two compounds

1:1 and 1:3, have been reported, and a 2:1 compound was produced in the oxidation of WC on copper plate at temperatures

below 610'^C. CUWO4 has a distorted wolframite-type structure.

Tungstates of the Group IIB elements form 1:1 wolfra

mite-type compounds, although all but ZnW04 show distortion.

The formation of a number of boron tungstates such

as 3:1, 1:1, and 1:3, has been reported, but their stabilities

have not been confirmed. In both AI2O3-WO3 and In203-W03 systems, the 1:3 compounds are known, and they are isostructural

with SC2W3O12 • No gallium tungstate has been reported.

Tungstates of Group IVA elements are known only in

the systems of tin and lead oxides where the cations are in

their divalent state. SnW04 is dimoprhic with an orthorhombic

low-temperature form and a cubic high-temperature form. Two

lead compounds, 1:1 and 1:2, have been reported. The 1:1 compound has the scheelite structure.

A 1:1 compound is known in the P2O5-WO3 system, and

no arsenic tungstate has been reported. Other members of the

Group VA elements, Sb and Bi, show a trivalent state in their

tungstate formation. The Bi203-W03 system has four compounds,

7:1, 7:2, 1:1, and 1:2, and the Sb203-W03 system has a 1:1 com

pound

.

Phase relations in the system Te02-W03 have been stu

died, but no compound has been reported.
58 MPSI - 3

RIC IN PHASE WITH RARE -EARTH CONSTITUTIONAL DIAGRAMS

K. A. Gschneidner, Jr., M. E. Verkade and B. L. Evans

Rare -Earth Information Center (RIC)

Energy and Mineral Resources Research Institute

Iowa State University

Ames, Iowa 50010

Background

The Rare-Earth Information Center (RIC) was established at the Ames

Laboratory by the U.S. Atomic Energy Commission's Division of Technical

Information in 1966 and transferred to Iowa State University's Energy and

Mineral Resources Research Institute (formerly Institute for Atomic Research)

in 1968 with funding provided through grants from world-wide rare earth industries. The Center serves the scientific and technical community by collecting, storing, evaluating and disseminating rare earth information with

particular emphasis on the physical metallurgy and solid state physics of the

rare earth metals and their alloys.

Data Base

All available resources including books, journals, reports, conference

proceedings, etc. are canvassed by the Center's technically trained staff of

three (1 full time and 2 part time). Rapid and flexible retrieval of stored

information is provided via a computerized system utilizing over 7000 keyword

descriptors plus author indexing. Keyword descriptors are assigned following

an examination of the original document rather than relying on only the title or

abstract as do some indexing systems. Conversion of the information base from

manually sorted punched cards to computer-read magnetic tape, begun in 1 9 73,

is about three -fourths completed and includes most of the approximately IZ, 000

journal articles held by the Center.

Publications

Utilizing this extensive information base, the Center engages in various

publishing activities in addition to providing specialized literature searches on

request. The RIC News, a quarterly newsletter containing items of current

interest in science and technology of the rare earths, is distributed free to over

3550 subscribers in the U.S. and abroad. State-of-the-art reviews, bibliographie

and data compilations, prepared and published by RIC, have included a survey of

rare earth metals in steel (IS-RIC-4), compilations of thermochemical data for

rare earth compounds (IS-RIC-5 and IS-RIC-6), and a critical review of selected

cerium binary phase diagrams (IS-RIC-7). These reports are currently available free from the Center or the sponsoring industry, Molycorp, Inc., which
59

MPSI - 3

funded the study. Distribution of the reports is aided by publication announcements placed in appropriate scientific and trade journals, periodic

notices in the RIC News and inclusion in abstracting journals.

Evaluation of Constitutional Diagrams

The staff of RIC has been involved over the past fifteen years with

critical evaluation of phase equilibria, crystallo graphic and thermodynamic

data on rare earth materials. The major effort has been primarily concerned

with metallic systems. The evaluations on consitutional diagrams and crystal

structures have been published as books, review articles or reports.

Rare Earth Alloys, K. A. Gschneidner, Jr., D. Van Nostrand

Company, Inc., New York (1961) 449 -i- xiii pp.

"Rare Earth Intermetallic Compounds" by O. D. McMasters and K. A.

Gschneidner, Jr., Nuclear Metallurgy 93-158(1964).

IS-RIC-7 "Selected Cerium Phase Diagrams" by K. A. Gschneidner, Jr.

and M. E. Verkade (September 1974) 50 pp.

"Inorganic Compounds" by K. A. Gschneidner, Jr., and "Alloys and

Intermetallic Compounds" by K. A. Gschneidner, Jr., Chapters 8 and

9 (pp. 152-251 and 252-323, respectively) of Scandium, Its Occurrence,

Chemistry, Physics, Metallurgy, Biology and Technology, C. T.

Horovitz, K. A. Gschneidner, Jr., G. A. Melson, D. H. Youngblood

and H. H. Schock, Academic Press, New York (1 975).

In addition to the above efforts the 'staff has also been involved in evaluating

and estimating thermodynamic data for rare earth materials which are of

special interest to the preparation and utilization of common metals, such

as steel, ductile iron, superalloys, etc. These data compilations include:

IS-RIC-5 "Thermochemistry of the Rare Earth Carbides, Nitrides and

. . Sulfides for Steelmaking" by Karl A. Gschneidner, Jr. and Nancy

Kippenhan (August 1971) 2 7 pp.

IS-RIC-6 "Thermochemistry of the Rare Earths. Part 1. Rare Earth

Oxides, Part 2. Rare Earth Oxysulfides, Part 3, Rare Earth Compounds

with B, Sn, Pb, P, As, Sb, Bi, Cu, and Ag" by Karl A. Gschneidner, Jr.,

Nancy Kippenhan and O. Dale McMasters, (August 1973) 67 pp.

"Thermodynamic Stability and Physical Properties of Metallic Sulfides

and Oxysulfides", by Karl A. Gschneidner, Jr., pp. 159-77 in SULFIDE

- INCLUSIONS IN STEEL, J. J. DeBarbadillo and E. Snape, eds. , American

Society for Metals, Metals Park, Ohio (1975).
60

MPSI - 4

Phase Diagrams and Thermodynamic Properties

of Ternary Copper Alloy Systems

by

Y. Austin Chang

Joachim P. Neumann

U. V. Choudary

Materials Department

College of Engineering and Applied Science

University of Wisconsin-Milwaukee

Milwaukee, Wisconsin 53201

Phase diagram and thermodynamic data for copper alloy systems are of considerable fundamental and practical interest in many aspects of extractive,

chemical, and physical metallurgy. These data have been reported for binary

copper alloy systems in a critical evaluation by Hultgren and Desai [1], which

forms one of the monographs in the series, "The Metallurgy of Copper", sponsored by the International Copper Research Association (INCRA) . Since commercial alloys usually consist of more than two components, it is imperative

to extend the work of Hultgren and Desai [1] to ternary copper alloy systems.

At the suggestion of Dr. L. McDonald Schetky of INCRA, a project to compile

and evaluate phase diagrams and thermodynamic properties of ternary copper alloy systems was initiated in 1972 at the University of Wisconsin-Milwaukee. A

total of 38 elements in addition to copper was considered for evaluation. These

38 elements are Ag, Al, As, Au, B, Be, Bi, C, Ca, Cd, Co, Cr, Fe, Ge, Hg, In,

Mg, Mn, Mo, Nb, Ni, 0, P, Pb, Pd, Pt, Re, S, Sb, Se, Si, Sn, Ta, Te, Ti, V, W,

and Zn. The non-metallic elements 0 and S are included because of the technological importance of ternary systems containing one of these two elements. A

simple calculation shows that all combinations of these 38 elements yields a
61

MPS! - 4

total of 703 ternary copper alloy systems. A literature search mainly based

on Chemical Abstracts through June 1973 indicated that data were available

for roughly 300 ternary copper alloy systems. In view of the rather large

number of systems and in view of the fact that some of these systems are of

less commercial interest, the total number of systems for inclusion in this

project was reduced to 181. As of October, 1976, a total of 85 ternary copper

alloy systems has been completed. These 85 systems are:

(1) 20 Cu-Ag-X systems where X represents Al, Au, Cd, Fe, Ge, In, Mg,

Mn, Ni, P, Pb, Pd, Re, S, Sb, Se, Sn, Te, Ti, or Zn;

(2) 17 Cu-Al-X systems where X represents Be, Bi,_Cd, Ce, Co, Cr, Fe,

Ge, In, Mb, Ni, Pb, Pd, S, Si, Ta, or V;

(3) 7 Cu-Au-X systems where X represents Co, Fe, Ni, Pb, Pd, Sn, or Zn;

(4) 2 Cu-B-X systems with X being either Ni or S;

(5) 8 Cu-Be-X systems where X represents Co, Mg, Mn, Ni, Si, Sn, Ta,

or Ti;

(6) 3 Cu-Ca-X systems with X being Ge, Mg, or Si;

C7) 1 Cu-Cd-S System;

(83 8 Cu-Co-X systems where X represents Cr, Fe, Mn, Ni, Pd, Si, Sn, or

Zn;

(9) 7 Cu-Cr-X systems where X represents Fe, Mn, Nb, Ni, Pd, Ta or Ti;

(10) 1 Cu-Ga-S system;

(11) 1 Cu-Ge-S system;

(12) 1 Cu-Mn-S system;

(13) 1 Cu-Mo-S system;

(14) 1 Cu-Nb-S system;

(15) 1 Cu-Pd-Pt system;

(16) 1 Cu-Re-S system;

(17) 4 Cu-S-X systems with X being Si, Ta, Ti or V;
62

MPSI - 4

and (18) 1 Cu-Ta-V system.

They contain a total of 166 diagrams (liquidus projections, isothermal

sections, isopleths and thermodynamic properties) and a total of 16 general

references and 360 specific references.

Reference

[1] Hultgren, R. , and Desai, P. D., INCRA Monograph I, Selected Thermodynamic

Values and Phase Diagrams for Copper and Some of Its Binary Alloys , The

International Copper Research Association, Inc., New York, 1971.
63

MPSI - 5

PHASE EQUILIBRIA IN VARIABLE VALENCE OXIDE SYSTEMS

William B. White

Materials Research Laboratory and

Dept. of Geosciences

The Pennsylvania State University

University Park, PA 16802

Some 40 elements react with oxygen to form a series of compounds in which

the element appears in more than one valence state. These include most of the

transition elements, a group loosely referred to as the Rydberg elements, in which

one of the stable valence states is formed by the creation of a nonbonding lonepair electron system, a few of the lanthanide elements, and most of the actinide

elements. The objectives are to compile a complete set of phase diagrams for

all variable valence element-oxygen systems. This is accomplished by assembling

the usually fragmentary diagrams from the literature into a single internally consistent (which does not necessarily mean "accurate") diagram and by using thermochemical calculations where possible to estimate missing parts of the phase diagram

The systems under study are tabulated in the table. Three types of systems

can be distinguished: (i) those in which the solid phases are refractory and in

which the oxygen fugacity in the vapor phase is low, so that equilibria can be

represented by mapping solid-vapor equilibria as fugacity lines on the T-X diagram

that shows the SS and SL equilibria; (ii) systems in which the oxygen vapor pressure is large, so that the effect of pressure on SS and SL equilibria must be

considered, and (iii) systems in which one or more oxides is volatile becomes an

important constituent of the vapor phase in some temperature-pressure regime.

Systems of type (i) are listed as "f-T-X" and of types (ii) and (iii) as "P-T-X"

diagrams in the table. For those systems whose status is "-H-+" enough data are

available to prepare nearly complete diagrams including melting relations, solidvapor equilibria, and compositions of nonstoichiometric compounds as a function

of oxygen activity. Systems listed as "++" are less complete and for systems

listed "+" there are only fragmentary data.
64

MPSI - 5

Status of Variable Valence Element-Oxygen

Binary Phase Diagrams

System Type of

Representation Status System Type of

Representation Status

Transition Element Systems Pt-0 P-T-X ++

Ti-0 f-T-X +++> Au-0 P-T-X +

V—

U

r— 1—

A

1 1 Rydberg Systems

Lr—

U

O T V t 1 1

1 1 1 As-0 P-T-X -HMil A f-T-X

P-T-X

ri* Sn-0 f-T-X -HFe-0 f-T-X Sb-0 P-T-X +

Co-0 f-T-X

P-T-X

++ Tl-0 f-T-X +

Ni-0 P-T-X + Pb-0 P-T-X 1' 1

' 1

Cu-0 f-T-X -H- Bi-0 P-T-X ++

IN D—

U

I — i—A.

1 ' '

1 1 1 Lanthanide Systems

CIO—

U

r— i—A, 1 1 1 Ce-0 P-T-X 1 t 1

1 1 1

iC—

u

D_T_V r— i—

A

j_ Pr-0 P-T-X

f-T-X

I 1 1

Oil d "D T V r— i—

A

1 "T Eu-0 f-T-X 1 1 1

Ka—

U

•Q T V r—i—

A

_j 1 T-r Tb-0 P-T-X

f-T-X

t 1 I

1 1 1

r a—

u

"D T* V r—i—

A

PT Actinide Systems

Ag-0 P-T-X ++ U-0 f-T-X +++

Ta-0 f-T-X +++ Np-0 f-T-X ++

W-0 f-T-X +++ Pu-0 f-T-X -HRe-0 P-T-X + Am-0 f-T-X +

Os-0 P-T-X + Cm-0 f-T-X

Ir-0 P-T-X ++ Bk-0 f-T-X +
65

MPSI - 6

PHASE DIAGRAMS FOR CERAMISTS

L.P. Cook, R.S. Roth, T» Negas and G.W. Cleek

Institute for Materials Research

National Bureau of Standards

-^1-..-- Washington, D.C. 20234

Compilation of phase equilibria data of interest to ceramists is

continuing, in accordance with the pattern established by the 1975 supplement to "Phase Diagrams for Ceramists". This latest supplement includes

critical commentaries discussing preparation of starting materials,

experimental methods, characterization of products, accuracy and precision

of data and of diagram. The following experts in various fields are serving

as Contributing Editors for the 1978 Supplement:

- J. J. Brown, Virginia Polytechnic Inst.

Fluoride containing systems

- L. L. Y. Chang, Miami Univ.

Tungstates, molybdates, carbonates

- R. C. DeVries, General Electric Co.

High pressure studies

- F. P. Glasser, Univ. Aberdeen

Alkali oxide containing systems

- F. A. Hummel, Pennsylvania State Univ.

Sulfides, phosphates

- K. A. Jack, Univ. Newcastle Upon Tyne

Nitrides, oxynitrides

- A. Muan, Pennsylvania State Univ.

First row transition metal oxide containing systems

- C. Semlar, Ohio State Univ.-

Anhydrous silicate - oxide systems

- C. A. Sorrell, Univ. Missouri-Rolla

Aqueous salt systems

- K. Stern, Naval Research Laboratory

Binary systems with halides only

- R. Thoma, Oak Ridge National Laboratory

Fused salts

- D. R. Wilder and M. Berard, Iowa State Univ.

R.E. oxide bearing systems

- H. S. Yoder, Jr., Carnegie Inst. Washington

Hydrous silicate systems, high pressure silicate studies
66 MPSI - 6

Scientists at NBS (Cook, Roth and Negas) with the help of the American Ceramic

Society (Cleek, Smith and others) are assuming much of the responsibility for

gathering the data from the literature and coordinating the preparation of

evaluations and final editing of diagrams.

Coverage according to chemical system for the various editions is as follows

:

1964 1969 1975 1978

Metal-oxygen systems 146 202 104 ^205

Metal oxide systems 855 408 401 'V655

Systems with oxygen containing

radicals 172 228 68 '^^120 Systems with halides only 483 718 145 ^365

Systems containing halides

with other substances 214 273 72 '^^160 Systems containing cyanides,

sulfides, etc. 43 82 20 ^140

Systems containing water 151 131 40 ^250

Results of a questionnaire are being analyzed to determine user interest as

a function of chemical system and user opinion regarding the critical com- mentaries, in order to guide the preparation of future editions.
67

MPSI - 7

NBS CRYSTAL-DATA CENTER

A. Mighell, H. Ondik, J. Stalick, R. Boreni

Institute for Materials Research

National Bureau of Standards

Washington, D.C. 20234

The NBS Crystal-Data Center abstracts and critically evaluates

crystallographic data. For a siibstance to be included in the crystaldata file, cell parameters must be reported for the material. These

parameters are determined primarily by powder and single-crystal x-ray

diffraction. Crystallographic data results from a variety of disciplines

and, consequently, is taken from over 300 scientific journals. The

total nimber of crystalline compounds now in the file is over 40,000.

The output of the project includes:

1. Crystal Data Determinative Tables: Used to identify crystalline

materials via the ratios of the cell parameters. The most recent volume

piiblished is the third edition. ^ A supplement to the third edition will

be issued in 1977.

2. Crystal Data Space-Group Tables: Materials are arranged by space

group. These tables can be used to identify materials of any given

space group or symmetry, and to identify isostructiiral materials. These

tables will be consonant with the third .edition of Crystal Data. They will

be published in the Journal of Physical and Chemical Reference Data in

the Spring of 1977.

3. NBS Magnetic Tape #9:^ This tape is an abbreviated version of the

third edition of Crystal Data and contains cell, space group, density,

formula, and determinative ratios. As supplements to the third edition

are published the tape will be updated.

4. Component of CIS (Chemical Information System) which is being set up by

NIH/EPA: The crystal-data file will be in the CIS system along with the

powder-data file, the Cambridge structural file, the mass spectroscopy

file and other scientific data bases. These files are to be used primarily

in the identification of unknown crystalline materials.

A principal use of the cell and chemical data is the identification

of unknown crystalline materials. Several recent developments give

great promise for the identification of unknown materials via singlecrystal work. They include the growth of the data base, advances in

lattice theory, and automation of the single-crystal x-ray diffractometer

.

To identify an unknown, one can start with a single crystal, mount it on

a diffractometer , determine a refined primitive cell, reduce the cell,

and check against a file of known reduced cells. The entire procedure

can be automated. As a result, the single-crystal x-ray diffraction

method can now complement the powder method for the routine analysis of

crystalline materials.
68

MPSI - 7

A major objective of the NBS Crystal-Data Center is to establish

close ties with other data efforts with common interests and to coordinate

our data evaluation with these centers (e.g. Joint Committee on Powder

Diffraction Standards, Cambridge Crystallographic Data Centre, The

Chemical Information System)

.

^ J.D.H. Donnay and Helen M. Ondik, "Crystal Data Determinative Tables,"

Third Edition, Vol. 1 and 2, U.S. Department of Commerce, National

Bureau of Standards, and the Joint Committee on Powder Diffraction

Standards (1972, 1973).

^ For infoinnation about the tape and its lease, contact the National

Technical Information Service (NTIS) , Department of Commerce, 5285 Port

Royal Road, Springfield, VA 22151.

DMONSTMTION : The NBS magnetic tape #9 desavibed undev item 3 of this

abstract will be accessed in an accompanying demonstration of "On-Line

Data Retrieval and Analysis Systems Such as OMNIBATA"^ by B. 3. Molina

and J. Hilsenrathj NBS.
69- MPsr

The NBS Alloy Data Center

G. C. Carter, D. J. Kahan, and L. H. Bennett

Metallurgy Division

Institute for Materials Research

National Bureau of Standards

Washington, D.C. 20234

Knowledge of the structure of materials is important in understanding several

industrially significant phenomena and applications such as aging, hardness,

occurrence of brittle intermetallic compounds, magnetic transition temperatures,

high-temperature solubility of impurities, corrosion resistance, solid

electrolytes and non-crystalline solids, as well as many other physical

properties. The study of a phase diagram appropriate to a particular material can often provide information important to its scientific and technical applications.

In recent years it has become increasingly clear that the need for reliable phase

diagrams far exceeds the availability, and the Alloy Data Center is now addressing

this problem in some detail.

As a result of this need, our present workshop has been organized, with as goals:

to assess the current national and international status of phase diagram

determinations and evaluations for alloys, ceramics and semiconductors; to

determine the needs and priorities for phase diagram determinations and

evaluations; and to estimate the resources being used and potentially available

for phase diagram evaluation.

Currently, several data centers thoughout the world are engaged in collecting,

critically evaluating, and disseminating phase diagram data. The Alloy Data

Center plans to interact with these groups and hopes to coordinate some of their

activities in order to help avoid costly and time consuming duplication of

efforts, as well as to identify areas of greatest needs and recommending programs

in these areas. In order to achieve these objectives, the Center has already

prepared a compendium of existing phase diagram compilations and other reference

material and a list of existing phase diagram evaluation groups (both data
I

I

i

'^^ MPSI-8

(2)

enters and groups involved in CALPHAD-type computational techniques ) . Updated

(lists with this information will be available at the workshop, as well as some

esults from a study on phase diagram data activities and data needs conducted via

questionnaire sent out to participants in this workshop.

i

i

he Alloy Data Center plans to critically evaluate phase diagrams in specific

areas, and has started with metal -hydrogen systems applied to a hydrogen storage.

ssistance in phase diagram evaluations carried out by other groups-is planned

through creating a central computerized bibliographic file with on-line

apabilities; development of an on-line system using graphical methods for the

numerical phase diagram data is also planned for user accessibility.

I

E

i

i

In general, the Alloy Data Center maintains an awareness of about 150 physical

roperties in metals and alloys, evaluating only those properties for which a pecial need exists and for which qualified researchers are employed in the Alloy

hysics Section, in which the Alloy Data Center is located. In the past, critical

ompilations in soft x-ray spectroscopy ^^-^ and nuclear magnetic resonance ^'^^ were

repared (the latter including some 800 binary phase diagrams) . Consequently, our

urrent bibliographic files which contain nearly all papers on the first two

subjects published up to recent years are not being kept up-to-date, while papers

jan phase diagrams are being annotated and entered at an increased rate for

production of a comprehensive bibliographic file. This file is expected to become

|::iuite large and warrants modifications of our current computerized system to an on-line system which can be queried from terminals located at user sites. The

bove-mentioned development of graphical methods for numerical phase diagram data

andling is a separate goal in numerical data dissemination.

'At the poster session, an exhibit of several of the phase diagram reference books,

(of the current annotated indexing system, and of some preliminary graphical

techniques for phase diagram display will be presented.

I

ICI) L. H. Bennett, D. J. Kahan, and G. C. Carter, Matls. Sci. Eng. 24_, 1 (19^6)

(2) L. H. Bennett, "Alloy Phase Diagram Activities of the Alloy Data Center",

5th International CODATA Conference, Boulder, CO., June 28-July 1, 1976.
71 HPS 1-8

(3) Soft X-ray Emission Spectra of Metallic Solids: Critical Review of Selected

Systems and Annotated Spectral Index, J. R. Cuthill, A. J. McAlister, R. C.

Dobbyn, and M. L. Williams, NBS Special Publication No. 369 (1974).

(4) "Metallic Shifts in NMR", G. C. Carter, L. H. Bennett, and D. J. Kahan, Progress

in Materials Science 20_, 1-2260, Pergamon Press (1977].

(5) File, described in NBS Technical Note 464, by G. C. Carter et al, (1968); the

file holdings up to 1970 published in "The NBS Alloy Data Center: Permuted

Materials Index", by G. C. Carter et al. (1971); the file holdings through

1972 made available in NBS Magnetic Tape 3, Alloy Data Center Tape and

Docummentation Parcel, Natl. Tech. Info. Ser. , Springfield, VA. 22151.

DEMONSTRATION: A demonstvation "Alloy Data Centev Graphiaal Methods" hy R. A.

Kivsdh and L. J, Swartzendniber^ NBS^ will he oarvied on during the poster session.
72

MPSI-9

Phase Equilibria in Cryolite Systems

Jesse J. Brown, Jr.

Department of Materials Engineering

College of Engineering

Virginia Polytechnic Institute and State University

Blacksburg, Virginia 24061

The electrolyte used in the Hall process for producing aluminum

metal consists basically of a fused mixture of alumina (Al^O^) and

cryolite (Na JOAlF ) . Other ingredients including AlF. , LiF, and CaF„

J Z are added to modify properties such as bath density, electrical conductivity,

and freezing temperature. The electrolyte composition now used was

determined largely by trial and error because of the incompleteness

of available phase equilibria data.

For the past five years, a research program jointly sponsored by

the Alcoa Foundation and the VPI&SU Research Division has been underway

in the Materials Engineering Department at VPIStSU. This program was

designed to critically review the existing phase equilibria data on

systems involving cryolite and to expand upon this body of knowledge

by determining the liquidus-solidus phase relationships in a portion

of the LiF-CaF^-AlF^-NaF-Al^O^ system.

Historically a variety of experimental techniques have been

employed to determine the phase diagrams of systems important to the

Hall process. Many of the early experiments were conducted using open

containers. This practice resulted in the publication of some inaccurate

phase diagrams because of the decomposition of many of the fluoride

compounds at high temperatures. In more recent years, it has become

standard procedure to encapsulate all samples in sealed platinum

containers. Quenching and Differential Thermal Analysis (DTA) experiments
73

MPSI-9

using samples sealed in the platinum containers have been used to revise

some of the early phase diagrams and to investigate new systems.

In this paper, the phase diagrams that are known in the LiF-CaF^-

AlF^-NaF-Al^O^ system are reviewed in a systematic manner and the

diagrams that have been determined at this University over the past

five years are included. The result is a current review of the phase

equilibria knowledge of cryolite containing oxy-fluoride systems of

importance to the aluminum Indus try
74

MPSI-10

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Huw npoussyTOHHHX (Jaa c onjicaHHeM b pnjie cjiy^aes cboiIctb cn-iaaoB.

OCieu 5-ro TOMa npeanojiaraeTCH 59 ne^aTHHX jikctob c paccuoTpeHiieu okojio 140 cwcTeu.

B Ka^ecTBe ochobhhx liaTepwajiOB fljifl HanncaHHH ir^pe^HCJisHHux
76

MFSI-10

Bme Tpy;i03 cLBTOdh vicnojiLsytoT cboio 0(3:::ipHyK] KapTOTOKy, Hauajio

KOTopoK ChLJiQ ncjiozsHO G^H^iM 113 Hic^ (A.^.Bo.t) sqs 3 I93I r., KornoflroTa3Jr:i2ajiiiC3 k visaaKiiio khi-ipm "[InHK ero cnjiasti" (CraMaapTrn3, 1933 r.), "H:iKeJi5 n ero cn-iasK" (43eTMeT::3;iaT ,IS32r.

)

H "KpetiHHCThi3 (5pOH3H ii tcc npoj,iiiiiiJi3HK08 np:i:i9KeH:i3 " (Odz)^;,:!:-:.

Hay^HO-TexHiiu. :!3;i-30, I935r.). iia KapT0T3Ka npo^ojT.-iajTa i-i^npsptiSHO nono.iHHTLCfi no noibiM JiiiTspaTypKHii ^CTOuHiiica:! '/i 3 HacTonme?

BpeMH BKJiioqasr b cedn KapTC^Kii no niiT3paTypHHM ;;aHHbiM no 1973-

-1974 r.r. BKJiKJqiiTsnBKO, K'aiszraH KapToqKa h3jIH5-i:ch noapodMiiLi pe-

$epaTou c npPL~cz3H:i5ii rpasHKOs h ladJiim opwrwHajiBKoro iicronHZKa

no jiBOiiHH!! cncTSiiaji h coAepsciiT jiaums , iicnojiBayeLiHe aBTopa:.:;!

B csoHx Tpy^ax npii on^icaHiiii toa iurii iiKoTi c:ict9?jh. KapTC^K:: cocTaa

JifliOTCfl tojILko uO nspBoiicToqKiiKaw. ilaze 2 tsx cjiy^aHic, Kor^a ni:sSTCfl aacjiyziiBaiomafl aObsp'/IH KOiim-ijiHuiiH (nanpiiLisp KHnrii XaKC^Ka,

3jiJiH0TTa H lilsHKa no aboiIkhm ciiCT3Ma2.[) , :i::3rDn;iiecH b h:ix cclijikii

Ha opiiriifiajiBHHe padOTii, acnojiBsyioTCH Kan <5;idjT:iorpa5aqecK:i3 ^anHHe 2JIH cocTaB-iSEHH noiipo(5KOii KapToqKii nc n3p3c:iGT0^K::y.a:.i. 3ro

odycJiOB.ieHO Teif, ^to b ynoiifiHyTbix padOTOx npH30iSTCH TcniKO ^iiarpanubi cocTOflKiifl 11 h8T HiiKaK^ix jaHEbix no CBOiiCTBa.v: cnjiasoB, ::cc.-i3-

jtOBaHiiH KOTopbix noc-Ty:si'iJi'.T 0CH0BaHH3ii a-iH nocTppsHiifl Airarpaiiu

B cjiy^ae He303Li0HH0CT:i osHaKOMJisHHH c nepBOMCTO^Hi'ii-cajiii - iicnojiB3yE3TCH AdHHHe KOUnJIJIHTHBHBIX pa(30T C CCLLJIKa^iil KaK Ha n'^pBOIICTOqHHK, Ta*K H Ha KOMnKJIHTIIBKyTO pa(5oTy.

