Engineering Metallurgy

PITMAN METALLURGY SERIES
FRANK
T.
SISCO,
Advisory Editor
Engineering
Metallurgy
Engineering
pitman
PUBLISHING CORPORATION
>*
Metallurgy
By
THE COMMITTEE ON METALLURGY

-4
collaborative writing group
of
metallurgy professors.
NEW YORK
TORONTO
LONDON
Copyright
BY
1957
PITMAN PUBLISHING CORPORATION

All rights reserved.
may
the
l>e
No part of this book reproduced in any form without

permission
of
written
the
publisher.
1.2
Associated Companies
Sir Isaac
London
Sir Isaac
Mcllraurne
Pitman & Sons, Ltd. Johannesburg
Pitman & Sons (Canada), Ltd. Toronto /
&9
/
,
QOZAfcl-
COTA
PRINTED
in
the United States of America
Coauthors
Theodore Allen,
Jr.,
M.S.M.E., Associate Professor of Mechanical En-
gineering, University of Houston, Houston, Texas; Engineer Associated
with Anderson, Greenwood and Co., Bellaire, Texas
Lee L. Amidon, M.S.M.E., Professor and Head, Department of Mechanical Engineering, South Dakota State College, Brookings, South Dakota
John K. Anthony.
Robert
E.
M.S.. Associate Professor of Physical Metallurgy, Uni-
versity of Arizona,
Tucson, Arizona
of Metallurgy,
Bannon, S.M., Professor
Newark College
of
Engineering, Newark,
New
Jersey
Francis William Brown, Ph.D., Associate Professor, Clarkson College of Technology, Potsdam, New York
Frederick Leo Coonan, D.Sc, Professor and Chairman, Department of Metallurgy and Chemistry, U.S. Naval Postgraduate School, Monterey,
California
Howard
P. Davis, M.S., Associate Professor,
Department
of
Mechanical
Engineering, University of
Wyoming, Laramie, Wyoming
Harold Vincent Fairbanks,

West Virginia
University,
M.S., Professor of Metallurgical Engineering,
Morgantown, West Virginia

State University,
Mars G. Fontana,
Ph.D., Professor and Chairman, Department of Metal-
lurgical Engineering,
The Ohio
Columbus, Ohio
Arthur R. Foster, M.Eng.,

ing,
Associate Professor of Mechanical EngineerNortheastern University, Boston, Massachusetts

Ph.D., Associate Professor of Metallurgical Engi-
Arthur C. Forsyth,
neering, University of Illinois, Urbana, Illinois
Richard Edward Grace, Ph.D., Associate Professor of Metallurgical Engineering, Purdue University, Lafayette, Indiana
Leonard
B. Gulbransen, Ph.D., Associate Professor,
Washington Uni-
versity, St. Louis,
Missouri
Joseph Gurland, D.Sc, Assistant Professor, Division of Engineering,
Brown
University, Providence,
M.S.,
Rhode
Island
Walter R. Hibbard,
necticut
Adjunct Associate Professor of Metallurgy, College of Engineering, University of Bridgeport, Bridgeport, Con-
vi
Coauthors
M.S.M.E., Assistant Professor of Mechanical En-
Walter M. Hirthe,
Wisconsin
gineering, College of Engineering, Marquette University, Milwaukee,
Abraham Eldred Hostetter,

John
Ph.D., Professor of Metallurgy, Kansas
State College, Manhattan, Kansas

J.
Flushing,
J.
Kaufman, Metallurgy Department, Academy New York
of Aeronautics,
New
Edward Krauss, M.S., Head, Department of Mechanical Technology, York City Community College, Brooklyn, New York
Hollis Philip Leighly, Jr., Ph.D., Chairman, Department of Metallurgy, University of Denver, Denver, Colorado
Irving
J.
Levinson, M.S., Professor of Mechanical Engineering, Lawrence
Institute of Technology, Detroit,
Michigan
Jules Washington Lindau, III, M.E., Associate Professor of Mechanical Engineering, The University of South Carolina, Columbia, South Carolina
James R. MacDonald, Ph.D., Chairman, Department

gineering, School of Engineering,
versity, Mississippi
of
Mechanical En-
The
University of Mississippi, Uni-
Omar
Don
C. Moore, M.S., Associate Professor of Chemical Engineering, Alabama Polytechnic Institute, Auburn, Alabama
R. Mosher,
B.S.,
Assistant Professor of Mechanical Engineering,
University of Colorado, Boulder, Colorado
Charles Arthur Nagler, Ph.D., Associate Professor, Department of Chemical and Metallurgical Engineering, Wayne State University, Detroit, Michigan
Richard O. Powell, College

Orleans, Louisiana
of Engineering,
Tulane
University,
New
Oran Allan
Kenneth
E.
Pringle, M.S.M.E., Associate Professor of Mechanical En-
gineering, University of Missouri, Columbia, Missouri
versity of Kansas,
Rose, M.S., Professor of Metallurgical Engineering, UniLawrence, Kansas
Philip C. Rosenthal, M.S., Professor of Metallurgical Engineering, University of Wisconsin, Madison, Wisconsin
Robert
E. Shaffer, M.S., Associate Professor of Engineering, University
of Buffalo, Buffalo,
New
York
Coauthors
vii
Walter
ing,
E. Short, M.S.M.E., Associate Professor of Mechanical EngineerBradley University, Peoria, Illinois
Floyd Sheldon Smith, M.S., ing, Alabama Polytechnic
Associate Professor of Mechanical EngineerInstitute,
Auburn, Alabama
GEORGE
ing,
V. Smith, Ph.D., Assistant Director for Metallurgical EngineerSchool of Chemical and Metallurgical Engineering, College of Engineering, Cornell University, Ithaca, New York
Sicmund Levern Smith, M.Met.E., Professor of Metallurgy, College of Mines, University of Arizona, Tucson, Arizona
Joseph William Spretnak, Ph.D., Professor of Metallurgical Engineering, The Ohio State University, Columbus, Ohio
Rocer Greenleaf Stevens,

William H. Tholke,
cinnati, Cincinnati,
Ph.D., Head, Department of Chemical Engineering, Southwestern Louisiana Institute, Lafayette, Louisiana
B.S., Instructor of
Metallurgy, University of Cin-
Ohio
John Stanton Winston, M.A., M.S., Chairman, Department of Metallurgy, Mackay School of Mines, University of Nevada, Reno, Nevada
Preface
Engineering Metallurgy was developed
standable
to present in a concise, under-
manner
the principles of ferrous and nonferrous metallurgy
for all engineers student

ate student engineers
will
employ
in
and practicing. Both graduate and undergraduneed a fundamental knowledge of the metals they their work. The emphasis, throughout therefore, is on
metallurgical principles rather than on handbook information; however, specific data are given so as to provide a realistic structure to reinforce the theoretical presentations. The practicing engineer who has had little
contact with the field of metallurgy, or who has had no formal work in metallurgy, will find in this book a sufficiently complete summary of all
of the essentials he needs to
know
to obtain a broad understanding of
the
field.
Keeping up with metallurgical developments in

art, as
all branches of the reported in the technical literature of the world, is difficult for
those actively engaged in the manufacture, processing, or the industrial use of engineering metals and alloys. For the thousands of such individuals, who work with or who use metallic materials but who cannot possibly find time to read everything, summaries such as this book have a well-defined place in the scheme of things.
Because metallurgy
is
such a dynamic and diversified art and science,
the preparation of a definitive, up-to-date, authoritative
work
in this field
required a bold approach. Forty professors actually engaged in teaching engineering metallurgy in universities across the country were asked to pool their knowledge and research to produce this text. Through intenthe scope and content of the book were defined and outlined by the group. Once the basic content had been selected, ideas for all chapters were channeled to experts selected to
first
sive questionnaire techniques,
on individual chapter committees. From these ideas and their own combined experience and research, each committee built chapter outlines. Overlaps and omissions were detected by the editorial staff and referred to the committees for alteration and preparation of rough draft. The coauthors read and checked the smoothness of presentation of the chapter, adding to and refining the draft. Thus were built the twentyserve three chapters of Engineering Metallurgy by the forty coauthors.
Chapters
through
6 deal
with the general principles of metallurgy
as they are related to engineering.
Chapter 3 (Factors Affecting Engineering Properties) will be especially useful to the student in gaining
ix
Preface
an appreciation of the over-all study of engineering metallurgy. In Chapter 6 (Phase Diagrams and the Simply Alloy Systems) the student is introduced to basic problems of equilibrium and alloying. Chapters 7 through 10 treat of the nonferrous metals and alloys. To these important
,
materials, a generous
amount
of space has been devoted so that com-
1 1 through 20 arc concerned with iron and steel with special attention given to the subjects of heat treatment and ferrous alloys. Machinability, corrosion, and the effects
plete coverage could be obtained. Chapters
of temperature are fully covered in Chapters 21 to 23.

All technical terms are defined as they are introduced, and stress
laid
is
upon fundamental
concepts. At the
end of each chapter there
is
a set of questions
tention
chapter.
and exercises constructed on the important definitions and
to help the student focus at-
principles presented in the
Principles, definitions,
precision
and
clarity.
and illustrative examples are set down with Drawings and photographs are used without re-
serve to amplify the discussion. In certain chapters, detailed tables are
included for the convenience of the reader. The Committee on Metallurgy is aware that the usage of this text and developments in the field will indicate areas needing revision. Professors
and students
are therefore urged to send comments on chapters to the publisher or chapter committees so that appropriate changes may be made in the next edition.
The
Editor
Contents
Preface
v
1.
Chapter
1.1. 1.2. 1.3.
Metallurgy and Engineering
Metallurgy as an Art
Metallurgy as a Science Metallurgy and Engineering
2 3
Chapter
2.1. 2.2.
2.3. 2.4.
2.
Fundamental Structure of Metals and Alloys

Principle
in Solids
5 5 9 9
11
Building Blocks of Matter
The Building-Up
Types of Bonding
Assemblages of Atoms
Defects in Crystals
Polycrystalline Aggregates
2.5.
2.6.
14 16 18 19
2.7.
2.8.
Interactions in Metallic Solutions
Liquid Solutions
Solid Solutions
2.9.
20 20
2.10.
Intermediate Phases
Chapter
3.1. 3.2.
3.
Factors Affecting Engineering Properties
...
23 24 29 32 33 36 37 38 40
Grain Size Control

Effect of
Grain Size on Properties
3.3. 3.4.
3.5.
Deformation of Metals
Slip in Single Crystals
Twinning
Deformation of Polycrystalline Metals
3.6.
3.7. 3.8. 3.9.
Hot Working
Cold Working
Annealing Cold Worked Metal
Factors Affecting Rccrysiallization Temperature and Grain
Size
xi
42 45
3.10.
xii
Contents
3.11.
3.12. 3.13. 3.14. 3.15.
Summary
of
Hot and Cold Working
46
47
Solid Solution Effects
Polyphase Structures
Allotropic Transformation
Precipitation
4.
49
51
Hardening
52
Chapter
4.1.
4.2. 4.3.
Static Properties of Metallic Materials
...
57
Properties of Metallic Materials
57
60
61
The
Relative Standardization of Static Tests
Tensile Strength
Elastic Limit, Proportional Limit,
ticity
4.4.
and Modulus
of Elas-
63
4.5. 4.6.
Yield Point
and Yield Strength
66 67
Elongation and Reduction of Area
4.7.
4.8. 4.9.
Hardness
69 72
Comparison of the Various Hardness Tests

Relation
among Hardness
Tests and between Hardness

73
and Tensile Strength for

4.10.
Steel
Relation
among Hardness
Tests and between Hardness
and Tensile Strength

4.11. 4.12.
for Nonferrous Alloys
....
. .
74 77 78
81
Shear, Compression,
and Bend Tests
Sonic Testing
Chapter
5.1.
5.
Dynamic Properties of Metallic Materials

Brittleness
Notch
and Transition from Ductile
to Brittle
81
Fracture
5.2. 5.3. 5.4.
Value of the Notched-Bar Impact Test
85 86 87
.
The Mechanism of Fatigue The Endurance Limit

Relation of the Endurance Limit to Other Properties
.
5.5.
5.6. 5.7.
5.8. 5.9.
88 89 92
The
Effect of
Notches on the Endurance Limit
....
...
Corrosion Fatigue
Increasing the Endurance Limit by Shot Pcening
Significance of
92 93 94
97
Endurance Data
5.10.
Damping Capacity
6.
Chapter
6.1.
Phase Diagrams and the Simple Alloy Systems
Solid State
Thermodynamics and Thermostatics
...
97
6.2.
6.3. 6.4.
Contents Concept of Dynamic Equilibrium

Cooling Curves
Solid State Mass Transfer
xiii
97
98
99
100
101
6.5. 6.6.
6.7.
The
Phase Rule
Solid State Solubility
Binary Systems
Intermetallic
101
6.8.
6.9.
Compounds
.
106
The
Peritectic Reaction
108 109
6.10.
Closure
Chapter 7. Heat Treatment of Alloys by Precipitation Hardening

7.1.
7.2.
Ill
Alloy Requirements
Step
Ill
I Solution Heat Treatment
112
7.3.
7.4. 7.5.
Step II Precipitation Heat Treatment (Aging)
....
14
Theory of Precipitation Hardening
114
Precipitation
The
Effect of
Time and Temperature During

Hardening
of
Heat Treatment
7.6. 7.7. 7.87.9.
117
Precipitation Precipitation
Aluminum
Alloys
Hardening of Magnesium Alloys Precipitation Hardening of Copper Base Alloys

Precipitation Hardening in
Strain
7.10. 7.11.
Aging and
Its
Low Carbon Steel Consequences in Low Carbon

in
.... .... .... ....

Steel
119
121
124
125 126
Precipitation
Hardening
Alloy Steels
126
Chapter
8.1. 8.2. 8.3. 8.4. 8.5.
8.6.
8.
Light Alloys as Engineering Materials
....
.
129
129 130
8.7. 8.8. 8.9.
Aluminum Economics of the Aluminum Industry Aluminum Ores Occurrence and Concentration Manufacture of Aluminum Physical Properties of Aluminum Chemical Properties of Aluminum Aluminum Alloys The Wrought Alloys Aluminum Casting Alloys
History of
131
132
133 134 135
136 140
143
8.10. 8.11.
Functions of Alloying Elements
Cold and Hot Working of Aluminum Alloys
147
xiv
8.12. 8.13. 8.14. 8.15.
Contents Heat Treatment of Aluminum Alloys

Corrosion Resistance of
148 150 152

155 158
Aluminum
Alloys
Joining of
Aluminum
Its
Alloys
Magnesium and
Beryllium
Alloys
8.16.
8.17.
Titanium
9.
159
161
Chapter
9.1.
9.2.
Copper and Copper- Base as Engineering Materials and Uses

of High-Purity
Properties
Copper
. . .
164
165 167
Constitution of the
Common
Copper-Rich Alloys
9.3.
Nomenclature of the Copper-Rich Alloys

Characteristics
9.4.
9.5. 9.6. 9.7. 9.8.
and Uses of the High Brasses
168
Silvers
Characteristics of the
Low
Brasses Brasses
and the Nickel
170
171
Properties of the
Wrought
Cast Brass and Cast Nickel Silver
172
9.9-
9.10. 9.11.
9.12. 9.13.
The Copper-Base Bearing Metals The Tin Bronzes Aluminum Bronze and Copper-Silicon
Copper-Beryllium Alloys
172
174
Alloys
176 177
The Copper-Rich
Copper-Nickel Alloys
in
184
. .
Copper and Copper-Base Alloys

Miscellaneous Heavy
Metals
Powder Metallurgy
186
Chapter 10. Alloys

10.1. 10.2. 10.3. 10.4. 10.5.
10.6. 10.7. 10.8.
Nonferrous
Metals and
190
191
The White
Lead and Tin
as Engineering Materials
. .
.
196 197
Zinc and Zinc Base Alloys as Engineering Materials

Nickel and Nickel Base Alloys
199 201
201
Cobalt Base Alloys
Other Miscellaneous High Temperature Metals and Alloys
The
Precious and Semi-Precious Metals and Alloys
202 203
Metals and Alloys in Atomic Power Applications
....
Chapter 11. The Manufacture and Composition of Carbon and Alloy Steels
11.1. 11.2. 11.3.
208 210 212

216
Definitions of Ferrous Engineering Materials
Iron Ore and the Manufacture of Pig Iron
Acid and Basic Processes
Contents
11.4. 11.5. 11.6.
xv
Bessemer Processes
217 220
Steels
Open-Hearth Processes
Manufacture of High-Quality
Processes
by the
Electric
226
227
11.7. 11.8.
Wrought Iron
Special Steel-making Processes
229
231
Steels
11.9.
Mechanical Treatment of Steel
11.10. 11.11. 11.12. 11.13.
Harmful Elements
Manganese
in
in
Carbon and Alloys
....
.
233 236
Carbon and Alloy Steels Carbon Monoxide, and Rimming and Killed Silicon and Other Degasifiers
Other Elements
Low-Alloy
Steels
Steels
237
239
11.14.
11.15. 11.16.
239
. .
240
241
High-Alloy Steels
Chapter
12.1. 12.2.
12.
The
Constitution of Steel
244
244 245
The
Allotropy of Iron
Iron-Carbon Phase Diagram Phase Changes and Microstructures of Slowly Cooled Plain
12.3.
Carbon
12.4.
Steels
247
251
Isothermal Transformation in Steel
12.5.
12.6.
The
Effect of
Cooling Rate
Effect of Alloying
Upon the Resulting Structure Elements Upon the Iron-Carbon Dia-
254
g
12.7.
256
Effect of Alloying
Elements on the Isothermal Transfor257 258 259
mation of
12.8. 12.9.
Steel
Effect of
Effect
Hot Working on Structure of Cold Working on Structure
Chapter
13.1. 13.2. 13.3.
13.4. 13.5.
Fundamentals of Heat Treatment of Steel Grain Size and Grain Growth

13.
263
264
Controlling and Classifying Grain Size

Effects of
265 267
Hot Working on Grain

and Hardenability
Size
Hardenability
269 270
270
Grain
Size
13.6. 13.7.
Quenching and Properties of Martensite
The
Instability of
Quenched Carbon
Steels
273
XVI
Contents
Retained Austenite and Cold Treatment
Structural
13.8. 13.9.
274 274
and Other Changes
in
Tempering
Chapter
14.1. 14.2.
14.3.
14.
The
Operations of Heat Treatment
278 279
280 280
281
Heating Cycle
Annealing
Normalizing
Spheroidizing
14.4. 14.5. 14.6. 14.7. 14.8. 14.9.
Quenching
for
Hardening
282
Tempering
Isothermal Treatments
284
285
'
Case Hardening Processes
289 293
Flame Hardening and Induction Hardening

15.
Chapter
15.1. 15.2. 15.3. 15.4.
Carbon Steel as an Engineering Material
...
297
Carbon-Steel Castings as Engineering Materials
....
.
298
300
Factors Affecting the Properties of Carbon-Steel Castings
Hot-Worked Carbon
Effect of
Steels as Engineering Materials

Static Properties of
302
Composition on
Steels
Hot-Worked
303
305
. .
Carbon
15.5. 15.6. 15.7.
Effect of
Composition on Other Properties

Steels as
Cold-Worked Carbon
Engineering Materials
306 307 308

311
The Important
Properties of Cold- Worked Steel
...
.
15.8.
15.9.
General Effects of Cold Working on Strength and Ductility

Variables Affecting the Properties of Cold-Worked Wire
Effect of
15.10. 15.11.
15.12.
Cold-Working on Dynamic Properties

as
312
Heat-Treated Carbon Steels

Effect of Section Size
312
315
on
the Properties of Heat-Treated
Medium-Carbon
Chapter
16.1.
16.2. 16.3.
16.
Steels
Low- Alloy Steels
as Engineering Materials
318
319 320 322
Balanced Compositions
in
Low- Alloy
Steels
General Effects of the Alloying Elements on Carbon Steel

Effects of
Phosphorus, Manganese, and Silicon
....
16.4. 16.5. 16.6.
Effects of Nickel
Effects of the
and Chromium
324
Other
Common
as
Alloying Elements
....
.
.
325 326
Low-Alloy Structural Steels
Contents
16.7.
xvii
Composition and Properties of the Low-Alloy Structural

Steels
327 328
Materials
.
16.8. 16.9.
16.10.
The S.A.E. Low-Alloy Steels The S.A.E. Low-Alloy Steels as Engineering The New Metallurgy of Low-Alloy Steels
Steels
331
333
16.11.
Similarity of Properties of Heat-Treated S.A.E. Low-Alloy
334
337
16.12.
The
17.
Engineering Properties of the S.A.E. Low-Alloy Steels

Hardf.nability
Chapter
17.1.
17.2. 17.3. 17.4.
17.5.
342
Hardness and Hardenability in Carbon Steels Hardness and Hardenability in Low-Alloy Steels Cooling Rate and Hardenability
....
...
343 344
344 346
Time Delay and
Hardenability
Variables Affecting Hardenability
346 348 349
17.6.
Methods of Determining Hardenability
17.7.
17.8.
The Jominy End-Quench
Hardenability Test
Relation of the End-Quench Test to Actual Cooling Rates and the Selection of Steel by Hardenability
Virtues and Shortcomings of the
350 352
353
17.9
17.10.
Jominy End-Quench Test
Hardenability Bands
Relation of Hardenability to Engineering Properties Relation of Tempering to Hardenability
. .
17.11. 17.12.
17.13. 17.14.
354
356 356
Fundamentals of Calculated Hardenability
17.15.
The The
18.
Accuracy of Calculated Hardenability

Effect of
360
361
Boron on Hardenability
Chapter
18.1. 18.2.
18.3.
Special Purpose Steels
364
Classes of Stainless Steels
364
Steels
Constitution of
High-Chromium
366
Relation of the Constitution of High-Chromium Steels to
Their Heat Treatment

18.4.
18.5.
367
Mechanical Properties of High

Steels
Chromium
Steels
...
369
Corrosion and Oxidation Resistance of High-Chromium

370
18-8 in 18-8
18.6.
18.7.
The Constitution of The Role of Carbon
372
374
xviii
Contents
Properties of 18-8
18.8. 18.9.
376
Steels
Recent Developments in Stainless

Superstainless Steels
378
381
18.10.
18.11.
18.12.
High-Nickel Steels and Special Iron-Nickel Alloys

Austenitic
19.
...
384 385
Manganese
Steels,
Steel
Chapter
19.1. 19.2.
19.3.
Tool
Die Steels, and Cemented Hard

389
Steels
Carbides
High-Carbon Tool
390 395
Low Alloy Tool Steels Medium Alloy Tool and

High Speed
Cast Alloys
Steels.
Die
Steels
396 397
19.4. 19.5. 19.6. 19.7. 19.8.
High-Alloy Tool and Die Steels
398
Steels
. .
Function of Alloy Additions in Tool and Die
402
404 405
Cemented Carbide Tools

20.
Chapter
20.1. 20.2. 20.3.
Cast Iron
as
408
an Engineering Material 410
White Cast Iron
Malleable Cast Iron as an Engineering Material
Engineering Properties of Malleable Cast Iron
.... ....
410 410 412
20.4.
20.5.
Gray Cast Iron
as
an Engineering Material
Structure of Gray Cast Iron
414
415
20.6.
Relation between Properties and Structure of Gray Cast Iron
20.7. 20.8.
20.9.
Effect of Effect of
Cooling Rate
Graphite Size on Structure and Properties
.
416
.
417
Evaluation of Gray Cast Iron for Engineering Applications
419 420
422 425
20.10.
Nodular or Ductile Cast Iron

Melting and Casting of Irons
as
20.11.
20.12. 20.13. 20.14.
Ternary System of Iron, Carbon, and Silicon
Heat Treatment of Cast Iron
430 434
Normal and Alloy Elements

21.
in Cast Iron
Chapter
21.1. 21.2.
Machinability,
Wear
Resistance, and Deep-Draw-
ing Properties Variables Affecting Machinability
438
438
. . .
Evaluation of Metallic Materials for Machinability
438
Contents
21.S. 21.4. 21.5.
21.6.
xix
Free Machining Steels

Relative Machinability of Steel and Nonferrous Alloys
.
440
441
Types of Wear
Variables Affecting
442
21.7. 21.8.
21.9.
Evaluation of Steel for
Wear Resistance Wear Resistance
443 444
445
Importance of Deep-Drawing Properties

Evaluation of Steels for Deep Drawing
Yield-Point Elongation, Stretched Strains, and ing Properties
446
21.10.
Deep Draw448
21.11.
Deep-Drawing Properties of Nonferrous Alloys

22.
....
449
452
Chapter
22.1. 22.2. 22.3.
22.4. 22.5. 22.6. 22.7. 22.8. 22.9.
Corrosion and Oxidation
Electrochemical Corrosion
452
454 456
EMF
Series
and
Passivity
Uniform Corrosion
Galvanic or Two-Metal Corrosion
Concentration Cell Corrosion
Pitting
456
458
459 460
462
.
Intergranular Corrosion
Stress
Corrosion
Dezincification
466
22.10.
22.11.
Erosion-Corrosion
468
469
471
Methods
for
Combating Corrosion
22.12.
22.13.
Corrosion Testing
Liquid-Metal Corrosion
472
472
22.14. 22.15. 22.16. 22.17. 22.18. 22.19.
High-Temperature Oxidation
Formation of Oxides
473
. .
Dependence of Oxides Growth upon Gas Pressure Dependence of Oxide Growth Upon Time Dependence of Oxide Growth Upon Temperature
Oxidation Prevention
474
477
479
480
Chapter 23. Effect of Temperature on Mechanical Properties of Metals

23.1. 23.2. 23.3.
485 486 486 488
The Importance of Creep The Engineering Significance of Creep The Creep to Rupture Curve
xx
23.4.
23.5. 23.6.
Contents
Determination of Creep
Effect of Variables
489
491
on Creep
Fatigue and
23.7. 23.8.
23.9.
Structural Changes
Combined Fatigue and Creep During Creep

. . .
493 495
Variation of Other Properties with Temperature
498
499
Design for Elevated Temperature Service

Variation
tures
23.10.
Mechanical
Properties
at
Reduced Tempera500 502
23.11.
23.12.
Effects of Metallurgical Variables
Design for Low-Temperature Service
....
...
503
Index
507
Engineering
Metallurgy
CHAPTER
1
Metallurgy and Engi nee r i ng

Don
R. Mosher, B.S., Assistant Professor of Mechanical
Engineering, University of Colorado, Boulder, Colorado
1.1.
Metallurgy as an Art
METALLURGICAL
nings in the stone age
difference in behavior
knowledge had
first
its
begin-
when some ancient craftsman
recognized the
amongst certain of the "rocks" with which he was
working.
brittle,
The
stones familiar to this primitive artisan were hard and
and were capable of being fashioned into tools and weapons only by tedious shaping, chip by chip. His first encounter with metal then, undoubtedly native copper or gold, must have been an exciting experience. Here was a substance which, instead of fracturing, yielded to the blows of his stone hammer. Here was a material which could be formed
much more precisely, which was pleasing to the eye, which could be worked to a keener edge, and which, moreover, somehow acquired greater strength the more it was worked.
From
carbon
is
the use of native metal to the deliberate reduction of an ore by a long step, and one which is the subject of much interesting
It
speculation.
seems likely that the
first
such reduction was accidental-
possibly the result of a fortunate combination of circumstances in which the heat of a campfire, together with carbon from the charred logs
succeeded in reducing copper ore contained in the surrounding stones, On other occasions the stones may have contained additional metals such as tin, and the result was a remarkably stronger metal. In time, the relationship between the
stones was recognized,
fire,
the charred logs,
and the
discoverer, the
and the particular types first metallurgist, began
of
to
produce metals at will. He and his progeny of the next several thousand years have accumulated a mass of information concerning the effects of variables in processing
upon
the properties of the final product.

1
Engineering Metallurgy
Metallurgy as a Science
1.2.
Questions concerning the reasons why these variables resulted in the

observed
effects
must certainly have been present
in the
minds of
these
pioneers long before the means were available to answer them.
With the
advent of the microscope and the X-ray, these inquiring minds began to supply the answers.
The science of metallurgy really began when Sorby, a British scientist, reported in 1864 the results of his investigations on the use of the microscope to study the structure of meteoric iron.
studies in the
This was followed by same general field by Martens in Germany, reported in 1878. The work of these two scientists, however, aroused little interest at the time, and nothing further was accomplished until Sorby showed to the British Iron and Steel Institute in 1886 some photomicrographs of iron and steel. This aroused much interest in the internal structure of metals, and from 1890 to 1920 many distinguished metallurgists devoted
themselves to developing a science of physical metallurgy.
early problem of metallurgy, which fairly cried for was that of the hardening of steel why steel containing considerable carbon was soft when cooled slowly from a red heat but hard when cooled rapidly from the same temperature. This problem occupied most of the workers in the science of metals for more than two decades.
solution,
The paramount
Despite the efforts of
many
brilliant minds,
which resulted
in a
volume
that
of published literature that amazes present-day metallurgists,
little
was wholly decisive was accomplished until confirmatory X-ray crystallography methods came into use about forty years ago. Although some cynics say that the X-ray has created more problems than it has solved, X-ray crystallography has been a useful tool in the study of the structure of metals and the constitution of alloys.
In the past three decades the science of physical metallurgy has changed remarkably. Always closely related to chemistry and physics, it has been greatly affected by the revolution that has occurred in these two sciences since 1920. The gap between chemistry and physics has been largely eliminated, and, as these sciences came together, the science of metallurgy changed from simple speculations on the structure of metals and alloys, as affected by composition or mechanical or thermal treatment and as observed by the microscope, to speculations which involve such complex abstractions as spinning electrons, statistical mechanics, electromagnetic theory, quantum theory, wave mechanics, and thermodynamics.
Present-day physical metallurgists are inclined to smile condescendingly
at the battles over
beta iron, cement carbon, and amorphous metal which

filled the transactions of the
3
years ago.
metallurgical societies forty or
fifty
It is
not
at all certain that
even broader smiles will not be in order thirty
years from structure
over the discussions of free energy, entropy, and mosaic filling our journals at the present time. Especially apropos in this connection are the words of a venerable man of science,
now
which are
Ambrose Fleming, who presented a paper to the first meeting of the London in 1873 and who, in a formal address to the same body of scientists on "Physics and Physicists of the Eighteen Seventies,"* summarized his seventy years of experience by saying:
Sir
Physical Society of
also be the hence a fellow of the physics of the nineteen thirties, he will have to record the great additions then made to knowledge of physical facts. But he may also have to say that our explanations and theories concerning them have all vanished, or at least been replaced by others also destined in turn to pass
When we come to look back then on the world of physicists during the eighteen seventies, what we find is that their inventions, discoveries of fact, and ascertained principles remain with us today of permanent value, forming part of our useful knowledge. But their theories and speculations as to underlying causes and nature have nearly all passed away. Perhaps it will
same with our present-day work. Physical Society gives a talk on the
If
some
sixty years
away.
1.3.

little
Until about forty years ago there was
need for the engineer to

steel,
know anything about metallurgy

rolled or cold-drawn,
since
untreated carbon
hot-
was used for at least 95 per cent of steel structures and machines. The engineer was interested primarily in four propertiestensile strength, yield point, elongation, and reduction of area-and in having available an ample supply of cheap steel which, in addition to meeting specifications for tensile properties, would machine easily and fabricate readily. It was considered sound engineering practice to build machines and structures that would carry a much higher load than was
anticipated; weight was
synonymous with quality, and the heavier the structure the better the design. High factors of safety were used; consequently slight variations in quality, such as lack of structural
geneity, surface irregularities,
and numerous
others,
made
little
homoor no
difference in designing.
This is no longer true. Weight and the strength-weight ratio (tensile strength divided by specific gravity) have become very important. Under the leadership of the automotive and aircraft industries engineers have come to realize that excess weight not only indicates poor design but is an inexcusable economic loss. The experience of the automotive
and
Nature,
v.
143, 1939, pp. 99-102.
the aeronautical engineer in designing lightweight structures and machines stimulated similar efforts in other fields of engineering. This
is
shown by the recent developments in machine tools, in lightweight way rolling stock, and even in bridge and building structures.
It
is,
rail-
of course, self-evident that the present-day emphasis on light
as exemplified by the automobile, airplane, and the streamlined train is directly related to the development of new types of steels and light nonferrous alloys and to new treatments for these materials. It is a moot question whether the metallurgist or the engineer was responsible for most of this development. Enthusiastic metallurgists insist that engineering progress has been the direct result of metallurgical progress; that engineers only improved their tools, machines, and structures because metallurgical art and science had produced new metallic materials for the engineer to use. There is no doubt that many engineers are too conservative and that engineering progress has at times lagged behind progress in metallurgy. On the other hand, examples could be cited where the metallurgist did not improve his product until insistent engineering demand forced it upon him. A discussion of whether this advance was pioneered by the metallurgist or the engineer is as futile as arguing whether the egg or the chicken came first; the essential fact is that important changes have taken place and that the
weight in engineering design
engineer should
know something
of the metallurgical progress that has
accompanied
It
is,
his changes in design.
therefore, the purpose of this

in metallurgical art
book
to outline the recent develop-
ments
This does not and refining, or of mechanical and heat treatment, or of thermodynamics and wave mechanics; it does mean, however, that sufficient details of the present state of metallurgical art and science are given so that engineers may recognize the importance of the variables, inherent in the manufacture and treatment of metals and alloys, that affect the engineering properties and the suitability of these materials for engineering applications.
in metallurgical science.
and
mean
that there are long descriptions of melting
QUESTIONS
1.
Distinguish between the art and the science of metallurgy.
2.
What
research tools have most profoundly influenced the development of
metallurgical science?
3. 4.
5.
To what
other sciences
is
metallurgy closely related?
How Why
is
progress in engineering
is it
and in metallurgy inter-related? becoming increasingly important for engineers to understand the
fundamentals of metallurgy?
CHAPTER

Leonard B. Gulbransen, Ph.D., Associate Washington University, St. Louis, Missouri
lurgical
Professor,
Joseph William Spretnak, Ph.D., Professor of MetalEngineering,
The Ohio
State
University,
Columbus, Ohio
In RECENT
and the application of wave mechanics
lurgy has resulted in a
alloys.
years the study of the solid state

to solid state physics
much
clearer picture of the structure of metals
and metaland
Physical and mechanical properties of the metals, such as tensile strength, ductility, electrical conductivity, diffusion, etc are dependent on structure, sometimes to a marked degree. For this reason it is desir-
able to discuss the structure of solids,
and
in particular the structure of
metals and
alloys.
2.1. Building Blocks of Matter

All metals are aggregates of atoms. Atoms consist of a nucleus and one or more planetary electrons. In general, except for applications of the nuclear reactions, it can be assumed that the atomic nucleus consists of
positively charged protons,
and neutrons with no
electrical charge.
Most
of the mass of the
atom
is
sum
of the masses of the protons
concentrated in the nucleus and is equal to the and neutrons in the nucleus. Negatively
charged electrons
sufficient to balance the positively charged protons in the nucleus, resulting in an electrically neutral atom, are found outside the nucleus. Electrons may be thought of as point particles, with a definite
mass and electrical charge; however, their motion must be described in terms of an associated wave. The part of science that deals with this problem is known as wave mechanics. The fundamental equation
de-
Engineering Metallurgy wave

is
scribing the motion of an electron and accompanying
De
Broglie's
equation:
A
= h/mV
x 1027
erg-sec)
,
where h
electron,
is
Planck's constant (6.62

is
is
the mass of the
the velocity of the electron,
and A
is
the associated wave-
Practical use of this equation is made in electron diffraction equipment. Application of De Broglie's equation, and Heisen berg's uncertainty principle, which states that the position and momentum (mV)
length.
of a particle cannot be exactly determined simultaneously, result in a
somewhat
different idea of
atomic structure than the
classical picture of
a nucleus and planetary electrons in definite fixed orbits. of the equations of
Application
wave mechanics
results in a picture of the
atom
as a
positively charged nucleus, with electrons in discrete, but "smeared out"

orbits.
The
is
limits of the orbit
can be described
in
terms of a probability
function, in which, the probability of finding the electron at the center of
the orbit
maximum, but
is
finite
and small
as
probabilities exist for finding
the electron at the limits of the "smeared out" orbit. This description of
atomic structure
sometimes described
an electron cloud picture.
State
2 p State
State
Fig. 2.1.
Electron cloud diagrams of hydrogen atom.
characterized by four
In the solution of the wave equation for a given atom, the electrons are quantum numbers; n, I, m t and m s . The quantum
is
number n
1
quantum number, and is related to the n may have any integral value from + to infinity. The quantum number / is related to the angular momentum of the electron and may have any integral value from to (n-1) The quantum number m, is related to the magnetic moment of the eleccalled the principal
total energy of the electron.
Number

tron and
may have any
value from
to
I.
related to the rotation of the electron
about
The quantum number m, is its own axis, and may have
values of i/ 2 . The four quantum numbers determine the energy of the electron in various states, with the result that an atomic system may be
fully described by specifying the values for the each electron.
quantum numbers
for
wave mechanics is the Pauli Exclusion Principle no two electrons in the same atom can have the same four quantum numbers. This principle in effect restricts a given electron to one and only one energy slate in a single atom. If then, two atoms are brought together to form a molecule, the electrons of each atom must occupy different energy states or energy levels. The idea of energy levels is important with regard to molecule formation and also to the formafurther result of
states that
which
tion of the solid state.
MAXIMUM NUMBER OF ELECTRONS

5P
to 5s
10 6
2
Up
3D
"i
Us
IS
Fig. 2.2.
Energy
level
diagram
of
an atom.
As an example of the above principles, consider the hydrogen atom. consists of a proton, + 1 charge, and a mass of approximately one atomic unit. The hydrogen atom must then possess one electron. In the lowest energy state, this electron would have an energy described by the quantum numbers n = 1, / = 0, = 0, and m, = + \/ 2 The next atom in the periodic system, helium, with a + 2 charge on the
The hydrogen atom
nucleus must possess two electrons.
The quantum numbers

,
describing
would then be: n, =1, I, = 0, mj, = 0, m, l = + \/ = and n, l = 0, wijj = 0, and 1, z m sl = \/z These two electrons have very nearly the same energy, the only difference being related to the spin quantum numbers m, and m tl Both electrons are confined to the same major energy level with n = 1, and only these two electrons can occupy this level. The next atom in the periodic system, lithium, must possess three electrons. Two of the electrons have the same quantum numbers as those for helium, but the third, n = 2, I = 0, m = 0, and m, = + i/ 2
these electrons, in order to fulfdl Pauli's exclusion principle,
A more common method

an atom
principal
the
is
of representing the electronic configuration of
to use the terminology of the spectroscopist, in
which the
quantum number n is listed, followed by a letter designating quantum number /, and indicating by a superscript the number of
(
For most metallurgical applicabetween energy states with different values for m and m, is so small that it may be neglected. According to this method of representation the hydrogen atom in its lowest energy state may be described as being in a (Is) 1 state; the helium atom in a (Is) 2 state; the
electrons in this particular energy state.
tions, the difference
lithium atom in a (Isf
(2s)
/
state etc.
1,
The quantum number
is
desig-
nated by s for
electrons, the
0,
for
for
2,
and
/ for
3.
By applying
of two
Pauli's exclusion principle, the s state
may
contain a
maximum
state a
maximum
of six electrons, and the d state a maxi-
mum of ten electrons.

ATOMIC NUMBER
1
ELEMENT
ELECTI ION CONFICUR ATION

(Is)
1
Hydrogen
2 3
i
Helium
Lithium
Beryllium
(Is)' (Is)' (Is)' (Is)' (Is)' (Is)' (Is)' (Is)' (Is)' (Is)' (Is)' (2s) (2s)
1
5
6 7
fi
Boron
(2s)'(2p)'
Carbon
Nitrogen
(2s)'(2p)'
(2s) '(2p) 3
Oxygen
Fluorine
(2s)'(2p)<
9
10
ii
(2s)'(2p)
Neon
(2s)'(2 P )
Sodium
<2s)'(2p) (2s)'(2p)
(3s)
12
Magnesium
of
(3s)
Fic. 2.S.
Table
atoms through atomic number 12 with energy
states.
Fundamental Structure
2.2.
of Metals
and Alloys
The Building-Up
Principle
Using the principles outlined in the previous section, the electron configuration of the elements can be determined through argon, atomic
number
18. However with the element potassium, atomic number 19, instead of progressing from a completed 3p energy state to the 3d state, the next electron falls into a 4s state. Calcium follows with two electrons
in the 4s
state.
This discontinuity in the building up principle results
from the fact that as electrons are added to energy levels further removed from the nucleus a resultant shielding of the positively charged nucleus takes place due to the intervening electrons, causing the energy of the 4s
have a lower value than that of the 3d state. Following calcium in the periodic table, the building up of the 3d state occurs in a normal manner, inside of a completed Is state. The electron configuration of nickel, atomic number 28, being (Is) 2 (2s) 2 " (3s) 2 (3p) 6 (2p)
state to actually
The electron configuration of element atomic number 29, copper, then becomes normal with a completed 3d state and a (4s) 1 valence state. Elements with atomic number 21 through 28 are known
(3d) 8 (4s) 2
.
as
transition elements
and are characterized by incomplete 3d energy
states.
In the second long period of the periodic table a similar series of elements occur with incomplete 4d energy states. The group of transition elements is important to the metallurgist because it includes many of our
most important metals, such manganese, cobalt, and nickel.

ATOMIC NUMBER
21
as iron,
titanium, vanadium, chromium,
TRANSITION ELEMENT
ELECTRON CONFIGURATION
(Is)'
Scandium
Titanium
(2s)'(2p)*
(2s) (2p)'
2
(3s)'(3p)(3d)>
(4s)'
(4s)* (4s) 8
(4s)'
22
(Is) 1
(ls)
(Is) 1
'
(3s)'(3p)(3d) 2
(3s)(3p)(3d)'
(3s) 2 (3p)(3d) s
23 24
Vanadium
(2s)*(2p) (2s)*(2p)
(2s)'(2p)
Chromium
Manganese
Iron
25
26 27 28
(Is)'
(Is) 2
(Is) (Is)
2 2
(3s) 2 (3p)(3d)
(4s)'
(4s)
2
(2s)'(2p) 6
(2s) (2 P)
2 6
(3s)'(3p)"(3d)
(3s) (3p)(3d)'
2
Cobalt
Nickel
Fig. 2.4.
(4s) 2
(2s)*(2p)
(3s)'(3p)(3d)
(4s)
Table
of
atoms of the transition elements.
2.3.
Types of Bonding in Solids
All solids can be classified in groups according to the bond formed between atoms in the solid state. The four types of bonds that may be formed in solids are:
10
(1)
The Van der Waal's bond The ionic bond (2) covalent bond The (3) The metallic bond. (4) These various types of bonds may all
be analyzed in terms of electronelectron, electron-proton, proton-proton interaction between atoms.
Van der Waal's bonding occurs between atoms or molecules in solids due to an induced polarity on one molecule with respect to another. This type of bond is electrostatic in character and the binding force is relatively weak. Solids formed by Van der Waal's bonding have low melting and sublimation temperatures, and low strength. Solids formed by the atoms or molecules of neon, argon, and iodine are examples of Van der Waal's
solids.
Ionic bonds can be considered to be the result of the transfer of an electron, or electrons from one atom to another with the net result that one atom becomes positively charged, and the other negatively charged.
On
the basis of the building-up principle, such bonds should tend to form between atoms with one or two electrons in the valence state and
atoms with one or two vacancies in the valence state. More stable electronic structures occur for completed energy levels; thus, when two atoms such as sodium and chlorine are brought together to form a solid, the valence electron of sodium is accepted by the chlorine atom to complete the valence state of chlorine, leaving a net charge of + 1 on the
The
1 on the chlorine atom. sodium atom, and resulting in a net charge of ionic bond is electrostatic in nature and results in a strong bond. Examples of ionic solids are sodium chloride, magnesium fluoride, magnesium oxide, and calcium sulfide.
The
covalent
bond
is
formed by
forces arising
from the sharing
of
is
electrons between atoms.
The
simplest example of this type of
bond
the formation of the hydrogen molecule from two hydrogen atoms. The lowest energy state for the hydrogen atom is the h state in which m = can be occupied by two electrons, it follows that \/ 2 and since this state formed between two hydrogen atoms, their elecif a molecule is to be energy level. Many elements with more than trons must share this lowest crystal structures in the solid state based on one valence electron form octet of electrons, required bond. To complete an this type of electron
,
for a stable structure, electrons are shared with
8-N neighboring atoms,
where
is
the
is
number
of valence electrons in a given element.
The
covalent bond a strong bond, because of the completion of an energy covalent solids are generally speaking hard and strong. level; so that solids are diamond, silicon, and graphite. Examples of covalent
11
features of both the ionic and cometal atoms are brought together to form a solid, a broadening and possible overlapping of energy levels occurs; so that, although a discrete number of electrons must occupy a given energy
The
metallic
bond has some of the
valent bond.
When
level,
according to the Pauli principle, the electrons in a given energy
level
may have more freedom

electric field.
to
move throughout
the solid lattice under
an applied
Solid
Decreasing interatomic distance

Fig. 2.5.
Broadening of energy
levels in
a solid.
The
metallic state is sometimes visualized as a structure consisting of positive ions arranged periodically in space, with a negatively charged
cloud of electrons surrounding the positively charged core. An explanation of the high electrical conductivity of the metals is based on the idea of unfilled or overlapping broad energy levels. An applied electric field
in either case
may
increase the energy of electrons in such bands
and
promote them
to a conduction band, resulting in a net flow of electrons
in the direction of the applied field.
characterized by filled
does not possess band.

2.4.
Insulators on the other hand are and empty levels. Thus, a normal electric field enough energy to promote electrons onto a conduction
Assemblages of Atoms
the seven crystal systems used by the crystallographer, the two to the metallurgist are the cubic and the hexagonal
Of
most important
12
systems.
Nearly
all
of the
common
metals and alloys of commercial imin describing solid structures.
portance belong to these two systems. Before discussing metal structures,

it is
important to define certain terms used

[.attire.
The Space
space lattice
is
defined as a lattice of lines divid-
ing space into equal sized prisms which stand side by side with all faces in contact, so as to fill space with no voids. All of the points of a space
lattice
have identical surroundings.

lattices.
It
can be shown that there are only
fourteen possible space
The Space Group. Starting with a given space lattice, there are many ways of building up actual crystals by placing atoms or molecules at
various points on the space lattice.
called space groups, of
Actually there are 230 such ways,

crystals
forming actual
unit cell
is
based on the fourteen
space
lattices.
The Unit
space lattice
Cell.
The
defined as a network of lines through

it
into prisms. Each unit cell in a and orientation with every other unit cell. The unit cell is the building block from which the actual crystal is constructed by repetition in three dimensions. The three most the points of a space lattice, dividing
is
identical in size, shape,
important unit
cells for
the metallurgist are the body-centered cubic,
the face-centered cubic, and the hexagonal close-packed.
/'
y
/
/
/*
y/
>f
.
7
\
/
i
Fie. 2.6.
The
three unit
cells.
In the cubic system all of the cube edges of the unit cell are of equal length and stand at 90 to one another. In the hexagonal system, three
axes on the basal plane of equal length stand at 120 to one another with the third axis of different length at 90 to the basal plane.
Special planes
and
special directions in crystals are of great
importance
aspects
in plastic deformation of metals, hardening reactions, of the behavior of metal crystals; therefore,
it is
and other
necessary to have
some
method
of describing such planes
and
directions.
13
The most common method

reference point.
is
to use Miller indices
and
indices of direc-
tion to describe the position of a plane
and
is
its
direction from a fixed
The
Miller index system
based on the space lattice

is
and unit
cell of the structure in
question, and
derived from the inter-
cepts of the plane along the axes of the space lattice.

are as follows:
(1)
The
three steps in-
volved in the determination of the Miller indices of a particular plane
Determine the intercepts

as a
of the plane on the three-crystal axes multiple or fraction of the unit cell edge.
(2) (3)
Determine the reciprocals of these three numbers.
Reduce the same ratio.
reciprocals to the smallest integers that are in the
The
three indices are then enclosed in parentheses. Planes that have the
Plane
Intercepts
Plane II
x axis
y axis z axis
= = =
=
a,,
x axis y axis
z axis
= = = =
oo
ao
oo
Reciprocals
x axis
=1
=
a
1
x axis
=
a.
oo
y axis
y axis
z axis
(111)
/.
axis
= =-r oo
(100)
Miller Index
Fig. 2.7.
Determination of Miller
indices.
same
integers, either positive or negative,
but in a different sequence

,
belong to the same planes (010) belong to the same family of planes, the [100] family.
family of planes.
The
(OlO)
(100) etc.
Indices of direction are derived by considering the motion that must be imparted to a point at the origin to move it in a required direction.
14
required indices are found by moving the point first along the X axis, then along the Y axis, then along the Z axis, in terms of the unit
The
distance along these axes.
The
three smallest integers in the same ratio
that will impart die required

direction.
motion
to the point are the indices of
Indices of direction are enclosed in square brackets.
Direc-
tions having the
same
indices, positive or negative,
but
in a different [100],
sequence belong to the same family.

[O'TO],
The indices
of direction
[001] belong to the same family of equivalent directions <100>. Note that reciprocals are not used in finding indices of direction.
2.5. Defects in Crystals
Tn idealized representations of metal

is
crystals, a
cell
is
model of
perfect crystals
used that possesses no imperfections and is repeated indefinitely through space with no disregistry among the unit cells. Such a model clearly is not representative of a real metal crystal. If it were, we should commonly experience tensile strengths of the order of magnitude of millions of pounds per square
generally used.
In this model, a unit
inch.
Real metal
crystals
and
|>olycrystalline aggregates are characterized

It is
by
the presence of several types of defects.

defects in three categories:
1.
convenient to
classify these
Surface imperfections
2. 3.
Line imperfections
Point or atomic imperfections.
Surface imperfections include the free surface of a crystal, the grain boundary or interface between two adjoining grains in a polycrystalline
aggregate, interfaces between two solid phases, the interface of a twin and the parent crystal, and sub-boundaries of the mosaic block structure.
Metal
crystals are
made up
of cubic crystallites about 10
cm. edge
the
length, called mosaic blocks.
There
is
a slight disregistry
among
blocks, giving rise to interfaces
formed by adjacent blocks.
Line imperfections are termed dislocations. There are two basic types
of dislocations, the "edge" type
are illustrated in Figure 2.8.
and
the "screw" type.
These dislocations
is
The
dislocation concept
the basis of the
modern
theories of plastic flow in metals.
Atomic imperfections include several types. The lattice vacancy is a normal lattice point from which the atom is missing. Interstitial defects consist of either a foreign atom in the interstitial space between normal lattice sites, or an atom from a normal lattice site removed to an intersti-
15
POSITIVE
DISLOCATION
SCREW DISLOCATION
Fie. 2.8.
Dislocations in Metals.
considerable distance from the vacancy so formed. Finally a substitute for a host atom on a normal lattice site, giving rise to a substitutional defect.
tial site at a
foreign
atom may
above account for the flow and fracture characterproperties including semi-conducting behavior, diffusion mechanisms, and creep characteristics of real metals and alloys. These
istics, electrical
The
defects listed
defects are the basis of the "prior history" effect so well
known in metals study of these defects by metal scientists has a two-fold purpose; namely (1) a better understanding of them and how they affect properties, and (2) exploration of possibilities of minimizing or eliminating these defects. For example, metal whiskers of diameter of
and
alloys.
The
about 10 cm. exhibit essentially theoretical strengths and arc thought to be free of dislocations.
'
16
Fie. 2.9.
Schematic representation of crystallization.
(Rosenhain)
2.6. Polycrystalline
Aggregates
In technical freezing processes such as the solidification of ingots in metal molds or castings in sand molds, many nuclei or starting sites beactive. A nucleus consists of a crystallite which is large enough to be thermodynamically stable in the presence of the liquid. Each nucleus grows until it impinges on its growing neighbors. This process is illus-
come
trated schematically in Figure 2.9.
The impingement
The
process yields metal
grains at the completion of freezing, since on the average, two neighboring nuclei have different orientations in space.
is
structure developed
generally termed a polycrystalline aggregate.
17
junction of two neighboring grains gives rise to a zone of distermed the grain boundary. The grain boundary is a few atoms in thickness and is essentially disordered in structure, showing viscous
registry
The
properties since the atoms in this zone belong to the lattice of neither of the two neighboring grains.
Some important
manifestations of grain
boundaries are the following:

(1)
They
are barriers to the propagation of slip, the basic
mechanism
is
of plastic deformation. metal.

(2)
The
smaller the grain
size,
the harder
the
Grain boundaries are high energy

cases,
sites; thus,
they are favored
sites
for nucleation of solid state reactions.
They may
also attract solute atoms
in
some
(3)
resulting in a segregation of the foreign

faster
atom
at the
boundary.
Diffusion
is
along grain
boundaries than in the
bulk
of the grain.
(4) At elevated temperatures, grain boundaries may contribute to deformation in creep by grain rotation. The grain size range usually encountered is from 10 to 250 microns (micron = 10* cm.) in diameter. The grain structure is usually studied
electrical sheet, grains are easily discernible
with the aid of a microscope. In certain cases such as cast structures and by the naked eye. An example of a polycrystalline metal is given in Figure 2.10.
Fie. 2.10.
Polygonal grains of high purity iron, etched. 500x-
18
2.7. Interactions in Metallic Solutions
The
initial
addition of solute atoms of species
to a
pure liquid or
solid metal of species
results in a liquid solution or solid solution
respectively.
If
The
solubility of
in
A may be
said that
extensive or restricted.
is
completely soluble in A, then

If
it is
is
completely miscible
in A.
is
not completely miscible in liquid A, then a second liquid
phase will appear. In solid metal A, limited solubility will give rise to the appearance of a second phase, which may occur in the form of another
solid solution, or as
crystal structure.
an intermetallic compound with
characteristic
mainly determine the miscibility of B in A, namely and the chemical interaction among the species. The ratio of the diameter of the solute atom B to the diameter of the solvent atom A must be such that B can either (1) substitute for A at a lattice site forming a substitutional solid solution, or (2) such that B ran fit in the interstitial space of the A lattice, giving rise to an interstitial solid
characteristics
Two
the size factor
solution.
The size
factor
is
illustrated in Figure 2.11.
Favorable
for
Favorable
for
interstitial
i
substitutional
solid solutions
solid solutions
i
j
0.59
0.85
1.0
1.15
Ratio of
Fie. 2.11.
size of solute
atom
to solvent
atom
The
size factor in the
formation of solutions in metals.
Chemical interaction has

atoms. In an assemblage of
these symbols.
to
do with the strength of the bond between
A and B
neighbors are A-A, B-B, and A-B.
We
atoms, the possible pairs of nearest can also refer to bond strengths by
In solutions, three general types of behavior
may be
ex-
perienced: ideal solution behavior, positive deviation from ideality, and negative deviation from ideality. In the case of ideal solution behavior,
the situation in
a given
bond
strengths
is
A-A
B-B
A-B. This
is
to say that
has no preference as to an A or a B atom as its nearest neighbor. (The number of nearest neighbors depends on the symmetry of the space lattice, and is expressed as the coordination number. Values
A atom
for the
common
and 8
lattices are 12 for the face
centered cubic and hexagonal

.
metals,
for the
body centered cubic)
In
this case
complete mis-

cibility in
19
the liquid
and
solid
state
is
expected, yielding the simple
isomorphous diagram. For the situation

tion
is
AB >
B
AA
HH
,
positive devia-
experienced, meaning
A atoms
prefer to cluster with other
atoms, and
B atoms
prefer to cluster with
tendency for phase separation. With sequence of binary diagrams is the following:
atoms. This gives rise to the increasing positive deviation, the

in the solid state
Isomorphous phase separation

peritectic with
minimum
gap
peritectic -h> eutectic

in the liquid region.
- eutectic with
a miscibility
For the situation
AB <
negative deviation from ideality
is
experienced, meaning A's and B's prefer to be associated. This leads to the tendency for compound formation. The sequence of phase diagrams
with increasing negative deviation is the following: Isomorphous ordering compound formation. An ordered solid solution is one in which the solute occupies
lattice sites
specific
and
is
not distributed randomly.
2.8.
Liquid Solutions
The concept of liquid solutions of metals is easy to grasp since we have common counterparts in our everyday experiences such as sugar dissolved
in coffee, salt dissolved in water.
liquid solution has some important
differences
from the
is
solid solutions.
Probably the most important
differ-
ence
is
that only "short-range order" exists. In a true solid, the crystalline
arrangement
order."
repeated indefinitely in space giving rise to "long-range a metal melts, an increase in volume occurs (only bismuth and gallium among the pure metals contract on melting) This increase in volume is accounted for by the formation of additional lattice vacancies and an increase in the interatomic distances, with a loss of long-range
When
It is believed that the liquid configuration is 12-15 atoms clustered about a lattice vacancy. As the temperature of the liquid is increased, the short-range order begins to disappear and the structure ap-
ordering.
proaches complete randomness.
Liquid metals and solutions

shearing
stresses.
The
in general have no ability to sustain thermal and electrical conductivities are about
The solubility of gases such as hydrogen increases with increasing temperature. When immiscibility occurs in the liquid region of an alloy, generally two liquid layers are formed because of difference in density of the two liquid phases.
50%
of the values for the solid structure.
20
2.9.
Solid Solutions
concept of solid solutions is somewhat harder to grasp. These solutions are in reality solute atoms dissolved in the crystal lattice of the host, or solvent metal. As previously mentioned, the solute atom may
substitute for a solvent
solution, or
it
The
atom on
a lattice
site,
giving a substitutional solid
space between the solvent atoms, giving an interstitial solid solution. These two types of solid solution are illustrated schematically in a two dimensional array in
interstitial
may
lodge in the
/'
s
/
7 /
,
<
y
i
s
'
2
/*
yC
yt
<-
/
/
,/
}
B
Fig. 2.12.
Schematic representation of solid solution.
Figure 2.12. Solid solutions are produced either by the freezing of the liquid solution, or by the diffusion of the solute atom into the lattice of
the solvent
atom in the
solid state.
The
(1) (2) (3) (4)
introduction of solute atoms into the lattice of the solvent metal
brings about some important changes in properties:
The electrical and thermal conductivities are reduced. The thermoelectric power is reduced. The strength and hardness are increased. The ductility is decreased.
of solid solutions
is
The formation
one of the fundamental methods of
hardening a metal.
2.10. Intermediate Phases
When the solid solubility of a solute species is exceeded, a second phase will appear in the microstructure of the alloy. These intermediate phases can be classified into six categories: (I) Intermediate solid solutions.
These solid solutions exhibit a range of composition and lie intermediate to the components A and B. Terminal solid solutions, on the other hand, start with pure A or pure B.
21
(2) Normal Intermetallic compounds. These are often called valency compounds since they show a definite stoichiometric ratio of A to B and a definite chemical composition. Examples are Mg 2 Pb, Mg3 Bi 2 , PtSn AlSb, MgTe, MnSn, and AuGa.
2,
(3)
Electron Compounds.
These compounds are characterized by a definite valence electron to atom ratio, a definite structure, and usually a range of composition. The
electron/atom ratios encountered are 3/2, 21/13, and 7/4. A common example of electron compounds is the Cu-Zn, or brass series of phases.
These electron compounds are found The Sigma Phase. (4)
in alloys of copper, silver,
and
gold.
The sigma phase is a hard, brittle phase found in certain alloy systems such as for example Fe-Cr. It has a tetragonal structure with 30 atoms
in the unit cell.
(5) Interstitial Compounds. These compounds involve small solute atoms, usually hydrogen, nitrogen, and carbon, which lie in orderly arrays between layers of the larger
solvent atoms.
They
are characterized by their high melting points,
high hardness, and metallic characteristics. The Laves Phases. (6)
Laves phases are compounds which form when the difference in size between solute and solvent is intermediate. They show the composition AB 2 with a size ratio of 1.2/1.
The
atomic
The formation of intermediate phases is another important method of hardening metals. The intermediate phases can further be classified as to being coherent or non-coherent. Coherent phases are those whose structure is continuous with the matrix structure and lead to precipitation hardening (age hardening) Non-coherent phases are those whose
.
discontinuous with that of the matrix and are simply mechanical mixtures. This class of intermediate phase leads to dispersion hardening. The hardness of such a mixture is mainly dependent on the average distance between the precipitate particles, or expressing it differently, the mean free path in the matrix.
lattice structures are
QUESTIONS
1.
Calculate the wave-length of an electron velocity of 1.8 X 109 cm/sec.
(m
9.1
10-28 grams) with a
2.
3.
4.
Calculate the wave-length of a particle of mass 2000 pounds and a velocity of 50 miles per hour. Would it be necessary to use wave mechanics to interpret the motion of this mass? Explain. Write the electron configuration of silver, molybdenum, and tungsten. Discuss the difference between the ionic and Van der Waal's bond.
22
5. 6.
How
do the metallic bond and the covalent bond differ? Show how two different space groups may be constructed on
centered cubic
lattice.
a body-
7.
Determine the number of atoms
8.
9.
in a body-centered cubic unit cell; a facecentered cubic cell. (Note that corner and face-centered atoms are shared by other unit cells.) Determine the Miller indices of a plane in the cubic system with intercepts is the length of the unit cell edge) (a V-i a, and \i a 'A a Determine the intercepts of a plane in the cubic system with Miller indices
,
of (235). Sketch the direction [101] in a face-centered cubic cell. 11. Enumerate the three classifications of defects encountered in real metal crystals and give examples of each type. 12. What is the influence of these defects in metals and alloys? 13. Define a grain boundary and list some important manifestations of grain
10.
boundries. Describe the two types of solid solutions formed in metal systems. 15. What is meant by the size factor in solid solutions? Give the favorable size factor range for the two types of solid solutions. 16. Discuss the arrangement of atoms in solid solutions exhibiting (a) ideal behavior, (b) positive deviation from ideality, and (c) negative deviation
14. 17.
from ideality. Give the sequence of phase diagrams expected for increasing (a) positive deviation from ideality, and (b) negative deviation from ideality.
Discuss the properties of liquid solutions of metals.
18. 19.
What
changes occur in physical and mechanical properties when

six categories of intermediate phases
B atoms
arc dissolved in the crystalline lattice of A, forming a solid solution?

20.
Enumerate the
and
describe the char-
acteristics of each.
CHAPTER

Philip C. Rosenthal, M.S., Professor of Metallurgical
Engineering, University of Wisconsin, Madison, Wisconsin
IF A
it is
"perfect" single crystal of metal

in the
is
tested,
neighborhood of a million pounds per square inch, exceeding by a hundred-fold or more the strength of the same metal in its ordinary polycrystalline form. According to dislocation theory, this great difference in strength between the "perfect" crystal and
its
found that
strength
is
the ordinary polycrystalline metal can be attributed to the presence in the latter of dislocations within the grains, and to the grain boundaries themselves, which in effect, represent a series of dislocations. Therefore, the properties of polycrystalline metals are limited at the start by this
characteristic atomic disregistry;
and whatever means we have available
for controlling their properties cannot eliminate this situation.
In addition to the inherent atomic imperfections that are present, other microscopic or even macroscopic imperfections may be introduced
during the manufacture of the metal

sions,
part.
These are such imperfecetc.,
tions as segregation of alloying elements, presence of non-metallic inclu-
seams, porosity, voids, dissolved gas,

its
properties of the metal and determine

factors
"quality."
which will alter the These "built-in"
cannot always be prevented and must be recognized as affecting the engineering properties to a greater or lesser degree. Starting with a material that is already limited in its properties be-
we can alter its properties within limits, through the utilization of one or more of the following processes or "unit operations" of engineering property control that are available to the engineer for his manipulation. These are:
cause of these imperfections,
23
24
1
Grain size control Mechanical working
Alloying
2. 3.
4. 5.
Heat treatment
Nuclear radiation. final engineering properties of a metal may therefore be thought resulting from a combination of positive and negative factors. The
The
of as
negative factors are the dislocations

segregation, inclusions, porosity,
are picked
and the additional imperfections of and any other undesirable factors that
of
its
up by the metal during the course
preparation and that
detract from the properties of the metal.
The
positive factors are those
combinations of the first four of the process variables listed above that are used to obtain the properties desired. To be most effective, any one or combination of these operations should be performed on metal having a "quality" consistent with the application and costs of the part. To illustrate the extremes possible, the metal going into an ordinary boat anchor and that going into a highly stressed landing gear of an airplane can be compared. In the first instance, the most important requirement is shape and weight, and strength is decidedly secondary. Metal going into this part could contain a number of the imperfections previously listed without seriously detracting from its serviceability. Furthermore, no strengthening would be required by any further processing. On the other hand, the highly stressed part of an airplane landing
gear would need to be very carefully produced to avoid any imperfections
and
excessive inclusions.
In addition, the metal would be alloyed and
properly heat treated and possibly mechanically worked to get the best
possible serviceability for the
negative factors
would be kept
minimum weight of at a minimum and
the part.
Here the
the positive factors
derived from the processing developed to the highest degree.
While knowledge concerning the control of all the variables affecting engineering properties is important to the engineer, it is with respect to the processes used to manipulate the engineering properties* that he is
generally concerned and these will be discussed primarily herein. References to the factors affecting the "quality" of the metal will be
necessary.
made when
GRAIN SIZE AND ENGINEERING PROPERTIES

3.1.
Grain Size Control
Although other factors such as alloying or heat treatment may have a more profound effect on metal properties, nevertheless control of the
The
metallurgical engineer, of course,
is
expected to be familiar with
all.
25
Fie. 3.1.
Partially solidified iron crystals
showing
their dendritic appearance (Howe).
grain size of the metal can be important because such properties as toughness, high temperature strength, machinability, and formability can vary appreciably with the grain size. How grain size can be confirst, following which some of the more important engineering aspects of grain size control will be discussed. Casting Process. When metal is melted and poured into castings, the metal solidifies as a mass of interlocked grains. The way the metal freezes
trolled will be discussed
final form it takes is related to its composition. It is not possible to consider here all the ramifications of solidification, and further consideration of this point is given in Chapter 6, but those factors affecting final grain size can be considered. As the temperature of the molten met;il is lowered by loss of heat to the mold walls, freezing commences by the nucleation of solid metal grains
and the
the
along the sides of the mold. The grains so nucleated are probably randomly oriented but a number will be so oriented that growth inward
26
Fig. 3.2.
Completely frozen gold alloy showing dendritic character of each grain and
grain boundaries. 100X.
will
be favored,
i.e.
in the direction of the temperature gradient.
At the
lower
same time that they grow inward,

rates in their other
these grains will also
grow
at
dimensions as well.
The
growth, however, will not
be like that of an expanding block but more on the order of a growing

tree,
with the main stem being represented by the growth inward and
the branches representing the lateral expansion.

is
This
tree-like structure
related to the crystallographic structure of the metal since the lateral

is
growth
not random
(as in
a tree)
but confined
to definite preferred
3.1, for instance,
directions.
In the growing crystals illustrated in Figure

is
the lateral growth in any one grain
confined to two major directions at

Crystals
right angles to each other. In addition to the secondary branches, there
are also tertiary branches extending therefrom.

this
which grow in
is
manner
are referred to as dendrites.
The
tree-like
or dendritic growth
rather
than a wall-like growth in these crystallographic directions
attributed to the fact that heat can diffuse
away from a protuberance
much more readily than from a flat surface; consequently, there will be a natural tendency toward local extension of the growing interface.
The
crystals in
Figure
3.1
are only partially solidified.
If
allowed
to
and assuming enough liquid metal available to satisfy their needs, the grains would eventually fill out until all available space would be occupied by solid metal and each grain would be separated from the other by an irregular grain boundary (Fig. 3.2)
freeze completely,
27
Fie. 3.3.
Polygonal or equi-axed grains of high-purity iron etched. 500 x.
If the
metal
is
pure, the dendritic structure displayed in Figure 3.2
but the grain boundaries will still be present. The in Figure 3.2 occurs because chemical heterogeneity is created during freezing and can be revealed by etching the solidified alloy. Such chemical heterogeneity would not be possible in a pure substance; therefore, evidence of the dendritic structure can only be obtained by draining liquid away from a partially solidified metal as was necessary to reveal the dendrites in figure 3.1.
visible,
will not
be
dendritic structure
shown
Whenever grains grow more rapidly in one direction than the others, they are called columnar grains. If they grow equally fast in all directions they are called equi-axed grains. Equi-axed grains of iron are
shown
in Figure
3.3.
is dependent on two factors: (1) the rate of nucleation, N, or in other words, the number of growth centers that form in a given amount of time, and (2) the rate of growth, G, of these nuclei. It should be quite obvious that if conditions are adjusted to give
The
final size of these grains
and their growth is at a moderate rate, grain size will be the other hand, only a few nuclei, growing at an equal rate, will produce a coarser grain structure. Both rates of nucleation and the
nuclei
small.
many
On
growth can be represented by complex thermodynamic functions involving a number of factors. The rate of nucleation in particular is usually affected by impurity particles or the container walls. Practically,
rates of
28
however, both of these rates are dependent on the cooling rate of the metal. As the cooling rate increases, the greater is the degree of supercooling of the liquid and the greater the rates of nucleation and growth.
The
It
is
relative changes of these
two
factors,
however,
is
such that for most
metals, rapid cooling produces a finer grain structure than slow cooling.
apparently impossible to repress completely nucleation in metal as
is
the case for glass which represents a material which does not develop an
appreciable rate of nucleation until

the rate of growth
is
it is
cooled to a temperature where
too low to be effective
and the
glass
remains a super-
cooled liquid.
Because nucleation of metals can be affected by impurities, some metals can be produced in a fine grain structure by the addition of certain
nucleating or "inoculating" agents. The addition of sodium to an aluminum-silicon alloy, for example, produces a fine grained alloy. Mechanical vibration can also induce nucleation.
mold other changes occur on the properties and behavior of the solid. Most metals contract on freezing. Since this normal contractual process
the cooling of liquid metal in a
During
that
may have
a bearing
occurs simultaneously with dendritic growth, interdendritic void areas
may develop may
that cannot be fed properly.
Also as metal cools, the solubility for certain dissolved gases or solids
change, resulting in their precipitation and entrapment within the
grains or
on grain boundaries depending on the degree and time of
these
changes. These conditions affect the "quality" of the metal as discussed

earlier.
Mechanical Working. The previous section has described how grain metals is controlled. Many metal parts, however, are produced from metal that has been cast into an ingot and then subsequently rolled or otherwise mechanically worked into a desired shape such as a forging, bar stock, plate, angle or some other form. This mechanical working can also change the grain sue of the metal.
size of cast
working is done at an elevated temperature (hot working) combined effects of the heat and working action will cause recrystallization, the size of these new grains being dependent on the amount of this mechanical action and the temperature at which it is performed. As long as the temperature remains high enough to assure spontaneous reIf the
the
crystallization, the
If the
lower that temperature, the finer will be the grain

at
size.
,
metal
is
worked
the original grains are cold working.
room temperature (or below for some metals) severely deformed and distorted. This is called
insufficient
However,
energy
is
available to cause this

set of
metal to seek a new orientation (nucleate) and grow into a new

grains.
29
raising the temperature of the metal (annealing) , a temperareached where recrystallization docs occur and a new set of grains develops as a result of nuclcation and growth in the solid state.
By
ture
is
The
size of these grains
can be controlled,
as
described later in this
chapter.
Powder Metallurgy. Metal powders can be produced by reducing oxides or other compounds, by electro-deposition, grinding, or by other means. If these are subsequently compressed and heated (sintered) a metallic compact is produced by interdiffusion of atoms between the particles, producing ultimately a metallic mass composed of grains having a grain size that is determined by the processing variables involved.
Allotropic Transformation. In metals which undergo an allotropic transformation in the solid state a new set of grains is produced as a result of the transformation. Thus, in iron, which is the best example of this situation, cooling it from the high temperature face-centered cubic form to the room temperature body-centered structure results in nucleation and growth of the body-centered structure from the original facecentered structure. The size of the grains is again determined
relative rates at
by the which nucleation and growth occur. Slow rates of cooling
promote large grain size. Other Methods for Controlling Grain Size. In addition to the foregoing methods, it is also possible to produce a solid metal of a certain grain size by deposition from a vapor or by electrodeposition from a
solution. In the latter case the characteristics of the plating bath determine the grain size of the deposited metal.
3.2. Effect of
Grain Size on Properties

values showing the influence of grain size on
Table
3.1 gives selected
the strength
and
ductility of
pure iron.
Table
3.
Effect of Grain Size
on Tensile Properties of Iron. *
Grain Size, Grains per sq. mm.

2.5 to
Tensile Strength
psi
Yield Strength ps ;
Elongation in 2
in.
9.7
23,900
to
33,700
5,900
8
,
to to to
6,500
20 200
,
28.8 to 35.3
44.8
to
35.6 to 77.5
109 to 135
38,200 to 41,600
42,200 to 43,300
300
50.7
15,100
22,200
42.8 to 45.3
Metals
Handbook, ASM, 1948
ed., p. 433.
30
is
These data show that there

result of decreasing grain size,
a substantial increase in strength as a
However, once the grain size mm. little additional change in properties is apparent. Since metal failure usually occurs by a process of slip (described
with an accompanying rise in ductility. reaches approximately 100 grains per sq.
later)
along certain crystallographic planes of the grains, followed by eventual fracture, the effect of decreasing grain size is to cause interference to
grains composing a fine-grained material thereby and altering the ductility, as compared to coarse grained metal where each individual grain is freer to slip and distort with less interference from neighboring grains. Figures 3.4 and 3.5 show further examples of the effect of grain size on the strength and ductility of metals. In the case of pure copper, very little change in properties is evident, but for the 65-35 Cu-Zn brass the strength and ductility are noticeably affected by grain size. In this case, the strength decreases and ductility increases with increase in grain size. In addition to affecting strength and ductility, grain size is also important in forming operations. Table 3.2, for example, shows the applislip
among
its
the
many
raising
strength
cations for brass of various grain
sizes.
The
coarser grained material
is
more
readily deformed but gives a rougher surface than the fine-grained
material. Similar effects are noticed in deep-drawing of low-carbon steel
where grain
size in excess of
about 0.0012 inches average diameter may
lead to a surface roughness after drawing referred to as an orange peel

effect (Figure 3.4)
.
On
the other hand, extremely fine-grained or annealed
low-carbon
that appear
3.5)
.
steel
may show another

This defect
is
type of defect after deep-drawing

is
called stretcher strains.
characterized by fine
after the
is
wavy
lines
on the surface of the part

too small
Also, a grain size that
deformation (Figure likely to make deep-drawing
difficult
because of high strength and low ductility.
Table
3.2.
Grain Size of Cold Worked and Annealed Copper Alloys.
Nominal Grain
0.015 0.025 0.035 0.050
Size,
mm.
Typical Use
Slight forming operations.
Shallow drawing.
For best average surface combined with drawing.
Deep drawing
operations.
thick gages.
0. 100
Heavy drawing on
Loc,
cit.
31
Fie. 3.4. Microstructure and surface structure of a fine-grained steel (A) and a coarse-grained steel (B). Orange-peel eficct is revealed in (B) after Erichsen cupping tests. (F Korber, Staht & Eisen, v, 47, 1927, p. 1158).
.
Machining operations are

steels, for
also influenced by grain size. Coarse-grained

if
example, allow for higher cutting speeds, but
finish
is
im-
portant a fine-grained steel is recommended. Metals under stress at elevated temperatures tend to elongate slowly with time (creep) This behavior is associated with grain boundary
.
movement, hence where
resistance to stress at high temperatures is important, a coarse-grained metal will be superior to a fine-grained metal. The tungsten filament in a lamp bulb, for example, is produced as a coarse-grained wire because of its better life. In other high temperature applications, such as turbines, jet engines, etc, the grain size of the metal composing the high temperature components will be a factor in determin-
ing
its
resistance to creep.
This
is
discussed in Chapter 23.
32
Eiigineering Metallurgy
Fie. 3.5.
Stretcher strains in
low-carbon
steel.
actual size
(1955
Supplement
to Metals Handl>ook).
EFFECT OF MECHANICAL WORKING ON ENGINEERING PROPERTIES

In a previous section the effects of mechanical working on grain
size
effects of
were described. mechanical working on the engineering properties that should be considered. Before these can be discussed, however, it is necessary to review briefly the principles dealing with the deformation of metals because some knowledge of this subject is helpful for an understanding
of the engineering applications of metal working.
In addition to these effects there are other important
3.3.
Deformation of Metals
a stress of a
When
is
magnitude
to cause only temporary displacement

is
applied to a metal, the resultant strain
termed
elastic strain.
If the
exceeds the limiting stress for elastic behavior, the permanent strain resulting is termed plastic strain. With increased application of stress beyond the elastic limit, metals continue to deform until they fail
stress
by fracturing. Most nonmetals and occasionally some metals are totally lacking in this plasticity and fail by fracturing with no permanent deformation. This is referred to as brittle fracture. Metals, in fact, are unique among structural materials in their ability to be deformed and it is only under special circumstances that they display a brittle fracture. Demonstrations of elastic and plastic behavior in tensile testing will be given in Chapter 4. From an atomistic viewpoint, a stress that causes elastic strain results in a temporary and small displacement of atoms from their normal posi-
33
Fig. 3.6.
An
octahedral or (111) plane.
Eight such planes can be constructed in a
given cube.
tions in the lattice so that the lattice

stress causes the
is
slightly distorted.
Release of the
lattice
atoms to return
to their
normal positions and the
regains
its
original shape.
are possible $/'/>
In the case of plastic strain, two basic processes of atomic movement and twinning. These deformation mechanisms are disfirst
cussed in the following sections,
then with respect

all
to polycrystalline metal.
with respect to single crystals and It will be impossible to cover
phases of this subject here, but the interested reader can find good
discussions of this topic elsewhere.
3.4. Slip in Single Crystals
In plastic strain there

the atoms
is a permanent displacement of the atoms, moving from one atomic position in the lattice to another.
The
particular crystallographic structure of a single crystal restricts the this straining to certain preferred planes. In the face-centered cubic metals such as copper, aluminum, or nickel the
movement occurring during
by slip is normally the (111) plane. This the octahedral plane that cuts diagonally through the unit cell as illustrated in Fig. 3.6. When this plane is viewed from a position at right angles to it, the atoms are close-packed much in the manner shown in Fig.
is
preferred. plane for straining
the other hand, it should be apparent from the left-hand illustration in Fig. 3.7 that other planes such as those parallel to the faces of the cube have a lower atomic density. Because of its high atomic density
3.7b.
On
A system of crystallographic indexing which indicates displacement of unity in the three crystallographic directions as measured from a reference point.
34
V
\
plane
(111)
(III) (a)
plane -^\
Fig. 3.7. Arrangement of atoms in the octahedral plane of the face-centered cubic unit cell as viewed from the side of the cube (left) and perpendicular to the face of the plane (right).
the octahedral plane has the greatest interatomic attraction and theresaid to be a strong plane. As a consequence, slip occurs parallel to plane rather than along some intersecting plane of lower atomic density. For slip to occur along a plane of lower atomic density would
fore
this
is
require that the stronger interatomic attraction existing on the octa-
hedral planes would have to be overcome an unlikely situation.
The
direction of slip
is
likewise limited.
These directions are shown by

lines of least resistance to
the arrows in Fig. 3.7
and correspond
to the directions parallel to the
lines of greatest concentration of atoms,
and the
one row of atoms past another. Any other directions within the octahedral planes would require a greater disturbance of atoms since the direction of movement would be tangent to some atoms but pass directly through others. The combination of slip planes and slip directions constitutes the
movement
of
slip system.
In face-centered cubic metals, four slip planes are possible as

3.6,
mentioned in Figure
fore 12 slip systems.
each having 3 slip directions. There are there-
Since slip depends on exceeding a critical resolved
shear
stress that
is
specific for a
given metal, metals crystals will not flow
or deform by slip unless the applied force can be resolved into shear
plane and in one of the slip directions. This is therefore flow always precedes fracturing in these crystals (unless a unique condition of equal
stress parallel to a slip
always possible in face-centered cubic crystals;
triaxial stresses exists)
hexagonal close-packed metal such
as zinc or
magnesium can
slip
only on the basal or (0001) plane. This plane represents the plane of greatest atomic density in this type of crystal. As in the face-centered
metals, there are also three directions of slip. In fact, there
is
nothing to
35
distinguish the basal plane of a hexagonal close-packed metal in atomic
arrangement from the octahedral plane of the face-centered cubic metals. differences come in the way atoms in adjacent planes are stacked above or below the reference plane. Because it has only the one slip plane and three slip directions, a hexagonal close-packed crystal has only
The
three slip systems,
and
it is
possible to orient such a crystal with respect
to the applied load so that the slip planes are
to this load.
perpendicular or parallel In such cases, no flow occurs and a brittle failure ensues.
the basal plane is so oriented with respect to the applied load that a shear stress can be resolved in one of the slip directions can flow occur. Metals having this crystallographic structure, therefore, are
Only when
not so ductile
as
the face-centered cubic type.
body-centered cubic metals are not so well defined preceding two cases, and one of several possible planes can represent the plane of major slip. The slip direction, however, is always
as in the
The
slip planes in
number.
the close-packed direction represented by the cube diagonals four in Around each of these four directions there are arranged 12
this represents a
is
possible slip planes; consequently, 48 slip systems exist in these metals.
Although
comparatively large number of
slip systems,
each system
less
regular
and
face-centered cubic metals.
densely packed than those of the In general, then, the body-centered cubic
less
metals require somewhat higher resolved shear stresses to initiate and less permanent deformation is possible in advance of fracture.
slip,
Manifestation of Slip. The visual evidence of slip is the appearance of numerous slip lines or slip bands upon microscopical examination of a polished metal surface after the specimen has been deformed plastically.
These
slip bands represent a permanent displacement of one part of a metal crystal with respect to the rest of the crystal. The resulting micro-
scopical difference in elevation
accounts for the appearance of lines

a microscope.
traversing the crystal faces
when viewed under
Repolishing
and etching will remove this evidence of slip because ment which produced the slip lines is now removed
severe distortion, however, the disturbance
is
the surface displace-
thereby. In cases of
so great that slip will be
evident even though the distortion preceded the polishing and etching. This is demonstrated by the cold worked brass in Fig. 3.1 1.
Strain Hardening. The amount of stress required for slip increases with an increase in the amount of prior deformation. In other words,
a strain-hardening action occurs which lends to retard or restrict further slip on a given slip plane. As the stress increases, slip is transferred to
other slip planes. This is the basis for hardening metals by cold working as described later. This mechanism is unique to metals and
36
represents one of
its
outstanding characteristics.
Putty or clay, for ex-
deformed and worked, but no hardening action occurs. Although much has been written about this hardening action and many
is
ample,
readily
theories proposed to explain it, the theory of dislocations is generally accepted today as offering the best explanation for the relatively low stress required to initiate slip and increased resistance to the slip as
deformation proceeds.
The low
stress
required to start slip
is
explained
on the
basis of a wave-like
movement
of a small dislocation "zone" across
the crystal rather than a block-like displacement of the entire grain.
The
Since
increased resistance to slip as deformation progresses

the dislocation theory
strain
is
attributed to an
interaction between dislocations created during the slip process.

is still
in the formative stage,

this
any explanation of
speculative.
hardening based on
theory
is
still
somewhat
The
theory does, however, offer the best overall explanation for metal behavior yet available.
3.5.
Twinning
Another mechanism accounting for plastic deformation of metal is twinning. This process has certain features similar to those of slip and other features which are dissimilar.
crystals
Like
slip,
in certain directions, but the planes
twinning occurs on certain crystallographic planes and and directions are not necessarily
slip.
the same as those for

required.
Also like
slip,
a certain level of shear stress
is
Twinning differs from slip in that the atomic movement is not from one atom position to the next but rather a fractional atomic distance. This results in a new orientation in part of the grain. This orientation is
such that the atoms in the area undergoing twinning present a mirror image of those in the original part of the grain when viewed along the
plane dividing the twinned area from the untwinned region as shown in Fig. 3.8. Although the figure depicts an atomic movement which in-
from the twinning plane, in reality the movement, of any one atom need only be less than one atom spacing with respect to a neighboring atom in order to accomplish the repositioning
creases the greater the distance
necessary for twinning.
Twins produced by mechanical action as just described are referred to as mechanical twins. Cold worked metals that are annealed also will exhibit annealing tivins which probably originated from mechanical twins. Mechanical twins are usually narrow and may be confused with slip lines. Slip lines should appear on an unpolished surface that has been strained; whereas, twin lines are usually evident only after etching. Furthermore,
37
Twinning plane*
Original
lattice
of
face-centered cubic
metal
as
Mirror
image
lattice
as
viewed parallel to twinning plane
(111).
created by atomic movement shown by arrows.
Fig. 3.8.
Diagram showing atomic movement required for twinning.
repolishing
appear. Slip usually shows
and etching would destroy a slip line but a twin would reup as lines; whereas, twins normally appear as
is
bands.
not capable of contributing as much permanent deformaIn face-centered cubic metals, therefore, it represents only a small part of the total deformation. On the other hand, in hexagonal close-packed metals, twinning is important not because of the deformation it permits but because twinning facilitates slip by aligning more slip planes in a favorable direction.
tion as slip.
Twinning
3.6.
Deformation of Pol j crystalline Metals

metals used in engineering are, of course, polycrystalline rather crystals. The mechanisms previously described apply to each
The
than single
of the single crystals composing the aggregate. However, the extent of the movement is governed by the presence of the surrounding grains. Consequently, the situation is a good deal more complex than in the ideal
case of a single crystal.
Cold working or stressing a polycrystalline aggregate composed of randomly oriented grains causes slip to occur in the most favorably oriented grains and on the most favorably oriented slip planes. As the
stress increases, additional grains less
favorably oriented are similarly
deformed. Severe distortion in one direction will cause the following effects in addition to the slip and twinning.
38
1.
The
lattice of
each grain that
is
deformed tends to rotate into the
direction of the applied load.

2.
In addition, the constraint by surrounding grains

lattice to
may
cause the
be bent.
3.
Deformation bands representing different degrees of orientation

within a grain appear in the microstructure.
4.
preferred orientation of the grains develops. This
is
sometimes
referred to as crystallographic fibering.
The
is
type of fibering that

of importance in the
develops depends on the metal being worked and the nature of the
stress
system that
is
operating. This effect
cold working processes applied to metals, because the properties

are similarly rendered anisotropic
lized by annealing
and when the metal
is
recrystal-
(discussed later)
a "recrystallization
texture,"
which
3.7.
If
is
also of a preferred orientation,
may
develop.
Hot Working
metals are mechanically worked at a high enough temperature,
they do not strain harden, but simply recrystallize into

grains.
new
sets
of
working is referred to as hot working. Hot working temperatures depend on the characteristics of the metal being worked. Thus, lead is essentially hot workable at room temperature because it will recrystallize during the working operation. Steel, on the other hand, must be heated to above a red heat before the operation
this occurs the
When
can be
classified as
hot working. In either case recrystallization occurs
simultaneously with the mechanical working, and the properties, with

the exceptions noted in succeeding paragraphs, are not changed much.
During the working process, the shape of the metal part is usually changed drastically. As an example, in forming bar stock, the metal starts out as a bulky ingot and ends up as an elongated bar. The same relative changes occur to a greater or lesser degree in forming the many other wrought shapes by rolling, forging, extruding, or by other metal working processes. The coarse ingot structure is refined by this operation and voids and porosity that might have been present in the original ingot are
largely eliminated, but the heterogeneity originally existing in the ingot
as a result of the
irradicated.
In
fact,
changes occurring during freezing is not completely the metal working tends to elongate areas showing
chemical segregation, and the inclusions are also strung out in the rolling direction. This has a tendency of producing a fiber-like structure in the
metal so that the properties when tested in the direction of rolling will not be the same as those obtained from tests made at right angles to the rolling direction. This type of directionality developed by the rolling
39
>
n*
- ' MMH
i
Fig. 3.9
Elongated slag inclusions
in rolled steel,
uneiched. IOOX.
Fie. S.10. Elongated sulfide inclusions in steel in the region of these inclusions, etched. 100X.
and evidence
of chemical segregation
is sometimes referred to as mechanical fibering to distinguish it from the preferred orientation effect which may occur as the result of cold working and referred to as crystallographic fibering. Examples of the elongation of inclusions and evidence of chemical segregation are given in Fig. 3.9 and Fig. 3.10.
process
The principal effect of this directionality is to lower the ductility and toughness in the transverse direction as compared to the direction of
40
rolling.
The
data in Table 3.3 illustrates
how
the V-notch
Charpy impact
also en-
values (which serve as a measure of toughness) vary with the selection of the test piece.
.Similar differences but not so
pronounced are
countered in the reduction of area values obtained in tensile

TABLE
70-F.
Influence of Directional
testing.
3.3.
Effects
on V-Notch Charpy Impact Values at
(9).
Specimen Transverse
Nature of
Steel
Specimen
Parallel
Tensile
to Principal
Principal
Strength
Rolling Direction
Rolling Direction
67-64 70-71
ft-lb.
137,500
Straightaway
rolled steels*
psi.
34-34 36-37
ft-lb.
142,000 134,000 132,000
43-44
54-49
75-76
62-61
Cross rolled
steels*
155,000 110,000
* *
44-47
53-56
ft-lb.
46-45
Cast
steel, as-cast
Same
*
steel
forged
110,000
102-122
ft-lb.
Notch
parallel to plate surface.

in. section to
**
From 2 x 3}^
A
X
in.
square bar.
Outside of the
effects
previously noted, hot working does not alter the
tensile properties of metals appreciably, particularly
when compared
to
the effects of cold working, which can effect a substantial change in

properties.
3.8.
Cold Working
results in a distortion of the grain structure as depicted
Cold working
Beginning with the hot tempered metals containing equi-axed grains, the successive stages of cold reduction produce increasingly greater distortion and elongation of the grains and generation of slip lines. Because of the grain fragmentation and disturbance of the lattice, there is an accompanying hardening action as shown by the accompanying Rockwell B hardness values. Tensile strength increases in about the same manner as hardness, and there is a simultaneous decrease in ductility and toughness. Changes in the tensile properties of brass and copper with percentage reduction in drawing are shown in Fig. 3.12. This hardening action is attributed to internal barriers to flow such as precipitated particles, impurity atoms, etc., to interactions between dislocations moving on different slip systems, and to formation of subboundaries within the grains (polygonizain the series of photomicrographs of Fig. 3.11.
soft
worked or
tion)
41
fe
s& m
ml&E&fmii
M
S
.a.
'-' -
1*3;
.-=H
'- :i
----. ::
-J -
-^-
;*-
<
Fie. 3.11.
Microstructure
of
70% Cu-30% Zn
sheet
brass
of
various
tempers.
Soft temper: 47 Rockwell B; i/ i/ hard: 82 Rockwell B; hard: 4 hard: 73 Rockwell B; 2 89 Rockwell B; spring temper: 94 Rockwell B. (Courtesy of R. A. Ragatz, University of
Wisconsin)
Cold working therefore provides a means for hardening pure metals It is a particularly useful process where the composition is such that hardening by heat treating cannot be used. The terminology
or alloys.
used in Fig. 3.11 (such as quarter hard, half hard, "spring temper") are commercial expressions for the degree of cold reduction obtained. De-
pending upon the final finishing processing operations required, a metal hardened by cold working can be ordered from the mill in any one of the "tempers" indicated. Where heavy subsequent forming operations are intended, the annealed or partially hardened metals are specified. But if little further forming is to be done and a metal of high hardness and strength desired, the full hard or spring tempers can be specified. The actual hardness and strength for each of the tempers would vary depending on the base metal used.
42
Q.
O O
140
120 100
Q
t
Soft 10
20 30 40 50 60 70 80 90
reduction on
the tensile properties of copper and brass.
Percentage Reduction by Drawing

Be.
5.12.
Eircct of cold
(ASM Handbook.)
Steel can also be cold worked, and cold finished steel has certain advantages not obtainable by other means. For example, not only does cold finishing provide a smooth, oxide-free finish, but the metal itself is
readily machinable
action.
This
effect
due to the increased brittleness induced by the rolling makes chip formation easier as compared to a steel of
the same hardness obtained in other ways.

3.9.
Annealing Cold Worked Metal

its
Because of be considered
strained
condition, cold
worked metal can be
re-
crystallized by reheating or annealing.
In practice, this probably should
as essentially a fabrication procedure inasmuch as the accompanying recrystallization and softening may be necessary to allow further forming operations on the metal, but it produces properties contrary to the usual requirements of engineering materials. However, it is important to be acquainted with the principles of annealing cold worked metals because this knowledge is necessary wherever cold working is
used for fabrication.
As cold worked metals are heated, eventually enough energy is supplied form nuclei for recrystallization. These nuclei grow at the expense of the deformed metal until the entire structure is composed of a new set of
to
grains.
(1)
It is
convenient to separate the process into three distinct stages:

(2)
Recovery,
Recrystallization,
and
(3)
Recovery. Recovery represents a

in
relief of internal stress

resistivity.
Grain growth. and a decrease

Internal stresses
thermelectromotive force and electrical
43
c
CO
QJ
.**
co
Wmm^/AalS^^^r^
'Recrysloll'
.c
Groin
D >~
CD
Rtcot/cry
notion
G'owin
Annealing
Fin. S.13.
Temperature
Schematic changes in recovery, strength and recrystallization on annealing
cold worked metal.
(ASM Handbook)
were originally developed during the cold working process. They represent a balance of compressive and tensile stresses within the metal. Their
magnitude and distribution are determined by the degree and type of cold working treatment used. These stresses are detectable only indirectly through the distortion that accompanies annealing or in the loss in
"spring-back" tendencies. "Spring-back" is the increase in diameter of a roll of strip after it has been removed from a mandrel around which it was
held.
is one of the factors must constantly bear in mind in design, and these stresses may be beneficial or harmful depending on how they occur within a part. For example, shot peening a helical spring can markedly improve its
The
presence or absence of internal stress
that an engineer
service
life, i.e., its
resistance to fatigue failure. Distortion occurring after

is
machining a cold-worked metal

residual stresses.
Fig. 3.13
an example of the harmful
effects of
shows schematically what happens to residual stress, strength, when a metal is heated in the recovery range. Recrystallization. When the metal is heated sufficiently high, recrystallation occurs. As shown by Fig. 3.14 this results in a rapid decrease in strength and increase in ductility. This process is both temperature and time dependent, but the former variable has the more potent effect.
and grain
size
44
._...
>
Lokt
T.P.
Pnoipnorued
E lee
T.P
wornc
0.10
Anneolinq
BO
70
I.
200
HOC
600
Temperature, deq Fohr 800 1000 1200 1400
014
*-jt
rr.Trrytr**.,'
vr
6
^.l ,-
^ Contract-.
at A'CQ
0i2
?;"
1.
SO 40 30 10
OlO
06
65
S5
006
J o E
O
5
S
IS J
f
004
-j
(Of
0.02
25
(00
?00
Annealing
Fic. 3.14.
300 4O0 tOO 600 700 Temperature, deq Cent
800
Elfect of annealing
on tensile properties and grain
size of four
commercial
grades of copper.
(ASM Handbook)
Grain Growth. Once a new

these grains will continue
if
set of grains
is is
established, the
growth of
the temperature
raised or the time of heatas well as
ing prolonged.
size is
The effect on
shown
for
the mechanical properties copper and brass in Figs. 3.14 and 3.15.
on grain
Annealing Temperature, deg Fahr ZOO 600 1000 1400

140
70 .g
CM
60 g 50
Grain
. ,
Site-
4Q
so Ci
20
Hard
43%Hard
24%Hord
63XHard-
in
ZOO 400 600 800 Annealing Temperature, deg Cent

on tensile properties and grain
size of
Fic. 3.15.
Effect of annealing
yellow brass
wire.
(ASM Handbook)

3.10. Factors Affecting Recrystallization Temperature and Grain
Size
45
There are a
effects
fairly large
number of
variables affecting the recrystalliza-
tion temperature
and the grain
size after recrystallization,
and
since these
it is
may be encountered
in the engineering utilization of metals
important that they be recognized.
800
1200
i-00
400
600
800
Annealing Temperature, deg Cent

Fig. 3.16.
Influence of
the amount of prior cold work on
the
recrystallization
temperature of high-purity copper. Annealed one hour at temperature. (Koster,
ASM
Handbook)
Percentage of Cold Work. Increasing the percentage of cold work lowers the recrystallization temperature. This is more apparent in Fig.
3.16 than in Fig. 3.15.
creases the size of the
new
Increasing the percentage of cold work also degrains (Fig. 3.17) There is, however, an
.
intermediate
restricts
amount of deformation
sites,
as illustrated
by
Fig. 3.17 that will
lead to excessive grain growth.
Apparently, this amount of deformation
nucleation to but a few
and
these nuclei therefore
grow
to
In an actual part where a variation in the amount of cold working might be experienced, annealing could result in a region of exlarge grains.
g E
i
f-iq.
in .c 77
JWOTTO
20
40
60
80
Degree of Deformation,
% C
Fic. 3.17. Influence of degree of deformation on the grain size developed at 950 (1742 F) in low-carbon steel. (Hanemann, ASM Handbook)
46
cessively large grains
which would effect the properties adversely. A cold punching operation would be a good example of a situation where this
If annealing is required, its temperature should be conkeep it below the recrystallization of the less severely worked metal but above that of the more severely deformed areas to avoid large
could occur.
trolled to
grains in the regions of critical deformation.
Composition. The actual temperature at which recrystallization occurs depends on the composition. Thus some metals like zinc may recrystalli/.e by working at room temperature. Other alloys such as those used in high temperature applications may not recrystalli/.e even when heated to 650C
(1200F) or above.
Annealing Temperature, deg Fohr
J00 400 500
too iso koo eso soo

Fie. 3.18. Effect of annealing lime on the softening of copper wire reduced by cold drawing. (Alkins & Cartwright, ASM Handbook)
93%
Effect of
previously cold reduced
Time. Time-tern (jeratu re relations for the annealing of copper 93% are shown in Fig. 3.18. This shows that
increasing time lowers the recrystallization temperature.

Effect of Initial Grain Size.
The
larger the original grain size, the
greater the
amount
of cold deformation to give equivalent recrystalliza-
tion temperatures
and time.
of Hot and Cold
3.11.
Summary
is
Working
Hot working
effect
is
used primarily for fabrication purposes and does not
cause a large change in tensile properties.
directionality or fibering
introduced, however, which has a tendency to reduce ductility

tested transversely to the rolling or
and toughness when

tion.
forming
direc-
Cold working raises strength and hardness and lowers the ductility. It an important method for hardening alloys that cannot be hardened otherwise or as an auxilary treatment along with other hardening processes. The effects of the cold rolling can be removed by annealing or
offers
47
tempering and can only be reintroduced by additional cold rolling. The combination of cold rolling and annealing has an effect on the recrystallizcd grain size of the metal,
and
the various factors affecting the
grain
size
and
recrystallization temperature
this process.
must be recognized
for a
proper utilization of
EFFECT OF ALLOYING ELEMENTS ON ENGINEERING PROPERTIES When one or more metals are added to another metal in the liquid
solidification the atoms of the added elebe a part of the lattice structure of the base metal as a solid solution or another phase will appear in the microstructure. Either
state,
it
is
found that upon
ments
will either
of these effects will alter the engineering properties of the base metal;
therefore, alloying represents
one
of the important
trolling them. Frequently, the effects of alloying are
methods for concombined with those
of heat treatment to further influence the properties.
3.12 Solid Solution Effects
binary alloy that exists as a solid solution has grains containing

sizes in
atoms of two
the lattice structure. This strains the lattice
and
in-
creases resistance
to deformation,
thereby serving to strengthen and
harden the
For two metals that are completely soluble in each other maximum hardening occurs at about 50 atomic percent of each. Coppernickel alloys are good examples of this case and Fig. 3.19 shows how several properties of these alloys change with
alloy.
in the solid state, the
composition.
nickel, the
Although the
maximum
strength occurs at about
70%
maximum
hardness (not shown)
occurs close to 50 atomic
percent (48 wt.%) nickel.
In addition to the mechanical properties, other physical properties are altered by solid solution alloying. Fig. 3.20, for example, illustrates how
electrical resistivity
and the the temperature
coefficient of electrical re-
sistance vary with nickel content in copper-nickel alloys.
This
illustrates
the important principle that the

tivity
maximum
heat and electrical conducof alloys
are obtained
from pure metals and that the presence

is
where high conductivity is desired. Other alloy systems may have only limited rather than complete solid solubility of the alloying element in the base metal. Such is true for many of the copper-base alloys, for example. In these alloys the solid solution hardening action increases with the amount of the alloy up to the limit of solid solubility, following which the properties are affected by the presence of another phase in the microstructure as described in the next
(impurities in this case)
definitely detrimental in those instances
48
40
60
80
Nickel, percent
Etc. 3.19.
Effect
of
nickel
on the mechanical properties of copper-nickel
alloys.
(Wise)
40 60 Nickel, per cent

.
Fie. 3.20.
Effect of nickel
on the
electrical properties of copper-nickel alloys.
(Wise)
49
section. The degree of hardening is usually inversely proportional to the range of solid solubility, so that those alloys of very limited solubility
exhibit the greatest percentage-wise influence

illustration of this point,
it
takes
0.6%
Sb,
on the properties. As an 4.6% Si, 4.7% Al, 12.1 % Zn

.
or 13.2% Ni to increase the hardness of pure copper by an increment of 14 Vickers DPH. (diamond pyramid hardness number) The order in which these elements are listed is also the order of increasing solubility of
these elements in copper.
Besides the aforementioned effects, it might also be mentioned that during the free/ing of alloys that exist as solid solutions at room temperature, there is a tendency for chemical segregation to occur within the growing dendrites as freezing progresses. Also, voids or a general porosity may develop or inclusions may segregate between or within grains. If the metal is further processed by working, the segregation and porosity
are fairly well eliminated and the inclusions more or less uniformly distributed and broken. If the metal is retained in the cast condition, however, these imperfections may have some bearing on the properties of the casting. These are examples of some of the factors affecting the quality of the metal.
3.13 Polyphase Structures

If
an alloy
is
room temperature,
1.
prepared which exceeds the limits of solid solubility the second phase may appear as:
in essentially pure form. Alloys of
at
The second component

and
the
aluminum
silicon are of this type, with the silicon
phase interspersed in
the properties of
aluminum
is
phase.
The
effect
of silicon on
Al-Si alloys,
2.
shown
in Fig. 3.21.
An
original solid
intermetallic phase, in itself a solid solution, interspersed in the solution. Copper-zinc alloys, with zinc exceeding
illustrate this behavior.
about 38%,
tion,
The
alloy at
room temperature
consists of separate grains of alpha
brass,
the original solid solu-
and beta
brass,
an intermetallic phase containing about
45%
solid
Zn.
(In the absence of the alpha phase, the beta phase can range in
composition from about 45 to

solution characteristics)
3.
50%
Zn.,
which indicates
its
intermetallic phase which is essentially an intermetallic compound. Carbon in steel precipitates as the compound Fe.-,C so that at room temperature steel consists of a mixture or iron and iron
carbide.
An
No
ing properties. There
matter what these extra phases are, they will influence the engineeris a tendency to generalize by staling that the effect
50
%
Fie. 3.21.
alloys.
6 8 Silicon
K)
Effect of silicon content in
annealed and hard rolled aluminum-silicon
(ASM Handbook)
of the second phase
is
proportional to the
is
amount
if
present, the properties
consequently being determined by the properties and amounts of the

individual phases present. This
only true
the second phase
is
rather
uniformly distributed in the parent phase; however, there are so many exceptions to this rule that it is perhaps better to generalize that the
effects of the
second phase are determined by
(1)
its
properties, (2)
the
amount
sidering
present,
and
(3)
its
distribution.
As will be learned when con-
steel, for example, the way the iron carbide is distributed will profound effect on the properties of the steel. Present as a network, around the grains it can lead to brittleness and poor machinability. Finely distributed throughout the steel, it contributes to high strength
have
and toughness.
Occasionally, a very small quantity of a given phase can be very harm-
due to the fact that it may be distributed in a manner to produce extreme brittleness. Examples of these effects are found with bismuth in copper, iron sulfide in steel, and graphite in cast iron. In the latter case, whether the graphite is distributed as essentially spherical particles or as elongated shapes referred to as flakes will determine whether the metal is strong and ductile or weaker ami brittle.
ful to properties
There
are so
many
different possibilities that
it
is
impossible here to
it
cover each of the situations that
may be encountered. However,
can
be stated that the presence of a second phase can produce a decided

strengthening effect or can be decidedly harmful depending on the three
factors listed previously.
In any event, by alloying to produce a second
Factors Affecting E?igineering Properties
51
phase we have available to us another method for controlling engineering properties, and in succeeding chapters, examples will be given to illustrate its importance.
understanding of the consequences of alloying it become familiar with the principles of alloying as enunciated in Chapter 6.
full
is
To
have a
necessary that one
EFFECT OF HEAT TREATMENT ON ENGINEERING PROPERTIES

The
upon:
1.
use of heat treatment to alter mechanical properties depends
An
2.
allotropic transformation as in the case of steel, or decrease in solid solubility of a second phase with decrease in temperature as exemplified by a fairly large number of binary sys-
tems having copper, aluminum, magnesium, iron, or a number of other metals as the base metal. Heat treating based on this effect is referred to as age hardening or precipitation hardening.
3.14. Allotropic Transformation
to
is
Iron undergoes an allotropic transformation from face centered cubic body centered cubic structure at 910C (1670F). When iron
alloyed with carbon
up to about 0.8%, this transformation is depressed lower temperatures and occurs over a temperature range. The normal product on slow cooling steels in this range of carbon content is a mixture
to
of iron (ferrite) and a product referred to as pearlite which
is
actually a
mixture of
ferrite
and
iron carbide.
Rapid
cooling, however, tends to
retard or repress this transformation with the result that other microstructural products are produced, and in the instance of very rapid
cooling a
new metastable phase

This phase
called martensite
is
is
produced instead of
iron and pearlite.
the hardest product obtainable for a
given carbon content.

softened
It is fairly brittle as produced and is usually and toughened by a subsequent tempering treatment: the higher the temperature of tempering, the softer and tougher the resultant
structure.
Utilization of the various heat treating possibilities based on the allotropic transformation in iron produces a variety of microstructural products
method
for controlling the properties of steel.
discussed fully
and properties. Hence, heat treatment represents a basic Inasmuch as this subject is in subsequent Chapters 12, 13, and 14, no details need be
presented here.
However, it should be pointed out that in addition to the operation of heat treatment, the engineer also has at his disposal the benefits avail-
'
52
able from alloying so that in steel

of alloying
are usually utilizing a combination For example, by varying the carbon content (alloying) the base hardness of the steel can be changed; whereas,
we
and heat treatment.
varying some of the other alloying elements will alter
its
susceptibility to
Combinations of these effects, therefore, provide a degree of control and versatility not obtainable by either method alone. Superimposed on these effects of alloying and heat treatment are those resulting from the quality of the metal as originally produced in the ingot and from the mechanical processing the steel may have had. These matters must also be kept in mind when designing a part.
heat
treatment.
|
105 F
1
/OT___
/
VVL /
a'
140 F
1
t
1
CHANCE
IN
1
SCALE
;
-J75 F
210 F-'
P
32 F r~
'
68 '0
10
20
30
40
SO
60
75 100
ZOO
Time al Aging Temperature. hours

Fig. 3.22. Quench-aging of a 0.06% carbon steel. Hardness after quenching from 717C (1325 K) and aging at indicated temperatures. (ASM Handbook)
3.15. Precipitation
Hardening
be considered
in detail here.
The
and
principles of precipitation hardening are discussed in Chapter 7
will therefore not
The
process involves
it
heating an alloy of selected composition to a temperature where

single phase
is
a
it
and then cooling it rapidly normally would be a two-phase structure as

with temperature.
to
a temperature where
a result of solubility
it
changes
phase
The
rapid cooling, however, retains
as a single
metal. It
is
then subsequently "aged" at
room temperature
or above to
toward the equilibrium two-phase structure. As a result occur during this treatment, certain alloys can be hardened appreciably. This hardening action is a function of time and tem|>eraturc as illustrated by Fig. 3.22. The maximum hardness reached is decreased as the aging temperature is raised. Also, the increase in aging temperature results in a rapid drop off in hardness which is referred to as overaging. Fig. 3.22 illustrates the fact that even in ironcarbon alloys, which were previously used to describe the principle of hardening by allotropic transformation, age-hardening can also be encountered. This aging effect depends on a slight solubility of carbon in
initiate a start
of
the atomic adjustments that

body-centered cubic iron.
perature.
53
This solubility increases with increasing temConsequently the necessary {but not exclusive) condition for
is
age hardening
present.
In addition to the hardness change illustrated by Fig. 3.22, there are also corresponding changes in strength, inverse changes in ductility and
toughness, and changes in electrical conductivity and other properties.
Aging may
also be
combined with metal working treatment
to provide
additional control over engineering properties.
EFFECT OF NUCLEAR RADIATION

For materials going into the construction of nuclear reactors, it is know about their relative absorption coefficient for neutrons. Materials with low neutron absorption coefficients are necessary where neutron passage is desired, or in other words, where the maximum utilizanecessary to
tion
and minimum waste

is
of neutrons
is
desired.
On
the other hand, a
high coefficient
necessary for shielding or control

is
purposes.
The
one of the engineering properties that must be established. As examples, elements like boron, cobalt, and cadmium have high absorption coefficients, but elements such as beryllium, sodium, magnesium, aluminum and zirconium have low coefficients. The property of neutron absorption plus related properties of strength, formability.
absorption coefficient, then,
UNIT
CELL
OF
URANIUM
WITH
PERTINENT
PLANES
INDICATED
PREDOMINANT
PLANES
PREDOMINANT
PLANES
""*
'
EFFECTS OF PREFERRED ORIENTATION ON DIMENSIONAL STABILITY OF URANIUM DURING IRRADIATION
Fic. 3.23. Effect of nuclear radiation on 'growth" of (Courtesy of General Electric Co. Hanford Works)
nuclear
fuel
material.
54
corrosion resistance, heat resistance, etc. must be evaluated for the design of nuclear reactors, and the metallurgy of the materials used to construct the reactor
is
therefore a very vital part of design.

it is
Besides the aforementioned requirements,

susceptibility of the metal to radiation
also necessary that the

Fig. 3.23
damage be known.
exposed
to
shows
what happened
atmosphere.
to a nuclear fuel material
an intense neutron
smooth cylindrical specimen increased in size or elongated and warped depending on crystal orientation. Proper
The
original
metallurgical treatment can considerably improve resistance to this type

of deterioration.
Structural
metals subjected to neutron
radiation
are
hardened or
It
strengthened and sometimes embrittled by such treatment.
has been
damaged by such exposure, metals tend to become cubic whereas the hexagonal and body-centered brittle. Raising the temperature causes less damage. Heat treating by
found that the face-centered metals are
least
annealing can be used to eliminate the embrittlement.
SERVICE FACTORS
In the preceding sections the factors affecting the engineering properties have largely been those concerning the processing and preparation of the
metal for service. There are, however, additional an influence after the part is placed in service.
effects that
may have
Lack, of attention to the problem of residual stresses as briefly discussed under cold working could lead to a premature failure of a part of fatigue. Besides originating from cold working, these stresses can also be
thermally induced as by welding or heat treating. Without going into the details of this point, since it requires a knowledge of the static and dynamic properties as discussed in Chapters 4 and 5, it should be emphasized nevertheless that the stress distribution created by design or metallurgy is unfortunately often overlooked and that many of the failures
which have been recorded can be attributed to

Another
22
service factor of
this omission.
is corrosion. It for corrosive conditions the properties of that part will deteriorate in
be covered should be quite obvious that when a part
extreme importance
to
in
is
Chapter
designed
time and cause failure unless a sufficiently resistant material is used or it is replaced frequently enough to avoid damage. By the same token, unexpected corrosion can seriously detract from the load-carrying ability of a part in service and possibly cause premature failure. These are additional factors, therefore, that the engineer must observe.
55
SUMMARY
There
is
a very close relationship

is
between the structure and properties

part at least to affect the final
of metals. Part of the structure

properties.
established during the manufacture of
the metal, and this can carry over in
Most of the structural modifications, however, depend on subsequent processing, and such operations as grain size control, metal working, alloying, heat treatment, and/or nuclear radiation are available
to the engineer for controlling the properties.
In certain applications,
in service as for
example, temperatures or under corrosive conditions. Then it is necessary for the engineer to recognize the effect this will have during the service
while the part
is
these operations
may continue
at high
of the part. It can be said, therefore, that unlike gases and liquids, the properties of solid metals depend on past history, rather than on the variables existing at the moment.
life
In order to gain an appreciation of the relationships and interrelationships involved in producing a given set of properties,
for the engineer to learn
it is
necessary
discussed in Chapter
in
2,
about the fundamental structure of metals as about the measurements of behavior as discussed
of alloying
Chapters 4 and
5,
and about the principles
and heat
treat-
ment
as discussed in
succeeding chapters.
With the exception of corrosion behavior which is dependent on surface conditions and chemical reactions, the behavior of a metal is governed by its internal structural condition.
QUESTIONS
1.
What
are the processes available to the engineer for controlling metal
properties?
2.
How
does the factor of metal "quality" enter into the problem of property
control?
3. 4. 5.
6.
Describe the freezing of a dendrite. Why is the dendritic structure absent on etched surfaces of pure metals? What two factors affect the final grain size of a freezing metal?
How
7.
arc these two factors affected by cooling rate and what additional variables beside cooling rate may be used to control grain size? Beside the growth of dendrites, what additional changes take place during
freezing that may affect the quality of a metal? Describe several ways besides the casting process which can be used to control the grain of metals.
8.
9.
Of what
examples.
practical
importance
is
grain
size
control? Cite
number of
10.
Compare
the slip behavior in the
face-centered cubic, hexagonal closecrystals.
packed and the body-centered cubic
56
11.
How Why
does the twinning mechanism differ from the

is
it
slip
mechanism and in
what respects
12. IS.
is
similar?
the twinning
mechanism important
in
some metals?
Describe a
number
of the structural changes accompanying cold working of
polycrystalline metal.
14.
Compare
ductility.
(a) tensile strength,
the effects of cold working and hot working on such factors as (b) directionality of properties, (c) toughness, and (d)
15. 16.
17.
Suggest possible applications for hard or spring temper brasses. Why is the relief of internal stresses during the recovery period when annealing cold worked metal of industrial importance? Why is annealing a cold-worked metal sometimes considered a fabrication
procedure?
18.
19.
20.
What damage may result from annealing at too high a temperature for a metal that has experienced a wide variation in the amount of cold work? What are the possible effects on properties when one metal is added to another to (a) form a solid solution? (b) cause another phase to appear? What basic ways are available for altering mechanical properties by heat
treatment?
21.
Explain how design for nuclear reactors involves factors not encountered
in other types of applications.
CHAPTER
Metallic Materials
Lee L. Amidon, M.S.M.E., Professor and Head, Department of Mechanical Engineering, South Dakota State College, Brookings, South Dakota
Walter
E. Short, M.S.M.E., Associate Professor of Mechanical Engineering, Bradley University, Peoria,

Illinois
4.1. Properties of Metallic Materials
I HE
properties of metallic materials are com-
monly divided into three general classes: (1) physical constants, (2) electrical and magnetic properties, and (3) engineering properties. The first class includes elastic constants, density and related properties, thermal expansion, vapor pressure, emissivity, and thermal conductivity. The thermal properties are affected by temperature and phase changes. Dimensions change and heat is absorbed or discharged at such times.
Problems in heat-treating operations
may be
anticipated as a
result.
These properties are of

lurgist.
interest to the physicist as well as to the metal-
in his
Usually, however, they are of interest to the physicist as a step study of theories of matter rather than as properties of metallic
Some of the physical constants are of interest to the engineer: the elastic constants surely are, because they are important in the design of structures; density is of interest if the strength-weight ratio must be considered, as in aircraft construction, high speed railway trains, and
materials.
motor-haulage vehicles; thermal expansion and thermal conductivity may be of importance for some engineering applications and of none for
others.
The
essential fact for the engineer to

is
constants as a group
know about the physical that in general they are determined by standardized
fairly precise, readily reproducible values that can be used in engineering design without trepidation regarding their meaning and accuracy. Values for the constants are well established and can be obtained in handbooks of physical tables.
methods that yield
57
58
Electrical
resistivity,
Engineering Metallurgy and magnetic properties include thermoelectric

properties,
magnetization, induction, permeability, and coercive forces.
These properties vary widely between different metals and their alloys and must be investigated thoroughly before making final selection for any given service. Aluminum on a weight basis may be a better conductor than copper and cheaper as well, but its tensile strength may not be sufficient to make it safe for the long spans desired on high-tension transmission lines so we compromise by using a steel core to provide strength and the result is an efficient carrier at low cost. Table 4.1 gives typical values of resistivity and the manner in which these values will change with temperature. The resistor elements for a dynamometer will call
for a material with great resistance to the flow of electricity while in a
Table
4.1.
Resistivity of Typical Metals
and Alloys
Resistivity at
20 C.
Temperature Coef.
Increase per
Material
Microhm-cm.
1.7241
C.
Copper
.00393 (0-100 C)
Aluminum
Iron
2.654
.00429 (20 C)
.0056 .0002
.0019
9.8
(0-100 C)
Constantan
(55% Cu, 45%

Ni,
Ni)
.
-19
(20-100 C)
(20
Nichrome (80%
20%
Cu)
107.9
C)
transmission line the
12
loss
should be
as
near zero as possible.
Magnetic properties are essential in the design of motors, generators, metering equipment, and huge lifting magnets. The magnetic properties are the result of the plus and minus magnetic fields
transformers,
set
up by
the electrons whirling in their orbits. Ferromagnetic materials
this property to the greatest extent. not form a permanent magnet but several atoms grouped together will form a magnetization unit. This small group is
such as iron, nickel and cobalt exhibit
Single atoms will
known
as a domain. There will be several domains in one metal grain. Ordinarily the domains of a metal bar will have random orientation in
which case the bar

netized.
If
will not
be magnetic.
An
external magnetic
field will
is
align the orientations found in the
many domains and
the bar
mag-
upon removal of the external field, the domains remain oriented we have a hard permanent magnetic substance. On the other hand if they tend to lose orientation then we have a soft or temporary
magnetic substance.
59
Temperature has a very decided influence on ferromagnetic materials. and finally to disappear altogether at what is known as the Curie temperature. This temperature is 1414F for iron, 2039F for cobalt, and 665F for nickel. The domains disappear at these temperatures, which for iron is below the point at which it becomes austenitic. These temperatures may be altered drastically by small additions of alloying elements or impurities.
Increase in temperature causes the magnetization to decrease
Electric properties are extremely important to the electrical engineer,
and the methods
for their determination are precise; but because of their limited application to general engineering, further discussion is beyond
the scope of this book.
From the standpoint of engineering in general and of those fields of engineering which deal specifically with the design, erection, and maintenance of structures and machines, the last class, engineering properties,
is
of vital importance.
classes: static
For convenience, they may be divided into three mechanical properties, dynamic mechanical properties, and
miscellaneous properties. There is a very close relationship between the engineering properties and the metal lographic structure, which will be
made
clear in later chapters of this book. Because of this relationship between micro-structure and physical properties, metallic materials are
structure sensitive.
In other words, they are affected by changes in the structure even though the chemical composition is unchanged. As we learn how to produce space lattices which are undistorted during the mechanical processing of our materials, much improvement in strength
and
physical properties
may
be anticipated.
Precise instructions for the physical testing of engineering materials
have been established by the American Society for Testing Materials and summarized in the Handbook of the American Society for Metals. It must be understood that the properties established by these tests are useprimarily in maintaining uniformity of material once a satisfactory The most useful form of testing is that made upon a completed structure under actual service conditions. Time and
ful
design has been established.
cost usually
limit this procedure; therefore, the following pages will evaluate the advantages and shortcomings of the various tests of a given material for use in engineering machines and structures.
It cannot be emphasized too strongly that the data from a small specimen should be accepted with caution unless it is certain that the
test test
piece
representative of the entire lot of material whose properties are being determined. A large number of specimens reduce the chances for error of even the most accurate and reproducible tests. The shape of the
is
designed part
may determine
to a large extent the distribution of stress
60
in a given cross-section.
The
presence of stress raisers
(holes,
sharp
changes in cross-section, scratches, inclusions)
may
increase the stress 3 to
5 rimes the average value. Ductile materials under static loading will yield
and little harm will be produced. However brittle materials and parts under repeated or reversed loading will start to tear and fatigue failure
of the part thus ultimately occurs.
Many
of these stress concentrations can be readily corrected by prop-
er design changes.
Frequently the magnitude of
stresses at
concentra-
tion points cannot be readily determined by analytical methods.

of brittle lacquers applied to the structure
The
use
under simulated
service con-
ditions will reveal trouble spots
which can then be corrected or eliminated. This design technique known as stress coating will supplement the
standard
test data.
The
use of strain gages in a similar
manner
will
determine the location, direction, and magnitude of the unit strain at locations where stress concentrations are suspected. The unit strain can then be used to calculate the actual stresses rather than the average stress that might be determined by the ordinary methods of design. Another method of determining stress concentrations is based on the optical
properties of transparent materials.
isotropic
tropic
Some of these materials are optically when in an annealed condition, but become optically anisowhen subjected to external stress. This method requires a plastic
model, which, of course, limits its use to a certain degree. Hidden stress raisers such as blow holes, slag inclusions, malformed space lattices or grain structures may be revealed by sonic testing described later in this chapter. Other methods frequently used to determine surface and hidden defects are radiography and magnetic particle detection. All of the above mentioned methods have the advantages of being non-destructive tests.
Physical properties, then,
structure itself
must always be considered in relation to the and sound engineering judgment used in its selection,
considering always the limitations of the material for a given service or

condition.
4.2.
The
Relative Standardization of Static Tests

a
Static
mechanical properties, which are
measure of the resistance of a
material to a steadily applied load, include tensile strength, compressive strength, torsional strength,
bending strength, hardness, and their
related properties, such as yield strength, elongation,
mined
incidentally to the
first
and others deternamed. The determination of some of
these properties has been given considerable attention by testing societies
in the principal metal-using countries with the result that methods and
specimens are
fairly well standardized.
61
The most important and the two most common tests for the evaluation of the static properties of metallic materials are tensile and hardness
tests.
The former
it
is
is
well standardized throughout the world. If the

is
tensile strength of a certain steel
reported as 60 kg. per
sq.
mm.
in
Germany,
certain that a standard specimen of the

lb.
have a strength of about 85,000

i/4-in.
per
sq. in. in
same steel will the United States and
that either value represents accurately the stress necessary to break a
specimen of that particular
steel.
The
tensile strength of a steel of

satis-
certain composition,
made by
a particular process, and of otherwise
factory quality can be used in the design of a bridge in Japan, even if the steel was made and the strength determined in France. Because hardness tests are made rapidly and cheaply and because they do not destroy the material, they are used widely. That hardness is not a definite prop-
makes the interpretation of Hardness tests are not standardized, although the measure of a specific kind of hardness, namely, resistance to indentation, is in a fairly advanced state of development. Hardness tests took on added importance during the war years as new and untried low-alloy steels were substituted freely for some of the older alloy steels on the
erty but a combination of several properties
some
of the tests difficult.
basis of the hardness of
an end-quench hardenability
test.
Static tests used less frequently,
not proceeded so
of these
is
far,
and for which standardization has include compressive, torsion, and bend tests. None
tests,
used so widely as are tensile or hardness

test,
although the
is
transverse
a form of bending,
is
the most widely used and
prob-
ably the most valuable single
test for
the evaluation of gray cast iron as
an engineering material. With this one exception, none of these tests is standardized, and it is not always easy to interpret the values obtained or to apply them to the design of engineering structures.
4.3. Tensile Strength
The commonly determined

area, are obtained
tensile
properties,
including
tensile
strength, yield strength, proportional limit, elongation,
and reduction of
.
on a single test specimen (see Fig. 4.5) The accuracy and reproducibility of the results depend upon the dimensions of the
specimen, the sensitivity of the machine, the alignment of the specimen in the machine, and above all on how accurately the specimen represents
the whole section. Considerable attention has been paid to these factors by the testing societies and the builders of machines in all countries,
with the result that reported values are about as accurate as for any
engineering property.
62
17.000
16.000
15.000
y
/'
14,000 13,000 12,000
/ c
11,000
hn
TS
10.000
9000 o
1
/,
/
1
1 1
/
/
1 i
:8O0o
| 7000
ta 6000
1/"
1/
Is 1
1
r
1
5000
p
I
1
4000
3000
1
_i
/
2000
1000
A
1
^
0006
1
c
0.002
0.004
0.006
0.002
0.004
St rain, inch
per inch
Fie. 4.1.
Stress-strain curves in tension for

steel.
(A) annealed low-carbon steel
and
(B)
cold-worked low-carbon
As
is
well
known, the
tensile strength of a
specimen
is
the
maximum
load before rupture

sectional area.
(point C, Fig. 4.1 A) divided by the original cross-
It is reported in pounds per square inch, tons per square (England) or kilograms per square millimeter (continental Europe) Specimens and other variables have been standardized by the
inch
American Society
unnecessary.
for Testing Materials
*so that further discussion

structural constituents
is
Owing
to the inherent variations
in
and
in as
composition which
may
in.,
cause variations in tensile strength of as

is
much
1,500 lb. per sq.
tural
a growing tendency to test full-sized strucmembers with large machines. This type of test is especially valuthere
able for structures that are riveted or welded.

If a tensile test
is
made on
,
a larger or a smaller specimen than
is
com-
monly used
(0.5 in.)
the tensile strength
may
be considerably higher or
lower than that obtained on the standard bar.
For ductile materials,
which include most

A. S. T.
rolled,
1955.
forged,
or heat-treated carbon
and
alloy
M. Standards,
63
\
STRAIN HARDENING BEGINS
Fic.
42.
Greatly enlarged view of stress-strain diagram in region near yield point.
steels,
the error
is
variation in strength
not great; for a brittle material, such as cast iron, the may be considerable if differences in cooling rates
of cast specimens of various sizes result in differences in structure.
been based on either the with the use of appropriate factors of safety. For example, a working stress for carbon steel may be of the order of 18,000 psi. although the yield point of this material may be approximately twice this value. It might be noted that the portion of the
of years, structural design has
tensile strength or the yield strength
stress strain
For
number
curve shown in Fig.

if
4.1
ably different appearance

It will
the curve
at point B would have a considerwere plotted with a different scale.
be noted from
is
Fig. 4.2 that a large
amount
of yielding at a rela-
tively constant stress will
occur before strain hardening begins.
This
phenomenon
the basis of recent
work
in the field of plastic design.
4.4. Elastic Limit, Proportional Limit,
and Modulus of
Elasticity
men concerning the meaning of the terms Elastic Limit, Proportional Limit, Yield Point, and Yield Strength. The elastic limit is the maximum stress that a material withstands without permanent set. Although it is practically
is
There
occasionally confusion
among
engineers and steel
impossible to determine the true elastic limit experimentally, it is possible with present-day extensometers to detect a relatively slight variation from Hooke's law,* and by careful testing the point of this variation can be fixed with considerable exactness on the stress-strain diagram
(point P, Fig. 4.1A)
The
load which this point represents, divided by
Hooke's law states that in clastic materials stress is proportional to strain. It is generally held that in metallic materials the application of stress, within the range
where deformation
is
elastic, actually
produces some plastic deformation.

purposes,
The amount,
however, is so small that for design, Hooke's law is valid.
all practical
and
especially for engineering
64
0.004
0.012
0.016
0.020
0.024
0.032
Strain, in./in.
Fic. 4.3.
Stress-strain
Institute,
"The Behavior
diagrams of common metals. (H. of Engineering Metals," p. 15.)
W.
Gillett, Batelle
Memorial
the cross-sectional area,
is
the proportional limit.

is
It is
frequently deter-
mined
seldom used in the design of structures. In most annealed and heat-treated carbon and low-alloy steels, the proportional limit is practically identical with the elastic limit and, as
in testing laboratories but
Fig. 4.1
shows,
is
slightly
is
limit of such steels
found
to
below the yield point. If the proportional be much below the yield point, it is likely
that internal stresses are present.

limit
is
The
is
determination of proportional
frequently
made
to detect the presence of such stresses.
Modulus
of elasticity in tension
It is
the ratio of stress to strain with-
in the elastic range.
given by the slope of the stress-strain curve
(see Fig. 4.1 A) up to point P. For carbon and low-alloy steels of any composition and treatment, the value is approximately 29,000,000 lb. per sq. in.; for aluminum alloys, the modulus in tension is about
alloys, about 15,000,000 determined in compression as lb. per sq. in. Modulus of elasticity may be Another for either method. well as in tension; values are about the same of rigidity, which shear modulus, or modulus important quantity is the (Young's modulus) the modulus of elasticity is invariably smaller than
10,000,000
lb.
per sq.
in.;
for copper
and copper
65
-*
A!
KM^se-r'*
0.002
0.004
0.006
0.008
Strain,
Fig. 4.4.
in.
per in.
Ptoc.
Am.
Stress-strain curves for two gray cast irons tested in tension. (/. Soc. Testing Materials, v. 32, 1932, II, p. 477)
W. Bolton,
The modulus
It is
of elasticity
is
a measure of the stiffness of the metal.
not appreciably affected by heat treatment. A part too springy in the annealed state will not have the condition improved by hardening. The modulus decreases with increases in temperature moderately at first, but may change very rapidly when some specific high temperature is
The rate of change varies with the alloy chosen. values of stress-strain diagrams and moduli of elasticity are
reached.
Some
shown
typical
in Fig.
There are some metallic materials-gray cast iron and austenitic alloy outstanding examples-which when tested in tension have a stress-strain curve that is curved from the origin (Fig. 4.4) Such materials have no readily determinable proportional limit and yield point. Moreover, they have no true modulus of elasticity; reported moduli are
steels are
.
arbitrary
values
that
measure
the
relative
stiffness
under
specified
conditions of loading, usually with a stress equivalent to 25 per cent of the tensile strength.
66
4.5. Yield Point
and Yield Strength
Engineering structures and machines subject to static loads are designed on the assumption that the stresses that must be withstood will not cause appreciable plastic deformation (permanent set) As plastic deformation probably starts in a large number of independent locations, it is difficult to determine where it actually begins. Plastic deformation does not become measurable until a large part of the section has been affected, and even then very sensitive equipment is necessary to locate this point the
.
proportional limit.
Fortunately, practical experience has
shown
that, at
ordinary temperature, the limit of usefulness of a metallic material is that stress which produces a plastic deformation that is readily detected.
Higher
stresses
than
is
this
may cause
This
considerable damage; with lower

stress
is
stresses the
damage
it
is
negligible.
the yield point. In ductile

of the specimen with
materials,
indicated by a
marked elongation
no increase in load. It is readily detected with a pair of dividers or by the drop of the beam of the testing machine. The yield point is of conit has the not well marked in hard materials, some of which have no true yield point. To overcome this disadvantage the American Society for Testing Materials recommends the use of yield strength in-
siderable value to engineers in the design of structures, but
disadvantage that
it is
stead of yield point.*

specified
set,
This
is
the
maximum
stress
that
produces a
In hard
stress-strain
usually 0.1 or 0.2 per cent of the gage length.
materials, the point can be readily determined
from the
curve
(point B, Fig.
4.
IB); in
soft materials,
it
corresponds closely to
the yield point determined by drop-of-beam.
yield strength is an important and readily determinable value and should replace the yield
The
point in
all
reports of tensile properties.

is
The
is
value for yield point
affected by the rate of strain, that
is,
by
the speed of the cross head of the machine. Generally, however, the error
not great for the speeds used in testing to determine whether a mawithin specifications. For example, increasing the rate of strain
to 2
terial is
from 0.2 about 2,000 lb per

tenfold, as
2-in.
per cent per min., increases the yield point only
sq. in.
The American
Society for Testing Materials

in.
specifies that the cross-head
speed should not exceed i/ 8
per min. for a
gage length.
Very soft materials, especially annealed low-carbon sheet, frequently have two yield points: an upper point, at which there is a decrease in stress (A in Fig. 4.1 A) marked by a sudden drop of the beam of the testing machine, and a lower yield point (B in Fig. 4.1 A) where strain
,
1
A.
S.
T.
M.
Standards, 1955.