Badop CTaTeit cocTasJioHiiH nojpodHHic KapToqeK npoiisBOziiTTCH:

!• nyTSM CHCTeMaTHV'ecKoro npocMOTpa uejioro pHiia sypHa-nos, :!3;;aBaeutDC B CCC? ii b JipyriEC CTpanax (^epe^^3HL sypHajioB c?j. hhs9);

2. nvTeu CLiCTeaaTnqscKoro npocwoTpa Metallurgical Abs-fcracts

In Journal Institute ot Kstals (London)

;

3. nyTefi cucTetiaTH^iecKoro npocuoTpa peiiepaTiiBHUx AypiiajioB

"MeiajiJiyprHH" h "Xhuha", HsaasaewKX e CCC?,
77

MPSI-10

KjiaccM^HKoUiiH KapTo^eK B KapTOTeKe no.iHOCTSfo OTs-^qasT npiiHflTO^ ;i3iiaHMfl TpyjiQB. Kasaot^y 3Ji3U3HTy nep:i05""scKott c:ict5-

UH II«ii-"'eHJieJiee3a npucBoea ro-qkaKOBu^ Hoiisp, coQT2iTCTByioin;iri oro

pacnojiOHeHiiio no HaLmsKOBaHiiio b pyccKow ajigaBiiT^, a dHHapHan ciicreUa 0(503KaqaSTCH apOdHilU q;iG-10M, COCTOHIHI^ll K3 nopfiSKOBIiX H0:43pC3

o(5oicc Bxo?.niniix b Hee ajieiisHTOB. ilo STOfl KJiaccaiiiEaiiim, HanpnM3p,

asoT 0(5o3Haq5H uiigpoii I, a-iioLiiiHiiii - migpoTi 3, BaaaAiiii - uHcpoil

7, a ciuian c;ict8ii: asoT-ajiSMiiHiiil - ^ipodnHM qncjiOM 1/3, cLTior^iiHiir: -

- sanaaM - 3/7, a30T - Banaa^iii - 1/7 n t.a. TaKan Hy?i?paij;;iH KapTOqSK AaeT B03IiOSHOCTB ^HCTpO paCCOpTIIpOEaTL vIX 'A pacnOJIOHIITB 5

KapT0T3Ke 3 TOM nOCJI3 A0BaT3JILH0CTIl , 3 KaKOH On:iCH5aiOTCH CHCT9i:iI.

HepeqeHB ciiCTe..iaTMuecKJi irpoc^aTpiiBasLiHx zypKa-ios:

1. ATOMHaH 3HSpriIH,

2. ^toKJiasH Ak2j:9M3iii KayK CCCP,

3. lypHaJi HeopraKHq^CKOii xinjiiii,

4.. SypKaji i7p'viKJia;i;K0i1 Xyiiiiiii,

5. lypnaji CTpyKTypHoTi xn?i:iii,

6« lypnaji cbHSinecKori x:iMir^^

7, 5l3B3CT7iH AKa23Mii:i HayK CCCP. HeopraKiiqecr;:i3 }£aT3pnajiH,

8,. HasecTUH AK3ji9;iii"ii KayK CCCP. i^sTaJiJiH,

9. MsBSCTiiH Bbicniiix yqedHHX 3a3353HHJi. UBeTHan iisTa;"::iiypr;iH

,

10. KpHCToJIJIOrpaf^Hfl

,

11. MeTaji-iOB3S3KJi3 H TspMimecKaH o6pac5oTKa ii-^TajisoB

,

12. yKpa;iHCKnit xJiLiiiqecKiiJl zypiiaji,

13. $K3HKa MOTSJIJIOB H iI3TaJIJI0B3A3H2e

,

I4» Acta Crystal 1 ograpMcay

15 • Acta Ketallurgica,

16. Conptes rendua Acad, Sci,, Paris,

17. Joum. Less-CoEinoa Metals,

18. Joum. Institute of Metals,
78

MPSI-10

19. Transactions ASM, 1 , iflOr

20. Transactions kllZjL (Trans, Metallur^. Soc. klVZ)^

21. Metallurgical Transactions c ^^ilO i

.

22*. Zeitschrift fir anorganische CherJ.e,

23. Zeitschrift ftir iCristallographie

,

24. Zeitschrift ftir Metalllcunde

.

n

Br-isf Summary

The 3rdj 4thj and 5th volumes of the '^Handbook of B-inary Metallic Systans

and the Methods of acmpilation a editing.

by A. E, Vol & E. K. Kagan

Leningvad, USSR
79

MPSI-10

An English translation of MPSI-10 prepared by G, MarinenkOt Analytical Chemistry

Division, Institute for Materials Research, NBS.

Brief Information on the Content of the Third, Fourth, and Fifth Volumes of the

Collection "Structure and Properties of Binary Metallic Systems" by A. E. Vol

and I. K. Kagan, As Well As Presentation Of The Methods Of The Work In Compilation

Of These Voltmes

A. E. Vol dnd I. K. Kagan

Leningrad, USSR

In all of the volumes a single principle of organizing the material was

adhered to; namely, both metals, as well as the T)inary syst^Tus which these metals

form, were arranged in alphbetical order in accordance with their chemical symbols

In the Rtissian language. At the same time for each system, dependi:?g on the degree

to which the system was studied, the following data were cited:

(1) . Phase Eiagram and Crystal Structures;

(2) . Physical and Mechanical Properties (Tnermodynamic, Mechanical, Electrical,

Thermoelectric and Magnetic Propertie-3, Surface Tension and Viscosity,

Vapor Pressure, Density, Heat Capacity.^, Thermoconductivity , and

Thermal expansion)

;

(3) » Mechanj cal Properties (Corrosion Stab.'lity under atmospheric conditio as,

- as well as in various other corrosive media and gasses , Oxidation

StabiL" ty at elevated temperatures) ; (4) , Enumer* tion of bibliography which was used.

The authors devote extremely great attentioi' to the question of fuller utilization

of data which are available in the literature on each of the considered systems. In

writing the third volume, which contained syste.Ti of Au, In, Ir, Yb, and Y, data were

utilized which were published until 1970-1971 inclusively. In preparation of the

materials for the fourth volume which included Cd, K, and Ca systems, data were utilized

which were published until 1973-1974 inclusively. In compilation of the fifth

volume, which contains 0, Co, and Si systems, literature data published until 1975-1976

inclusively were utilized.
I

80 MPSI-10

I

The third volume (amounting to approximately 70 printed pages) , publication

of which la expected to be in Nov. -Dec. 1976* the data are cited on 288 binary

I systems, including phase diagrams over the entire composition range and detailed studies

of the properties for 116 systems; for 23 systems phase diagrams are provided, but not

I

over the entire composition range and the descriptions of the properties are less detailed;

Information on the solubility in liquid and solid states, composition of the intermediate

^phases with the description in a number of cases of individual properties are given

I for 149 binary systems.

In constnicting the phase diagrams the preference was given for data which

I

were obtained with the study of the purest alloys with simultaneous use of several

modem methods of physico-chemical analysis. In thosi cases where the data available

I

to the authors were insufficient for a single-valued decision, two variations were

included in the book for the same phase diagram indicating the literature data

(which were utilized for the construction of each of these (see for example the

following systems: Au-In, Au-Pu, In-Mg, In-Na, In-Tl , Ir-Ti)

.

I The scope of literature utilized in the third volume can be illustrated with the

I following example: in considering the Au-Cu system, 345 literature sources were used,

for In-Sb system 214 sources were used, while for Au- Ag system, 162 sources were

j utilized. Thus, for these three sytems only, more thi'.n 700 literature sources were utilized.

I In the fourth voltone (approximated 50 printed pages) 163 systems are considered.

Phase diagrams are pro-*ided over the whole composition range and a detailed review

I of the properties of 5 i alloy systems is made. For tie remaining 109 systems,

information is given oi the mutual solubility of the :omponents of the systems and/or

I composition of the intermediate phases which are form»^d by the component metals

I along with a description of the properties of the alleys in a number of cases. The fifth volume is expected to be approximately 50 printed pages and to contain

I approximately 140 systems.

* , Translator's note: has been published by "Nauka", Moscow, 1976.
81

MPSI-10

The basic materials which were used for compilation of the above cited work were

the extensive card file of the authors, which was initiated by one of the authors

(A. E. Vol) back in 1931, when the books "Zinc and Its Alloys" ("Standartgiz" Publishing

House, 1933), "Nickel and Its Alloys" ("Tsvetmetizdat" Publishing House, 1932) and

"Silicon Bronzes and Their Industrial Aplications" ("Ob'Yedin. Nauchno-Tkhnich."

Publishing House, 1935) were being prepared for publication. This card file

vas continuously updated from new literature sources and at present includes

literature data up to 1973-1974 inclusively. Each card is a detailed reference with

the attached graph and tables of the original soiree on the binary systems and contains

data which are utilized by authors in their worV in describing these various systems.

The cards are compiled only from the original sources. Only in those cases, when

reliable compilations are available (for example., the books by Hansen, Elliott, and

Shunk on binary systems) , the references contained in those books to the original works

were utilized as bibliographic data for the compilation of a detailed card file on primary sources. This results from the fact cl:;T.t in the above works only phase diagrams

are given and there are no data on the properties of alloys, the studies of which served

as the basis for the construction of these phas€. diagrams. In a case when it is not

possible to become familiar with the primary source, the data of compiled works are

utilized with references both to the primary source as well as to the compilation

utilized.

Choice of arzicles for compilation of the detailed card file is performed is follows

1. By systanatic review of the whole series of journals which are published in

the USSR and other countries (for a list of journals, see below);

.2, By systeaatic review of the Metallurgical Abstracts in the Journal of

Institute of Metals (London)

;

3. By systematic search of the reference journals ("Referativni Zhumal")

"Metallurgiya" and "Khimiya", published in the USSR,

The classification of cards in the card file corresponds completely to the format

used in publishing the work. An ordinal number is given to each of the elements of

the peroidic system of elements of D. I. Mendeleev, which corresponds to its alphabetical

position in a list of chemical symbols in the Russian language, and binary systems are denoted by fractional numbers, which consist of both ordinal numbers of the elements

which comprise the system. In accordance with this classification, for example, nitrogen
82 MPSI-10

is designated by 1, Aluminum by 3, Vanadium by 7, and the alloys of the systems:

nitrogen-aluminum by 1/3, aluminum-vanadium by 3/7, nitrogen-vanadium by 1/7, etc. Such

numbering of cards enables one to quickly sort them and place them into the card file

in the sequence which corresponds to the description of the system.

The list of journals which are systematically searched:

1. Atomnaya Energiya (Atomic Energy)

,

2. Doklady Akademii Nauk SSSR (reports of the Acadeny of Sciences of the USSR),

3. Zhumal Neorganicheskoy Khimii (Journal of Inorganic Qiemistry) , 4. Zhumal Prikladn<-y Khimii (Journal of Applied Chemistry),

5. Zhumal Struktur.ioy Khimii (Joumal of Stmctural Chemistry),

6. Zhumal Fizitliestcoy Khimii (Joumal of Physical Chemistry)

,

7» Irvestiya Akademii Nauk SSR. Neorganicheskiye Materialy (News of the Academy of

Sciences of the USSR, Inorganic Material's),

8. Izvestiya Akademii Nauk SSSR. Metally (News of the Academy of Sciences of the

USSR, Metals),

9. Izvestiya Vysshikh Uchebnykh Zavedeniy. Tsvetnaya Metallurgiya (News of the

Institutions of Higher Leaming. Nonferrous Metallurgy) , 10* Kris talio grafiyc. (Crystallography)

,

11. Metaliovedeniya Termicheskaya Obrabotka Metallov (Metal Science and the Thermal

Treatment of Metals)

,

12. Ukrainskiy Khimicheskiy Zhumal (Ukrainian Chemical Joumal),

13. Fizika Metallov . Met aliovedeniya (Physics of Metals and Metal Science) , lA, Acta Crystallographica,

15. Acta Metallurgica,

16. Comptes rendus Ai-.ad. Sci. , Paris,

17. Joum, Less-Commi-n Metals,

18. Joum. Institute of Metals,

19. Transactions ASM,

20. Transactions AIMMZ (Trans. Metallurg. Soc. AIMS),

21. Metallurgical Transactions cl970,

22. Zeitschrift fur anorganische Chemie,

23. Zeitschrift fur Kris t alio graphie,

24. Zeitschrift fur Metallkunde.
83

MONDAY. 10 JANUARY. 1977

3 r 3 0 P M - 5:00 P Fl

PAPERS GIVEN BY POSTER

TOPIC II

EXPERIMENTAL TECHNIQUES IN PHASE

DIAGRAM DETERMINATIONS
84

MPSII - 1

The Determination of Phase Diagrams for Liquid

Oxides and Metallurgical Slags by

Hot-Wire Microscopy

by

H. Alan Fine

Dept. of Metallurgical Eng.

University of Arizona

Tucson, AZ 85718

Hot-wire microscopy has been used ^successfully to determine the

liquidus surfaces for many oxide systems. The technique, which lends

itself to measurements in all temperature ranges, can be used to determine liquidus surfaces for transparent or semi-transparent melts

under reducing, neutral or oxidizing atmospheric conditions.

A review of the previous work using hot-wire microscopy is presented and the limitations and the experimental idiosyncrasies of the

technique are discussed. The special equipment necessary for atmosphere

control within the hot-wire microscope are discribed and the application

of this equipment to measurements on metallurgical slags is discussed.
85 MPSII-2

EXPERIMENTAL TECHNIQUES IN PHASE DIAGRAM

DETERMINATIONS OF SUPERCONDUCTING COMPOUNDS CONTAINING

VOLATILE COMPONENTS AT TEMPERATURE UP TO 2200°

C

by

R. Fliikiger and J. -L. Jorda

Departement de physique de la Matiere Condensee

32, bd d'Yvoy

1211 - Geneva

SWITZERLAND

If one analyses all the work which have been published on superconductors

during the last 15 years, it is astonishing that the phase diagrams of the highest

Tc superconductors, such as Nb - Ge, Nb - Al and Nb - Ga are far from being really

known at the formation temperature of the superconducting A 15 phase, i.e., in

the range 1750<T<2200°C. The main reason is the lack of direct observations at

these temperatures, which are particularly difficult if one of the components,

as Ga, Al, Sb,... has a high vapor pressure at these temperatures. It is

evident that the contamination problem becomes more and more important, thus

limiting the choice in crucible materials.

We have developed facilities for measuring precisely the high-temperature

part of such diagrams, which consists in a combination of

1) HIGH-TEMPERATURE DTA up to 2200°C under an Argon pressure of 1 - 10 at.

2) SIMULTANEOUS STEPWISE HEATING of 10 samples of different compositions up

to 2200°C under an Argon pressure of 1 - 10 at.

After each step, the samples are cooled down to room temperature

and are analyzed microscopically. This technique is used for checking

the DTA thermal arrests, with steps of 5 or 10°C.

3) High-rate quenching techniques.

The work on these materials can only be judged on the basis of different

information on the same thermal arrest. Thus 1) and 2) are complementary , and

their combination is necessary.

It is clear that the temperature has to be measured simultaneously by different

methods and that different crucible materials have to be tested, in order to exclude

a possible influence on the thermal arrests.
MPsri

86

The analysis of the samples is done by microscopic obser-'/ation , chemical

analysis and microprobe measurements . The problem of suitable standards is very important, and has been solved by

melting of a single-phased alloy having a composition close to that of the

investigated samples, but melted under pressures of 100 and more atmospheres , in order to minimize the weight losses and thus the uncertainty in composition

In some cases, the standards would have to be formed even at higher pressures

leading to weight losses smaller than 0.5%.

The combination of all these techniques allowed us to determine the phase

diagrams of the systems Nb - Ga and Nb - Ge with a precision of ± 15°C in

temperature at 2000*^0 and 0.5 to 1 at. % in composition. These systems are

presented in detail. It is seen that the proximity of the A 15 phase regions

to the stoichiometric compositions Nb^Ga, and Nb^Ge respectively (both systems

are of the type shown in fig. 1), can only be determined by the combination

of 1) and 2).
MPSII - 3

Expcrirrontal Tcchniqucc In Phase Diagram Determinations ; Applications to Silicate Systems.

' F. P. Glasser

Department of Chemistry

University of Aberdeen

Meston ¥allc , Old Aberdeen

Aberdeen AB9 2UE , Scotland.

Many silicate systems relevant to oxide technology which

have been studied in previous decades require restudy using

improved phase- sensitive techniques. A number of examples

of the applications ox specific techniques and the results

obtained by their application to specific systems will be presented

Re- exaaninat ion of the Na^O-CaO-SiO^ system has disclosed

the presence of two inc ongruently-melting compounds, Na^SigO^^

and Na^CaSi-O^^. The former closely resembles Na^Si_0» both

in its optical properties and X-ray powder pattern.

Single-crystal studies and density determinations were

necessary to characterize Na^SigO^^ and to prove its formula.

The range of solid solution shown to exist on the Na^SiO^-CaSiO^

join were characterized by density and unit cell determinations,

combined wirh classical methods of determining the single-phase

limit of homogenity.

It is almost essential to be able to apply X-ray crystallographic metriods if the formulae of phases with complex chemistry

are to be elucidated. An example is the characterization of

the quaternary phase which occurs in systems of the type

BaO-CaO-MO-SiO^ (M = Mg, Co, Zn, Fe~"^), the quaternary

phase was shewn to be Ba2CaM2Si^0

^ ^ and is isostruc tural with

pellyit e

.

A thorough exploration of the subsolidus phase relations

in silicate systems is often neglected. It is, nevertheless,

an essential part of a phase equilibrium diagram. Compounds

may have a minimum terapei^ature of thermal stability as well as

: a maximum. The systems PbO-SiO^ and NapSiO^ - CaSiO^ - SrSiO^

will be used as illustrations. Experiments of relativelv
87

MPSII -

j-on^ duration are usually reqnirf>d to de tei-^rniiie these subsolidu

equ.i libria: brief experiments, especially those in which it

has not been demonstrated that reactions are reversible, are

unreliable to define the equilibrium state. In systems

where a phase is stable to liquidus temperatures it may

coexist with liquid over only a small range of compositions

and its existence is unlikely to be revealed except by very

detailed study of the liquidus. However, X-ray exsunination

of the products of subsolidus reactions will usually reveal

the presence of a new phase or phases. The history of the

Q phase in the CaO-MgO-A-d ^O^-SiO^ system and the discovery

of a second quaternary phase (designated R) in this

system are examples. Another important type of

subsolidus phase change occurs when solid-phase combinations

present at liquidus invariant points become less stable at

lower temperature with respect to some other permutation of

tlie phases occurring in the system. In the system

MgO-A<- ^O^-SiO^ cordierite and corundum are not compatible

phases either at liquidus temperature or at the solidus,

whereas below 1 360° , thoy become a stable assemblage.

Subsolidus equilibria in this system meet the criteria of

being fully reversible, although experiments of several

month^s duration are required to prove this.

Results of studies undertaken by the writer show that

definitive phase equilibrium diagram exist for only a few

silicate systems. In the future, the application of

predictive methods will be handicapped • if systematic efforts

are not made to both reassess and also check experimentally

the quality of these data. It is considered likely that

for the forseeable future, experimental and predictive

methods for the determination of phase equilibria will be

used in conjunction with each other rather than in competition.
88

MPSII - 4

PROTECTIVE COATINGS FOR

SUPERALLOYS AND THE USE OF PHASE DIAGRAMS

M.R. Jackson and J.R. Rairden

General Electric Company

Corporate Research & Development

Schenectady, New York

Compositional modifications to increase the strength of superalloys have produced parallel decreases in environmental resistance,

both for oxidation limited jet engine applications and hot corrosion

limited gas turbine applications. Coupled with the economic impetus

for longer and higher temperature service, this has resulted in

increased emphasis on high- temperature protective coatings. Initiall

simple aluminide coatings were formed by pack aluminization. With

greater demands on oxidation resistance, MCrAl (Y) coatings have

come into use (M is Ni,Co and/or Fe) , and duplex coatings have

been formed by aluminizing the MCrAl (Y) coatings. Other elements

are also of interest as additions to coatings, either homogeneously,

distributed throughout the coating or localized as an inner or

outer layer of the coating.

Phase equilibria in ternary and higher order systems can be

extremely useful in correlating coating/ substrate compositions,

microstructures and behavior. For example, the formation of coatings
89 MPSII - 4

on superalloy surfaces can be understood in terms of multi-element

diffusion between the elements added and the elements in the substrate. The coating degradation that results from interdiffusion

between coating and substrate in service is also a problem of multielement diffusion. For many superalloys, such as IN-738, IN-100

and Rene 80, the compositions are primarily Ni,Al and Cr, and can

be described approximately in terms of ternary or quaternary phase

diagrams. Both coating formation and coating degradation for the

superalloys have been mapped in terms of diffusion paths through

the ternary or quaternary diagrams. These paths are important

in pointing the way to modifications which may further improve

the stability of present coating compositions.

Unfortunately, the availability of complete information on phase

equilibria for the Ni/Al/Cr ternary system and pertinent higher

order systems is limited. Examination of coating/substrate systems

in terms of microstructure and microanalysis of the chemistries

allows reasonably accurate description of the phase diagrams.

These diagrams can serve as working hypotheses for understanding

coating formation and degradation. Thus, the phase diagrams

are important in understanding how to produce a particular

environmentally resistant phase at the surface and how to maintain that against diffusional interactions with the substrate.

The concept of graded or layered coatings involves an outer resistant

region of the coating and an inner region to maintain adhesion
90

MPSII - 4

to the substrate and/or prevent diffusional interactions with the

substrate. Again, phase diagrams can be used to characterize the

requirements for a stable coating/substrate system.

Specific examples of the application of phase diagrams to

the understanding of coating formation and degradation will be

presented: alurainization of superalloys, duplex aluminized coatings

the effects of Co on NiCrAl coatings, aluminization of platinide

coatings on superalloys, and the influence of Si additions on

NiCrAl coatings. '
17 0

T BI-19

ESTIMATION OF ISOTHEEMAL SECTIONS OF TERNARY PHASE DIAGRAMS

OF LITHIUM-COriTAINING SYSTEMS: THE Li-Al-Mg SYSTEM

M. L. Saboungi and C. G. Hsu

Chemical Engineering Division

Argonne National Laboratory

Argonne, Illinois 60439

In the development of high-temperature batteries, lithium and its

alloys are primary candidates for the negative electrode. The Li-Al electrode has promising features which led to an intensive study of the thermodynamic and electrochemical properties of this binary system.'^ Despite

the performance of cells with this alloy electrode, problems were encountered

which gave rise to a loss of capacity with repeated cycling. Addition of a

third element is being considered in an effort to overcome these limitations

.

Knowledge of the ternary phase diagrams and especially of the phases stable

at the temperatures of operation of the battery (643 K to 773 K) is vital

in this effort.

We report on computer-generated isothermal sections of a candidate system,

Li-Al-Mg, at four temperatures: T = 648, 673, 723 and 773 K. A computer

2

program developed by Kaufman and Nesor has been used. To summarize the

method, the solutions (binary or ternary) are treated as simple solutions.

Available thermodynamic data on the binaries are properly incorporated into

the Koehler equations to calculate boundary curves for each interaction

occurring in the ternary system. In the present case, thermodynamic proper3 4

ties of the Li-Al system were calculated using emf measurements ' and the

recent phase diagram^; emf measurements^ and the binary phase diagram were also

used to deduce necessary thermodynamic coefficients for the Li-Mg system.

Finally, the data selected by Hultgren et al.^ were used for the Al-Mg binary.
169 

TPSI-18

6—8

gaps in a number of ternary systems; the agreement has generally been

very good. An empirical extension of the theory to a broader range of systems, in which a pair of cations or anions have different charges, has

9 shown to lead to a good representation of the phase diagrams

.

The success of these calculations indicates their usefulness in evaluating the self-consistency of measurements and in the extrapolation of

data into unmeasured regions. The equations should also prove useful for

the storage of phase diagrams. The accuracy of such stored information

can be improved by treating the coefficients a, b, c, AG* and Z as somewhat

adjustable parameters and by adding more terms to eqs . (1) and (2) [e.g.,

one can add third order terms to eq. (1)]. Such procedures, when fully

developed, should permit the storage of complex ternary phase diagrams

with a mini mum number of parameters.

References .. :

-i-"

'

1. H. Reiss, J. Katz and 0. J. Kleppa, J. Chem. Phys. 36_, 144 (1962).

2. M. Blander and S. J. Yosim, J. Chem. Phys. 39, 2610 (1963).

3. M. L. Saboungi and M. Blander, J. Chem. Phys. 63(1), 212 (1975).

4. M. L. Saboungi and P. Cerisier, J. Electrochem. Soc. 121, 1258 (1974).

5. M. Blander and M. L. Saboungi, "Fundamental Aspects of Molten Salt

Solutions and Their Applications in Technology," in Proceedings of

the International Symposium on Molten Salts , edited by Pemsler et al..

The Electrochemical Society, Princeton, N. J. (1976) pp. 93-110.

6. M. Blander and L. E. Topol, Inorg. Chem. 5_, 1641 (1966).

7„ M. L. Saboungi and M. Blander, High Temp. Sci. 6_, 37 (1974).

8. M. L. Saboungi, H. Schnyders, M. Foster and M. Blander, J. Phys. Chem. 78,

1091 (1974).

9. M. L. Saboungi and M. Blander, J. Am. Ceram. Soc. 58_, 1 (1975).
163 TPSI-18

THEORETICAL CONCEPTS USEFUL IN THE CALCULATION OR

STORAGE OF PHASE DIAGRAMS OF IONIC SYSTEMS

Marie-Louise Saboungi and Milton Blander

Chemical Engineering Division

Argonne National Laboratory

Argonne, Illinois 60439

Eqtiations for the a priori calculation or for the storage of phase

diagrams and thermodynamic properties of molten ternary ionic systems can

be derived from a variety of models. We have focused on the confonaal

ionic solution (CIS) theory which rigorously takes into account the ionic

1-3

nature of the melts- Thermodynamic functions for ternary ionic systems

have been derived for cases in which all the cations have the same charge

and all the anions have the same charge.^ ^ For reciprocal systems, e.g.,

a"'",b'^/X ,Y , defined by the three components AY, BX and BY, the excess free

energy of mixing, AG , up to second order reads as:

2

AG^ - X^X^ AG- + a^X^ + a^X^ + a^^X^ + a^X^X^ - X^X,X^ iff^ (1)

where the X's are ion fractions, AG** is the free energy change for the metathetical reaction AX + BY = AY + BX, a's are coefficients deduced from the

four subsidiary binaries, and Z is a parameter taken to be 6.

For additive systems, e.g., A^b'*',c"*"/X , the excess free energy of

E mixing, AG , up to third order reads as:

AG^ - E Z a^^X.X^ + Z Z b^^X^X^ + c X^X^X^ (2)

where the coefficients b . . are derived from the three subsidiary binaries

and c is directly related to the b^^'s.

Using eqs. (1) or (2) and classical thermodynamic relations, one can

calculate phase diagrams of the two classes of ternary systems a_ priori from

data on the lower order systems. Comparisons of such calculations with

experimental data have been made for liquidus phase diagrams and miscibility
167

TI5I-17

A basic feasible solution corresponds to one comer of the polygon

delimiting the region of stability. The corner where Cu, Cu^S and

Cu^O coexist (Fig. 1) is a basic feasible solution for Cu^O. The object

in Phase 2 is to find all basic feasible solutions.

The algorithm for selecting the vector to enter the base in Phase

2 is modified as follows: The two vectors not in the base are labeled

A and B. Vector A is chosen to enter the base, Vector B becomes Vector

A, and the vector leaving the base becomes Vector B. The vector leaving

the base is chosen in the standard fashion so that the new solution is

also a basic feasible soluiton. This procedure is repeated until the

original basic feasible solution is obtained, yielding all corners of the

polygon

.

A new species is then chosen as the subject species and the entire

procedure repeated to yield the polygon delimiting its region of stability.

This procedure is continued until the region of stability is found for

all metal bearing species to yield the complete diagram.

Electrochemical as well as high temperature systems can be treated.

Additional non-metal bearing chemical species can be included at fixed

activities. For example, the Cu-O^-SO^ diagram changes markedly if

chlorine is introduced into the system"at a fixed partial pressure of

10~ atm.
166

TPSI-17

THE CALCULATION OF POURBAIX DIAGRAl'IS

USING A MODIFIED LINEAR PROGRAi^ING TECHNIQUE

Banry H. Rosof

Technology Division, Cabot Corporation, Kokomo , Indiana 46901

An algorithm for calculating Pourbaix Diagrams (both partial

pressure diagrams and potential pH diagrams) that is particularly suitable for use on a digital computer is presented. The algorithm consists

of two principal parts. In the first part, the thermodynamic conditions

under which a given phase is stable with respect to all other phases is

formulated as a set of linear inequalities. In the second part, the

set of linear inequalities is -solved by a modified linear programming

technique to yield the region in which the subject phase is the stable

phase.

Any chemical reaction can be written as

0 = E V.A., (1) s • g • 0 =|02 (g) + ZSO^Cg) + Cu^O - 2CuS0^(s). (2)

By convention Species 3 and 4 are taken as the metal bearing species.

The condition that Species 3 is stable wrt Species 4 (AG $0) can be

written after rearranging and after fixing the activities of all species

except Species 1 and 2 as Vl ^2^2^^'

-B =AG; 4- Z V RTC , (4)

i=3 ^

where

and

C. = Ina. or InP. (5)

(6) a. = v.RT.

1 1

In the present case |rT In Pq^ -f- 2RT In ^AG°, (7)

where the activities of the solid phases have been set equal to unity.

For Species 3 to be stable it must not only be stable wrt Species 4

but also stable wrt all other possible metal bearing species, e.g. Cu 0

must be stable wrt CuS, Cu^S, Cu, CuO, etc., as well as wrt CuSO . I?

there are n metal bearing species there are n-1 stability conditions,

each of the form given in Equation 3. The n-1 stability conditions, or constraints, define the region where Species 3 (Cu 0) is stable as a function of and (In P^ and In P^^ ). The constraints delimit a polygon in ^-^-^2 space. ^ ^

The problem of finding the region (of stability) that satisfies the n-1 constraints can be solved by a modified version of the linear programmxng technique known as the two phase simplex process.

In Phase 1 the standard tableau is set up, but the cost row is

omitted. (The "cost" row for Phase 1 is retained.) The conventional

Phase 1 algorithm is executed leading to a basic feasible solution.
STSTEN A-8-Y FE-CR-0

TEW* • CONSTANT » tS73.lSK Fe

9.0 O.IO

LOOIO<PT2> I r

Fe-O-O T=1573K

TPSI-16

0.20

I 0.30

I 0.40I o.:oc O.iO

I 0.70

I o.aoI 0.90

I Cr

1.00

I

log Po

-17.0*

-1.000

-1.300 -2.00O

-2.S0O

-3.000 -3.500

-4.000

-4.300 2 -5.000 -5.300

•6.000 -4.500

-7.000

-7.300

-e.ooo -8.300

-7.000

-9.500 •10.000 -10.300

-11.000

-11 .300 -13.000

-12.300

-13.000 -13.300

-14.000

-14.300

-15.000 -15.500

-14.000

-14.500 -17.000

EeEEEEEEEEEEEEEeEEEELEEEeEFEEESEEEEEEeEEEEEEEEEEEFrEEEtEEEEEEEEEEEEEEEEEEEEEEEE

JFEEt'EEFK'-'EifEEKr.EKirFtrXrf'FEt-rC.rKL'trECeF.f LEEELEESEEEEEEEEEEEEEESEEEc

E£EE££E£E£££cE lFFFFFf^rf^^Ff^FFfrf^FF^P^r>, ^ ^r, riTTT'T: — . . .»;.^^£EeEE££££E££E£i.

r FFFFFFFFr FFFrEf Fr "riTI-KFF(->-F-FH-l>-rr F

EEEEEEEEEEEEEEEEEEEEE'

:

£cE£rL££££E£££cC£EEf:E :

rFFFFFFFFFFFFFFFFFFFFFFFFK

FFFFFFFFFFFFFFFFFF, KFFFFFFFFFFFFFFFF^

n-FFFFFFFFFFFFFFFFFFFFFFFFFt-'VcF rFFFFFFFFFFFFFFFFFFFFFFFFFFFFFF

hFFFFFFFFFFFFFFFFFFFFFFFFFFFFFF FFFFFFFFrFFFFFFFFFFFFFFFFFFFFFF

Fl-FFFFFFFFFFFFFFFFFFFFFFFFFFFFrFFFF ^-fCFFFFFrFFFFFFFFFr FFFFrFFFFi

"^O't-iiJi/FFFr-FFFFFF ^F^,Cr)0

STSTEK A-9-r

TEMP " CONSTANT • 1173.1 IK Fe

0.0

L0010<PT2) :

' -3.200 -3.400

-J. 400

-3.300

-4.000 -4.200

-4.400 Pn -*-i<>° -4.300 -5.000

Fe-Ni-S-O T = 1173K loa p^r, = -ZO

log

-13.0-

m

Demonstvation . via divect hoohtp

It is hoped that an actual demonstration of the

to Montreal will be carried on during the poster

systd

sessvilm.
acility for the nalysis of hemical hermodynamics T ESI-16

-(a computerized Canadian thennodynainic data banlc)

A,D. Pelton, G,V/. Bale (Dept. de genie metallurgique , Ecole Polytechnique , Universite

de Montreal, Montreal) and V/.T. Thompson (HcGill University, Dept of Metallurgical

and Mineral Engineering, Montreal, Gajiada)

An interactive computer system for the treatment of thermodynamic data (including

phase diagram calculations) is being developed. The system will eventually contain

an e>ctensive data base. However, the facility will be much more than a data bank.

Rather, the system will be capable of performing sophisticated calculations using either

stored or user-supplied datao All input and output will be in conversationaJ. mode from

remote terminals from which users will contact the system via telephone. The

software has already been developed for a number of types of calculation.

One program is concerned with the calculation of generalized "predominance area

diagrams". A sample output is shown in Fig, 1, The user has specified the system

(Gu-S-O), the axes (partial pressures of SO^ and of 0^)* the limits of the axes, and

the constant temperature. The computer hsis calculated the diagram using stored data.

Any thermodynamically possible diagram can be calculated for systems of up to 5

components containing S,0,H,G,G1, etc« Axes and constants can be T, l/T, log(Y),

ln(Y), or RTln(Y) where Y is a partial pressure, an activity, or a ratio of partial

pressures or activities such as ?gq/Pq02'

A second program, involves the calculation of binary and ternary phase diagrams.

In Fig, 2 is an output of log p^ versus metal ratio in the ternary Fe-Gr-0 U2

system at constant T = 1573 K. Plots of comDOsition versus T at constant Pp, as

/ ' 2

well as at constant- Pqq/Pqq2» ^"f^c. are also possible. Gleajrly, the same program can also

be used to calcijilate binary phase diagrams. A calculated quaternary diagram for the

Fe-Ni-S-0 system is shovm in Fig. 3«

A third program is concerned with calculations involving chemical reactions. Nearly

any possible thermochemical calculation can be made for isothermal, adiabatic,

isentropic. etc. paths.

Other software routines are under development, FACT should be operational

on-line by the end of 1977• In the meantime, those interested in the ansuLysis of

specific systems with FACT should contact the authors.

SYSTEM CU-S -0

TEMPERATURE 950*00 KELVIN

Y = P<S*02)

10( Y)= 4*00 >!( :i< >}c j{( *>j< >|< *****>l< * ^ * >K * 5j< *i{< ;{< 10(Y) = 3*50 * CU2S * * 10( Y) = 3*00 * * CU*S*04 * 10( Y)= 2*50 * * *

.10( Y) = 2*00 * * * * 10(Y)= 1*50 * * * * 10( Y)= 1 OO * * * * 10(Y)= 0*50 * * CU20 ** * 10(Y)= 0*00 * * * * * 10(Y) = -0*50 * * * * * 10( Y) = -1*00 * ** * * * * 10< Y)= -1 SO * * * * CUO*CUSOI^ * 10(Y) = -2*00 * * * * * * * 10( Y) = -2*50 * * * * cu*a * * * 10(Y)= -3*00 * * * * * * * 10( Y)= -3*50 * * CU * * * * IOC Y)-= -4*00 * * * * * * * 10( Y)= -4 * 50 * * * * * **

10( Y)^= -5*00 ** * * : *

1 0 ( Y ) = -5»50 * * * *

.1. 0 ( Y ) ^= ~ 6 * 0 0 *********** III***************::{<*********************^i"

I I I I I I I

]• 113 -16*00 L0G10(X> 4,. 00

164

P(02)
163

TPSI-15

Effect of Irradiation on Phase Stability

P. A. Miodownik

Metallurgy and Materials Technology De'partment

University of Surrey ^ U. K.

The workshop has received notice that dr. Miodcfbrnikt together with L. Kaufman

(Manlabs) and G. Inden (Max Planck Inst.), in conjunction with J. S. Watkins

(British A.tomic Energy A.uthority) are cooperatively investigating the effect

of irradiation on phase stability , particularly in stainless steels. Some

interesting recent advances will be discussed by Dr. Miodownik, in part, in relation to some work on W-Re alloys performed by R. Williams (Oak Ridge)- ^

With the current interest in reactor programs ^ the problem should receive an airing

as a major field of specialized activity ^ which particularly raises the problem

of phase equilibrium at temperatures where normal diffusion rates are very slow and

it is difficult to obtain the necessary data by direct experiment

.

th

(1) E. K. Williamsi "Irradiation Effect in W-Re Alloys" - 6 Annual Spring

Meeting of the AH^IEj Pittsburgh (1974).

(Text for this post-deadline paper prepared by the ADC) .
162

TKI

The Gjy^ terms are the molar free energies of component M in Tl-phase

standard states at fixed temperature and non-metal activity. The terms are

the metal activities In solution with respect to the *^Gj|^ standard states. To

calculate the free energy curves, the thermodynamics of each stable solid or liquid solution must be known.

The Fe-Cr-O system will be used to illustrate these principles.
161

TPSI-14

CHARACTERISTICS AND CALCULATION OF STABILITY DIAGRAMS

by Scott McCormick and Yaz Bilimoria

Illinois Institute of Technology, Chicago, ILL, 60616

Stability diagrams are equilibrium diagrams that map phase equilibria in

systems containing both metallic and non-metallic components as a function of

temperature, non-metal chemical potential or activity, and X^, the ratio of M

atoms to metal atoms. They offer an alternative perspective on phase equilibria

and reaction paths in these systems. The characteristics and calculation of two

forms of stability diagrams for systems containing one non-metallic and two metallic

components will be discussed. In these two types of diagrams phase equilibria are mapped as a function of (1) non-metal activity and at constant temperature, and

(2) temperature and at constant or continuously varying non-metal activity.

These diagrams are similar in form to conventional temperature-composition

diagrams with horizontal tie lines and eutectic and peritectic- i ike features. The

lever law can be used to calculate the distribution of metal atoms between phases

in equilibrium. Non-metal activity-X^ plots are ideal for carrying out ternary

Gibbs-Duhem integrations with Schuhmann's method.

These types of diagrams can be calculated from plots of GIbbs free energy

versus X^ at constant temperature and non-metal activity. One mole of metal is chosen as the basis for the calculation. The two free energy ordlnates are the molar

free energies of the two metals. Temperature and non-metal activity are fixed, so that the condensed phases, stable and unstable, have the same non-metal chemical

potential. The free energy of the system is therefore minimized when the combined

free energies of the two metals ore at a minimum. The curves are of the form

= °C\ ^ Xg °C\ * RT (X^ In o\^X^ In a\ )
160

TPSI-13

compositioii indicated correctly that the fee phase at intermediate alloy

compositions tended to decompose to the -phase and the y-pha.se which are

respectively the Cu-rich and Fe-rich terminal fee solid solutions in the system.

In addition at 1367 K, which is indicated in the phase diagram to be the temperature at which the £ -phase decomposes peritectieally into liqioid plus y-ptiase,

graphical comparison of the free energies of formation of the liquid and fee

phases indicated equilibrium compositions for the liquid and y-phs-se in close

accord with experimental values. However, the free energy of formation of

the S -phase was much too negative which prompted modification of the excess

entropy term. This modification plus refinement of numerical coefficients

predicted compositions for the phase boundaries associated with the Liq-£^,

S-y» and Liq-Y equilibria in close accord with the published phase diagrsLm.

An expression was then developed for the free energy of formation of the

a and ^ phases which are respectively the low-temperature and high- temperature

bcc terminal solutions on the Fe-rich side of the system. This expression is

2 based on the approach of Hillert et al. and incorporates data for pure Fe.

Adjustable parameters were fixed on the bases of the peritectic reaction at

1751 K and the eutectoid reaction at 1123 K.

The final free energy expressions for the liquid, fcc-phases, and bccphases reproduce the experimental phase boundaries of the temperaturecomposition diagram generally to a fraction of an atom per cent and no instance

worse than at. %. These final free energy functions are expressed in terms

of mole fraction and temperature and, in the sense of consistency with the

observed temperature-composition diagram, adequately take into account the

Fe-Cu interaction parameters. Since the importance of interaction parameters

tends to decrease with the order of the interaction from binary to ternary to

quaternary, etc., the free energy functions for the binary system may be combined with similar functions for other binary systems to give a reasonable first

order prediction of multicomponent eqmlibria.

^' Institut fur Kernbrenstoffe und Theoretische Huttenkunde, Technische Hochschiile, 5100 Aachen, B.R. D.

'Ames Laboratory USERDA, Iowa State University, Ames, Iowa 50011, U.S.A.

1. J. F. Counsell, E. B. Lees, and P. J. Spencer in Metallurgical Chemistry

Symposium 1971 (HMSO, London, 1972) p. 451.

2. M. Hillert, T. Wada, and H. Wada, J. Iron Steel Inst. 205, 539 (1967).
159

TF5I-13

EVALUATION OF FREE ENERGY FUNCTIONS FOR THE PREDICTION OF PHASE EQUILIBRIA IN MULTICOMPONENT SYSTEMS:

THE Fe-Cu SYSTEM AS AN EXAMPLE

by O. Kubas chew ski, J.F. Smith, and D. M. Bailey

An estimation of the phase equilibria in a multi component system can

be made if free energy f-unctions are available for describing the formation

of the competitive phases in the system. Such functions can be generated by

combination of functions which describe the free energies of formation of

the phases in the contributory binary systems. The generation of such free

energy functions for the Fe-Cu binary system is here used as an illustration

of a general procedure for developing self -consistent free energy functions.

The basic procedure consists in utilizing any reliable thermodynamic data

which are available and then developing additional expressions and adjusting

parameters on the basis of experimental data for the phase boundaries in

the binary temperature-composition diagram.

In the Fe-Cu system extensive thermodynamic data were available only

for liquid alloys. These data result from a number of independent investigations

of both the enthalpy and free energy of alloy formation and in composite represent an extensive composition range at temperatures in the vicinity of 1800 K.

This temperature is sufficiently high that kinetic inhibition to equilibriiom is

unlikely so that the reproducibility of the data indicates reliability. The data

were then used to generate an analytical expression for the free energy of

formation of liquid Fe-Cu alloys as a fiinction of temperature and composition.

Subsequent refinements to the noamerical coefficients in this free energy function

were constrained to keep values within the range of scatter of the input experimental data.

Experimental data for solid alloys in the binary Fe-Cu system are lacking.

However, Counsell, Lees, and Spencer^ had made some calorimetric measurements of the enthalpies of formation of a few fee alloys in the Fe-Cu-Ni ternary

system. Through combination of these enthalpy values with data for the Fe-Ni

and Ni-Cu alloys plus some knowledge of the phase equilibria in sections of the

Fe-Cu-Ni system, they developed a set of functions for the thermodynamics of

formation of the fee phase in the ternary system. In the present work these

functions were extrapolated to the binary limit by setting the mole fraction of

Ni to zero. Graphical representations of the resultant free energy function vs.
158 TPSI-12 b

D» de Fontaine

References

1. D. de Fonta-fne, Acta Met. 23, 553 (1975).

2. R. Kikuchi, Phys. Rev. 81» 988 (1951).

3. W. Shockley, J. Chem. Phys. 6, 130 (1938).

4. J. Appl. Cryst. , Special Issue on Jiilich meeting. 8, part 2, April 1975.

5. R. Kikuchi and H. Sato. Acta Met., 22, 1099 (1974).

6. R. Kikuchi, D. de Fontaine, (to be published).

7. CM. Van Baal. Physica 64, 571 (1973).

8. R. Kikuchi, D. de Fontaine, M, Murakami and T. Nakamura, Acta Met, (in press).
TPSI-12 b

D. de Fontaine

regular solution or Bragg-Will iams entropy which in many cases can be 100%

in error, or lead to phase diagrams which are not even topological ly

correct.

In the CV method, the entropy contains no adjustable parameters so that

the excess configurational entropy is calculated completely from first principles. The vibrational entropy change on ordering is assumed negligible

by comparison. The enthalpy is expressed as a sum of pair, tetrahedra, ...

interactiors and, since the entropy can be obtained to a high degree of

accuracy, i fit of the theory to experimentally known coherent transition

temperaturas yields very reliable values of the basic energy parameters.

These, in turn, can be used to check or fit pair and many-body interactions

obtained from appropriate band structure calculations from which, in principle, a'll physical properties of alloys can be reduced. Furthermore, the

CV method also gives short-range order parameters, at arbitrary temperature

and concentration, in the form of pair and higher cluster frequencies, this

informaticn being of fundamental importance in x-ray and neutron diffraction

(4) studies 0* local atomic arrangements.^ '

Thus, complete coherent phase diagramscontaining several intermediate phases

can be copputed from a single free energy function with a minimum number of

adjustable interaction energy parameters, the physical meaning of which -.s

completely unambiguous. Hence the CV method can be regarded as providing a

bridge between experimental phase diagram determination and basic solidstate physics theories.

These ideas will be illustrated in the case of the (coherent) Cu-Au system,

for which an excellent fit to the phase diagram has recently been obtained,

following the ideas of Van Baal.^^^ Additional applications include ternary

systems which exhibit both ordering and phase separation. (8)
156 TPSI-12 b

FUNDAMENTAL CALCULATIONS OF COHERENT PHASE DIAGRAMS

Didier deFontaine and Ryoichi Kikuchi*

Departinent of Engineering and Applied Science

University of California, Los Angeles

By "coherent phase diagram" is meant a t2.7.per.iture-concentration diagram

indicating thermodynamic relationships betwea-i ordered and disordered

solid phases which can all be derived from tho same parent lattice. Often,

the coherent ordered phases are metastable wi :h respect to the incoherent

ones which are described in experimentally dev.ermined phase diagrams;

thus the coherent DO22 ordered phase is metastable with respect to the equilibrium incoherent Ni^Mo intermetallic, for example, although the former

can actually be obtained by appropriate heat i:reatments. The usefulness of

coherent (metastalbe) phase diagrams for the analysis of microstructure has

been pointed oi t.^^ ^

Incoherent phase diagrams cannot, at present, be computed from first principles, but they can be determined experimentally. By contrast, many coherent phase diagrams cannot be readily constructed experimentally, hence

a reliable theoretical model yielding useful prototype phase diagrams is

highly desirable. Such a model is provided by the Cluster Variation

(2) method first developed by Kikuchi in 1951.^^ In this method, the configurational entropy is treated in a very accurate manner, in contrast to the

* Permanent Address: Hughes Research Labs, Malibu, CA
155

TPSI-12 a

(NI) method. Different from the Newton-Raphson iteration technique,

the NI method almost always converges, and at each iteration staae the

grand potential decreases step by step [2,6].

These methods are illustrated using the tetrahedron approximation

for fee ternary alloys as examples. Both the clustering phase diagrams

and the order - disorder diagrams are shown [7].

*Permanent Address: Hughes Research Labs, Malibu, California 90265

1. R. Kikuchi and S. G. Brush, J. Chem. Phys. 47, 195 (1967).

2. R. Kikuchi, J. Chem. Phys., Dec. 1976.

3. R. Kikuchi, Phys. Rev. 81, 988 (1951).

4. R. Kikuchi, Acta Met. (in press).

5. R. Kikuchi and D. de Fontaine, Scripta Met., Nov. 1975.

6. R. Kikuchi, J. Chem. Phys. 60, 1071 (1974).

7. R. Kikuchi, D. de Fontaine, M. Murakami and T. Nakamura, Acta Met.

(in press).
154

TPSI-12

THEORETICAL CALCULATION OF PHASE DIAGRAMS USING

THE CLUSTER VARIATION (CV) M ETHOD

Ryoichi Kikuchi* and Didier de Fontaine

Department of Engineering and Applied Science

University of California, Los Angeles

The CV method is a hierarchy of approximate methods which are improvements of the Bragg-Wil 1 iams approximation. Each CV method is formulated

on a certain cluster of lattice points, called the basic cluster [1,2].

When a tetrahedron is chosen as the basic cluster, for example, the

probability that a configuration (i,j,k,l) of the tetrahedron appears in

the system is written as w^.^j^-j, and all the w^-jj^i's for different

configurations constitute the set of basic variables to be determined for

the equilibrium state. The primary claim of the CV method is its unique

way of writing the entropy expression in terms of w^.j|^^'s [3].

For diagram calculations, the CV method writes the grand potential

G = F - ly^-N^ (rather than the free energy F) in terms of w^. ' s, and

then minimizes G with respect to w^jj^-j's keeping T and the chemical

potentials ]i.*s fixed (rather than the compositions fixed). A phase

boundary is determined as the point at which two G-u curves (for the

two phases) cross [4,5].

In the process of minimizing G with respect to w.jj^^'s, a set of

algebraic equations (of high order) results. These equations are

solved using a special iteration technique called the Natural Iteration
153

TR5I-11

L. Kaufman

of sigma phase stability, eutectic formation and the location of melting point

minima in complex systems. The system operates on data supplied by the user

so that other inorganic, ceramic and metallic combinations can be considered.

At present, extension of the system and data base to oxide, nitride, sulphide

and fused salt systems is being explored. The ManLabs-NPL MATERIALS DATABANK

is accessible via TSO (time sharing option) through standard teletype terminals

which can be connected into the main computer by telephone anyvvhere in the U.S.

and Canada. Users can employ almost any commercial terminal to gain access

to^ the system and interact with the DATABANK. There are presently some fifteen

client organizations on the DATABA.NK and an overview of some of the problem

areas which have been considered will be presented.

REFERENCES

1. T. G. Chart, J. F. Counsell, G. P. Jones, W. Slough, and P. J. Spencer

International Metallurgical Reviews 20, 57 (1975)

.

2. L. Kaufman and H. Nesor, Metallurgical Transactions 5, 1617 (1974), 5,

1623 (1974), 6A, 2115 (1975) and 6A, 2123 (1975).

3. L. Kaufman and H. Nesor, Canadian Metallurgical Quarterly, 14, 221, (1975).

4. L. Kaufman and ri. Nesor, "Proceedings of the Second Conferences on In-Situ

Composites ," Lake George, New York, September 1973. Edited by M. R. Jackson,

J. L. Walter, F. D. Lemkey and R. W. Hertzberg (1976) pp 11-26 Xerox

Individualized Publishing, Lexington, Mass. 02173.

5. L. Kaufman and A. Nesor, Second International Conference on Rapidly

Quenched Metals, Massachusetts Institute .of Tt^chnology, November 1975.

Edited by N. J. Grant and B. C. Giessen. Else-ier Sequora, S. A. Lausanne,

Reprinted from "laterials Science and Engineeri ng (Volume 23, issue 2/3),

pp 119-125.

6. L. Kaufman and H. Nesor, "Computer Simulation for Materials Applications",

• Nuclear Metallurgy Volume 20, Part 1, Edited by R. J. Arsenalt, J. R.

Beelcr and J. A. Simmons. Library of Congress, No. 76-13801, ISBN No.

0-9501010, pp 63-74.

DEMONSTRATION. A demonstvatior. of on-line uss of the DATA BANK will be carvi.

on during the postev session.
152

TBI-ll

Application of Data Bank Methods to Calculation of the

. Thermochemistry and Phase Diagram of Metal and Ceramic Systems.

Larry Kaufman

ManLabs, Inc.

Cambridge, Massachusetts 02139

The system developed by National Physical Laboratory and ManLabs have been

coupled to provide a Metallurgical Thermochemical Data Bank for storage and retrieval

p£ data and calculation of binary and ternary phase diagrams. Approximately two

thousand data sets for pure elements and compounds are stored providing thermodynamic functiCiTS and differences for specific reactions in numerical form. Vapor

pressure data for gaseous products and solubility data for gases in metals and

dilute alloys covering the Henrian -range can be retrieved. Similar data for dilute solutions of metals in pure metals and binary alloys is also accessible.

The system can also be used to compute all of the forty-five binary systems

composed of the metals iron, chromium, nickel, cobalt, aluminum, niobium, molybdenum,

titanium, carbon, and tungsten. This facility- is available through explicit descriptions of solution and compound phases generated in terms of lattice stability',

solution and compound phase parameters which are employed to calculate the stable

and metastable phase diagrams and thermochemical properties of the binary systems.

The system can be used for calculation of the one hundred twenty possible ternary

systems composed of these metals over a wide range of temperature. Addition of

manganese, silicon, copper and boron to the data base is currently in progress.

When completed, this expansion will raise the total of binary systems to ninety

one and ternary systems to three hundred sixty four. A representative sample of

thirty ternary systems covering many of the important superalloys has been

computed and found to agree favorably with those cases where some phase diagram

data arc available. The level of agreement attained between calculated and

observed diagrams shows that the method provides an important tool for prcdictio.n
151

TFSI-10

Optimization of Phase Diagrams by a Least Squares Method

Using Simultaneously Different Data

E.-Th. Henig, H.L. Lukas, B. Zimmermann,

Max-Planck-Institut fur Metallforschung,

Institut fur Werkstoffwissenschaften,

Busnauer StraSe 175, D-7 Stuttgart 80

To optimize phase diagrams, thermodynamic and all other data

should by used simultaneously. Normally optimization is done

by trial and error methods. In this paper a least squares

optimization method is described. The equations of error are

constructed using two main ideas. If a measurement is described by p variables and has q degrees of freedom, there

are p-q corresponding equations of error. These equations

have to be constructed to be strongly dependent on one of the

dependent variables and weakly dependent on the p-q-1 other

dependent variables. The weight-function of the individual

equations of error is given by the reciprocal of the accuracy

of the value taking into account also the accuracies of the

variables temperature and concentration.

This method is used to optimize binary diagrams and in a similar way to correct extrapolated ternary diagrams. As an example

the results of the systems Ag-Bi, Ag-Pb and Bi-Pb and the

resulting ternary Ag-Bi-Pb will be presented.
150 TPSIe 10 20 30 40 50 60 70 80 90 Ni

af/.Ni

is- 2 Iso-thermal section diagram of Fe-Cii-Ui system at 1223
149

TPS 1-9

Qf/, Cr

Fig. 1 Iso-ther-ial section Diagram of Fs-Cr-Mi system at 1373 K
148

i_j system and the ternary i-j-k system, respectively. These parameter

were considered to depend on both concentration and temperature as

follows

:

Q. . = + Ax . (x .-X. )^+

ij ij J 1 IJ J X = X. + J^*? ., X, \r .X^

ijk ijk 1 ijk j ijk k V ^2)

S^^, = a"!^. + B'i^. T + C^, T In T

ij iJ ij = A^., + B^,, T + C^., T In T ijk ijk Ijk ijk

The coefficients in the above equations were evaluated by linear

programming using the binary data together with the experimental results

on the ternary systems. The values for the free energy °G. in eq.(l)

were taken from the literature values .

IV. Results

The isothermal section diagrams computed for Fe-Cr-Ni at 1373K, and

Fe-Cu-Ni at 1223K are shown in Figs. 1 and 2. These diagrams are

different in part from those of Kaufman and Nesor^^] Counsell et al^^^

( 7 ) and Bradley et al. , which were synthesized by computation using binary

data only^^^^^^ or constructed on the basis of experimental results in

( 7

)

a conventional way ; References

(1) A.D.Pelton and W.T.Thomson : Prog. Solid State Chem., 10(1975), 119.

(2) International Symposium on Metallurgical Chemistry, England, (1971)

International Symposium on Thermodynamics of Alloys, Munster , ( 1972 )

.

(3) L.Kaufman : Phase Stability in Metals and Alloys, Ed. by P.S.Rudman,

J. Stringer and R.I.Jaffee, McGraw-Hill, Mew York, (1967), 125-

(4) L.Kaufman and H.Nesor : Z. Metallk., 64(1973), 249.