Radius not less than'/ 8"
U \|
67
gj
Parallel section
.'
Nole
The gage length, parallel sect/on, and fillets shall be as

:-
o
,k
fiO.Ol"
shown, but the ends
may be of any shape

to fit the holders of the testing machine in such a way that the load shall be axial
2"i0.00S"A
Gage length
for elongation after fracture
h- ?gm/h mgnps-*^*-
3f mih between grips
>j<-
2g/n/n in grips-
"1
^r w =o.soo"io.o/o" to +0.003 to 0.005 ,
<
I
1
w+0.003to0.0OS" (See Note!
Zj
mm.
-t
>-}
Fig. 4.5.
Ifeduced section
\ ''Radius
0.5" to3"
6'min.
t = Thickness ofma ferial
Note: Gradual taper from ends ofreducedsection to middle. All machining dimensions are shown below and testing dimensions above specimen
Standard round and
flat
tensile specimens.
(AS.TM.
Standards E8-46)
hardening begins and where additional stress is necessary to produce further strain. The difference between the upper and the lower yield point is considered to be an indication of the deep-drawing capacity of annealed low-carbon sheet.
4.6. Elongation
and Reduction of Area
In the United States, the standard round tensile-test specimen has a diameter of 0.505 in. (cross-sectional area 0.2 sq. in.) in a gage length of 2 in. (Fig. 4.5 top) Elongation values determined on round specimens larger or smaller than the standard are directly comparable with the standard if it has a gage length equivalent to
.
G = 4.5vT
where
inches.
A the cross-sectional area in square Unfortunately, since the standard tensile specimens used in
is
the gage length and
Great Britain, Germany, and France have a different relation between gage length and cross-sectional area from that expressed by the above formula, values obtained in those countries, while always reproducible
where determined, cannot be compared directly with elongation values determined in the United States.
68
Fie. 4.G. BrineU hardness machines: left, hand-operated laboratory model; right, high-speed production testing model. (Courtesy of Tinius Olsen Testing Machine
Company)
For some products, especially for plate and thin sheet, specimens are may differ in size and shape from the standard (Fig. 4.5 bottom) Gage lengths for tensile specimens of such products vary from 2
used that
.
depending upon the material and its size. As elongation is reported as a percentage of the original length, the percentage elongation
to 10 in.,
of a given material
is
higher the shorter the gage, owing to the fact
that most of the elongation takes place in the "necking-down" that occurs
at the point of fracture.
When
tensile properties are
determined on
speciis
mens
that differ in dimensions from the standard, the gage length

if
always given. Even
a standard specimen
in.)
is
used, most metallurgists
report the gage length (2
so that there will be

as
no misunderstanding.
a
Reduction-of-area values are always reported
percentage of the
original area so that values for this property should be comparable.
69
clear, idea of the ductility of the
Elongation and reduction of area give a rough, but usually a fairly metal tested. Although engineers gen-
demand a relatively high elongation, metallurgists place more emphasis on reduction of area as a criterion of ductility and believe that the importance of elongation is usually overemphasized. It is doubtful if
erally
there are any applications for which an elongation of more than 8 or 10 per cent in 2 in. is needed. As an example of the exaggerated importance sometimes given to ductility, the crankshaft of the internal-combustion engine may be cited. For years crankshafts were made from highly alloyed steels which were carefully heat treated so that they would be as ductile as possible coincident with the high hardness required. The cast-iron crankshaft now used successfully in some automotive engines
shows very
little elongation in the tensile test resistance to single-blow impact.
and has
practically
no
It is generally true that in carbon steels and many nonferrous alloys high strength values are accompanied by low values of elongation and reduction of area and vice versa. This general relation does not always hold for alloy steels. One of the principal reasons why alloy steels are used in place of carbon steels is that a better combination of yield
strength
and ductility-as shown by elongation and reduction of area
(and impact resistance) -justifies their higher cost for many applications.
4.7.
Hardness
do not recognize hardness as ordinarily determined as a fundamental property of matter; to engineers it is a property of great importance. Everyone thinks he knows what hardness is, but no one has been able to define it satisfactorily. Probably as good a definition as any is that hardness is resistance to permanent deformation. Hardness is complex. First and most important, it is the resistance of a material to
Physicists
indentation. It is also the resistance to cutting with a tool, which involves resistance to indentation plus tensile strength and toughness. It is also
resistance
strength,
which likewise involves indentation and toughness.
to abrasion,
resistance,
There are at least eight methods for the determination of hardness, of which two-Brinell and Rockwell-are the more
frequently used.
The
on hardness testing is extensive. Since standards for making Brinell and Rockwell tests have been set up by the American Society for Testing Materials,* the methods for making these tests can be dismissed
literature
with a few words.

* A. S. T.
M.
Standards, 1955.
70
Fie. 4.7Rockwell hardness lesliug machine. strument Company)
{Courtesy of Wilson Mechanical In-
In the Brinell test, a definite load is applied to the piece to be tested by means of a hardened steel (or tungsten carbide) ball. The diameter or the depth of the resulting impression is measured, and the Brinell hardness number is calculated by dividing the load applied (in kilograms) by the area of the impression (in square millimeters) which is assumed to be spherical. Owing to a slight deformation of the steel ball
,
and
to the fact that the
impression
is
not truly spherical, the hardness
number
somewhat with the load applied and with the diameter of the ball. These have been standardized in this country: a 10-mm. steel ball and a load of 3,000 kg. are used for steel and a few nonferrous alloys; and the same ball and a load of 500 kg. are used for soft materials. The
varies
is applied for 20 to 30 sec, the diameter of the impression varies from about 6 mm. for soft materials to about 2.5 for hard materials and is measured with a micrometer microscope. The Brinell machine is shown
load
in Fig. 4.6.
71
Rockwell hardness machine (Fig. 4.7) is designed to test materials of widely varying hardness by interchangeable indenters. For hard materials, a diamond cone is used; for softer metals and alloys, -in. and
l/g-in.
The
hardened
is
y16
steel balls are
load of 10 kg.
material.
applied to
employed. In the Rockwell test, a minor force the penetrator below the surface of the
then applied. The hardness, which is indepth of penetration, is read directly on a scale, several of which are used.* A Rockwell hardness number is meaningless unless the scale symbol accompanies the value. Loads and scales used with the Rockwell machine are as follows:
is
The major
load
versely proportional to the
Major
Scale Pencirator
load,
kg-
Materials tested
A
B
Diamond cone
60
Tungsten carbide and other very hard materials.

Thin, hard
steel,
steel,
such as razor blades, nitrided
and
the like
Hi-in. ball
Diamond cone Diamond cone

H-in. ball
100 150 100 100
Soft steels, hard nonferrous alloys Steels of 90,000 to 350,000 lb. per sq. in. tensile
D
E
strength Materials with thin, hard surface layer; case-
hardened and nitrided

Soft materials,
steel
aluminum
alloys,
bearing metals,
and the
like
There
is
a third hardness
use, especially in the laboratory; this
mond pyramid
tests
is
is coming into relatively wide the Vickers test in which a diapressed into the surface of the material. Other hardness
test,
which
is
now rarely used, which determines hardmeasuring the rebound of a diamond-pointed weight falling from a fixed height; and a number of scratch tests in which needles of definite
ness by
include the scleroscope,
A laboratory hardness tester has been recently developed by Frederick Knoop at the National Bureau of Standards. A carefully prepared diamond pyramid is forced into a There are a number of other scales in addition to the ones listed in the
table i/ e -, i/ 4 -, and i/ 2 -in. ball indenters; these are used occasionally for special hardness determinations. There is also available a special Rockwell machine for the de termination of superficial hardness. All of these are discussed in A. S. T. M.
laboratory to detect differences in the hardness of the various constituents in an alloy but are rarely used industrially. new
hardness or diamond or sapphire points are dragged over the polished surface. Scratch tests are sometimes useful in the research
which are used with
Standards, F.18-42.
72
polished metal surface and the dimensions of the resulting impression

are read with a microscope.
The Knoop
it is
tester
is
flexible
and apparently
gives precise results, but at present
adapted only to the laboratory. A practical qualitative method widely used for the determination of the hardness of steel is the file test. In the hands of an experienced man, rubbing the
file
relatively slight differences in hardness can be detected by
material with a
of
known
hardness. Thus, a steel with a Rockwell

a
hardness of 54 can be differentiated from one which has
Rockwell
C C
hardness of 60. Obviously, too

tion for the
file test
much depends upon
the personal equa-
to
be useful except in the hands of an experienced
man.
4.8.
Comparison of the Various Flardness Tests

making hardness
In the
first
In
tests
by any method
number
of precautions are
necessary.
place, the
specimen must be rigidly supported,

place, the
and the load must be applied perpendicularly. In the second

surface tested must be
flat
and
relatively
smooth, and any surface scale

In the third place, specimens
or decarburized areas must be removed.
must be
specimen
thick
rests
enough
so that the material of the anvil
on which the
does not affect the indentation in the specimen. In general,
hardness impressions on thin sections are not accurate unless the material
has a thickness equivalent to 10 times the depth of the impression.
All tests for hardness by indentation cause strain hardening to
some
degree.
The
Brinell test
is
as close to
an
ideal test as possible as
it
distrib-
utes strain hardening over a relatively
wide
area,
but
it
lias
the dis-
may not be uniform and, further, that the method is too restricted in application. With a 500-kg. load, the Brinell test is quite satisfactory for aluminum alloys and for
advantage that the amount of strain hardening
brass
tensile strength
is
and bronze; with a 3,000-kg. load its use is restricted between 45,000 and 250,000 lb. per sq. in.
steels that are
lb.
to steels
with a
When
the test
used on
harder than 500 Brinell

,
(tensile strength greater
than 250,000
per
sq. in.)
there
is
likely to
all
be some permanent defor-
mation of the
tions
steel ball that
causes
subsequent hardness determinasteels
made with
this ball to
be inaccurate. For
is
with high hardness
a special tungsten carbide ball
used.
The Rockwell machine

of the Brinell
test.
is
designed to overcome some of the limitations
It is flexible
is
and can be used
for
hard materials,
it
makes
piece,
a small impression that
not likely to spoil the appearance of the

sec-
and
it
can be used to measure the hardness of relatively thin
7:5
tions.
Scleroscope hardness
For example, on
per
sq.
in.
steel of
20
100
150
24
30
40
50 60 70 80 90 100
150,000 lb.
strength the
tensile
minimum
method
is
thickness
60 200 250
that can be tested accurately by
the Brinell
0.15
in.;
'.on j\j
k
N^
\
L_
\
120
300
350
WO
160
Iftfl
with the Rockwell diamond cone (C scale), it is 0.06 in. The Rockwell machine also has the advantage that hardness numbers are read directly from the
scale; it is unnecessary to measure the width of an impression.
400
an
S450
m
\
\
MU V\0 <u
c
240 260 280
The Rockwell machine

fore,
is,
there-
550
ftYl
widely
used
for
routine
testing
and
for the inspection of
\
650
700
heat-treated parts.
f
V
\
SO
340
The
which
all
is
Vickers
hardness
test,
rapidly becoming standis
750
ardized,
the most flexible of
800
-10
10
20 30 40 50 Rockwell C hardness
60
70
Fie. 4.8. Relation of hardness values to each other and to tensile strength for carbon and low-alloy steels. (French and Sands)
tests and can be used without change of penetrator on materials of widely varying hardness by varying the load applied. The impression is
hardness
small and, owing to

shape,
its
diamond
very
is
can
be
measured
accurately.
ideal as a laboratory tool, at present so well adapted to routine testing as the Rockwell.
test,
The
Vickers
not
4.9. Relation
among Hardness
Tests and between Hardness and
Tensile Strength for Steel

All indentation hardness methods fail to measure the hardness of the undeformed metal. An exact mathematical correlation of the various hardness numbers is therefore impossible as the amount of strain hardening varies from test to test and, furthermore, varies from metal to metal. A large amount of time and effort has been expended in studying the relation among the hardness numbers as obtained by the Brinell, Rockwell, Vickers, and scleroscope machines. One of these correlations for carbon and low-alloy steels is shown in Tig. 4.8* A word of caution is
H.
J.
French and
J.
W. Sands
(editors),
Nickel Alloy
Steels,
Nickel Co., Inc.,
New
The
International
York, 1934.
74
necessary concerning such a correlation. Brinell values

to Vickers or
may be
converted
Rockwell
values, or vice versa, with
not more than 10 per cent, except for where the uncertainty becomes greater. The error in converting Brinell or Rockwell to scleroscope may be considerably greater than 1 per cent. The most recent conversion table and probably the most accurate for carbon and low-alloy steels was compiled by a committee of the Society of Automotive Engineers and the American Society for Testing Materials.* These values are reproduced in part in Table 4.2.
an expected error of hardness numbers over 500 Brinell
The resistance
to indentation
is
directly related to compressive strength.
For most carbon and low-alloy steels there is a fairly close relation between compressive strength and tensile strength; hence, indentation hardness values for such steels can be converted into tensile strength with reasonable accuracy. Results of a large number of investigations on
this relation indicate that the ratio of tensile strength
lb.
(in units of 1,000
per
sq. in.)
to Brinell hardness
number
varies
from 0.45 to
0.58,
and
heat treatment apparently has
no
effect
on the
ratio.
The
ratio obtained
most frequently is 0.47 to 0.50. Thus, if the Brinell hardness number is given, tensile strength can be calculated by multiplying the hardness
number by 480; the result should be accurate within =p 5,000 lb. per sq. in. The relation between the various hardness numbers and the tensile strength for carbon and low-alloy steels is shown in Fig. 4.8 and in Table 4.2. Although this relation is fairly accurate, there may be considerable variation in individual specimens. The actual ratio depends upon structure, with composition a possible complicating factor, and although in most cases the conversion may be made with an error of 5,000 lb. per sq. in., errors as great as 12,000 lb. per sq. in. may be encountered.
4.10. Relation
Tests and between Hardness and Tensile Strength for Nonfcrrous Alloys
among Hardness
In contrast to carbon and low-alloy steels, which all harden approximately the same amount when cold worked (strain hardened) and which show, therefore, a fairly close relation among hardness tests and between hardness and tensile strength, the nonferrous alloys differ considerably in their capacity for strain hardening and no such relation can be worked out for these materials as a class. For example, a high-strength duralumin that has been heat treated will have a tensile strength of around 70,000 lb. per sq. in. and a Brinell hardness (500 kg.) of 115; whereas a cast manganese bronze containing 55 to 60 per cent copper and 38 to 42 per
cent zinc will have a tensile strength of 90,000
1
lb.
per
sq. in.
and
a Brinell
A.
S.
T.
M.
Standards, 1955.
75
Table
Brinell. 10
4.2.
Approximate Hardness Conversion Numbers

Rockwell hardness nun ber
1
for Steel
mm.
ball,
3,000-kg. load
1
Vickers
d lamond-
ApproxiSclero-
B
Diameter
of
A-scale.
pyramid
hardness
D-scale.
mate
tensile
scale.
100-kg.
load. Hi-in. ball
C-scale.
Hardness
number
scope hardness
60-kg.
load.
impression
number
150kg.
load,
100 kg.
load.
(DPH)
number
strength. lb. *, per

sq. in.
mm.
diamond
diamond
diamond
2.40 2.45 2.50 2.55 2.60

2.65 2.70 2.75 2.80 2.85
653 627 601 578 555
*
*
81.2 80.5 79.8 79.1 78.4 77.8 76.9 76.3 75.9

75.1
60.0 58.7 57.3 56.0 54.7

53.5 52.1 51.0 50.3 48.8
70.7 69.7 68.7 67.7 66.7 65.8 64.7 63.8 63.2 61.9 61.0 58.8 56.8 54.6 52.8 51.0 49.3 47.6 45.9 44.2 42.0 40.5
697 667 640 615

591
81
79
77
75 73
71
323,000 309,000 297,000 285,000
wn
'JfWUf
'>--
534 514 495 477

461
* '
569 547 528 516 495
70
68 66 65
274,000 263,000 253,000 247,000 237,000

226,000 210,000 195,000 182,000 170,000
160,000 150,000 141,000 133,000 126,000
***/tf
'-
2.90 3.00 3.10 3.20 3.30

3.40 3.50 3.60 3.70 3.80
444 415 388 363

341
74.3 72.8 71.4 70.0

68.7
47.2 44.5 41.8

39.1 36.6
474 440 410

383 360
63
59 56 52 50 47 45 43
321 302 285
67.5 66.3 65.3

64.1
34.3
32.1
339 319
301
269 255
241 229
63.0 61.8 60.8

100.0 98.2 96.4 94.6 92.8
29.9 27.6 25.4 22.8 20.5 17.5 15.2
284 269 253

241
40
38
3.90 4.00 4.10 4.20 4.30

4.40 4.50 4.60 4.80 5.00
217 207
197
187 179 170 156 143
228 218 207

196 188 178 163
36 34 33 32 30 28 27 26 24 22
118,000 111,000 105,000 x 100,000 '0*i</' 95,000
90.7 89.0 86.8 82.9 78.7
150
90,000 87,000 83,000 76,000 71,000
By tungsten carbide
less
ball.
hardness of
rolled
than 100. Copper hardened with arsenic, in the coldcondition, will have a Rockwell B hardness of 95 to 100 and a tensile strength of about 60,000 lb. per sq. in.; whereas admiralty
(hard)
metal containing 71 per cent copper, 28 per cent zinc, and 1 per cent tin and of the same Rockwell B hardness will have a tensile strength of 95,000 lb, per sq. in. or higher.
76
only nonferrous alloy for which hardness conversions have been
is
The
worked out Table 4.3.*
cartridge brass.
Some
of these values are collected in
All the thousands of other alloys, with the possible exception of the high-nickel alloys, which apparently harden much like steel, are quite evidently a law unto themselves, and each must be considered
as a special case.
Table 4.3. Approximate Hardness Conversion Numbers Copper, 30 Per Cent Zinc)
Brinell,
for
Brass
(70 Per Cent
10-mm.
ball
Rockwell hardness number
Vickcrs
diamond
Diameter
of
Hardness number
scale.
scale.
impression,
3,000-kg.
mm.
2.00 2.10 2.20 2.30 2.40 2.50 2.60 2.70 2.80 2.90 3.00 3.10 3.20 3.30 3.40
3.50 3.60 3.70 3.80 3.90
*
load*
500-kg. load
100-kg. load,
Ke-in. ball
60-kg.
load, Ho-in. ball
Tscale. t 30-kg.
pyramid
hardness
load,
Hs-in. ball
number (DPH)
653
601 555 514
158 143 130 119 109 100
91.0 85.5 79.5 74.0

68.5
108.0 105.5 102.5 99.0 96.0
75.5 72.5 69.5 66.0 62.0

59.0 55.5 52.5 48.0 43.0 38.5 34.0 29.0 23.0 18.0
183 165 149 135 123
477 444
415 388 363 341
321
93 86 80 74
69
65
61
63.5 59.0 54.0 47.5 40.0 33.5 28.7

18.5 12.5
93.5 91.0 88.0 84.4 80.0
113 105 98
90
82
77 73 66
57
53 50 48 45 42
77.0 74.0 68.5 65.0 61.0

56.5 53.5 47.0 40.0
62
58
302 285 269 255 241
12.0
54
52 48
45 43
40
For steel, included for comparison. Rockwell superficial hardness: initial load 3
kg.;
major load 30
kg.
If the
proper precautions are observed, indentation hardness

if
tests
are
accurate and readily reproducible; and

of machinability
A. S. T.
judgment
steels
is
used, the tests
give a reasonable approximation of the tensile strength
and wear
resistance for
most
and a rough idea but not for most
M.
Standards, 1955.
77
nonferrous alloys. Their greatest value lies in their speed and cheapness, which make them ideal for checking uniformity of heat treatment and as an acceptance test for hardened steels, especially tools and dies, and
for a
number
of other metallic materials.
4.11. Shear, Compression, and
Bend
Tests
The
or torsion
determination of the resistance of a material to failure by shear is important for many engineering applications, especially for
for such tests nor the
shafts subjected to twisting, for rivets holding two plates together, for keys in shafts, and the like. Neither specimens
methods of making the tests are standardized. Stress-strain diagrams may be plotted from a torsion test, from which the maximum torque
(torsional or shearing strength)
,
yield point or proportional limit,

rigidity)
and and
modulus of elasticity in shear (modulus of mined. There is no accurate relation between

the
tensile strength,
may be
is
deter-
torsional strength
the torsional strength about 75 per cent of the tensile strength.

steels,
but for carbon
generally
rials that fracture;

it
Compressive strength can be determined accurately on brittle mateon ductile materials, which flatten without fracturing, can be determined only when a limiting amount of deformation is
is
specified.
Compressive strength is a common test for cast iron, as this frequently used in compression, but is rarely made on steel. The compressive strength of cast iron is 3 to 4 times its tensile strength.
metal
are becoming increasingly valuable for some of the new These steels are used in structures primarily to save weight, and the bend test is useful to determine the relative
tests
Bend
low-alloy steels.
stability of ductile materials are tested, the specimen does not fracture when bent; hence, the test can also be used to detect deep-seated flaws and other internal defects or to discover brittle areas in and around a weld. A variety of the bend test-the transverse test-is a useful measure of the quality of cast iron and has been used so widely for this purpose that virtual standardization has been
these materials
under load.
When
effected.
Transverse
tests of cast
iron are
made on
standardized bars.
As
dis-
cussed in Chap. 20, the results are reported as the load necessary to fracture a specimen of definite diameter held on supports a specified distance apart. In the United States this is usually reported as transverse strength in pounds; abroad, and to some extent in the United States, it is reported as modulus of rupture in pounds per square
inch.
The
test is
usually
a cast bar without machining; removing the surface layers of the bar may cause a slight change in values. The deflection in inches (that is, how much the bar bends before breaking) is also re-
made on
78
Fie. 4.9.
Oscillograph screen showing diagram obtained by sonic
tester.
ported.
The
transverse test gives an indication of toughness, flexibility,
surface condition,
test for cast iron.
and even machinability and
is
the most valuable single
4.12. Sonic Testing
Large forgings, castings, and weldments are inspected for hidden flaws by x-ray radiography. Recently the sonic tester has been developed for non-destructive testing of all types of machine elements. This apparatus is portable and can be used on a part even when it is completely assembled in the machine. This makes possible inspection during manufacture, but it also can reveal fatigue cracks and defects in highly stressed machine
machine has been placed in service. High-frequency compression waves are produced by a quartz crystal placed directly on the work surface or the crystal may be carried on an
parts after the
oil film.
The beam
of vibrations flows through the metals
and are
re-
back from the bordering surfaces. The reflections are then recorded on an oscilloscope, A on Fig. 4.9 being true top surface reflection and C the bottom surface reflection. An internal crack would also send back a reflection as shown by the pip at B. Location of the defect can also be determined from die oscillograph. The length from A to C represents the
flected
work depth. AB same scale. This
is
ability to
then the distance from top surface to defect on the measure depth makes it possible to gage the
79
SEARCH UNIT AT POSITION

Fro. 4.10.
SEARCH UNIT AT POSITION

(Courtesy Sperry Products, Inc.)
Surface
Wave
Testing of a Shaft.
progress of corrosion in piping

fluid.
and pressure
vessels
even when
filled
with
The majority of ultrasonic testing is done by x-cut quart/, crystals which send waves directly through the specimen. However, Y-cut crystals or plastic wedges may be used to propogate surface waves which can follow curved surfaces and thus reach otherwise inaccessible locations. Fig. 4.10 shows this technique being used to check the fillet areas of a shaft for
fatigue cracks, such a crack being revealed by the surface
wave unit
in
position
2.
QUESTIONS
1.
Define
properties?
2.
What
mechanical properties. What are the five most useful static engineering property is standard throughout the world? materials, because of their magnetic properties, are most useful in
static
What
the design of motors, generators,
Curie temperature. reached?
What happens
and transformers? Define domain. Define to the domain when this temperature is
80
S.
How
What
accurate
is
mined? What variables

4.
the tensile strength of a metallic material as usually deteraffect this accuracy? What factor is most important
in using tensile-test data in engineering design?
5. 6.
7.
are the advantages and disadvantages of testing a completed structure under actual service conditions? Discuss the use of aluminum as an electrical conductor. Distinguish between elastic limit and proportional limit. What is modulus of elasticity, and what does it represent? Can proportional limit and modulus of elasticity be readily determined on all metallic materials? Give the reason for your answer. Give approximate values of modulus of elasticity for (a) steel, (b) aluminum
(c) copper. Describe three methods of testing which will allow the designer to determine the location and magnitude of stress concentration in a given speci-
alloys,
8.
9.
men or structure. What modulus is

which
is
a measure of the stillness of a metal.
Can
metal part
not
stiff
enough
in the annealed state be
improved by hardening?
10.
What
is the difference between yield point and yield strength? What is the importance of these values to engineers? How does the speed of testing
affect the yield point?

11.
What phenomenon
into a
occurs
on the
stress-strain
curve which has developed
new
science
known
as plastic design?
12.
13.
Define elongation and reduction of area. How are these values determined? What is the effect of gage length on elongation? What properties are components of hardness? What precautions are necessary in the accurate determination of hardness? Describe briefly the method of determining hardness
well,
14.
by the
Brinell,
and Vickers machines, and
give the principal advantages
Rockand diswill a
15.
When
advantages of each. a part is so designed that

ductile material react as
stress
concentration
is
present,
how
16.
compared with a brittle material? What will be the reaction if the stress is released and then reapplied? Convert a hardness of 40 Rockwell C to Brinell and Vickers values and to
tensile strength.
How
accurate are these conversions?

is
If
of an annealed carbon steel
85,000
lb.
per
sq. in.,
what are
the tensile strength its approxi-
mate
17. 18.
Brinell, Vickers,
and Rockwell
hardness values?
structure sensitive?
What do we mean when we say a material is What hardness tests are commonly used for
ferrous alloys?
nonferrous alloys? Why is it impossible to convert hardness values to tensile strength for most non-
19.
What
is
the value of the shear test?

(b)
What
is
the value of the
bend
test
(a)
for ductile materials?
for brittle materials?

is
What
is
the relation be-
tween the strength of a metallic material

20.
in torsion
and
in tension?
docs the sonic tester function? What of testing as compared with x-ray analysis?
How
the advantage of this

is
method
How
a defect in the specimen
located?
Dynamic Properties of
CHAPTER
Oran Allan
Metallic Materials
Pringle, M.S.M.E., Associate Professor of Mechanical Engineering, University of Missouri, Columbia, Missouri
iHE
design
of
engineering structures
and
machines that are subject to static loads is based upon tensile strength and yield strength with an ample factor of safety. Few failures of such structures and machines occur. This, however, is not the case with moving parts of machines which fail so frequently that it has been estimated that
metal failures are caused by dynamic loads. For this and engineers are now paying more attention than ever before to the resistance of ferrous and nonferrous materials to dynamic stresses and to methods of determining the dynamic properties.
all
95 per cent of
reason, metallurgists
The
principal
(fatigue)
strength,
dynamic properties impact resistance, endurance and damping capacity measure the ability of the
material to withstand suddenly applied or pulsating loads. Endurance strength has been the subject of much study and in some respects might
even be called a standardized property. Impact resistance and damping capacity are not standardized; hence, the values obtained by impact and
damping
tests
may mean
very
little
unless the
method and
the specimen
used are known. Such tests are more valuable as a method of comparing various materials or various grades of the same material than as a means
to obtain values
which can be used
in design.
5.1.
Notch Brittleness and Transition from Ductile to Brittle

Fracture
In applications involving impact loads it is necessary to know the influence of speed of loading or strain rate on the mechanical properties of 81
82
.
Stress
Stress
atMN
M-,
Fie. 5.1.
Typical notches or
stress
raisers
occurring in machines and structures.
(Moore)
knowledge, there is always a considerable increase in yield strength of metals at high strain rates; for example, over a range of strain rates from 103 to 102 in. /in. per sec. the yield point for mild steel increases by as much as 100 per cent. The ultimate strength also increases at high strain rates but to a lesser degree, and at very high strain rates the yield point of mild steel approaches the value of the ultimate strength. These considerations might lead one to conclude that there is less likelihood of failure under impact
the materials.
According
to present
loads than static loads. Unfortunately however,
it is
now
well
some commonly
tures,
ductile materials can fail in a brittle fashion
known when
that sub-
jected to certain insidious combinations of high strain rates, low tempera-
and notch
effects.
is preceded by a considerable amount of plastic deformation; since the force required for fracture thus acts through a comparatively large distance, a relatively large amount of energy is absorbed. A brittle fracture is preceeded by little or no plastic deforma-
ductile fracture
tion;
therefore very
little
energy
is
required to produce this type of
fracture.
brittle
Some
materials,
like glass,
always fracture in a completely
manner. On the other hand, a few metals, among them the plaincarbon and low-alloy steels, behave in a ductile manner under some con-
Dynamic
83
Charpy Impact specimen

-?-
/--
ajs.*'
Y-45"
0. J/5"
^0.01-Bad.
Alternate Charpy
impact specimen
0.395?'
*SM
-l.l024~iO.OI9P
-o.OOO-
1 0.001 \
)
0.3I5~0.00I- '-O.OI'Rad.
.
Izod impact specimen

Fie. 5.2.
Standard impact specimens.
(American Society of Testing Materials)
ditions, such as in the ordinary tensile test; however, they can break in an almost completely brittle manner under certain other conditions. The
three most important conditions which tend to bring about this transition from ductile to brittle behavior are high strain rates due to shock
low temperatures, and the presence of notches (Fig. 5.1). Thus may bend without breaking under a static load at room temperature if smooth, but may snap with a brittle fracture if a sharp notch is located in the region of stress, and/or the load is suddenly applied, and/or the temperature is sufficiently lowered.
loads,
a certain steel part
In testing,
it is
often convenient to hold constant the notch condition
and strain rate and to use the temperature zone or transition temperature at which ductile behavior ceases as an index of the susceptibility of the
Many different types of tests and specimens have been used. The Charpy and Izod tests are common in the United States. The specimens used are shown in Fig. 5.2. The pendulum of the
material to brittle fracture.
testing
machine
falls
the notch.
The
from a definite height and breaks the specimen at energy absorbed during fracture is measured from the
backswing of the pendulum. Typical results are shown in Fig. 5.3. It can be seen that a drastic decrease in ability to absorb impact energy occurs when the temperature is below the transition range. In order to understand how brittle fracture can occur in ordinarily ductile materials, it must be realized that several entirely different mechanisms can cause fracture. The brittle type of fracture occurs when
the highest tensile stress reaches a critical value,
and
is
almost indepen-
84
-I7S
Temperature, deg.C.
-150
tJ
-I2S
,J
-100
1
-75
A,
-50
!_,
-25
I '
70 r
+25
-300
-250
-200
-150
-100
-50
+50
+100
Temperature, deg. F.
Tig. 5.3.
Transition
temperature
steel;
steel;
curves
for
various
steels:
(A)
18-8
austenitic
stainless steel;
(B) annealed low-carbon 3.5 per cent nickel steel;
(C) annealed low-
carbon 13 per cent chromium

nickel, 0.6 per cent
chromium
(D) normalized 0.35 per cent carbon, 15 per cent (E) annealed 0.35 per cent carbon steel; and (F)
normalized 0.35 per cent carbon

others had
notch.
steel. Specimens for steels B and E had keyhole notch; (The International Nickel Company)
dent of other types of
stress.
On
the other hand, the ductile type of
fracture occurs only after plastic yielding has taken place, which begins
when
the
maximum
is
shear stress reaches a critical value. As the load on a

is
ductile material
increased, the critical value of shear stress

critical
ordinarily
reached before the
value of tensile
stress,
consequently plastic
deformation and ductile fracture result. If by some means the critical shear distress could be raised so high that the critical tensile stress were reached first, brittle fracture would occur. This is exactly what happens at high strain rates, since increasing the strain rate raises the
Low temperatures have a similar effect, since the yield strength of most metals increases by a factor of around 2 as the temperature is lowered from room temperature to the boiling point of hydrogen.
yield strength.
The
but
brittle tensile strength
is
also affected
by strain rate and temperature,
to a lesser degree.
Since brittle fracture results from exceeding a critical tensile stress and ductile fracture from exceeding a critical shear stress, any means by
Dynamic
which shear
85
is reduced or suppressed will tend to promote This is what is accomplished by notches. Consider a cylindrical tensile specimen with a circumferential notch or groove. As the load is increased, the first effect of the notch is to produce elastic
stress in a part
brittle fracture.
stress
concentration at the root of the notch.

is
With
further increase in
load, the elastic limit
reached, and plastic yielding relieves the stress concentration. As the core of the circumferential notch undergoes plastic
elongation,
it
must
also contract in a transverse direction, pulling in
on
the metal surrounding the notch.

verse direction.
The surrounding
metal then pulls
back out on the notch core, subjecting it to biaxial tension in the transActually, however, the notch core is in a state of triaxial tension, as the external axial load on the specimen is still acting. In a system of equal triaxial tensions, the shear stress is zero. Thus the effect of the notch is to suppress all or part of the shear stress which would
ordinarily be present in the tensile specimen, leaving the
tensile stress to
way open
for the
high to exceed the critical value for brittle fracture. This effect of the notch is called plastic constraint. In addition to high strain rates, low temperatures, and notches, numerous other factors tend to a lesser degree to promote the transition from
sufficiently
become
ductile to brittle fracture.
Some
of these factors are: increased size of
part, large grain size, pearlitic rather
than martensitic microstructure,
certain deoxidation practices,
and prior cycles of fluctuating load. Although the ferritic steels are the most important alloys which exhibit the phenomonon of a transition from ductile to brittle fracture, other metals, such as zinc alloys, tin alloys, and magnesium have been shown to behave similarly. On the other hand, aluminum, copper, nickel, and austcnitic steels (Fig. 5.3) have thus far failed to show a transition temperature.
5.2.
Value of the Notched-Bar Impact Test
It is evident from the foregoing discussion that the chief value of the notched-bar impact test is in classifying materials according to their tendency toward brittle fracture. It is rapid and cheap and gives informa-
tion that
no other
it
test gives at present,

its
provided that
evaluation.
common
sense
and
experienced judgement are used in

of development
In the present state
has a
number
of disadvantages.
Transition tempera-
one type of specimen and machine cannot be directly correlated with values obtained with different specimens and machines;
similarly, test results
tures obtained with
parts
under
service conditions.
inherently brittle
cannot be directly correlated with results on full size Furthermore, it is not a reliable test for materials like cast iron and hardened tool steels. De-
86
Fig. 5.4. Typical fractures of fatigue specimens with unclistortcd area (A) (Moore) and (B) at side. (Johnson)
in center
spite these disadvantages, the engineer
and metallurgist have found the
notched-bar impact
exclusion
test to
be a valuable tool.
test to detect steels

it is
It is used primarily as an with high tendency toward brittle fracture.
In industry
mobiles,
used by manufacturers of ordnance, aircraft, and autosteel
who
have found as a result of experience, that
which ex-
ceeds a certain
minimum impact
resistance in the laboratory gives satis-
factory service in applications
where low temperatures and shock loads
are encountered.
5.3.
The Mechanism of Fatigue man

has used metal for moving parts, he has noticed that
Ever since
would sometimes fail were relatively low. Usually the failure would be sudden: an axle that had been forged from steel of excellent ductility would snap off short as if it were brittle. Examination of the fracture would show a dull area usually surrounding an oval-shaped area of bright
after a period of satisfactory service such a part
stresses
even though the
crystals (Fig. 5.4)
Although
all
details
of
the
mechanism
of
fatigue
failure
are
this
not
pro-
thoroughly understood, the main events which occur during gressive type of failure may be summarized. Under repeated
stress the
metal yields at one or more local areas of weakness, usually at some surface defect where elastic stress concentration occurs. Eventually the atomic bonds are broken, resulting in submicroscopic cracks at the ends of which
Dynamic
87
I'io.
5.5.
R.
R.
Moore
high-speed
machine
for
rotating-hcam
fatigue
testing.
may be high concentrations of stress. As the stress on the piece is repeated, the crack or cracks spread. After a time there is so little sound metal left that the normal stress on the piece is higher than the strength
there
of the remaining material,
and complete fracture
occurs.
of a typical fatigue fracture is explained by the fact that as failure proceeds the severed surfaces rub and crush each other and
The appearance
produce a dull appearance; while the remaining unfractured portion preserves the normal grain structure up to the moment of fracture.
5.4.
The Endurance Limit

is
perhaps not the best word to use in referring to the type of it is too firmly entrenched in metallurgical and engineering terminology to be dislodged. The term endurance is
failure
Fatigue
under discussion, but
also
of a metal or alloy is the stress below which the material will not fail if subjected to an infinitely large number of cycles of stress. It is determined in a number of ways, the most common of which is by alternate flexure, usually known as the rotating beam method. A polished specimen of suitable size, which is rotated in a specially designed machine (Fig. 5.5) is subjected by dead weights to alternate tensile and compressive stresses.
,
commonly used. The endurance limit
A number of identical specimens are prepared from a single material. he first is run at a stress which is considerably higher than the expected endurance limit, and the number of cycles causing failure
I
is
noted.
The
for
stress
reduced for the next specimen; this process for steel, there is no fracture after 10 7 cycles of stress.
is
is
continued until,
stress
(S)
The
88
'104
105
106
I0
108
Cycles
Flo, 5.6,
Typical S-N curves for carbon
steels.
(Moore and Kommcrs)
each
number of
.
(Fig. 5.6)
The
cycles (N) is plotted; the result is the S-N diagram value for S which the horizontal portion of the curve
represents
is
the endurance limit.

steels
Although same is true

limit,
for
have a definite endurance limit, it is doubtful if the most nonferrous alloys. At any rate, the S-N diagram for
nonferrous alloys usually does not show an abrupt knee at the endurance but rather consists of a gradual curve with the portion at lower stresses becoming approximately horizontal only at a very large number of
cycles of stress.
In reporting results of fatigue

life,
the endurance strength (or fatigue strength)
tests on nonferrous alloys corresponding to a certain
number
a well
such as 500,000,000, is usually given, since not found. The importance of determining the endurance limit or endurance strength, even though the test takes a long period of time, is evident when
of cycles of fatigue
denned endurance
limit
is
it
is
recalled that airplane propellers, turbines, etc.

life.
may
easily
run a
billion cycles during their useful
5.5. Relation of the

If
Endurance Limit
is
to
Other Properties
determined by the rotating-beam method using carefully polished specimens of proper design, the value obtained for most carbon and alloy steels is about one-half the tensile strength (Fig. 5.7) As there is a fairly close relation between tensile strength and
.
the endurance limit
hardness,
limit
follows that there is also a close relation between endurance and hardness; the former is about 250 times the Brinell hardness number (Fig. 5.7) There seems, however, to be no correlation between endurance limit and any other property of ferrous alloys.
it
.
Dynamic Properties
Brinell hardness
,,0
of Metallic Materials
89
number
600
100
200
300 400 500
20
40
60
80 100 120 140 160 180 200 220 Tensile strength, thousand lb per sq. in.
240
260
280
Fig. 5.7.
ness.
Relation of endurance limit of (Moore)
steel
to tensile strength
and Brinell hard-
The above relations among endurance limit, tensile strength, and hardness hold for carbon and alloy steels of any composition and heat treatment except those treatments which produce very high hardness,
and may be used
ever, the actual
as approximations in design. For refined design, howendurance limit of the material must be determined, as this may in individual cases vary between 35 and 65 per cent of the tensile strength. Cast steel (not heat treated) has an endurance limit of about 0.4 times the tensile strength, somewhat below the average for wrought steel. Cast iron has a ratio of 0.3 to 0.35. Attempts to correlate endurance strength of nonferrous alloys with tensile strength are not very successful; the endurance strength may be less than 25 per cent or more than 50 per cent of the tensile strength.
5.6.
The
Effect of Notches
on the Endurance Limit

polished specimen
The endurance limit of a carefully as much as 50 per cent by a notch.
may be reduced
In actual machines and structures notches of some sort are almost invariably present in some form such as
rough surfaces, tool marks, holes, screw threads, keyways, fillets, inclusions, gas cavities, etc. (Figs. 5.1, 5.8) The effect varies with the kind of
.
90
Fie. 5.8.
fillet
about
Failure of a crankshaft starting in a sharp \/ 2 in. above and to the left of the arrow.
fillet.
The
crack started in the
the notch sensitivity of the material. For hard notch can be approximately predicted by the elastic stress concentration as calculated by mathematical theory or as determined by photoelastic studies. For ductile steels the effect of the notch is usually
notch,
its
location,
and
steels the effect of the
less severe.
The effect of a number
of different surface conditions
is
shown
in Fig. 5.9.
As a general rule the damaging effect of a notch in carbon and alloy and in some nonferrous alloys increases with its sharpness, that is, with increase in the ratio of its depth to the radius of its root. Usually a notch becomes harmful of this ratio exceeds 28 or 30. When shallow notches are present, hard steels with their relatively high endurance limits are superior to low strength steels. On the other hand, with sharp notches present, a soft steel with low notch sensitivity may be superior to a high-strength high-endurance steel with high notch sensitivity. Gray cast
steels
Dynamic Properties
91
Tens
GO
le
strength .thousand
100
'
lb.
per sq
160
1
in.
80
120
1
140
1
180
i_
200
aIC
b
c
20
in
*40
\s \ \
s
S.
J
P<0
5
\e
i
"fin
\f
9
1
B o o 70
V- notch
flO
.
"
-
y\l
O.lmm.
7.5
so -
mm. tj>
inn
i3
iJ
i)
a3
9> 3
K j
15
E 3
>
Tensi e str<
ngth kg.p er
sq. mrn.
Fig. 5.9. Decrease in endurance limit for carbon and low-alloy steel specimens having the following surfaces: (a) polished, (b) ground, (c) roughened, (d) circumferential V notch, (e) decarburized, (f) corroded in tap water, and (g) corroded in
salt water.
(Z.
Ver. deut. Ing., v. 77, 1933)
iron,
although inherently
fact to
brittle,
is
relatively
insensitive
to
notches.
Another important
remember
is
that a decarburized surface, while
not acting as a notch, lowers the endurance limit of the whole section to that of a steel whose carbon content is the same as the surface layer,
since fatigue failure usually originates at the surface. As Fig. 5.9 shows, the effect of a decarburized surface may be greater than the effect of a sharp notch.
Chafing or fretting the polished surface of steel or nonferrous alloys, a form of wear which occurs in parts which are intended to fit tightly
but which
limit.
slip slightly
under fluctuating
loads, reduces the
endurance
92
5.7.
Corrosion Fatigue
If a polished metal specimen becomes corroded before testing, the endurance limit is lowered somewhat, an effect which would be expected in view of the roughening of the surface. On the other hand, if a polished
specimen
stress,
corroded simultaneously with the application of repeated is lowered to a much greater degree. As a matter of fact, there is probably no true endurance limit in corrosion fatigue, since with sufficient time the corrosion alone would produce failure even at very low stresses. Some data indicate that carbon and low-alloy steels
is
the endurance limit
subjected to simultaneous reversed stress and corrosion will
fail at stresses
5000 cycles or more)

as as
low
lb.
.
per
sq. in. if
they are run long enough
(100,000,000
The
data given in Fig. 5.9 indicate that a combination

a loss of
of corrosion
limit
if
and fatigue causes

is
about 50 per cent of the endurance

if
the tensile strength

is
low, and a loss of about 90 per cent
the
strength
is
high.
The
corrosion fatigue strength of most nonferrous alloys
likewise only a small fraction of their endurance strength in air. For high resistance to corrosion fatigue a material must have an oxide skin which is tightly adherent and at the same time flexible enough to withstand repeated stressing without breaking. Among ferrous alloys, only the high-chromium stainless steels normally have such a skin. Corrosion
of carbon and low-alloy steels results in corrosion products which, being
and expose the underlying surface to further some highly alloyed steels, are reduced by simultaneous corrosion and repeated stressing to a common low level of resistance, there are only two things to be done in such applications: use a stainless steel, or protect the surface by plating with some metal that will form a continuous corrosion-resistant coating. According
brittle,
fracture readily
attack. Since all ferrous materials, except
to present
knowledge, electroplated zinc or cadmium coatings are
best.
5.8. Increasing the
Endurance Limit by Shot Peening
Shot peening,
or fatigue
life
if
properly controlled, can increase the endurance limit
25 to 100 per cent or more. Shot peening consists of sub-
jecting the surface of a finished metal part to a hail of metallic shot that has been released by the blades of a revolving wheel or by an air blast.
The
work the outer layer, and hardness and decreasing the ductility of this region. At the same time, the cold working introduces longitudinal compressive stresses near the surface. Surface-rolling is an alternate method that produces the same effects. The resulting increase in endurance limit is due to two factors: (1) the increase in strength of the surface layer due to the cold work; and (2)
shot, in striking the surface with force, cold
increasing the strength
Dynamic
93
the residual compressive stresses set up in the surface layer. Opposed to these favorable circumstances, however, are the roughening of the surface
and the formation of a large number of shallow

localized stress concentration.
if
pits that
is
may
cause
If the
shot peening
carefully
done and
the size of the shot
result of the operation
life. Shot peening is manufacturers for improving the life of crankshafts, camshafts, connecting rods, steering knuckles, transmission shafts, gears, and other parts.
and the velocity of impact are controlled, the net is a marked increase in endurance limit or fatigue now used regularly by some automotive and aircraft
5.9. Significance of
Endurance Data
Endurance limits that have been obtained under controlled laboratory conditions on carefully designed polished specimens are valuable in the design of machines and structures subject to repeated stresses, but they should be used only with full realization of their somewhat limited significance. Such endurance data give information of one kind only; conditions in service are rarely so simple that these data can be used without
considering other factors.
Most structure and machine parts are subjected to more or less random fluctuations of load; however, most fatigue tests are run under conditions
of constant
maximum and minimum

satisfactory
no completely
method
stress. At the present time there is of correlating the behavior of a speci-
men under cycles of varying stress amplitude and the behavior of another specimen under cycles of constant stress amplitude. It is certain, however, that the
history.
If a
endurance limit of a specimen may be affected by its stress specimen is understressed, or subjected to a few million
as
lower than its ordinary endurance limit, its final determined later will be considerably increased. If a repeated stress slightly above the endurance limit is applied for a small number of cycles, an improvement similar to that produced by understressing is sometimes observed. On the other hand, higher values of repeated stress and larger number of cycles may damage the material, and its endurance limit as subsequently determined will be reduced.
stress slightly
cycles of
endurance limit
Another important factor is surface condition. Parts in actual service are rarely as highly polished as most laboratory fatigue specimens, and full consideration should be given to the character of the surface, including the possibility of corrosion and accidental defects, and to how much a roughened surface may reduce the endurance limit. All in all, a great many complicating factors including surface condition, variable stresses, external and internal stress raisers both intentional and unintentional,
notch
sensitivity, possible decarburization
during heat treatment, residual
94
Cast iron
mmmtmHmmmm
Carbon s+eel
Aluminum
Fie. 5.10.
alloy
carbon
steel,
Damping
curves for cast iron,
and an aluminum
alloy.
(Pohl)
stresses,
and combined
stresses
must be considered
in problems involving
fatigue.
5.10.
If a
Damping
Capacity
is
metal or alloy bar
supported
at
one end and
if
the free
end
is
hammer, the bar will vibrate for varying lengths of time depending upon the composition, the stress imposed, and other factors, but at a uniformly decreasing rate owing to the internal friction of the material which dissipates the energy as heat and sound. The dissipation of energy per unit volume of the material for one cycle of stress is the damping capacity. It may be reported as inch-pounds per cubic inch,
struck with a
or as centimeter-kilograms per cubic centimeter, per cycle.

capacity
loop.
ratio.
is
Damping
usually measured by the area of the stress-strain hysteresis
The
ratio of this value to the work of deformation is the damping This increases with the capacity of the material to damp out
vibration.
There is apparently no direct relation between damping and any other mechanical property. In most cases the ability of a steel to damp vibration decreases as the tensile strength increases.
Of
ferrous materials, the
strong alloy steels usually have the lowest, and cast iron and low-carbon
steels the highest
damping
capacity.
tions to this generality as steels of the
strength
may have
very different
There are, however, many excepsame composition and tensile damping capacities. Typical curves
Dynamic Properties
showing
It
95
free vibrations
Fig. 5.10 for cast iron,
clamped only by internal friction are shown in carbon steel, and duralumin.
has been suggested that the endurance limit might be predicted from capacity, although attempts to correlate the two have not been successful. There is, however, some evidence that damping capacity is related to notch sensitivity. For, example, cast iron has a high damping
damping
capacity and
is
relatively insensitive to notches;
duralumin, with
vibrations.
high
notch
sensitivity, has a very
low capacity to
damp
question, however, that the
damping
capacity of a
There is no material is an im-
portant criterion for

crankshafts
in
internal
If
quently occur.
applications. For example, in combustion engines resonant vibrations frea material with high damping capacity is used, the
its
usefulness in
many
energy of vibration is dissipated by internal friction and the peak amplitude of the vibratory stresses is held to a low level, thus minimizing
the possibility of fatigue failure.
QUESTIONS
Define the terms notch brittleness and notch sensitivity. Give an example to illustrate the importance of each of these properties in engineering. 2. What is the chief value of the information gained from notched-bar impact tests?
1.
3.
What
are
some disadvantages
of the
common methods
of notched-bar im-
pact testing?
4.
Why
is
a fatigue fracture usuallv characterized by a bright area surrounded
by a dull area?
5. 6.
7.
Define the terms endurance limit and endurance strength.

Sketch typical S-N curves for a steel and an
aluminum
alloy.
(a) the en-
How many
durance
alloy?
cycles of testing arc usually necessary to determine limit of a steel, and (b) the endurance strength of
an aluminum
8.
A recent
What
expedition exploring Greenland experienced considerable difficulty with breakage of almost new vehicle tracks. What was the probable cause
of these failures?
is
9.
the approximate endurance limit of
alloy steel with a tensile strength of 150,000 psi and a ultra-high strength steel with a tensile strcngdi of
surface,
and
(c)
annealed
steel
with a
quenched and tempered ground surface, (b) 280,000 psi and a ground Brinell hardness of 200 and a V(a)
notch?
10.
If
service,
11.
a suspension spring on your automobile breaks after 60.000 miles of what is the most probable cause of failure?
What is the approximate endurance limit of a steel having a tensile strength of 140,000 psi if the surface is (a) ground, (b) heat treated with a smooth but decarburized surface, and (c) heat treaded with a rough, pitted, oxidized surface?
96
12.
Engineering Metallurgy The

gear teeth of an automobile transmission
testing machine,
may
fail in fatigue.
Assuming
that the endurance limit of the steel lias been determined on a rotating*
beam
13.
what
factors
would you consider
in deciding
upon
an
a suitable operating stress in the gear teeth?
During preliminary
abrupt
fillet.
testing of a
crankshaft, fatigue failure occurs at
dimensional restrictions it is undesirable to increase the fillet radius. Can you suggest another method by which the fatiguestrength of the fillet may be substantially increased?
to
14.
Due
What
advantage would gray cast iron have over other materials for use
as
a frame for a precision

15.
machine
tool?
Railroad car axles are frequently surface-rolled over the region where the wheel is pressed on. What benefit may be gained by this operation?
16.
The
elastic stress concentration factor of a notch or similar discontinuity can frequently be determined by photoclastic studies of plastic models. To what extent can information of this type be used in predicting fatigue behavior of metal parts with similar discontinuities?
17.
are available, fatigue testing of actual parts
Although fatigue data for standard specimens of many different materials under simulated service conditions is widely practiced. Can you suggest some reasons for this?
using a high-
18.
Under what
conditions might there be no advantage in strength steel for a part, even though it is heavily loaded?
19.
For certain applications, such as bridge cable and helical springs, colddrawn steel wire strengthened by work-hardening is preferred over steel wire strengthened by quenching and tempering. Why?
20.
Why
can the shank area of
a bolt
be turned
down
to considerably less
dian
the root area of the threads without decreasing die strength of the bolt
under fluctuating loads?

CHAPTER
Theodore Allen,
Jr.,
M.S.M.E., Associate Professor of
Mechanical Engineering, University of Houston, Houston, Texas; Engineer Associated with Anderson,
Greenwood and Co., Bellaire, Texas John K. Anthony, M.S., Associate Professor
of Physical
Metallurgy, University of Arizona, Tucson, Arizona
6.1.
Solid State
Thermodynamics and Thermostatics
1 HE study of physical metallurgy would hardly be complete without the mention of solid state physics; indeed, it is just a small portion of that vast field. For reason of simplicity the metallurgist often refers to a "system." A system may be defined as an arbitrary portion of matter which has been isolated from the rest of the universe by prescribed boundaries. The system is merely separated by these boundaries from its environment for the purpose of analysis. A phase may be defined as a portion of homogeneous matter in a system. When a system undergoes a phase change, this change must take place at a rate which is infinitesimally slow, or equilibrium can not be maintained during the change. This is not novel, for thermodynamic processes which are reversible necessarily require the state point to pass through a series of quasi-static or quasi-equilibrium states. In this sense, then, reversible or equilibrium changes should be classified as thermostatics while actual changes which proceed at a finite rate are truly thermodynamic changes of state. The study of metallurgy includes such non-equilibrium phase changes as those that produce coring, segregation, and other irreversible processes as well as those processes which are carried out slowly enough to produce a "near equilibrium" change of state.
6.2.
Concept of Dynamic Equilibrium

has been said in the preceding paragraph, one might infer
is
From what
that this concept of equilibrium
a static sort of thing;
such
is
not the
97
98
case.
a macroscopic point of view this assumption would be tolerfrom the microscopic point of view the picture is a dynamic one. To be specific, two phases of a pure substance may be in equilibrium with one another, and the molecules of one phase may be escaping into
able, but
From
the other phase, while those of the second phase are escaping into the first, ff this exchange were taking place so that the net transport of mass,
momentum, and energy

brium.
It
is
is
zero, then the
a well established fact (the

its
two phases would be in equiliSecond Law of Thermodynamics)

existed
that nature tends to equalize
potentials; a system, then,
equilibrium
if
no unbalanced tendency
would be in which would bring about
a change of state provided this tendency was active. With respect to the escaping tendency of a component from one phase to a second phase in chemical equilibrium with the first, it may be said
that the fugacity of a
fugacity of that
persist.
component in one phase must be equal to the same component in the second phase for equilibrium to
6.3. Cooling
Curves
Useful in equilibrium studies are cooling curves. These curves present it is being heated or cooled. Consider the cooling of liquid O. The (temperature-time) curve a
the temperature history of a system while
for
from some arbitrary temperature, say 80F, is a line with a negative slope. The temperature decreases with time until a temperature of approximately 32 F (corresponding to standard pressure of 14.696 psi, abs.) is reached. At this point the formation of another phase
it,
starting
(ice)
occurs.
is
The
.
cooling curve
is
is
then a horizontal line until
all
of the
liquid
frozen
(the delay
of this chapter)
sults in a
Upon
explained by the phase rule in section 6.5 completion of solidification, further cooling re-
drop
in
simplest possible because only tem.
temperature with time. Such a cooling curve is the one component, H,0 is present in the sysis
The
concentration and nature of a component
required to specify
In the above example, there was one phase (liquid, composed of 100% H a O) at the start of cooling. Next, two phases coexisted (liquid and solid, each composed of 100% H,0) Finally, a single phase (solid, composed of 100% FLO) existed. Frequently a system may contain two or three components. Such systems are referred
.
the composition of a phase.
to as binary
and ternary systems, respectively. The number of components is not limited to three or any number in particular. Suppose the water had been cooled very rapidly from SOT. Chances are very good that ice would not have formed at 32F, but at a somewhat
99
lower temperature. It is possible to cool the water below 32F without the formation of ice. However, the addition of a small crystal of ice to serve as a nucleus causes solidification. Freezing can also be brought about by disturbing a super-cooled liquid. Super-cooled liquid water in this state is not characterized by stable equilibrium. This illustration serves to point out the influence of cooling rate on equilibrium. The only way to freeze liquid water at exactly 32F (if this be the "absolutely correct"
freezing point)
is
to cool
it
infinitesimally slowly; otherwise the solidifi-
cation will begin at a temperature lower than 32F, the amount of departure being a function of the cooling rate. The depression of the freez-
ing point
is brought about because of time necessary for solidification to begin after the freezing point is reached. The student of thermodynamics will again recognize the influence of time on the irreversibility of proces-
ses.
When
employed
ice
is
melted, the melting begins at a temperature slightly

the heating rate
is
above 32 F
if
greater than zero.
way frequently
is
to determine the "correct"
freezing or melting point
to
construct a heating
and a cooling curve based on a minimum rate of temperature change and to interpolate between the "depressed" freezing point and the "elevated" melting point.
Cooling curves for alloy systems can be determined experimentally for various concentrations of the components, and these curves may be used
to construct equilibrium or constituent diagrams such as presented in
Section 6.7 of this chapter.
6.4. Solid State
Mass Transfer
it is
The
is
rate of mass transfer or diffusion, as
commonly
referred to,
given by Fick's
Law
in the following
fundamental form
m=-DA^ ax
in
? is the change of concentration dx in the direction of the diffusion path, per unit of path length, A is the cross sectional area of the path (this area is normal to the path) and D is a coefficient of mass diffusivity. The minus sign indicates that the mass
is
,
which
the mass transfer rate,
transfer takes place in the direction of decreasing concentration. It is through the process of diffusion that a solid solution of several metals may
be homogenized. If a large concentration of one component exists in a localized form in a solid solution, it will diffuse. The concentration provides a gradient which gives rise to the mass transfer.
100
process of diffusion
is
The
very slow for solids at ordinary

coefficient
room
temperatures.
However, the
of mass diffusivity
varies ex-
Because of
centration
ponentially with the absolute temperature of die material being diffused. this increase in diffusivity at elevated temperatures, a conis
diffused in a matter of minutes at 1500F that
would prob-
ably take several centuries at
room temperature. For
this reason, alloys
which are heterogeneous because of rapid and irreversible cooling are homogenized at elevated temperatures in annealing ovens.
By
6.5.
gations
the process of dilfusion (a "self-homogeni/.ing action") solid aggrebecome homogeneous (and thence become phases)
The Phase Rule
In the latter portion of the nineteenth century, the phase rule was advanced by J. Willard Gibbs. It is largely because of the work of Gibbs that our knowledge of phase equilibria is as advanced as it is today. The
is a short explanation of how the phase rule may be derived. Equilibrium is assumed; therefore, the fugacity of a component in one phase is equal to the fugacity of the same component in any other
following
phase.
If there are
phases in the system, then equilibrium provides
(N p -1) equations per component. In a system of N components, there are N c (N p -1) fugacity equations. The concentration of all the components in a particular phase must sum to unity. This fact provides N p independent equations. The number of variables that are independent,
(also called degrees of
freedom)
are then equal to the difference be-
tween the
total
number
of variables
and the number of independent
equations relating these variables. The total number of variables are N c N due to composition plus any two thermodynamic coordinates. It follows then that
N =
r
[N c
N p + 2] [N.
f
(N p-1)
2
or
N =N-N +
This
is
the phase rule of Gibbs. By way of illustration, attention is again directed to the freezing of the water. When two phases of the one
component were coexistent, the phase rule indicates that there was only one independent variable. This is evidenced by the fact that once the pressure (a thermodynamic coordinate which was arbitrarily taken as
independently chosen, the temperature is fixed. for two phases and one component. Upon completion of freezing, one phase existed. Now there are two variables that are independent according to the phase rule. After solidification is complete, the temperature varies although the pressure has been arbipsi,
14.696
abs.)
is
(in this case at
32F)
trarily selected.
101
further application of the phase rule, the following quesadvanced. Can three phases of a single component exist simultaneously? The phase rule indicates that this is possible, but that there would be no independent variables. This means that the state where the three phases coexist is fixed ( that is, there is a definite temperature and
tion
is
To examine
pressure for a given

fest itself)
.
The
component where triple phase coexistence can manitemperature and pressure are not arbitrary once the
is
component
(the system in this case)
selected.
The
reader will recog-
nize this concept as the "triple point" in physics.
The
lurgy.
fixed.
phase rule
It
is
is a valuable tool in the field of experimental metaluseful in predicting the phase equilibria once the system is
phase rule does not apply to the prediction of state configurafrom non-equilibrium effects, nor is the rule applicable to a vacuum. The phase rule is based on the assumption of equilibrium
tions that result
The
and
the existence of a system.
6.6. Solid State Solubility
Solid phases form solutions mechanism of explanation here

liquid solutions.
do liquid and gaseous phases. The the same as that for the familiar Solid solutions can be formed by atoms of the solute
as
is
much
replacing atoms in the crystalline structure of the solvent. This type of solid solution is referred to as a substitutional solid solution. Another
common
type of solution
is
the interstitial solid solution, in which the
atoms of the solute locate in the

of the solvent.
solution.
interstices of the crystallographic planes Iron, iron-carbide alloys are examples of this type of
The
to as a metalloid, since
smaller atoms of carbon are the solute. Carbon is referred it has metal as well as nonmetal characteristics.
One of its predominant

resistance slope.
nonmetallic properties
is its
negative temperature-
Section 6.7 shows equilibrium diagrams of some binary systems with varying degrees of solubility between components. It is possible to have supersaturated solutions in the solid state; martensite is a common ex-
ample of a
6.7.
solid solution containing
an excess of carbon.
Binary Systems
The constitution of metallic alloys is studied by preparing a series of high-purity alloys ranging in composition from 100% of one constituent or component to 100% of the other component. Suitable specimens of these alloys are subjected to treatments that produce a state of equilibrium. This step is followed by studying the changes in length, electric
resistivity,
microscopic structure, atomic structure, absorption or libera-
102
M.P. of
Ni
CC =
alpha
solid solution of Cu+Ni
Cu
Ni
f
0%N;
100% Cu
25%Ni 75% Cu
50% Ni
50%Cu
Composition (by
75%
wt.)
Ni
lOOZNi
25% Cu
0%Cu
Fig. 6.1.
Equilibrium diagram
for the
Cu-Ni system.
tion of heat (thermal analysis)
alloy
is
and other changes that occur when the heated or cooled to room temperature or sometimes to the melting
,
point and above.
The
plotted against the composition; the result
temperatures at which the changes occur are is an equilibrium diagram
(also called a constitution or phase diagram) of the series. A diagram showing changes between two metals is called binaiy equilibrium diagram.
Solid Solution Alloys.
or miscibility in
all
A few binary alloys exhibit complete solubility proportions and temperatures in the solid state.
These are called solid-solution alloys. Typical of this type is the Cu-Ni system. Development of an equilibrium diagram for Cu-Ni by thermal analysis is shown in Fig. 6.1. (The cooling curves shown have been
previously discussed in Section 8 of this chapter)
The
is
line, 1-2-3-4-5,
is
the liquidus line,
and everything above and everything below

<x )
this line
liquid or melt (also indicated as
m)
this line
The
is
line, l-2'-3'-4'5, is the solidus line,
solid solution or alpha (also, indicated as
(The various solid phases not necessarily only solid solutions of an equilibrium diagram are generally shown by letters of the Greek alphabet
starting
from the extreme
left
of the diagram
a.
/?,
etc.)
To
trace the cooling of an alloy of Cu-Ni, refer to Fig. 6.2.
Here
alloy
"A" was chosen, containing

dotted line)
Cu, which represents approximately the composition of Monel metal (shown by the vertical
63% Ni and 87%
103
\rm
Tc-
_ftrja
Td
Cu
Composition
Equilibrium diagram for
Ni
Fig. 6.2.
63%
Ni and
37%
Cu.
The following stages on cooling may be noted (cooling must be slow enough so that equilibrium conditions prevail) 1. At temperature Tm, the alloy is completely molten.
:
2.
3.
4.
5.
molten until the temperature reaches Ta. crystals of solid solution appear and will have the composition as shown at a' (by drawing a horizontal line from a until it intersects the solidus line) The composition may be read by dropping a vertical line from a' to the composition axis. On further cooling to Tb, more solid solution crystals appear, with the composition changing along the solidus line from a' to b', and the composition of the remaining melt is shown by dropping a vertical line from b on the liquidus line to the composition line. Thus, on cooling between Ta and Td, the composition of the melt
alloy stays
The
At Ta, the
first
become richer in Cu from a to d and the composition of the from a' to d'. At any temperature, Tc, between Ta and Td, the relative amounts of solid and melt may be calculated as follows:
will
solid solution crystals will vary
Let
Wt =
total
weight of alloy,
of solid.
(or)
Wm = weight of melt,
Ws = weight
Then, Wt = And, Wt X
of
Wm + Ws,
Cu
Ws = Wt Wm.
[6.1]
Cu
in the original alloy will represent the total present.
amount
Wm x % Cu m will represent the amount of Cu present in the melt. Ws X % Cu, will represent the amount of Cu present in the solid.
(Cu n
,
& Cu
represent the composition of the melt
and
solid re-
104
spectively as read by
dropping
vertical lines
from
&
c',
the horizontal line at temperature

solidus lines.
Tc
intersects the liquidus
where and
Then:
Wt X
% Cu
Wm X % Cu m
100
100
Ws X
"
% Cu
100
6.2,
By substituting the value of Ws from Equation 6.1 in ated and Equation 6.2 becomes:
Ws
is
elimin-
Wt X
(or)
100
% Cu = Wm X % Cu
100
n,
Wt X
"
%
100
Cu,
Wm X % Cu
100
Wt x % Cu- Wt X % Cu 8 = Wm X % Cu m -Wm X Wt (% Cu _ % Cu ) = Wm (% Cu - % Cu )
B ra 8
Cu
At temperature Tc, the composition of the original and the composition of the melt is 54% Cu, and the composition of the solid is 28% Cu.
Let 100# represent the
100 (37-28)
total
alloy
is still
37%
Cu,
weight of the original
alloy; then,
= Wm
(54-28)
Wm
.".
= 1Q0X9 =34.5#
26
or 34.5%;
Ws =
65.5# or 65.5%.
Principle.
The Lever
Since the length of the horizontal line
is
pro-
portional to the composition, the above problem

so-called lever principle.
may be
solved by the
Illustration
The The The
length of the line c-Tc-c'
is
26 units
17 units
length of the line c-Tc

length of the line Tc-c'
is is
9 units
100
Therefore,
% of solid = -1^X 26
'
= 65.5%
.
c-Tc-c7
100,
and
% of melt =
ratio for
-^ X
*6
is
100
34.5%
Tc-c'
c-Tc-c'
100.
The
the melt
the distance from the nominal analysis the distance from the nominal
(fulcrum of the lever) to the solidus line over the total distance between
the lines.
The
ratio for the solid
is
analysis to the liquidus line over the total distance.
The
lever principle
may
be used to determine the relative amounts of

(both phases
each phase
when two
phases are present
may
be solid)
105
The
total
horizontal
lines of the
boundary
distance is always measured between the two two phases present, and the fulcrum is taken at
the nominal analysis of the binary alloy.
the
Application of the phase rule shows that a one-phase region, such as cc or areas, is trivariant: i.e.. there are three degrees of freedom.
N
1
+N =N +2 +N = 2+2 N =3
f
used in selecting a pressure of one atmosused in selecting a temperature which will locate the vertical position, and the third is used in selecting the composiis
One
degree of freedom
phere, the second degree

tion,
is
which locate the
lateral
position.
Thus, the three degrees are

in the single
utilized in fixing the position of
any point
phase area.
When
two phases are coexistent, as in the
m+
<x
region, there are
two
degrees of freedom.
N +N =N +2 2 + N = 2 + 2 N =2
p
f f
degree of freedom is used in fixing the pressure at one atmosphere. Therefore, if the remaining degree of freedom is used in fixing the
One
temperature (vertical position)
it if
follows that the compositions of the

first,
two phases are then fixed; or, the temperature becomes fixed.
Binary Eutectic Alloys.
in
the compositions are selected
then
the
liquid state
solid state, a
When two metals arc soluble in all proportions but only partially soluble in each other in the eutectic will be formed between the limits of solid solubility.
binary eutectic is a finely divided mechanical mixture of two solid phases and will exhibit a definite composition and definite melting point.
Cu-Ag form
alloys of this type as
shown in
Fig. 6-3.
Consider an alloy containing 6% Cu and 94% Ag. On cooling from some temperature above the liquidus line, the first phase change will occur when the temperature reaches the liquidus line. At this point, a, alpha solid solution will start to separate, with an initial composition as shown by drawing a horizontal line until it intersects the
crystals of
b. On further cooling, the composition of the alpha change along the solidus line and the composition of the remaining melt will change along the liquidus line; with more and more alpha crystallizing out and, consequently, less and less of the melt remaining. At point c the last of the melt will crystallize and the alloy will consist
solidus line at point

will
of solid alpha.
On
further cooling to the solubility line at point d, beta
solid solution will start to precipitate
from
the alpha as the solubility of
106
X
1200
108.1
1000
800
600
Solvus (or)
solubility line
Solvus
line
(or)
solubility
400
10
20
30
40
Wt.
Ao
Fig. 6.3.
50
60
70
80
90
Cu
Cu
for the
Equilibrium diagram
Ag-Cu system.
beta in alpha decreases with a decrease in temperature as shown by the
shape of the solubility
line.
Consider an alloy containing

the melt approaches the
to crystallize at the liquidus line.
20% Cu and 80% Ag. Again alpha starts On further cooling, the composition of eutectic composition. When the temperature has
remaining melt
will
dropped to the
eutectic, the
have reached the eutectic
composition. At this point, and on further extraction of heat, the melt

will crystallize isothermally to Eutectic.
Therefore, the various areas
may be
described as follows:
Area Area Area Area Area Area
1.
2. 3. 4. 5.
Two phases consisting of alpha plus precipitated beta. Two phases consisting of alpha plus eutectic. Two phases consisting of beta plus eutectic. Two phases consisting of beta plus precipitated alpha. A single phase consisting alpha solid solution only.
A
single phase consisting of beta solid solution only.
is
6.
Since the eutectic
a finely divided mechanical mixture of both alpha

(1, 2, 3, 4)
and
beta, the
combined area
can be designated as consisting
of alpha plus beta, but they will
be
in different physical states as described
above.
The precipitation of one solid phase from a solid solution is a very important factor in the heat treatment of alloys such as those of Al, Mg,
107
Atomic
10
%
40
Ca
50 60
70
20
30
60
90
Fie. 6.4.
Equilibrium digram for the Mg-Ca system.
and Gu. This type of treatment is known as "aging" or precipitation hardening and will be discussed in more detail in Section 6.8. Application of the phase rule will show why the eutectic reaction must
occur at a constant temperature.
N p + N = N + 2
f
N, N,
=2+ =
1
Again, one degree of freedom is used in fixing the pressure at one atmosphere; therefore, neither the temprature nor the composition of any of the phases can change during the course of the eutectic reaction under
equilibrium conditions.
6.8. Intermetallic
Compounds
Many alloy systems will exhibit one or more intermetallic compounds. This type of compound is generally very hard and brittle, and, under proper conditions, may impart additional strength ami hardness to an
alloy.
ally.
Therefore, intermetallic
compounds
are very important industri-
Compounds
of this type have a definite chemical formula, eg.
and have a
definite melting point

.
that shows as a
Cu s Al, maximum on the
liquidus line (Fig. G.4) This melting point may sometimes be higher than the melting point of either component. Phase diagrams of this type may be conveniently studied by considering them as two-part diagrams, i.e. the system Mg-MgXa and the system
108
^=^-
7s
is is
be
the solidus line. the CuAla solubility line.
*/
<
%Cu
Fig. 6.5.
4-56
' i
Al.-rUh end
of
Cu-AI phase diagram.
Mg2 Ca-Ca.
types.
Fig.
If
]Jy this
method the diagram

the Al
rich
is
simplifies itself into
two eutectic
6.5
represents
an alloy containing
2% Cu
will
end of the Cu-AI phase diagram. heated to temperature T, and held for a
become
a
sufficient length of time, the alloy will
homogeneous
this
solid sol-
ution.
Rapid quenching
then retain the alloy in
condition at
room temperature. This is known as solution treatment. On reheating this alloy up to temperature T,, (below the solubility line be) the intermetallic compound, CuAl 2 will precipitate from the solid solution. The amount of this precipitation will depend on time, temperature, and solubility. This step in the heat-treatment is known as aging or precipitation
,
hardening.
The
physical properties of certain alloys
may be markedly changed
by the heat-treatments described above.