(5) R.J.Orr and J.Chipman : Trans. Met. Soc. AIME, 239(1967), 630.

(6) J .F . Counsell, E.B.Lees and J.Spencer : Metallurgical Chemistry, Ed.

by O.Kubaschewski, HSMO, London, (1972), 451.

(7) A.J.Bradley, W.F.Cox and H . J . Goldschmidt : J. Inst. Metals, 67(1941)

189.
147

Analysis and Synthesis of Phase Diagrams of

Fe-Cr-Ni, Fe-Cu-Mn and Fe-Cu-Ni Systems.

Mitsuhiro Kasebe and Taiji Nishizawa

Department of Materials Science,

Faculty of Engineering,

Tohoku University, Sendai, Japan

I. Introduction

In recent years remarkable progress for the analysis and synthesis

of phase diagram^s has been achieved by means of computer calculations

combined with thermodynamic studies ^^ ^ ^ ! Following these lines of

approach, we have also done extensive work to establish the phase

diagrams of alloy systems composed of iron and its horizontal

neighbors in the periodic table. In this paper, the phase diagrams

of Fe-Cr-Mi, Fe-Cu-Mn and Fe-Cu-Mi systems are reported. Since the

phase diagrams of these systems presently available involve a great

deal of uncertainty, these should be reexamined experimentally and

thermodynamically

. TPS 1-^-1

t

ll!

1

I

I

II. Experimental i

Ternary diffusion couples were employed to obtain equilibrium data

over a wide composition range. The ternary couples were prepared by Ij^

joining a third metal piece onto one side of the binary couples of a

first and a second component, which had been fully annealed for moderat-J|

ing the concentration gradients.

After equilibration at a fixed temperature between 1123 and 1523K,

the ternary couples were examined by microscopy and micro-probe analysis,

and the concentration profiles across the interphase boundaries were

|||

obtained. The equilibrium compositions were determined by extrapolat- W

ing the concentration profiles to the position of the interphase boundar>^

III. Thermodynamical

The free energy of a M-component solution was expressed by an m

extended regular solution approximation as follows:

TM

N N-l N N-2 N-1 N

G= E x.(°G.+RT In x.)+ E Z x.x.n..+ ZEE x.x.x,J7.., (1)

i=l " " " i=l j=i+l "

J "J i=l j=i+l k=j+l ^ J ^ ^Ji^

where x^ is the atomic fraction, and °G. is the free energy of the ith

component at T K; ^ and Q. are interaction parameters in the binar

I
146 T I5I-8

The results show that the thermodynamic tables for wustite cannot

be slgnLficantly Improved except by better data for the reported

second-order comiposLtlon- and temperature-dependent structural

effects within the solid solution. The therm.odynamlc tables for hematite

can be Improved by better data on the solid solution limits for both

hematite and magnetite as well as the effect of com.posltlon on the

activity of the Fe^O^ and Fe^O^ components In the solid solutions. The

therm-odynamlcs of m.agnetlte below 1000 K cannot be significantly Imiproved through existing experimental techniques. There are no Indications that magnetite and hematite have a residual entropy at the zero

of absolute tem.perature due to Internal disorder.
1^5 TPSI-8

Thermodynamic Data for the Fe-0 System

Evaluated Using a New Computer-Aided Strategy

John L. Haas, Jr. and James R. Fisher

National Center for the Thermodynamic Data of Minerals

U. S. Geological Survey

National Center, Stop 959

Reston, Virginia 22092

This paper will desoribe the oomvutational teohn-iques

-. enployed in evaluating the example given in this abstract

Tables of thermodynamic properties and their confidence limits

fromi 0 to 1800 K at one atm were obtained for the oxides wustite

FCq 947*^' n-.agnetite Fe^O^, and hemiatite Fe^O^. In addition to

reflecting the calorim;etry accurately, the set is in better agreem.ent

•with the known phase equilibria than previous sets. We evaluated the

published exper irr.ental data for the phases and their interactions using

the program. PHAS20. PKAS20 is a weighted m>ultiple regression

routine which com.bines an em.pirical equation for the heat capacity with

the functional relations am.ong heat capacity, entropy, enthalpy, free

energy, equilibriumi constants, and electrochemiical potentials for a

group of c hem. ic ally related phases. Confidence lim.its for the tabulated

data were obtained frox-n the program^ RECKON, using the sam.e relations

the refined constants, the variances , and covariances, and statistical

theory.
144

TISI-7

The flexibility of polynomials has also been useful in the

compilation and exploitation of the phase diagrams of oxide systems.

Because many of the solid phases are stoichiometric, a relatively

good picture of the diagrams can be derived from the knowledge of

the liquidus surfaces. Representing them as polynomials:

T-j^j^^ = P (composition)

allows simple interpolations and extrapolations and the calculation

of crystallization paths. The example of blast furnace slags (in the

system CaO-SiO-,-A1^0^-MgO) will be presented.
143

TPSI-7

Polynomial Representation of the Excess

Free Energy of Multicomponent Systems and

their Use in Phase Diagram Calculations

H. Gaye

IRS ID - PCM 57

Maizieres - les - Metz

France

and

I

1]

II

ij

li

C. H. P. Lupis

Department of Metallurgy and Materials Science Ij

Carnegie - Mellon University

Schenley Park, Pittsburgh, Pa. 15213

I

i

Various polynomial formalisms can be proposed for the

representation of the excess free energy of multicomponent solutions

- for the partial molar properties, the "interaction coefficients" ' approach provides polynomials in terms of solute mole fractions; |

- for the integral excess free energy, symmetric expressions in

terms of all mole fractions can be used.

||||

An advantage of polynomial formalisms is that the coefficients

can be mapped into one-dimensional arrays , so that the number of compcU

nents and the order of the polynomials can easily remain unrestricted.

Several applications of these formalisms to the integration |

of the Gibbs-Duhem equation will be presented. To that effect, a new

method of integration was derived. It is based upon the expressions:

||||

1 RT

_ ^ ^ MG^/RT) ^( G-/RT ) m

i 1 InY, = InT, + (for i = 2,3,...in) II

I

i
142 TPS I -6

series expansion of the excess free energy of mixing in the variable {-1+2X).

Other advantages and disadvantages of the three polynomial forms are discussed,

along with the conversion matrices used to convert from one polynomial form

to another. It is suggested that both Redl ich-Kister and Bale-Pel ton coefficients should be reported when experimental data are fitted.

The capabilities of our program are described in terms of the subroutines

currently available. Applications to a variety of multiphase binary systems

of engineering importance are shown, including examples of calculated phase

diagrams.

References

1. e.g. F. E. Spencer, Jr., J. C. Hendrie, Jr. and D. Bienstock, 6th Internat.

Conf. MHD Elec. Power Generation, VoU II, p. 181 (1975); T. G. Chart,

J. F. Counsell, G. P. Jones, W. Slough and P. J. Spencer, Internat. Metal.

Rev. 20, 57 (1975)

2. C. W. Bale and A. D. Pelton, Metal. Trans. 2323 (1974)

3. 0. Redlich, A. T. Kister and C. E. Turnquist, Chem. Eng. Progr.

,

Symposium Series, 48, 49 (1952)
141 T PS I - 6

A PROGRAM FOR BINARY PHASE EQUILIBRIA USING THE REDLICH-KISTER EQUATIONS

Isaac Eliezer and Reed A. Howald

Chemistry Department, Montana State University

Bozeman, Montana, 59715

A variety of mathematical forms have been proposed and used to describe

the relationship between thermodynamic properties and composition in binary

systems. The subject has been reviewed periodically since the early 1900'

s

without any consensus being reached on what are the best mathematical forms,

primarily because there is a basic conflict between the requirement of convenience and the requirement of satisfying the Gibbs-Duhem relationship. The

subject is currently of special importance because the availability of large

high speed computers permits the application of the equations to a wide range

of materials problems encountered in many engineering applications.

Power series in mole fraction are well adapted to the general representation of data and to computer calculation of phase diagrams. At least three

different power series in mole fraction have now been programmed for computers:

1 2 a simple power series, the modified Legendre polynomials of Bale and Pelton,

and the Red! ich-Kister equations (the present work).

We have chosen to program the Redl ich-Kister equations

log Yi

= [A+B(-1+4X)+C(-1+6X)(-1+2X)+D(-1+8X)(-1+2X)^+..-]

log Y2 = [A+B(-3+4X)+C(-5+6X)(-l+2X]+D(-7+8X)(-l+2X)^+..-]

(where X is the mole fraction of component 1 and y is the activity coefficient)

primarily because the same set of coefficients appears in the equation for

both components. These coefficients are the coefficients in a simple power
140

T PS I - 5

and

X^^ + + - J

There are very few three component systems for which sufficient data are available to evaluate more than six of these terms.

The equations and programming have been checked by application to the

solid and liquid phases in the iron-nickel -carbon system. Parameters are

shown for several three component systems, and calculations of phase equilibria in three component systems are described and compared to the original

experimental data. The additional work required to extend the calculations

to four and five component systems is outlined. Such systems composed of

selected oxides will be suitable models for the slags encountered in metallurgy, magnetohydrodynamics and other advanced technologies.
T PSI-S

THE MATHEMATICAL REPRESENTATION OF ACTIVITY DATA IN THREE COMPONENT

SYSTEMS AND ITS USE FOR THE COMPUTATION OF MULTIPHASE EQUILIBRIA

Isaac Eliezer and Reed A. Howald

Chemistry Department, Montana State Universitv

Bozeman, Montana, 59715

The activity coefficient of each species in a three component system (and

other thermodynamic properties as well) can be expressed as a Redlich - Kister

expansion in the sum of the other two mole fractions, T = X. + X. .

log Y^- = [A^ +B.(-3+4T)+C.(-5+6T)(-l+2T)+D.(-7+3T)(-l+2T)^+---]

The coefficients in this equation are functions of S defined as X./(X.+X. ),

the Redlich - Kister coefficients for the three binary subsystems, and an

additional set of parameters describing interactions of all three components

at once (B-j23s ^312' ^^321' ^^^'^^

Typical equations for the calculation of the coefficients A^. through

H^ are shown. We have derived these equations, and programmed them for

computer calculation. The operation of our computer program is described.

By transforming the parameter matrix, activity coefficients and activities

can be calculated and printed for each of the three components.

The terms which are required beyond those for the binary systems, B-J23,

etCc , can be evaluated making use of a set of two dimensional orthogonal

functions for the excess free energy of mixing divided by X^X^X^. The first

four functions in this set are

1

(X^"X2)

11-3X3)
138

T PSI

References

:

1. U. V. Choudary and Y. A. Chang, A Thermodynamic Method for Determining the

Activities from Ternary Miscibility Gap Data: the Cu-Pb-0 System, Met.

Trans. 7B, Dec. issue (1976).

2. U. V. Choudary, Y. E. Lee and Y. A. Chang, A Thermodynamic Analysis of the

Copper- Lead-Sulfur System at 1473 K, Met. Trans., in review (1976).

n^ - No. of atoms of the ith component

'*' - Denotes the value at the metal-rich boundary

- Denotes the value at the metal -poor boundary

Fig. 1 A schematic of an isothermal section showing a miscibility gap

in a ternary system A-B-C.
137

TPSr-4

been determined and are difficult to determine experimentally. Yet, these

values are of practical interest. This method has been successfully applied

to the systems Cu-Pb-0 and Cu-Pb-S [1,2]. In the Cu-Pb-S system, the experimentally determined activity values along the miscibility gap are in excellent

agreement with the predicted values. For the Cu-Pb-0 system, no experimental

data of the activities are available. Since the proposed method was developed

from classical thermodynamics, the thermodynamic values predicted should be

exact if the phase equilibria data are correct.

In the present study, the method is used to predict the chemical potentials

of Cu, Ag and S (or Se) for the ternary systems Cu-Ag-S (or Se) along the miscibility gap.

Since the development of the thermodynamic method is given in Ref. [1],

only the relevant relations for the calculation of the activities along the

miscibility gap boundary for the Cu-Ag-S (Se) system are given below:

In a. yAg

r^n ag

^Ag,

yH - yI r a.

^Ag=0

Ag -^Ag

>^s - >^*S Xu

In aCu

= \ln a

L Cu

'Ag

y*

^Ag=0

^Ag

/

y

* - V*

Ag ^S ^Ag ^S in

Ag

Ag

Cu

y; 0 ^Ag

where the ratio of the activities of silver to copper along the miscibility gap

boundary may be obtained from the relation:

Jin Ag

Cu

In

^Cu

In

Y

Ai'

Cu.

0 RT

pAH - AH,

r Ag_

Y

1 - y

'Ag

^S ^>'S

^Ag

^S = °

S(Cu) Ag J

The terras y, AH and -^H^g th® above relation represent the activity coefficient, int

and partial molar enthalpies in the binary Cu-Ag solutions. Also, the sulfur

(selenium) potentials are estimated along the pseudo-binary Cu^S (Se) -Ag^S (Se)

.
13 8

TPSI-4

Computation of the Component Activities from

Ternary Miscibility Gap Data: Cu-Ag-S (Se)

by

U. V. Choudary and Y. A. Chang

Materials Department

College of Engineering and Applied Science

University of Wisconsin-Milwaukee

Milwaukee, Wisconsin 53201

Phase equilibria and thermodynamic properties of alloy systems are closely

interrelated. For instance, if we know the Gibbs energies of all the competing phases in any binary or ternary system as a function of composition and

temperature, we may compute the phase diagram of this system. Conversely,

from the experimentally determined phase diagrams we can often extract useful

thermodynamic data of the alloy phases. This approach becomes extremely useful when it is experimentally difficult if not impossible to determine the

appropriate thermodynamic properties.

Recently Choudary and Chang [1] developed a thermodynamic method to calculate the thermodynamic activities (_ot the chemical potentials) of the component

elements A, B, C from a knowledge of the miscibility gap and the thermodynamic

properties of C in A, B (see Fig. 1). This method is particularly applicable

to ternary systems where the third component C (see Fig. 1) is a non-metal such

as 0, S, Se, etc. Many of these systems are of extractive metallurgical interest,

and are characterized by a ternary miscibility gap in the melt with one of the

boundaries lying close to the A-B boundary binary. For many of these systems,

the tie-line distributions within the miscibility gap have been determined

experimentally. But the chemical potentials of the components A, B and C have not
135

TPSI-3

Other possibilities include suggestions (c) that the compositional

data are probably at fault as in RuBa/ OSB2 and AgB2^^^/ or finally

(d) that the structure simply does not exist as reported, examples

AuB2^^'^ ^ W2B5, and Ru2B5'^-^K All the above suggestions and predictions have been supported by independent evidence.

While the current use of Pauling's metallic radii can indicate

problem areas in phase deteirminations , it cannot prove a phase is

either correctly characterized or the most stable of several possible

structures. Current plans include modifying the computer program to

ultimately estimate heats of formation and make possible the selection of the most stable of known alternatives.

References

1. L« Pauling, "Nature of the Chemical Bond," 3rd ed. (Cornell

University Press, Ithaca, New York, I960) , p. 400 ff

.

2. F. L. Carter and R. Mazelsky, J. Phys. Chem. Solids, 25_, 571

(1964).

3. F. L» Gairter, J. Less-Common Metals, 47_, 157 (1976).

4. F. L. Carter, "A Mechanism for the High Temperature Transformation and the Resultant Premartensitic TiNi(ll)," Symposium on

TiNi and Associated Compounds, Ed. F. E. Wang, 20 Feb 1968,

NOLTR 68-16.

5. F. L. Carter, "Valence Bond Formation in the Rare Earth Compounds having the CaCus Structure," Proceedings of the Ninth

Rare Earth Research Conference, Virginia Polytechnic Institute

and State University, October 10-14, 1971, Vol. II, p. 617.
134

A VALENCE BOND TEST FOR THE VALIDITY OF

INTERMETALLIG AND SEMICONDUCTING STRUCTURES

TPSI-3

Forrest L. Carter

Naval Research Laboratory

Washington, D.C. 2037 5

In the course of studying chemical bonding in transition metal

intermetallic compounds and semiconductors, we routinely apply the

metallic radii approach of Pauling ^'^^. Starting with known composition and x-ray structure, the application of Pauling's metallic radii

provides one with an estimate of atomic valences, charges, bond orders,

and bond hybridization. With experience, we have learned that if the

semiempirical approach of Pauling cannot be self-consistently applied

within certain limits (to be discussed) , then either the structure or

composition is seriously in error. In short, for a very wide selection of compounds one has a test for the correctness of a phase description provided the x-ray data is available.

The basic equations for Pauling's metallic radii treatment are

quite simple. An atom's valence V^ may be calculated as V^ = ^n^^j

where the bond orders nj_j are calculated from the observed distances

to its j neighbors by the equation

dj_j = Rj_ + Rj - 0.600 log n^j

The single bond radii R^ and Rj are given by a simple empirical formula for each row of the periodic table but are a function of effective

charge, the valence, and the d and p hybridization of the bonds.

Generally these equations must be combined with equations involved

with the appropriate bookkeeping of orbitals and electrons. It is

our observation that the validity of reported structural and compositional data may be questioned (a) when charge transfer is excessive,

i.e. I AQ j > 1-5, or (b) when valences are abnormally high or low, or

(c) when excessive d or f character must be used to achieve selfconsistent calculations. The range of results varies considerably,

starting with the suggestion that either (a) further structural

refinement is desirable as in the cases of ZnSb (2). Ta 3B4 and

RUjLl^s^"^^ , or (b) that the structure is unstable at ambient temperatures as in the cases of TiNi (CsCl structure) ^"^^ and SmCos*^^- .
133

TI5I-2

The. relatively smooth trends outlined above have been very useful in

predicting the formation of undiscovered phases in binary metal -boron systems,

and in predicting unstudied melting behavior and unmeasured melting temperatures.

These trends along v/ith published lower limits on melting temperatures and

reasoning based upon phase relationships have been used to make such predictions,

particularly for the rare-earth boride systems. The predictions and available

data have been used in constructing temperature - composition phase diagrams.

Research supported by the National Science Foundation, grants No. DMR-72-03133

and DMR -76-14448.

(1 ) Karl E. Spear, Phase Behavior and Related Properties of Rare-Earth

Borides. Chapter II in Phase Diagrams, Materials Science and Technology , Vol. IV (A. M. Alper, Ed.) Academic Press, New York (1976), pp. 91-159.

(2) Karl E. Spear, Chemical Bonding in A1B2-Type Borides. J. Less-Common

Metal

s

47, 195-201 (19761.
132

TPSI-2

CORRELATIONS AND PREDICTIONS OF METAL-BORON PHASE EQUILIBRIA*

Karl E. Spear

Materials Research Laboratory

Material Sciences Department

The Pennsylvania State University

University Park, Pennsylvania 16802

Attempts have been made to find correlations relating the phase equilibria

of metal boride systems with the positions of the metals in the periodic

chart. Both the group number (valency) and period number (size) significantly

influence which phases form in a particular system, and the relative stability

of each phase type. Particular emphasis was initially placed on the rare-earth

boride systems (1), but the correlations have been extended to include transition

metal and actinide metal borides as well as what little information is available

on the borides of metals from groups lA, IIA, IIIA.

Metals with unfilled d-shells and larger sizes favor the

formation of the more boron -rich phases such as MBg, MB^^* ^^66* Smaller

metals with a significant number of d-electrons tend to form M^B, M2B, M^B^,

and MB type phases. The metal boride with the highest melting temperature in

a given M-B system tends to follow similar compositional trends with size and

number of d-electrons. For example, the larger rare-earths have MBg phases

with the highest melting temperatures. This shifts to the MB^ phase for the

smaller rare-earths, then to the MB2 di borides for the titanium and vanadium

group metals, and then to the MB monoborides for metals like iron.

The di boride phase with the AlB2-type structure is the most common

metal boride phase. The metals forming the diboride possess a wide range of

sizes and electronic configurations. The reason for this appears related to

the ability of metals to deform from a spherical shape in this structure (2).

This also helps to explain its relatively high stability.
131

TKI-l

the ternary mixing equation proposed by Kohler to predict free energies,

activities, and phase equilibria in ternary systems.

The ternary miscibility gap for the Au-Cu-Ni system has been calculated at several temperatures and compares favorably with the experimentally determined phase diagram. Calculations of the phase equilibria

for several isotherms in the Au-Cu-Ag system have been made. These are

presented along with the optimization technique used for the phase

equilibria determinations

.

References

:

,'l:.\r- M. L. Boyle, C. J. Van Tyne, and S. K. Tarby, "Computer Synthesis

and Analysis of Phase Diagrams and Solution Thermodynamics" in

Computer Simulation for Materials Application , edited by R. J.

Arenault, J. R. Beeler, and J. A. Simmons in Nuclear Metallurgy ,

, 20_, (1976) , p. 187-197.

2. F. Kohler, "Zur Berechnung der thermodynamischen Daten eines

ternaren Systems aus den zugehorigen binaren Systemen,"

Monatshefte fur Chemie , 91 , (1960), p. 738-740.

3. J. L. White, "The Thermodynamics of the Liquidus-Solidus Gap in

Binary Alloys: The Silver-Gold Systems," Transactions TMS -Ali'IE ,

215 , (1959) , p. 178-181.

* M. L. Boyle, C, J. Van Tyne, and S. K. Tarby are former graduate

student, graduate student, and professor respectively in the

Metallurgy and Materials Science Department at Lehigh University,

Bethlehem, Pa., 18015.
130 TPSI-1

COMPUTERIZED CHARACTERIZATION OF THE Au-Cu-i^i

AND Au-Gu-Ag TERNARY PHASE DIAGRAI4S

by

* M. L. Boyle, C. J. Van Tyne , and S. K. Tarby

Information synthesized for binary systems by a computer method^ has

been used in conjunction with Kohler's^ equation for mixing in ternary

systems to characterize the Au-Cu-Ni and Au-Cu-Ag systems.

A computer program employing a least squares technique has been

developed to analyze concurrently activity data, integral heat of mixing

data, and phase diagram data in order to generate a set of a-parameters

for binary systems . The a-parameter is defined as

a^2 = ^i/^l-^l^^

where Yj_ the Raoultian activity coefficient and X-j^ is the atom fraction

of component 1. These a-parameters were given a composition and inverse

temperature dependence of the form

•^12 = f.o^^2i+l ^^2i+2/^^

where n is the order of the a-parameter representation, the Aj's are

constants determined by the least squares analysis, and T is absolute

temperature. Each a-parameter characterizes a single phase region in a

binary system. The integral and partial molar solution thermodynamic

quantities as well as the activities of each component can be calculated

from the a-parameter for any given temperature and composition in a one

phase region. A pair of a-parameters for two different phases can be used

to predict two phase equilibria in a binary system.

The a-parameters of the liquid and solid phases for the Au-Cu, Cu-Ni,

Au-Ni, and Ag-Cu binary systems have been determined by this computer

technique. The solid and liquid phase a-parameters for the Ag-Au system

were obtained from White ^ . These binary a-parameters were then used with
129

TUESDAY. 11 JANUARY. 1977

3:30 P n - 6:00 PFI

PAPERS GIVEN BY POSTER

TOPIC I

COMPUTATIONAL TECHNIQUES FOR

PHASE DIAGRAM CONSTRUCTION
128

T-5

References

1. Vanadium and its Alloys. J. Iron and Steel Inst., 1950, Vol. 164,

pp. 149-159.

2. Lattice spacings and structures of metals and alloys. Pergamon Press,

London, 1958, pp. 1044.

3. Lattice spacings and structures of metals and alloys. Vol. 2, Pergamon

Press, Oxford, 1967, pp. 1446.

4. S true ture Repo rts

.

International Union of Crystallography, Oosthoek, Utrecht.

Volumes 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30A, 30B , 31A, 31B

,

32A, 32B, 33A, 33B, 34A, 34B , 35A, 35B.

5. The Crystal Chemistry and Physics of Metals and Alloys, Wiley & Sons, New York,

1972, pp. 806.
127 T.5

assembled and sent to the publisher for photo-offset printing. It so happened

that this process turned out to be very much more rapid than the original one where

the ms . was sent to the publisher who then went through it marking it for the

printer, who set it in print. Thereafter the general and section editors went

through up to four proofs to ensure correctness of the data. From this, one may

conclude that unless a continuous data-bank operation is to be established at

the same time as the production of ms . , hand-typing operations may still be cheaper

and as rapid as computer-based operations, unless these are fully funded to provide

day workers necessary for the operation. These observations are very cogent to

the production of volumes of critically assessed data on phase equilibria, since

computer handling of such operations is likely to require the development and

successful operation of special programmes.

Finally a remark or two on comparative costs may be interesting. When I

first became general editor of Structure Reports producing volumes in the early

1960s, a consumer buying the volumes obtained an average of 7 pages per Dutch florin

(D fl) spent, whereas critically evaluated data on a similar subject produced by a

commercial company ran at one page only per D fl., if my recollection is correct.

Nevertheless, the production of Structure Reports was unsubsidized , and over the

years they were self-financing and made a modest profit. In more recent years

the costs of typesetting volumes of Structure Reports began to increase alarmingly

so that the price per page doubled. However, the changeover from typesetting to

photo-offset printing of hand-typed ms. pages again halved the cost of a printed

page. A certain loss of elegance results from the change from typeset pages with

unjustified lines, but as far as I am aware this has not produced adverse comments,

the users finding that any moves to reduce costs are welcome.
L26 T-5

(4)

As a general editor of Structure Reports for some 15 years , I have

further experience of organizing numerous co-editors. Structure Reports is a

series of annual volumes, which report in critical fashion all crystal structure

determinations published in the year to which the volume is attributed. It is

divided into three sections: Metals, Inorganic and Organic, each having its own

co-editor assigned for the year in question. The work of a section co-editor

thus comprises reading the appropriate literature, checking data and producing

critical reports thereon which, when appropriately combined and edited, constitute

the ms. The general editor is responsible for producing lists of structural papers

to be read and for general coordination and checking of the different ms., reading

proofs, etc. The trouble with this organization, where each editor takes on the

work out of a sense of goodwill to the crystallographic community and in exchange

for a relatively small honorarium, was that due to accidents or personal problems,

one section of a volume frequently delayed the publication of the whole for several

years. At one point the situation was so bad that Structure Reports volumes were

only being published some 10 years after the year whose work was critically reported.

Recently this back-log has been eliminated and Structure Reports now are appearing

in the shortest possible time; only 2-3 years after the work that they report is

published. Thus all volumes and up to and including 1973 were published by the

end of 1975.

An interesting reason for the rapid publication transpired to be a switch to

direct photo-offset printing of typed ms. instead of having printers set the ms

.

in monotype, as was the earlier practice. This change was adopted primarily because

the cost of typesetting the volumes was making them too expensive for individuals

to purchase. At the. time of the change, using any typing service to produce pages

with justified lines was as expensive as setting the ms. in monotype, so "moonlighting"

typists were engaged to type the pages of ms. in a standard format. The general

editor then read the pages in proof and had corrections done before the ms. was
Remarks on Producing and Publishing Critically Evaluated Data

W. B. Pearson

Faculty of Science, University of Waterloo

Waterloo, Ontario, Canada

Selected paragvcphs of a full paper to appear in the formal proceedings

As somebody who has been concerned for nearly thirty years with critical

compilations of phase equilibria and structural data on metals and alloys in

particular I offer some thoughts on "how to get the job done".

My general conclusions are as follows: a fully computer-based operation,

is by far the most elegant, since with appropriate programming it can lead to

books printed directly from magnetic tapes, but such a system requires very

considerable financial backing, even if it goes no further than data handling

and storage and does not proceed to the ultimate step of book production direct

from the data files. Although computer programmes can be readily used to calculate

and check data, the use of computers in no way obviates the need for experts to

find the data in the literature and to critically evaluate it. In contrast to

computer-based operations, a system of data handling by hand, using part-time

typists as required, although far less elegant, is still workable and gives the

final product at less cost.

Secondly, in order to get a critical data compilation prepared (unless

there is sufficient money available to employ as many full-time assessors as is

necessary) , it is much better to support a single person (or possibly two) fulltime for the two or three years that may be required for the project, than to

organize a team of many people on a "moonlighting" basis for nominal honoraria,

each of whom is expected to complete a portion of the compilation. In the latter

case the work is likely to become indefinitely delayed due to some members of the

"team", for various reasons, not completing their assignments.
124

T-4

Some Thoughts on the Distribution of Reference Data

Dr. Howard J, White, Jr.

Office of Standard Reference Data

National Bureau of Standards

Washington, D.C. 20234

Some of the characteristics of the existing methods of distributing reference data will be discussed. Strengths and weaknesses

of the various methods will be pointed out. There does not appear

to be one superior method, but rather various methods or combinations

of methods are indicated for individual cases. The problem of

distributing reference data on phase diagrams will be considered

specifically.
123

T-3

Phase-Diagram Format: and Distribution - Users' View

J. D. Livingston, General

Electric Co. Schenectady, N. Y.

Various aspects of users ' needs for phase-diagram information will be introduced

for discussion. User needs vary in their breadth and depth, and access to computer data bases will probably play an increasing role for in-depth needs. However,

for the immediate future, most materials scientists and engineers will probably

prefer phase-diagram compilations in book form. Presently, metallurgical phasediagram compilations in English are in an unsatisfactory state. The Constitution

of Binary Alloys series is already 12 years out-of-date, and no satisfactory compilation of ternary and higher-order phase diagrams exists- An up-to-date compi1 at ion of such data is sorely needed, perhaps similar in format to Phase Diagrams

for Ceramists . Completeness, currency, and easy accessibility should have higher

priority than critical evaluations. If updating is achieved through annual volumes

(like the Russian series), a cumulative index is necessary, preferably indexed by

all components. Another possible approach to updating is the issuing of frequent

supplements in looseleaf form, to allow incorporation in alphabetical order. If

the lag between publication and compilation remains long, a current -awareness

journal on phase-diagram information may be uegful.
122

T-2

The Representation of Phase Equilibria

by

A. Prince

Hirst Research Centre

General Electric, Ltd.

United Kingdom

Phase diagrams are graphical presentations of the phase

relationships in heterogeneous systems. A phase diagram consists of

a coordinate framework enclosing geometrical elements representing

the phase relationships (the phase complex). The coordinate framework

is based on a coordinate simplex, which is equated to the concentration

(composition) diagram of the system, combined with other geometrical

elements representing the externally variable pairameters such as temperature and pressure. The representation of compositions in n-component

systems is considered using the Kurnakov simplex generalisations. Consideration is given to secondary methods for representing compositions

in which the concept^ of electron concentrations, electron-vacancy

numbers and average group numbers sire introduced.

The representation of phase relationships in binary amd multicomponent systems is considered from the point of view of models, their

projections and sections. The handling of systems with variable valency

of a component is included as is the case of reciprocal systems.

Phase relationships caji be represented analytically. Topological relationships between the- geometrical elements of a phase diagram

and its sections are useful for generalising the basic rules of construction for simple systems (n « 2 op 3) to more complex systems.
^^^ Panel 1

A. Navrotsk;

(6) J. C. Phillips, Phys. Rev. Lett- 27 1197 (1971) j

(7) A. Navrotsky and A. Muan, J. Inorg. Nucl . Chem. 33 35(1971 )

]

(8) A. Navrotsky, J. Solid State Chem. 11 10(1974)

i

)
120 Panel 1

A. Navrotsky

Of special interest to this symposium might be a comparison of the

state of the art in oxide systems versus metallic systems. Oxide

phase diagrams are often dominated by rather stable stoichiometric

ternary and quaternary compounds; thus calculations must correctly

include and predict these stabilities. In metallic systems, compounds

usually (but not always) have relatively low stability and more extensive homogeneity ranges, leading to a greater emphasis, in calculations,

on solid solutior thermodynamics and defect chemistry. For geologic

applications, the effect of high pressure on phase stability is very

important, and the thermodynamic aspects of P - T stability relations

have been more fully explored for silicates than for alloys. In

oxide systems "tnereoretical " predictions of phase stability have been

based largely on considerations of size and charge. This has led to

good qualitative understanding but has been of little help in quantitative prediction of phase diagrams. The ionicity scale proposed by

Phillips (6) has been used for analyzing semic( nductor phase diagrams.

The theory of medial and alloy phase stability is somewhate more advanced

than for oxide systems. Further developments in both fields would benefit from greater interaction and awareness of problems common to metals,

ceramics and minf?rals.

References

(1) H. C. Helgeson, in preparation. • .

(2) H. L. Haas and J. R. Fisher, Amer. Jour. Sci. 276 525(1976)

(3) 0. M. Kevrick and J. Slaughter, Amer. Jour. Sci. 276 883 (1976)

(4) A. Muan, Proc. Brit. Ceram. Soc. 8, 103(1967)

(5) B. J. Wood. Amer. Mineral, 61 599(1976)
119 Panel 1

PHASE DIAGRAM CALCULATIONS

IN CERAMIC AND MINERAL SYSTEMS

A. Navrotsky

Chemistry Department

Arizona State University

Tempe, AZ

Emphasis in this area has been more on the calculation of thermodynamic

parameters from measured phase equilibria rather than on the calculation

of phase diacrams from stored numerical data. Major efforts have been

made (a) to v^xtract thermochemical data for minerals from P - T stability curves [1,2,3), (b) to calculate activity - composition relations

in ternary oxide and silicate solid solutions from subsolidus phase

relations (4, 5, 9) and (c) to obtain thermodynamic parameters for

phase transitions for series of structurally and chemically related

materials, e.g. the wurtzite - rocksalt transition in oxides and

chalcogenide.^ (6,7) and the olivine - spinel transition in silicates

and germanat?s (8). Questions to be discussed include the following,

(a) What is the inherent accuracy and precision of the thermochemical

data derived from phase diagrams for silicate systems? (b) What efforts

exist, or anj needed, for compiling, evaluating, and updating such data?

(c) What are the most useful and/or most correct equations to use to fit

the data? Particularly, what power series for heat capacity and what

formalism (regular solution, subregular, or other) for activities? What

accuracy can be expected in fitting activity data to phase diagrams?

(d) What "theoretical" developments can we expect for these largely

ionic systems - lattice energy calculations, structure-properties correlations, ionic vs covalent bonding, stabilities of special structures,

etc.?
118 Panel 1

ENERGETICS OF NONEQUILIBRIUM ALLOY PHASES - AN ABBREVIATED ABSTRACT.

A more data-iled abstract is given in TPSI-21j pip 131-134^ of the Abstract Booklet.

B. C. Giessen

Inst, of Chemical Analysis, Applications and

Forensic Science, and

Department of Chemistry

Northeastern University

Boston, Mass.

Interest will be focussed on the energetics of nonequilibrium alloy phases;

i.e., metastable and unstable metallic phases, and their role in extended phase

diagrams. Specific examples include amorphous metals, metastable disordered

nonnal (s-p electron) metal alloy phases, and metastable ordered alloy phases.

Examples for vapor quenched, melt quenched, and electrodeposited phases and

their phase diagram representation will be discussed.

REFERENCES:

1. A. K, Sinha, B, C. Giessen and D. E. Polk, Metastable Phases Formed by

Rapid Quenching from the Liquid and Vapor Phase, in Treatise on Solid State

Chemistry , N. 3 Hannay, Ed., Vol. Ill, Plenum Press, New York, p. 1., 1976.

2. B. C. Giessen, Crystal Chemistry of Rapidly Quenched (Splat • Cooled)

Metastable B Metal Alloy Phases, Adv. in X-Ray Analysis , C. S. Barrett,

6. R. Mallett, ?.nd J. B. Newkirk, Eds., Plenum Press, N. Y., Vol. 12,

p. 23 (1969). ,

3. B. C. Giessen, Classification and Crystal Chemistry of Ordered Metastable

Alloy Phases, Proc. Second Internat. Conf. on Rapidly Quenched Metals , M.I.T., 1975, Section I, M.J. Grant and B. C. Giessen, Eds., M.I.T.

Press, Cambridge, Mass. 1976, 119.
117 P^^el 1

R» L. Dreshfield

can be applied to two phase alloys in general and possibly may be

extended to other multiphase regions of mul ticomponent alloys.

REFERENCES

1. Boesch, W. J., and Slaney, J. S.: Met. Progress, Vol. 86, No. 11,

July 19^^, pp. 109-111.

2. Woodyat';, L. R.; Sims, C. T.; and BeaHie, H. J., Jr.: Prediction

of Sigma-Type Phase Occurrence from Compositions in Austen i tic

Superalloys. Trans-AIME, Vol. 236, No. 4, April 1966, pp. 519-527.

3. Kriege, 0. H. , and Sullivan, C. P.: The Separation of Gamma Prime

from Udimet 700. Trans. ASM, Vol. 61, No. 2, June 1968, pp. 278-282.

4. Mihalisin, J. R.; and Pasquine, 0. L.: Phase Transformations in

Nickel-Base Superalloys. AIME International Symposium on Structural Stability in Superalloys, Seven Springs, PA, September 4-6,

1968, rp. 13^-171.

5. Dreshfiild, R. L.i Estimation of Gamma Phase Composition in

Nickel -3ase Superalloys. Met. Trans., Vol. 2, May 1971, pp. 13^1-

13^6.

6. Dreshfi'ild, R. L,, and Wallace, J. F. : The Gamma-Gamma Prime

Region of the N i-Al -Cr-Ti -W-Mo System at 850*0. Met. Trans.,

Vol. 5, January 197^, pp. 71-78.

ti
.116 Panel 1

R. L. Dreshfield

While PHACOMP served well to control the composition of alloys

at the melt shop to prevent detrimental phases such as sIgma, experimentally determined phase compositions indicated that the assumption

3 ^ of gamma prime sto ichiometry was inaccurate, * Also, no single calculation method or criticaT average electron vacancy number could be

Identified which would work well on a broad range of alloy compositions.

in an effort to avoid assigning an arbitrary stoichiometry to

gamma prime, the Mi-Al-Cr-Ti diagram was analyzed using analytical

geometry to determine the~gamma composition, c iven the alloy's composition.- The problem was Created by first icentifying the tie line

on which thealloy lay, then finding the intet section of that tie

line and the gamma sotvus.^ •: ""^ . -

To" better describe the superal Toys cdristitutrdn, this study was

conducted to model the gamma -gamma prTnie region of the N i -Al -Cr-W-Mo '

6

system '3 1 SSO^C. Analytical geometry principles were again used to

allow the estima:ion of both the gamma and ganma prime composition,

given the aTloy cdmpos~itron. ~"lt was also observed that the formation

of addi:tional phase's~~cbul d be predicted from tiree parameters: the

Ni corttent of the alloy, -the 'rate of change Vf Al with respect To Cr ~

"

along ^he'^le -l ine, and "a function of YhV-Cr, Mo, and U content" in the

gamma phase. - - • - " - ^' -- = ' --" ~ --

Thfe- computational- procedure* was shown to' be applicable to commercial- Ml"- base aHoys. - Tt iS suggested- that these same techn iques ' " "

'
115

Panel 1

ESTIMATION OF CONJUGATE PHASE COMPOSITIONS IN MULT! COMPONENT SYSTEMS

by Robert L. Dreshfleld

NASA-Lewis Research Center

Cleveland, Ohio

ABSTRACT

Recent advances in gas turbine technology have resulted in applying a group of complex mul t i component Ni-base alloys known as

"supera 1 1 oys" at temperatures and for times which may cause precipitation of phases which can significantly reduce their load bearing

life. To allow melters to control their melt compositions to avoid

1

' these phases, a computational method called "PHACOMP" was developed. *

This method was in effect an effort to determine if the desired composition was in the two phase field (gamria and gamma prime) of a phase

diagram based on the Ni-Cr-Al-X system. To determine if the alloy

was stable, the melt composition was use< to estimate the "residual

matrix" (y) composition. This was accomplished by reducing the melt

composition by the amount of alloy elements thought to precipitate

either during solidification or processing. The precipitates were

assumed to have nearly fixed stoichiometries. The average electron

vacancy concentration was then calculated for the y phase and compared

to an empirically set critical value to estimate if undesirable phases

might precipitate In service.
114

PANEL 1

CWUTATION AND PREDICTION OF

PHASE DIAGR/V'^S

Moderator: 0. J. Kleppa

The James Franck Institute

University of Chicago

Chicago , IL

Panel Members: L. Brewer

Inorganic Materials Research Div.

Lawrence Berkeley Laboratories

University of California

Berkeley, CA

D. de Fontaine

Materials Department

University of California

Los Angeles, CA

R. L. Dreshfield

Materials Processing and

Joining Section

NASA Lewis Research Center

Cleveland , OH

B, C. Giessen

Dept. of Chemistry and

Mechanical Engineering

Northeastern University

Boston, MA -

L. Kaufman

ManLabs , Inc

.

Cambridge, MA

A. Navrotsky

Chemistry Division

Arizona State University

Tempe, A2

Some of the panelists will give additional details with a poster or demonstration

during poster session TPSI^ in the Tuesday afternoon program.
113

TUESDAY. 11 JANUARY. 1977

2:00PM -3:30PM

REVIEW OF PHASE DIAGRAM

REPRESENTATIONS.

FORMAT

AND

DISTRIBUTION
112

T-1

Theory of Alloy Phases

R. E. Watson

Brookhaven National Laboratory

Upton, NY 11973

H. Ehrenreich

Harvard University

Cambridge, Mass. 02138

and

L. H. Bennett

National Bureau of Standards

Washington, D.C. 20234

We will survey theoretical approaches to phase stability in alloys

ranging from model calculations (in the manner of Stringfellow,

Engel-Brewer, Miedema, etc) through pseudopotential approaches to efforts

which endeavor to solve the Schrodinger Wave Equation. Topics to be

considered will include phase stabilities of elemental metals, and of

ordered compounds, and problems taking disorder into account.

We will discuss the predictive abilities of various approaches and

especially the insight which the more rigorous methods provide in

parameters entering model calculations.
Ill

TUESDAY. 11 JANUARY. 1977

9:00 Afi - 12i30 PM

REVIEW OF

THEORY OF ALLOY PHASES

AND

PANEL ON

COMPUTATION AND PREDICTION

OF PHASE DIAGRAMS
110

THE EMPLOYEE'S LOUNGE

DEMONSTRATION VIDEO TAPE

Thermochemical Data Center

I. Ansara

Laboratoire De Thermodynamique Et Physico-Chimie

Metallurgiques

Domaine Universitaire

38401 Saint Martin D'Heres

France

TV/0 DEMONSTRATIONS IN CONJUNCTION WITH

MPSI-7 On-Line Computer Manipulations

J. Hilsenrath, B, B. Molino

Office of Standard Reference Data

National Bureau of Standards

Washington, DC 20234

MPS! •8 Alloy Data Center Graphical Methods

R. A. Kirsch, L. J. Swartzendruber

National Bureau of Standards

Washington, DC 20234

THE GREEN AUDITORIUM

FOUR INSTRUCTIONAL

MOVIES

Contributed by H. McKinstry

Materials Research Laboratory

Pennsylvania State University

University Park, PA 16802

Produced at Pennsylvania State University
109

FiONDAY. 10 JANUARY. 1977

3:30 PM - 6:00 P

DEMONSTRATIONS DURING THE

POSTER SESSION
108

MPSII-16

The author of this abstract is unable to attend the workshop.

A full paper will he published in the workshop proceedings.

Phage - Eiagram of a Metal - Gas Systeto,

V.K* Sijiha

Department of Materials Science

National Institute of Jbtindry

and Forge Technologj

Hatia,. Ranchi-834003, India.

Phase dLagram is an indispensable means for representing physicochemical state of a system in terms of the state varLahles, pressure (P),

Conposition (C), and temperattare(T)« For metallic or other systems

wtiere none of the components is gas, the phase diagram is conventionally

represented in the form of T-C diagrams at fixed pressure of 1 atm.

A similar representation is, hovjever, inadequate for metal-gas systems

because of t!ie pronounced effect of gas par+.ial pressure in fi:d.ng

the physico-chemical state. The author, therefore, recommends that

in latter cases the T-C diagram must be st^? )lemented either with the

isothermal P-C diagrams or the P - T isochoi'es. The P - C - T data

contained therein will then provide not only a better understanding

of the existence of equilibrim phases in terms of the state variables

but also an easy means for computing the vai'ious thermo-dynamic functions.

The present paper demonstrates a better way of representing the phase

diagram of a metal-gas system, with particular reference to the binary

Zr - system. The method of determining the various thermo-dynamic

functions fi'om the phase diagram ia also discussed*
107

MPSII-15

ftiase Qiagrajn of a Sbacinien at Hi^ Temperatiires

•under external tensila or aiear Stress or both.

K«M. Khanna

Materials Science Efept

National Institute of Foundry

and Forge Technology

Hatia, Ranshi-^3^^)03, India,

Hiaae diagrams are graphs that give relationships between

various phases in a system as a function of temperature, pressure

and c en?) osit ion. To my mind, phase changes at high temperatures

under tensile or shear stress or both have not been studied so far. Similarly the corresponding phase diagrams have also not

been studied. It will be interesting to plot the phase diagram of

a epecimen under external tensile or d^ear stress or both, keeping

pressxire confftant and varyizig the tenperature. Having done so ve can hive a better insight into the control of micro-structure*

Ue caTi have an idea of the life time of a specimen that works at

high -emperatiares under external tensile and ^ear stress*

Exper:'.mental 3tudi*=s can be made by p. -ovidlng a tensometer type

attachment to the dilatometer*
m

IV

106

DEMONSTRATIONS

Monday 10 Jan., 1977, 3:30 PM - 6:00 PM

VXDEO TAPE REPLACED WITH NEW FILM

demonstration VIDEO TAPE listed in the program, to be shown during the

mnaay poster session in the Employee's Lounge by I. Ansara of the Thermochemical

Data Center, Grenoble, France, is being replaced with a FILM illustrating some

^^Bnples on the calculations of phase diagrams.

Tuesday 11 Jan., 1977, 3:30 PM - 6:00 PM

ADDED FILM (Green Auditorium)

"Generation of Phase Diagrams from Free Energy Curves"

contributed by C, H. P. Lupis, Carnegie Mellon University,

A 22 minute instructional color film sponsored by NSF.
105

MPSII-14

INDUSTRIAL N'Hr.PS by

Paul J . Fopi ano Army Materials 5 Mechanics Research Center

Watertown, Massachusetts 02172

COMMERCIAL TIT.WIUM ALLOYS

Many commercial titanium alloys employ aluminum and vanadium as major

alloying elements. In the investifjation of the phase transformations which

occur during the heat treatment of tl\ese alloys, the presence of two or iiiore

phases complicates the interpretation of the mechanical and physical property

data. The major strengthening mechanisms can often be related to the composi- ~

tions of the alpha and beta phases in equilibrium at the solution temperature.

Standards made up with various amounts of aluminum and vanadium were analyzed

chemically and on an electron microprobe. A calibration curve was thereby

developed for the titanium rich corner of the ternary diagram. Application of

this calibration curve was demonstrated on the most popular comme/cial titanium

alloy, Ti-6A1-4V. Various solution-treated conditions in the alpha plus beta

field were investigated. The compositions of the alplui plus beta [Phases were

determined and compared to the published literature which had been developed

before the probe was generally available.
104

MPSII - 13

STUDIES OF THE Fe-C-B PHASE DIAGRAM BY AUTORADIOGRAPHY

Thomas B. Cameron and John E. Morral

Department of Metallurgy and

Institute of Materials Science, U-136

University of Connecticut

Storrs, CT 06268

The iron rich corner of the Fe-C-B phase diagram is being investigated

in the first step of a study probing the mechanism behind boron hardenability in steel. The major problems encountered in this type of study

are first, obtaining accurate measurements of soluble boron concentrations,

on the order of 30 ppm or less; and second, maintaining high purity

samples since boron will react with other elements, notably nitrogen, in

the. ppm range. For these reasons a novel approach is being used in the

phase diagram study. Boron concentrations are being measured by neutron

autoradiography along the carbon gradient of a carburized Fe-B alloy.

The autoradiography technique allows measuring boron concentrations of

5 ± 1 ppm and the use of somewhat massive samples prevents contamination

during processing. Isothermal sections of the austenite - borocarbide

solvus are obtainable by this technique.
103

MPSII - 12

USE OF SEGREGATION PHENOMENA IN SOLID SOLUTIONS AS A METHOD FOR

DETERMINING SOLIDIFICATION DIAGRAMS. APPLICATION TO SOME Sc^O^-Ln^O^ SYSTEMS

T. M. Badie

Laboratoire des Ultra-Refractaires

Centre National de la Recherche Scientifique

France

Controlled freezing offers opportunities for determining liquidus and

solidus surfaces or curves of multicomponent or binary systems, respectively.

We have tried to make the best use of its rarely exploited possibilities

in studying the systems Sc^O^-Ln^O^, Ln = La, Nd, Sm, Gd, Dy, Ho, Er, Tm, Yb,

Lu and Y

.

In this study, the results obtained by high temperature X-ray diff ractometry

and direct thermal analysis in a solar furnace are compared with those obtained

by segregation analysis in solid solutions.

Segregation phenomena which are connected with the freezing of the liquid

out of equilibrium, are studied by X-ray dif f ractometry and electron microprobe

at room temperature. The products are obtained by normal freezing from liquid

mixtures in a solar furnace. The moving rate of the liquid-solid interface was

-3

10 mm/s and 5 10 mm/s. The analysis of those phenomena brought about a better

knowledge of the nature of the solidification diagram as well as the localization

of the invariant points.

The results obtained in the systems Sc202-Ho20^ and ^^2*^3~^^2^3 examples.

In the systems Sc^O^-Ln^O^; Ln = Ho, Er, Yb, the set of experimental

information on solidification diagrams is compared with calculations based on

two experimental results from the systems' liquidus. Based on the calculated

data of mixtures in these systems, the solidification diagrams of neighbouring

systems (Ln = Y, Tm, Lu) are predicted.
102.

MPSII - II

c) The solid solubility range (SSR), for those compounds that are incongruentmelting type and superconductors, exists only on the A-rich side of the

stoichiometric composition (i.e., never on the B-rich side). In contradistinction,

the compounds of congruent-melting type and not superconducting have their SSR

extended on both sides of the stoichiometric composition.

These correlations can all be reconciled in terms of the "A-chain integrity"

which is a manifestation of the basic electronic properties in these compounds.

Subsequently a new dimension in the interpretation and use of phase equilibrium

diagrams is offered.
101 MPSII - 11

PHASE EQUILIBRIUM DIAGRAMS IN TERMS OF

ELECTRONIC STRUCTURE

Frederick E. Wang

Materials Division

r..:- Naval Surface Weapons Center

. White Oak, Silver Spring, Md. 20910

Heretofore, interpretation and use of the phase equilibrium diagrams

are invariably limited to the knowledge of both the macroscopic and microscopic arrangements of atoms within the system. However, atomic arrangement

in a given solid state is only half of the story; the other half is electronic

arrangements. Since a phase equilibrium diagram is a manifestation of all

the thermodynamic properties involved, it must contain information concerning

electronic arrangements as well as atomic arrangements. This contention is

dramatically demonstrated in the correlation of the electronic properties of

the A3B (g-W) type compounds and their phase equilibrium diagrams. Based on

the 23 A3B compounds for which the phase equilibrium diagram as well as the

superconducting critical temperature (Tq) are known, the correlation falls

into three major categories:

a) The A3B compounds which are formed from congruent-melting type are

not superconductors while those formed from incongruent-melting type are.

For example:

Nb3lr, Cr^Si, V^Pd - congruent melting type

non-superconducting

NbnGa, V-Ga, Mo^Os - incongruent melting type

superconductors

b) Among the compounds which are superconducting, their individual

superconducting critical temperature (T^,) is directly proportional to their

solid solubility range (SSR) at room temperature as observed in the phase

diagrams

.
100

MPSII - 10

USE OF HIGH ENERGY ION BEAMS IN PHASE DIAGRAM DETERMINATION

J. E. Smugeresky

Metallurgy and Electroplating Division 8312

S. M. Myers

Ion-Solid Interactions Division 5111

Sandia Laboratories

Livermore, CA 94550

Phase boundaries can now be investigated by using a new approach which

utilizes high energy ion beams. The technique uses ion implantation and

ion backscattering analysis combined with diffusion annealing treatments.

Ion-implantation of solute elements into the matrix is used to create a

super-saturated solid solution in the first -0.1 ym of the sample. After

isothermal annealing the composition versus depth profile is monitored

nondestructively via 2 MeV He backscattering. Using these profiles and the

appropriate boundary conditions for the diffusion equation, the phase

boundaries can be obtained. The advantage of this technique lies in the

ability to monitor very low solubilities like iron in beryllium as well as

extending data to 600K or almost 300K lower than has been measured by

diffusion couples. Application of this technique to both binary and

ternary systems will be described.
99

MPSII

squeezed. This capsule bursting method was found by the authors to be useful

in the study of phase equilibria of systems in which the reaction rate of

hydration was rapid.

In RCl solutions, equilibrium temperatures in the system MgO-MgCOH)^

obtained are generally lower than that in pure water. For example, equilibrium

temperatures at 1000 kg/cm were 517 C in 5 mol % LiCl solution, 559°C in 5

mol % NaCl solution and 537°C in KCl solution. On the other hand it was 595*^0

in pure water.

The three equilibrium curves in RCl solutions were nearly parallel and

steeper than that in pure water. It seems that the equilibrium curves in 5

2

mol % NaCl solution crossed that in pure water below 200 kg/cm .

From these results, the capsule bursting method is seen to be a good

method for the study of phase equilibria under hydrothermal conditions whenever

the reaction rate of hydration is rapid.
98" MPSII - 9

Phase Equilibria in the System MgO-RCl (R = Li, Na, and K) Solution

under Hydro thermal Conditions by Means of A Capsule Bursting Method

Shigeyuki Somiya, Kazuo Nakamura,

Shin-ichi Hirano and Shinroku Saito

Research Laboratory of Engineering Materials

Tokyo Institute of Technology

Ookayama, Meguro, Tokyo, 152, Japan

Brucite, MgCOH)^, is one of the raw materials to produce basic bricks.

Brucite is obtained from sea water by precipitation or as natural rock. Brucite

has been known to occur in nature in hydrothermal veins. It is well known

that the hydrothermal solutions often contain alkali chlorides. Though a considerable

amount of research has been carried out for phase equilibria in the system

MgO-MgCOH)^ in pure water, the literature that can be found on the phase equilibria

in the system Mg(OH)2-MgO in alkali chloride solution, is scarce.

The purpose of the present work is to clear up the effect of the alkali

chlorides such as LiCl, NaCl, and KCl on the phase equilibria curve of the system

2

MgO-MgCOH)^ up to 1500 kg/cm by means of a capsule bursting method.

In order to study equilibrium curves, a gold capsule including the desired

quantity of MgO powder and 5 mol % RCl solution was sealed by an electric arc,

and two capsules, 3 mm in outside diameter and 35-50mm in length, were inserted

into one test-tube of Roy-Tuttle type hydrothermal vessel. The quantity of H^O

in the capsule was from 0.6 to 0.8 in molar ratio to MgO converted to MgCOH)^.

After treatment under high temperature and high pressure, the pressure was released

quickly and then the vessel was quenched in cold water. This is called the "Capsule

Bursting Method."

If the set point of temperature and pressure was on the high temperature side

of the equilibrium curve, the capsule would be burst by unreacted solution. In

contrast, if it was on the low temperature side, water inside the capsule was

completely consiamed to form Mg(OH)^. Therefore the capsule would not be burst but
97

iMPSII -

INTERRELATIONS BETWEEN PHASE DIAGRAMS AND

HYDRIDING PROPERTIES FOR ALLOYS BASED ON THE

INTERMETALLIC COMPOUND FeTi

by

G. D. Sandrock*, J.. J. Reilly**, and J. R. Johnson**

ABSTRACT

Hydriding alloys based on the intennetallic compound

FeTi have potential for the safe and convenient storage of

hydrogen, both for mobile and stationary applications. In

spite of its simple formula, the hydriding behavior of FeTi

is quite complex and a strong function of alloy microstructure

.

The alloy microstruccure , in turn, depends on composition, not

only deviations from stoichiometry but also various impurities.

In this paper we discuss some of the interrelations among

composition, microstructure, and hydriding behavior that can

be related to phase diagram information- In particular, we will

discuss the Fe-Ti, Fe-Ti-0, and Fe-Ti-Mn phase diagrams and thei

relationships to hydriding properties. The use of hydriding dat

to infer metal -hydrogen phase diagrams will also be briefly

discussed.

*The author is with The International Nickel Company, Inc.,

Paul D. Merica Research Laboratory, Sterling Forest, Suffern,NY

**The authors are with Brookhaven National Laboratory, Department

of Applied Science, Upton, NY 11973
MPSII - 7

References

1. Goldstein, J.I. andOgilvie, R.E., Trans TMS-AIME . 1965, vol. 233,

p. 2083.

2. Goldstein, J.I. and Ogilvie, R.E. in X-ray Optics and Microanalysis , ed by R. Castaing, P. Deschamps , and J. Philibert, Hermann, Paris

(1966), p. 594.

3. Widge, S., Master's Thesis, Lehigh University (1976).

4. Goldstein, J.I., Hewins , R. , and Rotnig, A.D. Jr., Proc. 7 th Lunar Science

Conference

,

to be published.