6.9.
The
Peritectic Reaction
may be called an inverse or fake eutectic rewherein a liquid and a solid react isothermally to form a new solid. By examining Fig. 6.6, it will be noted that alloys of Li and Mg lying between the points a & P will first contain alpha solid solution and melt after crossing the liquidus line on cooling. At the peritectic temperature all of the melt will react with some of the alpha to form the
peritectic reaction
The
action,
new
to
solid,
beta solid solution.
Between points
P and
and
at
the
Peritectic temperature all of the alpha will react
form
beta.
If
with some of the melt an alloy were chosen such that its composition was ex-
109
40
50
60
Li
%
Fig. 6.6
Wi of
Equilibrium diagram for the Mg-Li system.
acily as
shown
at the peritectic point P, then,
on cooling
to the peritectic
temperature,
all of
the solid, alpha,
would
react with all of the melt to
form beta.
6.10. Closure
In recent years considerable progress has been
solids,
made
in
the field of
in the
and these achievements are
reflected in
no small measure
science of metallurgy as well as in other subdivisions of solid state physics.
New developments include transitors, transducers, solid rocket fuels, high temperature sealants, metal production technology, "light weight"
radiation shields,
and a host
of other innovations.
is
The
success
salient feature of the real progress in all of these fields
that
was accomplished by thorough consideration of the fundamental nature of the problem. The metallurgist of the future should be well versed in such items as quantum theory, radiation, and fundamental rheology. The physicist has helped the engineer to understand aspects of the solid state phenomena, but there is a need for further investigation by the research engineer.
110
QUESTIONS
1.
to the "lever principle", would such a rule apply to a two phase region in any plane where extensive properties were used as coordinates? Assume equilibrium exists and recall that an extensive property of a multiphase system is the sum of that extensive property for all phases of the system.
It is known from thermodynamics that constant pressure boiling of a pure substance (one component) takes place at constant temperature as long as the vapor is in contact and in equilibrium with the liquid. Explain this.
With reference
2.
S.
Can
the "triple point" referred to in paragraph 6.5 ever appear as an area
4.
5.
on a plane of thermodynamic properties? Explain. During a certain experiment, pertinent to cooling a binary system, a specimen was "isolated" and observed to contain five phases, apparently coexisting. Give several conclusions and substantiate. With reference to the lever principle in paragraph 6.7, how was equilibrium
assumed or implied
in the derivation?
6.
Using the law of mass transfer as given in paragraph 6.4, derive the partial differential equation for three dimensional, unsteady state diffusion.
7.
Using the equilibrium diagram
for copper and nickel calculate the proportions of solid and liquid for an alloy containing 30% Ni. at a temperature of 2200 deg.F. What are the concentrations of each component in the liquid and the solid?
8.
Compute
the volume of a unit mass of mixture containing 80% (by mass) water vapor and 20% liquid water in equilibrium with the vapor. The pressure of the mixture is 50 pounds per square inch absolute. Reference to vapor tables will be necessary here. Was the so called "lever principle" employed in the above computation? HINT: See Problem 1 above.
9.
upon cooling
10.
For copper-silver phase equilibria discuss the transformations taking place for the following alloys: 5% copper, 20% copper, and the
alloys exhibit a characteristic such that there exists a composithat has a lower melting point than cither pure component. Show
eutectic composition.
Some binary
tion
that this point the
is a point of tangency for the liquidus and solidus. Would tangent to both curves at the above point be a horizontal line on the equilibrium diagram? Substantiate your answer.
common
1.
12.
Can water exist in more than one solid phase? Discuss. How many degrees of freedom exist for the following
(a)
situations:
(b)
(c)
A diatomic gas. A pendulum swung by A locomotive making a
an elastic and extensible cord. run between two cities on a specified
track.
Heat Treatment of Alloys

CHAPTER
by Precipitation Hardening
Harold Vincent Fairbanks, M.S., Professor of Metallurgical Engineering, West Virginia University, Morgantown,
W.
Va.
Arthur R.
Mechanical
Foster,
M.Eng.
Associate
Professor
of
Engineering,
Northeastern
University,
Boston, Massachusetts
X RECIPITATION
called dispersion or age hardening,
is
hardening,
sometimes
the most important
method
of
strengthening nonferrous metals through heat treatment. This treatment has been used very effectively with the light alloys of aluminum and
magnesium. It has also been applied to a number of heavy alloys of metals such as copper, iron, nickel, silver, and lead. The susceptibility
upon the manner in which component metals combine rather than upon the properties of the dominant metal.
its
of an alloy to precipitation hardening depends
The
In the
process of precipitation hardening consists essentially of two steps.
first step, an unstable condition is produced in the alloy structure through the formation of a supersaturated solid solution. This step is
called solution heat treatment

state for the alloy.
and produces
comparatively
soft,
ductile
The second step requires a certain degree of precipitation of the supersaturated phase to impart the increased hardness and strength to the metal. If this step is carried out at room temperature, the process requires several hours or days
the other hand,
if
quires
much
less
and is sometimes called age hardening. On an elevated temperature is employed, the process retime and is called the precipitation heat treatment.
7.1. Alloy
Requirements
for alloys to be heat treated
is
There are two main requirements

precipitation hardening.
by
The
first
requirement
that the solubility of the
HI
112
dissolved constituent decreases with decreasing temperature.
The second requirement is that there be some coherency between the precipitating phase and the matrix phase. It is this coherency or lattice conformity between the two phases which brings about the internal crystal stresses
required for strengthening of the alloy.
Another influencing factor which governs the degree of hardening is the quantity of available material for precipitation. The slope of the solid solubility curve (solvus line) and the composition of the precipitating phase determines the
amount
of material available for precipitation.

is
The
closer the precipitating
phase
to the solid solubility curve

is
on the
phase diagram, the more the material that

ture, the larger will be the
available for precipitation.
Also, the greater the decrease in the solubility with decreasing tempera-
amount
of material available for precipitation.

either a solid solution or
The
precipitating material
may be
some
inter-
mediate phase or compound.
However, it must be remembered that a large quantity of material available for precipitation does not insure that heat treatment of the alloy by precipitation hardening is possible. In the Mg-Pb system, magnesium
can dissolve 46 percent lead
percent lead at
at
the eutectic temperature and only 2
alloy shows but little strengthening effect of precipitation hardening due to the small amount of coherency of the precipitated phase with the matrix material.
room temperature. This
7.2. Step I
7.
Solution Heat Treatment
The process of precipitation hardening is divided into two steps: first, the solution heat treatment, and second, the precipitation heat treatment.
schematic representation for the process of precipitation hardening

1
is
given in Fig.
The alloy to be solution heat treated must have a composition that meets two requirements: (1) that at an elevated temperature a solid
is formed, and (2) that the solid solution can be retained upon rapid cooling to room temperature. A typical alloy used for precipitation
solution
hardening
is
shown
as alloy
in Fig. 7.1.
(1)
The
(2)
process for solution heat treatment has two parts:
heating,
and
quenching.
In heating, the alloy is heated to a temperature above the solvus line but below the solidus line. The alloy is held at this temperature for a sufficient period of time to produce a solid solution. For some alloys the temperature range is fairly narrow between the solvus and solidus lines. It is very important not to heat above the solidus line as incipient melt-
ing of the alloy will take place destroying the dimensions of the fabricated
Heat Treatment of Alloys by Precipitation Hardening
113
PHASE
DIAGRAM
PRECIPITATION
HARDENING
Temp.
Composition
Kic. 7.1.
Tlmt
Schematic representation for the process of precipitation hardening.
Also, too high a temperature can produce excessive grain growth. the other hand, the temperature should be above the solvus line in order to take advantage of the material available lor precipitation hardening and to produce as homogeneous a solid solution as possible.
part.
On
In quenching, the heated alloy
is
cooled to room temperature rapidly

alloy at
enough
phase
is
to retain the solid solution.
The
room temperature
is
now
in a state of nonequilibrium as only the supersaturated solid solution

present.
is
The
retention of the potential precipitating phase in solid solution
the prime requirement of quenching to room temperature. It is important that the alloy be quenched as uniformly as possible as uneven quenching forms areas of high stress in the alloy which will produce
soft spots in
the subsequent hardening treatment.

first
The
stressed areas
will
harden
and then become

is
softer during the subsequent heat
treatment which
necessary for the
main body
of the material to obtain
maximum hardness.
The result of the solution heat treatment is a supersaturated solid solution condition in the alloy. The alloy in this state may be softer than in the annealed condition, but generally it is found to be harder than
the annealed state for the alloy, as shown in Fig. 7.6. However, the material after solution heat treatment is still ductile and may be cold worked.
Some alloys start to harden upon standing at room temperature. Any deformation required after solution heat treatment for these alloys should be done immediately before the hardening begins. In order to arrest this hardening action, the metal may be placed in a deep freeze which lowers
the rate of atomic diffusion due to thermal activity. This fact was
made
114
use of in the storage of
aluminum rivets for assembling of airplane parts during World War II. However, most alloys are fairly stable at room temperature after solution heat treatment.
7.3.
Step
II
Precipitation Heat Treatment (Aging)
The
second step in the process of precipitation hardening brings about
the hardening
and strengthening of the

line,
alloy.
This
is
achieved by
re-
heating the unstable solution heat treated alloy to some temperature be-
low the solvus
but
sufficiently
above room temperature
to allow
mobility of the atoms held in supcrsaluration.
This precipitation temperature
is
held for a definite period of time
until the hardness of the alloy has reached the
maximum
it
or desired value,
and then the
alloy
is
either
quenched or
air cooled to
room temperature.
Once the
migrate.
alloy has reached
room temperature,
will retain the desired
properties due to the lack of mobility of the atoms in the crystals to
Attention must be paid to the proper temperature and to the time at
temperature in order to insure maximum hardness and strength. high a temperature and too long a time will cause softening of the
Too
alloy,
and the advantages of
this
method
of heat treatment will be
lost.
For some alloys the entire second step is carried out at room temperature. This is only possible when the mobility of die atoms in the alloys are sufficient at room temperature to cause the desired hardening and
strengthening of the alloy.
7.4.
Theory of Precipitation Hardening
The heat treatment of alloys by the precipitation hardening process depends upon obtaining an unstable state for the alloy by solution heat treatment, and then controlling the degree of approach toward the stable state for the alloy during the precipitation heat treatment. The maximum hardness and strength are obtained before the equilibrium or stable
state for the alloy is reached.
The
actual hardening
precipitation heat treatment step.
and strengthening of the alloy occurs during the The mechanism involved may be di(I)
vided into three stages:
the pie-precipitation stage,
(2)
the inter-
mediate precipitation stage, and (3) the equilibrium precipitate stage.* Fig. 7.2 shows sketches of the various stages in precipitation.
* For an excellent discussion on Precipitation see "Report on Precipitation" by H. K. Hardy and T. J. Heal in "Progress in Metal Physics", edited by Bruce Charles and R. King, Interscience Publishers, Inc., Vol. 5. pp. 143-278. 1954.
115
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D.
ooo
oo oo
Supsrsoturot. d
solution
BOlid
Pit -precipila'e
hlttrmtdletc
precipitate
Equilibrium
prtcipitote
Fig. 7.2. Sketches showing the various stages in precipitation. matrix atoms. Filled-in circles represent solute atoms.
Open
circles represent
In the pre-precipitation stage, the solute atoms segregate along specific crystallographic planes of the matrix phase in preparation for nucleation.
These clusters of atoms are called knots or Guinier-Preston Zones, having been detected by Guinierf and Preston;}; with X-rays.
In the intermediate precipitate stage, nucleation
the resultant
is
is
is
taking place and
This new form of thin plates from 2 to 50 atoms thick and 20 to several hundred atoms long or wide. There is a lattice coherency present between the precipitated phase and the matrix phase which results in a
lattice of the precipitating
new
phase
present.
lattice
in the
highly stressed area in the matrix surrounding the intermediate precipitate.
In the third stage, the precipitate has grown to such a size that the coherency forces between the two adjacent crystal lattice systems are over-
come and
the precipitate becomes its own independent crystal entity. This relieves the major stresses in the area and softens the metal. It is during the second stage in which the intermediate precipitate is formed that maximum hardening and strengthening of the alloy occurs. This is due to the fact that a flexible dislocation cannot move easily through the regions of localized stresses. The greater the number of
these localized stresses per unit volume of material the greater is the strengthening of the metal due to the increased force required to push the dislocations through the many stress barriers.
fCuinier, A., Nature 142 (19S8) 569. j Preston, G. D., Nature 142 (1938) 570.
116
solute phase
This precipitation process is one of nucleation and growth of the from a supersaturated solution. The driving forces involved for the diffusion of the solute atoms include: (1) thermal energy, (2) the
supersaturated condition of the matrix phase, and (3) stresses which were developed due to quenching in the solution heat treatment step. The nucleation throughout the alloy does not necessarily start at the same time in the alloy during the precipitation heat treatment. Therefore, it
is
the statistical average effect which
for a given temperature.

stages at the
is produced at a given time There are undoubtedly particles in all three
same
time.
Fie. 7.3.
0.02 per cent iron,
500x;
Structure of an alloy containing 3.94 per cent copper, 0.02 per cent silicon, and remainder aluminum. (A) as cast, 100x; and (B) quenched, etched. (Courtesy of Aluminum Research Laboratories)
If the
temperature of the alloy

stage cannot take place.
is
maintained
sufficiently low,
if
even
the
first
On
the other hand,

is
the temperature
for the precipitation heat treatment

prevail.
its
too high, only the third stage

alloy
may
loses
This
is
called overaging.
The
becomes
softer
and
strength. It
may become
in Fig. 7.3.
as soft as in the
annealed
state.
Photomicro-
graphs showing microstructure of an

aents are
aluminum
alloy with various treat-
shown

Optimum
tamp.
117
Strength
-Tim e
Fie. 7.4. Effect of strength of the alloy.
precipitation
heat
treatment
temperature
and
time
on the
7.5.
The
Effect of
Time and Temperature During
Precipitation
Heat Treatment
carried out
Both the temperature at which the precipitation heat treatment is and the length of time at temperature are important. As the
is
temperature
increased the mobility of the atoms in the supersaturated
This means that the growth' of the unstable submicroscopic platelets in the transition phase is speeded up. This also
lattice structure increases.
means that they will attain the critical size at which they shear away from the parent alpha phase sooner. The result of this is that optimum hardness and strength are attained more quickly. This is shown in Fig.
7.4.
Increasing the time of treatment causes the growth of stable precipitated particles of the second phase with marked losses in the strength
alloy along with other changes in the properties of
Fig. 7.5.
and hardness of the the alloy as shown in

atoms
is
temperature is lowered, the diffusion of the solute impeded. In an extreme case this may mean that it is completely suppressed and no increase in hardness or strength can occur. In other cases the improvement is less than the optimum amount. The temperature which is required to prevent hardening of the solution treated metal varies with the alloy. Some aluminum alloys must be
stored at sub-zero temperatures to suppress hardening, but beryllium copper, after solution treatment, remains soft at room temperature indefinitely.
If the precipitation
Some data on hardness of 24S aluminum is included in Fig. 7.6. This graph indicates that increased temperatures will speed the rate of hardening. At 240F it shows that little overaging occurs in a week. It is
118
Ten tile S trength
Propertie*
Log
Fie. 7.5.
Time
on
alloy properties-
Effect of precipitation heat treatment time
interesting to note that the furnace cooled specimen
is
much
softer
than
the solution treated material. This indicates that the alloy in the solution treated condition
soft as the
where the solid solution is maintained, is not as equilibrium structure which contains relatively large particles
is
of hard, brittle second phase. This

is still
because, in the case of 24S, the copper
in the solid solution with the
aluminum
in the solution treated
specimen. Since the atoms of copper are of a different size than those of aluminum, the movement of dislocations along the various planes in the
is impeded. This results in greater strength and hardness. Both the temperature and the length of time at the chosen temperature must be specified if satisfactory results are to be obtained in the precipitation hardening process. It may be possible to shorten the time in the heat treating furnace by raising the temperature. Care should be taken that proper temperature and time be selected from published data or, if
lattice structure
information is not available, that they be established experimentally. can be seen from Fig. 7.4 that although higher than optimum temperatures may reduce the attainable strength slightly, the shortened time may reduce the heat treating costs sufficiently to justify the slight reduction in
this
It
physical properties.

80
1
119
240 F aging temp.

70
r~~
75 F aging temp.
60
f
1
/8 F
agina temp
SO
C0
4Q
20
10
Fu noce coo led to
re*
om
temp.
3 4 Time, days
Fie. 7.6. Rockwell B hardness vs. time for 24S. Solution treated 1 hour at 970 K. Furnace cooled specimen cooled very slowly. Other specimens water quenched prior
to precipitation hardening.
7.6. Precipitation
Hardening of Aluminum Alloys

of precipitation hardening with
Extensive use
is
made
many
alloys of
aluminum. Wrought
alloys
may
be strengthened by either cold work or
The
is
latter usually results in a smaller decrease
in ductility for a similar or even greater increase in strength. In castings,
precipitation hardening
especially useful since
no cold working can be

all
performed.
The
binary phase diagrams for Al-Cu, Al-Mg, Al-Si, and Al-Zn

rich alpha phase as the temperature decreases.
show
the characteristic decrease in the solubility of the alloying element in the
aluminum
Few com-
mercial alloys are true binary alloys, but the phase diagram for aluminum and the major alloying element usually points the way to possible successful heat treatment.
120
700
SO
SO
10
Copper, per cent

Fie. 7.7.
The aluminum-copper phase
diagram:
inset,
the aluminum-rich portion.
{Dix and Richardson)
The Al-Cu phase is shown in Fig. 7.7. Wrought alloys 1 IS, 14S, 17S, and 24S all contain 4.0 to 5.5 percent copper plus minor amounts of silicon, magnesium, manganese, lead, and bismuth, while casting alloys
such
as No. 108, 112, 142, 195 and 212 contain 4 to 8 percent copper as the major alloying element. In alloys containing up to 5.5 percent copper all
the theta phase should go into solid solution with the alpha phase
on
heating to about 1000F. A casting alloy such as No. 212 containing 8 percent copper, 1.2 percent silicon, and 1 percent iron cannot dissolve all the theta phase when solution treated as the alpha phase when heated
below the eutectic temperature can hold only 5.5 percent copper. However, this alloy can be hardened just as the other Al-Cu alloys and
to just
the undissolved hard, brittle theta particles will serve to improve the machineability of the alloy. In the presence of magnesium and silicon, other intermetallic compounds which are susceptible to age hardening
as it shows hardening at each end of the diagram. The magnesium rich end of the diagram will be treated in Section 7.7. It can be seen from the phase diagram that aluminum can dissolve 16 percent magnesium at the eutectic tempera-
may be formed such as Mg,Si, AlXuMg, or AlCuMgSi. The Al-Mg phase diagram shown in Fig. 7.8 is of interest
the type of partial solubility required
for precipitation
ture of
844F and very
little at
the alpha phase alloys to

intermetallic
room temperature. On slow cooling of room temperature, the beta phase which is an
compound of Mg2 Al 3 precipitates. Casting alloy No. 220 containing 10 percent magnesium has the best physical properties of any
Heat Treatment
of the
of Alloys by Precipitation
Hardening
is
121
aluminum
base casting alloys.
Its
major disadvantage
its
poor
capability which requires special foundry techniques and inhibitors to prevent deep surface defects.
diagram shows a decreasing solubility of silicon in is lowered. However, the amount of the silicon rich beta phase which is suppressed upon solution treatment is not great enough to produce a commercially important improvement
The
Al-Si phase
as the
aluminum
temperature
in physical properties.
Silicon rich casting alloys are used extensively,
but not in the heat treated state. When silicon and magnesium are used together in an aluminum alloy, an intermetallic compound of Mg 2 Si is formed which allows effective
heat treatment.
The
solubility of this
compound
in
aluminum
increases
from 0.27 percent at 390F. to a maximum of 1.85 percent at 1100F., which is the eutectic temperature. Silicon in excess of the amount forming Mg2 Si does not affect the solubility of the compound in aluminum, but an excess of magnesium does reduce its solubility. Therefore, it is necessary to be sure no excess magnesium is present. Wrought alloy SIS (l%Si, .6%Mg, .25%Cr) is of this type. 61S is slightly more complex (.6%Si, l%Mg. .25%Cu, .2r,%Cr) in that it contains copper, which further complicates the mechanism of precipitation hardening by increasing the number of intermetallic compounds which
form.
offset
The
the
small
ill
amount
of
chromium added
is
to both alloys tends to
effects
of iron which
present as an impurity. Casting
alloys 132, 355,
and 356 are heat treatable Al-Si-Mg alloys. They have considerably higher silicon contents (5-12%) than the wrought alloys
mentioned. This improves their ratability. Although a high percentage of zinc can be dissolved in aluminum at elevated temperatures (82.8 percent at 720F. compared with 5 percent
just
show only limited response to precompounds such as MgZn2> MgZn, and AlMgZn are formed and these alloys will respond very well to precipitation hardening. The wrought alloy 75S containing 5.6 percent zinc, 2.5 percent magnesium, 1.6 percent copper, 0.3 percent chromium and 0.2 percent manganese is essentially a Zn-Mg alloy. It
cipitation hardening.
at 248F.)
alloys of these elements
With
the addition of magnesium,
develops
the
best
mechanical
properties
of
any of the commercial
aluminum
alloys.
7.7. Precipitation
Hardening of Magnesium Alloys

is
Precipitation hardening
since the close
especially useful with
magnesium base
alloys
packed hexagonal crystal lattice structure will allow only limited amounts of cold work. The major alloying elements are alu-
122
Atomic Per Cent Al
10
i
20
i
30
1
40
1
50
1
60
'
70
i
80
1
90
1
"C
600
500
463"
ruA
400
*36 *
Si
./
, Mg/I,
451"
/
\
..
5
t.V
6
1II
300
fi
200
'
.1
-L
80
10
20
40
50
60
70
to
Weight Pet Cent AL
Fie. 7.8.
Aluminum magnesium
8c
phase diagram.*
By permission from Structure Hill Book Company, Inc., 1949.
Properties of Alloys, Brick
&
Phillips,
McGraw-
minum, zinc and manganese. The manganese strengthens the alloys by going into solid solution with the magnesium while both the aluminum and the zinc show the decreasing solubility required for successful precipitation hardening. Fig. 7.8 shows that 12.6 percent aluminum is
soluble in
magnesium
is
at the eutectic
temperature of 815F. while
less
room temperature. Zinc shows virtually no solubility in magnesium at room temperature and has a maximum of 8.4 percent at 646F. The precipitating phase is an intermetallic compound MgZn. Many alloys contain substantial amounts of both aluminum and zinc
than 2 percent
soluble at
so that a ternary
diagram
is
necessary to
these alloys.
The change
7.9.
in solid solubility
show the phase relationships in and the identity of the phase
is suppressed by solution treatment is diagram, it can be seen that casting alloy C containing 9 percent aluminum, 2 percent zinc, and 0.2 percent manganese should precipitate only Mgi 7 Al 12> but alloy H containing 6 percent aluminum, 3 percent zinc, and 0.2 percent manganese also precipitates some Mg3 Zn 2 Al 8 These are the two most commonly used casting alloys. Solution treatment not only improves the strength of the alloys but also
or phases in which precipitation

indicated in Fig.
On
this
123
%i<\
Fig. 7.9. Section of ternary diagram for Mg-Al-Zn system. Isothermal lines show the limits of solid solubility at the various temperature levels. To the left of the
dashed line the structure consists of solid solution and MgAl. The solid dot shown on the diagram represents the composition of Alloy C which shows this type of microstructure. To the right of the dashed line the structure will consist of solid solution, Mg1T Al M and Mg37.njAlj. Alloy H whose composition is represented by the small circle on the diagram is an alloy of this type.*
,
improves the ductility considerably, because the

eutectic
brittle
interdendritic
compounds
are dissolved.
The
precipitation treatment reduces
most applications. It causes a marked change in tensile strength. Of the wrought alloys only 0-1 containing 8.5 percent aluminum, 0.5 percent zinc, and 0.2 percent manganese, and ZK-60 containing 5 percent zinc, 0.7 percent zirconium have enough alloy content to be effectively precipitation hardened. Extrusions and forgings are usually worked at high enough temperatures and cool fast enough in the atmosphere to be effectively solution treated. Thus, they need only to be precipitation hardened after fabrication is completed.
for
the ductility, but leaves
enough
increase in yield strength with
little
The precipitation of a second phase with its different crystal lattice dimensions results in the growth of the piece during precipitation hardening. If such dimensional instability cannot be tolerated at the service
Busk and Miranda Trans. AIME.
IG6. 346. 1946.
124
is
temperature, a stabilization heat treatment

sists
required.
Stabilizing conprecipiof
of heating to a temperature
somewhat higher than the usual

to
tation
hardening temperature
allow
partial
is
precipitation
the
second phase.
The
degree of transformation
greater than will occur at

is
no further tendency for This is essentially ovei aging and causes some loss in physical properties. This type of heat treatment may be applied to other precipitation hardening alloys as well as the magnesium base alloys discussed here.
the service temperature, and, therefore, there
is
precipitation while the part
in use.
C
5,
10
Atomic Percentage 15 SO IS 30
Beryllium 40 35
1000
(600
700
1200
600
-
1000
500
300, Co
B 3 Weight
10
Percentage
Beryllium
Fig. 7.10.
Copper-rich
portion
ot
the
copper-beryllium
phase
diagram.
(H.
F.
Silliman)
7.8. Precipitation
Hardening of Copper Base Alloys
is not used as extensively with copper base with the aluminum and magnesium alloys, but there are several alloys with which it may be used very effectively. Commercial beryllium-copper alloys contain from to 2-\/ A percent beryllium plus \/ percent nickel inhibit excessive grain growth at the to A solution treatment temperatures. The phase diagram shown in Fig. 7.10 indicates a maximum solubility of 2.1 percent beryllium at 1590T. The figures given in Table 7.1 indicate that precipitation heat treatment is extremely effective with these alloys and that when combined with cold
Precipitation hardening
it is
alloys as
Heat Treatment
of Alloys
by Precipitation Hardening
125
working, tensile strengths approaching 200,000 psi may be obtained. The usual heat treating cycle consists of solution treatment at 1450F.
followed by a water quench and reheating to 480 to 620F. for 2 to 3 hours. The high strength, corrosion resistance, and fatigue resistance of
these alloys
recommend
their use for springs, diaphragms,
and non-spark-
ing tools.
Moncl metal which contains 67 percent nickel and 30 percent copper amounts of iron and manganese forms a single homogeneous solid solution as do all the alloys in the binary Cu-Ni series. However, if 3 percent aluminum is added producing K-Monel or 4 percent silicon
plus small
is
added producing S-Monel, the metal
is
responsive to precipitation
hardening.
Tin bronzes show little tendency towards precipitation hardening although the phase diagram indicates that it is possible. The low temperatures at which the alpha phase becomes unstable which is 570F.
and 95 percent copper prevents any appreciable preThe addition of up to 8 percent nickel, however, promotes the precipitation of a Ni-Sn rich constituent which improves the physical properties considerably beyond those of the ordinary tin bronzes. The data in Table 7.2 indicates the effectiveness of precipitation hardening on a commercial alloy of this type.
for 5 percent tin
cipitation of the delta phase.
7.9.
Precipitation Hardening in
Low Carbon
Steel
In Chapter 12 where the fundamental structure of carbon steels will be is defined as alpha iron holding in solution small amounts of silicon, phosphorus, carbon, and other elements. Of the elements which may be in solution in very small quantities in alpha iron, three: carbon, oxygen, and nitrogen can, under suitable conditions, cause
discussed, ferrite
Fig. 7.11 shows the approximate solubility of these in iron. It will be noted that the slope of these curves resembles the slope of the solubility curves of the other alloy systems discussed in this chapter.
mon
Precipitation hardening in carbon steel is a phenomenon that is comonly in the low carbon grades. Since these steels are used rarely in the quenched conditions, precipitation hardening due to iron carbide or
iron nitride retained in solution by quenching, followed by slow spontaneous precipitation at room temperature or more rapid precipitation at slightly elevated temperature is seldom encountered. It is, however,
possible, by quenching a steel containing 0.04 to and by precipitation treatment at 140F. for 10 to
0.10 percent carbon

15 hr. to increase the
Brinell hardness from 120 to 160.
126
Oxygen, percent
.K .04
irJBOO
.os .on
.to
%
*IS00
D
\.a*i SolidSol. \l x4
1
V soo
'
k.
SB
i^
,
a Sum'
|
/
1
i
>
w
j*
g-
Solution
|
BOO
400
j
a: Soiio Solution
1
"^jC
aOMM
.05
./<?
A
.
.>
B
.01
e
.02.05
Carbon,
per cent
Nitrogen, per cent
Fig. 7.11. Iron-rich portions of the (A) iron-carbon, (15) iron-oxygen, and (C) ironnitrogen phase diagrams, showing changes in solubility of carbon, oxygen, and nitrogen with temperature. (Epstein)
7.10. Strain Aging and Its Consequences in
Low Carbon
Steel
There
steels
is
another variety of precipitation hardening in low carbon

as strain aging.
If steels
known
susceptible to aging are strained by
cold working, a hardening constituent, probably iron carbide, iron oxide, or iron nitride, precipitates during straining and for some time afterward.
This
is
accompanied by increased hardness and strength and by de-
The effect of the precipitation can be detected by cold working a rimming steel and a deoxidized steel of the same composition and by testing a sample of each immediately and at intervals of several weeks or months. Strain aging frequently has undesirable consequences. Low carbon sheet for automobile bodies and fenders are given a light final cold working after hot rolling to prevent stretcher strains. This produces conditions ideal for precipitation of the hardening constituent. Unless the sheet is deep drawn immediately, the loss of ductility may be so great that the steel will not withstand the drawing operation successfully. Strain aging has been known to cause failures in boiler plate in the strained areas around rivet holes.
creased impact resistance.
7.11. Precipitation
Hardening
of
in Alloy Steels
alloy steels, only those con-
Of
the large
1
number
common low
taining about
percent copper are subject to precipitation hardening.
The
at
solubility of copper in alpha iron increases

to 1.4 percent at
from about
0.4 percent
steels
room temperature
1.5
1525F.
Low
carbon
con-
taining 0.7 to
percent copper can be hardened by a heat treatment
sists
causing precipitation of the hardening cons titu tent. This treatment conof heating to If>50F., cooling to room temperature, and reheating

for 3 or 4 hr. at 930F.
127
Precipitation hardening increases the tensile

is
strength
and
yield strength about 20,000 psi. Ductility
decreased, but
the precipitation hardened copper steels are not brittle. of investigations have been concerned with the precipitahardening of highly alloyed steels which contain 2 or 3 percent titanium and also with stainless steels containing tungsten.
tion
number
Table 7.1 Typical Properties 0.25% Co (or 0.35% Ni).*
of Beryllium-Copper Alloy 0.032" Thick Strip
2% Be,
Condition
Tensile Strength
(psi)
Yield Strength
(psi)
Elongation
Rockwell Hardness
(%)
50
5
Number
B 60
Solution treated Precipitation hardened Solution treated and cold rolled
72,000 175,000
107,000
25,000 80,000 70,000
41
37.1%
Solution treated cold rolled 37.1 %and precipitation hardened
* Metals
B 97.5
195,000
p. 934.
110,000
42.5
Handbook, 1948 Edition,

Properties of
Table
7.2
Type
Ni-Vee Bronze (88% Cu,
5%
Ni,
5%
Sn,
2%
Zn)
Property
Tensile Strength, psi Yield Strength, psi Percent Elongation
Brinell
*
As Cast
50,000 22,000
40 85
Heat Treated*
85,000 55, 000 10
180
Hardness
Number
at 1400F., water
Heated 6-10 hours
quenched, and reheated 6-10 hours at 500F.
Courtesy of the International Nickel Co., Inc.
QUESTIONS
1.
2.
Define precipitation hardening. Why is it sometimes called age hardening? Discuss the characteristics that an alloy must possess to be precipitation
hardened.
3.
4.
Discuss what happens if too high a temperature is used during: (a) the solution treatment, (b) the precipitation heat treatment. Discuss what happens if the alloy is held for too long a time at temperature during: (a) the solution treatment, (b) the precipitation heat treatment. Discuss the constitutional changes
5.
which take place during precipitation
hardening.
128
6.
How
does precipitation hardening

(a) tensile strength,
effect
an alloy
in
properties:
(b) yield strength,
(c)
regard to the following hardness, (d) elonga-
7.
tion, (e) electrical resistance, and (f) corrosion resistance. Discuss the effect of precipitation hardening on the movement of dislocations within the metal.
8.
9.
Explain why alloys arc sometimes precipitation hardened at temperatures higher than the temperature at which optimum strength occurs. Explain why wrought magnesium alloys may be precipitation hardened directly after fabrication without a formal solution treatment?
10.
What
use
is
is
meant
by:
(a)
overaging,
(b) strain aging,
(c)
stabilizing?
What
made
of each?
11.
If
an alloy were to contain 4% aluminum, 2% zinc and 94% magnesium, what phases would be present in the slowly cooled state at room temperature?
12.
What
alloying element
added
to
the following materials will

(a) tin
make them
(c)
susceptible to precipitation hardening?

alloy steel.
13.
bronze,
(b)
monel,
low
14.
whose solubility in aluminum decreases with temperathem be used effectively as binary precipitation hardening alloys with aluminum? Why is a moderate amount of Mg used with the major alloying element Zn
List four elements
ture.
Can
all
of
in
15.
75S?
alloying clement produces the strongest commercial casting alloy of
is its
What What
to
Is
aluminum? What
16.
major drawback?
three alloying elements present in a plain carbon steel
may
cause
it
17. 18.
respond to precipitation hardening? precipitation hardening used extensively with low carbon
steels?
Explain.
List
some
practical applications for precipitation hardening.
Light Alloys as
CHAPTER
8
Francis Wii.uam Brown, Ph.D., Associate Professor, Clarkson College of Technology, Potsdam, New York
8.1. History of
Aluminum
ALUMINUM
Danish
scientist
was
first
made
in
1825
by
named Oersted by means
of a reaction between
aluminum
metal
chloride with a potassium-mercury amalgam. In 1845 Henri Sainte-Claire Devilie produced globules of aluminum meta] by heating sodium
method was improved by using cryolite as the flux. The very nature of these raw materials indicates the large amounts of energy that are required to make aluminum and why this metal under these processing conditions was very costly. Aluminum was produced by Charles M. Hall, in 1886, by the electrolytic decomposichloride; later this
with anhydrous
aluminum
aluminum oxide (alumina) dissolved in molten This process has continued since 1886 to the present as the only economical process for the manufacture of aluminum. The first major industrial demand for aluminum was in the aircraft field because of aluminum's unusual combination of lightness and strength. The discovery of the aluminum-copper alloy duralumin and its heat treatment by Wilm in Germany stimulated the use of aluminum. Wilm's early work was done in connection with Zeppelin's development of the dirigible. Prior to the First World War, the Aluminum Company of America supplied the U. S. Navy with duralumin sheet for the Navy's dirigible. The aircraft industry was primarily interested in the strengthtion
cryolite.
of anhydrous
weight ratio of the high-strength aluminum alloys; whereas, most other industries were concerned primarily with the cost. It was only about twenty-five years ago that these alloys were considered seriously for automobile, truck, and bus construction and for railroad rolling stock;
their
consideration for bridge and building construction
is
even more recent.
129
130
8.2.
Economics of the Aluminum Industry

,
For about thirty years after aluminum metal was first produced (1825) was a laboratory curiosity worth about $100 per pound. In 1857, Sainte-Claire Deville, as the result of research supported by Napoleon III, succeeded in bringing the price down to S25; two years later, to $17 per pound. Despite the fact that alumina was a very abundant oxide and could be produced economically in pure form, cheap aluminum was impossible because of the high cost of metallic sodium and the aluminum chloride. By 1886, the cost price of aluminum was reduced to $8 per
it
pound,
still
too high for
common
down
use.
The
electrolytic reduction process
1886 brought the price
to $1 per pound.
developed by Charles M. Hall in In 1943, the price for
aluminum
arise here
ingots reached $.15 per pound.

is,
question that might readily

steel
"can this cost be cut drastically so that aluminum and

basis?"
are
on an equal price
less
In 1893,
than 100 tons were produced in the United
States; ten
years later domestic annual production increased to 3,000 tons. In 1915,
world production was 85,000 metric tons; in 1939 this had increased to 675,000 tons, of which the United States and Germany each were responsible for 175,000 to 200,000 tons. The peak world production of aluminum during the Second World War, in 1943 was 2,176,000 net tons, of which considerably more than half was produced in the United States.
This country's consumption of aluminum in 1952 was distributed over

the following
fields:
32%
Transportation
10% Consumer
15% Building Construction 14% Miscellaneous 13% Electrical

It is
6% 6% 4%
Durables Chemical Uses Machinery & Equipment Packaging
interesting to note that, despite the fact that during the
war
aluminum expanded very much more than iron and steel, the total production of primary aluminum in the United States for the year 1943 was approximately equivalent to the average amount of steel
the output of
ingots produced in 3
great difference in production
working days during the same year. Reasons for this and cost may be deduced by comparing
the properties of the high grade ores of each of these metals.
Aluminum
Iron
Name b Source
of
Main
U. S. Ore
Bauxite (Arkansas)
Cryolite
Hematite (Minn.)
Secondary ore Combined water <%) Combined metal (%) Density of ore
(Greenland)
25% 32%
2.55
None None
50%
4.90
131
The
transportation costs for the
aluminum
greater distances involved
and
their higher
ores are higher due to the bulking values. The aluminum
2.3); this
ores have specific gravity values near to that of the siliceous gangue (2.2 means gravity concentration of the ore is difficult. The ship-
ping costs of bauxite are decreased by calcination of the bauxite to remove water and other volatile matter. The lower percentage of aluminum in
the ore is another factor that leads to higher processing costs. A comparison of the Hall Process and the Blast Furnace Process will further bring out the comparative economics of these two commercial metals. A com-
parison of the costs of aluminum and steel should be made on the basis of the finished article and not on the relative price per pound of ingot metal. Because the specific gravity of aluminum is approximately onethird that of steel, less aluminum by weight will be used. In addition there are economies that result from the unique combination of the properties of aluminum, namely, ease of fabrication, (1)
machinability,
costs, (5)
(3)
low
cost
good (2) good surface color and polish, (4) low maintenance of distribution, and (6) high scrap value.
8.3.
Aluminum Ores
Occurrence and Concentration
Although aluminum occurs in nature in a higher percentage than iron, the major share exists in the form of clay. Bauxite, the principal ore of alummum, consists of a mixture of the mono- and tri-hydrate of aluminum oxide. Bauxite has been formed in nature by the weathering of clay; bauxite deposits are found primarily in warm countries because high
temperatures and rainfall accelerate this hydrolytic degradation of the The main source of supply of high grade ore (50-65% alumina) in this country is from Arkansas; in South America it is found in the Guianas. The impurities in bauxite ore are the oxides of iron, silicon,
clay.
and titanium. Since

it is
these impurities are difficult to separate physically, evident that high-grade deposits are very desirable. Aluminum is more chemically reactive than iron and silicon; therefore
is
it
difficult
and
costly
to
remove these undesirable impurities from
the crude metal.

process is the most commonly used process for the concenand purification of bauxite. The fundamental principle involved in this process is "that alumina differs from these other oxides in being amphoteric, i.e., weakly acidic and basic." Alumina will dissolve in hot
tration
The Bayer
concentrated alkali but

process are as follows:
is
insoluble in cold dilute alkali.
The
steps in this
high-grade bauxite is finely ground; (2) ore is digested with hot, concentrated sodium hydroxide (caustic soda) to form the soluble sodium aluminate; (3) the insoluble (red mud) oxides
(1)
132
off; (4)
of iron, silicon, and titanium are filtered

ate
is
the hot
sodium aluminit is
diluted with water, seeded with crystals of alumina hydrate, and

(5)
allowed to cool;
pure hydrated alumina

(6)
settles out;
filtered off
and calcined to form alumina, tion and used over again.

8.4.
the filtrate is
concentrated by evapora-
Manufacture of Aluminum
The electrolytic reduction process for the manufacture of aluminum is dependent on the fact that anhydrous alumina dissolves in molten cryolite to give an ionic solution of high electrical conductivity. The passage of direct current through this molten electrolyte deposits aluminum at the cathode and oxygen at the anode. Since iron and silicon are objectionable impurities, the iron cell must be properly lined with a material of high purity and of a conducting nature so as to function as the cathode. The anodes must likewise have similar properties. Ordinary carbon fulfills
the conductivity requirement but not the purity one.
The
lining of the cell
and the anodes are made from fabricated parts of petroleum coke. The oxygen formed at the anode combines with the carbon to form carbon dioxide gas; therefore, the cost of these electrodes is an important economic factor. When metals are manufactured by an electrolytic process, the weights
of the metals deposited are proportional to their equivalent weights.
The
ratio of weights of
some common
31.8.
It is
industrial metals deposited
by the
same amount
12.1, iron 18.6
of current vary in order listed:
aluminum
and copper
evident that
magnesium the economical manu9,
facture of
energy.
aluminum Aluminum plants

relative
necessitates large
amounts
of low cost electrical
are therefore located near hydroelectric plants.
A measure of the
is
manufacturing problems of iron and aluminum
indicated by the listed data.
Aluminum
(Hall process)
Iron
(Blast furnace)
Type
of operating unit
Capacity of unit, per day
Lining of unit
Small, semi-batch 1000 lbs. Petroleum coke
large, continuous
700-1500 tons Refractory bricks

IfiOO'C
.63
II).
Temperature of operation Weight of metal per lb. ore Weight of carbon per lb. metal.
Value of gaseous by-product Agent used to remove impurities.
Electrical
lb.
.
lOOO'C 50 lb.
. .
.75 lb.
8"i ll>.
none
Caustic Soda (Bayer Process)
85 Btu/cu. ft. Air, iron oxide
Energy Requirements per 12 metal Energy requirements ratio

(theory)
KWHr.
1
133
The aluminum mum) aluminum,

The
cell
produced by the Hall process
consists of
99%
(mini-
the major impurities being iron and silicon.
Aluminum
of high purity (99.99%)
may be obtained by
an electro-refining process.
used in the Hoopes process consists of three molten layers, the bottom anodic layer of crude aluminum-copper alloy, the intermediate
layer of
salts,
and the top cathodic

Properties of
layer of pure
aluminum.
8.5. Physical
Aluminum
its
low
The most generally recognized physical characteristic of aluminum is density. The lightest metal, magnesium, is two-thirds as dense
(sp. gr. 2.70);
as
aluminum
whereas, iron and
steel are three
times as dense.
The
density of most aluminum alloys range 2.70-2.80, which means that aluminum and its alloys roughly weighs .1 lb. per cubic inch. The low density of aluminum can be attributed to its low atomic weight (27)
and
its
great chemical reactivity. These two properties in addition gener-
ally indicate
heat, high heat of fusion,
such thermal properties as low melting point, high specific and high coefficient of thermal expansion.
The melting point (1220T.) and heat of fusion (94.6 cal.) are slightly higher than corresponding properties of pure magnesium. Its very high specific heat and its linear coefficient of thermal expansion are second
to
magnesium. The high
solidification shrinkage
(6.6%)
as well as its
"hot shortness"
make
the casting of pure
aluminum
rather unsatisfactory.
The electrical conductivity of metals, in decreasing order, are silver, copper, gold, and aluminum. Pure aluminum has 64% of the electrical conductivity of copper on an equal-volume basis but has a 212% value on an equal-weight basis. It is therefore the best commercial electrical
conductor on the
latter basis.
The
basis.
best thermal conductors, in decreasing

is
order, are silver, copper, gold,
and aluminum; aluminum
the best
conductor on an equal-weight
This parallelism between

pressed by the
to
electrical and thermal conductivity is exWiedemann-Franz law. Another relationship that appears be indicated is that these two physical properties are related to crystal
all
structure since
line structure.
four of these listed metals have a face-centered crystal-
The low density and

erties of
melting point of aluminum are related to its propbeing soft (Brinnell Value 16) and relatively low tensile strength
(8,500 psi).
In view of
erties of
its
low melting point and "hot shortness," the
tensile prop-
aluminum rapidly aluminum and many of its
decrease with a rise of temperature; therefore,

alloys are not well suited to elevated tempera-
134
ture applications.
Aluminum and
all
of
its
alloys
become stronger and

it
is
tougher at subnormal temperatures.
Aluminum
is
a very malleable and ductile metal; in fact,
second
best of the commercial structural metals. These properties are related to its face-centered cubic crystalline structure, for we note that copper,
and gold are very malleable and ductile and have face-centered cubic structure. Under standard testing conditions, pure aluminum will
silver
stretch 60 per cent of
its
length before breaking.

strength,
high ductility, malleability, and
adapted
to
working by most methods of
With the combination of aluminum and its alloys are forming and fabrication.
high degree of plasticity and relative chemical inertness to normal conditions, aluminum can be easily finished to a high polish. The brilliance of aluminum paint is due to the high reflectivity of the
Due
to the
finely
divided
flat flakes.
Aluminum is an excellent reflector of radiant energy of all wave lengths. The high durability of aluminum paint is largely due to the efficient reflection of the ultraviolet rays;
ultraviolet rays destroy the oil film in
paints and lead to loss of adhesion.

reflectors of the
most modern
telescopes.
Aluminum is used as thin films on the Aluminum foil is important in

its
the thermal insulation field because of

radiation.
high
reflectivity of infrared
Three important requirements
of a
molten metal for
satisfactory casting
arc low surface tension, high fluidity,
and
relative chemical inertness.
is
Molten aluminum has a surface tension of 520 dynes per centimeter which one third that of molten iron, both at their respective melting temperatures. Pure molten aluminum has a fluidity 50 per cent that of molten tin; the normal impurities of commercial aluminum increase this value to 70 per cent. Molten aluminum is protected from oxidation by a thin oxide film; excessive agitation must be avoided to prevent the removal of this oxide film. Two other properties of molten aluminum contribute to its poor castability, first its reactivity with moisture to form aluminum oxide and hydrogen, second the high selective solvency for hydrogen gas
which leads to high-porosity
cast metal.
8.6.
Chemical Properties of Aluminum

very high solution potential of
The
aluminum demonstrates
that
it is
the second most chemically active structural metal. In spite of this great activity, aluminum offers great resistance to normal weathering. This
relative inertness
can be attributed to the presence of a thin protective and adhering oxide film. Other outstanding features of this oxide film

are
its
135
itself,
its electrical
chemical inertness, water insolubility, ability to and thermal insulation properties.

chemical inertness of this film
is
mend
and
The
dilute
indicated by fact that
aluminum
tanks are used for storage and shipment of concentrated acetic acid,
and concentrated
the oxide film,
is
When
serts
itself;
nitric acid, and strong hydrogen peroxide. removed, the active nature of the metal asfor example, caustic soda and strongly alkaline solutions
readily attack
aluminum.
When
alkaline degreasing solutions are used to

is
clean aluminum, a corrosion inhibitor such as silicate of soda
added.
Aluminum
in contact
with mercury or
its salts will
show
accelerated cor-
rosion due to the removal of the oxide film.
In the melting of aluminum and subsequent handling operations, precautions should be taken to avoid, as much as practicable, contact with moisture, water vapor, or other materials that will react with aluminum
The amount of dissolved gas can be kept at a low low temperature, short operating time, minimum agitation, and low absolute humidity of the atmosphere.
to
form hydrogen
gas.
amount by using
The
great affinity of
the steel industry.
aluminum for oxygen is illustrated in its use in The amount of aluminum required for the deoxidation
is
of molten iron and steel

are used, the excess
usually less than
lb.
per ton.
When
it
1-1 1/ lbs. 2
aluminum
functions in another manner:

steel.
leads to
the subsequent formation of a fine-grained
similar deoxidation reaction is involved in the thermite welding and repairing of large ferrous alloy sections, railway and street car rails,
etc.
Thermite
It is
consists of a
scale.
ignited by
means
of flashlight
mixture of granulated aluminum and mill powder or another primer, which
aluminum, followed by a violent reaction form aluminum oxide and molten iron. The excessively high temperature (4500F.) is due to the great heat of reaction, the low specific heat of iron, and the absence of any volatile product. A modified thermite releads to localized melting of the
to
action
is often used in the manufacture of pure high-melting metals as vanadium, chromium, molybdenum, and manganese. Atmospheric nitrogen is a very inert gas but will react with aluminum and chromium, at elevated temperatures, to form metallic nitrides. The presence of .851.2% aluminum in the nitralloy steel plays an important role when being surface hardened by nitriding. The stainless steels and
other
8.7.
chromium
alloy steels
do not require aluminum
for this purpose.
Aluminum
Alloys
alloying elements used in the manufacture of
The important
aluminum
alloys are copper,
manganese, magnesium,
zinc, nickel,
chromium, and
136
silicon.
In special purpose alloys the elements titanium,
tin, lead,
and
bismuth are intentionally added. For example, lead and bismuth are added to the extent of .5% each in the free machining alloy; those metals
are insoluble
in
aluminum and
are
therefore
present
as
colloidal
dispersion which functions as a lubricant.
The
total alloy
7% and 16%
content of the wrought and casting alloys are usually maximum, respectively. The three main important strength-
giving elements in the wrought and cast alloys respectively are coppermagnesium-manganese and copper-magnesium-silicon. Silicon also plays
a very important role in the castability of alloys.
The
individual alloys are designated by numbers, the wrought alloys as
a four digit
Two
Zn)
;
number, and the cast alloys as a two- or three-digit number. high-strength wrought alloys are 5056 (5% Mg) and the 7075 (5%
the alloys that have excellent castability are 43, 355, 356.
are two classes of
wrought aluminum alloys: (1) alloys that are not heat treated and that owe their properties to strain hardening by cold work, (2) alloys whose strength may be improved by heat treatment and whose properties may be altered still more by cold deformation.
There
8.8.
The Wrought
Alloys
The
various tempers of commercial wrought
aluminum
alloys until
letters.
recently have been designated
by a system of numbers and
The
new temper designation consists of a letter indicating the basic temper which may be more specifically defined by the addition of one or more digits. The letter F means "as fabricated," O "annealed, recrystallized,"
and
H"strain
give a detailed
meaning
hardened." The latter as per follows:
may be
modified by numbers to
Strain hardened Strain hardened

digits.
only HI, plus one or more digits. and then partially annealed 112, plus one or more
Strain hardened
and then stabilized-H3, plus one or more
digits.
In dealing with the heat-treatable type of alloys, the letter following the alloy number signifies that it has been hardened by solution treatment. The specific combination of basic operations is indicated by a number:
6061-T5 means
and
artificially aged.
that alloy 60G1 has been hardened by heat treatment The various basic operations are as follows:
(cast
T2 T3
Annealed
products only).
Solution heat treated

condition.
T4 T5
and then cold worked. Solution heat treated and naturally aged to substantially stable
Artificially
aged only.