5. Cliff, G. and Lorimer, G.W. , Proc. 5th Euro. Cong, on Electron Microsco ., 1972, p. 140.
95 MPSII - 7

Experimental Determination of Phase Diagrams

with the Electron Microprobe and Scanning Transmission Electron Microscope

A.D. Romig, Jr. and J.I. Goldstein

Department of Metallurgy and Materials Science

Lehigh University, Bethlehem, PA, 18015

Within the past dozen years the electron microprobe (EMP) has proven

itself a valuable tool in the determination of phase diagrams (solid phase

regions). A literature survey indicates that since the first application of

this technique, to the determination of the Fe-Ni phase diagram, in 1965 (1),

at least 14 binary, 18 ternary, and several higher order metallic systems

have been analyzed with the electron microprobe.

The most powerful aspect of this technique is that one can determine

the location and orientation of tie lines even when the bulk phases are not in

equilibrium (2) (i,e,, concentration gradients across a continuous phase). This

advantage is best realized when one is considering a system where true bulk

equilibrium cannot be attained, either because diffusion rates are so slow

that the bulk equilibrium condition cannot be reached in a reasonable time

period, such as Fe-Ni-Co (3), or where the phase diagram is to contain a metastable phase where heat treatments long enough to produce homogeneous

phases are also of sufficient length to cause the metastable phase to decompose, such as Fe-Ni-C (4).

An important set of factors, unique to the determination of interface

compositions with the electron microprobe and which affect the accuracy of the

measurements are: (1) spatial resolution; (2) x-ray absorption; and (3) x-ray

flouresence. These affects are mainly attributable to the finite size of

the x-ray excitation volume. Even under optimum conditions it is not possible

to generate x-rays from a volume with a diameter much less than 1 cm. Typically,

a trace is made across the boundary at 1 \im intervals, and the interface com- position determined by extrapolation to the interface position. This is a reasonable procedure, unless the concentration gradient is too steep. To

improve the resolution of interface composition discontinuities, a smaller

excitation volume is desirable. Errors attributable to extrapolated interface

compositions could be minimized and steeper gradients could be measured.

The newly developed scanning transmission electron microscope (STEM) will

allow x-ray excitation from volumes less than ClOp-m in radius. The technique

requires thin foils which are transparent to the incident electron beam (typically 100 kv) (5). The use of thin foils and high excitation voltages eliminates

the flourescence and absorption problems present in microprobe analysis, thus

permitting the use of a relatively simple matrix correction technique.

The STEM methods have just recently been developed to the point where

phase diagram determination is possible. Research results on the Fe-Ni-Co

system using this technique will be presented.
94

MI5II-6

In perturbed angular correlation experiments the nucleus is prepared in

the second excited state . This can be done, for example, by using

57 57

radioactive Co which decays to the level of Fe. As the nucleus decays

to its ground state, it emits two gammas in coincidence. ^The coincidence rate

varies sinusoidally with time with a period given by T = — = h/AE^.

All three techniques, then, sense the splitting in one or more nuclear

levels produced by interaction with the hyperfine field present in the

material. Since the hyperfine field itself depends upon crystal structure,

chemical composition, and magnetic ordering of the material, it is possible to

use the hyperfine interation as a phase label. Several specific examples of

this use will be discussed, including Mossbauer studies and NMR of Ti-Fe and

Ti-Fe-H alloy systems, NMR studies of AuIn2-AuAl2-AuGa2 pseudobinary alloys

and PAC studies of Ni-Hf alloys.

*Also consultant. Alloy Physics Section, Institute for Materials Research, National

Bureau of Standards.

1. e.g. Hyperfine Interactions , ed. by A. J. Freeman and R, B. Frankel, (Academic

Press, New York, 1967).

2. I. D. Weisman, L. J. Swart zendruber, and L. H. Bennett, Nuclear Resonances in

Metals: Nuclear Magnetic Resonance and Mossbauer Effect , chapter VI-2, in

Techniques of Metals Research , ed. by R. F. Bunshah (John Wiley § Sons, 1973).

3. G. C. Carter, D. J. Kahan and L. H. Bennett, Metallic Shifts in NMR , Progress in

Materials Science 20 , 1 (1976)

.

4. M. Frauenfelder and R. M. Steffen, in Alpha-, Beta- and Gamma-Ray Spectroscopy , Vol. 2, ed. by K. Seigbahn (North Holland Pub. Co., Amsterdam, 1966), p. 997.
93

MPSII-6

HYPERFINE FIELDS = Techniques for Mea surement

N M R MOSS PAC

PREQUENCY ENERGY TIME

The nucleus has three energy levels of interest - a ground state (spin

I^) and two excited states (spins and . All of these levels are split

by the hyperfine field, assumed here to be a static magnetic field.

In NMR one looks only at the ground state (indicated by the heavy lines) . and observes the level splitting, AE^, by observing transitions between the

split levels caused by external application of a radio-frequency field, v, A

resonant absorption of RF energy is observed when the RF frequency satisfies

the condition AE 00= hv . Since onlyy the ground o state is involved, no nuclear

radiations are emitted.

In the Mossbauer effect, the ground state and the first excited state are involved. Nuclei in the ground state are excited to I^ by the absorption of

gamma radiation. Then I^ decays back to the gound state with the emission of

a second gamma ray. The transitions observed here are between a split

sublevel of I^ and a split sublevel of I^. Since several gamma ray energies

can cause the excitation, absorption can occur at each of these. The

absorption spectrum, then, has resonances whose positions depend upon the

hyperfine splitting of both states I and I,

.
92

MPSII-6

Nuclear Hyperfine Techniques and the Determination of Phase Diagrams

R. C. Reno*

Department of Physics

University of Maryland Baltimore County

Baltimore, MD 21228

and

L. J. Swart zendruber, G. C. Carter and L. H. Bennett

Institute for Materials Research

National Bureau of Standards

Washington, DC 20234

Within any material there exist internal electric and magnetic fields

which are produced by the positively charged atomic nuclei and the negatively

charged core and valence electrons. The fields depend upon the arrangement of

these consituents (e.g., spatial ordering of the ion cores) as well as interactions between the constituents (e.g., chemical bonding and electron

exchange effects) . A particularly important class of internal fields is that

present at the positions of the atomic nuclei. These fields interact with the

nuclei and shift the discrete energy levels which describe possible nuclear

excitations. The fine structure of each atomic nucleus is therefore altered

(slightly) and these hyperfine changes are then described in terms of

hyperfine fields acting on unperturbed nuclei"'".

The hyperfine field is, therefore, a subclass of all internal fields

present in materials but it has particular significance because the

vntevaction between this field and the nucleus can be measured by several

techniques. This review will discuss three well-established techniques for

2 3 measuring the hyperfine interaction - nuclear magnetic resonance (NMR) '

, the

2 Mossbauer effect (ME) and the perturbed angular correlation of gamma rays

4

(PAC) . It will discuss how the hyperfine interaction is influenced by the

chemical, magnetic and structural properties of the material involved and will

illustrate how each of the above techniques can be used to provide information

useful in constructing phase diagrams.

All three of the above hyperfine techniques detect a change in the

nuclear energy levels of the atom at the site studied by observing transitions

between levels. A comparison of all three techniques is made with the aid of

the following schematic nuclear energy level diagram for ^^Fe nuclei.
91

MPSII - 5

APPLICATION OF THE SCANNING ELECTRON MICROSCOPE (SEM)

TO THE STUDY OF HIGH TEMPERATURE OXIDE PHASE EQUILIBRIA

L» P. Cook and D. B. Minor

Institute for Materials Research

National Bureau of Standards

Washington, D,C. 20234

The use of the electron microprobe x-ray analyzer in phase equilibrium

studies has been demonstrated both for ceramic and metallurgical systems.

The energy dispersive x-ray analyzer (EDX) - equipped scanning electron

microscope (SEM) , a more recently developed member of the family of electron

microbeam instruments, offers many of the advantages of the electron microprobe and has other features making it a uniquely useful tool in the study

of phase equilibria. This instrument has particular potential for certain

aspects of oxide research.

The characterization of powdered oxide starting materials is not a trivial

problem, particularly if grain size is of the order of a micron. Techniques

for mounting oxide powders so as to eliminate specimen charging are reviewed.

For bulk x-ray analysis using an EDX system, careful attention must be paid

to powder aggregation, grain size, surface geometry and instrumental operating

conditions. Examples of x-ray analysis of finely homogenized powdered starting

materials prepared at closely spaced compositional intervals are given. If

suitable care is exercised this technique could conceivably be used to sample

milligram or smaller quantities of powder as a check on the effectiveness of

the homogenization process used. The effect of parameters such as grain shape,

size, size range and porosity (of compacted powders) on experiments can be

monitored

.

For the examination of the products of high temperature experiments, the

SEM is especially useful. Quench experiments can be examined in total without

special sample preparation other than carbon coating, and after SEM examination

the usual x-ray diffraction and optical examinations can be made. Sintering

effects due to grain boundary melting and recrystallization can in some

instances be distinguished from effects due to a small amount of equilibrium

melt present along grain boundaries and in interstices. This type of phenomenon

is ordinarily observable with only great difficulty, if at all, in the conventional light microscope using the immersion technique. Evidence for liquid

immiscibility can be observed, and the presence of minute amounts of crystalline

phases in quenched melts can be detected on fractured surfaces. Crystal

morphology can in some instances be used to distinguish equilibrium from nonequilibrium (quench) crystal growth. Equilibrium phases of variable composition

can be quantitatively characterized by their chemistry.
171

TISI-19

To our knowledge, reliable measurements in the Li-A.l-Mg system have been

g carried out only in the Mg-rich comer at T = 648 K. The calculated portion

< the phase diagram is in reasonably good agreement with the experimental result

Despite inherent limitations in such computations, they remain important

in ultimately deducing phase relations. The present calculations should be

considered as a good approximation to the phase diagram. These results

can be refined by incorporating, in a thermodynamically self-consistent way,

very few experimental data at key compositions. A reliable phase diagram

can thus be computed with a minimum number of measurements.

References

1. P. A. Nelson et al., USAEC Report AiIL-8109, 1974.

2. L. Kaufman and H. Nesor, "Treatise on Solid State Chemistry," N. B.

Hannay, Ed., Plenum Press, New York 5_, 179-232, 1975.

3. S. P. Yatsenko and E. A. Saltykova, Russ. J. Chem. Phys . 48^, 1402

(1974)

.

4. M. L. Saboungi and M. Blander, J. Electrochem. Soc. (in press).

5. K. M. Myles, F. C. Mrazek, J. A. Smaga and J. L. Settle in "Proceedings

of the Symposium and Workshop on Advanced Battery Research and Design,"

March, 1976, ANL-76-8, p. B-50.

6. M. L. Saboungi and M. Blander, J. Electrochem. Soc. 122 , 1631 (1975).

7. R. Hultgren, P. D. Desai, D. T. Hawkins, M. Gleiser and K. K. Kelley,

"Selected Values of Thermodynamic Properties of Binary Alloys,"

American Society for Metals, Metals Park, Ohio (1973).

8. J. A. Rowland, Jr., C. E. Armantrout and D. F. Walsh, Trans. AIME 333

(1955) .
172

TISI-20

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174

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I
175 T 151-20

An english translation prepared by D. B. Butrymcwicz^ Diffusion Data Center^ NBS

A literal translation is given sznae the exact words interpreted in different

disciplines (e.g. Chemistry versus Physics) can lead to different "english" and thus

different physical model interpretations.

Cybernetic Prediction of the Formation

of Chemical Compounds in Uninvestigated Systems

by

E. M. Savitskii, V. B. Gribulya, N. N. Kiseleva

Baikov Institute of Metallurgy

Academy of Science of the USSR

Moscow

Calculations of the existence and stability of the metallic as well as other

inorganic phases on the basis of "first principles" remains an unresolved

problem. On the other hand, the occurrence and existence of phases is determined

by many factors (size and properties of atoms as well as their constituent

particles, interactions of physical media, effects of external physical fields,

composition, temperature, pressure, kinetics). The magnitude of these parameters

is variable and unique for each specific phase.

One can take into account simultaneously a large number of these factors in

view of the capabilities of cybernetic devices under the conditions of assigning

mathematical-logic system of analysis of the interactions between these factors.

In fact we deal with a complex cybernetic system. The cybernetic approach to

chemical systems as to complex systems with latent, however guiding, links

(or ties) enables one to develop self-educating computer programs which would be

capable of predicting the behavior as well as properties of chemical systems.

The attempt to obtain prediction from "first principles" suggests the use

of the fundamental characteristics of atoms of the atoms as the starting dataatomic number, distribution of electrons in accordance with energy states in

the atom, as well as others. However depending on the problem under consideration,

different characteristics of chemical elements from the known phases can be

utilized, which are the concepts of the zone as well as the other physical

theories for the structure of matter.

Our first research in this area began in 1966 (1). Using binary systems

we were able to show the possibility of predicting the existence of inorganic

compounds of definite composition; AB, A^B, A^B /2-4/, as well as the phases

with definite cirystal structure (Laves-pnases , sigma-phases , A15-type phases

et al) . As the primary data for these predictions, information on the

distribution of electrons in accordance with the energy states in isolated atoms

were taken. Many of the compounds which were predicted have been now

synthesized. According to our calculations, the reliability of our predictions

is no less than 90%. For certain compounds, types of crystal-chemical

reactions for the formation of the compounds (5), crystal-structure type (6), as well as certain physical properties, such as critical temperature of

transition to the superconducting state (7), and melting point (8) were predicted.
176

TF5I-20

Taking inCo account the future perspective of this inquiry, we have started

investigations into the predictability of ternary-chemical systems as well

as the creation of a larger cybernetic system. We first of all made

predictions on the most representative classes of the compounds of practical

interest (ABO^, AB^O^, ABO^, A^B^O^, AB^S,) (9), as well as the most widespread types of crystal structures (perlcovskites , spinels, periclase) . At

present we are conducting the work and aquiring experience with the prediction

of ternary inorganic compounds and verification of the accuracy of prediction

v±th known experimental data.

The obtained predictions provide for a significant expansion of the areas

of search for inorganic materials with specific desireable properties. They

extend our capabilities of theoretical calculations of phase diagrams and new

phases as well as shows the correlation between existing concepts of phase diagrams

as an instrument of understanding physi-chemical systems. They require also

a more specific understanding of chemical compounds, conditions for their

formation, stoichiometry, equilibrium state, kinetic data, and wider (broader)

formulation of the thermodynamic phase rules which would take into account the

interactions of various physical fields, vacuum, dispersity of the system, etc.

References

1. E. H. Savitskii, Tu. V. Devingtal and V. B. Gribulya, "Recognition of Binary Phase

Diagrams of Metallurgical Systems with the assistance of an Electronic Calculating

Machine", Dokl. Acad. Nauk SSSR: 178, 1, 79-81, 1963

E. M. Savitskii, Yu. V. Devingtal and V. B. Gribulya, "Solubility Ranges of A^B

type Intermetallic Compounds with the assistance of an Electronic Calculating

Machine", Dokl. Acad. Nauk SSSR: 183, 5, 1110-1112, 1968.

3. E. M. Savitskii and V. B. Gribulya, "Computer-Based predictions concerning Inorganic

Compounds in Binary Systems", Inorg . Matls.: 7_, 973-980, 1971; translated from

Izv. Akad. Nauk SSSR, Neorganicheskie Materialy: 7_, 7 , 1097-1104, 1971.

4. E. M. Savitskii and V. B. Gribulya, "Prediction of Rare Earth Metal Compounds by

means of Computers", J. Phys. Chem. Sol.: 33_, 1853-1860, 1972.

5. E. M. Savitskii, Yu. V. Devingtal and V. B. Gribulya, "Recognition of Formation

[Peritectic] type reactions and estimating the width of Homogeneous Metallic Phases

with the assistance of an Electronic Calculating Machine", Dokl. Acad. Nauk SSSR:

185 , 3, 561-563, 1969.

6. E. M. Savitskii and V. B. Gribulya, "Solubility Ranges of Binary Sigma -Phases with

the assistance of an Electronic Calculating Machine", Dokl. Acad. Nauk SSSR: 220 , 5, 1066-1069, 1975.

7. E. M. Savitskii, Yu. V. Devingtal and V. B. Gribulya in "Superconducting Alloys

and Compounds", pp. 7-20, Nauka, Moscow, 1972.

8. E. M. Savitskii and V. B. Gribulya in "Structures and Properties of Heat-Resistant

Metallurgical Materials", pp. 3-10, Nauka, Moscow, 1973.

9." N. N. Kiseleva, B. I. Pokrovskii and N. B. Vashchenko in "Planning and Automating

Experiments in Scientific Investigations", 308-315, Sovradio, Moscow, 1974.
177

TPSI

THE DETERMINATION AND REPRESENTATION OF METASTABLE PHASE DIAGRAM FEATURES

AND SOME KINETIC CHARACTERISTICS OF ALLOYS

Bin C. Giessen

Institute of Chemical Analysis, Applications and Forensic Science

and Department of Chemistry

Northeastern University, Boston, Mass. 02115

The current strong interest in non-equilibrium alloys, especially amorphous

metals, has focussed attention on the possibility of systematically presenting

metastable equilibria in phase diagrams and even including kinetic features,

primarily in order to depict their composition dependence.

The non-equilibrium phases of prime interest are the following (we use

the term "phases" here for constitutional entities and not necessarily in the

Gibbsian sense):

1. Metastable extensions of terminal or intermediate solid solutions;

2. Metastable intermediate phases;

3. Amorphous alloys.

These phases have been dealt with in detail in many recent papers, e.g.,

References 1-4; alloy constitutional aspects are emphasized in references 1,

3, 5. Especially in reference 5, the constitutional requirements of metastable

phase formation have been discussed intensively and the kinetic aspects are

treated in terms of solidification theory.

Because most metastable metallic phases studied to date either have two

components or two groups of closely related components, and because they are

principally prepared from the melt, we focus here on binary systems; we also

disregard pressure effects. We treat three types of phase diagram-related

plots involving nonequil ibrium phases:

I 1. x-T phase diagram representations and related diagrams;

I

I
178

TPSI-21

2. Free energy diagrams;

3. Diagrams involving kinetic parameters.

1. x-T Diagrams

a. x-T diagrams showing metastable phases, and the equilibria

involving them, especially metastable melting reactions. This representation

should be as complete as possible, including all metastable phases that could

energetically form from the liquid in constrained equilibrium upon supercooling

of the latter to 0 K.

b. x-T^ diagrams containing T^, the cross-over temperatures of

the free energy curves of the respective phases at composition x. These curves

are of considerable practical importance as, for liquid-solid transitions, they

define the composition limits within which metastable phases or metastable

extensions of equilibrium phases can be retained by supercooling of the melt

to a given temperature if equilibrium phase formation is prevented and glass

formation does not intervene.

c. x-T^ plots, showing the composition dependence of the

temperatures of phase transitions involving a property A of metastable phases,

such as magnetic or superconducting transitions.

d. x-AT^ plots, giving the supercooling temperatures AT^ required

for the formation of a given metastable phase.

2, Free Energy Diagrams

G-T-x diagrams (three dimensional for binary systems) and their G-T^^ _ (-Qpstant)

and 2-x^y ^ '-onstant) Diagrams of this type can incorporate nonequilibrium phases having free energies exceeding those of phases that can be

included in x-T diagrams; knowledge of these phases over at least a certain free

energy range is a requirement for a complete description of a given alloy system
179

TPSI-21

in terms of fundamental concepts, as they should correctly predict not only

equilibrium phases but also more energetic phases.

3. Diagrams Involving Kinetic Parameters

a, x-T„ and x-T^ plots of T^, the glass transition and , the

g c 9 c crystallization temperature, vs. alloy composition. As T^and depend on

the heating rate, t, three dimensional representations x-T^-t and x-T^-T are

required. At present, two dimensional t-T^ plots (which yield the activation

energies of crystallization) exist for some selected compositions x, and x-T^

and x-T^ data taken at fixed T are available for some systems.

b. T-T-T (time-temperature-transformation) pi ots at fixed compo7 8 sition, both for nonequil ibrium phase formation and decomposition. The

former are especially useful for an interpretation of the occurrence of

amorphous metals in terms of operational parameters such as the cooling rate;

the latter describe their thermal stability below T , Relations of the

c reduced glass transition temperature to the cooling rate also exist.

These diagrams and the techniques used in their determination will be

discussed. Their purpose is to present thermal and other parameters for

the total range of condensed phases amenable to experimental or theoretical

study.

1. B.C. Giessen and R. H. Will ens, in: Phase Diagrams ; Materials Science and

Technology, Vol . III . , A.M. Alper, Ed., Academic Press, N.Y. , p. 103 (1 970).

2. B.C. Giessen, in Proc. Second Internat. Conf. on Rapidly Quenched Metals , M.I.T., 1975, N.J. Grant and B.C. Giessen, Eds., Section I, M.I.T. Press,

Cambridge, Mass. 1976, p. 119.

3. A.K. Sinha, B.C. Giessen and D.E. Polk, in Treatise on Solid State Chemistry , N.B. Hannay, Ed., Vol, III, Plenum Press, New York, p.l. (1976).

4. H. Jones, Rep. Prog. Phys. 36 , 1425 (1973).
180

T 151-21

5. J.C. Baker and J,W. Cahn, in Sol idifi cation , American Society of Metals,

. Metals Park, Ohio (1971), p. 23.

6. B.G. Lewis and H,A. Davies, Proc. Second Internat. Conf. on Rapidly Quenched

Metals , M.I.T., 1975, N.J. Grant and B.C. Giessen, Eds., Section II, Mater.

Sci. Eng. 23, 179 (1976).

7. H.A. Davies, J. Aucote and J.B. Hull, Scripta Met. 8,(1974) 1179.

8. T. Masumoto and R. Maddin, Mater. Sci. Eng. 19,(1975) 1 .
TPSI-22

Theses Report

An Analitical Method of Construction and Representation of Diagrams

of Equilibrium of Mult icompone nt Systains

0. S. Ivanov, A. I. Udovsky and A. M. Gayduicov

A. A. Baykov Institute of Metallurgy

Academy of Sciences

Moscow, U.S.S.R.

A method of construction of phase boundaries of diagra-s of

equilibrium of multiconponent systems is proposed, proceeding ' from the knoun experimental diagrams of equilibrium of twocomponent and other subsystems and limited number of additional izpsriments for alloys of multicompcnent systems in question. An analitical record of surface of one/tv;cphase phase bcjjidary for multicompcnent system in question is presented in two parts. The

first part is determined by computea analitical e.^pressions for

the corresponding Irnown phase boundaries as a whole ( as a whole

along all curves for twocomponent subsystems ), and as net by separate points of binary subsystems, as it is realised by the er.is-^

ting analit'Lcal methods. The second part is computed irrespec^iive

of the firsu one by the method of th* least squares, proceeding

from the erjerimental dita for more than binary alloys. The p:.'Cposed method allows to construct analitically smooth phase boundaries of diaj;;raijs of equilibrii^m of dependence prcperty-compcsi ti

on ( v.'ithin the limits of a definite phase field ), practically,

of any compler shape for a system v/ith the arbitrary n^umber of con

ponsnts. 2y v;ay of illustration the first part of surfi.ce of licui

dus in the system U„UC-UIT computed wdth the help of a computer is

presented as an analitical record as v;ell as in a graphic representation for a fa-:ily of 13 isotherms.

The proposed method is developed conformably to ccnstructicn

of diagroras of equilibrium of threcor.ponent systems or. ccnditicn
182 TPSI-22

that all the binary su-baystGins are eutectic. To our aiind, practical

ly,. it can be spread to any types of diagrams of equilibrium of

multicociponent ay stems,.

On these grounds a pro^'ramme of actions is proposed: I) for an

analitical generalization and representation of the whole accumulat«d erperiiiental material on the dia^rans of equilibrium for

double, threefold and more complex systeis, usually graphic represented, 2)ke!iping of these data in a con;puter's memory, 3) their

delivery from a computer in different forms ( a-^ia-^i'tical, tablelike» ^ra^hic) ,4)an analitical calculatioi^roceedinga from these

data and a lixoited number of e:?:periisental data of unknown diagiams

of equilibrium of more complex systems, 5)comparison and coordination with the help of a computer of experimental data on thermcdynamic parameters for the excess enthalpy and entropy of alloys as well as for the difference of the enthalpy and entropy between dif

f«rent phases of pure components and the thermodynamic calculation

on the basis of these parameters of the unkncra diagrams of equilibrium of multicomponent systems, 7)the use of diagrams of equilibrium ai.d computers for the calculation of the thermodynamic and

physical parametersof the metallic phases in order to use them later on in the quuntum-mechanical calculations of the unknown diagramsof equilibrium, thermodynamic and physical properties of alloyi

of multicomponent systeas.

Step by step programme of realization of this complex task

is proposed.
The author of this abstraat is unable to attend the workshop; his paper will

not he presented. A full paper will he published in the workshop preceeav-^s.

THE CALCULATION OF MLTICOMPONSNT ALLOY PHASE DIAfflRAilS AT THE NATIONAL PHYSICAL

LABORATORY, UK

T G- Chart

National Physical Laboratory

Tedding ton, Middlesex, England

Members of the Division of Chemical Standards, National Physical Laboratory,

are currently engaged in the calculation of ternary and quaternary phase

diagrams of relevance to superalloys and related materials , from the thermodynamic data for the binary systems involved. Computer methods involving the

minimization of G-ibbs energy are utilized. At present we are in a position to

calculate isothermal sections in over 100 different ternary systems. In order

to extend this range an extensive programme of critical assessment of thermodynamic data for binary systems, mainly involving transition metal-boron and

transition metal-silicon systems is being undertaken. The full scope of this

work will be described, and recent examples of calculated ternary diagrams

included.
184

The authoT of this abstract will not present this paper by poster. A full

paper will be published in the workshop proceedings.

I. The isomorphous binarj metallic systems of Ag-Pd, Cb-Ti,

Mo-W, Mo-V, V-W and Cb-W have been calculated from the available

information of heats of fusion, heats of vaporization, molar

volumes, heat capacities, melting temperatures, etc, of the pure

components with various theoretical models of ideal, regular,

smd quasi- chemical using computing techniques without recourse to

extensive experimentation. The equations for the phase boundaries

for these models are:

SYNTHESIS OF BINARY METALLIC SYSTEMS

I. ISMORPHOUS SYSTEMS

II. SIMPLE ETJTECTIC SYSTEMS

S.S. Balakrishna and A.K. Mallik,

Department of Metallurgical Engineering,

Indian Institute of Technology, Bombay,

INDIA

+ RT Oji (1-XL)/(1-Xi) 0 )

)

))

for ideal case

and + RT In (XT/Xi) = 0

-t- RT In (l-XL)/(l-2a) Xi2 B - 1J?L )

) for regular

) solution case

+ RT In (XI/Xi) = (l-Xi)^B-(l-XL)^L )

AF^"^ RT In (l-2L)/(l-3i) = RT | ILa^ /J-^Xa 2a
AJ^"^^ RT In (XI/Xx) = RT f /fC InCX^^-*-!)- 2X^ ^

+ X^(1^3X^) Xi2 « 4X^ (1^^ X^) Xi3 ^ 6X2 ^ |

- ( 1ii(Xl+1)-2Xl 2L X^d+SXj^XL^ - 4x| (1+ ^

>-l)

^

+ (i + |. Xj^ XL^) _J for quasi- chemical model.

II. Ihe simple eutectic binary metallic systems of Ag-Si,

Szi-Al, An- Si, Be- Si, Bi- Cd have been calculated from the available

thermodynamic data of heats of fusion, heats of vaporization,

molar volumes, heat capacities, melting temperatures, etc. of

the pure components with various theoretical models of ideal,

regular and quasi- chemical using canputing techniques v/ithout

recourse to extensive experimentation. The equations for phase

boundaries for these models are:

AJ^"^^ + RT In (1-XAL)=0, )

j for ideal case

Apf^^ + RT In XBL = 0 ) AFf^^ + RT In (1-XA.L)=-- L (XAL)^, )

) for regular solution

2 )case

AFf^^ + RT In (XBL) = - L (1 - XBL) )

and AF^*^^ + RT In (1 - XA.L) = -RT |X^ (XA.L)2 /i-SX^CXAL)

6Xl (J

+ I

\j){JkL)^J
186

AFg RT In (XBL) = HT | ^"(In ZXjiXBL)

+ XjJU-i-ZXj) (XBL)^ - 4X^ ^i'^^L^ (2BL)^

+ 6X^ (J I

CXBL)^) + (InCXs 1) - 2Xg + Xg (l+SXg)

- 4X3 (1-*^ Xg) + 6Xg (J f ^s))-7 for quasi- chemical model.

The phase diagrams in ideal cases with or vri. thout Gp data

remain same in all the systems considered.

All the theoretical models are compared

with the ezperimentally observed diagrams

from ASM Handbook,
The author of this abstvaat will not present this paper by poster,

paper will he published in the workshop proceedings.

k full

Quantitative Fits to Phase Lines and High Temperature

ThermodTnamic Data for Systems Forming

Semiconductor Compounds

Robert F. Brebrick

Metallurgy and Materials Science Program

Marquette Univeristy, Milwaukee, WI 53233

We have been interested in phase diagrams of binary systems involving

compound or elemental semiconductors. These are relatively simple compared

to the diagrams for some metallic systems and consequently a more detailed

investigation of the process of theoretically constructing these phase

diagrams is not unmanageable. For a congruently-melting, narrow

homogeneity- range compound the composition dependence of the compound's

Gibbs free energy of formation can usually be neglected, an approximation

often implicitly made in thermochemistry. The general thermodynamic

equations connecting the solidus and liquidus lines of the compound are then separable. A liquidus equation can be obtained^ which is general as far as the liquid phase is concerned and therefore be used with any model.

Certain properties of the compound enter this liquidus equation as input parameters. These are the idealized composition Casually the

stoichiometric composition), the melting temperature and the heat of

fusion, and the temperature dependence of the enthalpy and entropy of

formation of the compound form its pure liquid elements. In the derivation

of this equation the properties of the liquid and compound are seen to be

linked through the requirement that the congruent melting involves a zero change in Gibbs free energy. This furnishes two equations which hold at

the melting point and which connect the enthalpy of formation and heat of

fusion with the heat-of-mixing of the liquid at the stoichiometric

composition on the one hand, and the entropies of formation and fusion with

the entropy of mixing of the liquid on the other. For brievity we refer to

these equations as the auxiliary relations. If the experimental liquidus

lines. for the compound can be satisfactorily duplicated with some model of

the liquid phase then the second half of the problem, the calculation of

the solidus lines, can be attacked using one of the known thermodynamic

models for a defect semiconductor compound. Alternatively, provided

certain other data are available, such as the partial pressure of one element along the three-phase curve for the compound, a calculation or theoretical fit of the solidus lines can be directly attempted without

first establishing an appropriate liquid phase model.

SnTe^

The latter approach has been followed for the com.pounds PbTe and

. Aside from confirming the validity of the defect model used and

establishing values for some of the intrinsic, high temperature properties

of the compounds, the results potentially furnish the starting point for a calculation of the homogeneity range for all Pb/Sn ratios in the PbTe-SnTe pseudobmary.
188

The former approach of calculating the liquidus lines has been

followed for some III-V systems^ in which the compound solidus lines are not well established but appear to be so close to the stoichiometric

composition as to make their previous determinations by Hall measurements

significantly biased by accidentally present, unknown impurities. An

extension and refinement of previous efforts in this area is interesting

not only in its own right but also as a potential starting point in the

construction or reliable interpolation of the liquidus surfaces in ternary

and quatenary systems constructed from these binaries. Considerable

technological effort is presently concerned with crystal growth of ternary

and quatenary semiconductor compounds. A summary of some central features

of our approach and results follows for the calculation of the liquidus

lines

A quantitative measure-of-fit a(T) is defined as

2 ? 2 a (T) = y (T. ,-T. , /-n

>l j,cal j,obs UJ

where Tj is an observed liquidus temperature and Tj is one

calculated for the observed composition using some model for the liquid

phase (which usually contains adjustable parameters). A critical value of

a, '^Qxit' chosen as characterizing the accuracy of the experimental

data. All fits with cr i Cj^p^t- are judged equally .valid. This latter choice

proves significant since when the liquidus points are fit alone one usually

finds that a < crj,pj_^ for a significantly wide, highly-correlated range in

the adjustable parameters. As a result, only certain properties of the

liquid phase are well established and these at only some temperature within

the range of experimental temperatures used"^. A similar behavior usually

appears in the determination of the second law enthalpy and entropy for

some constant pressure process from an experimental determination of the

Gibbs free energy change as a function of temperature^. When the enthalpy

and entropy of compound formation at the melting point are known, the

auxiliary relations can be used. These appear generally to be quite

restrictive. The auxiliary relations can be satisfied and the liquidus

lines fit^ to within critical value of iCC for InSb, 8°C for GaSb, 16'C

for InAs and 10*C for GaAs. The liquid phase model is defined in terms of

temperature independent heats and excess entropies of mixing given by

AhJ: = Wx( l-x){ l+a(x-l/2)} C2)

M

/^sj-/® = Vx( l-x){l+c(x-l/2)} (3) M

where W, a, V, and c are constants. The values of W and V are fixed by the

auxiliary relations. Satisfactory fits are obtained for a range of values

along a line in the c-a plane. Treating the III-V compound - Group V

eutectic temperature as accurate to within ± 2°C (except for GaAs)

generates a 2nd line in the a-c plane and effectively eliminates the range

of a-c values to a single point. The liquid parameters thus established.
189

the remaining high temperature data are found to be fit in a quantitatively

satisfactory manner. The simpler variants of the model in which a, V and c are zero (strictly regular solution) or in which a and c are zero (quasiregular solution) can fit the liquidus points satisfactorily but not

if the auxiliary relations are applied and if the other thermod^^/namic data

are to be fit well also. This liquid model is essentially the same as that

used by Kaufmann and Nesor to fit many complex metallic systems and is

essentially a truncated version of the series representation used by Lupis.

Qualitatively it appears to be applicable to many metallic liquids.

Unfortunately it proves inadequate for the more ionic II-VI and IV-VI melts

and an important problem is the identification of a liquid solution model

or models that is adequate for these systems.

Because the model defined by Eqs . (2) and (3) is of wide, if limited,

applicability, its critical point behavior is of interest. For the simpler

quasi-regular version (a=c=0) syiranetrical normal, or inverted miscibility

gaps can appear^. For the model defined by Eqs. (2) and (3) an additional

flexibility appears in that the critical composition can be made to fall

anywhere in the composition range and normal and inverted miscibility gaps can occur in the same system, i.e. for appropriately fixed values of W, a,

V, and c. Near the critical point the width of a normal miscibility gap

goes as (T/T^-l)^/^.

1. R. F. Brebrick, Met. Trans. A (in press).

2. R. F. Brebrick, Abstracts of Papers Presented at 1976 Electronic Material

Conference, J. Electronic Materials Cto be published).

3. R. F, Brebrick, Quantitative Fits to the Liquidus Lines and High

Temperature Thermodynamic Data for InSb, GaSb, InAs, and GaAs , submitted

to Met. Trans.

4. R. F. Brebrick and R. J. Panlener, J. Electrochemical Soc. , 121 , 932

(1974).

5. R. F. Brebrick, High Temperature Science, 8_, 11 (1976).
190

TUESDAY. 11 JANUARY. 1977

3:50 P M - 6:00 P M

PAPERS GIVEN BY POSTER

TOPIC II

FORMAT AND DISTRIBUTION

OF PHASE DIAGRAM DATA
191

TPSir

•ARLF.S OF COflTFMTS AM^ n jr't.i LAT I VE flM^jprT i''nr.y

FOR "PHASE niACRAMS OF riETALLir Sv.ctc"'^/'

fl. ^1

. AHEFV, EniTOR, VOIJ'MES i - iq

Trnnn 1 citC'i anH Connilnr' by

Coulson 'A, Sciieijornann

flA^^A

Lev/ is Resf^arc*^ Ccntor • C 1 nvo.l an'-f^ Ohio

Phase dlciTran i n"^ornr? t i on Is nn innnrtnnt "^p.ctor in Hoc^Itp nn-'

cIg ve 1 or>nen t c)<^ nlloys. Phasn dinrrran \nfnrnp,tinn f -^o pp'^ 1 \/ accessible for binary systens. In^ornation fnr hi-^'-'r^r or'-'^r

systers, however, is not ns rea-^il^' acc^*-. i b 1 e . "''he '-m s t conn re hens i ve source o^ nhaf^e Hiafrran in^ori^ation ^nr ^^Irary an'^

hir^her order systems is the cnnnilation and annual s'l on 1 pnon

edited by fl. V. A/^eev an'1 prodticed by th^ H'^'^P Aca'-'pr-iy

Sciences. They are, hov/ovf^r, sone^'/hat dl-Pfirnlt an-^ rttn^'^r snr-f^ to

use by those v/ho cannot read the Russian lan^rijaTf^ bpcau'^p tboir

Tables of Contents are in Russian and because they '^o not ha^'o a curnul at i ve i ndex . This translation is designed to aid in the 1 r> ii 1 1 M r. a 1 1 on tl

Af;eev compilations. It is conoosed of tv/o section!^. "^h^

section n:Ives the Tables of Contents ^nr volumes 1 t^rouTh 1'^ (195n - 1176) vyi tb the phase dlarrrams i'.'entlfipd by che'-'Ical

s ymbol

.

The second section of this translation is a cumulatlv'o In'^ox o-^

phase diagrams included In the Afjeev comn I 1 at i '^ns , \/oli!no<^ 1 through 19 ( 1059 throurb 1976). The phasr> dtafTr.-<ms ar" llsf^d in

alphabetical order by chemical symbol. Throiic^hoti t Section 2, t^^e

f ol 1 oiv i n.n; convention is used. "^he volune Is Tilven ^ v' Roman

numerals. Pa.Tes are deslp;nated by Arabic numerals. er.a'-'nle,

the notation 'Vll-2n5' refers to volume 7, nr^f^n '/bore ^^ta

for one system extends to follov/in.'^ pafrpe;^ onlv/ t^^e ^Irst oaTe Is

i ven .

It is hoped that this publication v/Ill facilitate usf^ Arrppx/

compilations and the enornnus amount of nha'-,p M\r\n-rn^ I n ^ n r'-^a 1 1 on

v/hich they contain.
192

11511-2

J. E. Selle

•iGtals and Cerainics Division, Oak Ridge National LaboraCory~

Oak Pvidge, Tennessee 37330

A large six color wall chart is described which gives pertinent

information on binary phase diagrams such as: the general type of

diagram, degree of solubility, number of eutectics, lowest melting

eutectic, number of intermetallic com.pounds, etc. Detailed information

is given on the data presented on the chr.rt, its form.at, comparison of

various binary' systems with presentation on the chart, and souie typical

uses of a chart of this type.

^Research sponsored by the Energy Research and Development Administration

under contract with the Union Carbide Corporation.

^Operated by Union Carbide Corporation for the Energy Research and

Development Administration.
193

TPSri-3

Standards for Publication of Phase Equilibrium Data

Eric R. Kreidler

LIGHTING RESEARCH AND

TECHNICAL SERVICES OPERATION

Lamp Materials Research Lab #13 61

General Electric Co.

Cleveland, Ohio

A paper on phase equilibria typically receives a review before publication and may not be critically evaluated again until it is included in

a compilation. Since most phase diagrams will eventually be published in

handbooks or compilations such as Phase Diagrams for Ceramists , it is Important that the initial review process be critical and constructive. It is

suggested that a set of published standards for phase equilibrium papers

would assure uniform treatment of data and would help both journal reviewers

and compilers to properly assess the value of individual papers. A brief

survey of the literature quickly reveals the wide variation in quality.

Papers range from speculations based on a few haphazard experiments to

thorough studies based on hundreds of experiments and using complementary

experimental techniques. The purpose of standards should not be to preclude

publication of incomplete or exploratory work, but to assure that such works

are based upon sound data. Sandards should be used to prevent publication

of erroneous diagrams, and if properly written and used can improve the

general quality of work done on phase equilibria.

The establishment of standards is the responsibility of the concerned

scientific community. A committee of phase equilibrium experts representing

the disciplines metallurgy, ceramics, mineralogy, semiconductor technology,

geochemistry, etc. could accomplish the task. The purpose of this presentation is not to formulate standards but to point out some of the problems

which are frequently encountered in phase equilibrium studies. The areas

to be considered are; tests of equilibrium, accuracy of results, failure to

provide documented data in support of diagrams, diagrams which violate the

phase rule, misuse of terminology, and inappropriate experimental techniques.
194

TPSII-4

FORMATING AND DISTRIBUTING EVALUATED REFERENCE DATA

BY THE OFFICE OF STANDARD REFERENCE DATA

AT THE NATIONAL BUREAU OF STANDARDS

S. P. Fivozinsky and G. 3. Sherwood

Office of Standard Reference Data

National Bureau of Standards

Washington, D.C. 20234

The Office of Standard Reference Data at the National Bureau

of Standards manages a complex of data evaluation centers located

in university, industrial, and other Government laboratories as

well as within NBS. The centers are engaged in the compilation

and critical evaluation of numerical data on physical and chemical

properties retrieved from the world scientific literature. This

system of centers, the National Standard Reference Data System

(NSRDS) , is a means of coordinating on a national scale the production and dissemination of critically evaluated reference data

in the physical sciences. The primary focus of the NSRDS is on

well-defined physical and chemical properties of well-characterized

materials or systems.

The Office of Standard Reference Data, as coordinator of the

system:

- establishes needed data centers in technical areas which

fall within the scope of the program

- maintains close contact with other data compilation

activities both in the U.S. and abroad to encourage

exchange of data and avoid needless duplication of effort

- identifies, by contacts with users, areas where needs for
195

TPSII-4

evaluated reference data are increasing or decreasing, and

formating procedures which will make the outputs of the

system as useful as possible

- distributes evaluated reference data through a variety of

output channels

The output channels include:

- Journal of Physical and Chemical Reference Data

a quarterly journal containing data compilations and

critical data reviews, published for the National Bureau

of Standards by the American Institute of Physics and

the American Chemical Society

- NSRDS-NBS Series

a publication series distributed by the Superintendent of

Documents, U.S. Government Printing Office

- appropriate publications of technical societies and

commercial publishers. Handbook publications are an

important element of this category

- magnetic tape data files - sold through the National Technical

Information Service

The outputs of several NSRDS centers are directly or indirectly related

to phase diagram applications in metallurgy and ceramics; examples include

alloy data, data on diffusion in metallic systems, properties of

substances at high pressures; properties of superconducting materials,

and thermodynamic data of minerals. Some recent publications on these

subjects aret
196

TPSII-4

1. Butrymowicz, Daniel B., Manning, John R. , Read, Michael E.,

"Diffusion in Copper and Copper Alloys, Part IV. Diffusion

in Systems Involving Elements of Group VIII," J. Phys . Chem.

Ref. Data, _5(1) 103-200 (1976).

2. Chang, Y. Austin, "Phase Diagrams and Thermodynamic Properties

of Ternary Copper-Silver Systems," J. Phys . Chem . Ref . Data

(in process)

3. Donnay, J.D.H. and Ondik, Helen M.. , Crystal Data Determinative

Tables, Third Edition , Vol. 1, Organic Compounds, Vol. 2,

Inorganic Compounds, Swarthmore, PA, Joint Committee on Powder

Diffraction Standards, Vol. 1 (1972), Vol. 2 (1973).

4. Hultgren, R. and Desai, P. D. , Selected Thermodynamic Values

and Phase Diagrams for Copper and Some of Its Binary Alloys ,

New York, International Copper Research Association, Inc. (1973)

5. Roberts, B. W. , "Survey of Superconductive Materials and

Critical Evaluation of Selected Properties," J. Phys . Chem.

Ref . Data, 5(3) 28.1-821 (1976).

6. StvuLl, D. R. and Prophet, H. , JANAF Thermochemical Tables ,

Second Edition , NSRDS-NBS 37, U.S. GPO (1971)

. , Reprint No. 50, "JANAF Thermochemical Tables, 1974

Supplement," J. Phys . Chem . Ref . Data , 3(2) 311-480 (1974).

Reprint No. 60, "JANAF Thermochemical Tables, 1975

Supplement," J. Phys . Chem . Ref. Data , 4(1) 1-175 (1975).

Examples of outputs, formats, and dissemination mechanisms will

be displayed along with more general information on the National

Standard Reference Data System, and the activities of the Office of

Standard Reference Data.
197

TUESDAY. 11 JANUARY. 1977

3:30PM-6 :00PM

DEMONSTRATIONS DURING THE

POSTER SESSION
198

DEMONSTRATIONS DURING THE POSTER SESSION

IN THE EMPLOYEE'S LOUNGE

TV/0 DEMONSTRATIONS IN CONJUNCTION WITM POSTERS

TPS I -11 APPLICATION OF DATA BANK METHODS TO CALCULATION OF THE

THERMOCHEMISTRY AND PHASE DIAGRAM OF METAL AND CERi^IC SYSTEMS

MTDATA ON-LINE T H E R M 0 C H E M I C A

CALCULATIONS

. U\RRY KAUFMAN^ MANLABS, INC.^ O^MBRIDGE^ MASSACHUSETTS

T PSI-16 FACILITY FOR THE ANALYSIS OF CHEMICAL THERMODYNAMICS - A

COMPUTERIZED CANADIAN THERMODYNAMIC DATA BANK

AN ON-LINE DEMONSTRATION

A. D. PELTON^ DEPT. DE G^NIE METALLURGIQUE, ^CQLE POLYTECHNIQUE^

UNIVERSITY DE MONTR^L, CANADA
199

WEDNESDAY. 12 JANUARY. 1977

9:00 AN - 12:30 PFI

USER NEEDS FOR

PHASE DIAGRAM INFORMATION

PANEL II ON

PRIMARY PRODUCTION

AND

PANEL III ON

MATERIALS PROCESSING
200

PANEL II

PRIMARY PRODUCTION

Moderator: J. F. Elliott

Department of Materials Science and Engineering

. M. I. T.

Cambridge , MA

Panel Members: P. Amman

Ledgemont Laboratory

Kennecott Copper Corporation

• Lexington, MA

H . Larson

American Smelting and Refining Company

South Plainfield, NY

R. D. Pehlke

Metallurgy Department

University of Michigan

Ann Arbor, MI

Information on phase equilibria is often of great importance in

the design, operation and control of processes employed in the primary

production of metals. Several case studies of specific processing systems

in the industry are presented to show the nature of information that is

needed and how the information is utilized. Examples are employed to

show where such information has, and has not, been available.
201

COMMENTS RELATED TO THE PANEL II TOPIC

This contvibution is fvom an audience particiyant, not a panel

member. A paper on this COMMENT will appear in the proceedings.

USER NEEDS FOR PHASE DIAGRAJ^IS

by

Dr. Paul J. Fopiano

Army Materials & Mechanics Research Center

Watertown, Massachusetts 02172

In multicomponent systems where two ore more phases have important

effects on the properties of the alloy, it is rare that the phase compositions

are known. Sometimes these compositions can be ignored with impurity but

other times this is not the case. In the latter category, the determination

of a single tie line only may be required or, because of the prevalence of

several alloys using the same alloying elements, a more thorough investigation

of phase compositions is justified. In few of these cases, however, is the

construction of a phase diagram carried out and widely disseminated. As a result, much otherwise useful data is lost before it can become a useful part

of a databank. Examples of one of each type of application are included to

indicate the normal limits to which we go to satisfy a specific need. It

might be added that without the advent of the probe microanalyzer , little of

this work would have been carried out.

TYPICAL EXAMPLES OF PHASE COMPOSITION

Determinations in Commercial Alloys

Titanium-Aluminum-Vanadium Alloys

In the investigation of the phase transformations which occur during the

heat treatment of commercial titanium alloys, the presence of two or more

phases complicates the interpretation of the mechanical and physical property

data. The major strengthening mechanisms can often be related to the compositions of the alpha and beta phases in equilibrium at the solution temperature. Many titanium alloys of commercial interest employ aluminum and vanadium

as major alloying elements.

Several standards were made up with various amounts of aluminum and vanadium. The nominal compositions are given in Table 1. Chemical analyses of

these alloys were also determined. A probe analysis of these standards yield

for our experimental conditions the calibration curve in Figure 1. The least

square slope of these lines is given analytically as:

w/o V = I^ . 529

486

w/o Al = I,, + 27

Al

1048

where w/oV, w/oAl = weight percent vanadium and aluminum.
202

COMMENTS PANEL II TOPIC P. J. Fopiano

! Table 1. NOMINAL COMPOSITIONS OF

STANDARD ALLOYS IN WEIGHT PERCENT

^ np mo n AT vV

76 2 2

77 2 4

78 2 8

81 4 2

82 4 4

83 4 8

84 8 2

85 8 4

86 8 8

43 12 0

44 0 12

15,000

13,000

-511.000 s

"29,000

c

3oU

>7,000

^---'-'Z : 55,000

. - 1 3.000

1,0000 0 2 4 6 8 10 12 14 Aluminvim of Vanadium (Weight Percent)

^ .\ y Chemical Analyiis

FIGURE 1. Mean Number of Counts (per 30 sec.) Versus Chemical Analysis of

Aluminum and Vanadium Standards

ly = counts (vanadium) /30 seconds

I., = counts (aluminum) /30 seconds

Utilization of this data for the most popular commercial alloy of titanium,

Ti-6A1-4V is illustrated in the following discussion. Five solution-treated

conditions (all in the alpha beta field) were investigated (Figure 2); i.e..
203

COMMENTS PANEL II TOPIC ^- Fopiano

Table 2. NUMBER OF COUNTS (per 30 sec) AND CORRESPONDING

COEFFICIENT OF VARIATION FOR THE ALPHA AND BETA PHASES

FOR SEVERAL SOLUTION TREATMENT CONDITIONS

Sample Designation Phase Counts/30 Seconds

(and Solution Temp) (a or s) (Coeff. of Variation)

AT uV P-1 a 7301 1307

(1750 F)

6 6052 2519

(2.6) (4.3)

P-2 a 7849 1475

(1700 F) [ \ .0)

3 6150 3040

(1.1) (2.3)

P-3 a 7078 1593

(1650 F) (A 0)

S 5779 3686

(1.6) (3.7)

P-4 a 7664 1709

(1600 F) (1.4) (2.5)

6 5570 4062

(2.2) (2.3)

P-5 a 7398 1747

(1550 F) (1.3) (4.7)

B 4723 4551

(2.8) (3.7)

1750, 1700, 1650, 1600, 1550 F with designations P-1 through P-5 respectively.

In order to get large enough fields to examine with the probe microanalyzer

,

it was necessary to heat all specimens to 1850 F for one hour furnace cool to

the solution temperature (Figure 3 - 1550 F) and hold for the times indicated

in Figure 2.

Probe analysis data of both the alpha and beta phases are presented in

Table 2. The measured compositions of the alpha and beta phases are shown

in Table 3 (P-l through P-5) . Estimated compositions from published literature is also shown in Table 3 for specimens solution treated at _1562^165 2,

and 1742 F. An approximate retrofit of our data to published work on the

Ti-6A1-4V alloy is shown in Figure 4. The published work was done before the

probe was generally available and was typical of a type of publication then

popular. In no sense, however, could it be considered a complete phase

diagram even for the titanium-rich comer.
204

COMMENTS PANEL II TOPIC P. J. Fopiano

2 4 6 8

Vanadium (Weight Percent)

10

FIGURE 2. Schematic Representation of the 6A1 Section

, of Titaniim Corner of Ti-Al-V Ternary

FIGURE 3. Solution-treated Ti-6A1-4V Alloy. Mag. 500X
205

COMMENTS PANEL II TOPIC P. J. Fopiano

Table 3. EFFECT OF SOLUTIOfl TEflPERATURE ON THE COMPOSITIONS

OF THE ALPHA AND BETA PHASES IN Ti-6A1-4V

Solution Treatment

Temperature

(deg F)

Weight Percent

Alpha Beta Vol % £

Al V Al V

1550 (P-5) 7.08 2.30 4.53 8.07

1 C.C 0

1 obc 8 2-1/2 2 8 25

1600 (P-4) 7.34 2.22 5.34 7.06

1550 (P-3) 6.78 1.98 5.54 6.26

1652 9 2-1/2 2 6-1/2 38

1700 (P-2) 7.52 1.74 5.89 4.96

1750 (P-1) 6.99 1.40 5.80 3.89

1742 10 2 4 5 64

1850 1850

o

5A1

I I

\ J_

4 0 2 4 6 Vanadium (Weight Percent)

FIGURE 4. Correlation of Probe Data with Published

Isothermal Sections (Ref. 5)

43XX Steel

Even though the 43XX steels have been utilized for many years, no phase

diagram was available in the literature when the investigation on "Partially

Austenitized 43XX Steel" was initiated. A "pseudo" iron-carbon phase diagram was then determined by microstructural analysis. A copy of this "pseudo
206

COMMENTS PANEL II TOPIC P. J- Fopiano

iron-carbon phase diagram for 4300 steels is shown in Figure 5. This is an example where even a very nudimentary phase diagram data was helpful and

necessary to develop an optimum compositional and temperature requirements

for a new application of a very old alloy.

irao

I6S0

1600

1550

'500

I M50

1«0

: . . 1350

1300

120

0 0.1 0.2 0.3 O.i 0.5 0.6 0 7 0.8 0.9 1.0

Cartwn *

FIGURE 5. Constitution Diagram for 4.3XX Steels

Partitioning of Impurity Elements in Iron-Carbon Alloys

The addition of even small amounts of certain impurity elements to ironcarbon alloys can result in a severe loss in ductility when tempered at 500 C

The partitioning of these elements between the ferrite and the carbide phases

was felt critical to better understanding of the problem. Electron probe

microanalysis, carbide extraction, and x-ray diffraction techniques were

employed to this end. Figure 6 shows some of the data and Figure 7 shows the

iron-rich end of the binary phase diagram for one of the impurity elements,

antimony. Again, the phase diagram was gemain to the better understanding of

the problem.

Heat Treatment of a Modified Tool Steel

In the heat treatment of a modified tool steel where the carbon level is

lowered considerably, a much higher hardening temperature than normal was required to eliminate the low temperature ferrite phase which was considered

o Austenite Region

Two-Pnase field A Three-cnase Field

X Initial Too-Ptiase Stale
207

COMMENTS PANEL II TOPIC J- Fopiano

• Fe-SIHJJ3% C

I ' I

' ' '

I

'

I

'

I

I ! I I I' I I I I I I I I [ 0 2 4 6 8 10 12 14 16 Q 2 4 6 7 14 » Sb 1 Sb

a. Fe-Sb binary alloys. b. Fe-Sb and Fe-Sb-C alloys.

FIGURE 6. Ferrite Lattice Parameter as a Function of Antimony Concentration

Alloys were Annealed at 600 C Unless Otherwise Indicated

FIGURE 7. The Iron-Rich End of

the Iron-Antimony Binary Phase

Diagram Based Upon Present Results, Showing the a-Solvus

L I I l_J I L

0 4 g 12 % Sb
208

COMMENTS PANEL II TOPIC P. J- Fopiano

undesirable for the application. It turned out, however, that the ferrite

could be reduced only to an irreduceable limit before the hardening tempera

ture became so high as to create a distortion problem. A qualitative probe

analysis indicated no significant alloy transfer to the ferrite for normal

hardening times and the relatively low amount of delta ferrite could be

ignored. This is a very simple example but, in general, phase amounts and

compositions would be invaluable in the investigation of the general class

of tool steels.

The above examples are typical of the needs of the metallurgist in his

investigations of alloys for the important information contained in phase

diagrams. Any help that the metallurgist can get in this area whether it

be a data bank of available (readily retrievable) information or approximat

computational diagrams (generally for mult i component systems) would be

welcome , -
209

P .A N E L III

A T E R I A L S PROCESSING

Moderator: Wm. Rostoker

Department of Materials Engineering

University of Illinois

Chicago , IL

'anel Members: E. R. Kreidler

Lamp Business Division

General Electric

Cleveland, OH

R. Mc Nally

Ceramics Research

Corning Glass Works

Corning, NY

L. Mondolfo

Consultant

Clinton, NY

S . Prochazka

Ceramics Branch

Physical Chemistry Laboratory

General Electric

Schenectady, NY

G. R. Speich

Research Laboratory

U. S. Steel

Monroeville, PA

The members of this panel have provided abstracts of their invroduotory

statements (pp 162 - 168)

.
210

PSTTT

PANEL DISCUSSION - MATERIALS PROCESSING

Eric R. Kreidler

LIGHTING RESEARCH AND

TECHNICAL SERVICES OPERATION

Lamp Materials Research Lab #1361

General Electric Company

Cleveland, Ohio

The kinds of phase equilibrium data useful in the sythesis of

luminescent materials (phosphors) and thermionic emission materials will

be discussed. Although specific and perhaps unusual examples are used,

similar questions and needs arise in the preparation of many electronically

active materials.