Table
I
137
8.1 Temper Designations for hat Arc Not Heat Treatable (*)
Strain
Hardened Wrought Aluminum Alloys
New Temper Designation({)

Strain
Old Temper Destîahon
Strain
Hardened
only
Hardened and then

Annealed
Strain
Hardened and then
Partially
Stabilized
(Alloys 1100
14
'/2
and 3003)
H H
*A
-H12 -H14 -H16 -H18 -H19
-H22 _H24 -H26 -H28
Extra Hard (Not Standard)
(Alloys 3004, 5052, 5056J)
#{J % H
^
Extra Hard (Not Standard)
Alloys listed also available in and F tempers, are standard for the alloys listed. (t) The alloys 3004, 5052 and 5056 may also be obtained in the Conditions.
( )
-HS2 -H34 -H36
H39 -O
(t)
The tempers shown
-HI and -H2 type '~
T6
T7 T8 W
Solution heat treated and then artificially aged. Solution heat treated, then stabilized. Solution heat treated, cold worked and then artificially aged.
-T9 Solution heat treated, artificially aged and T10 Artificially aged and then cold worked.
Solution heat treated-unstable temper.
then cold worked.
In Tables 8.2 and 8.3 there are listed the important wrought alloys in order of their increasing tensile properties, together with other important physical properties. The number of alloying elements and total alloy percentage for the nonheat-treatable are less than the heat-treatable alloys. principal characteristic of the wrought alloys, especially the heatis their high strength-weight ratio. The typical mechanical properties of the annealed and fully hardened alloys are listed
treatable type,
in
The
Tables
These properties are applicable to room temperature but are satisfactory for the range from about 0 to 150F. All of the aluminum alloys become stronger and tougher at subnormal temperatures. Due
8.2
8.3.
and
to the fairly
rapid decrease in tensile properties, and sometimes the de-
138
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2024
2014
H<
139
all
velopment of hot shortness and/or excessive oxidation,

alloys are not well suited for high
aluminum
temperature application.
alloys (500-kg. load,
The
Brinell hardness of the
wrought
varies from approximately 30 to
10-mm. ball) 85 for untreated alloys and from 30 to
120 for the heat-treated material, depending upon the temper. Even the
aluminum alloys are much softer than the softest steels. Endurance limits (based on 500 million cycles) are low; the endurance ratio is highest for the annealed alloys and is only about 0.25 for heat-treaied high-strength sections. It is characteristic of the annealed alloys that the endurance limit is higher than the yield strength.
hardest
The modulus of elasticity for tension or compression, measured in kips per square inch, ranges from 10,000-10,600, except wherein the high
(12%) increases it to 11,400. The values for the annealed and hardened form of a particular alloy is the same. The modulus of elasticity for shear, measured in kips per square inch, ranges from 3, 800-4000, the high silicon alloy value being 4300.
silicon
The thermal and electrical conductivity of the wrought alloys are less than the pure metal, the higher the alloy content the greater the lowering. An annealed alloy has higher values than the strain hardened and/or
heat-treated
alloy.
at
The
thermal coefficient of expansion per degree
room temperature is almost the same for most wrought alloy varying from 124-135 x 10", the only marked exception being when very high silicon (12%) is present, when the value is 108 x 10-7 The cold
Fahrenheit
.
working of alloys does not appreciably change these values; whereas, heat treatment makes an increase of several per cent.
The
resistance to corrosion of
aluminum
alloys
is
usually very
satis-
factory, the strain-hardening type alloys being generally superior to the
heat-treatable type.
The
presence of relatively large amounts of coppcr
or zinc reduces the over-all resistance to surface attack. The resistance to high temperature oxidation is best insured by the presence of the
alloying element nickel.
Maximum resistance to corrosion of the heat-treatable alloys is dependent on the solution heat treatment being followed by a very rapid quench; therefore, thick sections arc not as resistant as thin sections due
to their slower rate of quench.
Artificial
aging usually
effects a
marked
improvement
in resistance to corrosion.
Some sheets, plates, and tubes arc produced with a surface coating of pure or low-alloy aluminum that are metallurgically bonded to the core during hot working. These coatings offer electrolytic protection to the
core against corrosion.
This protection includes cut edges and areas where the coating may be scratched or abraded.
140
8.9.
Aluminum
Casting Alloys
The
casting alloys are designated by a

is
number
of
some instances the number

variation
in composition.
preceded by a
letter,
two or three digits. In which indicates a slight
For example, the three casting alloys 214,
B214, and F214 contain 3.8% magnesium but differ in the silicon content. Casting alloys may be of two types: (1) the nonheat-trcatable alloys, and
(2) the heat-treatable alloys. The condition of heat treatment is designed by appending some symbol, as 195-T4. The elements used in aluminum casting alloys are primarily copper, silicon, and magnesium. The minor alloying elements are zinc, nickel, manganese, iron, and tin. The requirements for the sand, permanent mold, and die castings arc not necessarily the same, although many of the
alloys are used for
both sand and

is
die.
all
The 5%
binary silicon alloy
is
the
only listed alloy that
used for
three types of castings.
Aluminum finds little use in the production of castings because of its low strength and inferior casting qualities. Two exceptions are the induction motor rotors and cable clamps, which require the higher electrical
conductivity of aluminum.
The commercial
ties
casting
aluminum
alloys
and
their important proper-
are listed in Table 8.4. Note that the total percentage of alloying ele-
ments is generally greater than that of the wrought alloys. Some of the important characteristic properties of molten casting alloys such as good
fluidity,
a high percentage of alloying elements.

fication leads to
low surface tension, and low pouring temperature necessitate The low temperature of solidi-
low gas solubility and porosity, and

(1)
fine grain structure.
The important
die casting are
tendencies,
casting characteristics for a sand
and
(2)
freedom from hot shortness,
a permanent low shrinkage
and (3) pressure lightness. Low gas absorption is a very important property for a sand-casting alloy. A die-casting alloy should have freedom from hot shortness and mold-filling capacity.
scores of
and shape can be made from aluminum alloys, each having unique properties or foundry characteristics. Where only a few castings are required, or where the castSand
castings of almost unlimited size
ing
is
relatively large,
sand castings are indicated.
On
the other hand,

if a
when
large
numbers of
relatively small parts are required, or
smooth
surface
permanentmold or die castings are to be preferred. Some typical permanent-mold castings are shown in Table 8.4. The method of casting, too, affects the properties to be expected from a given composition, permanent-mold and die castings usually having a somewhat higher strength than sand castings.
desired,
and a minimum amount of machining are
In general,
when
the
number and
the size of the castings to be
made would

justify the use of
141
any of the three methods, die castings are the cheapest and can be cast to the closest tolerances, while sand castings will cost the most and will require the broadest tolerances.
A comparison of the mechanical and tensile properties of the sand permanent mold, and die castings is best made by listing the typical
values for alloys 43.
Permanent
Sand
Tensile strength Tensile yield strength Elongation (% in 2")
19,000
Mold
2 3000 9 000
'
r)ie
30,000 16,000
8,000
8
9,000
10
Compressive yield strength Brinell hardness Shearing strength
10
9,000
45
16,000
19,000
14,000
Although the casting alloys have a greater alloy content than the wrought, the improvement as compared with pure aluminum is primarily greater in the casting properties rather than the mechanical properties.
The maximum tensile strength of the commercial aluminum alloys in the "as-cast" condition for the sand, permanent mold, and die castings are approximately 27,000, 35,000, and 46,000 psi. respectively. The
tensile properties of
solution heat treatment.

stituent
some casting alloys are further improved by This type of alloy contains at least one conis
whose
,s
solid solubility
substantially greater at elevated temperaof this alloying
tures than at
room temperatures. The usual amount

it is
completely soluble near the melting point of the alloy. Heat treatment finds limited application with die castings because of blistering and possible loss in dimensional accuracy.
element
such that
The
yield strengths in tension
practically equal.
in the design of
The
some
ments are available that
and compression for the cast alloys are yield strength in compression is very important aircraft structural members. Some special treat-
T6 3nd T62 condition hav * ê respective tensile strengths , 36,000 and 40,000 psi; the compressive yield strengths under these condi-
raise the compressive yield strength to a value almost as high as the tensile strength. For example, sand casting alloy
*LZ
tions are respectively 25,000
and 38,000
psi.
of elasticity of most aluminum casting alloys is approximately 10,300 kips; therefore this property is about one third that of steel The Brinell hardness of "as-cast" alloys range 40-70 (500-kg. load, 10-mm. ball) whereas, for the heat-treated alloys the hardness value is 75-100 The endurance limits for the alloys range 5,500-9,500 psi. This gives an endurance ratio of .25-.38 for cast alloys and .17-28 for the heat-treated
;
The modulus
142
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alloys,
143
based on a rotating-beam test of 500 million cycles. These ratios are one third to one half of those usual for carbon and low-alloy steels. Inasmuch as the total percentage of alloying elements is usually greater
in casting alloys than wrought, the melting point, and the thermal electrical conductivity, are much lower for the former class.
and
The
melting
range and the specific gravity range (2.66-2.92) are wider for the casting alloys because of their higher alloy content. The specific gravity and the thermal and electrical conductivity values are lower for the die castings than the sand and permanent mold casting alloys.
Centrifugal castings have been very popular for many ferrous and nonferrous alloys because the molten metals and alloys are cleansed of oxides and inclusions by the centrifugal action thereby improving the
mechanical
of
small differences in the specific gravity between the usual oxides and inclusion present in molten aluminum alloys makes this type
casting of a limited advantage.
properties.
The
8.10. Functions of Alloying Elements
The
and
cast
advantages and limitations of commercial aluminum as a wrought metal may be summarized as follows. Its advantages
as
wrought metal are high electrical and thermal conductivity, excellent malleability and ductility, excellent formability, good machinability, and unusual resistance to normal corrosion. The limitations include low tensile properties, poor high-temperature tensile properties, and high temperature brittleness. Molten aluminum has the desirable properties of low surface tension and good fluidity, the undesirable properties are high selective hydrogen gas solubility, high solidification shrinkage, and
great chemical reactivity towards air and moisture. The cast metal has the unsatisfactory properties of high thermal coefficient of expansion, hot shortness, gas porosity, and coarse grain structure.
The
tensile
addition of the alloying elements

properties
is
primarily to increase the

qualities
and improve
certain
fabricating
of
wrought metal; they function to increase tensile strength and castability of the alloy casting. Such alloying always results in the improvement of some properties and in the further limitation of others. The changes involved depends upon the type and amount of alloying elements,
the
the
resulting grain structure, size
and distribution of insoluble constituents,
homogeneity, etc. Copper. The most important and commonly used alloying element is copper. The intermetallic compound CuAU forms a eutectiferous series with aluminum; the eutectic alloy contains 33% copper and melts at 548C. The maximum solubility of copper in solid aluminum
at elevated
144
temperatures
is 5.65% and less than .25% at room temperature. The copper content of the high-strength wrought alloys usually ranges between 4-4.5% copper. Although tensile properties increase progressively above this range, higher copper alloys are not commercially practicable because of difficulty in working. The high-strength alloys of this type include
alloys 2011, 2017,
and 2024.
The electrode
potentials of commercial
aluminum and
the intei metallic
compound CuAl 2
are .84 and .53 volts respectively.
This relatively
is
great difference means that the corrosion resistance of the copper alloys
much
less
than those of the other alloying elements. Improper heat treatalloys can further decrease their resistance
ment of the copper-aluminum

to corrosion.
an alloying element in the casting alloys leads to inand decreased surface tension of the molten metal. The cast metal is improved by the freedom from hot shortness, decreased porosity, increased tensile properties, and finer grain structure. Silicon. The second most important alloying element in aluminum alloy is the metalloid silicon. It differs from the other soluble alloying elements in not forming an intermetallic compound with aluminum. It forms a eutectic having the composition of 11.6% silicon by weight and melts at 577C, The solubility of silicon in solid aluminum at the eutectic and room temperatures are 1.65% and less than .05%. Although silicon is a rather hard constituent, it is evident that due to its low solubility and inability to form an intermetallic compound, the binary
Copper used
as
creased fluidity
silicon alloys are
not markedly strong.
A
is
comparison of the strength

given by the tensile yield
Si)
giving properties of silicon
and copper
strength values of the sand casting alloys
#43 (5%
and #195 (4.5%
Cu)
namely 8,000 and 34,000
psi respectively.
role in the casting alloys. Its im-
Silicon plays
an extremely important
portant contribution to the molten alloy are very high fluidity and low solidification shrinkage. The shrinkage of an 8% silicon-aluminum
binary alloy
is
5.6%; the 11.6% silicon-aluminum alloy
(eutectic)
is
3.8%. The presence of silicon influences the properties of the solid cast metal in having a lower coefficient of thermal expansion, absence of hot shortness, and a lower degree of porosity. An unusual property of silicon
in a casting
is
to
form a sound outer
sure tightness.
The
silicon alloys 43, 355,
(>ermanent mold castings.
which leads to presand 356 give excellent sand and The two die-casting silicon alloys, #13 and
layer or skin
#360 are very
satisfactory.
The
of the
ability of silicon alloys to
"undercool" leads to the modification

its
normal eutectic composition and
properties. In 1921 A. Pacz
145
discovered that very rapid cooling or the addition of .05% metallic
sodium
(or
sodium
fluoride)
results in the
formation of eutectic alloys
containing as high as
14%
silicon,
having a freezing point 10-15 degrees
lower than normal. This modified alloy has a finer grain structure; it is stronger and more ductile than the eutectic alloy. The silicon content of wrought alloys is usually less than 1%: one
exception
treatable aging.
is
the forging alloy 4032.
The
presence of silicon in the heat
wrought
alloys generally increases their response to artificial
The
its
presence of silicon in
aluminum
alloys does not materially decrease
corrosion resistance, probably due to the formation of a protective

film.
siliceous
The 5%
binary casting alloy
#43 and wrought

acids.
alloy
4032
resist
atmospheric weathering, chemicals and food
Inasmuch
is
as silicon
and aluminum
are both amphoteric, this type of alloy
not
very resistant to alkaline conditions
and
solutions.
The
strength
and corrosion
resistance
of
silicon-aluminum
alloys
are markedly increased by the presence of
magnesium due
to the forma-
compound Mg^.Si. Magnesium. The eutectic of magnesium and aluminum contains approximately 33% magnesium and the melting point is 451 C. The solubility of magnesium in solid aluminum at the eutectic and room temption of the intermetallic
eratures
is
14.9% and
in
less
than
4%
respectively.
This variation in the

the alloys susceptible to
solid solubility with temperature renders
some of
improvement
tensile
properties
by heat treatment.
magnesium-aluminum solid solution is approximately equal to that of aluminum; therefore this type of alloy shows excellent corrosion resistance. In addition, these alloys show the
electrode potential of
The
4%
highest resistance to alkaline corrosion, such resistance increasing with
magnesium
content.
Binary alloys containing more than 4.5% magnesium are susceptible to stress-corrosion cracking particularly when they are in the cold worked
condition.
This corrosion
highly anodic to the

electrode potentials
due to the fact that the insoluble phase is magnesium-aluminum solid solution. The of the two components are respectively 1.07 and
is
4%
volts. This stress corrosion is prevented by the addition of small amounts of manganese and chiomium.
.87
Magnesium is second to silicon in effectively increasing the fluidity of molten alloys. The fluidity of the binary 6% magnesium alloy is approximately the same as the binary 5% silicon alloy. Magnesium is a more reactive metal than aluminum; therefore it reacts more readily with air and moisture. Molten casting alloys of magnesium-
146
considerable dross, a tendency that increases with mag-
aluminum form
nesium content. Alloys containing

larly
5%
or
more magnesium
cast in ordi-
nary green sand molds show surface discoloration and porosity, particu-
when
thick sections are
involved.
High magnesium-aluminum
should be heat treated in a controlled atmosphere or for a

processing time so as to avoid surface oxidation.
minimum
of
Magnesium ir Silicon. The magnesium silicide forms an eutectic with aluminum containing 13% Mg 2 Si and melts at 595C. When an excess of silicon (over that required to form the magnesium silicide) is present, a
ternary eutectic of aluminum,
Mg .Si
L
and
silicon results,
is
550C.
silicon,
The
composition of
this ternary eutectic
melting point approximately 13%

solubility in
6% magnesium
and
81% aluminum. maximum
The Mg,Si
solid
at
constituent in the binary alloy has a
aluminum of 1-85% at the eutectic temperature and less than .2% room temperature. These alloys have the ability to respond to heat
treatment and have tensile properties comparable with those of the heattreated
4% copper alloys.
corrosion resistance of this type of alloy
is
The
very satisfactory beis
cause the electrode potential of
Mg Si
2
(.83 volt)
almost the same as
aluminum. Alloys of this type, such from most other heat treatable alloy
as alloys 6053, 6061 in
and 6151, differ showing no appreciable decrease
in corrosion resistance after heat treatment.
Manganese. Manganese and aluminum form an eutectic containing 2.2% manganese by weight and melting at 657C. The intermetallic compound of these metals has the formula MnAl e The solubility of manganese in the solid aluminum at eutectic and room temperatures is .65
.
less than .1 respectively. This low solubility indicates that the most common manganese alloy 3003 (1.25% Mn) is a non-heat-treatable alloy. The electrode potential of this intermetallic compound is the same as aluminum, therefore this alloy has exceptional corrosion resistance. Inasmuch as manganese and its compounds are not toxic, this alloy is used in equipment for preparing and processing of foods. It is also used extensively for the manufacture of cooking utensils, conduit and pipes, pressure vessels, architectural applications and builders hardware. Nickel. Nickel forms an eutectic: with aluminum which contains 6.5% nickel and melts at 640C. The composition of the intermetallic com-
and
pound
eutectic
is
NiAlt
The
solubility
is
of nickel
.06%,
in
solid
aluminum
at
the
and less than .04% respectively. The addition of nickel to the copper-aluminum type alloys definitely improves the high temperature properties and retains the high thermal
and room temperatures

properties.
147
The forging alloys 2018, 2218 and 4032 are ternary alloys aluminum, copper and nickel. Their uses are for forged cylinder heads and pistons, jet engine impellers and compressor rings and other applications wherein high strength at elevated temperatures is necessary. Zinc. Aluminum and zinc form an eutectic consisting of 95% zinc and 5% aluminum, melting point 440C. The solubility of zinc in solid
of
aluminum
tively.
at the eutectic
and room temperatures
is
70% and 18%

One important
is
respec-
Zinc
is
a low melting and highly volatile metal.
limita-
tion of binary
and complex zinc-aluminum
alloys
their great loss in
strength at elevated temperatures. For example, castings
made from A612
and C612
of 200F.
are not
recommended
for use at temperatures greatly in excess
These casting alloys have the marked advantage that without heat treatment they have tensile properties comparable with the aluminumcopper and aluminum-silicon heat treated alloys. They offer the advantage that they can be heated to the temperature required for brazing
and will regain their original properties after a few days. The zinc wrought alloy 7075 has very good strength and good resistance to corrosion. This wrought alloy in the T6 condition in extrusions has a tensile and yield strength of 88,000 and 80,000 respectively.
8.11. Cold
and Hot Working of Aluminum Alloys

of cold working in the fabrication of sheet, rod, wire,
The purpose
tubing, extrusions,
and
like
basic
products are
(1)
increased
tensile
properties, (2) grain refinement, (3)
improvement
in surface appearance,
and
(4)
improvement
of dimensional properties.
Aluminum and its alloys on cold working undergo strain hardening. The tensile properties increase with the amount of work, in some instances almost proportional to the fractional reduction of the initial
Alloy
Tensile Strength
1G.0OO 19,000
Yield Strength
6,000 17,000
19,000
Elongation in 2 in.
3003-O 3003-H-12 3003-H-I4 3003-H-16 3003-H-18

Alclad
202-1 -T4 2024-T3 2024-T36 2024-T81 2024-T86
30
10 8 5 4
21.000 25,000
29,000
64.000
22,000
26,000 42.000 44,000 53,000 60,000 66,000
19
18
11
64.000
67.000
65,000 70,000
6 6
148
cross section.
The elongation decreases with increasing amount of cold work. As a general rule the initial cold work produces a relatively greater
effect
than subsequent reductions of equal amounts.

is
The
effect of
cold
work
two types of wrought alloys. The degree of strain hardening in aluminum and its alloys has an important effect on their temperature of recrystallization. It is usual to make
listed for the
50%
or higher reduction in cross-sectional area between annealing or heat
treating operations in order to prevent the development of excessively

large grain structure.
In the fabrication of the commercial basic products there
ment
used,
of the surface properties
due
to tool surface
is an improveand shape, lubricants
and the burnishing
effect
obtained by the cold work.
The
greater
the degree of reduction and the inherent hardness of the alloy, the brighter the surface.
Straightening and flattening operations are performed cold and are

usually conducted so as to introduce a
Plate, rod
minimum
of strain hardening.
thickness, followed
and bar are hot worked nearly to the desired by cold work to obtain greater dimensional accuracy.
structures.
aluminum ingots are hot worked to convert them to wrought Hot working is carried out during the manufacture of extrusions and forgings. The hot working of aluminum alloys require about 30-40% more power than for steel. Extrusions are made in the shape of
cast
The
rods,
bars,
is
and complicated
cross
sectioned materials.
is
The extruded
its
section
highly fibrous in structure which
parallel to
direction of
extrusion, therefore the tensile properties are often
much
higher than
other hot- or cold-worked products of same alloy.
Another difference between aluminum and steel is that aluminum does not form scale during heat treatment; therefore a suitable lubricant should be used during hot rolling. Die lubricants are generally used during hammer and pressing forging; extrusions usually do not require
lubrication.
8.12. Heat Treatment of
Aluminum
Alloys
The
to
(3)
three basic types of thermal processing that are

alloys are
(1) (2)
commonly applied
and
aluminum
annealing, precipitation heat treatment.
solution heat treatment,
alloys
The strain-hardening which results from cold working of the aluminum may be removed by annealing. The annealing process likewise re-
moves most of the temper resulting from solution heat treatment. This
thermal treatment permits recrystallization to take place; the higher the temperature used, the greater the rate. The rate of recrystallization is
149
also dependent upon the alloy involved and the severity of the cold work. Complete annealing is almost instantaneous for alloys 1100 and 5052 at 650F., and for alloy 3003 at 750F. The rate of cooling thereafter is not
critically
important although rapid cooling
may
lead to
some
distortion.
The temperature
alloy
used for annealing the heat-treatable type of
aluminum
must be carefully controlled and as low as practicable so as to prevent the dissolving of the intermetallic compound. Castings of non heat-treatable alloys are often annealed for the purpose of relieving internal strains, increasing their ductility
Some
alloys are
improved
in strength
range of 900-1000F., given a
and shock resistance. and hardness by heating in the rapid quench, and then aged at room temp-
erature and/or at slightly elevated temperatures. The alloy after quenching has fair ductility and malleability and is subjected as soon thereafter to
forming or other fabricating processing. Some
alloys spontaneously in-
crease in tensile properties within a short period of time; other alloys age so slowly that they are artificially aged by heating in the range 250-400F.
Such heat-treatable
that has a
alloys
contain
principal
alloying constituent
marked
increase in solid solubility at elevated temperature.
In most instances this alloying constituent is an intermetallic compound. The 4i/ copper-aluminum alloy 2024 has CuAlj as its hardening 2
agent;
its
solid solubility at
room and
elevated temperatures
is
.25% and
5.65%
respectively.
All this intermetallic
compound
goes into solid
solution at elevated temperatures and continues to remain in solution after rapid quenching due to the marked decreased mobility of the system. This unstable supersaturated solution has good ductility and malleability; therefore
During
it is formed into proper shape as soon as practicable. the next few hours fine precipitation of submicroscopic particles
of this hard intermetallic

the tensile properties.
compound
takes place, progressively increasing
Other heat treatable alloys such as 6061 undergo a similar transition during heat treatment and quenching, but differ in the respect that the rate of precipitation of submicroscopic particles is extremely slow at
room temperature,
of 250-400F.
it is artificially aged by heating in the range normally hardened by room temperature aging may be further increased in tensile properties by this artificial aging. The time required to reach the maximum strength by artificial aging
therefore
The
alloys
decreases as the aging temperature is raised; the value of the maximum strength, in turn, decreases. The precipitation of the hardening constituent from solid solution that results from artificial aging is accom-
panied by small changes in

properties.
specific gravity
and therefore dimensional

alloys after artificially
The 5% and 6% copper-aluminum
150
length of approximately .01%
aging show a decrease in

respectively.
and .15%
The
response to
is
artificial
the material
strain
aging for alloy 2024 is greatly enhanced if hardened after solution heat treatment and prior
In this instance the increase in tensile
a reduction of
to precipitation heat treatment.
and yield strengths is more than doubled by working prior to artificial aging.
6%
by cold
The
for
percentage of alloying elements

longer.
in casting alloys is
higher than
cast-
wrought
is
alloys, therefore the solution heat
treatment time for
and the finer grain structure of wrought alloys results in a greater degree of improvement in tensile properties by heat treatment for the wrought alloys.
ing
much
The
greater uniformity
The solution heat treatment of alloys containing high amounts of magnesium should be done with proper atmosphere control so as to
prevent possible oxidation along the grain boundaries.
condition
erties
is
This oxidation
of clad
manifest by minute surface
blisters,
decreased tensile prop-
and embrittlcment. The time of solution heat treatment

should be kept
at a
alloys
minimum
so as to prevent changes in composi-
tion
diffusion
and electrode potential properties of from the core.
the surface coating
due
to alloy
The cooling rate during quenching is often critical. The alloy 2024, improperly quenched, forms a non-uniform precipitation of microscopic and larger size particles of AIXu which makes the alloy susceptible to
localized corrosion.
8.13. Corrosion Resistance of
Aluminum
Alloys
its
The
excellent corrosion resistance of
aluminum and
alloys
is
due
it
primarily to the adhesion and chemical inertness of the oxide film.

differs
Inasmuch as this aluminum oxide is a nonconductor of electricity from iron rust (cathodic) in not causing galvanic corrosion.
Galvanic or "battery action" type of corrosion
is
encouraged wherein
electrode
the alloying metals or

potentials
their
intermetallic
compounds have
than the base metal. The solid solutions and the insoluble intermetallic compounds of manganese, chromium, magnesium and MgoSi have electrode potential values almost equal to aludifferent
much
minum;
FeAl s
,
therefore alloys involving these constituents
show good corrosion
resistance.
The solid solutions of copper, and the insoluble constituents NiAl3 CuAl 2 and Si, have much lower solution potentials than
,
aluminum, therefore
to corrosion.
alloys of these constituents
show only
fair resistance
151
The poor corrosion resistance of the improperly quenched aluminum copper alloys is due to its heterogeneous nature. Alloy 2024 on solution
heat treatment and properly quenched consists of a uniform supersaturated solid solution; its homogeneous nature makes it very resistant to
corrosion.
The subsequent
aging of the alloy leads to the uniform precipi-
tation of submicroscopic intermetallic

resistance to corrosion.
compound which
is
also
shows good
When
the alloy
quenched
slowly, the
CuAL
precipitates out at the grain boundaries as non-uniform microscopic and larger sized particles. The phase adjacent to the cathodic intermetallic compound consists of areas of depleted solid solution (anodic). The
localized corrosion that lakes place in this alloy
is
termed intergranular
corrosion.
When
increased
a
if
mild quench
the alloy
is
is
necessary, the resistance to corrosion

artificially aged.
subsequently
may be In the case of thick
sections, the rate of cooling,
even by immersion in cold water, is often not great enough to produce material completely free from susceptibility to this intergranular attack. This condition may also be discouraged by the use of alclad materials.
One of the most effective methods for increasing corrosion resistance of an aluminum alloy is to use alclad material or by applying a surface coating of pure or low alloy aluminum. The surface layer must be
anodic to the base metal, hence the protection is both mechanical and The present products available with this type of cladding are sheet, tube and wire. One limitation of this type of product is that during heat treatment, temperature and time should be very carefully
electrolytic.
controlled so as to avoid excessive alloy diffusion into the clad layer, thereby decreasing its effectiveness in protecting the core from corrosion. Alclad 2024 sheet improperly heat treated should be checked by proper
tests for excessive
"copper diffusion."
Another commercial process used to protect aluminum alloys from corrosion is by the surface oxidation by electrolytic means. The process
is known as anodization because the aluminum is made the anode and the iron tank the cathode, the processing solution being dilute sulphuric
or chromic
acid.
The
anodic film
it
natural oxide film; therefore

cal insulation, abrasion
is thicker and more uniform than the has increased corrosion resistance, electri-
hardness and chemical inertness. An unusual property of the anodic film, especially right after its formation, is its great
power of adsorption. The
excellent anchorage
is
minum
for paint films
and dyes
power of anodized aludependent upon this great power of
adsorption.
152
acid dip treatment, anodi/ation, painting with zinc
Chromic
chroma te
alloys are
primer, and other like processing and treatments of
aluminum
based on the passivation action of chromic acid and chromates, and

their adsorption in the oxide film. When an aluminum alloy in use shows excessive corrosion, this condition may be stopped by cleaning area, painting with chromic acid solution, drying and then painting.
It
is
important that aluminum assemblies should consist
as
much
as
possible of the
same
alloy or alloys of like solution electrode potential.
Rivets should be of the same alloy as the base metal, and if different, should be of an alloy that lias a slightly lower potential so that the rivets would be cathodic. Galvanic corrosion can be markedly retarded
if
the rivets can be electrically insulated by anodic treatment. Welding-
same alloy or of slightly lower potential than the base metal. Inasmuch as brazing and soldering involves foreign metals, adjacent areas must be carefully protected from galvanic corrosion. When two metals are involved that have marked difference in potential,
rods should likewise be of the
it
is
good practice
is
to coat
potential value.
The
steel cable
one with a metal intermediate in electrode used in aluminum cable for transmission
of electric current
plated with zinc to discourage galvanic action.
8.14. Joining of
Aluminum
its
Alloys
joined by fusion and electric-
Aluminum and
alloys are usually
resistance welding, brazing
and
riveting.
in that the filler material has a
much
Brazing differs from welding lower melting point that that of the
parent material so that the latter does not melt. The common types of fusion welding are the gas and the arc processes.
The
three brazing processes are classed by the methods used in applying
the brazing heat, namely, furnace, torch,

resistance welding
is
and dip
brazing.
The
electric
classified as spot,
seam, and
flash.
The main difference in the welding technique and procedure of aluminum and its alloys as compared to the iron alloys is primarily due to the
very high thermal coefficient of expansion and high temperature oxidation of
aluminum, and thermal and
electrical insulating pro]>erties of
its
oxide coating.
The
the use of properly designed parts
high thermal expansion of aluminum and its alloys necessitates and carefully prepared joints so as to
minimize buckling and distortion. The filler rod and the base metal are both provided with a flux coating to maintain an oxide-free metal surface during the welding process. The commercial flux materials consist of mixtures of saline chlorides-fluorides. -Proper ventilation must be provided in the welding area because the fumes of the flux are both
153
disagreeable and irritating to the welder and highly corrosive to nearby metal structures and materials. The welded part must be given a mechanical cleaning or chemical pickle treatment so as to completely remove
residual saline material
due
to
its
toxic
and
corrosive character.
torches,
Gas welding involves the use of oxyhydrogen and oxyacetylene
the flames in both instances being neutral in character. The gas welding has its main application with materials ranging from .0401 inch in thickness.
The main
tungsten
arcs.
arc processes include metal, carbon, atomic hydrogen,
and
The
metal-arc
is
particularly suitable for heavy material;
have been welded satisfactorily. Difficulties is used with material less than 5/64 inch thick. The carbon-arc is used for manual and automatic welding; the produced welds are comparable in structure and appearance to gas welds but with less distortion. The atomic hydrogen process is applied
to 21/g inches
thicknesses
up
are experienced
when
the metal-arc
welding but differs in the respect that it by moving the torch away from or towards the work. One limitation of the atomic hydrogen-arc process is the difficulty of removing the residual flux from the welded assembly. The tungsten arc uses an inert gas shield to protect the arc and the weld area; this method has two advantages: satisfactory welds can be (1) made with equal facility in vertical, flat, and overhead positions, and
as gas
is
in
much
the same
manner
possible to control the heated zone
(2)
no
flux
is
required.
All commercial alloys are not readily adaptable to fusion or electricresistance welding. The alloys that are commercially fusion welded are 1100, 3003, 5052, 6053, and 6061. In some instances the welding is
and/or costly. One limitation of the heat-treatable type of alloys that the high temperature of welding tends to decrease the mechanical strength and the corrosion resistance.
difficult
is
The proper choice of welding rod is very important particularly when dealing with alloys having large amounts of alloying elements. The two
most weldable alloys 1100 and 3003 use 1100 welding rod.
strength alloys 5052, 6053,
The
high-
and 6061,
fairly difficult to weld, are
welded
with 5% silicon-aluminum alloy filler rod. This 4043 alloy rod has a melting point much lower than pure aluminum, excellent fluidity and wetting properties, and low shrinkage contraction, thereby insuring a
the important applications of fusion welding is the salvaging of aluminum alloy castings that have foundry defects, and the repairing of cracked or broken castings. Castings should be preheated in a furnace
to
minimum One of
of shrinkage stresses and cracks.
approximately 800F. This thermal treatment avoids thermal
stress,
154
amount of welding gas required. It is important that careful temperature control is maintained during this preheat treatment so as to avoid "burnt" material and possible collapse
reduces the welding time and
of the casting.
The
areas adjacent to the welded sections of the strain-hardened alloys
The weld metal has tensile properties almost equal to the annealed metal but lower in ductility. Assemblies of
are annealed by the welding heat.
heat-treatable alloys should be welded prior to heating or given a reheat
treatment so as to improve the tensile and corrosion resistance properties. Electric-resistance welding has been a large factor in reducing the cost
making joints, improving products, and speeding up production. This type of welding is usually applied to strain-hardened type of alloys,
of
but
is
often used with the heat-treatable alloys particularly of the alclad
type.
The
aluminum and
In addition
technique and equipment employed for the resistance welding of its alloys is considerably different than that used for steel.
the electrical capacity required
for
aluminum
is
several
times greater.
The
three types of equipment are classified on the basis
of the electrical system used for supplying the welding current, namely,
(1)
energy storage.
alternating current, (2) magnetic energy storage and (3) condenser The proper choice of electrode shape and its proper
is
maintenance
spot welds.
very important in obtaining high quality and strength

electrode must have high electrical
The welding
and thermal
conductivity and fairly good strength; electrodes are usually

copper-silver alloys.
made
of
Weld pick-up and
the softening of the tip are pre-
vented by having cold water circulating through the electrode.
Some
machines use refrigerated water circulating at a rate of 2 gallons per minute and to within 3/8 inch or closer of the tip face.
The material to be welded must first be freed of oil and grease, dirt, and surface oxidation because these substances have electrical insulating properties. The surface contamination may be removed by an alkaline
degreasing bath whereas the oxide coating necessitates mechanical abrasion or chemical etch methods.
The
metal must be spot welded within
a few hours of chemical etch because the oxide film will reform.
Bra/ing has been used in production on certain alloys such as 1 100 and 3003, and to lesser degree on the heat treatable alloys 6053 and 6061.
The copper-aluminum
tensile strength
alloys
and 5056 show poor workability during
brazing operations; the resulting joints and adjacent areas have decreased
compared
and corrosion resistance. The advantages of brazing as and arc welding are as follows: (1) it can be used with thinner material, (2) the costs are lower, and (3) the surface appearance
to gas
Light Alloys
is
as
155
superior. The torch-brazed joint has the tensile strength comparable to a weided joint and has almost the same degree of corrosion resistance. Riveting is the most commonly used industrial method of joining the
structural
rivets are
aluminum alloys, particularly the heat-treatable type. The made of commercial aluminum, the magnesium-silicon alloys
6053 and 6061, and the copper alloys 2017, 2024, and 2117. All except the
are received from the manufacturer in the hard, heat-treated condiRivets of 2017 and 2024 are solution heat treated, quenched, and driven as quickly as possible; whereas, the other type of rivets are driven
first
tion.
"as received."
It is advantageous from a strength point of view to use rivets having about the same mechanical properties as the base metal; whereas, from
the driving standpoint

softer.
From
it is
it is usually advisable to have the rivets somewhat the corrosion resistance angle it is advisable to have the
rivet of the
same composition or electrode potential

driven.
as the material in
which
For example, alclad sheet alloys are usually riveted
with 6053 or 6061 because of their excellent corrosion resistance and
aluminum in their electrode potential value. Rivets that are solution heat treated prior to driving arc generally processed in large quantities, quenched in cold water, washed
nearness to
with 2017
alcohol,
and placed
in refrigerated cabinets. Solution heat treated
and 2024 alloy rivets harden at room temperature over a two-hour period, making them unsuitable for driving thereafter. The rivets will remain
soft for
36 hours if kept at 32F., or lower, after quenching. Small insulated boxes of cold rivets are kept in refrigerated cabinets near the individual work areas. Large rivets of 2017 alloy are usually driven in the hot condition. They are solution heat treated at 930-950F. for approximately fifteen minutes, inserted in the hole and driven. The relatively cold driving tools and the base metal function as quench. Steel rivets in aluminum-alloy structures
are driven hot in the customary fashion; they are heated to I800F. and driven as quickly as possible.
When the service conditions are severe or dissimilar metals are involved, special treatments should be applied to prevent corrosion. Various methods are used, such as application of zinc chromate primer prior to assembly, use of good grade of joint compound before assembly, use of anodized aluminum alloy rivets; and if steel rivets are involved, they are metallized with aluminum or zinc after driving.
8.15.
Magnesium And
is
Its
Alloys
its
Magnesium
a very unusual metal:

its
properties
is
any other commercial metal, and
behavior
do not run parallel to not as predictable. Mag-
156
nesiuni holds the unique position
among
the structural metals in having
the lowest density, the highest machinability, and has an inexhaustible
source of supply.
The
low specific gravity of magnesium (1.74) means that

1/4
it
is
2/3 as
dense as aluminum and
that of iron
and
steel.
The
cutting speed for
magnesium and
its
alloys
is
twice that of free-cutting brass and four times

1
part in 770 of magnesium therefore one cubic mile of seawater could produce nine million tons of magnesium. There is also a vast supply of magnesium in magnesite and dolomite.
that of cast iron. Seawater contains
low melting point, high near the melting temperature, good thermal and electrical conductivity, low density, high strength-weight ratio, and non-magnetic and non-sparking propis
Magnesium
similar to
aluminum
in
its
solidification shrinkage, hot shortness,
low
tensile strength
From a chemical point of view these two metals have low atomic and equivalent weights, and high electrode potentials. It markedly differs from aluminum in its crystal structure, (H. C. P.) fair malleability and ductility, fair cold workability, poor notch sensitivity, non-protective oxide coating, and lower corrosion resistance. Magnesium is much more chemically reactive than aluminum due to the physical and chemical
erties.
,
nature of
its
oxide coating.
of
fl)
The manufacturing procedures and processes much like that of aluminum in the respect that
magnesium are very the impurities must
be removed from the ore rather than from the produced metal, (2) requires large amounts of energy, (3) requires high temperatures, and (4)
reduction involves nonaqueous reactions.
process for making magnesium is by molten solutions of magnesium chloride. The formed molten magnesium floats on the surface and must be protected by an inert atmosphere since it chemically absorbs both oxygen and nitrogen. Another limitation of this (Dow) process is that the chlorine constitutes a health and corrosion hazard.
the electrolytic reduction of
The most important commercial
Two lesser important processes are the chemical reduction of magnesium oxide by carbon and silicon respectively. In the carbothermic (Hansgirg) process, briquets of magnesium oxide and carbon are heated at 2000C. to form magnesium vapor and carbon monoxide gas. This reaction mixture on cooling would reverse to the original raw materials; this is prevented by rapidly cooling and diluting with natural gas or other inert gases. The fine magnesium powder that results by this "shock" action must be purified by distillation. The Pidgcon process depends on the fact that silicon in the form of ferrosilicon will remove the oxygen from magnesium, that the formed silicon dioxide is a non-

volatile material,
157
and metallic magnesium under reduced pressure can The Hansgirg and Pidgeon processes are more expensive than the Dow process, but have the advantage of not depending on electric power.
be
distilled at 1150C.
The improvement of magnesium by addition of alloying elements is not very great. The main alloying elements are aluminum, zinc, and manganese. Zinc is more effective than aluminum in the improvement
of mechanical properties but offers the disadvantage of decreasing
its
corrosion resistance.
of manganese
compromise
alloy AZ-63 consists of

is
6%
made by using both. The aluminum and 3% zinc. The main function
is
often
to increase the corrosion resistance.
The minor
tin,
alloying elements are beryllium, calcium, cerium, silicon,
and zirconium. Beryllium decreases the tendency of burning during the melting and casting. Calcium reduces oxidation during melting and heat treatment, and increases the reliability and formability of magnesium sheet. Cerium increases the high temperature strength. The
main function
and
metal.
of silicon is to increase the fluidity of molten magnesium to decrease the hot shortness and cracking tendencies of the solid
Tin
increases ductility,
and zirconium
leads to grain refinement.
The
very undesirable elements and their approximate

,
maximum
tolerance
and iron (.005%) Magnesium alloys are somewhat difficult to roll; therefore structural members are usually extruded. Cold working, bending, and deep drawing can be satisfactorily accomplished under carefully controlled conditions and with frequent annealing. Most mechanical processing is done at
temperatures above 225C.
are copper (.1%), nickel (.01%)
Pure commercial magnesium sheet in the annealed and hard-rolled conditions have the respective tensile strength values of 27,000 and 33,000
psi. Most magnesium alloys have tensile strength in the range of 40-50 thousand psi, and the maximum of sixty thousand. Special
costly alloys
containing
thousand.
3%
silver or
6%
cerium have
tensile strength of sixty-five
The
heat-treatment processes of
aluminum except
readiness with
alloys
magnesium alloys is similar to that of the temperatures involved are considerably lower. The
in the air
which magnesium oxidizes
precautions and
its
new techniques
are involved.
means that special Although aluminum and

baths, violent ex-
plosions
may be heat treated in molten sodium nitrate may take place with the alloys of magnesium.
One outstanding advantage of magnesium and its alloys is its excellent machinability. Cutting fluids are used primarily as a coolant to prevent the magnesium from catching on fire. The turnings from machining
158
fire
operations also represent a potential

are unsatisfactory for putting out
hazard. Dry sand should be
available in these areas because water or the
common
fire
extinguishers
magnesium
likewise
fires.
The
casting
of
magnesium
requires
special
conditions.
Molten magnesium is usually protected by an inert atmosphere of sulphur and sulphur dioxide. Green sand castings can not be used unless inhibitors
magnesium will react with the moisture. The subsequent finishing of the casting involves metallic dust that represents
are present; otherwise the a
fire
hazard.
of
magnesium and its alloys under normal conUnder highly humid conditions and other severe conditions, magnesium and its alloys should have a protective film or coating. Magnesium alloys prior to fabrication are usually shipped
ditions
is
The corrosion resistance
very satisfactory.
with a film of
pickle
is
oil
or a
chrome
pickle treatment coating.
The chrome
is
superior to the
oil film for protection,
but the former
easier to
remove prior
to spot welding.
Magnesium alloys may be joined by gas and arc welding, electric-resistance welding, and by riveting. Most of the wrought alloys can be joined
by gas welding using neutral flames of oxyhydrogen, oxyacetylene and oxycarbohydrogen
The
filler
rod should have the same composition
as the
parent metal
or have a lower melting point.
must be used during welding due to the ease of oxidation of magnesium. Magnesium alloy sheet, extrusions, forgings, sand and permanent mold castings are often welded by using an inert gas-shielded arc method. These alloys may be resistance welded after they have been cleaned of surface contamination and oxide coatings. Magnesium may be riveted by the most conventional methods. Magnesium-alloy rivets cannot be used because of their rapid work hardening at room temperature. The rivets generally used are the 5%
flux
magnesium-aluminum alloy 5056, which has a like electrode potential. Most processed magnesium alloy parts and assemblies that will be used where corrosion is greater than normal are given a final chromate treatment.
offers
The chromate
good anchorage
treatment results in the removal or passivation of

for a paint film.
all
foreign metals
and produces an adhering protective
coating. This coating
8.16. Beryllium
Beryllium resembles magnesium in

close-packed crystalline structure,
similarity to
its
low density
its
and
(1.84) its hexagonal poor cold workability. Its

,
is shown by its low equivalent weight, its amphoand the refractory and protective nature of its oxide film. The outstanding property of beryllium is its great power of producing
aluminum
teric properties,
159
hardness and strength in other metals; it suffers the two great limitations of high cost and toxicity. Its cost is high because (1) its ores are not common, (2) the concentration of beryllium in the ores is often less than 4% average, (3) its manufacture by the modified thermite or Gold-
schmidt process is a costly one. The most important alloy of beryllium is the beryllium-copper alloys, which have high fatigue and corrosion resistance, good electrical and thermal properties, and are virtually non-sparking. The 2% alloy on
heat treatment, quenching, and aging develops a hardness equal to Rockwell C-40.
Amounts in the order of .01% beryllium in molten aluminum and magnesium decrease their oxidation and combustibility markedly, and
reduce their
of beryllium
viscosity, particularly in the case of
aluminum. Small amounts

steel.
may be
used to case-harden iron and
beryllium are very toxic and give rise to lung diseases that are often fatal. Beryllium is available commercially in the form of 12% beryllium-copper alloy.
8.17. Titanium
The vapors and powdered
Titanium in one of the most abundant metals in the earth's crust, the main ores being ilmenite (iron titanate) and rutile (titanium oxide) It is made by the modified thermite or Goldschmidt process.* The very
important properties of titanium as a structural metal are its high melting point (1820C.) its high tensile strength at ordinary and elevated temp,
eratures,
corrosion.
low density (4.5) and its high resistance to ordinary In the annealed and cold-worked (60% reduction) condition the commercial metal has the respective tensile strengths 78,700 and 111,500 psi. Exposure to accelerated corrosion tests using salt spray for 30 days has little effect on commercial titanium.
its
relatively
Titanium, like magnesium and beryllium, has the hexagonal packed crystalline structure; therefore its workability likewise
at
close-
ordinary
temperatures is poor. When titanium is heated to 875C, it undergoes a transition to an body-centered cubic structure; hence its workability markedly increases at this temperature. There is a 5.5% volume change during this allotropic transformation. One limitation of titanium is that it will readily unite with and burn in oxygen at 600C. and with nitrogen at 800C. At elevated temperatures titanium will likewise unite with carbon and hydrogen.
is a very important additive element in the steel industry. great affinity of titanium for carbon is taken advantage of and carbide precipitation avoided in 18-8 stainless steel by the presence of titanium, the amount being about five times that of the carbon content.
Titanium
The
And now produced
widely by the Kroll process.
160
presence of .5-1% titanium in 17-7 stainless steel leads to a ferritic
The
structure.
The
grain refinement of
aluminum and
is
its
alloys
by the
presence of small amounts of titanium

for dissolved oxygen, nitrogen
due
in part to
its
great affinity
and hydrogen. Titanium

steel.
acts likewise as a
scavenger for oxygen and nitrogen in
QUESTIONS
1.
What
that
2.
in the earth's crust? What is the metal inexhaustible in its supply? Magnesium oxide has been reduced industrially by the action of carbon to form metallic magnesium. Why cannot aluminum be economically made
is
the .most
abundant metal
is
in the
3.
same manner?
impurity as a metal oxide,
in the Bayer Process?
if
What
present in bauxite ore, could not be
removed
i.
5.
Aluminum is often melted in iron pots which are usually protected by a coating of whiting or other insulating material. Why is this protective coating important? The general rule regarding gases is "they decrease in solubility in liquids with rise of temperature." How would you explan why the solubility of
hydrogen increases with
rise
of
temperature
when
present
in
molten
aluminum?
6.
Accurate control of temperature is very important during the solution heat treatment of aluminum alloys. What are the relative advantages of a molten bath and an air furnace?
7.
What
it
8.
9.
test solution would you use on a large assembly to determine whether was an aluminum alloy or a magnesium alloy? What are the main obstacles of manufacturing aluminum from clay? Excessive rates of heating metal lead to cracking. In view of the fact that aluminum alloys are good conductors of heat and that the nitrate bath is a
fair
conductor,
is
why
is
the heating in this bath
still
rather slow?
(What
in-
sulation film
10.
involved?)
processing room wherein the Hall process is conducted must be provided with good ventilation. What gas and vapor must be conducted away? 11. Why does the presence of high silicon in aluminum alloys lead to superior fluidity? To lower degree of contraction? 12. How do you explain why magnesium has the highest machinability among the commercial metals? Why arc its turnings so much more combustible than those of aluminum? 13. Why should the heat treatment of magnesium be made in an air furance rather than a molten nitrate bath? 14. Aluminum sheet arrives at the plant with fine (tissue) paper between each sheet. Give three reasons why this has benefical results. 15. After aluminum has been anodized, and then given cold and hot rinses, it should be painted within one hour thereafter. Why should this time be important? 16. What precaution should be made regarding machining or processing of beryllium alloys? 17. How do you account for the fact that titanium has high strength at elevated temperatures?
18.
is passed into molten aluminum on two occasions. What are two conditions that are eliminated by this action. Give reasons for both.
The
Chlorine gas
CHAPTER
Copper and Co pper -Base Alloys as Engineering Materials

Waiter
R. Hibbard, M.S., Adjunct Associate Professor
of Metallurgy, College of Engineering, University of Bridgeport, Bridgeport, Connecticut
Roger Greenleaf Stevens,
Ph.D., Head, Department of Chemical Engineering, Southwestern Louisiana Institute, Lafayette, Louisiana
1 HESE
metals are such an integral, but com-
monly unnoticed, part of our daily life that even the housewife in the kitchen and the clerk in the store would find it difficult to establish a new routine of existence if copper suddenly disappeared from the world. Judged solely from the standpoint of absolute value to mankind, copper and its common alloys, the brasses and the bronzes, cannot compete with carbon steels, but each is of vital importance to our civilization and
could
It
hardly be eliminated without destroying or at least seriously

the elixir vitae of
crippling most branches of industry.
has been said with justification that electricity

civilization.
is
machine
if
It
is
difficult to
conceive of an electrical industry
copper and its ores had never been known, unless nature had provided with a substitute of equal conductivity, plasticity, and cost. Second only to high conductivity in importance is the resistance of copper and
man
some of the copper-rich alloys especially sea air and sea water.
to corrosion
in certain environments,
The average automobile uses 45 lb. of copper and its alloys, the average steam locomotive 4,500 lb., and the modern steamship more than 3 million lb. as castings, in pipes and tubes and in electrical equipment.
No metal has proved so suitable for steamship propellers as manganese bronze; four of these, weighing 37 tons each, drove the Queen Mary across the Atlantic Ocean in four days.
With two or three exceptions, the copper and copper-rich alloys discussed in this chapter have been important engineering materials for
161
'62
years and, unlike
some of the light alloys discussed in the previous chapter, are covered by specifications of the American Society for Testing Materials.* In addition, most of them also conform to specifications adopted by the Society of Automotive Engineers, the Association of American Railroads, the American Society of Mechanical Engineers
(Boiler Construction Code)
U.S. Navy,
the American Standards Association, the and the U.S. Army, and to general federal specifications.
,
These standards especially those issued by A.S.T.M. -should be consulted for exact chemical composition and for minimum mechanicalproperty and other requirements which must be met before the material can be considered to be of good commercial quality. Although copper is present in the earth's crust to the extent of only 0.01 per cent, ore deposits of commercial importance are fairly widecopper-ore deposits of commercial United States contain on an average somewhat less than 2 per cent copper. In the important ores, copper occurs as the oxide, carbonate, silicate, and sulphide, of which the last named is the most abundant. In some parts of the world, notably in the vicinity of Lake Superior, long weathering of copper ores followed by
iron
ores,
spread.
Compared with
quality are lean.
The
ores of the
reduction of the resulting oxide or the carbonate, or the deposition of copper from solution, has produced large deposits of relatively pure native metal, which was distributed far to the south by the glaciers. Native copper was the only metal (except small quantities of meteoric iron) used by the American Indians for tools and weapons until the
white
man arrived. The production

process,
of high-purity copper from lean sulphide ores
is
complex
but copper exceeding 99.9 per cent purity can be probrief, the process consists of
duced cheaply. In
concentrating and roastto
ing the complex sulphide ore (copper, plus iron, plus other metals)
form oxides and

oxide.
to eliminate
some
is
The
roasted concentrate
and arsenic as the smelted with coke and a flux in a

of the sulphur
reverberatory furnace to remove part of the iron.
The copper and

is
iron
sulphides fuse into a matte containing about 40 per cent copper. This
matte
is
charged into a Bessemer converter and
blown
in a
manner
similar to the refining of pig iron to produce Bessemer steel.
The copper
and the remaining iron sulphides are oxidi/ed, and the iron oxide combines with silica to form a silicate slag. The result of these reactions is
"blister copper" containing 95 to
97 per cent copper and considerable
copper oxide.
'Sec A.
S.
T. M. Standards, Part
2,
1955.
163
In addition to copper oxide, blister copper generally contains small amounts of sulphur, iron, lead, arsenic, antimony, selenium, tellurium, nickel, and other elements, usually including some gold and silver. In some ores, in fact, the silver and gold are worth so much that the copper
could be called a by-product of the refining of the more precious metals. Although the amount varies, a typical anode melted from blister copper frequently contains 30 oz. of silver and nearly i/ oz. of gold per ton. 2
melting and casting the blister copper into Electrolytic copper contains 99.95 per cent or more copper, with sulphur as the principal impurity. About 25 per cent of the electrolytic copper produced is used for making copperfinal step in refining
is
The
blocks which are electrolyzed.
base alloys; the remainder is melted in a large reverberatory furnace, oxidized to remove sulphur, and then "poled." This consists of inserting green wood poles beneath the surface of the molten metal. In the reaction between the wood and the molten copper oxide
is
enough oxygen removed so that the remainder, 0.03 to 0.04 per cent, when evolved during solidification, exactly balances the normal shrinkage of the metal.
Poled copper
is
known
as "tough-pitch." Its density in the cast condition
approximately 8.5 gm. per cu. cm., compared with 8.94 for the pure metal. Tough-pitch copper is used for wire for electric conductors, for
is
sheets,
and
for
many
other purposes.
Lake (Superior) copper, which constitutes about 15 per cent of the commercial copper in the United States, is-as previously mentioned-a
high-purity native copper
It differs
and does not
usually need electrolytic refining.
it may contain a small amount (which does not affect conductivity) and from 0.002 to 0.04 per cent or even more arsenic, which, in the higher amounts, may reduce relative conductivity as much as 40 per cent.
from
electrolytic
copper in that
of silver
recent development in copper refining
is is
the production of oxygen-
free copper. particles,
Oxygen in tough-pitch copper

this
present as cuprous oxide

solid metal.
which are almost completely insoluble in the

oxide
is
For
most purposes
is is
not harmful, but if extremely high ductility essential, the copper should be practically free from oxygen. The oxide also harmful if the copper is heated in an atmosphere containing hy-
drogen
common one
as this gas diffuses into the metal, reacts with the oxide, and causes brittlencss. There are two types of oxygen-free copper. The more
is produced by deoxidizing the molten metal with phosphorus or some odier element having a high affinity for oxygen. The residual phosphorus, although only about 0.02 per cent is present, reduces
the electric conductivity as
much
as
20
j>er cent.
To
,
produce high-conis
ductivity oxygen-free copper
(known
as
OFHC)
very pure copper
164
melted and cast in an atmosphere free from oxidizing gases. A recent innovation consists of granulating brittle copper cathodes, which have been deposited electrolytically and which are free from oxygen, followed
by "coalescing" these in a press at high temperatures, which welds the

particles together
and extrudes
the metal as a solid bar.
Copper is malleable and is hot and cold worked into sheet, plates, and a variety of other shapes. As in the case of most other metals and alloys, cold working increases strength and reduces ductility.
tubes,
9.1. Properties
and Uses of High-Purity Copper

electric conductivity of all the
Copper has the highest
common
metals.
On
a strength
basis, its
conductivity
is
more than
twice that of high-
purity aluminum.
in the
About one half of the 800,000 tons of copper consumed United States in the average peacetime year is used for electrical
equipment and
for wire in light and power lines. When annealed, highpurity copper has a conductivity of 100 per cent according to a standard set up in 1913 by an international commission. Recently improved
methods of purification have resulted

per cent.
in conductivities as high as 102
Copper
is
also the best heat

it
which makes
(and
its alloys)
conductor of any of the commercial metals, useful as cooking utensils and as radi-
ators and other heat-dissipating apparatus. In general, copper and the copper-rich alloys have excellent resistance to corrosion by the atmos-
phere and by water. Owing to this corrosion resistance and to a reasonable price, copper and some of its alloys are widely used by the building
and water hardware and interior fixtures. When exposed to the atmosphere for long periods, copper oxidizes and forms a green patina which is ornamental in addition to being adherent and protecting the underlying metal from further attack. Approximately 10 per cent of the copper consumed annually is used by the building industry.
pipes,
industry for roofing, down-spouts, gutters, screens, drainage
and
for
Copper and copper-rich alloys have a wide range of mechanical propAnnealed high-purity copper has a tensile strength of approximately 30,000 lb. per sq. in., an elongation in 2 in. of about 60 per cent, and a reduction of area of as much as 90 per cent. It is, therefore, weaker and more ductile than high-purity iron. At the other extreme, precipitaerties.
tion-hardened copper-beryllium alloys

190,000
lb.
may have
a tensile strength of
per
sq. in.
with accompanying low ductility.
The tensile strength of high-purity copper may be increased to 65,000 or 70,000 lb. per sq. in. by drastic cold working; elongation is lowered

to about 5 per cent.
165
According to Gillett,* the endurance limit of annealed tough-pitch copper is approximately 10,000 lb. per sq. in., and
cold working increases
of elasticity
capacity
is
it to as much as 20,000 lb. per sq. in. The modulus approximately 16 million lb per sq. in. The damping almost as high as that of cast iron.
is
For some applications the low strength of high-purity copper wire is a distinct disadvantage. Unfortunately, most alloying elements added to increase strength reduce conductivity to a fraction of the value for
high-purity
strength
copper.
satisfactory
and decrease amounts of cadmium.
in conductivity results
compromise between increase in from the addition of small
1100
40 50 60 Zinc, per cent
%V
M.
100
Frc. 9.1.
The
copper-zinc phase diagram. (A. Phillips and R,
BricKft
9.2. Constitution of the
Common
Copper-Rich Alloys
None
of the four series of
copper-zinc,
copper-tin,
important binary copper-rich alloys namely, copper-aluminum, and copper-nickel-can be
heat treated in the sense that sterling silver or many of the aluminumrich alloys can be heat treated. Sections of the copper-zinc and the
copper-aluminum diagrams arc given
in Figs. 9.1
useful alloys of copper with zinc (brass)
and 9.2. Most of the and of copper with aluminum
H. W. Gillett, Metals and Alloys, v. 3, 1932, p. 200. \ Metals Handbook, American Society for Metals, Cleveland, 1939, p. 13G7.
166
less
(aluminum bronze) contain

per cent
copper.
than 40 per cent zinc and
less
than 10
aluminum
respectively
and
are,
consequently, ductile single-
phase alloys consisting of a solid solution of zinc or of aluminum in If the zinc in brass exceeds about 35 per cent, beta phase appears, reducing ductility and impact resistance. Only one such alloy,
the
Muntz metal, containing -10 ]>er cent zinc, is used widely, and in this amount of beta is so small that ductility is not seriously affected.
Similar to conditions in the copper-zinc system, most of the wrought
per cent per cent
aluminum bronzes are single-phase alloys containing 5 to 9 aluminum (see Fig. 9.2) If the alloy contains more than 9.5
.
aluminum, beta phase appears, reducing the
ductility.
Although the beta

is
phase cannot be retained in solution by quenching, there

10.5 to
1 1
the possibility
of securing transition structures by quenching a wrought alloy containing
per cent aluminum. per

sq. in.
The
result
is
a tensile strength of 100,000
to
110,000
lb.
pared with 65,000 to
and an elongation of 10 to 15 per cent, as com85,000 lb. per sq. in. and 35 to 50 per cent elongaAtomic Percentage Aluminum K> JS 20 2S SO
%
_5
Weight Percentage Aluminum

Fig. 92. The copper-rich portion of the copper-aluminum phase diagram.t Fink, L. A. Willey, and C. S. Smith)
(W. L.
ilbid., 1948, p. 1160.

tion for the alpha-phase alloy. in the
167
is
No
precipitation hardening
possible
binary copper-rich copper-aluminum alloys.

principal commercial copper-tin
1
The
alloys
are alpha-phase alloys
and contain
to 10 per cent tin
only important binary alloy is per cent tin and which is deoxidized in melting with a small amount (less than 0.5 per cent) of phosphorus. Tin increases the hardness and
cold-rolled phosphor bronze used for springs has a about 100,000 lb. sq. in. with 5 per cent tin; this increases to 120,000 lb. per sq. in. with 10 per cent tin. No heat treatment is possible with commercial copper-tin alloys. Copper and nickel form a continuous series of solid solutions free from any phase change. The strength of the solid solution of nickel in copper increases with the nickel from about 35,000 lb. per sq. in. for very low
tensile strength of
and usually also zinc, lead, or both. The phosphor bronze which contains 4 to 10
strength of copper.
nickel to 80,000 for 60 per cent nickel; elongation decreases from 70 to 45 per cent in 2 in. There are a large number of important copper-nickel
owing to their controllable color, to their corrosion resistance, or to their thermoelectric properties, are used for coinage, ornamental metal work, ship construction ( especially in parts exposed to salt water) thermocouples, and in other special applications. An alloy higher
alloys which,
,
Monel metal-containing 65 per cent nickel and 35 per cent copper-is widely used because of its high resistance to many corrosive
in nickel,
mediums.
9.3.
Nomenclature of the Copper-Rich Alloys
Although the copper industry is no worse than the steel industry in names and in confused nomenclature, so many misnamed alloys are commonly used that some attention to this subject seems advisable. The most common examples of confused nomenclature
the use of trade are calling a copper-zinc alloy bronze if it has a color resembling that of the copper-tin alloys and calling a copper-zinc-nickel alloy nickel silver if it has a silvery-white color. This confusion is regrettable, but in most
cases
years of usage.
alloys
tion,
is
nothing can be done about it, as the names are firmly fixed by The important fact to remember about the copper-rich
that the
name may
be more descriptive of color than of compositin
and that a "bronze" may contain no
and may even be
a brass;
likewise, nickel silver contains
no silver.
The usual name and the typical compositions of some common copperrich alloys are given in Table 9.3. It is evident that manganese bronze
(item 43)
9
,
hardware bronze (item
19)
and
10) are in reality brasses.
The
, and commercial bronze (items only true bronzes given in Table
168
9.3 are items
49
to 59,
silver,
which are copper-tin

formerly
alloys deoxidized
silver,
is
by phosthe
phorus.
of a
Nickel
known
as
German
name
of
containing 17 to 42 per cent siderable part of the copper is replaced by nickel.

brasses,
group of
zinc, in
which a con-
The composition
Another example of confused nomenclature is the casting alloy containing 85 per cent copper and 5 per cent each of zinc, tin, and lead. As this alloy contains 5 per cent tin, it is as much of a bronze as it is a brass, but it is called red brass* and is, consequently, sometimes confused with wrought red brass which contains 85 per cent copper and 15 per cent zinc.
is
four of these alloys
given in Table
9.3.
9.4. Characteristics
and Uses of the High Brasses
As shown by the diagram in Fig. 9.1, 39 per cent zinc dissolves in copper at room temperature. Alloys containing less than this percentage of zinc when in a state of equilibrium are, therefore, single-phase solid
as alpha brasses. As shown also by Fig 9.1, about 36 to 39 per cent zinc may have a duplex structure if heated to a high temperature but should be single phase at room temperature. Actually, however, owing to a phenomenon known as coring, cast alloys usually have a duplex structure if the zinc is higher than 31 or 32 per cent. A zinc content of 35 per cent is about the maxi-
solutions
and are known
alloys containing
mum
for an alloy that is to be fabricated as a single-phase material. Although there is a continuous series of alpha brasses containing from 5 to 39 per cent zinc, these alloys are commonly and arbitrarily divided into two classes: high brass, containing 30 per cent or more zinc, and low brass, containing approximately 25 per cent zinc or less (Table 9.3)
Since zinc
is cheaper than copper, it follows that high brass is used as widely as possible, and that the zinc content is usually close to the upper limit, which is about 35 per cent. Although the alpha brasses can be hot worked commercially if they
are free from lead, they are not so plastic at elevated temperatures as the beta alloys. In common with most solid solutions they are, however,
plastic at
room temperature and can be
readily drawn, rolled, or
spun
into a variety of shapes.
In fact, these alloys combine a degree of plasticity, strength, ductility, corrosion resistance, pleasing color, and low cost unattainable in any other material of engineering importance. Alloys 13, 14 2 9 are used for a large variety of cast and wrought sections,
,
especially
hardware and pipe
fittings, for
tubes and pipe, for ornamental
The
and lead
1
casting alloy containing 85 per cent copper and 5 per cent eacli of tin, zinc, is also known as composition metal and in many foundries as ounce metal
1
because the composition corresponds approximately to

oz. of zinc,
lb.
of copper.
oz. of
tin.
and
oz. of lead.

sections
169
grillwork, springs, screens,

rivets.
and building trim, for cartridge cases, automobile radiator cores, and tor many kinds of nails, screws, and
copper-zinc alloys are used because of their color, as stated They change from warm red copper color of copper to commercial bronzes (Tables 9.3 items 9 and 10) which have a bronze color to red brass (item 11) which is reddish hence its name. Some of these alloys in the above range duplicate the color of gold alloys and are used for manufacture of gold filled metals. Then comes low brass (item
previously.
12)
Many
pinkish, to cartridge brass (item 13) which is yellow, to yellow brass (items 14 and 15) which are greenish-yellow and finally to Muntz metal (item 16) which has the color of cast statuary bronze.
is
whose color
Muntz metal and its modification, manganese bronze (item 16 and 48, Table 9.3) usually contain beta phase at room temperature (see Fig. which reduces plasticity when the alloys are cold. These materials 9.1) are, however, characterized by extreme plasticity at a red heat and can
, ,
readily be extruded or rolled.
Owing
to their resistance to atmospheric

especially
and water corrosion, these two

tubes.
alloys,
are used extensively for extruded or hot-rolled pipes
manganese bronze, and condenser
is used for preheaters, evaporators, air-conditioning equipment, and in other applications where high resistance to salt water, fresh water, oil, or steam is required. Admiralty metal is an alpha-phase alloy and is not so easily
Muntz metal is now being replaced, particularly for condenser tubes in marine equipment, by a brass known as admiralty metal. This contains not less than 70 per cent copper, 1 per cent tin, and the remainder zinc. Other than for condenser tubes, admiralty metal, so called because it was developed by the British Admiralty,
hot worked
as
Muntz metal and manganese
bronze, but
it
is
readily
worked when
cold.
is
In genera], the machinability of the annealed, non-leaded brasses
about the same as that of low-carbon steel, in other words, they are too soft and gummy to be cut readily. Cold working, however, improves machinability, which is also greatly improved by adding lead. Item 29 (Table 9.3) can be machined readily in automatic machines. If
this
given a machinability rating of 100, the same brass containing only 1 per cent lead will have a rating of 70 (determined under the same conditions), and item H without lead-will have a rating of only 30. However, lead reduces the yield strength; it also makes the brass more
is
alloy
difficult to deform cold and makes it virtually impossible to work the alpha-phase alloys at elevated temperatures.
170
9.5. Characteristics of the
Low
Brasses and the Nickel Silvers

is
(items 9 and 10 are called bronzes because of their color) are used for hardware, ornamental and architectural sections, wire for screens, and for costume jewelry, in addition to being used for tubes, pipe, radiator valves, and other fittings for lowred.
As the amount of zinc in brass Items 8, 9, 10, 11, and 12
reduced, the yellow color changes to
pressure water and steam.

ing," a
to a
An
advantage of the low brasses

is
is
that,
when
the copper exceeds 80 per cent, the alloy
not subject to "season crack-
phenomenon
prevalent in the high brasses

stress.
when they
are exposed
is
the spontaneous failure of the stressed material after a considerable time in a corrosive environment, especially in atmospheres containing ammonia. The time element depends upon the severity of the stress and the severity of the corrosion. Stress caused
combination of corrosion and
Season cracking
by cold working, or applied

brasses, are readily
externally,
is
necessary for failure of this type.
The low
are difficult
9.3)
brasses, like the

is
high
deformed cold pro-
vided the lead content
Also like the high-zinc alpha brasses, they to hot work although commercial bronze (item 9, Table
low.
truded, provided that
can be rolled or pierced and, to a limited extent, pressed or exmore than traces of lead are absent. Most nickel silvers have a copper content of 45 to 65 per cent. A
fairly
common
alloy
is
the one containing 75 per cent copper, 20 per

zinc,
cent nickel,
and 5 per cent
usually sold under the trade

as
name
Ambrac. All the nickel

nickel.
If the
silvers
can be classed
low brasses containing
only alpha phase.
copper plus nickel exceeds 63 per cent, the alloys contain They can be hot worked readily only if the zinc is
about 40 per cent or less than 10 per cent, but they can be
cold worked easily.
Nickel silvers are valuable because of their white color, a corrosion resistance that is
generally superior to that of
the
common
brasses,
good
f
Fig. 9.3.
*
on the color
mechanical properties, and moderate cost. The effect of composition on color is shown by Fig. 9.3. The nickel silvers
are used chiefly for ornamental
Nickel. per cent

Effect of composition
of nickel silver.
(Kihlgren)'
work as a base for and gold-plated ware.
silver-

9.6. Properties of the
171
Wrought Brasses
wrought brass and nickel silver are As the commercial copper-zinc alloys do not
Some
collected
typical tensile properties of

in
Table
9.3.
respond to heat treatment, variations in properties are obtained by cold working and annealing which results, as in the case of some of the alumi-
num
alloys, in various tempers, ranging from soft to half-hard, to hard, and to spring temper. With the possible exception of manganese bronze and nickel silver, the tensile strength of all the annealed brasses is very
similar to that of annealed or hot-rolled low- or medium-carbon steel, but the yield strength is much lower. As the brasses cost five to ten times
steel, the chief justification for the widespread then ease of working cold, their pleasing color, and their corrosion resistance, especially to water and steam. In general, the low brasses are more corrosion-resistant than the higher zinc alloys, especially in impure water and in salt water. The high brasses, in addi-
as
much
is,
as
low-carbon
use
of course,
tion to being subject to season cracking are also subject to "dezincification," or removal of the zinc, when the alloy is exposed to impure water
or salt water.
time.
The
mass of copper.
to this
action is apparently electrolytic and leaves a spongy Dezincification can cause failure in a relatively short
less
Alloys containing 20 per cent or
zinc are not usually subject
form of corrosion. Manganese bronze has high resistance to salt water but may be subject to season cracking and dezincification. The endurance limits of the brasses are low, ranging between 10,000 and 20,000 lb. per sq. in. for 100 million cycles, which is equivalent to an endurance ratio of 0.20 to 0.35, or about half that of steel. Annealed brasses have a definite yield point (as evidenced by the drop of the beam) but cold-worked alloys have not. Values for yield strength reported
in the literature are usually the stresses causing an extension of 0.5 per
cent under load.
These values are usually much lower than the yield strength of steel which corresponds to a permanent elongation of 0.2 per cent of the gage length. The modulus of elasticity (secant modulus,
see p. 65) alloys
varies
for
and
from 15 million lb. per sq. in. for the copper-zinc manganese bronze to about 19 million lb. per sq. in. for
The mechanical properties of brass and of nickel silver are affected by grain size which, in the case of worked material, depends
nickel silver.
on annealing temperature. Material with large grains has lower strength
and higher elongation than

strip)
fine-grained material
(except in very thin
T. E. Kihlgren, Metals Handbook, American Society for Metals, Cleveland pp. 1443-1445.
1939
172
9.7. Cast Brass
and Cast Nickel Silver
There are at least a thousand varieties of brass that are melted and poured into sand molds. Most of these, however, fall into the nine genwhich specifications have been issued by the American Society for Testing Materials, the Society of Automotive Engineers, or by the United States government. Some typical compositions and properties of the most commonly used alloys are collected in Table 9.1* The properties of cast brass are determined on test bars cast separately from the same metal (A.S.T.M. specification B208-46T) and tested either with or without machining their surface.
eral classes of alloys for
As shown by the data
in
Table
9.1, the cast brass,
with the exception
of manganese bronze, are relatively
ductile and have a very low yield strength. Nickel silver has better properties than the copperzinc alloys containing no nickel, and when the zinc is omitted completely,
weak and
as in the case of cupronickel, the properties are

silvers
even better.
The
nickel
are,
however, considerably more costly than the other brasses.
The
cast brasses are easily
considerable lead, as most of

corrosion in
architectural
fittings
machinedespecially when they contain them do and have a high resistance to many environments. They are, therefore, widely used for and ornamental castings, especially hardware and statuary;
to sea, air,
and other parts exposed
and water or steam; plumbing

is
fixtures for water; valves
and other parts in chemical equipment; laundry

a favorite casting
and dairy equipment; and many others. Nickel silver alloy for automobile and household hardware and where alkaline waters or chemicals are encountered.
9.8.
for
industrial use
The Copper-Base Bearing Metals

principal copper-base bearing metals
The
(bearing metals are dis-
cussed more fully in Chapter 10.) are those in Class
On
a tonnage basis this
group
is
According to Clamer.t about 10

dized, or not, with less than
1
C of Table 10.2. more widely used than the others. million lb. of alloy CI (either deoxiis
per cent phosphorus)
used annually in
the United States.
The
leaded bronzes, alloys CI to
are employed by the railroads
and the
C5 and C8 and C9, automotive industry; alloys C2
and C3 are
suitable for small bushings
and bearings; others are better

ed,,
Cast
Metals Handbook, American
Foundrymen's Association, Chicago. 3rd
1914, pp. 604-648.

t
G. H. Clamer, Metals Handbook, American Society for Metals, Cleveland, 1939,
pp. 1428-1429.

. B 8 8 X
173
ON^
^-
a; -a
r"-c>ooooo-*-oinuiu"iir)
.a
ooooooooooo oooqoooooo ooooooooooo

<nOhtoinifl--QinM O00r-r-r--t-NMNCO
ooooooooooo ooooooooooo OOOOOOOOOOO

ooomcncîcoo>oofn
c
cj
o (S
in
in <- to
B c
a
r.
r- en
M-- O
CO
'5
3 o
CO
"r- n
m mm
^j-
Z
i/lvOsONOh-Wh-OOvOi/IÔ
r-cJomcoor^moincs
3.0.0
a
.3 -3
IfI! 1
i -2 si
II zo
174
alloy
fitted for general-service bearings;
C5
is
suitable for high speeds
and low bearing
The
moderate speeds and heavy loads. properties of the copper-tin-lead alloys vary with composition.
loads,
and CI
for
At room temperature, the property ranges

are as follows:
Property
Tensile strength, lb. per sq. in Yield strength, lb. per sq. in Elongation in 2 in., per cent
for alloys
CI
to CIO, inclusive,
Range
of values
28,000 to 40,000 14,000 to 18,000

1
to 20
Compression, lb. per sq. in., for a deformation of 0.001 in Brinell hardness (500 kg.)
10,000 to 13,000
55 to 75
(alloys C6 and C7, and alloy CI as well) are used movable bridges and turntables which act as bearings subject to slowly or intermittently applied heavy loads. Most of the alloys in group CI to C7 are used as large bearings ("brasses") in locomotives. Alloys CI, C8, and C9 are used extensively by the automotive
The
hard bronzes
in castings for
industry.
The
high-lead alloys
C10 and Cll
are a fairly recent
development and,
as steel backed, are used in internal-combustion engines for aircraft
and
automobiles, trucks, and tractors.

12,000 to 22,000
These
alloys are
inferior in tensile
properties to the other copper-rich alloys: tensile strength varies from

lb.
per sq.
in.;
yield strength
from 5,000
to 10,000 lb.
elongation from 5 to 12 per cent; and Brinell hardness (500 kg.) from 25 to 40. In general, however, they are superior to the white metals; their melting temperatures are much higher, and their properties
in.;
per sq.
are not so
much
if
affected
is
peated flexure which important,

seizure.
by temperature. They are also resistant to reimportant with present-day engine speeds. Most
which
acts as a lubricant
lubrication fails momentarily, the heat generated by the
friction sweats out a film of lead
and prevents
railroads were the first to use the high-lead alloys on a general adopting alloy C5 for a large number of bearings. In airplane and automobile engines, these alloys are now used for crankshaft, drivescale,
The
shaft,
and connecting-rod
1
bearings.
The most
up
recent development
is
the
addition of
to 2 per cent nickel, or
to 1.5 per cent silver, for conis
trolling segregation and sweating of the lead, which both in the molten and the solid state.
insoluble in copper
9.9.
The Tin Bronzes

industrial copper-tin
little as
1
The most important
alloys
are
the
phosphor
as II
bronzes which contain from as
per cent to as
much
per

cent tin.
175
All wrought phosphor bronzes are alpha-phase alloys, deoxidized by adding enough phosphorus to remove all but a trace of oxygen.
used of these alloys (items 51 to 57, Table are the ones containing approximately. 5 and 8 per cent tin; another popular alloy contains about 10 per cent tin. Owing to their high resiliency and endurance limit, these bronzes are used for springs and
9.3)
The two most commonly
diaphragms.
Phosphor bronze
is
hot worked with
difficulty,
but cold working
is
easy and the alloys are available in six tempers. These, and the range of tensile strengths for each temper and each alloy, are given in Table 9.2. The actual tensile strength depends on the thickness of the sheet.
(in 2 in.) varies from 40 to 60 per cent for soft sheet to less than 10 per cent for the harder tempers. The endurance limit in the hard temper is approximately 25,000 lb. per sq. in., and the modulus of
Elongation
elasticity is 15 million copper-rich alloys.
lb.
per
sq. in.,
about the same
as that of other
Table
9.2.
Tensile Strength of Phosphor-Bronzc Sheet
Temper
Reduction by cold
rolling,
Tensile-strength range, lb. per sq.

for bronze containing
in.,
per cent
Soft
5%
40,000 55,000 72,000 84,000 91,000 96,000
tin
8% tin
53,000 69,000 85,000 97,000 105,000 110,000 67,000 84,000 to 100,000 to 112,000 to 118,000 to 122,000
to
to
10%
58,000 76,000 94,000 107,000 115,000 120,000
tin
to
Half-hard...
20.7
37.1 50.0 60.4
to
to
Hard
Extra hard Spring Extra spring
.
55,000 70,000 87,000
to to
to to to to
to
68.6
98,000 to 105,000 to 109,000
73,000 91,000 109,000 122,000 129,000 133,000
Another important copper-tin alloy-which is used in the cast condition-is one containing a small amount of zinc. This alloy, known variously as government bronze, zinc bronze, or more commonly gun
as
metal (in the late Middle Ages it was used for casting cannons) contains 88 per cent copper, 10 per cent tin, and 2 per cent zinc-or 88 per cent copper, 8 per cent tin, and 4 per cent zinc. It is cast 'readily in the foundry, has a red color, and combines fine grain with considerable
,
strength, toughness,
and resistance to salt-water corrosion. Gun metal is used for joints and fittings, bolts, nuts, valve and pump parts, bushings and bearings for steam lines, and especially in naval construction. The tensde strength of cast and unmachined specimens varies from 30,000
to
lb.
45,000
per
sq. in., the yield strength
from 13,000
to 15,000 lb. per sq.
176
in.,
Engineering Metallurgy and the elongation (in 2 in.) from 15 is high. The modulus of elasticity is
to
40 per cent. Impact
re-
sistance
15 million lb. per sq. in.
9.10.
Aluminum Bronze and
Copper-Silicon Alloys
The
by
copper-rich copper-aluminum alloys combine the strength of a
steel with high resistance to corrosion by the atmosphere, by a large number of neutral and acid salts of low concentration, and by sulphuric acid. They are more resistant than manganese bronze to salt water and have good strength and ductility. The single-phase commercial alloys contain 10 per cent or less aluminum. It was noted in 9.2 that, if the aluminum is higher than this, the structure
salt water,
medium-carbon
and properties can be changed by thermal treatment. This is also true of the complex alloys containing 5 to 10 per cent aluminum and several per cent of iron, nickel, or manganese. By controlling the composition and by heat treatment the tensile strength of the wrought alloys can be varied from 65,000 to 125,000 lb. per sq. in., with elongations varying
inversely with the tensile strength
tion
9.3,
from 5
to 70
per cent.
and
typical properties of alloys in
common
use are given in
The composiTable
items 60 to 63.
Aluminum
alloys can
bronze is hard to handle in the foundry. The alpha-phase be hot and cold worked readily, but they are hard to machine.
corrosion resistance,
its
Owing
to
its
strength and toughness, and
its
low
coefficient of friction against steel,
aluminum bronze
is
used for gears,
valve stems, bolts and nuts for propellers, and for various small parts;
as cast,
it is
used for gun mounts, gears, bearings, propellers,

pieces, especially for service in salt air
pump
parts,
and ornamental
and
salt water.
The
copper-silicon alloys, usually
known
as bronzes, of
as
which some 20
to 25 are available
under such brand names
Duronze, Olympic, Ever-
dur, Herculoy, and others, contain 90 to 98 per cent copper, 1 to 4.5 per cent silicon, and small amounts of zinc, iron, or manganese, or if easy machinability is desired 0.25 to 0.50 per cent lead. Strictly speaking,
the copper-silicon alloys are copper strengthened by
to 5 per cent of
other elements.
The
strength
and
ductility of these alloys are approxisteel,
mately the same
as those of
low-carbon
and the corrosion
resistance
and
ease of hot
and cold working

is
are about the
same
as those of copper.
Strength as well as ductility increases as the silicon increases

4 per cent. This
.
up
to
about
shown by the typical properties in Table 9.3 (items 66 to 69) Thermal conductivity and electric conductivity are 8 to 10 per cent of the corresponding values for copper, and the modulus of
elasticity is 15 million lb.
per
sq. in.
177
is
The
in
principal advantage of the copper-silicon alloys

industrial waters, in sulphuric
their corrosion
resistance in both
marine and industrial atmospheres, in sea water and

in
many
and
chlorides,
and
most
alkalies
and hydrochloric acids, sulphates and alkali salts. They are also re-
and to many organic acids but are readily attacked by and other strong oxidizing agents. The alloys can be used for working stresses up to 10,000 lb. per sq. in. at temperatures of 250F. (120C.) or below, and they can be readily welded by oxyacetylene, metallic-arc, and resistance methods.
sistant to alcohol
nitric acid
The
copper-silicon alloys are
now used
extensively for bolts, screws,
rivets, boilers, tanks,
for fans, ducts,
and sewage disposal, parts and other ventilating and air-conditioning equipment,
for laundries
equipment
chemical and electrical equipment, containers for gases and chemicals, and for many other purposes.
9.11. Copper-Beryllium Alloys
years.
Copper-beryllium alloys are a development of the past twenty-five Their strength and endurance limit, after age hardening, are high
copper-rich alloys.
when compared with other

corrosion resistance that
is
This, combined with a

as of high-purity copper,
practically the
same
and comparatively high

$1,000 a
it is
electric conductivity,
would be responsible
for
fairly extensive use if the cost
pound
in
were lower. Beryllium metal, which cost 1927, had been reduced to less than $40 by 1937, and
estimated that the price could be lowered further to S5 to $10 a pound if there would be more demand for the metal. Assuming, howis $15 a pound, an alloy of 97.5 per cent per cent beryllium would cost between $0.55 and $0.75 a pound in ingot form, which is still too high for extensive commer-
ever, that the cost of beryllium

2.5
copper and
cial use.
At
grain.
present, copper-beryllium
alloys
contain
1.85
is
to
2.25
per cent
refine the
beryllium.
To
some
0.35 per cent nickel or cobalt
added to
The
alloys can
available as sheet, rods, wire,
be hot and cold worked, but not easily, and are and tubes. As indicated, they respond to
If hot worked or welded, they are given a solution treatment by heating to 1425 to 1475F. (775 to 800C.) for 30 min., followed by quenching in water. The alloys are usually cold
precipitation-hardening treatments.
worked
(315C.)
after the solution treatment.
for
to 4 hr.
They are aged at about 600F. depending upon the properties desired. Typical
properties are as follows:
178
Table
9.3.
Composition, and physical
NOTE: The
petiftcation
tabulated values arc average and, because of manufacturing limitations, should not be utei for purpoui. Within manufacturing limitations and when o tpceifitd, these products will
be manufactured to applicable current
ASTM
Specifications.
|s
Nominal Composition, per cent

Item No.
Name
Alumi-
l!
<
Others
Copper
Zinc
Tin
Lead
num
Phosphorus
Manganese
C0PPER8
1.
Electrolytic
Tough Pitch Copper-100
99.9+ 99.9+
20
0.02
10 to IS oz. Silver
20 20 20
20 80
3. 4.
6. 8.
Silver Bearing Coppcr-112 Silver Bearing Copper-113
99.9
99.
per Tont
25 to 30 ot. Silver
Phosphorlzed Arsenical Copper-108 Tellurium Copper-127
99.68 99. JO 99.00
0.02
1.00
Pit Ton' Arsenic, 0.30
Tellurium,
0.50.
80
BRASSES
8.
Oilding-4
95.00 90.00 87.50 85.00
5.00
10.
20 20 20 30
00
12.50
15.00
80.00 70.00
14.
20.00
10
30.00 34.00
37 00
30
30 40 40
0.50 2.25 1.75 0.25 0.50 1.60 1.00 0.25 0.50 1. 00 2.00 2.50 3.25 1.80 0.60 1.00 2.00 2.50
Yellow Brass-59
66.00
63 00
60.00
40.00
LEADED BRASSES
17. 19.
Leaded Commercial
llronzo-201
SO. 21. 22.
Hardware Bronze-267 Leaded Tube Brass-220 Leaded Tube Brass-218

Fre- Cutting
90.00 88.50 85.00 66.50 66.50

(10.50
9.50 9.25 13.25
50
Drass-282 23. Leaded Tube Brass-257 24. Threading Brass-223

20. 27. 28. 29.
Tube
Medium- Leaded
30. 31. Leaded Muntz Metal-274 32. Free Cutting Muntz Metal-293 33. Forging Brass-2S0 34. Architectural Bronce-280
Brass-229 High-Leaded Brass-235 Extra-lllgh-Leaded Hrass-238 Freo Cutting Brass-271 High-Leaded Brass-243
66.00 65.00 64.50 04.50 64.00 62.50 61.50 61.50 60.00 60.00 60.00 56.00
33.25 33.00 31.90 33.00 34.75 35.00 34.50 34.00 35.00 35.25
.SvTil
90 90 50 60 90 70
50 60 70 80 100 100
39 in 39.00 38.00 41.50
90 60 70 80 80
1 0.034 to
0.051% Silver.
0.085 to 0.102% Silver.
NOTES
The
values given are to be considered only as a general guide, and variations In properties due to manufacturing variables
must bo expected.
Higher values for strength and hardness arc obtained by a greater amount of cold working but are limited In general to relatively narrow sheet, small-diameter rod and wire, and smalt-diameter thin-wall tubo. Wide sheet and plate, large-diameter rod, and large sizes of wire and tube have. In general properties between those given for hard and soft tempers, (a) These relative vbIucs are given in comparison with Free Cutting Brass-271, arbitrarily given a value of 100, and are only an approximate Indication, there being no ready means for accurately comparing the machinablllty of metals. They arc a reasonable guide to relative tool life and amount of power required for cutting.

properties of standard copper alloys
179
>.
=
Elongation,
3^.
Applicable
Form
(b)
ASTM
Tensile Strength, psi.
% in 2 In.
( Unless othe wise noted)
Yield Strength
0.5
elon-
gation under
load,
]>si.
Rockwell Hardness No.
r,
g
O
<5
^ 5 fc
o
>
5*>
1 -
ciZ-n
Specifi-
cations
-;==
5
iz
9
v a.
13 l8
Mis?
Hard
(c)
Soft
Hard
(c)
o
Soft
Hard
(c)
Soft
Hard
(c)
Soft
mi
226
(Sheet
B152
B124, B133 BI. B2, B3 B42, B75 B88, Blll.lt
'
JRod
iWire
000 45.000 66,000

4fi.
33,000 32,000 35,000 35,000 33,000
35
1(e)
1
45 35(e) 45 35
351 45 45
40,000 40.000
10,000 10.000
B51
B50 B50
B51
B5I
F35) F35
! '
1083
0.322
.000009b
101. c
(Tube
Sheet Sheet
45,000 46,000
10
B302 B152
B152
B75. Bill B301
40.000
10,000
10,000
10,000
F40
1083
I
0.323 0.322 0.322

0.323 0.323 0.323
.0000098 .0000098 .0000098
85.0
100.5
100. f
197
5 5
10 18
12
F3
F35
F40 F35 F35 F45
1083
223
223 112 215 222
46,000 45,000 45,000 45,000
33,000
35,000 32, 000 32,000
40,000 40,000 40,000 40,000
10.000 10,000 10.000 10.000
1083 1080 1070 1079
Tube Rod Rod

Sheet /Sheet
45
B50 B50 B50

B61
.0000098 .0000098 .0000098
45.0 90.0 99.0
B36
B36, B130 B134
\WIrc
Sheet (Sheet
B36
B134
B-13.
(Wire
(Tube
(Sheet IWiro
(Sheet
Bill,
55,000 62.000 80, 000 65.000 69,000 88,000 69,000 73,000 100,000 76,000 110.000 76,000 73,000 65,000 105,000
35,000 37.000 38, 000 38,000 40,000 42,000 40.000 43,000 47,000 47.000 50,000 47.000 45,000 46,000 50,000 54.000
6 6 J(e)
r.
38 40
40(e)
44,000 47,000 50,000 55,000
11.000 12,000
13,000 15.000 15,000 16,000 17,000 17.000 17,000 17,000
1065
1045
0.320
0.318 0.317 0.316
.0000101 .0000101
56
139
B70
,
B,
.|
43.0 40.0 37.0
108 100
42 45
42(c) 50
B73
B76|
B3 B5
1)5
1035
|
.0000102
.0000104
Kc)
10 8 1(e) 10 1(e) 10
55,000
00,000 62,000
B135 B36 B134

B19, B36
1)131
B76
B81
1025
j
92
(Wire .Tube
Sheet
50 45(e) 65
50(e) 60
B10
f
iooo
1
0.313 0.308
.0000106
.ooooiii
32.5
27
81
B83 B83 BS0
'B20i
955
930
B135
70
69 69
B36
B134
10
20 1(e)
(Rod
(Wire
Sheet
60 60 50(e) 45
62,666 60,000 50,000
B20 BIS
B20'
0.306
0.305 0.303
.0000112 .0000114
26.0 26.0
28.4
B75
920 905
20,000
B'
B70 B58
B.V,
.0000116
73
Sheet
Rod Rod Tube Tube Tube Tubo

Sheet Sheet Sheet Sheet Sheet
B121 B140 BI40 B135 B135 B135
"
iii2i
B121
62,000 51,000 52.000 73.000 73,000 73.000 73,000 73,000 73,000 73,000
i3.Wl
B121
3121
Rod
Sheet Sheet
Tube Rod Rod
B16 B121 B171 B13S B124
73,000 58,000 73,000 80.666

1
37,000 37.000 40,000 45,000 45.000 45.000 45,000 45,000 45.000 45,000 45,000 45,000 47,000 45,000 54,000 54,000 54,000
Ml
6 IS 20 10
10
40 40 45 55
55
9 10 9
S
55 55 55
55 52 50
8
/
18 7
60
50
47,000 45,000 43.000 60,000 60.000 60,000 60,000 60,000 60,000 60.000 60.000 60,000 42,000 60,000
6o,'66o'
....
45
40 45 25
rm
12,000 12,000 15,000 17.000 17.000 17,000 17,000 17,000 17,000 17.000 17.000 17,000 18,000 17,000 20,000 20.000 20.000
Bl Bl
B5
B15
1)1.'
1045 1040 1025
B80 B80 B80 B80 B80 B80 B80 B80 B80 B70 B80
935
935
B15 B15 B15

B15 B15 B15 B15 B20 B15 B45 B45 BI5 B65
935 935 930 925

923
920
905
"
B86
895 908 900 900

895
0.318 0.319 0.317 0.307 0.307 0.308 0.307 0.306 0.300 0.306 0.307 0.307 0.307 0.305 0.304
0.304 0.305
884
0.305
.0000101 0000102 .0000104 .0000112 , v Q] | g 0000113 0000112 0000113 0000113 on mis 00OO1I3 0000114 0000114 0000113 0000116 0000116 0000115 0000116
. ,
42.0 42.0
311.0
104
105 93
28.0 26.0 26.0 26.0 20.0 26.0 26.0 26.0 26 25.5 26.0 20.0 26.0 26.5 28.0
68 68
68 68 68
68 68 68
68
62
68
68 68
82
7i
Courtesy American Brass Co.
NOTES
(b)
(c
>
(Continued)
t
'
? 1 conductivity: given for soft annealed metal; in hard temper conductivity Is slightly --.. lower. Klongation of wire, percent in 10 in. for copper is about 10,000,000 psl. The addition of zinc to copper reduces the modulus, to about 14,000,000 psl. for Yellow Brass. Pot most bronzes, the value is " TheEdition of nickel about fWOOO0 >"> "" to copper Increases the modulus, Cupro Nickel, 30%-702 showing about 20.000,000 psi.
YOUX 1'S MODULUS OF ELASTICITY
r< (e)
wlro 008 ta d,ametcr; Tub,, SS&r ?SSm ES&VSST Sl"* M0 thleki Rod ia reduowi about 37% in thioknoss by m rm ^- and grants ERR srâwasss ssr * PClrlc
ta "
'
'"
'
dlttraeter:
"
'
"'
'
'
J:!
"
>
. .
180
Table
9.3
Continued.
NOTE: The
specification purposes.
tabulated values are average and, because of mnnhctoring limitations, should not be used tor Within manufacturing limitations and lehen so specified, these products will
>
ASTM
Specifications.

Item
11 $9
Others
No.
Name
Copper
Zinc
Alumi-
Tin
Lead
num
Phos-
Manganese
phorus
SPECIAL BRASSES
94.97
36.
37. 38.
39.
4.00
0.90 10.00 14.00 17.00 18.00 20.98
27.96 29.00
39.25
1.00 1.75
High Strength Commercial Bronze286
0.03 0.10
1.00 Silicon, 1.00
20
Ambronze-421
Manganese Red
Silicon
Red
40.
Trumpet
Brass-507 Hrass-1027 Brass-435

.
41.
Ambraloy-927 (Aluminum -Brass)..

Admlralty-439
90.25 88.00 85.00 82.00 81.00 77.00 71.00

70.00
Nickel, 1.00
80
20
1.00 2.00 1.00 1.00
Arsenic, 0.04
30 30 30 30 30 30 30
42. Arsenical
44. 45. 47.
Naval Brass-450 Tobin Bronze"-452

Leaded Naval Brass-612
60.00 60.00 60.00 60.00 58.50
0.75 0.75 0.75 0.75 1.00 6.70 1.76
39.25 38.55 37.60 39.25
30 50
80
0.25
Iron, 1.00 30
PHOSPHOR BRONZES
49. 50. 51 . 52. S3. 54.
Phosphor Phosphor Phosphor Phosphor Phosphor
Bronze-356 Bronze-361 Bronze, (A )-302 Bronze, (A j-303 Bronze-314
98.70 98.24 95.95 95.75 95.17

94.75
. .
1.25 1.75 4.00 4.00 4.00
0.05 0.01 0.05 0.25 0.08 0.25

1.00
20 20 20 20
0.25
Iron, 0.50
20 20 SO 20 20
Phosphor Bronte, (A )-351

Leaded Phosphor Bronze, (B)-379.
5.00
5.00 6.50
65.
93.90 93.20
0.10 0.30 0.25
57.
Phosphor Bronze, (C)-353
91.75
8.00
58.
Phosphor Bronze, (D )-354

Free Cutting Phosphor Bronze-610.
.
89.75
10.00
0.25 4.00
0.10
20
59.
87.90
4.00
4.00
90
ALUMINUM IBRONZE8,
60.
Ambraloy-901
95.00
5.00
20 20
Nickel, 0.50; Iron, 0.60 Nickel, 5.00; Iron, 2.50
61.
Ambraloy-928
92.00
89.25 82.00
8.00
0.40 9.26 9.50
1.00
62. Avlalitc'-915 63.
20 20
Ambraioy-917
'
Trade-Mark Reg. V.
S. I'at. Off.
t 1.25"
and over.
NOTES
The
must be expected.
values given are to be considered only as a general guide, and variations In properties due to manufacturing variables
Higher values for strength and hardness arc obtained by a greater amount of cold working but arc limited in general to relatively narrow sheet, small-dlamcler rod and wire, and small-diameter thin-wall tub*;. Wide sheet and plate, large-diameter rod, and large sizes of wire and tube have, In general, properties between those given for hard and soft tempers, (a) These relative values are given in comparison with Free Cutting Druss-271, arbitrarily rfiven a value of 100, and are only an approximate Indication, there being no ready means for accurately comparing the machinabllity of metals. They are a reasonable guide to relative tool life and amount of jwwer required for cutting.
181
=
Elongation,
5%
~Q
i?*^
Applicable
Korm
(b)
ASTM
Specifi-
Tensile Strength, psl.
% In 2 In.
Yield Strength
@ 0.5 % elongation under

loud, psl.
(Unless otherwise noted 1
Rockwell Hardness No.

a.
5 1
J3
3h
^S-c
cations
ii 1 ..a J. _M R fi
8*jn
S
*3
KM*
CO
Hard
(0)
Sort
Hard
(e>
Sod
Hard
(c)
Soft
Hard
(o)
Soft
1
a
>S
fcji E = S
ttti
Sheet
no,
ooo
40,000
6 12
40
50,000 60,000
15,000
B70 B80
BS
B15
1060
0.320 0.320 0.316 0.316 0-310

.0.313 0.301
.0000101
38.0 32.0 27.0 22.0

14.7
95
81
Rod Tube
Sheet Sheet
70,000 69,666 90,000 80,000 85,000

86, 000 7(1,000
Tube
Tube
(Sheet
BUI
B171 Bill B291 B171 B21. B124 B21, B124 B21 B2I, B124
B124, B138
\Tube
1
Sheet Sheet
Rod Rod Rod Rod Rod
63.000 63,000 63.000 63,000

75,
000
46,000 40,000 55,000 48,000 52,000 48,000 52, 000 47,000 56,000 56,000 56.000 56,000 56,000 60,000
58
1
7 8 10 10 io 10
46 60 60
65 65
55,000 50,000 60,000
20,666 15,000 20,000
B76 BOO
B85 B83 B65 B65 B6S B66 B85
135
20,000
18,000 20,000 17,000 22.000 22,000 22.000 22,000 22,000 30.000
B35 B25 B30

B25\ B30I
1030 1015 990

1005.
.0000102 .0000104 .0000105

.
69
57
11000 10S
970
.0000108 .0000112
.0000111
27.5 22.6
24.7
39 70
58
64 43 67 67
65 65 40
45
935
945
0.308 0.308 0.304 0.304 0.305 0.305 0.302
62,000 35.000 35.000 35.000 35.000 45,000
B20
B501 B50f
16.0
25.8
30 35
28 2i 20
885 885 890 890 890
.0000119 .0000117 .0000119 .0000118 .0000119
38 35 30
BSD B50 B50
25.8 26.0 26.0 23.0
67 67 58
Sheet
Wire
Sheet
BIOS
moo
B139
11103
Tube Rod
[Sheet
65,000 105,000 80,000 70,000

(15,000
{Rod
(Wire
B139
III.'.9
Rod
Wire
(Sheet
B139 B103 B139 B159 B103 B139 B159 B139 B169

Bill BI69
BI24, B150
1)124,
80,000 65,000 110.000 65.000

120,000 93,000 80,000 130,000 102,000 85,000 145.000
Rod
iwire Sheet [Rod .Wire
40,000 45,000 48,000 48,000 48,000 48,000 48,000 52,000 48.000 57,000 00,000 60,000 62,000 06. 000 65,000 68,000
UO
8
15
48
40(c)
50.000
14,000
20,000 20,000 20,000 20,000 20,000
B75
B86 B80 B75 B86 B75
F60
SO 50
50 50 50 40(c) 40 40(e)
30
8
30
1(e)
65.000 58,000 55,000 65.000 55,000

55,000 68,000
B28 B2S B28

B281
1075 1070 1050 1050 1055 1050 1050 1040

1025
0.321 0.321 0.320 0.320 0. 322
.0000099 .0000099 .0000099 .0000100 .000010
43.0 37.8
18.4 18.0 16.4
126
85 47 47 44 47
B28}
1
0.320 0.322 0.319 0.318
.0000099
.0000099 .0000100 .0000101
18.0
18.4 12.0
25
20.000 24,000 24,000
B75
B94 B98
B25
He)
10
30
48 33
30
65 AS
40(c)
B50
BflOl
13.0
He)
12 25
65 65
40(c)
70,000
28,000
B55
1000
0.317 0.320
.0000102 .000010
11.0
29
He)
20
Rod
Sheet
60,000
45,000
B76
22,000 22,000 25,000 25.000 40,000
1
1000
12.2
33
92,000
Rod Tube
Sheet
105,000
Rod Rod
(Plate
80,000
95,000
ios.ooo
55,000 55,000 60,000 65.000 65,000 80,000 90,000
65
65,000
B92
B3.il
65
60 7 30 16 12
B35j
1060
101(1
0.295
0.281
.0000099
17.0 14.8 12.8 7.S
46
41 85 22
60 65 22
12
65.000 50,000 55.000
BM
BSOl
B50!
.0000099
.0000094
B150
1042
0.274 0.274
B171
B124, B150
Rod
60.000
BIOS
1055
.000009
NOTES
(b)
(c)
(Continued)
for which properties are given: Sheet, 0.040 in. thick; Rod, 1 in. dlumeter; Wire, 0.080 in. diameter; Tube, 1 In. diameter x 0.065 In. wall thickness. Hani temper: values arc for soft sheet that has been subsequently reduced about 37% In thickness by cold rolling; and for Rod, w ire and Tube of commercial hard drawn temper. (d) Electrical conductivity: given for soft annealed metal; in hard temper conductivity is slightly lower. (e) Elongation of wire, per cent In 10 in. S OF ELASTICITY for copper is about 16,000,000 psl. The addition of zinc to copper reduces the modulus, to about 14,000,000 psi. for Yellow Brass. For most bronzes, the value is about 15,000,000. Tho addition of nickel to copper Increases the modulus, Cupro Nickel, 30%-702 showing about 20,000,000 psl.
Form
YOUNG
MODULUS
182
Table
9.3
Continued.
NOTE. The
specification purposes.
tabulated values are average and, because of manufacturing limitations, should not he met lor Itliin manufacturing limitations and when so specified, these products will
ASTM
Specifications.
22

Item
II
Others
Name
Alumi-
No.
Copper
Zinc
Tin
Lead
Nickel
num
ManSilicon
ganese
M
20
20
CADMIUM BRONZES
64.
Hltenso'-901
99.00
66. 11 ltenso--965
98.60
0.60
Cadmium, Cadmium,
1.00...
0.80.
COPPER-SILICON ALLOYS
66. 67.
Everdur"-1010
95.80
95.60 98.25 90.75
7.25
3.10
0.40
1.10
30 60
EvordurM012
Everdur'-1015
3.00
1.60 2.00
1.00
68.
0.26
30
60
69.
Evcrdur'-IOM
CUPRO NICKELS
70.
Cupro Nickel, 10%-755 Cupro Nickel, 30%-702
88.35 68.90
10.00
0.40 0.60
Iron,
25
20 20
71.
30.00
Iron. 0.50
NICKEL SILVERS
72.
Nickel Silver, 10%-76I

Nickel 8llver. 18%-719 Nickel Silver, lS%-724
65.00
25.00 17.50
10.00 18.00
20 20
73.
64.50
74. 7S.
55.00 45.00
27.00 42.00
1.00
18.00
20
2.
Leaded Nickel
Sliver, 10%-25
10.00
CO
60
8PECIAL ALLOYS
76. 77.
Calsun Bronze*-951
95.50
99.05
2.00
2.50
20 0.10
Chromium Copper-999
Trade-Mark Reg.
Chromium,
0.85.
20
\>.
8. Pat. Off.
NOTES
The
values given are to be considered only as a general guide,
for strength
and
variations In properties
due
to
manufacturing variables
and hardness are obtained by a greater amount of cold working but are limited In general to "** ft 1 d srooll-dlamcter thin-wall tube. Wide sheet and plate largeân, SfEZi H&t^fffiS ""f eter rod, and large sizes of wlro and tube have. In general, properties between those given for hard and soft tempers (a) These relative values are given in comparison with Free Cutting Brass-271, arbitrarily given a value of 100,' and are only an approximate indication, there being no ready means for accurately comparing the macliinabllity of metals They are a reasonable guide to relative tool life and amount of power required for cutting.
Higher values
SSfSR
SS
183
i
Elongation,
"3
*
"31*.
JSd"-
Applicable
form
(1))
ASTM
Specifi-
Tensile Strength, psi.
% in 2 in.
Yield Strength
(Unless otherwise noted)
@ 0.5 % elongation under

loud, psl.
Rockwell Hardness
o
&
6fi
6
S.
i.
N 0.
a o C
JS
>,
cations
= 2 IS SS o' -#=K
w; _ 3 S~
St"*
2---
"3
Hard
(c)
Soft
Hard
(c)
Soft
Hard
(c)
Soft
Hard
(o)
Soft
<3wS.
IShcet
\Wirc Wire
Sheet
B105 B105
55.000 90.000 95,000
37,000 40.000
42. 000
1(e) 1(c)
50 40(e) 40(e)
48.000
12,000
B65
F471
1076
0.321
.0000098 .0000098
87.0 60.0
199 13S
1070
0.321
1)96,
B97
Rod
Wire
B98, B124
Rod
Sheet
Rod
'
B99 B98 B97 B98

B99, BIOS
BJ24,
95.000 90,000 145.000 90.000 65,000
58,000 58.000 60.000
7 18
Me)
18 8 IS
60 70 50(e)
60,000 60,000 60,000 50.000 55,000 50,000
22,000 22,000
B92 B90
1)90
B35'.
B35
I
1019 1019
0.308 0.308 0.316 0.278
.0000100 .0000100
.00000911
6.5
19
Wire
Tube Rod Tube

1
BlW
70,000 122,000 65,000
40,000 40.000 42,000 40.000 95,000
6.5
11.0
IS 31
46 50
40(c)
15.000 15,000
B77
1)80
F55 F55
Ke)
8
1055
1005
50 25
15,000 53.000
B71
F55 B87
.000010
9.2
as
Bill
B122, B171
Sheet
Rod
1
Wire iTuhe
Sheet Sheet
BUI
B122 B122
lll.il
60,000 77,000 70, 000 95.000 70.000
44,000 55, 000 55, 000 58,000 55,000
15
40
25
40 40
35(e)
57,000 70,000 60,000

60,000
22,000 22,000 22.000

22,
BOS B84 B80
B25 B35 B35

B35.
U45
1225
0.323 0.323
.0000093 .0000090
9.2
26
17
Ke)
10
4.6
45
000
B80
B87 B85 B93 B85
Rod
Wire
Sheet
Rod
Wire
B206 B122 B151 B206
Rod
Wire Rod B105
(()
88,000 85.000 70.000 110.000 99,000 80,000 130, 000 70,000
55,000 58,000 58,000 60,000 00,000 60,000 65,000
4
20
42 40
70.000 70.000
20,000 22.000
45
40(C) 45 45 40(0)
B30 B40 B40 B45 B45
1010
0.313 0.316
.0000091
8.4
27 IB
1110
.0000090
6.0
Ke)
4
20
75,000 60. 000 40,666
22,000 22,000
1055
0.314
.0000093
.000011
5.3
17
21
Ke)
IS
B70
925
0.303
7.0
135,
000
02, 000
\Rod
72,000
000 000 03.000

52, 35,
Ke)
20 25
40(e)
40 25
57,666 61,000
15.000
45.000
B70 B77
Fgq
1054 1075
0.308
0.321 0.321
.0000099 .0000098
B65
1075
19.0 50 u 40.0 80.0 187
NOTES
(b)
(c)
(Continued)
for which properties are given: Sheet, 0.040 in. thick; Rod, 1 in. diameter; Wire, 0.080 in. dia ncter; Tube, 1 In. diameter x 0.065 in. wall thickness. Ilard lemper: values arc for soft sheet that has been subsequently reduced about 37% in thickness by cold rolling; and for Rod, \\ Ire and Tube of commercial hard drawn temper. (d) Electrical conductivity: given for soft annealed metal; In hard tempor conductivity is slightly lower. (e) Elongation of wire, per cent in 10 In. (f) Properties after heat treatment (alloy 77). YOUN'O'S OF ELASTICITY for copper is about 16,000,000 psi. The additon of line to copper reduces the modulus, to about 14,000,000 psl. for Yellow Brass. For most bronrts, the value Is about 15,000,000. The addition of nickel to copper increases the modulus, Cupro Nickel, 30%-702 showing about 20,000,000 psi.
Form
MODULUS
184
Typical Propcrlics of Copper-Beryllium Alloys
Tensile
Yield
strength, lb.
Condition
strength, lb.
per sq. in.

Soft
per sq.
in.
Elongation in 2 in., per cent

45 6.3
Brincll
hardness
Average treatment
Maximum
treatment ....
70,000 175,000 193,000
31,000 134,000 138,000
2.0
110 340 365
The endurance
in.
limit
is
usually between 35,000 and 45,000 lb. per sq.
depending on the treatment.
The endurance ratio varies from approxiof elasticity averages 18 million lb. per
mately 45 per cent for the unhardened alloy to about 20 per cent for fully
hardened material.
sq. in.
The modulus
alloy.
In these properties the copper-beryllium alloys are far superior to
any other copper-rich
They also have relatively high wear

to
resistance
resisting
and corrosion
resistance
and are superior
phosphor bronze in
metal-to-metal wear
when run
against steel.
to a limited extent for springs, gears,
At present they are used diaphragms, bearings, and for

a
other small parts in the electrical and the aircraft industries.
Chromium copper (Table

which
is
9.3,
item 77)
is
heat-treatable
alloy
extensively used for welding electrodes,
grid support rods,
and
for lateral wires in electronic
vacuum
tubes.
silver,
1
A
iron,
copper-silver-iron
alloy
is
containing 6 per cent
per cent
copper remainder,
S.
also a heat-treatable alloy
used by the Signal
Corps of the U.
9.12.
Army
for field telephone wire
during the Korean war.
The Copper-Rich Copper-Nickel
Alloys
Copper and nickel dissolve in each other in all proportions in the solid and their alloys are free from phase changes. Some of the most widely used industrial alloys contain from 2 to 30 per cent nickel (the
state,
cupronickels)
or 45 per cent nickel
(Constantan)
Of
the important
nickel-rich alloys, the best
known
is
Monel, containing 68 per cent nickel.
This group
is
discussed briefly in the next chapter.
Nickel increases the tensile strength, the yield strength, and the en-
durance limit of copper,
as
Even the strongest

per cent in 2
to white.
in.
alloys are ductile
shown for annealed alloys in Fig. 9.4. and have an elongation of 45 to 50
tion of increasing
As noted in the discussion of nickel silvers, the addiamounts of nickel to copper changes the red color 15 per cent nickel alloy has a faint pink tinge, and a 20 per

cent nickel alloy white.
is
185
practically
The
five-cent coin of
United States, the is an alloy of 75 per cent copper and 25 per cent
the
"nickel,"
nickel.
The most common

trial alloys
indus-
contain
15, 20,
30 per cent nickel.

bullet jackets
The
15
and and
20 per cent alloys are used for
and
high
for a large
variety of parts in
which the
ductility,
white
value.
color,
and corrosion
resistance are of
They were formerly used for condenser and other

tubes for marine engines and
oil refineries,
plications
but in these apthey have largely
been replaced by the 30 per cent alloy. This material can

40 SO Nickel, per cent
readily be hot and cold worked and can be soldered, brazed, and welded. It is one of the most resistant of the
Fig. 9.4. Effect of nickel on the mechanical properties of copper-nickel alloys (Wise)
copper-base alloys to salt water and to many of the cor-
rosive solutions of the chemical industry.
The
cupronickels are generally
resistant to the atmosphere, to industrial waters,

alkalies.
and
1
to
many
acids
and
The
30 per cent alloy, containing also

is
per cent manganese

ells, tees,
and
per cent iron,
cast into
a large variety of couplings,
and other
fittings for valves,
pumps, and other similar applications.
The cupronickels do not respond to heat treatment. As in the case of most solid-solution alloys, high strength can be attained only by cold working with concomitant loss of ductility. Cold working with reduca
tion of 60 per cent increases the tensile strength of a 30 per cent nickel alloy from 50,000 to 85,000 lb. per sq. in. and reduces the elongation
from
50 to 4 per cent in 2
in.
Some
of the copper-nickel alloys have important electric properties.

9.5,
As shown by Fig
the electric resistance
is
at a
peak and the tem-
186
is
perature coefficient of resistance
practically zero in the alloy contain-
known as Constantan, has high and uniform thermoelectric force against copper and iron and is used extensively for thermocouples for the accurate measurement of temperatures below 1800F. (985C.)
ing 45 per cent nickel. This alloy,
40
Nickel, per cent
Fie. 9.5.
Effect of nickel
on the
electrical properties of copper-nickel alloys.
(Wise)
It
should be evident from the discussion in
this
chapter that the en-
gineer has available a wide variety of wrought and cast copper-rich alloys
and machines. There are so many of these alloys an intelligent choice of a specific one is sometimes difficult, especially in view of the fact that a large number of them are proprietary alloys for which extravagant claims are occasionally made.
for use in his structures
that
9.13.

is
in
Powder Metallurgy
young
science.
Powder metallurgy
iron was formed into
a very old art and a very

a
Sponge
dis-
weapons
steel,
thousand years ago, but when
man
he discarded the more cumbersome method of powder metallurgy, and the art was lost until relatively recently. With the exception of filaments for the electric-light bulb, which have been
covered
to
how
melt
187
made by powder-metallurgy methods

powder metallurgy has come
for fifty years, and the perfection of hard carbide tools twenty -five years ago, most of the development in
in the past fifteen years.*
The process underlying the production of powder compacts is well known and need not be reviewed here. Broadly it consists or preparing
metal or nonmetal powders of the proper size and physical characteristics, forming them into the desired shape, compacting under high
and sintering at the proper temClose tolerances can be maintained and no machining of the finished part is ordinarily necessary. Despite the high cost of the equipment for carrying on the various operations, great savings result in many
perature.
applications, especially for a large
difficult
pressure
(10 to 100 tons per sq. in.),
number
of identical parts that are
or expensive to machine from solid metal. The properties of a part made from powder depend on the character of the raw material and upon the pressing and sintering-in other words,
on the homogeneity and the absence (or presence) of voids in the finished part-and they range from about 50 per cent to practically the same
as for the solid metal or alloy.
One
of the great advantages of powder
or metals and nonmetals, that do not alloy in melting can be readily combined into an article having unique and often very desirable properties. Of the several million pounds of copper, for example, that are compacted by the methods of powder metallurgy a large proportion goes into porous "oilless or "self1
metallurgy
is
that
dissimilar metals,
lubricating" bearings for electrical machinery, automobiles, machines, and household appliances. More than a billion such bearings are in use.
oil less bearingf is made by compacting 87.5 to 90.5 per cent copper powder, about 9 per cent tin powder, and about 1.5 per cent graphite. These bearings are made with a controlled number of
The most common
voids (by regulating the density)

15 to 35 per cent
lubricant and, if machine. Sometimes
when installed, they contain they are, therefore, both bearing and properly made, will function as such for the life of the
,
so that,
impregnated
oil;
3%
lead
is
added for improved properties.
Engrs.,
meetings in the field were held at Massachusetts Icchnology in 1940 ami 1941. The papers presented were published in Urgy '" edited by John Wu,ff Am i(an Society for Metals, Cleveland ,Lo 1942, !L 622 pp. The first conference of the Powder Metallurgy Committee of the In * titute of Mini "S a"* Metallurgical Engineers was held in February, foTT^K 1944. The 12 papers presented were published in Trans. Am. Inst. Mining Met
Inst.ti.te of
'
'The
first
general technical
"
y. 161, 1945. pp. 524-634. See also Seminar on Theory of Sintering" and other papers in rrans. Am Inst. Mining Mel. Engrs., v 166, 1946, pp. 474-587. See also Proceedings of Com. B-9 of A.S.T.M.
fA^.T.M.
specifications
B202-51T.
188
Copper and copper-base alloys compacted with graphite are also used and other parts of motors and generators, to take advantage of the antifrictional character of the graphite and the current-carrying capacity of the copper. Depending on the strength required, the amount of graphite may be 50 per cent or more. Thousands of contacts for making and breaking electrical circuits are produced by compacting copper and refractory metal, such as tungsten or molybsuccessfully for brushes
denum or the carbides of these metals. The principles underlying the art of producing powder compacts
are
not simple. Not only must such variables as particle size, pressure, and sintering temperature be controlled carefully to secure the density, hardness,
tural
and strength desired (all of which arc changes resulting from diffusion must
directly related)
but struc-
also be taken into account.
The
size
size
structure should resemble that of the solid metal or alloy, the grain
fine, and the voids (if present) should be uniform in and distribution. Powders of an alloy may, when compacted, have a structure and properties different from those resulting when the powders of the metals are used and alloying is accomplished during sintering. On the other hand, prealloying may cause increased resistance to compression and result in less dense compacts. Whether the compact is prepared by hot or cold pressing, whether the powders contain gas, whether they oxidize easily all of these are important factors and none has been
should be
thoroughly studied.
its
In general the metallurgy of producing metal parts from powder is in infancy and considerable advance can be expected in the next few
years.
Other than
for the
manufacture of hard carbide
tools, discussed
in a subsequent chapter, the process has been used successfully in produc-
ing parts of iron,

steel,
steel,
iron phis graphite, steel plus copper, stainless

alloys,
copper and copper-base

iron-nickel
and economic
loys,
alloys and
factors are favorable
aluminum and aluminum-base allist is growing rapidly. Where the future of powder metallurgy seems
the
secure.
QUESTIONS
1.
2. 3. 4. 5.
6.
What are the properties of copper that make it useful commercially? What are the composition and properties of common brass? What is Muntz metal? Commercial bronze? Name two methods for making copper alloys free-machining.
Define dezincification.
7. 8.
What What
are nickel silvers

is
intended
when
and their most valuable property? the term "high brass" is used in the
brass industry?
Give the eutectic composition of the copper-zinc alloy system.

9.
189
10.
11.
manganese bronze, and what is its principal use? Compare the composition and properties of cast brasses, and cast manganese bronze.
is
What What
is
red brass? Admiralty metal?

Is it
a true bronze?
cast nickel silvers,
12.
What
are the principal metals in the copper-base" bearing alloys? Name their principal characteristics and uses. What are the uses for highlead, copper-base alloys? Mow do those compare as bearings with the white metals?
some of
13.
What What What
is
the effect of phosphorus
on the properties
the properties
of copper-tin bronzes?
arc the phosphor bronzes? phor bronzes.

is
Name
and some
uses of phos-
14.
amounts of cold working and varying amounts phosphor bronzes? What is the approximate composition of gun metal? What are the properties and uses of gun
the effect of varying of tin
on
the tensile strengths of
metal?
15.
What
16.
aluminum bronze? Indicate some of its and uses. Indicate the approximate composition and some of the applications of
is
the general composition of
characteristics
copper-silicon alloys.
17.
Indicate the approximate composition, properties before and after precipitation-hardening, and applications of the copper-beryllium alloys. What is the
18.
What
reason for their limited use? is the effect of increasing amounts of nickel on the tensile properties and endurance limit of copper? What are the properties of copper-nickel alloys? Name some of the copper-nickel alloys.
19.
What
general classes of materials may be combined by powder metallurgy Name and give the properties of some articles made by powder metallurgy methods from copper combined with other materials.
methods?
20.
How
are metal-powder compacts
erties of articles
made by
the methods of
made? What variables determine powder metallurgy?
the prop-
CHAPTER
Miscellaneous Heavy Nonferrous Metals and Alloys

William H. Tholke,
Instructor
of
B.S., in
10
Metallurgical Engineering,
University
of Cincinnati,
Metallurgy,
Cincinnati,
Ohio
1 HE preceding chapters on the light metals, copper, and copper base alloys have dealt with the two largest nonferrous metal industries. Before taking up the complex field of iron-carbon
and the metallurgy associated with the working and manufacturing of these materials, it would be well to look briefly at the remaining commercial nonferrous metals and their alloys, how they are used, and the part they play in the overall metals picture.
In terms of density or specific gravity most of these metals are heavier than iron. Table 10.1 lists these metals in alphabetical order with their
alloy steels, cast irons
alloys,
Some categorizing may be done in terms of the physical characteristics of the metals, and the metal elements with which they are alloyed. Some of these metals such as Pb, Sn, Sb, Bi, Cd, and In have low melting temperatures. The alloys of Pb and Sn are often referred to as the white metals. Then, there are those metals
which have
high melting temperatures as well as good corrosion resistance. These are the metals Ni, Cr, Co, W, Mo, and Re and their alloys. A third group comprises those metals and alloys which by virtue of scarcity of supply
respective specific gravities.
and semi-precious metals. These arc the metals Pd, and Rh. And, lastly, a new. group which has come into prominence through the development of atomic energy. These are the elements Th, Tm, U, and Zr.
as the precious
are
known
Ag, All,
Pt,
190
Miscellaneous Heavy Nonjerrous Metals and Alloys

Table
10.1.
191
Miscellaneous Nonfcrrous
Heavy Metals and
their Specific Gravities
Specific
Melting
Specific
Melting
Gravity
Temp. F.
Gravity
Temp. "F.
2651
Antimony
Bismuth
(Sb)
(Bi)
Cadmium Chromium
Cobalt
(Cd)
(Or)
Columbian or Niobium Copper Gold Indium

Iridium
[Iron
(Co) (Cb)
6.62 9.80 8.65 7.19 8.90 8.57 8.96

1
1167 520 610 3430 2725 4380

1981
Nickel (Ni) Palladium (Pd) Platinum (Pt)
Rhenium Rhodium
Silver
(Re) (Rh) (Ag) (Ta) (Th)
8.9 12.0 21.5 20.0 12.4 10.5

16.6 11.5 9.35 7.30 19.3 18.7 6.0 7.13 6.7
2830
3224 5740 3570
1761
(Nb) (Cu)
(Au)
(In)
(Ir)
9 32
.
7.31
(1*0
Lead
Mercury
(Pb)
22.5 7.87 11.34

13.6 10.2
1945 314 4450

28021 621
Tantalum Thorium Thulium Tin

Tungsten
5425 3300
449
(Tm)
(Sn)
(VV)
Uranium (U) Vanadium (V)

Zinc (Zn) Zirconium (Zr)
(Hg)
-38
4760
Molybdenum
(Mo)
6170 2065 3150 787 3353
LOW MELTING METALS AND ALLOYS

10.1.
The While Metals

"white metals"
is
The term
tin in
usually reserved for alloys of lead
and
which one or both of these metals may comprise the major percentage of the total alloy content. The remaining alloying elements present may be one or more or the following: antimony, arsenic, bismuth, cadmium, copper, indium, silver, and zinc. The white metal alloys are
often
plate, babbits,
more commonly known by their trade names such as pewter, terne and silver solders. Their applications find greatest usage
in the fields of (1) bearing materials, (2) type metals, and (3) low-melting fusible alloys such as the solders and safety fuse plugs.
The bearing metals must meet many requirements

qualify as a good bearing material.
is
before they can
These may be divided into three principal classes. First in importance proper structure, that is, a soft matrix with sufficient plasticity to conform to slight irregularities in the machining and alignment of the shaft, to allow any abrasive particles in the lubricant to become embedded in
, ,
the bearing metal (to prevent scoring of the steel journal) and to retain (to prevent mctal-to-metal contact) combined with a number of uniformly distributed particles which resist wear. Some metallurgists,
oil
however,
now
good bearings and
claim that wear-resisting particles are not necessary for that the structure is of minor importance. Such claims
192
are strongly supported by the successful use of the steel-backed silver
bearings
and by
the
cadmium
bearings.
Second, the mechanical properties must be satisfactorily balanced.
The
bearing must
strength,
resist the shock of impact loads,
and
it
must have
sufficient
ductility,
and
resistance
to
compression not to crack or to
squeeze out under heavy loads, especially at the operating temperatures,
which may be 200 to 300F. (95 to 150C.) and in the modern airplane
even higher.
The
third requirement
properties.
is
easy melting
and casting and, most important,
good bonding
as a backing
In other words,
when
cast in a strip as thin as
0.01 in., the metal
must adhere firmly
to the steel or
bronze piece used
and should not
spall off or separate
from the backing during
For some purposes, especially for large railroad bearings, it must be possible to remelt and recast the bearing metal without excesoperation.
sive loss
by oxidation.
In addition, the bearing metal should have high thermal conductivity,
by the lubricants used, and it should be cheap. bearing metals. Typical compositions of some common alloys in these different classes, with the specification numbers adopted by the American Society for Testing Materials and the Society of Automotive Engineers, are given in Table 10.2. The white metals include the tin-base (class A, Table 10.2) and the lead-base (class B) alloys. The 14 alloys in these two groups and the numerous unimportant modifications that have been advocated from time to time are old and well known. The tin-base alloys, commonly called babbitts, are widely used in automobile engines and in a large variety of machines where speeds are high and loads are light or at most only fairly heavy. Lead, added (alloys A4 and A5) primarily to reduce the cost, is objectionable if operating temperatures are high as it forms a fusible eutectic with tin and lowers the temperature at which incipient melting takes place. The following illustrates the effect of lead: the temperature at which alloy A5 (18 per cent lead) is completely liquid is about 565F. (295C.) the corresponding temperatures for alloys Al and A2 (no lead) are 680 and 670F. (360 and 355 C). The properties of the tin-base alloys vary somewhat with composition but are usually within the following ranges:
resistance to corrosion
There are four
classes of
Properly Tensile strength, lb. per sq. in., at 70"F. (20C.) Tensile strength, lb. per sq. in., at 200F. (95C.) Yield strength, lb. per sq. in., 70F. (20C.) Yield strength, lb. per sq. in., at 200F. (95C.) Brincll hardness (500 kg.) at 70F. (20"C.)
Brincll hardness
Range
of values
12.800 to 17,500
6,700 to 10,000 4300 to 6500 2.100 to 3,200 17 to 27
(500 kg.) at 200-F.
(95C.)
8 to 14

Table
10.2.
193
Typical Compositions of
Some Common
Bearing Mclals
Specification
Nomina] composition, percent

Sn
91
Class
A.S.T.M.
S.A.E.
10 110
Sb
4.5 7.5 8.3
12 15
Pb
Cu
4.5 3.5
Zn
Cd
Others
Al
2 3 4
5
B23-46T1
2 3
89
4
5 11
83.3 75
65
8.3
10
18 3
87 20
6.8
15 15 15 15
2 5.7
1.5
Bl
2
B23-46T6 7
8
14
10
5
3 4
S 6 7
8
10
11
63.5 75 80 83
85
15
10 15
1
12
90
84
15
19
15
86
10
7 9
CI
2
3 4
5
B144-46TA
792
10 7
5
80 83
85 78
0.0 to 0.9 P
3
1
D
E
B22-46TA B
791
7
5
15
25
6
7 8
19
16
4 4 4 8
70 80 83
89 85
3 3
0.0 to 0.9 0.0 to 0.9
P P
9
10
n
Dl
2
3
1
793 48 480
30
35
70
65
17P* 17C* 17R*

18
180
98
0.6
98.5 98.3 +
99.75+ Ag 98.50+ Ag 99.75+ Ag

1.2 Ni 0.7 Ag
t
* t
17P is plated, 17C is cast, and 17R is 0.5% Ca, 0.5% Na, 0.1 % Li + Al.
rolled,
In the case of these alloys, the "tensile strength" is the stress producing a deformation of about 25 per cent, and the "yield strength" is the stress producing an elongation of 0.125 per cent of the gage length.
The
lead-base white metals (class B,
Table
10.2)
are cheaper than the
tin-base alloys but are not so satisfactory for operation at high speeds
and
194
loads.
medium
They
are used extensively by the railroads for freight-
passenger-car bearings, in electric motors,
and
in
and some machines. Alloys
ties of this
B2 and B4 are used in a number of bearings in automobiles. The propergroup of alloys also vary with composition, usually within the
following ranges:
Property
Tensile strength, lb. per sq. in., at 70"F. (20C.) Tensile strength, lb. per sq. in., at 200F. (95C). Yield strength, lb. per sq. in., at 70-F. (20"C.) Yield strength, lb. per sq. in., at 200F. (95-C.) Brinell hardness (500 kg.), at 70F. (20"C.)
Brinell hardness (500 kg.), at 200F. (95 C.)
.'
Range
of values
12,800 to 15,500 5.00 to 8,000 2,800 to 3.800 1,200 to 2.000

15 to 22
6 to 11
It is
evident from these values that the lead-base alloys are inferior in
properties to the tin-base metals.
strength of the white metals decrease

lb.
As the temperature increases above 200F., the tensile and the yield still more; values of 2,000 to 4,500
per
sq. in.
are
common
for tensile strengths at 300 F.
(150C.)
Elongation and reduction of area increase with temperature as, for example, from 15 to 30 per cent and from 18 to 40 per cent respectively.
The
constitution of the white-metal alloys

Essentially, the structure
(Fig.
is
complex and
is
imperfectly
known.
10.1) consists
of a solid-solution
matrix in which needles or. cubes of a hard constituent, probably an intermetallic compound such as SbSn, are embedded. Considerable work has been done recently to determine the effect of
small amounts of
cadmium on
the tin-base alloys. Apparently,
per cent
cadmium
increases the tensile strength
and hardness 10
to 20 per cent at
normal temperature and at 200 to 300F. (100 to 150"C.) The copper base bearing materials as listed in class G of Table 10.2 have found wide application particularly in the automotive and other
transportation
fields.
The
leaded bronzes
(alloys of copper, tin,
and
lead) in general are slightly superior to the white metals; their melting
temperatures are much higher and their properties less affected by the operating temperature range encountered by bearings of this type. They also have better fatigue life which is affected by repeated flexure.
Recent trends
or
in bearing materials
have been
in the direction of silver
cadmium based alloys, the oilless bearing as made by powder metallurgy, and aluminum base alloys with tin as one of the principle alloying
more complete picture of bearing
is
elements. For a
tion
alloys, their
composi-
and
properties, the reader
referred to the
ASM Metal's
The
tin
type metals are a series of lead based alloys
Handbook. with minor amounts of
and antimony which arc used
in the printing industry.
The
choice of
195
Fie 10.1. Structure of tin-base bearing metals (A) containing 86 per cent tin, 6 per cent antimony, and 8 per cent copper; and (B) containing 82 per cent tin, 10 per cent antimony, and 8 per cent copper: etched. 150x- (Courtesy of O. W. Ellis)
on the printing method used. In linotype machines it is advantageous to have an alloy that freezes at nearly a constant temperature, hence the use of the ternary eutectic mixture of 84% lead, 12% antimony, and 4% tin. This alloy freezes at 462F. and makes possible close temperature control as well as good delineation of the type characthe cast strip. In other printing methods a harder alloy may be and this may be obtained by adding copper in small amounts to the type metal or by solution heat treating and precipitation hardennecessary
ters in
alloy depends
The
ing an alloy which has the necessary amounts of tin and antimony. artificial aging operation often times can be accomplished in one hour at 185F. or 1 minute at 212F.
alloys are ideal for these applications since they must have low melting temperatures, (2) low cost, and (3) good casting characteristics. Tin imparts to the alloy fluidity which makes for ease of casting,
(1)
These
and the antimony increases the hardness and decreases contraction during freezing. Both elements together lower the melting point of the alloy and makes possible precipitation hardening if needed.
The fusible alloys are those which are noted principally for their low melting temperatures usually in the range of 125 to 450F. The solders, which are primarily mixtures of Pb and Sn, could be included
196
in this category; although their melting range is usually considered as being from 360 to 570F. However, when alloying elements such as
antimony bismuth, cadmium, and Indium are alloyed with lead and
tin,
the melting temperature of the resulting alloy

alloys are used in the vital parts of safety safety
may be
as
low
as
I7F.
These
mechanisms
in fire
and
equipment. They are alloyed to melt or yield at specified temperatures thus releasing fire doors or sprinkling equipment. However, caution should be exercised in using these alloys where static
explosion
tensile loads are applied.
tures, they similarly
Since these alloys have low melting temperahave low recrystallization or cold working temperatures. Hence, most of these alloys will under go creep at room temperatures under static loading. Other uses for these alloys include patterns in precision casting methods, forming dies for aluminum and magnesium,
filler
material inside thin walled tubes during forming operations, cores

electroplated,
and forms on which other metals may be in tanks and cylinders of compressed gas.
10.2.
and
safety plugs
Lead and Tin
as
alloys of lead
While the preceding discussion has dealt with the

tin,
and
both metals are used
in considerable quantities in
commercially pure
form.
Lead is a soft metal (tensile strength of 2,000 psi) which is easily formed by most fabricating methods. Part of this ease of fabrication results from the crystal structure of the metal which is face centered cubic, and part from the fact that it will recrystallize at room temperature. Thus all forming operations at room temperature results in hot working the lead. Aside from its formability, lead is primarily noted for its corrosion resistance both to atmospheric conditions and to the acids sulphuric and hydrofluoric. As such it is used in relatively pure form as sheet and pipe in plumbing and building applications, in acid plants, and in the handling of chemicals. Lead or its alloys is rarely used in strength applications where static loads exist, since it will undergo creep at room
temperatures.
as tetraethyl
The
principal uses for lead are
(1)
in storage batteries (2)
lead in gasolines (3) as a cable sheathing material (4) as alloying element in solders and (5) as a building material. This is in the
order of the total yearly amounts used.

alloying with small
Lead may be strengthened by amounts of cither antimony or calcium which pro-
duces a precipitation hardenablc alloy. The resulting room temperature tensile strengths are as high as 12,000 psi.
Terne Plate, which is a lead based alloy containing 15 to 25% dipped onto sheet steel, is a competitor to zinc-coated products.
tin
It
hot has
197
the good corrosion resistance of both lead and tin and the bright appearance and formability of tin plate at a much lower cost than tin plate.
Tin in the commercially pure form has essentially only one application, the tin can. This involves depositing a thin layer of tin uniformly over a steel sheet by either hot dipping or electroplating. The latter,
while
more expensive, has helped conserve tin by producing a thinner coat. Tin has good corrosion resistance particularly to foods and fruit juices hence its use in the packaging and canning industries. However, on
steel the coat
lytic cell
must be continuous to be protective. Otherwise an electrowould be established and the steel would corrode preferentially.
10.3. Zinc
and Zinc Base Alloys as Engineering Materials
Zinc may also be considered as one of the low melting point metals, having a melting temperature of 787F. This plus its good atmospheric and salt water corrosion resistance are the characteristics which gives
The largest use of commercially pure in the galvanic protection of steel products-ga/wmzzmg sheet, tube, and wire. The protective coat is applied either by hot dipping the steel in molten zinc or by electroplating. The latter produces a
its
is
zinc
place in the metals industry.
zinc
and without forming a brittle between the zinc and the steel which will crack and flake off when the product is bent. In recent years, over 40% of the zinc used in the United States has gone into galvanized
intermetallic
thicker coat providing longer protection
compound
at the interface
products.
Second, in importance in the use of zinc is the die casting industry. Here, zinc alloys containing up to a combined 6% of aluminum, copper,
alloying
and magnesium are used. An increase and some dimensional stability
in strength
is
is
achieved by this
taining copper.
The
attained in those alloys condie casting alloys have a characteristic of shrinking
due to some phase change which occurs upon aging. Approximately two-thirds of the total shrinkage occurs in the first month, and this is often times made to occur at an accelerated
rate by heating the
in size apparently
parts 3 to 6 hours at 212F.