Most phosphors consist of a dilute solution of optically active

ions (activators) in an optically inactive host material. The green

luminescent material, zinc orthosi 1 icate (Zn^ Mn SiO.), in which

- 1.0 atomic percent of the zinc ions are repT^ced^by Mn activator

ions, is a typical example. The optical properties of phosphors are determined by the nature and concentration of activators and by the

nature of the host material. In synthesizing phosphors, phase equilibrium

data are often used to determine expected solubility limits of activators

and to establish sythesis conditions over which the host material is

stable. Examples will be given of these uses. Some phosphors require

processing in special oxidizing or reducing atmospheres to obtain the

activator ions in the desired oxidation state. Although phase equilibrium

data, useful for specifying these atmospheres, seldom exist, the practical

advantages of having such data will be indicated.

Thermionic emission materials are used to coat the cathodes in

discharge lamps. Their purpose is to enhance electron emission by

lowering the energy barrier to emission (i.e. the work function). Confusion

often exists about the identity and relative importance of the phases

present in these mixtures. An example of how phase equilibrium studies

were used to eliminate .such confusion will be presented.
211

PSIII

Equilibrium Diagrams in Non Ferrous Alloys

by L. F. Mondolfo

Consultant

RD # 1, Clinton, NY 13323

Equilibrium diagrams are the plot of the structure of the alloys; trying

to work without them is the same as taking a trip thrdugh unknown country

without a map. It can be done, but the chances of taking a wrong turn and

having to backtrack are 100%.

A few examples will show what can be done with equilibrium diagrams in

the non-ferrous industry. In the continuous casting of brasses, when changing

from a 80% Cu, 20% Zn to a 70/30, the pouring temperature has to be lowered

some SCC, but the speed of descent and the amount of cooling water used

remain the same. When changing from a 70/30 to a 60/40, only a few degrees

lowering of the pouring temperature is required, but if both the speed of

descent and the amount of cooling water are not reduced, one ends either with

a split ingot or a spill-out. As can be seen in the equilibrium diagram, both

the 80/20 and 70/30 in the solid state are composed mainly of ductile a phase, whereas the 60/40 is mainly S phase, less ductile (and more sensitive

to impurities) , which must be cooled more slowly.

In the welding of high strength AlZnMg alloys the amount of copper

present has a decided effect. In Cu-free alloys there is a strong tendency for

cracking in the weld zone, in Cu-bearing alloys there is less cracking and

concentrated in the zone near the weld. From the AlCuMgZn diagram it can be

seen that the Cu-free alloys are within the solid solubility limits and contain

little or no eutectic to feed the shrinkage at the end of solidification.

Shrinkage cracks are formed. The Cu-bearing alloys contain a low melting

eutectic that feeds the shrinkage and elimiates shrinkage cracks. However

in the zone adjacent to the weld, extensive eutectic melting takes place and

cracking concentrates in this deteriorated zone. Similar examples are the Mg base alloys that contain Al and Zn. They are

in the solid solution range and therefore have very poor castability. A look

at the MgSi diagram suggests a possible remedy: the addition of 0.25 - 0.30% Si

to the alloys provides a large amount of eutectic, which gives an excellent

castability.
212

PSIII Mondolfo

In the zone refining of Al the binary diagrams predict that Cu, Mg, Si,

Zn, whose eutectic composition is far from the solid solubility limit, can be moved to the end fairly rapidly and easily, whereas Mn, which has a eutectic composition very close to the solubility limit, will move extremely

slowly. Cr, Ti, V, Zr, which undergo peritectic reactions with Al , will move

backwards to the starting end. Experimental results confirm the predictions.

The addition of Mg to Zn die casting alloys to neutralize Pb; the choice

of the heat treatment temperature of AlCuMg alloys, as function of the Si

content; Mn additions to AlMg alloys to improve corrosion resistance; additions

of Co or Mn to AlSi alloys to correct for Fe; the Cr content of CuNi alloys

that makes them heat treatable; additions of Al to MnCu alloys for high

damping capacity are all examples of the use of equilibrium diagrams in

non-ferrous alloys, that cannot be discussed for lack of time.

However there are serious difficulties in the use of equilibrium diagrams.

For example there are some 20 different diagrams published, for the AlZn

system, all presented by reliable investigators. Obviously only one can be

correct, and not necessarily one of the 20!

Another serious problem is that most alloys contain more than 2 elements,

and often may contain as many as 8-10 elements. Reliance on binary diagrams

may be grossly misleading, but the multicomponent diagrams are not available

and, if available, difficult to read or interpret.

In recent years there has been relatively little work on the determination

of equilibrium diagrams; most structural work has been concentrated on the

intermetallic compounds, usually the ones in the middle of the diagram, where

seldom one finds useful commercial alloys. The fault for this to some extent

resides in the Universities. When somebody decreed that determination of an equilibrium diagram was not a fit subject for a PhD thesis, one of the major

sources of useful diagrams dried up. Research on intermetallic compounds on the other hand survived: by bringing in thermodynamic and crystal lographic

relationships, fancy theoretical papers can be prepared with much less

experimental work and effort and ingenuity needed for the accurate determination

of a multicomponent diagram.
213

PSIII Mondolfo

The aluminum and magnesium industries, which where bom in an era when

metallurgy was becoming a science, are in a favorite position: many more

diagrams are available for Al or Mg alloys than for older metals. However even

in these industries there is need for more diagrams. The Concorde airplane

uses a large amount of AlCuFeMgNiSi alloys yet the AlCuFeNi diagram, which

is vital for the understanding of the alloys, is very poorly investigated and

far from established. Those people who have the money to fly the Concorde

should ask themselves "How does it feel to fly a plane whose equilibrium

diagram is not known?"
214

PSIII

'•'^ Phase Equilibria in the Development

of High Temperature Structural

Ceramics

Savante Prochazka

General Electric Research and Development

P. 0. Box 8

Schenectady, New York 12345

Oxidation resistance, low thermal expansion and low creep rates are

first-approach criteria for the development of high-temperature engineering

ceramics (temperatures ISOO^C and above) . Prime candidates are covalently

bonded compounds, SiC, Si^N^, Si-Al-O-N solid solutions and perhaps AIN, some

transition metal borides and materials based on combinations of these

compounds. Single phase ceramics are believed to offer the highest

temperature capability, but the presence of some other specific phases is

usually required for fabrication purposes and for microstructural control and

control of related properties. All consolidation processes developed for these

materials involve chemical reactions, additions and thermal treatments.

Information on phase equilibria is essential for understanding fabrication

processes, which are usually established empirically, and the behavior of the

materials at high temperature and their interactions with the environments.

The types of chemical processes and equilibria which need to be

understood in this field of ceramics may be grouped into the following

categories.

A. Pure compound in equilibrium with its decomposition products:

ex. SiC^^j - C(^^ * Si^g^ * Si^Cjgj . SiC^

(g, - • •

SijN^ -"2Cg) ^''^g) *''2«(g) *
215

^SIIT Prochazka

B. Stability of polymorphs and the effect of some species on phase

transitions between polymorphs:

ex. S - Sic a - SiC

effect of N^, 0^, metals (Si) etc.

a - Si3N^ -> 3 Si3N^

effect of 0^, metals (Si) etc.

C. Limits of nonstoichiometry in pure compounds.

D. Solubility limits in pure compounds of species used to promote

sintering.

ex. B, Be, Al, La, in SiC

E. Phase relations, composition ranges and esp. solidus and liquidus

temperatures in systems of interest

ex. Si - Al - N - 0

Si - Mg - N - 0

Si - C - B

Si - Al - C - N

F. Phase relations in oxidation products:

ex. Si^N^ + MgO ^ SiO^ + Mg^SiO^ 2 MgSiO^

G. Interaction of the parent material and its oxidation products in

the environment of combustion products containing

CO, SO^, Na20, V^O^ etc.

H. Interaction of nickel and cobalt based refractory alloys with the

base material

!h of the information does not exist; its generation will be slow and will

lire unconventional techniques.
216

PSIII

Application of Phase Diagrams in Processing

of Low-Carbon Low-Allov Steel

Gilbert Speich

United States Steel Research Laboratories

Monroeville, Penn.sylvania

Applications of phase diagrams in the processing of

low-carbon low-alloy steels are generally concerned with the

effect of rather small amounts of alloying elements on phase

equilibria, T-here are principally two classes of alloying

elements; minor alloying elements, such as Cb(Nb), V, 0,

Al, S, and N, which are present in amounts of less than 0.1

percent; and major alloying elements, such as Si, Cr, Mn, Mo,

and Ni, 'which are present in am.ounts between 0.2 and 2 percent. In the case of minor alloying elements, information

on solubility products of various carbide, nitride, sulfide,

boride, or oxide phases is important. For instance, in the

case of Cb or V, precipitation of CbC or W (C) is an imiportant

strengthening mechanism and also serves to pin austenite grain

boundaries and inhibit recrystallization . Therefore, information on the solubility product of CbC or VN(C) is important

to specify Cb and V levels where precipitation can occur at or

during cooling from hot-rolling temperatures. Another exam.ple

is S, which is present as MnS in most plate steels. The

ductility and toughness of plate steels is primarily controlled

by the shape and amount of MnS inclusions. Ductility or toughness can be increased by decreasing the sulfur content or by

adding rare-earth additions for shape control. Therefore,

information on the MnS solubility product or on solubility

products involving rare-earth oxysulfides is important.

In the case of major alloying elements, phase equilibria

are of interest because of the possibility of using this information to predict their effect on austenite start and finish

temperatures, on hardenability , or on martensite start and finis

temperatures. However, because of the complexity of these

phenomena in steels containing several alloying elements, and

because of the large body of empirical information already

available, the effect of these elem.ents is still analyzed by

use of empirical formulae.
217

COMMENTS RELATED TO THE PANEL III TOPIC

This contribution is from an audienae participant, not a panel

member. A paper on this COMMENT will appear in the proceedings

.

Phase Diagram Information for Processing of Superconductors*

David Dew-Hughes

Brookhaven National Laboratory

Upton, New York 11973

The bronze process, in which filaments of niobium are dra'Am

down in a Cu-Sn bronze matrix and reacted to form the A-15 compound Nb^Sn is now an established route for high current density

superconductor. The ease with which Nb Sn, V Ga and V Si can be

produced by this technique has prompted attempts to similarly form

the potentially superior A-15 compounds Nb Al, Nb Ga and Nb Ge

.

These efforts to date have been unsuccessful.

The superconducting properties of A-15 compounds are maximized

in well-ordered, stoichiometric samples. The A-15 phase field in

the Nb-Al, Nb-Ga and Nb-Ge systems does not include the stoichiometric composition. The presence of a stable j or c-related compound

pushes the range of homogeneity of the A-15 compound to the Nb-rich

side of the 3:1 composition. A ternary A-15 compound forms close

stoichiometry in the Nb-Al-Ge system, presumably because of a

*This work was performed under the auspices of the U.S. Energy

Research and Development Administration.
218

COMMENTS PANEL III TOPIC D. Dew Hugh.

miscibility gap between Nb^Al and Nb^Ge^ . A similar situation als

exists in the Nb-Al-Si system. The existence of this miscibility

gap may be related to the eutectic in the Al-Ge and Al-Si systems.

If so J are there other ternary systems based on Nb which show a

eutectic and a stoichiometric ternary A-15 compound? Phase diagram studies on Nb-based ternaries are needed to resolve this

point.

In the bronze process^ the presence of copper suppresses the

formation of Sn-rich, Ga-rich or Si-rich phases in the production

of Nb^Sn, ^3^^ ^S^'^ respectively. In attempts to make Nb^Alj

Nb^Ga and Nb^Ge by this process^ the compounds Nb^Al^ Nb^Ga^ and

Nb^Ge^ are preferentially formed. Is it possible^ by adding a

suitable fourth element^ or by using some element other than

copper as a matrix^ to successfully produce the A-15 compounds?

Phase diagram data on ternary and quaternary systems based on Nb

and Cu are needed here^ together with a better understanding of

the factors which govern relative phase stability.
219

WEDNESDAY. 12 JANUARY. 1977

2:00PM-3:30P

user needs for

phase diagram information

(continued)

PANEL IV

PRODUCT APPLICATIONS
PANEL IV

PRODUCT APPLICATIONS

Moderator: F. L. VerSayder

Materials Engineering and Research

Pratt and Whitney Aircraft, U. T. C.

E. Hartford, CT

Panel Members: C. Greskovich

Research and Development Center

General Electric Company

Schenectady, NY

R. I» Jaffee

Fossil Fuel & Advance Systems Division

Electric Power Research Institute

Palo Alto, CA

B. H. Kear

Materials Engineering and Research Lab

Pratt and Whitney Aircraft, U. T. C.

Middletown, CT

A. I. Mlavsky

Senior Vice President of Technology

Tyco Laboratories, Inc.

Waltham, MA

P. Slick

Bell Telephone Laboratories

Allentown, PA

The end use of materials in sophisticated applications is often influenced by an understanding of the subtle effects of phase equilibria. Thus, the panel is composed of

members from industry so as to focus attention on phase diagrams from the viewpoint

of the use of materials. The backgrounds of the panel members represent involvement

with a broad spectrxim of materials. The topic areas will include glasses, ceramics,

electronic materials, aerospace (high temperature) materials, energy (nuclear)

materials, as well as eutectics and others. Each of the panel members will give a brief informal presentation of production application where information on phase

equilibria was of crucial importance to the success of a materials application or where such information will be a prerequisite for future success. Subsequently,

the audience will be invited to participate from the floor.
221

PS IV

COMMENTS RELATED TO THE PANEL IV TOPIC

Th-Ls Qontvihution is frcm an audience participant^ not a panel

msnber. A paper on this COMMENT will appear in the proceeding s.

THE APPLICATION OF THE PHASE DIAGRAM

TO THERMAL ENERGY STORAGE TECHNOLOGY

Dr. J. E. Davison

University of Dayton Research Institute

Dayton, Ohio 45469

and

Mr. Jerry E. Beam

United States Air Force Aeropropulsion Laboratory

Wright- Patterson Air Force Base, Ohio 45433

ABSTRACT: The application of phase diagramsto thermal energy storage

is discussed. The properties of pure components, their melting points and

enthalpies of fusion, are reviewed as a selection criteria for these applications. The performance of elemental components, inorganic oxides, and

inorganic fluorides are compared. The application of information available

in the temperature- constitution phase diagram to determine the type of

liquid- solid transformation, the temperature and composition of the transformation, and a determination of the enthalpy of the transformation is

presented. Specific needs for the development of phase diagrams for a thermal energy storage technology base will be presented.

(DC., *1 'i'c'?.-'.

1
COMMENTS RELATED TO THE PANEL IV TOPIC

This contribution is from an audience participant, not a panel member. A paper on this COMMENT will appear in the proceedings,

THE NEEDS FOR PHASE EQUILIBRIA DATA IN THE DEVELOPMENT

OF MAGNETOHYDRODYNAMICS

R. A. Howald and I. Eliezer

Chanistry Department, Montana State University

Bozeman, Montana 59715

A major research program on thermodynamic properties and phase

equilibria involving inorganic substances is needed for study of the

uses of coal in magnetohydrodynamic power production.

Liquid or gaseous slag constituents, sulfur compounds and other

inorganic materials dissolve protective oxide layers on alloys and have

deteriorating effects on ceramic materials used in MHD channels and other

components of the MHD power plant. These materials also affect the

electrical conductivity of gases in the MHD energy converters and affect

the emission of pollutants. A comprehensive study of the high temperature

equilibria of the materials involved under the conditions of operation of

MHD power generation is necessary. These include broad ranges of

temperature, pressure and oxidation potential, i.e. 1000-2500 K, 1-20 bars

excess oxygen, excess carbon, various moisture contents, etc. The number

of constituents is large and the effects on the equipment and the effluent

gases, liquids and solids are numerous and complex. The constituents

include ions (e.g. K+, OH", e", Na^, H^O^, SO^", etc.) and related

neutral species, gaseous and liquid coal slag components (e.g. K2O, MgO,

Si02j AI2O2J FeO, etc.), sulphur compounds (e.g. K^SO^, K^S , SO^, etc),

refractory materials (e.g. Zr02, LaCrO^, AI2O2, Si02, etc.) along with

the standard combustion gases.
223

COMMENTS PANEL IV TOPIC R. A. Howald and I. Eliezer

Since the addition of potassium seed compounds (K^SO^, K^CO^, etc.)

is necessary to achieve the necessary electrical conductivity in open

cycle MHD the interactions between potassium oxide and various refractory

oxides are particularly important. Coal slag has actually been used in

operating MHD channels as a continually replaced protective coating over

the electrodes. Thus the vapor pressures of potassium oxide over typical

slag compositions are important. For economic reasons it will be

necessary to recover and recycle most of the seed compound, presumably

as K2S0^. In this connection additional phase equilibria data on

solubilities of various oxides in liquid potassium sulfate are needed.

Similar data on ce.sium compounds are important in the engineering

design of closed cycle MHD systems.

Large high temperature heat exchangers constitute one of the major

capital expenses for MHD. Thus phase relations involved in the preparation and useful lifetime of high temperature ceramics should be kricwn in

detail

.

To sum up, information on the phase relations of contacting phases,

solid, liquid and gas, in a variety of MHD systems is vital both to

establish the extent of interaction and to locate temperature and pressure

regimes in which deleterious reactions will and will not occur.

Much of the above information is needed for gas turbine engine

development as well as for MHD.
224

WEDNESDAY. 12 JANUARY. 1977

:y:-> ^ : 0 0 P n - 4 : 3 0 P 1^

SUMMARY OF THE WORKSHOP

BY

J. F. ELLIOTT

DEPT. OF MATERIALS SCIENCE AND ENGINEERING

M.I.T.

CAMBRIDGE. MA
225

4.3 Index to Abstracts

Ageev, N. V., 46

Ageeva, D. L., 46

Aldinger, F., 51

Amman, P., 2C1(P)

Ansara, I., 51,110

Badie, T. M. , 103

Bailey, D. M. ,160

Balakrishna, S. S., 185

Bale, C. W. , 165

Beam, J. E. , 221(C)

Bennett, L. H. , ^2, 69, 92, 112

Bilimoria, Y., 162

Blander, M. , 169

Boreni, R. , 67

Boyle, il. L., 130

Brebrick, R- F., 188

Brewer, L., 114(P)

Brown, J. J., Jr., 7Z

Cameron, T. B. , 104

Carter, F. L. , 135

Carter, G. C, 42, 69, 92

Chang, L. L. Y. , 56

Chang, Y. A., 60, 137

Chart, T. G., 184

Choudary, U. V., 69, 137

Cleek, G. W. , 38, 56

Cook, L. P., 38, 65, 91

Davison, J. E., 221 (P)

de Fontaine, D., 144 (P), 155, 157

Dew-Hughes, D., 218(C)

Dreshfield, R. L., 114 (P) 115

Ehrenreich, H. , 112

Eliezer, I., 140, 142, 222

Elliott, J. F., 201 (P), 224

Evans, B. L. , 58

Fine, H. A. , 84

Fisher, J. R. , 146

Fivozinsky, S. P., 195

Flukiger, R. , 85

Fopiano, P. J., 105, 202(C)

Gaydukov, A.M., 182

Gaye, H., 144

Giessen, B. C, 114(P), 118, 178

Glasser, F. P., 86

Goldstein, J. I., 95

Greskovich, C, 220(P)

Gribulya, V. B., 173, 17 6

Hcirhneidner . K. A.. Jr.. 58

Haas, J. L., Jr., 14 6 Hasebe, M., 148

Henig, E.-Th., 54, 152

Hilsenrath, J., 110

Howald, R. A., 140, 142, 222

Hsu, C. C, 171

Ivanov, 0. S. , 182

Jackson, M. R. , 88

Jaffee, R. I., 220(P)

Johnson, J. R. , 97

Jorda, J. -L. , 85

Kagan, E. K. , 74, 79

Kahan, D. J., 42, 69

Kaufman, L. , 114 (P), 153, 199

Kear, B. H. , 220 (P)

Khanna, K. M. , 107

Kikuchi, R. , 155, 157

Kirsch, R. A., 110

Kiseleva, N. N., 173, 176

Kleppa, 0. J., 114(P)

Kolesnikova, T. P., 4 6 Kriedler, E. R. , 94, 210CP) , 211

Kubaschewski, 0., 160

Larson, H. , 201(P)

Livingston, J. D., 123

Lukas, H. L., 54, 152

Lupis, C. H- P. , 144

Mallik, A.. K. , 185

McCormick, S., 162

McKinstry, H. , 110

McNally, R. , 210(P)

Merrill, L. , 48

Mighell, A., 67

Minor, D. B. , 91

Miodownik, P. A., 164

Mlavsky, A. I., 220(?)

Molino, B. B., 110

Mondolfo, L., 270(P), 212 (P)

Morral, J. E. , 104

Myers, S. M., 100

Nakamura, K. , 98

Navrotsky, A., 114 (P), 119

Negas, T., 38, 56

Neumann, J. ?• , 60

Nishizawa, T. , 148

Ondik, H. 67
226

Pearson, W. B. , 125

Pehlke, R. D. , 201 (P)

Peltoa, A. D. , 165, 199

Petrova, L. A., 46

Petzow, G., 54

Prince, A., 122

Prochazka, S., 210(P), 215(P)

Rairden, J. R. , 88

Reilly, J. J., 97

Reno, R. C, 92

Rhines, F. N. , 52

Romig, A. D., Jr., 95

Rosof, B. H., 167

Rostoker, W. , 210 (P)

Roch,. R. S. , 38. 65

Saboungi, M.-L., 169, 171

Sandrock, G. D., 97

Savitskii, E. M., 173, 17 6

Scheuermann, C. M., 192

Selle, J. E., 193

Sherwood, G. B., 195

Shina, V. K. , 108

Slick, P., 220(P)

Smith, J. F., 160

Smugeresky, J. E., 100

Somiya , S .

, 98

Spear, K. E., 135

Speich, G. R., 210(P), 217 (P)

Stalick, J., 67

Swartzendruber, L. J., 92, 110

Tarby, S. K. , 130

Thompson, W. T.,

Thurmond , C . D . , 3 9

Udovsky, A. I., 182

Van Tyne, C. J., 13 0

Verkade, M. E., 58

VerSnyder, F. L., 220 (P)

Vol, A. E., 74, 79

Wachtman, J. W. , 38

Wang, F. E. , 101

Watson, R. E. , 112

White, H. J., Jr., 1^4

White, W. B., 63>

Zimmerman, B. , 152
227

5. Information Program for Phase Diagram Data Center Representatives

An added day, Thursday 13 Jan 1977, was scheduled for infomial interaTctions

among data center representatives. To keep the group small enough that informal discussions were likely to result, all foreign center representatives

were invited, but only a limited number of US center representatives. The program

listed below, was highly successful, with ten data center participating, from

France, Germany, the USSR, Canada, the U.K., and Japan (see listing below).

Details of current data activities and future evaluation plans were described by

each of these centers, laying the groundwork for future collaboration. Already

some overlap of efforts in evaluations on the multicomponent systems of 3e-based

alloys has been avoided in this manner, and availability of ternary phase

diagram bibliographies (U.K.) and unevaluated phase diagram literature (USSR)

has been clarified, facilitating tranendously , a major undertaking of a ternary

phase diagram critical compendium (Germany) .

PROGRAM THURSDAY 13 JAN

9:00-10:00 visit OSRD, (H. J. White, Jr.)

10:00-12:45 discussions with data center representatives

11:00- 2:00 fleeting in Dining Room B

12:45 Lunch

Discussions by E. L. Brady, Associate Director for Information

Progress Foreign Visitors (see attached list for possible visitors)

and by E. Horowitz, Deputy Director, Institute for Materials Research

2:00- 3:00 Discussions continued.

3:30- 5:00 Visit NBS Data Centers and Labs:

Chemical Thermodynamics Data Center

(D. D. Wagman, W. H. Evans, V. B. Parker)

Phase Diagrams for Cermists Group, and Labs of that section

(R. S. Roth, L. P. Cook)

Alloy Data Center

(L. H. Bennett, G. C. Carter, D. J. Kahan)
228

, , / ^.^v; -.: Workshop Participants of Program, 13 Jan 77

I. Ansara, Phase Diagram Data Center, Grenoble, France

Y. A. Chang, Ternary alloy evaluation group, U. Wisconsin

E. -Th. Henig and G. Petzow, Initiating a major ternary phase diagram

evaluation program. Max -Planck Inst., Stuttgart, Germany

J. H. Westbrook, Director, Data Center and. Chairman, CODATA Advisory

panel, G. E. Schenectady

A. D. Pelton and W. T. Thompson, compilation and prediction of phase diagrams

U. Montreal and McGill U., Canada

A. D. Prince, compilation of ternary and higher order phase diagrams.

Hirst Res. Cntr., G.E., U.K.

S. Somiya, critical evaluation of ceramic phase diagrams, Tokyo Inst, of

Tech. , Japan

T. Kolesnikova, Institute for Scientific Information, USSR Academy of

Sciences, Moscow, USSR

J. F. Smith, Ames Laboratory, representing 0. Kubaschewski, Thermodynamic Data

Center ,• Aachen , Germany

1
229

WORKSHOP ORGANIZING COMMITTEE

Members from NBS

L. H. Bennett, chairman

G- T. Armstrong, C. J. Bechtoldt, D. B.

Butrymowicz, G. C. Carter, L. P. Cook,

J. R. Cuthill, P. R. deBruyn, D. J. Kahan,

M. B. McNeil, R. L. Parker, R. M.

Waterstrat, H. J. White

Members from other Organizations

N, Ault, Norton Co., Worcester, MA

J. Elliott, M.I.T., Cambridge, MA

S. G» Epstein, Alximinum Association,

New York, NY

L. Kaufman, ManLabs, Cambridge, MA

R. Laudise, Bell Telephone Laboratories,

Murray Hill, NJ

J. D. Livingston, General Electric,

Schenectady, NY

E. S. Osborne, Carnegie Geophysical Lab.

Washington, DC

E. C. Van Reuth, Defense Advanced Res.

Projects Agency, Arlington, VA

Schrade F. Radtke, Intl. Lead-Zinc Research

Organization, New York, NY

R. Reynik, National Science Foundation,

Washington, DC

E. Salkovitz, Office of Nav il Research,

Arlington, VA

L. M. Schetky, International Copper Research

Assoc., New York, NY , C. Scheuermann, NASA Lewis Research Center,

Cleveland, OH

M, Semchyshen, Climax Molybdeniim Corp.

Ann Arbor, MI

J. Swisher, Energy Research & Development

Admin., Washington, DC

ARRANGEMENTS COMMITTEE

Ronald B. Johnson, Chairman

Sara R. Torrence

NBS-114A (REV. 7-73)

U.S. DEPT. OF COMM.

BIBLIOGRAPHIC DATA

SHEET

1. PUBLICATION OR REPORT NO. 2. Gov't Accession

No.

3. Recipient's Accession No.

4. TITLE AND SUBTITLE

Workshop on Applications of Phase Diagrams In Metallurgy

and Ceramics

5. Publication Date

6. Performing Organization Code

7. AUTHOR(S)

L. H. Bennett and G. C. Carter

1. Performing Organ. Report No.

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

10. Project/Task/Work Unit No.

11. Contract/Grant No.

12. Sponsoring Organization Name and Complete Address (Street, City, State, ZIP)

National Science Foundation, Defense Advanced Research Project

Agency, Office of Naval Research, National Aeronautics & Space

Administration, Energy Research and Development Administration,

and U. S. Army Research Office

13. Type of Report & Period

Covered

Final

14. Sponsoring Agency Code

15. SUPPLEMENTARY NOTES

16. ABSTRACT (A 200-word or less factual suimnary of most significant information. If document includes a significant

bibliography or literature survey, mention it here.)

A workshop was held at the National Bureau of Standards, Gaithersburg, Md.,

January 10-12, 1977, to assess the current national and international status of

phase diagram determinations and evaluations for alloys, ceramics and semiconductors;

to determine the needs and priorities, especially technological, for phase diagram

determinations and evaluations; and to estimate the resources being used and potentially available for phase diagram evaluation. A one-day meeting was held following

the workshop for the international data center representatives from France, Germany,

Canada, the U.K., Japan, the USSR, and the USA, in a further attempt to assess currently on-going phase diagram data evaluation activities and to stimulate interaction and cooperation between these centers.

This report includes highlights of the workshop, description of a new poster

board design used in the poster sessions, lists of attendees and demonstrations, the

program, and descriptions of the presentations.

17. KEY WORDS (six to twelve entries; alphabetical order; capitalize only the first letter of tfie fint key word unless a proper name; separated by semicolons) Computer predictions; Critical evaluations; Data compilatipns

;

Industrial needs; Phase diagrams; Theory of phase diagrams; Thermodynamics.

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