largest user of zinc die
The automotive industry is probably the castings. Many of the accessories, functional parts,
this method. It is an easy and economical way of producing precision parts which need little in the way of finishing operations. Quite often they will be chrome plated to enhance their appearance. The other applications where zinc die castings are used are in household appliances, office equipment, radios, toys, and telephone apparatus.
and decorative trim are produced by
198
properties
The mechanical
similar to those of
of
the
zinc
and
zinc
base
alloys
are
aluminum and magnesium. Pure

psi.
zinc has a tensile
strength of about 20,000

a
The
high strength die casting alloy has
psi. However, this is not imply that zinc may be used for strength purposes. For at room temperature, zinc and its alloys undergoes creep at loads exceeding 6,000 psi. This is as may be expected from its low melting temperature.
tensile strength
to
of approximately 52,000
meant
The
fatigue strengths for these metals are of the

psi
same order being from

this
700 to 8500
depending upon the
alloy.
The
fabricating characteristics of zinc are
good considering
metal
has a hexagonal close packed crystal structure.

cation arises from the fact that pure zinc
at
Some
of the ease of fabri-
is hot worked when fabricated room temperature. Zinc and its alloys may be fabricated by practically all of the known methods rolled, drawn, spun, extruded, and cast. Some
difficulties are
encountered
in the joining of zinc,
but with proper techni-
ques
it
may
be gas welded or soldered.
Other uses for zinc include (1) use as an alloying element in brasses, photoengraving plates, (3) dry batteries, (4) weather stripping and building materials, and (3) more recently as expendable anodes for cathodic protection of underwater steel structures.
(2) in
HIGH TEMPERATURE METALS AND ALLOYS

was in steam In these applications the operating temperatures were in the range of 1000 to 1200F. Other uses at slightly higher temperatures were in ore roasting furnaces. Howearly use of metals for high temperature usage
in
The
power generation and
the petroleum industry.
and economy are of primary consideration while mechanical strength of secondary importance. More recently with the development of the gas turbine, jet engines, and atomic energy, the operating temperatures have been edging upward and the emphasis is more on mechanical strength along with corrosion resistance. The early high temperature metals and alloys involved the alloy steels and the nickel base alloys. As temperature and strength requirements have increased the trend has been toward nickel, cobalt and chromium based alloys. With the development of the cermets a new
ever, in these applications corrosion resistance
approach to high temperature alloys has been made. In cermets, the high temperature strength is attained from an intermctallic compound
usually a carbide of tungsten, titanium, chromium, tantalum, or
noibium
is
embedded
in
a matrix of cobalt or nickel. Other examples involve
metal oxide embedded in a metallic matrix.
The problem
here
one
is
of improving the creep resistance of the metal or alloy.
To
do
this it
199
necessary to produce a continuous matrix or network which has very good strength and corrosion resistance, hence the carbides or metal oxides. This then is surrounded by a metal which has good oxidation and corrosion resistance.
10.4. Nickel
and Nickel Base Alloys

is
The
Hence
differs
metal nickel
will
in
many
respects similar to iron.
Its
mechanical
properties,
it
modulus of
and atomic diameter are quite similar. alloy with many of the same elements found in steels. It
elasticity,
its corrosion characteristics. It resists oxidizing conditions very well but will be susceptible to attack in reducing condi-
principally in
tions particularly if sulfur
is
present.
will
It
resists
it, is
quite well
and
often,
where price
permit
atmospheric corrosion used as a cladding ma-
terial on other metals for this purpose. Nickel termediate layer in the chrome plating of steels.
is
also often used as
an
in-
Nickel Alloys. As aforementioned, nickel will alloy with many of the other metal elements. It forms a continuous series of solid solution alloys with copper. It has a high solubility for such other metals as Co, Cr, Fe,
Mn, Mo, Ta, W, and Zn. The elements Al, Be, Si, and Ti have only limited solubility and alloys of Ni containing small quantities of these metals often exhibit precipitation hardening characteristics. Some of the
better
known
nickel base alloys are as follows:
Monels are a series of nickel-cop[>er base alloys containing approximately 65% Ni and 30% copper with small amounts of silicon, aluminum, manganese and sulfur. The Monels are primarily noted for their strength and corrosion resistance.
The Inconels contain appreciable quantities of chromium and iron with smaller amounts of titanium, aluminum, and niobium. These alloys find application where high temperature corrosion and oxidation resistance is important.
at high temperatures.
The Nimonic alloys were developed as a series which had high strength An early alloy containing 80% Ni and 20% Cr had
appliances.
as a heating element in electric furnaces and Modifications of this alloy gave rise to the present Nimonic series. The latest developments in this series has large quantities of cobalt in place of the nickel and small amounts of molybdenum, titanium,
been used quite successfully
and aluminum.
The
Hastelloys are another series of high temperature alloys developed
by the Haynes
Stellite Company and originally were nickel base alloys containing appreciable quantities of molybdenum and iron. However, the newer alloys showed decreases in the iron content with this being
200
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replaced by larger amounts of chromium, tungsten,
precipitation
alloys
201
and
cobalt.
Some
have been made containing small amounts of titanium and aluminum. The Hastelloys are fabricated by the normal working methods but due to their high strengths and good oxidation
resistance require heavier fabricating equipment or higher temperatures to obtain the desired deformation. Table 10.3 lists some of the typical alloys falling in these various categories. They find application where operating temperatures are in the range of 1300 to 1800F.
and corrosion
10.5. Cobalt Base Alloys
The element cobalt finds its greatest application in alloy form. It is used in other metal systems to increase strength and corrosion resistance and, combined with chromium forms a series of alloys known as Stellites. The stellites will have cobalt contents ranging from 67% down to 37.5%, and with chromium contents ranging from 20 to 27%. The remaining elements present will consist of varying amounts of the following elements, Ni, W, Mo, Nb, Ti, and Fe. In addition to the above elements, these alloys will all contain carbon percentages from 0.1 to 0.5%, and the carbon will be present in carbide form making these alloys very hard and brittle. As such, with one or two exceptions, these alloys are usually
By virtue of their physical properties they are primarily used where high strength and abrasion resistance is required at high temperatures. Their normal operating temperature range ,s from 1350 to 1800F. Other uses for cobalt are in magnetic materials where it is alloyed with Al, Fe, and Ni in "Alnico," and Fe plus r High Temperature Metals and Alloys
cast directly to their final shape.
V in Vicalloy.
10.6. Other Miscellaneous
temperature applications in the range of 1800 to 2000F. Some of these metals and alloys will only be mentioned briefly here but will serve to show possibilities and shortcomings. Recent work with alloys of iron, chromium and aluminum; or iron, molybdenum, and aluminum whose alloys are known as "Ironals" have shown promise as good high temperature alloys. It is important that little or no carbon be present. Operating temperatures will be limited to approximately 2100 to 2300F. Chromium base alloys are also possibilities, but chromium is difficult to melt due to its high vapor pressure and is very reactive with oxygen and nitrogen which makes the alloy very brittle. Experimentation with the metals molybdenum, niobium, rhenium, tantalum and vanadium
all of
Recent experiments have indicated the direction in which future research must be aimed in the development of alloys for future higher
which
202
have high melting temperatures, as can be seen in Table 10.1, are for the most part limited in use at high temperatures due to their oxidation reactions. The oxides of Mo, V, and Re all volatilize at temperatures
below 1200F., while Ta and Nb form spongy oxides quite rapidly at or above this temperature. It therefore appears that if these are to be used for high temperature applications they will have to be clad with another
metal or ceramic which will keep oxygen away from the base metal.
OTHER METALS AND ALLOYS

10.7.
The Precious and Semi-Precious Melals and

and
Alloys
The
They
metals and alloys which find themselves in this group are here by
their usage as coinage
virtue of their scarcity in nature
and
jewelry.
are the metals
silver, gold,
platium, and the allied platium
group-
palladium, iridium, osmium, rhodium, and ruthenium. Most of the metals are found in nature in the metallic form or alloyed with the ores
of copper, lead, nickel, or zinc.
Usually they are present in very minor
amounts and thus are obtained as by-products and only when the economics of the operation make it worth while. Silver. The element silver in the pure form is a soft white metal with good corrosion resistance and high electrical conductivity. Since it is
quite soft,
it
is
rarely used as a
pure metal except perhaps

it is
as a plating
on jewelry items.
the
When
used as a base metal,
alloyed with copper,
common
Silver
alloys being with
10%
copper
tents.
as sterling silver.
is
The
silver solders
copper in coinage, and with 7.5% have still higher copper con-
also used in
with tungsten and
an amalgam in dental alloys and is combined molybdenum by powder metallurgy for use as heavy
As aforementioned,
it
is
duty
electrical contacts.
used rather widely in
electroplating of hardware, light reflectors and costume jewelry.
The
amounts used here are quite small and their cost is negligible. However, they add materially to the eye appeal and reflectivity of the base metal and improve the oxidation resistance of the part. Gold, like silver, is quite soft and corrosion resistant. Similarly, it is rarely used in pure form due to its softness, the one exception being as gold leaf in sheet form with a thickness of approximately 0.00005 inches. In this form it can be used in lettering, display, and decorative
applications.
More
often
it
is
alloyed with copper, silver, or platium for
jewelry applications.
it
When
alloyed with platinum, palladium, and nickel
takes on the characteristic white color and becomes white gold. Gold can also be plated on jewelry either by dipping on the molten metal or
by electroplating.
The
latter yields heavier coats. Still thicker coats are
203
obtained by cladding with sheet material by rolling, soldering or brazing the sheet to the base metal. The other application for gold is as a medium of exchange on an international basis, for it is accepted throughout the world.
The platinum
lysts,
metals while better
known
for their jewelry applications,

as cata-
in actuality, find greater application in
commercial uses such
high temperature corrosion resistant materials, electronics, and the chemical industry. With the exception of palladium, the other metals platinum, iridium, osmium, rhodium, and rutheniumall cost more per ounce than gold. Of this group, only platinum is used in pure form. The others being used as alloying elements in platinum. Platinum is used in
making chemical and medical apparatus usually

iridium.
as an alloy containing In pure form, platinum wire is used for a platinum-rhodium alloy wire as a high temperature thermocouple. This couple readily
high temperatures and oxidizing atmospheres that cause other Rhodium is sometimes used as a replacement for silver on plated articles which will be subjected to sulfur atmospheres. Rhodium has a silvery appearance but will not tarnish under these conresists the
metals to
fail rapidly.
ditions.
10.8. Metals
and Alloys in Atomic Power Applications
While considerable interest has been shown in recent years in the application of atomic energy for power purposes, much of the information has of necessity been withheld due to security reasons. However, the part metals play in this new industry can be broken down into four fields: (1) as fuel elements, (2) as structural materials or moderators, (3) as control materials, and (4) materials which can be irradiated and
ber
come gamma ray

In the
first
emitters.
it is
category, as fuel elements,

fission.
necessary that the material
undergo atomic
While many of the elements high in the period table in terms of atomic number are radioactive, only uranium and perhaps thorium may be used as fuel elements. It is necessary that the fuel material be rather plentiful in nature and undergo fission at a rapid enough rate to make it economically feasible as a source of energy. In the second category, the structural materials in an atomic reactor should be able to withstand the temperatures involved, should not trap or absorb neutrons, and should have good corrosion resistance. The metals which meet these requirements are aluminum, beryllium, and zirconium. Zirconium seems to be the preference particularly where high temperatures are encountered.
204
fission
In the third category are those metals which actually control the
rates in a reactor.
The boron
and
steels are the materials
commonly used by
nature
being
virtue of availability
ease of fabrication.
is
Hafnium, which has a

as prevalent in
is
greater capture cross section than the steels,
not
and hence
veloped.
is
not as widely used.
However,
this
a field which
all
is
thoroughly investigated and other alloys will in
probability be de-
In the fourth category are the metals cobalt, cesium, thulium, and iridium. These metals when irradiated become radioactive and isotopes of these metals are used as gamma ray emitters. The metal isotopes and their halflife periods are listed in Table 10.4.
Tablc
Isotope
10.4 Radioactive Isotopes
Av. Energy*
Radiation Output mr/hr*
Half Life
Cesium 137
Cobalt 60
Iridium 192
670
1200
KV KV 375 KV
3750
14000
5950
27
yrs.
5.3 yrs.
75 days
Approximate
**Milli-roentgcns per hour at a distance of 12 inches.
These metals find wide usage in radiographic examination of metal

parts for internal defects.
In
many
applications they have advantages
over x-rays. In general they are less costly, have greater portability,
and
can be used in smaller places. ler than a cube 14 inch on each side. Exposure times for the radiographic films are about the same as for high voltage x-rays.
is
The gramma
ray source usually
smal-
QUESTIONS
which are noted primarily for their low melting temperatures? 2. What are the "white metals," and for what are they principally used? 3. What are the principal requirements of a bearing alloy? 4. Why is a eutectic alloy used in linotype machines? 5. How does tin and antimony affect the casting characteristics of alloys containing these elements? 6. What are the principal uses of lead, tin, and zinc? 7. Which of the metal elements do we consider as being high-temperature
1.
List five metal elements
materials
8.
What
is
cermet?
How
is
strength at high temperatures attained in a
cermet?

9.
205
10.
What are the better known nickel-base alloys, alloying elements in them? In what ways is the element cobalt like nickel? cobalt?
and what
are the principal
What
other uses
is
made
of
11.
of the elements have high-melting temperature; be used as high temperature metals or alloys? 12. Why are the metals gold, silver, platinum, palladium,
13.
Many
why can
they not
14.
etc. so expensive? are the four categories for metals with respect to atomic energy? are the requirements of metals that arc used as fuel elements in atomic reactors?
What What
is it important that the structural materials in atomic reactors not absorb neutrons? How do they differ from the control materials? 16. Which of the elements are commonly used as gamma ray emitters in radiographic examination?
15.
Why
17.
How
do gamma
rays differ
from
x-rays?
206
Manufacture of Metals
207
CHAPTER
The Manufacture and Composition of Carbon and Alloy Steels

Howard
P.
11
Davis,
M.S.,
Associate
Professor,
Depart-
ment of Mechanical Engineering, University of Wyoming, Laramie, Wyoming Floyd Sheldon Smith, M.S., Associate Professor of Mechanical Engineering, Alabama Polytechnic Institute, Auburn, Alabama
MAN
years.
For almost half of this time he used
has been using iron for at least 5,000 it as a precious metal which
came from heaven as meteorites and which was seized when found and laboriously worked into jewelry, charms, and amulets. These he wore for personal adornment or to ward off the evil spirits that harassed him daily. For the last 2,500 years, he has had terrestrial iron, reduced from its ores, and it is characteristic that the first use he made of it was to fashion weapons. Damascus swords, made by the Moslems in the Middle Ages from steel imported into the Near East from India, and by the famous families of Japanese sword makers between a.d. 500 and 1500, are the finest specimens of the early steelmakers' art which have come down to us. They were made by welding alternate strips of high- and low-carbon steel into a bar, forging out this composite material, doubling it over and reforging again and again until a laminated strip of the finest quality resulted. This was drawn out into a sword or dagger blade, heat treated, sharpened, and finally etched with a dilute acid to bring out the laminations. Such a blade is shown in Fig. 11.1, in which the blade and scabbard are photographed against a background of the damask pattern near the dagger point, magnified eight times. Man's next use of iron was to fashion tools, so that he could make life easier for himself. Since the beginning of large-scale manufacture about 1870, steel production has increased greatly each decade; by 1953 the world was using over 258 million tons a year. Of this the steel industry of the United
States has
been producing about 100 million tons annually.
208
The Manufacture and Composition
209
Fie. 11.1. Damascus steel dagger. The background is a photograph of the etched damask pattern of the blade. 8x- (Ziegler, Mining and Metallurgy, v. 20, 1939, p. 69)
The
use of chemical analysis for determining the composition of steel
and cast iron did not become general until about seventy years ago, more than a decade after large-scale steelmaking by the Bessemer and the open-hearth processes had been introduced. For many years the analysis of steel and cast iron consisted of the determination of carbon, manganese, sulfur and phosphorus, silicon, if present, and alloying elements when these were specially added. Only in
210
the past few years has
it been realized that these common elements tell only a part of the story of the composition and that in addition some ten or twelve other metals, metalloids, and nonmetals may be present. As a
result, the
chemical composition of unalloyed
steel is
it
is
seemed thirty years ago; on the contrary, worthy of considerable attention.

as
it
no longer as simple very complex and
many
Despite the fact that commercial carbon steels and cast irons contain other elements in addition to carbon, metallurgists look upon them
as alloys of the metal iron
the greatest effect on their structure
and the metalloid carbon because carbon has and properties.
Commercial carbon steels contain, in addition to carbon, varying amounts of manganese, silicon, sulfur and phosphorus, and small percentages of oxygen, nitrogen, and hydrogen. Occasionally they also contain small amounts of copper, nickel, chromium, molybdenum, lead, arsenic, aluminum, and tin. Some of these are added intentionally to improve the quality, but most of them are picked up from the raw
materials used in the various processes. Steel
men commonly
divide these
elements into three
classes:
harmful, beneficial, and neutral.
11.1. Definitions of Ferrous Engineering Materials
For many
years
committees
of
metallurgists
in
English-speaking
steel,
countries have been trying to define carbon steel, alloy

concisely, but
It
cast iron,
pig iron, wrought iron, and other products of the industry precisely and
with
little success.
would be a waste of space, and probably even confusing, if the complex definitions for the numerous products of the iron and steel
industry were
all set
down
at once.
containing
defined as a commercial alloy of iron and carbon than 2.0 per cent carbon, less than about 1.30 per cent manganese, less than 0.5 to 0.6 per cent silicon, small amounts of adsteel
less
Carbon
may be
ventitious elements, and

alloy contains
no intentionally added special element. If the 2.0 per cent carbon and is poured direct from the blast furnace into cast iron molds of uniform size, or is used in the molten condition as an intermediate product, it is called pig iron; and if this pig iron (usually with the addition of scrap) is remelted and poured
more than
into a sand mold, thereby assuming the desired shape of the finished
section,
alloy containing
iron
as cast iron. This means that whether an iron-carbon more than 2.0 per cent carbon is called pig iron or cast depends upon whether the material is an intermediate product or a
it is
known
finished product.

Pig iron and cast iron have been some of the necessary distinctions
211
differentiated here chiefly to indicate

in formulating definitions of ferrous
products. Pig iron is of little interest to the engineer; cast iron is an important engineering material and is discussed in some detail later.
Ingot iron
is
a commercially pure iron. It contains between 99.75
and 99.90 per cent iron. The common elements, carbon, manganese, silicon, sulfur, and phosphorus, account for about half the impurities; the occasional elements make up the other half. Ingot iron resembles carbon steel in that it is melted and refined by the basic open-hearth
process, but
it is
lower in carbon (about 0.02 per cent) than the lowest
carbon
steels
is
made
Ingot iron
industrially, which range from 0.04 to 0.08 per cent. used chiefly in the form of galvanized and enameled sheet.
The
iron is a low-carbon material and is no longer widely used. nature of the refining is such that this material contains a larger proportion of solid nonmetallic inclusions than low-carbon steel made
processes.
Wrought
by the usual
to the nature of the process and the comwrought iron when rolled has relatively low strength but is ductile and tough, and is easily welded. It is used for staybolts, rivets, some grades of pipe, boiler tubes, and especially for heavy chains and hooks. Wrought iron has well-marked directional
Owing
position of the inclusions,
properties.
is no precise and concise definition of alloy steel, but practically seldom any difficulty in distinguishing between carbon and alloy steels. The practical criterion is: if an element, not used primarily for deoxidation or degasification, is added to carbon steel or is present adventitiously in the amount required to produce a desired specific effect, the resulting material is an alloy steel.
There
is
there
why the dividing line between carbon placed at exactly 2.0 per cent carbon. Although this percentage is fixed primarily for convenience, it has considerable scientific justification. The 2.0 per cent carbon concentration marks the maximum
It
may
be asked legitimately
steel
and
cast iron is
solid solubility of
this
carbon in iron
at
concentration graphite a
common
very high temperature, and below form of carbon in cast iron is
not ordinarily present under normal conditions of treatment.
For convenience, the commercial iron-carbon alloys may be divided

into four classes:
Low-carbon steel Medium-carbon steel High-carbon steel Cast iron and pig iron
Less than 0.25 per 0.25 to 0.65 per 0.65 to 1.70 per 2.50 to 4.50 per
cent carbon
cent carbon
cent carbon
cent carbon
212
11.2. Iron
Ore and the Manufacture of Pig Iron
four essential raw materials of the iron and steel industry arc iron ore, coke and coal, limestone, and scrap steel and scrap cast iron. The iron
ore used in the United States
(Fe 2
is chiefly hematite, an impure ferrous oxide containing between 45 and 55 per cent metallic iron and between 20 and 35 per cent earthy matter, known as gangue, which is made up of silica, alumina, calcium oxide, magnesium oxide, and water, plus
The
g)
varying small amounts of phosphorus and occasionally sulfur. Hematites and other usable iron ores are widespread throughout the world; the commercial ores in the United States are estimated at more than 10 billion tons, of which 90 per cent is located near Lake Superior and in Alabama. Iron ores
are graded by phosphorus content into
WOT
800'f
and non-Bessemer (basic) As phosphorus is not removed in the blast furnace, the ore must not contain more than approximately half the amount of this element permitted in Bessemer steel.
ores.
Bessemer
Iron ore
blast
is
reduced by coke in the
furnace, limestone being used to
flux the
The raw
gangue and the ash of the coke. materials, in the approximate
ratio of 2 tons of ore (frequently includ-
ing some scrap steel or cast iron) to 1 ton of coke and i/ ton of limestone, are 2
air,
charged into the top of the furnace, and preheated to 1000 F. (540C.) or
is
above,
a
blown into furnace through

of
nozzles
(called
number
tuyeres)
near the bottom.
The
blast
furnace,
Fig. 11.2.
Cross
section
of
modern
blast furnace
showing tem-
perature and chemical reaction levels. (Based on Camp and Francis)
is a with firebrick; 90 to 100 ft. high, 17 to 20 ft. in diameter at the top, and 24 to 28 ft. in diameter at the bosh (just above the tuyeres) Operation is entirely continuous: The
shown
steel
in cross section in Fig. 11.2,*
shell
lined
raw
materials,
carefully
weighed and
Based on
J.
M. Camp and
C.
analyzed, are charged into the top at B. Francis, The Making, Shaping and Treating of
cd., 1940, p. 288.
Steel,
Carnegie Steel Co., Pittsburgh, 5th

Limestone 774
213
't5fi8
Coke 1954
Row
materia!^
B^^3gfi
Ore, elc. 3925
Air
8500+
5000
10000
Sasesl2,000
_]
Products <
Kj
Slag 867
Ftc. 11.3.
the
modern
blast furnace.
Relative proportions by weight of the raw materials and products of (Boylston)
frequent intervals and slowly settle to the bottom, the downward pressure being slightly greater than the upward blast pressure plus the friction of the burden on the walls of the furnace.
As the charge
settles,
the temperature increases

is
(Fig. 11.2)
until near
and the spongy iron is heated to incandescence. Here it starts absorbing carbon, which lowers the melting point. The iron then becomes pasty, absorbs carbon more rapidly, and finally melts, trickling down over the remaining unburned
practically all reduced
the bosh the iron ore
incandescent coke into the hearth.
forms
a fusible slag that
and
that floats
The calcium oxide in the limestone lower in specific gravity than the iron on top of the molten metal in the hearth from where it is
is
much
drained
at regular intervals. The molten high-carbon iron is drained from the hearth into ladles every 5 or 6 hr. and then is either poured into
molds to solidify as pig iron or used in the molten condition in the manufacture of Bessemer or open-hearth steel. A modern blast furnace produces between 800 and ,200 tons of pig iron every 24 hr. and, barring shutdowns for economic conditions, will operate continuously for years.
1
The average proportion of the raw materials entering the blast furnace and of the resulting products is shown graphically in Fig. 11.3.* The slag is mostly waste and must be disposed of, a considerable problem in some plants. As Fig. 1.3 shows, an enormous volume of gas is given off. This gas, which totals more than 100 million cu. ft. a day for a single furnace,
1
contains 20 to 25 per cent carbon
monoxide and has

Sons, Inc.,
a heating value of
York, 1935, p. 71.
H. M. Boylston, Iron and
Steel,
John Wiley &
New
214
90 to 100 B.t.u. per cu.
to generate
ft.
It
is,
consequently, used to heat the blast and

blast furnace
is not efficient. by-product and to the
power.
Thermally the iron
Owing, however,
iron
is
to the value of the gas as a

is
operation of large units, the over-all efficiency
relatively high,
and pig
made
cheaply.
Chemistry of the Blast Furnace.
The
preheated
lb.
air,
which
in.,
into the furnace under a pressure of 15 to 20
per sq.
blown comes into

is
immediate contact with incandescent coke forming large volumes of carbon monoxide gas. This gas, together with the carbon in the coke,
reduces the iron oxide by two general reactions:
Fe 2 O s
+ 3 CO * 2 Fe -f 3 C0
+ 3 C *
2 Fe
2,
(1) (2)
Fe 2 O s
+ 3 CO.
Both reactions are reversible and may proceed in either direction depending upon the temperature and other conditions prevailing at the
The net result, however, is reduction of the oxide to metallic iron. Both reactions are progressive: the Fe 2 O s is reduced first to Fe 3 4 then to FeO, and finally to Fe. Reaction (1) predominates
various levels in the furnace.
,
upper part of the furnace (see Fig. 11.2) beginning at a temperature of about 400F. (210C.) reaction (2) begins at a temperature of apin the
, ;
proximately 1200F. (650C.) and continues until the iron oxide

pletely reduced in the zone of the bosh.
is
com-
The chemical reactions in the blast furnace are essentially reducing so that any easily reducible oxides in the iron ore or the coke (in addition to the iron oxide) are also reduced. Thus, all the phosphorus and most
of the manganese will be found in the iron. Oxides of silicon and sulfur are more stable but are partially reduced. The remaining oxides of
calcium, magnesium,
acted
and aluminum are very refractory and are not upon by the carbon or carbon monoxide even at the highest
temperature of the furnace.
To
flux these refractory oxides, the necessary

calcines in
amount
of limestone (CaCO.,)
must be charged. The limestone
the upper part of the furnace and, together with the calcium and magnesium oxides in the ore, combines chemically with the alumina and with
part of the
silica to
form a
fusible slag
composed of calcium, magnesium,
and aluminum
silicates.
The
carbon,
pig iron, tapped from the furnace, contains about 4 per cent all the phosphorus, and most of the manganese in the raw ma-
terials. The amounts of silicon and sulfur in the iron are controlled to some extent by a careful selection of raw materials but chiefly by regu-
lating the chemical characteristics of the slag, that
is,
by controlling the
proportion of calcium oxide to
silica,
and by controlling the tempera-

ture.
215
The
latter
of the blast, the
amount
depends upon the amount of coke, the temperature of water vapor in the blast (the humidity)
and other
variables. The operation of a modern blast furnace and the production of cheap pig iron of satisfactory quality is an art which demands long experience and skill of a high order.
Operation and Use of the Cupola. The cupola is a vertical, cylindrical type of furnace, consisting of a steel shell lined with firebrick. Usually the charging door is located 10 to 25 feet above the bottom of the furnace. Air enters the cupola through the tuyeres, located near the lower end of the cupola. Fuel, metal, and flux enter the cupola through the charging door. The initial charge of coke is known as the "bed charge." The metal is deposited on the coke. Then alternate layers of coke and iron are added. Generally a limestone flux is charged on the coke. The purpose of the flux
is
to
form
a slag
with the
dirt,
impurities in the metal,
and
the coke ash.
The metal charge ordinarily consists of local gray iron scrap, purchased gray iron scrap, pig iron, and steel scrap, where increased strength is
desired.
The proportions of various metals in the charge are governed by the type of castings desired. The base of the charge is pig' iron. Since the pig iron is of known composition, the greater the amount of pig iron and the smaller the amount of scrap, the more uniform will be the
composition of the resulting castings. For high grade castings, such as automobile cylinders, the percentage of pig iron will range from 25 to 50 per cent of the charge, while for low grade castings, almost no pig iron will be used. Fluorspar, soda ash, and a number of proprietary fluxes are sometimes used in combination with the limestone to thin the slag and
also to aid in the removal of sulphur.
Air is introduced into the cupola to aid in the combustion of the coke, which in turn melts the metal. Under ordinary conditions the blast pressure will range from 8 to 20 ounces per square inch, depending on the height of the cupola and the number and character of the metal charges. The ratio of the coke and metal charges are ordinarily one pound of coke to eight pounds of iron. The charges are very carefully weighed. As the metal charge becomes molten it trickles down through the bed charge of incandescent coke and is collected in the crucible zone of the furnace. The liquid slag which collects above the molten metal is drawn
off
iron
through the slag notch located just below the tuyeres. The molten is drawn off through the tap hole, located at the bottom of the
cupola, into crucibles

iron castings.
and poured into sand molds
to
form gray
cast
216
11.3. Acid
and Basic Processes

and
the manufacture of steel are chemical
in large-scale industrial operations in that the
The
reduction of iron ores
processes
and are unique
chemical reactions involved take place at high temperatures, nearly always above 2000F. (1100C.) and usually in the range 2500 to 3500F. (1370 to 1925C). Few refractory materials withstand such temperatures. The only ones that are available cheaply arc the oxides
of silicon, calcium, and magnesium.
These are
relatively inert at
normal
temperatures but become active chemically at steelmaking temperatures: silica (Si0 2) becomes an active acid, and calcium and magnesium oxides
become
active bases, reacting at high temperatures; thus,
CaO + SiOs - CaSiO s MgO + Si0 2 -> MgSi0 3

.
(3) (4)
It is characteristic
of silicates such as these that they fuse at temperatures
much
lower than the fusing temperatures of the oxides.

slags
Molten metals are refined by
which are
essentially silicates of
calcium, magnesium, and iron and are formed by a reaction between

definite amounts of a basic oxide and the acid oxide silica. Depending on whether the basic or the acid constituent is in excess, the slag will have a basic or an acid reaction at steelmaking temperatures. The character of the refractories used in the furnace which is decided by economic considerations determines the character of the slag and thus determines whether the process is basic or acid.
has an acid lining, the slag must be acid and destroy the furnace lining. Thus, in an acid process the slag must contain an excess of silica, and in a basic process, where the lining is magnesium oxide, the slag must contain an excess of calcium oxide. The advantages of acid and basic steelmaking processes may be summed up as follows: Advantages of Acid Process. Acid slags contain less free oxide than basic slags. Consequently, if all other things are equal, acid steels will be cleaner and of higher quality than basic steel. Acid refractories are much
It is
if
obvious that,
it
a furnace
in character or
would
attack
cheaper than basic refractories.
Advantages of Basic Process. The basic slags will remove phosphorus steel. Therefore, lower priced scrap and pig iron can be used since it is not necessary to avoid small amounts of phosphorus and sulfur.
and sulfur from the
basic, acid, or neutral
Fluxing materials used in the steelmaking process are classified as according to their chemical activity at elevated
Silica
is
temperatures.
the only substance that
is
classified as a strictlv

acid fluxing material.
217
Sand, gravel, and quartz are available in large
be used as acid fluxing materials, but normally they are not used because the lining of the furnace will furnish all that is required. In basic processes, silica might be used as a flux if excess lime has been charged or where the raw materials are too low in silicon.
in sufficiently state to
amounts and
pure
Iron and manganese oxides act as basic materials

processes,
when
present in acid
but they are not normally added for this purpose and therefore are not classified as fluxing materials. The most common basic fluxing materials are limestone and dolomite, limestone being mostly CaO, while dolomite
double oxide of calcium and magnesium. "Burnt" lime, is usually added in the basic open hearth when more than the amount furnished by charged limestone is found to be needed
is
a calcined limestone,
at a later stage of the heat.
In order to
make
the slags less viscous without changing their acid,
basic, or oxidizing properties,
point such as flourspar (mostly 11.4. Bessemer Processes
a neutral substance with a low melting CaF 2 ) is most commonly used.
Forty years ago, 25 to 30 per cent of the so-called tonnage steels were
made
in the
steel,
Bessemer converter.
The
price differential
in
favor of
Bessemer
averaging S2 to $4 a ton, disappeared some years ago owing to the increasing scarcity and higher cost of low-phosphorus ores. This
condition, coupled with the disadvantage that Bessemer steel containing
more than about
0.20 per cent carbon
is
to be inferior in quality to steel of
considered by many metallurgists comparable carbon content made
by the basic open-hearth process, has resulted in the decline of Bessemerproduction to about 3 to 4 per cent of the total. During the past 15 years it has leveled off to between 3 to 6 million tons per year. The Acid Bessemer Process. The acid Bessemer converter is a pearshaped steel vessel lined with silica brick and mounted on trunions by
steel
which
it
can be
tilted 180 degrees.
The bottom
making
steel
contains a large
number
of tuyeres to admit the blast. In the converter
by the Bessemer process
is tilted forward, and 15 to 25 tons of molten pig iron are poured into the belly of the vessel. It is then turned upright, and at the same moment the blast is turned on. Refining begins immediately. No
is needed as sufficient is generated, by the reaction oxygen with the carbon and other elements in the pig iron, to raise the temperature several hundred degrees.
external source of heat

of
The
blast of air entering the converter forms large

it
oxide as soon as
strikes the
volumes of iron molten metal, which immediately oxidize
218
Fie. 11.4.
Bessemer converter
in operation.
(Courtesy o\ Jones and Laughlin Steel
Corporation)
the manganese and silicon.
The phosphorus
is
oxidized; but as there
is
no excess of lime, stable phosphate is not formed, and none ment is removed from the metal. Sulfur is also unaffected.
of this ele-
The
color
progress of the chemical reactions
is
followed by observing the
and length of the flame shooting from the mouth of the vessel. Refining is complete in 10 to 15 minutes when the manganese, silicon, and carbon in the pig have been reduced to a low percentage, after which the converter is tilted forward and the metal is poured into a ladle from

which
it is
219
poured into ingot molds. Harmful oxides are eliminated as and the proper amounts of carbon and manganese are secured by adding an alloy of iron, manganese, and carbon to the ladle as
far as possible,
the contents of the converter are transfered to the ladle.
of
slag-making materials are added; the slag formed is composed silicates of iron and manganese oxidized from the pig iron plus some silica eroded from the lining. It is acid in character.
No
compound
Owing to the rapidity with which die reactions occur and to the large volume of iron oxide formed, acid Bessemer steel usually contains more
iron oxide than basic open-hearth steel. The production Bessemer plant of three vessels is 5,000 to 6,000 tons in 24 hours. To produce the same tonnage of basic open-hearth steel, a battery of twenty 100-ton furnaces is needed.
dissolved
from
For many years, the Bessemer process has been important in the steel industry, but, in contrast to the open-hearth process, little attention has
been paid
to the chemistry or
metallurgy of refining. In 1940, however,

steel instituted a
some of
process,
cell is
the larger plants
making Bessemer
study of the
and some noteworthy developments

to
resulted.*
photo-electric
determine precisely the end of the blow, and a removing phosphorus by treating the molten metal in the ladle. Very recently a method has been worked out for deoxidizing Bessemer steel, so that it is apparently equal in quality to open-hearth steel of approximately the same composition, with the object of using this deoxidized material for seamless tubes and pipes.
process has been developed for
now being used
Basic Bessemer Process. This process is not used in the United mainly because the iron ore being used, and consequently the pig iron being produced from it, is not suitable for this process. It is
States,
The
necessary that there be at least 2% phosphorus present in the pig iron in order that the oxidation of the phosphorus during the afterblow can maintain the temperature of the bath high enough to prevent solidification.
The
silicon content
must be low in order that the expensive
basic
lining last as long as possible.
operation of the basic process is similar to that of the acid process is added, so the slag formed is basic and the phosphorus will be removed. After the manganese, silicon, and carbon have been oxidized out there is the additional afterblow during which the
except that lime
phos-
The
phorus
is
oxidized out of the
steel.
These developments in Bessemer steel arc described in papers by Graham. Work. McGinley and Woodworth, Yocum. lulton. Bowman, Wright, and Dunkle in Transactions, Iron and Steel Division, American Institute ot Mining and Metallurgical En-
gineers, 1941, 1942, 1944. 1945.
220
cost of the basic process
life
is
The
higher than the acid process due to the
higher cost and shorter
of the basic refractory lining, the longer
blowing time and the fact that lime has to be added to the process. In Europe, where this process has been used with success, the high phosphorus ores necessary are available, and there is also a market for the slag as a fertilizer, which helps overcome the higher cost of the process.
Cut-away model of a modern open-hearth furnace showing roof con(upper left), bottom and port construction (lower left), cutaway checker chamber showing brick construction (lower center), and stack (right). (Courtesy H. W. Graham, Jones and LttUgMitt Sled Corporation)
Fie.
11.4A
struction
11.5.
Open-Hearth Processes
Description of the
Modern
Plant.
The
typical open-hearth furnace has
a capacity of 100-150 tons, with the largest furnace in the United States
having a capacity of 350 tons. The furnace is a chamber about 80 ft. long and 18 to 20 ft. wide. The hearth is shaped like an elongated saucer, the inside dimensions being about 40 ft. long, 14 to 18 ft. wide, and
in. deep at the center. The hearth lining consists of a mixture of burned magnesite and basic slag sintered into place. The furnace is fired
20 to 30
221
ftC,
I1.4B
tesy \y of Carnegie-Illinois Steel
Pouring molten blast-furnace iron into the open-hearth furnace. (CoxrCorporation)
with
is
gas, oil, tar,

is
or powdered
used, this
also pre-heated.
coal, using preheated air, and if a lean gas At the center of the back wall is the tapping
hole, 8 in. in diameter, in such a position that when opened it will drain all the steel from the hearth into the ladle. There is a hole for the slag
runoff at the top level of the hearth and toward one end of the furnace. walls are made of silica brick, 13i/ in. thick, and extend 8 ft. above the charging floor level. The charging doors make up most of the front wall of the furnace and are lined with silica brick and have water cooled
The
222
frames, the bottom of the doors being just a few inches above the slag line.
The
arched roof
is
12 in. thick,
it
made
of silica brick,
and
is
built in-
dependent of the walls so that

rebuilding the furnace.
can be replaced without completely
To
attain the high temperature necessary to

is
make
steel,
the regenera-
tive principle
used. White-hot exhausi gases from the furnace are led
through
a series of brick
checker-work chambers on the way to the stack.
After about 15 minutes, these exhaust gases are diverted to another set of
checker chambers at the other end of the furnace, and the cold air is led through the heated checkers on the way to the furnace. The direction
of the exhaust and incoming gases
is
reversed every 15 minutes initially,
and the time interval

ally controlled
is
reduced
as the
temperature of the furnace apreversal of the gases

is
proaches the tapping temperature.
The
automatic-
depending on the temperature of the checkers and the furnace. The regenerative process makes it possible for the gases to attain a temperature of approximately 3500F. (1925C.) as they sweep
across the hearth, in addition to creating a saving in the
amount
of fuel
used in the furnace.
hot metal mixer
is
usually located in the

It is
same area with the bank
of open-hearth furnaces.
storing as
a large refractory-lined vessel capable of
molten metal from the various blast open hearth. Some are equipped with heating devices but mostly they depend on the heat from the hot iron as it comes from the blast furnace to maintain a molten condition in the mixer. The mixer makes it possible to have a molten metal with a more consistent chemical composition available to the open hearth, so that a wide variation in the charge is not necessary, and also to decrease the time from charge to tap of the furnace, because of the retained heat. This also tends to cut down on the fuel used. Operation of the Process: Charging. The order of charging the maas 1500 tons of
much
it
furnaces until
is
needed
in the
terials into the
furnace
it
is
quite important.
The
limestone
is
charged
first
in order that
will not enter into the slag reaction until the desired
is
time.
Any
ore charged into the furnace
placed on top of the limestone.
The
light
limestone and ore protect
the hearth
from damage during the

II
charging of the scrap iron which follows immediately.
the scrap
is
and bulky
it
may be
necessary to melt part of
it
down
in order to
charge the rest into the furnace.
When
the furnace reaches a temperature
somewhat higher than the melting point of the pig iron, the molten iron is poured into the furnace from a ladle, using a spout placed in
one of the charging doors.
The
ratio of the
amount
of steel scrap to pig iron in the charge
varies according to the price of the scrap.
When
the price of scrap
is
low,

the charge might consist of
223
75%
or
more
scrap and
but
iron
if
is
the price of scrap

possible.
is
high, then a charge of
25% or less pig iron, 25% scrap and 75% pig
Melting the Charge. As soon as the steel scrap is charged into the it is heated with a hot oxidizing flame that will cause the scrap to melt and become oxidized. This oxidized material later becomes infurnace,
strumental in the purification of the pig iron by oxidizing out the impurities. If enough oxides are not provided by the oxidation of the
scrap, additional oxidation
is
obtained by the ore that
is
charged
in
on
top of the limestone hot metal
in
the charge.
This oxidation usually
takes place
for about two hours after the start of charging,

is
when
at that time the
added
to the furnace.
The Ore Boil. As soon as the hot pig iron is added to the furnace the oxides present begin to react with the impurities in the iron. First to be removed are silicon and manganese, forming SiO and MnC) which, along
a
with FeO, combine to form the early slag. At the same time the oxygen is combining with the carbon in the pig iron to form CO which, when
escaping, causes the slag to "froth" and increase in volume to such a degree that a considerable amount will overflow through the slag runoff hole.
In this
manner much
is
of the silica that
would have
less
to
be
neutralized by the limestone
eliminated, requiring
limestone to be
charged into the furnace. It is interesting to note that a good deal of iron is lost here (as FeO in the slag) and that sometimes this slag is recharged into the blast furnace to recover both the iron and the
,
man-
ganese from their oxides.
The Lime Boil. After the ore boil has subsided, the temperature of the furnace has reached the point where limestone will calcine, giving off large volumes of C0 2 This characterizes the "lime boil," which is much more
.
violent a boil than the "ore boil." At the same time the lime formed by calcination rises from the bottom of the hearth and replaces the iron and manganese oxides in the slag, with any excess of lime tending to make the slag more basic. The basic property of the slag makes it more capable of retaining phosphorus in the slag as a phosphate. This lime boil also tends to mix thoroughly the contents of the hearth so that the chemical composition and the temperature are more uniform from top to bottom.
The Working
specific aims.
Period. During the working period there are several These include: (a) lowering of the phosphorus and sulfur
content below the
maximum
values specified, (b) eliminating the silicon

(c)
and manganese residue not oxidized out during the melting period,
eliminating the excess carbon as quickly as possible, (d) conditioning the slag so that it will be of the proper viscosity and have a basic chemical
224
composition, and
(e) raising the temperature of the bath to approximately 150F. above the melting point of the steel to be tapped.
Tapping
the
Heat.
When
the carbon
content has been reduced
to the desired
amount and
the temperature of the steel has been raised to

is
the tapping temperature, the heat
ready to tap.
is
The
clay plug
and a
the
portion of the dolomite that
fills
the taphole
removed.
The
rest of
dolomite is burned out with an oxygen torch, and the taphole is cleared by using tapping rods from the front of the furnace. The center of the ladle is placed off center in order to cause a swirling action and to insure rapid
melting and good mixing of the ladle additions.
Ladle Additions. Usually included in the ladle additions are alloys manganese to remove oxygen and sulfur, alloys of silicon that also remove oxygen, and aluminum which is added to further the deoxidizing
of
process and also to control the grain size. In order to increase the carbon content of the steel after tapping, some carbon is recovered from the
manganese alloys, and if more is needed it can be obtained by adding ground anthracite coal to the ladle. Other intentionally added elements may be added either in the furnace or in the ladle. All ladle additions should be added before any slag comes from the furnace, otherwise they become mixed with the slag causing high alloy losses and a possible phosphorus reversion. By using varying amounts of these alloying elements, high quality steel of any desired carbon and manganese content can be made.
Chemistry of the Basic Process.
process.
is
Oxygen
used to
basic open-hearth is an oxidation some form of iron oxide (iron ore) oxidize the carbon, silicon, manganese, phosphorus, and part
in the air or in
The
of the sulfur in the charge.
In the basic open-hearth process limestone

scrap and pig iron; and
to lime
slag.
(CaCO s )
is
charged with the
when
the metal
is
melted, this limestone, calcined
(CaO) by the heat,
rises to the
top of the molten bath to form
Iron oxide in the form of iron ore

rust,
oxide which, in the form of

reactions
Si
iron oxide oxidizes the silicon
is added to augment the iron was on the scrap and pig iron. The and manganese first, according to the
+ 2 FeO '-* SiO a +
2 Fe,
(5) (6)
Mn + FeO -> MnO + Fe, MnO + Si0 2 - MnSiOg, FeO + SiO, -* FeSiO.,.
The manganese and
iron silicates, of low melting point
(7a)
(7b)
and low
specific
gravity, rise to join the slag.
The
phosphorus
is
then oxidized:

2
225
(8a)
4- 5
FeO - Pa
5 Fe,
5 + 3 FeO (FeO) ,PaOB + 3 CaO
Pa
- (FeO) a P3 B , - (CaO) 3 P s O., +

(8b)
is
(8b)
3
FeO.
(8c)
The
iron phosphate
formed by reaction
is
unstable, but in the
presence of an excess of lime, reaction (8c)

stable calcium phosphate
takes place,
formed and
also leaves the metal
and the more and joins

low
the slag.
Reactions
(5)
to
(8)
are exothermic
is
and take place
at relatively
is
temperatures, as the charge
melting or just after melting

Fe,
complete.
The
oxidation of carbon,
C + FeO - CO +
by reaction
is
(9)
endothermic and takes place only at high temperatures. (9) When all the impurities have been eliminated as far as possible or desirable, the molten metal usually contains less than 0.10 per cent
carbon,
less
than 0.20 per cent manganese,

less
less
than 0.01 per cent silicon
and usually
Sulfur drops from above 0.04 or 0.05 to 0.025 or 0.035 per cent. As the result of these oxidizing reactions the molten metal also contains a relatively large quantity of dissolved iron oxide which, as discussed in Section 11.10, is harmful.
than 0.03 per cent phosphorus.
contains too little manganese to combine with the sulfur. To remove harmful oxide and to ensure the presence of sulfur as manganese sulfide, manganese is added to the molten metal in the furnace or as it is tapped from the furnace. This reacts with dissolved iron oxide, Mn + FeO - Fe + MnO, (10) to form manganese oxide which is insoluble in the molten metal and which rises to the top to join the slag. The Acid Open Hearth Process. The open-hearth used in the acid
It also
process
smaller,
is
similar to that used in the basic process except that

slag
is
it is
usually
is
and since the

ore
is
acid, the lining of the furnace hearth

initial
made
of acid material also.

scrap.
No
charge consists of cold pig iron and added because the iron oxide is basic and would react
The
with the lining of the hearth. For this same reason scrap alone is not used as a charge, for it would oxidize and have the same detrimental effect on the furnace lining. Only manganese, silicon, and carbon can be removed readily; therefore a premium grade of pig iron and scrap
that
is
low in both phosphorus and sulfur
is
necessary.
This tends
to increase the cost of acid steel over the basic type.
The
acid slag tends to
be less oxidizing than the basic slag, and for this reason there are fewer oxide inclusions in the steel when it is poured, resulting in a "cleaner" steel. The acid steel is usually tapped at a higher temperature, in order that the steel may stand in the ladle for 30 minutes or more, thus
226
Fig. 11.5.
electrodes (Courtesy of
Heroult electric furnace tilted for tapping, showing American Bridge Company)
arrangement of
giving what inclusions are present a chance to rise to the surface and
enter the slag.
11.6. Manufacture of High-Quality Steels
High-quality carbon and alloy steels are
by the Electric Processes made by the acid open-hearth
and the acid and basic electric process (Table 11.1). Most carbon tool steels and special alloy steels are made in the basic-lined electric furnace.
Selected steel scrap
furnace,
is
shown
in Fig. 11.5,
melted in an arc or induction furnace. produces most of these materials
The
arc
in lots of

5 to 70 tons; the induction furnace, with a capacity
chiefly to melt high-alloy steel
227
to 5 tons,
is
up
used
scrap without
loss of costly alloying metals.
The
steels
large arc furnaces are used chiefly for the production of low-alloy
by duplexing, that is, by refining further a charge of molten steel that has been partly refined by the acid Bessemer or the basic open-hearth
If
process.
the scrap contains too
much carbon and
phosphorus, these elements
are oxidized together with the silicon
and manganese, under conditions similar to those outlined for the basic open-hearth process on p. 224. When oxidation is completed, the slag is removed and a new one is added, composed of lime, fluorspar, and silica sand or crushed ferrosilicon.
This
is
slag,
which
consists principally of calcium silicate
when
melted,
deoxidized, and strongly reducing conditions are established
in the furnace by scattering

face.
powdered coke or
ferrosilicon over the sur-
Since slag and metal tend to be in equilibrium, eliminating iron
oxide from the slag also deoxidizes the metal. Furthermore, a strongly reducing slag will remove sulphur almost completely from the metal.
Owing
to the
complete deoxidation of the slag and
to the absence of
oxidizing gases a condition attained only in the basic electric process-
much sounder
steel can be made by this process than by either the acid Bessemer or the basic open-hearth process where gases and slag are
strongly oxidizing at all times.
The acid electric process combines the nonoxidizing character of arc heating with the lining and slag of an acid process. Acid electric steel is
usually not so well deoxidized as basic electric
steel,
but
it
is
cheaper.
The
for
small acid electric furnace
is
especially suitable for intermittent

arc, is
operation and, owing to the high temperatures of the
widely used
melting
steel for
small high-grade castings.
The acid process is also used to produce ingots, high-quality forgings, ordnance and alloy steel. The furnace charge is usually all scrap, and practically the same purifying procedure is used as in the acid The steel can be more thoroughly deoxidized since the oxidizing effect of the furnace gases on the slag is eliminated. The process is used mainly to melt and refine carefully selected scrap low in
open-hearth.
phosphorus and
sulfur, as the process will
remove
neither.
The
general features of the various steelmaking processes arc sumin
marized
11.7.
Table
11.1.
Wrought Iron
iron
is
Wrought
with
1
a ferrous material of highly refined iron incorporated

silicate slag.
to
4 percent of a ferrous
Two
primary methods are
228

used in
its
229
(2)
manufacture:
(1)
the puddling process, and
the Aston or
Byers process.
In the puddling process, a charge, weighing about 600 pounds, of iron

scrap, pig iron, iron ore,
and mill scale are melted and refined in the puddling furnace. The fuel used for heating and refining the charge is
bituminous coal burned on grates at one end of the furnace. After the charge is molten, it is mixed by the operator, using the puddle bar. During the refining period, the oxidization of the carbon, silicon, and man-
ganese
is
brought about by reaction with the iron oxide. As the refining
progresses, the melting temperature rises, so the temperature within the

is not sufficiently high to keep it molten, and it becomes a plastic mass known as a puddle ball. The puddle ball is then removed from the furnace, squeezed and rolled into bars to eliminate much of the en-
furnace
trained slag.
The
is
bars,
known
as
"muck"
bars, are cut into short lengths,
fastened together in piles, reheated to a welding temperature and rolled.

If
this
process
repeated a second
time,
the product
is
known
as
double-refined iron.
The Aston
silicon
or Byers process consists of melting Bessemer grade pig iron
in a cupola and refining
it in a Bessemer convenor until the carbon, and manganese are removed. At the same time, an iron silicate slag of the same composition as that produced in the puddling operation is prepared in an open-hearth furnace.
predetermined rate into a ladle, called The temperature of the metal is higher than that of the slag and the former rapidly solidifies. Gases are liberated during the solidification period and the metal disintegrates into
is
The
refined metal
poured
at a
a thimble, containing the molten slag.
small globules sinking to the bottom of the thimble to form a spongy mass. This operation is known as shotting. The excess slag is then poured
and the solidified ball of metal, containing slag, is transferred to the squeezer and rolls where the same procedure follows as in the case of puddled iron. Wrought iron is a highly ductile material and is used for
off
pipe and pipe
fittings, bolts, sheets, bars,
and
plate.
11.8. Special Steel-making Processes
The acid Bessemer and the basic open-hearth Most of the carbon and all of the silicon and manganese are oxidized in the converter and then the metal is transferred to the basic open-hearth where the phosphorus, sulfur, and the remainder of the carbon are removed. Under good conditions an open-hearth may produce up to twice the tonnage per week by the duplex process.
Process.
The Duplex
are used in succession.
230
Super-refining Process. This
is
The
is
a special
duplex process
in
which
purified basic open-hearth metal
transferred to a basic electric furnace,
deoxidized, and finished into high-quality electric steel. Care is taken to have the residual manganese as high as possible in the open-hearth
product.
Carbon
is
added
to
bring
this
component near the required
no further oxidation is required the basic carbide slag is immediately charged, and dcoxidation and de-sulfurization are carried out by the carbide and the residual manganese in the metal. The Triplex Process. This process is carried out in two ways: (1) a combination of the acid Bessemer and two open-hearths in succession, or (2) a combination of the duplex and super-refining process. The first is used when pig iron is very high in phosphorus. The open-hearth is tapped and charged into another open-hearth where a new slag is built up and the rest of the phosphorus and carbon removed. The Talbot Process. This is a process that results in a very large tonnage of metal in a very short period of time. The increase in capacity is obtained by using a bath of metal forty or more inches in depth. The first charge, usually consisting of pig and scrap, is worked down to the desired composition, and about one third of the metal is tapped. Ore and limestone are added to the bath to produce a very basic oxidizing slag. Molten pig iron, equal to the metal tapped, is poured through the
finishing range. Since
The reaction is so rapid that the silicon, manganese, and most of the phosphorus is removed. The charge is then worked down to the required carbon and phosphorous content as the temperature is raised. For a period of from 3 to 6 hours, the bath is purified, and another heat is tapped
slag.
The
slag
is
reoxidized,
the end of a
more pig added, and the procedure repeated. At week the furnace must be drained and the lining patched,
making
the process very expensive.
The Duplex Talbot Process. This process is a combination of the Talbot and Duplex processes. Metal from the Bessemer converter, free of
is poured through the oxidized slag, the phosphorus being removed almost immediately. The addition of pig iron raises the carbon content and aids in deoxidation.
carbon, silicon and manganese,
The Monell Process. Limestone, ore, and sometimes steel scrap, are charged upon a basic hearth and heated until pasty. Molten pig iron is then added. The low temperature will remove the phosphrous very
The silicon, manganese, and carbon is worked down in the usual manner. The Campbell Process. A charge of pig and scrap is melted in a Campbell tilting basic furnace and the phosphorus, silicon, manganese and part of the sulfur are removed. The furnace is tapped and the metal
rapidly with a violent reaction.

charged into an acid open-hearth furnace. An acid slag the heat is finished by the usual acid procedure.
is
231
built
up and
The Crucible Process. The crucible process consists of melting properly proportioned scrap, fcrro-manganese and charcoal in a closed crucible.
This
to
is
primarily a mixing and refining process. Each crucible holds 50

is
100 pounds of metal, which
heated
in
a gas fired regenerative
furnace for approximately four hours for complete refining.

11.9. Mechanical
Treatment of
Steel
Ingot molds: Types, Sizes, Shapes. Most of the steel made in the United States is cast into ingot molds of one type or another, irrespective of the type of steel, for further fabrication into desired shapes. This is done, rather than casting into desired shapes directly, because of the
better physical properties obtained,
and because
it
can be done
much
more
cheaply.
Two
is
general types of ingot molds are used in the United
States: the big-end-up
and the big-end-down. As their names imply, the
big-end-up
the bottom.
mold
larger at the top,
and
the big-end-down
is
larger at
Most
steel is solidified in
the big-end-down type mold, since
it is suit-
able for the cheaper semi-killed steels
and
for the
rimming-type
steels.
These steels avoid shrinkage or actually increase in volume in the molds by the evolution of gases on cooling, thereby avoiding the formation of "pipe." By the use of a "hot-top," a refractory collar added to the mold, killed steels may be poured into big-end-down molds because the steel in the hot-top section is kept molten and will fill any cavity produced by
shrinkage.
Big-end-up molds tend to produce less pipe since there is a larger volume of steel at the top of the ingot, and it remains molten longer. However, when used with killed steels, a hot top is generally used. Big-end-up ingot molds are more costly and are generally reserved for high-quality and alloy steels.
Bottom-poured ingots are those in which the metal is introduced from the bottom, usually into big-end-up molds with refractory hot-tops. Due to the complicated arrangement for pouring, they are more expensive and are usually reserved for high-quality and high-alloy killed steels.
Hot Working. After the ingot has solidified, it is transferred to a soaking pit or heating furnace to equalize the temperature and to heat it to a temperature at which the steel is very plastic. It is then hot
worked by
product.
rolling, pressing, or forging
it
into a finished or semifinished

steels
few special carbon and alloy
used in very heavy sec-
232
tions, such as large guns, axle shafts, armor plate, and the like, and a few tonnage products are worked from the ingot directly into the finished section. It is, however, considered better practice, whenever the size
of the finished product permits, to reduce the ingot to a section known as a bloom, slab, or billet, which is reheated, either with or without
intermediate cooling and inspection, and
is
rolled into finished products.
These may be
rails,
structural shapes, plates, sheets, strip, pipe

sizes
bars, or rods of a
wide variety of
the large rolling mill, especially into a multitude of small articles.
and tubes, and forms. Finished sections from bars and rods, may be fabricated further
Hot working has two primary objects: (1) to produce various shapes and sizes economically, and (2) to improve the structure and properties by breaking up the coarse crystal structure of the ingot. Cold Working. A large tonnage of hot rolled bars, rods, sheets, pierced tubing, and other hot rolled products are worked at room temperature. This operation is known as cold working. Cold working is a finishing operation and the articles coming to this stage have been roughly shaped by hot working. The general methods of cold working are cold rolling, cold drawing, cold pressing, or stamping. Hot rolled shapes are finished by cold rolling and cold drawing processes to produce smooth surfaces, accurate dimensions, and increased strength. The drawing of hot rolled rods through dies is used principally in making wire and in finishing seamless steel tubing. In the cold pressing or stamping process, plate and sheet for various purposes are often shaped between dies by means of a
heavy hydraulic
press.
Cold working also has two primary objects: (1) to produce sections, sizes, and shapes that cannot be produced economically by any other method, and (2) to produce certain combinations of properties, especially very high strength accompanied by considerable ductility, that also cannot be secured economically by any other process. The mechanical treatment of steel is an art that has been perfected
mechanically until
it is
now
in a relatively high state of development.
Hundreds of millions of
have been invested in rolling mills and forging plants that are marvels of mechanical efficiency and low-cost production. Modern rolling mills, such as the recently developed condollars
tinuous strip mill, are, in
fact,
such marvels of costly perfection.
Although the mechanical equipment used and the methods of hot and cold working are a fascinating field for discussion, they are of little con-
who uses steel and who does not care whether strip on a continuous or a hand mill so long as it has the properties he requires and is cheap enough for him to use economically. The effect
cern to the engineer
is
rolled

of hot and cold working
interest to
233
on the structure and properties, a subject of great most engineers, is given more consideration elsewhere in this
book.
and other metallic materials that have been hot or cold worked some instances, cast) frequently must be joined together to form the finished structure. The principal methods of joining are welding and riveting. The equipment and the methods used for joining are of much interest to engineers but are hardly wilhin the scope of a book on elementary metallurgy and are, therefore, not discussed further here.
Steel
(or, in
11.10. Harmful Elements in Carbon and Alloys Steels
The five so-called harmful elements present in all steels in varying amounts, but mostly in small fractions of 1 per cent, are phosphorus, sulfur, oxygen, nitrogen, and hydrogen. Phosphorus. In the amounts usually present in carbon and alloy steels phosphorus is combined with the iron as iron phosphide (Fe 3 P) which
,
dissolves in solid iron as sugar dissolves in coffee.
Although metallurgical
opinion is not wholly unanimous, most available data, plus many years of experience with acid steels containing 0.07 to 0.12 per cent phosphorus, indicate that this element makes steel cold short, in other words, brittle
when
cold, particularly in its resistance to impact. This brittleness is more marked in high-carbon steels than in low-carbon grades and is apparent if the amount of carbon plus phosphorus is above 0.30 per cent. The
static ductility
is
not appreciably affected.
Because of the brittleness caused by phosphorus, the maximum amount permitted is usually given in engineering specifications. This varies from
a
per cent in rails and railway materials, structural and other products of the basic open-hearth process. In tool steels and other high-grade high-carbon and alloy steels, the maximum permitted is usually 0.03 and occasionally even 0.02 per cent.
shapes, sheet, strip,
to a
maximum of 0.10 to maximum of 0.045
0.12 per cent in low-carbon acid Bessemer steels
The
Table
average
11.1.
amount
of
phosphorus in various grades
is
shown
in
Despite the fact that, in general, phosphorus has a bad name and for nearly a hundred years has been considered a nuisance that should be
it has been discovered lately that it has its good the tensile and the yield strength and improves other proj>erties, including the resistance of steel to some varieties of corrosive attack. Some of the new low-alloy high-strength steels contain about 0.10 per cent phosphorus used together with small amounts of copper,
kept as low as possible,

points.
It raises
nickel, or
chromium. The carbon, however,
is
low.
234
Sulfur. In a
manner analogous
to that of
phosphorus, sulfur will com-
bine with iron to form iron sulfide (FeS), which dissolves in molten iron.
However, manganese, if present, having an affinity for sulfur which it does not have for phosphorus, will rob the iron of its sulfur to form manganese sulphide (MnS) This compound is almost completely insolu.
ble in solid iron. Consequently,

fide
is
when
the iron solidifies, manganese sul-
present in the mass of metal as discrete particles.
These
particles,
together with oxides and silicates, are
known
to the metallurgist as solid
nonmetallic inclusions
the mill by the
present,
at a
or,
more simple,
as inclusions,
and
to the
man
in
is
more
expressive term dirt. If insufficient manganese
some
of the sulfur remains as iron sulfide.
This compound melts
with the result that the
temperature lower than the usual temperatures for rolling or forging, steel is likely to crack during hot working. This
is
brittleness or fragility at elevated temperatures
known
as hot shortness.
Practically all commercial steels contain plenty of manganese, so that
engineers
who
use steel at elevated temperatures need not worry about
hot shortness caused by sulfur.

the fact that manganese sulfide
Of much more
if
interest to engineers
is
particles are always
present and that

is
they
may be
present in large amounts
the sulfur
high.
If these
particles segregate in vital areas, they
may have
a deleterious effect
on the
impact resistance may be greatly reduced. Any particle of dirt in the metal, if large enough, if the shape is favorable, and if it is strategically located, may act as a stress raiser and cause failure, especially by fatigue, much sooner than would normally be
ductility of the steel; in fact,
expected.
Sulfur has few virtues

phorus,
Its
is
it
is
a real nuisance
is
when present in steel. Compared with phosand is, therefore, kept as low as possible.
only benefit, so far as

present in the proper
known now, is that, if the manganese sulfide amount and is well distributed, it makes the
steel easier to
machine. Steels that are machined automatically at high
speeds and that are used for parts that are not subject to high impact
stresses
contain 0.080 to 0.150 per cent, or even more, manganese sulfide.
With higher sulfur percentages the manganese is frequently increased from the usual amount in low-carbon steels, namely 0.30 to 0.60 per cent,
to O.fiO to 1.65 per cent to ensure that
no iron
II. 1.
sulfide
is
present.
The
the
average sulfur percentages for various grades of steels

different processes are
made by
shown
the
in
Table
amount
tions.
of the range
is
maximum
In general, the higher permitted by the usual specificaspecial variants of the basic
slags that are essen-
Oxygen. All
steel,
is
except that
made by some
electric process,
melted and refined by gases and

tially oxidizing.
235
At the high temperatures used, oxygen combines avidly with iron, carbon, manganese, silicon, and some other elements that may be present, forming a variety of gaseous or liquid oxides. Some of these dissolve in molten steel and are thrown out of solution when the steel solidifies, others are deoxidized by later slags or by alloys added especially
The result of these deoxidizing reactions, which are some processes than in others (see Table 11.1), is to produce a steel which is more or less free from oxygen and its reaction products. Even under the best conditions, however, the steel is never
for this purpose.
more
effective in
wholly cleansed; hence,
all steels when solid contain a larger or smaller quantity of gas cavities or solid inclusions bearing oxygen in some form. These oxides or combinations of oxides (silicates) form, together with
sulphides, the most

dirt
common
if
source of the solid nonmetallic inclusions or

steels.
found
in
commercial'
Like
sulfide
inclusions,
oxides and
act as stress
silicates, if
segregated or
present in large particles,
may
raisers or as loci of
weakness where, under favorable conditions, failure
may start.
Inclusions that are entrapped in the steel ingot
solidifies arc usually in the
size
(or casting)
when
it
form of small rounded

to those
particles varying in
from those which are submicroscopic

a polished surface
which can be seen
on
with the unaided eye. At high temperatures most
of the inclusions are plastic. Consequently, when the ingot is rolled or forged, they elongate into stringers or threads. It should be emphasized
that inclusions, once they are entrapped in the steel, may be distorted, elongated, or otherwise changed in form by hot or cold work, but they
cannot be removed or even diminished in amount by any treatment. No commercial carbon or alloy steel is wholly free from dirt. The amount present and the degree of dispersion of the particles depend to a considerable extent
upon
the nature of the melting process.
As indicated in
Table
inherently the cleanest, acid electric steel ranks next, and acid Bessemer steel ranks lowest. The process itself is,
11.1, basic electric steel is
however, not the only factor. Also important are quality of the raw materials used and the skill of the man who makes the steel.
It
has been well
known
if
for
many
is,
years that most ferrous materials
exhibit directional properties, that

resistance, are lower
some properties, notably impact determined on a specimen cut at a right angle to the direction of rolling than if determined on a specimen taken longitudinally. Elongated inclusions are an important factor in causing this
difference in properties.
Owing to the impure raw materials available to the iron and steel industry and to the necessity of using-except in a few restricted cases-
236
oxidizing reactions to get rid of these impurities economically, one of the chief problems of steel men has been to eliminate the harmful effects of
oxygen and
its compounds by deoxidizing as thoroughly as possible. For more than sixty years one of the principal tenets of metallurgists has been "the more complete the deoxidation, the better the steel." Within the
past twenty or twenty-five years, however,
it has been found that the phrase "for certain steels" should preface this doctrine of deoxidation. McQuaid, Bain, and other investigators in this field have shown that
a certain degree of oxidation

alloy steels in
may be very desirable in some carbon and which a control of the grain size is advantageous. The amount of oxygen in solid steel varies from a trace to as much
as 0.02 per cent: few steels contain less than 0.005 per cent; the average
amount
grades.
as
in commercial carbon steels is probably between 0.01 and 0.015 per cent, with the higher amounts found normally in the lower carbon
Most of the oxygen probably all of it in most steels is present an oxide or silicate. Small amounts of oxygen are difficult to determine accurately by chemical analysis, and it is even more difficult to determine in what form it exists in the metal. Nitrogen and Hydrogen. Although the mechanism is not well understood, it is generally conceded that the presence of either nitrogen or hydrogen in carbon and alloy steels will tend to increase their brittleness.
11.11. Manganese in Carbon and Alloy Steels
Manganese
sulfur to form
sulfide;
is
grades of steel because
an essential and it performs
beneficial
a vital
manganese
sulfide, a less
element in nearly all dual role: It combines with obnoxious impurity than iron
it deoxidizes the .metal by reacting with oxygen to form an oxide which is less soluble in molten steel than iron oxide and which, therefore, will leave the metal more readily. The amount used varies with the grade of steel and with the amount of oxidation in melting; enough is added to most steels so that, after its
and, as noted previously,
purifying action has been completed, 0.30 to about 0.75 per cent, occasionally as
of manganese also increases the strength of steel. Either alone or, preferably, in combination with relatively small amounts
small
much as amount
1.00 per cent, will be left in the metal.
of other alloying elements,

properties
that
it
the
so-called
produces such a favorable combination of intermediate-manganese alloy steels are

fields of
finding increasing use in
some
engineering, especially for
rail-
road rolling stock and in bridges.

the
They were
also widely used during
war
as a substitute for low-alloy steels containing considerable nickel.
237
The amount
per cent.
of manganese in these steels ranges from about 1.00 to 1.90 There is considerable confusion, even among metallurgists, about the dividing line between these steels and carbon steels as some steels that are made and used as intermediate-manganese alloy materials may contain 1.00 per cent or even less, and a few steels that have for years been classed as plain carbon steels rails are an example contain as much as 1.00 per cent or even more manganese. If carbon steel and intermediate-manganese steel cannot be differentiated by their manganese content, they can sometimes be classed according to the industrial application for which they were made. This is a glaring example of the
slipshod terminology that has

steel industry
grown up over the years in the iron and and that confuses maker and user, metallurgist and engi-
neer, alike.
11.12. Carbon Monoxide, and
Rimming and
Killed Steels
between oxygen and carbon in the molten metal large volumes of carbon monoxide gas are formed. Most of this gas is given off during refining; some of it, however, remains entrapped and, unless removed by silicon or other degasifier as described in 11.13,
As a
result of the reaction
Most of this remaining carbon monoxide escapes during solidification. Owing, however, to the viscosity of the metal just before it solidifies, some of the gas remains entrapped to form cavities of varying size in the ingot or casting. These
it starts
will be
still
in the metal
when
to solidify.
cavities-blow holes as they are commonly called-will usually weld in rolling or forging, especially in low- and medium-carbon steels, and will disappear. If, however, the inner surface of the cavity becomes oxidized, which frequently happens in heating for rolling when the cavity is near the surface or if the steel is high in carbon, the surfaces of the cavity do
not weld and the result
is
1
1
a defect
known
as a
seam
(Fig.
.6).
Seams
are usually located on the surface of the rolled section where they can be
detected and removed by machining, chipping, or grinding; but they may
be internal, and
failure will start.
if
so they
inclusions, act as loci
may, like where premature
Kic.
11.6.
Scams on the surface of a
steels are frequently classiaccording to the method of removing gas cavities or rendering them innocuous, as killed, or rimming
Carbon
fied
shaft.
2x-
types.
238
Killed
steels,
which nearly always contain more than 0.25 or 0.30 per
cent carbon, are those which must be thoroughly sound and free from
The descriptive adjective comes from the action of the molten metal when poured into the ingot mold: it lies perfectly quiet with no evolution of gas; there is neither bubbling nor churning of the upper surface of the metal. Killed steels are degasified by silicon, alumigas cavities.
num, or other
killed.
degasifiers. All plain

steels,
carbon forging
steels,
all
rails,
all
high-carbon tool and spring
and
all alloy steels
are thoroughly
Rimming
of
solid
(Fig.
steel so called from the rim
metal next to the mold wall

low-carbon
basic
is
11.7) is
steel in
openpartly
hearth
which deoxidation
not degasified.
completed in the furnace or in the ladle

but which
steel
is
is
When
a
the
poured into the ingot mold and

is
begins to solidify, there
brisk but
controlled evolution of gas which results

in
an ingot having a sound gasfrec surface
and
in locating the blow holes so far below the surface that there is no danger of their becoming oxidized when the ingot is heated for rolling (Fig. 11.7). The blow
holes will weld completely in rolling,
and
the result
face free
especially
is
a material with a clean sur-
from seams. Rimming steels are suitable for sheet and strip, notably for thin, deep-drawing stock used in large tonnages for automobile bodies
and
fenders.
Close control of the slag
composition (particularly the amount of

iron oxide)
steel that
,
slag viscosity,
is
and the pouring

to
temperature,
necessary
produce a
it
rims properly
when
solidifies.
Most
ing
Fig. 11.7. Cross section of
basic
open-hearth
steels
contain-
less
made
an
in-
than 0.15 per cent carbon are so that they rim; steels containing
f
0.15 to about 0.25 per cent carbon, used

jd
, '
got of rimming steel about onetwentieth natural size. (Courtesy of American Rolling Mill Company)
structural shapes
<
and plate, "
'
are killed or are partly killed.

11.13. Silicon and Other Degasifiers
239
Like manganese, silicon is beneficial and is added to carbon steel as a purifier and, in larger amounts, as both purifier and alloying element.
It
is
effective in
removing oxygen and
is,
therefore,
added
to those grades
of steels (usually containing more than 0.30 per cent carbon)

gas cavities do not weld readily or are otherwise harmful.
in
which
is so used in a fe"' medium-carbon and high-carbon basic open-hearth steels
Silicon
(for
example,
rails)
in practically all acid open-hearth

It
is
steels,
and
in all basic electric steels.
and acid electric added rarely to such lowsteels
carbon basic open-hearth
steels as structural material, wire, sheet, plate,
and
which are used for monoxide gas is silica (Si0 2 ), which reacts readily with manganese oxide and iron oxide, forming silicates. These are insoluble in the molten metal and are of such low specific gravity that they readily leave the steel. Silicon thus
pipe and tinplate.
strip or to those
low-carbon Bessemer
The
reaction product of silicon with carbon
carries deoxidation farther than

degasifier.
Enough
is
added
to
manganese and is in addition an effective complete the purifying reactions and leave
0.10 to 0.40 per cent in the finished steel.
There is occasionally some confusion but not so much as in the case manganese in distinguishing between a silicon-treated carbon steel and a silicon alloy steel. Some specially deoxidized open-hearth steels
of
used in bridge construction, containing around 0.25 per cent silicon, have been and still are termed silicon steels by civil engineers. This is unfortunate, and it is hoped that the tendency to call a material silicon
steel
only
if
the silicon
is
0.50 per cent or
more
will
spread.
Steels containing 1.50 to 2.25 per cent silicon
per cent manganese are used widely for springs,

0.5 to 5.0 per cent silicon
in the construction of
become more wideand about 0.75 and steels containing
and small amounts of other elements are used dynamos and other electric apparatus. Small amounts of aluminum and titanium are added to some grades of carbon steel as final deoxidizers and degasifiers. It has been discovered recently that aluminum, probably through the agency of minute alumisize of carbon and one of the major recent developments in ferrous metallurgy, it receives detailed attention elsewhere in this book. Both aluminum and titanium are also used, in much larger amounts than is necessary for deoxidation and degasification, as alloying elements.
num
oxide particles, can be used to control the grain
alloy steels.
As
this
is
11.14. Other Elements

Since the introduction of alloy steels some
fifty
years ago there has

steel
been a gradually increasing contamination of carbon
by nickel.
240
copper, and other alloying elements owing to the inadvertent mixture of alloy-steel scrap with the other scrap. In the case of elements that oxidize
readily, for example,
chromium, vanadium, aluminum, titanium, and a

is
few others, the contamination
not serious, as they are largely oxidized

refining, leaving usually not
and removed during melting and
traces in the steel. In. the case of such alloys as nickel
more than and copper, which
do not
normally increase slowly over a is not of such serious consequences for steels made by a process that uses also a large proportion of pig iron, which is normally free from nickel and :opper, as it is in steel made using a large percentage of scrap (Table
will
oxidize, the
amounts present
period of years.
The amount
of these elements in the scrap
11.1). In the latter the scrap may contain an unsuspected 0.10 to 0.25 per cent nickel and 0.05 to 0.10 per cent copper, sometimes even enough to
affect the properties materially.
recent development in free-machining steels
is
the addition of lead
This element is insoluble in carbon steel, but by special methods of addition to the molten metal it may be incorporated as a suspension so finely disseminated throughout the metal that it is not easily visible in an unetched section with the microscope. These submicroscopic particles of lead apparently act as an internal lubricant and in addition cause the chips to break up readily. Recently reported data
indicate that a lead content of 0.10 to 0.25 percent greatly increases ease
to low-carbon material.
of machining but has no appreciable effect
on mechanical properties. Carbon steel may be contaminated with small amounts of arsenic, tin, and antimony, traces of which may be present in iron ores and may persist through melting and refining. These metals may also be picked up from scrap containing bearing metals or tin cans. The amounts present
little is known about the small amounts of most of these adventitious elements. According to the present state of our knowledge, their effect, with the possible
are small, rarely exceeding 0.05 per cent. Very

effect of
exception of that of antimony, which is assumed to be harmful, may be called neutral. During the war, when some detinned scrap was used in the manufacture of open-hearth steel, considerable attention was given
to the effect to tin. It was found that small amounts of this metal do not cause hot shortness in rolling; they do, however, increase hardness and reduce toughness. Tin, therefore, may be considered definitely harmful in
some grades of
steel, especially in
those used for deep drawing.
11.15. Low-Alloy Steels
A large number of metals (and some metalloids and nonmetals) have been alloyed with carbon steel, either alone or in various combinations, and the resulting properties have been studied more or less completely.
241
These include manganese, silicon, nickel, chromium, vanadium, tungsten, molybdenum, copper, and phosphorus as the more common alloying elements and cobalt, aluminum, zirconium, titanium, nitrogen, lead, boron, and selenium as the less frequent additions. Steel may also be coated or plated with zinc (galvanizing) tin, lead, chromium, or nickel,
,
but such products are not classed as alloy steels. There are two general classes of alloy steels:
neering
the
steels
(1)
the low -alloy engicorrosion-
and
(2)
the high-alloy tool and die
steels,
and
heat-resistant steels
is
and special-purpose alloys. In tonnage, the first class more important; in value to man, both are probably of equal importance, for both have played a vital role in the development of our
Before
present-day machine-age civilization.
World War II there were several hundred low-alloy engineering which some 70 to 80 were considered as standard by the Society of Automotive Engineers. These steels were divided into eight main
steels, of
classes:
intermediate-manganese, silicon-manganese, nickel, nickel-chronickel-mo-
mium, molybdenum (including chromium-molybdenum and
lybdenum), chromium, chromium-vanadium, and tungsten steels. There were also a large number of low-alloy structural steels, most of them developed between 1933 and 1939, that contained small amounts (usually less than 1 to 1.5 per cent) of nickel, copper, chromium, manganese,
silicon,
binations.
phosphorus, and molybdenum in various proportions and comThese were developed to satisfy a demand for a material of
"Irish stew steels"
better properties than carbon steels but cheaper than the S.A.E. grades.
These have been nicknamed

accurate designation.
by
Gillett, a
happy and
11.16. High-Alloy Steels
There are almost

classes.
as
many
varieties of the high-alloy steels as there are
of the low-alloy grades.
These
special materials
can be divided into three
The
first
includes the well-known high-speed steels

steels.
and
the
closely allied die
and valve
The primary
requirement
is
hardness,
especially at elevated temperatures,
(10 to 25 per cent) of tungsten,
smaller amounts of
relatively
which is attained by large amounts chromium, and occasionally cobalt, plus vanadium, molybdenum, or silicon, together with
high carbon percentages.
all the highly alloyed steels used primarily because of their corrosion resistance or scale resistance at normal and at high temperatures. The basic element in these steels is chromium, in
The
second class includes
amounts ranging from 10 to 35 per cent, either alone or together with varying amounts of silicon, manganese, nickel, copper, or molybdenum. The best known steels of this group are the cutlery steels, containing
242
stainless steels,
about 0.35 per cent carbon and 14 per cent chromium, and the soft containing low carbon, 15 to 25 per cent chromium, and 6 to 20 per cent nickel, which are used widely for building trim, hardware and fixtures on buildings and automobiles, various kinds of utensils and
more recently, in the construction of railroad equipment and aircraft. Not so well known but just as important are the highly alloyed steels containing nickel, chromium, molybdenum, cobalt, and other alloying
metals, used in steam plants, oil refineries, gas turbines, including jet
engines, and in other applications where high stresses
and high temperathe re-
tures are encountered. Also in this second class are the alloys containing
up
to 65 per cent nickel, 15 to 20 per cent or

iron.
more chromium,
mainder being
resistivity
These are the
heat-resistant alloys of high electric
that are used for the heating elements of all our domestic
and
industrial heating appliances.
The
third class includes a large

uses.
number
of alloys of highly specialized
but important
They
arc the steels with special magnetic and electric
properties, alloys with special expansion characteristics, steels with ex-
ceptional wear resistance, and

that by
are not manufactured in large tonnages,
means of them
the
Although these materials some are of such importance communication and other industries have
others.
many
experienced a veritable revolution in the past twenty or twenty-five years. Nearly all the high-alloy materials are made in electric arc or induction furnaces. Alloy steels are much more costly than carbon steels so that
care
is
exercised to keep the quality as high as possible. Selected scrap

is
is
used, deoxidation
carried farther,
and sulfur and phosphorus are usually

steels.
required to be lower than in carbon
QUESTIONS
1.
Name
What
the four principal
raw materials
of the iron
and
steel industry.
Name
the two
2.
main
classes of final products.
are the general principles underlying the reduction of iron ore in
Name the two principal reactions in the blast furnace, and give the approximate temperatures at which each reaction takes place
the blast furnace?
most readily.
3.
In the manufacture of pig iron, describe how the amounts of phosphorous, sulfur, and silicon are controlled in the product.
4.
What
is
blast furnace slag,
and where does
it
come from? What
are
its
principal (unctions?
5.
Describe the acid Bessemer process. What are die raw materials used? Describe the principal oxidizing reactions. How does the cost and quality of the Bessemer process compare with the basic open hearth?

6.
243
7.
8.
9.
Sketch briefly the general features of the basic open-hearth process, and compare it with the acid open-hearth process in (a) raw materials, (b) slags, (c) chemical reactions, (d) general quality of the product. Give two advantages of acid open-hearth steel production over basic openhearth production. Give two advantages of basic open-hearth production over acid open-hearth production. Describe the regenerative principle of the basic open hearth. Give two reasons for its use. Differentiate between the "ore boil" and the "lime boil" by describing the
reactions in each.
10.
Describe
silicon,
how
the
impurities,
such
as
phosphorous, sulfur,
manganese,
and carbon are eliminated
in the basic
11.
12.
13.
Give four advantages of the electric steel. Do they have any disadvantages? Describe the manufacture of wrought iron. What are its uses? How does wrought iron differ from ingot iron? What stcelmaking process would you recommend for the production of
steel for the following:
open hearth. processes for making
14.
wire for suspension cables? (b) sheet steel for for airplane engines? (d) rails for mainline railway track? (e) armor plate for a battleship? (f) small highstrength castings? (g) tools for machining automobile connecting rods? Compare the usual amounts and the principal effects of sulfur and phos(a)
tin
cans?
(c)
alloy-steel
crankshafts
15.
16.
phorous in carbon and alloy steels. Describe the principal functions of manganese and silicon when added to carbon steel. Why is manganese a valuable alloying element? Describe the essential differences between rimming and killed steels. How
do
17.
these two classes ordinarily differ in carbon content? Give a practical definition of low-alloy steels. Define high-alloy
steels
and
give the characteristic property of the classes of high-alloy materials.
The Constitution of S tee I

CHAPTER
12
Hollis Philip I.eighly,
Jr.,
Ph.D., Chairman, Depart-
ment
of Metallurgy, University of Denver, Denver,
Colorado
John Stanton Winston, M.A., M.S., Chairman, Department of Metallurgy, Mackay School of Mines, University of Nevada, Reno, Nevada
are those referred to as steels.
carbon
in
most common group of alloys in use today These alloys consist primarily of iron plus varying amounts, to which may be added various alloying ele-
1 HE
ments to achieve the desired properties. Steel is used in tremendous quantities to produce necessities and luxuries; without steel our civilizanot intended to indicate, historically On the contrary, steel was produced as early as 1200 B.C. However, it is only within the past century that methods have been developed to produce steel in large quantities cheaply enough to make it a material of very common usage.
tion
would be quite
primitive. It
is
is
speaking, that steel
new
material.
12.1.
The Allotropy of Iron

effects of
The
carbon additions to iron are intimately associated with
the allotropy of iron. In the process of freezing and cooling to atmospheric temperature, iron undergoes two allotropic transformations. Upon solidification at 2802F.
(1539C.)
iron assumes a body-centered cubic struc-
At 2552 C F. (I400C.) this structure transforms into a facecentered cubic structure (y Fe). This structure persists clown to 1670F. (910C.) where it transforms back to the body-centered cubic structure (a Fe). Actually, 8 and a iron are the same form of iron. They are often regarded, however, as distinct modifications because of the two ranges in temperature in which the body-centered cubic structure is stable. The transformations of iron from one crystal structure to another are accompanied by changes in various properties; such as, density, electrical conductivity, and thermal change. The thermal change consists of an
ture
(8 Fe).
244
The
245
Time
Fig.
12.1.
Cooling curve for pure iron.
absorption of heat during heating and an evolution of heat during cooling. Fig. 12.1, the cooling curve for pure iron, illustrates how the measurement of the changes in a given property at transformation may be used for determining the temperature of transformation.
12.2. Iron-Carbon Phase
Diagram
In the previous chapter it was shown that iron is reduced from its ore by means of carbon and that the resulting product, pig iron, contains approximately 4% carbon. Two effects of the carbon immediately evident are that it lowers the melting point of the iron and makes the resulting
alloy brittle. It
process
is
to
was also shown diat the chief function of the steel making lower the carbon content to the proper level in order to
obtain a certain combination of desired properties. The effects of carbon are so strong that its content is specified in hundreths of a per cent.
The
alloys
is
best approach to understanding the nature of the iron-carbon to study the phase diagram of the system shown in Fig. 12.2.
as cementite
In pure iron-carbon alloys, the carbon not in solid solution usually occurs (Fe3 C) which contains 6.68 per cent carbon by weight.
,
Although cementite
such that
in steels
metastable and decomposes, given sufficient time at elevated temperature, into iron plus graphite, conditions are generally
is
and pure iron-carbon alloys the carbon is present as Therefore the phase diagram chosen for study concerns the equilibria between iron and cementite; and thus, in reality, is the ironiron carbide diagram. Although this diagram covers a small proportion of the possible combinations of iron and carbon, it includes the entire range of commercial iron-carbon alloys (plain carbon steels and cast irons)
cementite.
246
Atoms per
4 6
cent, carbon
10
12
14
16
IS
20
\"Hypoeutectoid\Hyptreutectoid
/rons-r*
Stee/s
Fie. 125.
Iron-carbon equilibrium diagram.
Carbon
is
soluble to a limited extent interstitially in each of the allo-
tropic forms of iron.
Inspection of the iron-iron carbide diagram shows
that a-iron can dissolve a
maximum
0.1
of 0.025
per cent carbon, y-iron
up
to
2 per cent
in
and 8-iron up to alpha, gamma, and delta
per cent. These solid solutions of carbon
iron are
named
ferrite, austenite
and
l-ferrite,
respectively.
The greater solubility of carbon

is
in face-centered
gamma
iron
than in body-centered alpha or delta iron

size
probably due
to the larger
and more favorable location of the

little
interstices in the face-centered
structure.
Since delta iron has
to
do with
it
the final microstructure of ironit
carbon
alloys,
sidered further.
and
0.5
be conbetween 0.1 It should be noted, however, that in alloys per cent carbon content austenite is formed by a periiectic retransforming as
does to austenite,
will not
fall
action.
and 2 per cent carbon more than 2 per cent carbon a eutectic reaction occurs producing austenite and cementite. The typical eutectic structure which forms is known as iedeburite. Alloys containing this brittle structure cannot be hot- or cold-worked but must be cast, and are therefore known as cast irons.
Alloys whose compositions
between
0.5
solidify as austenite.
For those
alloys containing
The Constitution
of Steel
247
All alloys with compositions between 0.025
and
undergo
pearlite,
12.4)
.
a eutectoid reaction at 1333F.
(723C.)
when
austenite con-
taining 0.8 per cent carbon decomposes, at constant temperature, into
an intimate mixture of
less
ferrite
and cemcntite
is
(Figs.
12.3F and
plain carbon steel of this composition
called a eutectoid steel.
Steels
having
carbon or more carbon than

respectively.
(Fig.
this are called
hypoeute-
rtoid
and hypereutectoid
From
the cooling curve for pure iron
12.1)
it
is
evident that
arrests are experienced
when
the transformations occur.
Such
arrests
are also present in the cooling curves for iron-carbon alloys.

tures at
critical
The
tempera-
which
these transformations in the solid state occur are called
temperatures or critical points.
The
loci of these
points (lines)
on the phase diagram are given symbols. In hypoeutectoid alloys, A 3 and Aj are the upper and lower critical temperatures (lines GS and PS Fig. 12.2); in the eutectoid alloy and hypereutectoid alloys, A. and A,
t
coincide (line
SK
Fig. 12.2)
is
and, therefore,
is
designated
A ll3 The
.
zone
between
A3
and A,
known
as the critical range.
Some
of the other lines appearing on the phase diagram have also been
given symbols.
The
plus cementite (line SE)
curve separating the fields austenite and austenite is designated A,., and the line of temperatures of
transformation of B-iron to y-iron (line
AHJB)
is
called A^. the iron-iron
An understanding
of the phase relationships

final
shown by
is
carbide diagram and the
microstructures attained
best obtained by
following the process of solidification

representative alloys of the system.
and subsequent cooling

Steels
of several
12.3. Phase
Changes of Slowly Cooled Plain Carbon
the completion of solidification all steels consist of austenite while atmospheric temperature they consist of ferrite and cemcntite. Their microstructure depends upon the relative amounts of ferrite and cementat
At
and the way upon the carbon

ite
in
which these are arranged.
This, in turn, depends
content.
The phase changes in carbon steels cooled slowly from a high temperature can be illustrated by three steels containing (A) 0.30 per cent carbon, (B) 0.80 per cent carbon, and (C) 1.30 per cent carbon. These
are indicated in Fig. 12.2 by lines xx', yy'
and
zz'.
is a solution of carbon in molten iron. Upon slow cooling, there is no change until the solidification temperature 2768F. (1520C.) is reached. Here solidification of S iron
At 2820F. (1550C), the
first steel
(xx')
begins and progresses with further cooling until at 2720F. the peritectic reaction of S + liquid - austenite occurs with an excess of liquid in this
case.
Further cooling causes ihe liquid to disappear so that at 2687F.
248
Fig. 12.3.
(B) 0.20 per cent carbon steel;

steel;
Microstructures of slowly cooled iron-carbon alloys: (A) low-carbon iron; (C) 0.40 per cent carbon steel; (D) 0.80 per cent carbon (E) 1.3 per cent carbon steel; (F) pearlite at high magnification; etched. A to
F,
E,
lOOx:
1.000X-
The
(1475C.)
249
solidification of austenite is complete.
The
white-hot
steel,
which consists wholly of a solid solution of carbon in gamma iron, cools unchanged until a temperature of 1512F. (822C.) is reached. At this point on line A 3 (GOS) the austenite is saturated in iron (ferrite) If the temperature falls slightly, the excess iron is precipated in the form of alpha phase. Since the austenite loses no carbon during the process,
,
.
the loss of
some
iron as alpha phase by the austenite
is
equivalent to in-
creasing the carbon content of the austenite. ues to

fall,
As
the temperature contin-
precipitation of alpha iron

is
and
increase of carbon content of the
austenite (since there
progressively less austenite for a constant
amount
of carbon) occur continuously.
When
the temperature reaches that of the
A i (PSK)
the austenite
is
saturated with carbon. Further cooling results
in simultaneous precipitation of alpha iron
and carbon
(as
iron carbide)
This process goes
to
completion, which
is
to say that the austenite dis-
appears completely. If the cooling is very slow through the temperature interval from line
A s (GOS)
to just below line A (PSK), the excess ferrite which is first formed assumes the shape of discrete polyhedral grains, and the remainx
ing austenite, containing 0.80 per cent carbon, transforms to the pearlite
aggregate in which the ferrite and cementite particles are in the form
of relatively large laminated plates.
steel consists of 36
If
The
structure of the slowly cooled
per cent pearlite and 64 per cent excess ferrite.*
a piece of slowly cooled carbon steel is polished and etched with and examined with the microscope, the relation between the carbon content and the amount of free ferrite (etches light) and pearlite
dilute acid
(etches dark)
Micrograph
carbon;
it
clearly evident. This relation is shown in Fig. 12.3. shows the structure of iron containing practically no consists wholly of polyhedral grains of ferrite. In B, the steel
is
containing 0.20 per cent carbon, the dark grains of pearlite are numerous, and in C, the material containing 0.40 per cent carbon, they are still more
numerous.
F,
The
parallel plates of cementite
and
ferrite
making up
the
pearlite aggregate are
shown
clearly at high magnification in

is
and when viewed by
the electron microscope, as
micrograph evident from Fig.
12.4.
Referring again to Fig. 12.2 (line yy'), at 2820F. (1550C.) a steel containing 0.80 per cent carbon is a solution of iron carbide in molten iron. As the molten metal cools, it is unchanged until a temperature of 2670F. (1468C.) is reached where solidification of the austenite begins.
This
is
not complete until a temperature of 2520F.
(1380C.)
is
0.30 per cent carbon is equivalent to 4.5 per rent Fe C. Since 1 part of Ke is 3 aC associated with 7 parts of ferric to form pearlite. 4.5 per cent Fe,C plus 31.5 per cent ferrite form 36 per cent pearlile.
250
reached.
is
It will
be noted that with higher carbon the solidification range
wider.
in
is
After the steel has solidified completely, the solution of cementite gamma iron cools unchanged until a temperature of 1333 (723C.) reached. Owing to the fact that the steel contains 0.80 per cent carbon
and, therefore, the exact amounts of cementite (12 per cent) and iron (88 per cent) to form the aggregate pearlite, there will be no preliminary precipitation of alpha iron from the saturated austenite, as was the case with the 0.30 per cent carbon steel described in the previous section.
steel cools through the A x temperature of 1333F. (723C.) the austenite undergoes precisely the same change as was described for the last stage of transformation of the 0.30 per cent carbon steel, that
is, simultaneous precipitation of alpha iron and iron carbide. There is no further structural change as the steel cools from A x to room temperature, and if cooling through the A temperature is slow, the cementite and ferrite form well-defined plates as shown in Fig. 12. 3D and, at high magnification, in Figs. 12.3F and 12.4.
x
As the
In the case of a steel containing 1.3 per cent carbon (19.5 per cent cementite), represented by line zz' in Fig. 12.2, the changes taking place
during slow cooling are fundamentally analogous to those taking place in a 0.30 per cent carbon steel. The essential difference is (in addition to a wider solidification range) that the A cm line marks the preliminary
separation of excess iron carbide rather than excess alpha iron. When a steel containing 1.3 per cent carbon cools slowly, at 1640F (893C.) the austenite is saturated with carbide. Further cooling results in precipitation of this excess carbide from the saturated austenite, which continues as the temperature falls from 1640F. to 1333F. (the A x tem-
perature) The remaining austenite, which now contains 0.80 per cent carbon (12 per cent cementite) here transforms to pearlite, as in the preceding case. At room temperature, the structure is made up of grains
. ,
of pearlite (etches dark)

(light)
.
with a network (or needles) of excess carbide
This structure
is
shown
in Fig. 12.3E.
all
The
discussion to this point has
been concerned with slow cooling.

changes take place.
In heating carbon
steels, the reverse
For example,
per cent
a 0.30 per cent carbon steel
that has been cooled slowly consists at
room temperature of a
structure of 36 per cent pearlite

is
and
(>4
excess ferrite. If this steel
heated slowly, no change takes place until a

is
temperature of 1333F. (723C.)

of the pearlite transforms to
just exceeded.
Here, the alpha iron
gamma
iron
and the cementite goes into
solution. As heating
is
continued, the excess alpha iron changes to
gamma
The
251
Fie. 12.4.
lica.
mm.
Electron micrograph of pearlite in eutectoid steel. Polystyrene-silica rep20,000x. etched. Approximately i/ i micron 0001 A in. on the micrograph
(Courtesy of C.
S.
Barrett)
iron and is absorbed by the austenite. At 1512F. (822C.) , these changes are complete, and the steel, now a solid solution of 4.5 per cent cementite in gamma iron, remains unchanged to the melting point.
12.4. Isothermal Transformation in Steel
Considerable work has been done in studying the effect of continuous

cooling
upon
the structure
and properties of
steels.
The
effect of the
various alloying elements was
known
in a rather general way, however,
available. In 1930, Davenport and Bain # presented a paper describing the results of a study of the isothermal transformation of steel. This paper resulted in a further extensive study of many iron-carbon alloys, which gave a better understanding of the mechanism
no good explanation was
of austenite decomposition
and the part played by the alloying elements.

published in the Atlas of Isothermal
The
results of these studies are
Transformation Diagrams.^
E. S. Davenport 117-154.
and E. C. Bain, Trans. Amer.
Inst.
Min. & Met. Eng

Steel Corp., 1951.
90 1930
p.
Atlas of Isothermal Transformation Diagrams, U.
S.
252
1 1 1 1
Avsrtvit
.
aunt
_
A, TCMPOIAIVfiC
jurtrmre
A is
V
-
"
\
\
\
\
\
WLHSTC W*J
[.....!._..
130000
ICCOO00
10OMITHMIC TIUC
Fig.
12.5.
Schematic Drawing of a Typical Isothermal Transformation Curve Re-
vealing Significant Features.
The
form
to as
results of isothermal transformation studies are presented in the
of diagrams such as the
one
in Fig. 12.5.
These are usually referred

with time as the
left
TTT
curves
(time-temperature-transformation)
as the ordinate.
abscissa
and temperature
The
curve indicates the
beginning of transformation with the right curve showing the completion. In the case of high or low carbon steels, the formation of the pro-eutectoid cementite or ferrite is usually indicated on the diagram as an additional
feature.
To
construct a
TTT curve,
it is
necessary to heat thin specimens of the
desired steel into the austenite region for sufficient time to obtain a
homogeneous structure. The specimens are then quenched into a pot of molten lead or salt which is maintained at some constant temperature, i.e., isothermal, below the austeniti/.ing temperature. These specimens are kept in the molten bath for varying time intervals from second to as much as 10 5 seconds or longer. At the end of the desired time interval, the specimen is quenched into cold water causing the isothermal trans1
formation
is
to be- terminated. Any austenite not transformed isothermally transformed by quenching to martensite. The specimens quenched
isothermally at a particular temperature are prepared metallographically
and etched.
Microscopic examination will reveal that the isothermal

field.
transformation product appears as dark areas in a white
The
The
253
el
<
'
Fie. 12.6.
Micrograph of coarse pcarlitc formed by isothermal transformation

(left)
at
I275F. 600X.
Ftc.
12.7.
Fine
pcarlitc
formed by isothermal
transformation
at
1200F.
600X.
(right)
Fig. 12.8.
specimen
is
Nodular pearlitc formed by isothermal transformation at 1100F. This only partially transformed. 600X. (left)
Fig. 12.9.
is
Bainite formed by isothermal transformation at 850F. This specimen only partially transformed. 600 X. (right)
254
white
ing.
field
represents the untransformed austenite prior to water quench-
time associated with the specimen showing the smallest amount of dark area is assumed to be the time lor the beginning of isothermal
transformation at the particular temperature while the end of transfor-
The
mation
surface.
is
determined by the specimen showing
completely darkened
By repeating the experiment
at several different temperatures,
enough data are obtained to make similar to that shown in Fig. 12.5.
possible the construction of a
diagram
The
transformation products obtained arc a function of the transforma-
tion temperature.
Near the eutectoid temperature very coarse
pearlite
forms as
ture
is
is
shown
in Fig. 12.6 while finer pearlite forms as the tempera-
reduced
(see Fig. 12.7) until at the
"nose" of the curve a very fine
pearlite forms in nodules giving nodular pearlite, Fig. 12.8.
Below the
temperature of the nose, a product forms, which only occurs during

isothermal transformation, bainite, Fig.
material
is
12.9.
The
exact nature of this
not well understood but it appears to be some sort of very fine mixture of fcrrite and cemeiuite. The above description applies to
those alloys
ferrite
which do not
yield a pro-cutectoid constituent.
Pro-eutectoid
is
or pro-eutectoid cementite forms before pearlite
formed.
12.5.
The
Effect of Cooling Rale
Upon
the Resulting Structure
steel was However, during the heat treatment of most steel parts, it is not possible to remove the heat within the extremely short time as is done for obtaining a TTT diagram. As a result, the surface may be very severely quenched whereas the interior may cool very slowly. Such varia-
In the previous section, the isothermal transformation of
discussed.
tion in cooling rate will certainly result in different structures.
was observed that isothermal transformation just below the austentemperature caused the austenite to transform very slowly into coarse pearlite. As the temperature was reduced, the transformation was
It
itizing
more rapid and
the pearlite
became
finer.
In Fig. 12.10 there
is
shown
schematic drawing of a portion of an isothermal diagram with some typical continuous cooling curves. Curve A shows very slow cooling, such as might be expected in furnace cooling. The austenite exists until the curve reaches the beginning of transformation at which lime coarse pearlite begins to form. It continues to form until the transformation is complete. Now curve B shows moderately slow cooling that might be expected in
still
air cooling of steel. Austenite exists until the
curve meets
pearlite
is
the beginning of the transformation curve at
which time medium
begins to form and continues to form until the transformation

plete.
comfiner
The specimen
cooled as shown by curve
C would
have
still
The Constitution
i
of Steel
1
255
4vsr/riir StablC
*00
"\
_-A_.
_i
*l ItltPCHASVBj
. -
400*
--*. -\
\r/stc
w
w
OC*
-
Itf^Rtfl
\
*"%^
400"
00
IMMITHMIfi IIMt
**
SCO*DS
Fig. 12.10. Schematic Representation of an Isothermal Diagram and Various Continuous Cooling Curves.
critical cooling rate as shown by curve D shows that the would transform into martensite without any pearlite forming. Martensite begins to form at the temperature shown as 3 and increases as the temperature is reduced. Any cooling rates more rapid than
pearlite.
The
austenite
will result in
complete transformation into martensite, Fig.
12.11.
w
*-..
'
-*
\f
......
--"'
Fie. 12.11.
Martensite formed by water quenching after austenitizing. 600x-
256
12.6. Effect of Alloying Elements
Upon
the Iron-Carbon Diagram
In Section 12.2, the iron-carbon phase diagram was discussed in detail. the effect of the common alloying elements upon the eutectoid temperature and composition will be discussed as well as the effect of the alloying elements upon the physical properties of steel. Alloying ele-
Now,
ments tend to divide themselves into two groups: those that widen the
range of
ture
gamma
stability by increasing the S-y transformation
tempera-
and lowering the y transformation temperature and those that narrow the range of gamma stability by lowering the 8-y transformation temperature and raising the y transformation temperature. The common gamma stabilizers are manganese, nickel, cobalt, copper, nitrogen and carbon, while the common alpha stabilizers are silicon, chromium, tungsten, molybdenum, phosphorus, vanadium, titanium, aluminum, boron and sulfur. Nickel and manganese are such strong gamma stabilizers that it is
possible to have stable austenite at
as occurs in the austenitic stainless steels
room temperature such and Hadfield steel respectively.
Certain of the alpha stabilizers reduce the gamma region to a narrow loop and may result in ferrite existing continuously from the liquidus
temperature to room temperature. By an element being an alpha or

raises
gamma
stabilizer
means
that
it
either
or lowers the eutectoid temperature respectively.
cated previously, nickel and
manganese
are
gamma
As was indistabilizers and thus
reduce the eutectoid temperature, nickel being a bit more effective than manganese. The other gamma stabilizers have a similar effect however rather reduced. By the same token the alpha stabilizers raise the
eutectoid temperature, thereby reducing the region of
gamma
stability.
Titanium has the greatest effect in raising the eutectoid temperature followed by molybdenum, tungsten, silicon and chromium in decreasing
order.
Most alloying elements have an
effect in
reducing the carbon content
This results in a completely pearlitic alloy with less carbon than indicated by the iron-carbon diagram. Again, titanium has the greatest effect in reducing the eutectoid carbon content with molybdenum, tungsten, silicon, manganese, chromium, and nickel in descending order. This effect reduces the amount of cementite and causes the steel to be softer and less brittle. Most alloying elements have a useful effect upon the heat treating of steel; certain alloying elements have other useful properties. One of the
necessary for the eutectoid composition.
properties
is
the ability of strengthening the ferrite to obtain sheet

for the fabrication of high strength, lightweight obvessels, railroad cars,
and plate materials

jects
such as pressure
truck bodies,
etc.
These are
The
257
usually referred to as high-strength, low-alloy steels being sold under

several trade names.
They
rely
on the
fact that phosphorus,
manganese,
strength-
copper, titanium and silicon form solid solutions with ferrite and thereby
strengthen
it.
Nickel,
molybdenum, and aluminum are mild
ened.
Another property that alloying elements have is their ability to form carbides. These carbides may have a grain refining action on the
austenite during heat treatment to prevent excess grain growth.
also
They
may
help block creep in high temperature applications. In the case
of certain types of stainless steel,
columbium and titanium are used to form a more stable carbide than chromium and thus enhance the
steel.
corrosion resistance of the
Columbium, titanium, zirconium, vana-
dium, tungsten, molybdenum, and chromium are considered as strong carbide formers while manganese is only moderate. Phosphorus, nickel, sulfur, cobalt, and copper have no effect in the formation of carbides while aluminum and silicon tend to cause the carbides to decompose,
precipitating graphite.
12.7. Effect of Alloying Elements
on the Isothermal Transformation
of Steel
Referring back to Fig.
labeled pearlite
is
12.5,
and
if
bainite.
we see that there are regions on the diagram By comparing this figure with Fig. 12.10, it
it
apparent that
thick sections are to be completely hardened,
will
be
necessary to displace the curve to the right, thus requiring a longer time to elapse before the beginning of transformation. This is precisely the
effect of alloying
elements on the
it is
TTT
curve.
By
suitable selection of
alloying elements,
possible to displace the curve

air cooling.
is
enough
to
permit
complete hardening of quite large pieces by

Usually the
of
its
effect of
an alloying element
determined as a function
ability to displace the pearlite or bainite region to the right. In the
case
of the pearlite region, manganese, molybdenum, phosphorus, and chromium have the greatest effect in that order, while silicon, nickel, and copper have much smaller effects. The displacement of the bainite
is
region to the right

Silicon, nickel,
greatest with
manganese, phosphorus, and chromium.

ability while
and copper have reduced
molybdenum
has
no
effect
on the bainite region.
It is interesting to
left.
note that sulfur has a
slight tendency to displace the curve to the
By
careful selection of
proper alloying elements, the beginning curve for transformation can be displaced considerably to the right. It should be noted that small additions of several alloying elements are more effective than one large addi-
2 J
tion. This is evident in the alloys that have been developed recently with their multi-element additions.
The
treatment of
line labeled
addition of alloying elements has another effect in the thermal steel. In Fig. 12.5 it can be seen that there is a horizontal
s.
This
is
the temperature at
form.
It
continues to form as the temperature
which martensitc begins to is reduced. Most of the
common
alloying elements tend to reduce the M, temperature, carbon being quite strong in its ability. The other elements reduce the M, in the following order; manganese, vanadium, chromium, nickel, copper, molyb-
denum,
aluminum and cobalt tend Alloy additions may lower the M, to such an extent that complete transformation of austenite to martensite mav not be possible
tungsten. Silicon has no effect while
to raise the
by quenching to room temperature.

cooling in order to form martensite.
It
may
require subatmospheric
12.8. Effect of
Hot Working on Structure
So far, the discussion in this chapter has been confined to the phase and structural changes in carbon steels when they are heated or, more
important, cooled at varying rates between the temperature where ausIt was stated that there is no change in the austenite if it is heated or cooled between the transformation temperature and the melting point. This is true. There is no change
tenite
is
stable
and room temperature.
in the internal structure of the austenite grains, but there
may be
a great
change
in the size of the grains.
If
carbon
steel is
heated above the trans-
formation temperature, the austenite grains grow, and the higher the temperature the larger the grains.
Small-grained steels are generally considered to have better properties than coarse-grained material of the same composition. Since grain size at room temperature depends largely upon the grain size of austenite when it is ready to transform, the grain size of austenite should be small. One of the important factors affecting the grain size of austenite, and of
pearlite
and
ferrite, is
mechanical working.
usually begins by crystallization
is
When
it is
molten
steel cools, solidification
at the wall of the
mold, and
if
if
the temperature of the steel

is
high
when
poured, and
is
the ingot or casting
large
and
of favorable shape,
these crystals
may become
up
very large (Fig. 12.12).
Hot
rolling or forging,
is
which
plastic,
ordinarily carried out at temperatures at which the metal
breaks
the large crystals and elongates the fragments in the

is
direction in
which the work
applied. These elongated grains, together
with elongated inclusions, give carbon and

directional properties.
many
of the alloy steels their
The
259
Large columnar crystals in a steel ingot, natural FIG. 12.12. Schroder, Atlas Metallographiats, Berlin, 1927)
size.
(Hanemann and
Austenitc grains, even
when
plastically
broken and deformed, have

is
the tendency to grow together again. This tendency
the greater the
higher the temperature. Hence, if the finishing temperature of hot working is much above the transformation temperature, grain growth may
occur while the
steel is
is
cooling to the transformation temperature, espeis
cially if the section
so large that cooling
slow.
For
this reason,
if
hot-
rolled or forged steels are to be used without subsequent heat treatment,
and if a fine grain is desirable, the hot-working temperatures and the amounts of reduction are controlled so that the finishing temperature will not be much above the transformation temperature. Thus, the steel will cool below this teni]>erature before appreciable grain growth has taken place. The effect of hot working in breaking up the coarse grain structure of cast 0.20 per cent carbon steel is shown in Fig. 12.13B.
12.9. Effect of Cold
Working on Structure
Cold working is usually defined as mechanical deformation of steel at temperatures below the transformation temperature. In practice it is
260
Fig. 12.13.
rolled; etched.
Structure of a 0.20 per cent carbon steel:
(A) as cast,
and
(B) as hot
100x-
generally carried out at

at these bars,
room temperature. If steel is plastically deformed low temperatures as in drawing wire, cold rolling or extruding or cold rolling sheet the pearlite and ferrite grains are elongated
which work
is
in the direction in
applied.
This mechanical distortion

is
results in rapid increase of hardness
and
brittleness.
At atmospheric temperature, the

lizing into their
rigidity of the steel
so great that
the distorted grain fragments cannot rearrange themselves by recrystal-
normal equiaxed shape. Hence,
if
cold working
is
con-
tinued, the hardness and brittleness accompanying the fragmentation of the grains will increase with the the steel
steel
is
annealed,
it
will fail.
amount of deformation until soon, unless The amount of cold deformation that
its
will
stand depends upon
ductility,
which, in turn,
is
related
directly to chemical composition
and prior heat treatment. Thus, annealed low-carbon wire will withstand more reduction by drawing before failure, or before reheating for recrystallization becomes necessary, than
annealed medium- or high-carbon wire. The unstable structure of cold-worked steel* and its accompanying hardness and brittleness are caused by the distortion of the ferrite and
and not, as in quenched steel, by the presence of submicroscopic particles of carbon in a distorted alpha-iron lattice. But, as
pearlite grains
The structure of severely cold-worked steel is unstable in that the fragmented grains will recrystallize if given the opportunity; that is, if the steel is heated to the
proper temperature, which is considerably below the A transformation. Actually, x however, owing to the rigidity of the material at room temperature, the fragmented
grain structure will persist indefinitely.
The
261
Fig. 12.14.
as cold- worked
Structure of a 0.20 per cent carbon steel and annealed; etched. 500 X-
(A) as cold-worked
and
(B)
the stability of quenched steel can be increased by tempering (see Chap. 13), so can the stability of structure of cold-worked steel be increased by reheating below the transformation temperature. This is known as process
annealing.
Structural changes which occur are not gradual.
when cold-worked
steel
is
reheated
Cold-worked steel is softened by heating to 800 to 1200F. (425 to 650C), the exact temperature depending on the com-
and the amount of cold work. Reheating at the proper temperature effects complete recrystallization and restoration
position, si/e of the section,
of the original structure and properties. The material can then be cold worked again until grain distortion and its accompanying brittleness have again become so serious that another reheating is necessary. The effect of cold working on the structure of a 0.20 per cent carbon steel (whose structure as hot-worked is shown in Fig. 12. ISA) is illustrated in Fig. 12.14A. The effect of reheating on the distorted grain structure is shown in Fig. I2.14B. Note that after annealing the grains are equiaxed, and all indication of distortion has disappeared.
QUESTIONS
1.
Describe the changes taking place in cooling from 3,000F., iron-carbon alloys having the following carbon contents, 0.3%, 0.8%, 1.5%, 3.0%, 4.3% and 5.0%. When crossing a two phase field, indicate how each phase changes in quantity and composition.
the lever rule, give the composition and amounts of the phases present in the above alloys at the following temperatures, 2,500F 2 000F 1,500F., and 1,000F. Describe the crystal structures of delta iron, austenite, and ferrite. What is the crystal structure of pearl ite? How does it differ from the previous mentioned phases?
2.
Using
3.
262
4.
Modern Metlallurgy
Give the range of carbon contents for carbon diagram, give one reason that
ductility.
jor Engineers
steel cast
and
cast iron.
From
the iron-
irons frequently
have limited
5.
6.
diagram. What is the Describe in detail, the method of constructing a white constituent which is present in specimens which are only partially transformed? Where does it originate? Sketch the curve from Fig. 12.5. Superimpose on this diagram curves representing your opinion of the transformation curves for alloys containing manganese, silicon, phosphorus, nickel, copper, chromuim, and molyb-
TTT
TTT
denum. Sketch
7.
the position of the
M,
also.
12.2.
Sketcli
the iron-carbon diagram from Fig.
Superimpose on
this dia-
gram, the position of the eutectoid temperature and composition for alloys containing, titanium, molybdenum, tungsten, silicon, manganese, chromium,
and
8.
nickel.
9.
10.
Define the term carbide former. Give several examples of carbide formers. Define alpha and gamma stabilizer. Give examples, why gamma stabilizers are important. What are columnar crystals and how are they formed? What is the effect of hot working on the crystals? Why should the finishing temperature of hot working be just above the transformation temperature? What is cold working? How docs it affect the structure and properties of
hot worked steel? What happens to die structure and properties when cold worked steel is reheated to 800 to 1,200F.? Define the terms, hypoeutectoid, hypereutectoid, and eutectoid as used in
steel.
11.
Describe the difference that will occur when such steels are slow cooled from the austenite region. 12. Sketch the unit lattice cells for austenite and ferritc. Point out the differences. Which is the closest packed cell? Since carbon is an interstitial atom, indicate where it fits in the austenite unit cell. 13. From the iron-carbon diagram in Fig. 12.2, point out the various reactions which occur. Indicate the reactants and products. 14. From the iron-carbon diagram, indicate the amount of pearlite present in alloys containg 0.3%, 0.8%, 1.2%, and 1.9% carbon. What is the other
15.
constituent in each of the alloys? Cast iron is quite extensively used and is rather inexpensive as compared with cast steel. From the material presented in this chapter, give reasons
to explain this situation. Describe the changes that take place during the solidification and subsequent cooling of molten pure iron. Compare these charges with those that occur in copper. 17. Define the term ferrite strcngthener. Why are these important? Give ex10.
amples of
18.
ferrite strengtheners.
Describe the formation of martensite. Upon what variables is martensite formation dependent? 19. When steel is cold worked, how arc the mechanical properties affected? Describe applications where cold worked steel is superior to annealed steel. 20. Describe the solidification of steel in a large ingot mold. Consider the differences which would occur at the surface and interior of the ingot.
CHAPTER
Fundamentals of Heat Treatment of Steel

Abram Eldrkd HoSTETTER,
lurgy,
13
Ph.D., Professor of Metal-
Kansas State College, Manhattan, Kansas
JL
HE
process of quenching
and tempering
steel to
improve
its
hardness and wear resistance has been used for at least
3,000 years.
Some
of the early tools and

Little
weapons
testify to the skill of the
was known, however, regarding the nature of the changes taking place in the steel during heal treatment, and the success of these early metal workers is a tribute to their patience and persistence in developing the art of heat treating. Medieval literature is filled with the magic heat-treating processes developed by these early iron
early metal smiths.
The Spanish swords of Toledo, for example, gained world renown because of the supposedly mysterious properties of the water in which they were quenched; the famous swords of Damascus were heated to the color of the rising sun and were quenched by plunging them into the belly of a fat Nubian slave. A favorite quenching medium was urine, and this is understandable since
we know
that chloride brines and other salt solutions extract heat from red-hot steel 10 to 20 percent faster than water alone.
to the heat treatment of steel is somewhat more has been learned about the complex reactions taking place during the heat treatment of steel and various factors such as alloy content, cooling rate, tempering temperature, etc. are much better underscientific.
workers, especially for the treatment of swords.
Today our approach
Much
stood today.
Our knowledge of the structural changes taking place in by no means complete, but with the knowledge we have, heat treatment processes can be prescribed to give desired properties with a
metals
is
minimum
of "trial
and error" procedure.

263
264
1650'
1530 K
0.6
0.8
Per cent carbon
Fig. 13.1.
Schematic representation of the grain
size of
carbon
steel as affected
by
heating.
(Stoughton)
13.1. Grain Size
and Grain Growth
two means by which the grain size of carbon steel can be first is by cold working the metal and annealing it at a temperature below the critical range. This is called process annealing. The grain size thus produced depends mainly on the extent of cold working and the annealing temperature. The second method is by heating the metal above the critical range where, as described in Chapter 12,
are
There
changed.
The
austenite
is
produced. With the formation of austenite, recrystallization

13.1
takes place, resulting in a fine grain structure (Fig. 13.1)
with raising temperature is coarse-grained hypoeutectoid steel is slowly heated, grain refinement starts at the lower critical range (1330F.) and gradually proceeds throughout the critical range. Grain refinement is then complete at the upper critical temperature. This is In Fig.
the change
in
grain
size
indicated by varying sizes of circles.
If a
not a reversible process however. That is, on cooling, the grain size does not revert back to the original large grain size, but remains the maximum
size
reached while above the
critical range.
On
cooling, the austenite
grains convert to ferrite and pearlite or martensite, depending on the
cooling rate. In either case the grain

reflects
size
observed at room temperature

In the case of eutectoid and
the prior austenitic grain

steels,
size.
hypereutectoid
grain refinement takes place at the eutectoid tem-
perature as shown in Fig. 13.1.
In case a steel has a fine grain at
room
Fundamentals of Heat Treatment of
Steel
265
temperature there will be little or no change in grain size when it is heated through the critical range. If a steel is heated to produce fine-grain austenite and then heating is continued several hundred degrees higher, the fine grains of austenite
grow
to a larger size as
shown
in Fig.
13.1.
Time
also plays a part in
determining the final grain size. At higher temperatures the grain growth is rapid, while at temperatures just above the transformation range, there is little tendency for grain growth. The eventual grain size of steel therefore depends on both the temperature to which it is heated and the time it is held at this temperature. The effect of temperature on grain growth is shown in Fig. 13.2. Two pieces of steel containing .40% carbon were heated above the critical range and cooled slowly. Sample A was then heated to 1550F. (in the
fine grain range Fig. 13.1) and held there for 30 minutes, and sample B was heated to 1900F for 30 minutes. The samples were cooled slowly, well below the critical cooling rate, and as a result, both samples are soft and consist of grains of ferrite and pearlite. The grain size of sample B,
however, is much larger then that of sample growth at 1900F.
because of the grain

the hardness and the
rate,
When
Chapter
rate,
austenite
is is
cooled to
room temperature,
resulting structure
12.
dependent on the cooling

is
If
cooling
as indicated in slower than the critical cooling rate, pearlite
if quenched faster than the critical cooling produced. The grain size in both cases, however, is the same if they were heated to the same temperature. Thus the grain size depends on the temperature to which a steel is heated, but the hardness depends on the cooling rate and is quite independent of the grain size.
would be produced, and

martensite
is
may be hard or soft, depending on the cooling rate, and be fine or coarse grained, depending on the temperature to which the steel was heated.
Steel
13.2. Controlling
and Classifying Grain Size
When
steel
certain range of temperature (Fig. 13.1)
gram growth.
gradually heated above the critical range, there is a where there is little tendency for Above this range, grain growth becomes more and more
is
apparent as the temperature rises. It has been found, however, that by adding definite small amounts of aluminum or other deoxidizers to carbon and alloy steels, the tendency for grain growth at elevated temperatures can be controlled. That is, the fine-grain temperature range
(Fig. 13.1)
is
broadened so that a carbon
steel
containing the proper
amount
of
aluminum can be heated
to 1830F.
and
still
remain
fine
266
grained, whereas a similar steel without the
aluminum would quickly become coarse grained at this temperature. The research work of McQuaid and Elm, along with other investigators,
has served to emphasize the importance of grain

steel.
size in the
heat
For many and every precaution was taken in hot working and heat treatment to avoid it as far as possible. This idea is now known to be wrong in some cases. Coarse-grained steels machine more easily and harden more deeply than fine-grained steels. On the other hand, finegrained steels do not crack so readily when quenched and in general have greater toughness at low temperatures. The grain size of steel can be classified in terms of a standard scale established by the American Society for Testing Materials. The graintreatment of
years a coarse-grained structure was con-
sidered to be undesirable
size class are
numbered to 8. In this system the number of grains per square inch at 100X is 2"1 where n is the grain-size numbers. Photo1
graphs of each of the grain-size
handcomparing books, and the grain size of a sample is readily obtained by the grain size of these photographs with that of the sample when viewed or photographed at 100X. Table 13.1 lists the ASTM grain-size numbers
classes are available in metallurgical
and the corresponding grains per square inch. Three sizes are shown in Fig. 13.3 as they appear at 100X.
Table
A.S.T.M. Grain-Size Numbers
different grain
13.1.
Grains per Sq. In. at 100X
A.S.T.M. Grain-Size Number

Average
1 1
Range
1 J/
or
to
to
less
2
3
4
2 4
8
lj^to 3
3
6
6 24
to 12 to 48 to
5 6 7
16
12
32
64 128
24 48
96
96
or
more
Another system standards. This set

to coarse grain.
for
classifying grain
consists of ten
The
grain size
its
ing
it
and
visually
is
matching
size is the Shepherd fracture broken steel specimens graded from fine of a sample is then determined by breakgrain size with one of standard specimens.
This method
especially useful
where metallographic
facilities are
not
Fundamentals
of
Heat Treatment
of Steel
267
MM
5&isik
etched. IOOx-
;i"i^jj
Fie. 135. Structure of 0.40 per cent carbon steel (A) heated just above the transformation temperature and slowly cooled and (B) overheated and slowly cooled;
available.
The
fracture standards are prepared by hardening
breaking them.
The sample
and then being tested or compared to the standards

to get a valid
must
It
also be in the hardened condition must be remembered that the grain

is
comparison.
size referred to
si/e.
above the transsteels,
formation temperature
ever, little austenite
is
austcnitic grain
In most carbon
how-
alloyed
steels,
and
at
room temperature, except room temperature we are concerned with

retained at
in highly
grain size
of the transformation product
bainite etc.)
on cooling (martensite, ferrite, pearlite, By proper polishing and etching of martensite, the previ-
ous austenitic grain

condition
size is revealed since the grain size of the martensite follows that of the previous austenitic grain size. Steel in the martensitic
may also The broken surface
be notched and broken to display the grain size. many small facets. The facets follow the fracture planes through the grains and thus their size gives an indication of the martensitic grain size. On slow cooling hypoeutectoid steel, the
consists of
austenitic grain size
is
reflected
in
the grain size of the ferrite and
pearlite since the proeutectoid ferrite forms at the austenitic grain

aries
as
bound-
and the pearlite forms shown in Fig. 13.2b.
in the
body of the parent
austenitic grain
13.3. Effects of
Hot Working on Grain Size

hot worked at temperatures around 2000F., the grains
When
steel
is
are broken
up
into finer grains. This fragmenting process keeps the grain
268
Fig. 13.3.
(B) grain size 5;
Typical structure of slowly cooled carbon steel having (A) grain and (C) grain size 8; etched. 100X-
size 2:
size fine
even though there
is
a great tendency for grain growth at this
temperature.
The two
factors thus offset each other,
and the grain
struc-
ture remains fine during the hot working. If, however, the hot working is stopped and the metal held at the hot working temperature for a short time, grain growth takes place rather fast, and after cooling to room temperature, the grain would be coarse. In this case the steel should be reheated to a temperature above the critical range in order to refine the grain. Hot working may be continued as the temperature falls to a point just above the critical range. In this case there is little chance for grain growth, and the grain remains fine. When steel is cast as an ingot, the grain size is very large and columnar. Hot working is employed
this coarse condition and produce a improve the physical properties. thus greatly
to
break up
fine grain structure
and
'
Fundamentals of Heat Treatment
of Steel
269
1600
1600.
K
1400
1200 1000
si 800
Q-
1400
vV"
(200
VK
V
\
1000
-T 800 o.
K^
MS
l)
\ CV
1
\
Ms\
600
400
200
E * 600
400
200
\
Mf
\\
x\ *)
\ Mf
.
Time
A
Fig. 13.4.
Time
B
typical
alloy steel.
A. The Cooling curve
ing curve
carbon steel. B. The curve for an the cooling rate on the outside of a bar. Coolrepresents the cooling rate in the center of a bar.
TTT curve for a O represents
TTT
13.4. Hardenability
If a one-inch bar of carbon steel containing .70% carbon is quenched in brine, the outside of the bar will be hard (close to Rc65) while the center of the bar %vill be only Rc30 to 35. Such a steel is said to have low harden-
The structure on the outside would be martensite because the cooling rate on the outside portion of the bar was faster than the critical cooling rate as shown in curve O, Fig. 13.4A. The structure of the center of the bar would be pearlite since here the cooling rate is much slower than the
ability. critical
hardened
cooling rate as shown in curve C, Fig. 13.4A. How deep the outside shell will be depends upon the critical cooling rate since all of the steel that is cooled at the critical cooling rate or faster will be hard. If a one-inch bar of an alloy steel is quenched, as just described for a
steel,
carbon
and only martensite has high hardenability (hardens deeply). The actual cooling rate of the two steels at a given distance from the surface is essentially the same, but the curve for the alloy steel would be observed. Such a
steel
the bar will be hardened to the center,
TTT
shown in Fig. 13.4B. In this case the cooling rate represented by curves O and C are both faster than the critical cooling rate because the TTT curves plots sufficiently far to the right. Thus a
plots to the right as
comparison of the relative position of the curve for various steels on the time scale affords a quick qualitative means of comparing their
TTT
270
relative hardenability.
The
role of alloying elements in determining
curve has been covered in Chapter 12. There are applications in industry where only surface hardness needed and high hardenability is not important. For such applications
the position of the
TTT
is
it
carbon steels. For certain uses, however, such as aircraft parts, uniformly high strength and hardness is generally required through the part. In these cases it becomes necessary to use an alloy steel such as S.A.E. 4140 in order to have sufficient hardenability. When a steel has high hardenability, a slower quench (oil quench) can
usually
is
good economy
to use
hardness in a rather large section. Since this is the case, it is unwise to use a brine quench because such a quench is much faster than necessary and greatly increases the chances of cracking the part. Such steels are referred to as oil hardening steels, and steels with low
be used
to obtain full
hardenability arc called water hardening
steels.
13.5 Grain Size and Hardenability
When carbon steel is heated to a temperature just above the critical range and quenched in brine, very shallow hardness is obtained. If, however, the same steel is heated high enough to produce a coarse grain before quenching, the hardness is much deeper. The increased depth of hardness
indicates a slower critical cooling rate as explained earlier.
his
would
mean that an increase in grain sizes makes the transformation more sluggish, and transformation is slower in starting at a given temperature. The
TTT
curve
is
thus
moved
effect
which is the same added to the steel.

a
when the observed when certain

to the right
grain size
is
increased,
alloying elements are
Because of the shallow hardening feature of fine-grained carbon steel, coarser grain may be desirable even though coarsening of the grain may induce some brittleness. The actual grain size desired in carbon
somewhat
may therefore be a compromise of moderately fine grain in order to avoid the severe brittleness associated with a very coarse grain and not have the low hardenability associated with the very fine grain. In alloy steels, however, this dilemna is not encountered since hardenability
steels
is
afforded by the proper alloying elements.
13.6.
Quenching and Properties of Martensite

12, increasing progressively
As discussed in chapter
the speed of cooling,
up
to a certain rate,
sively
from 1333 F.
it
lowers the A, transformation temperature progresWhile (723C.) to approximately 1020F. (550C.)

.
this increase in rate affects the
forms,
does not affect
speed with which the gamma iron transthe completeness of the transformation. The
Fundamentals
of
Heat Treatment of
Steel
271
finer.
If,
increased cooling rate causes the pearlite lamella to
become
however, the cooling rate
enon
occurs.
The
more, an important phenomtransformation temperature is suddenly depressed

is
increased
still
to 480F. (250C.)
or lower,
and
the steel, especially
if it
contains
more
than about 0.30 per cent carbon, becomes very hard and brittle. The rate of cooling that is just fast enough to suddenly depress the A^ temperature to 480F. is known as the critical cooling rate and is attained by quenching a high-carbon steel in water or an alloy steel in oil. The changes taking place when high-carbon steel is cooled at the
critical rate
are not wholly understood.

follows:
or faster are in general simple, although some of the details In brief the mechanism of quenching is as
(723C.)
,
At a temperature above 1333F.
the structure In cooling
is
austenite, the solid solution of carbon in
slowly than the critical rate, the
iron changes to body-centered alpha iron and the carbon is thrown out of solution as iron carbide. If cooling is faster than the critical rate, the change of facecentered gamma iron to body-centered alpha iron is arrested and an in-
gamma iron. face-centered gamma
more
termediate crystal structure, the body-centered tetragonal, is formed. The carbon, instead of being wholly expelled from solution, is entrapped in the tetragonal lattice as a supersaturated solution. The result is a highly
strained, very unstable crystal structure containing a multitude of en-
trapped submicroscopic particles.

Steel fails under stress by slipping or gliding along crystallographic planes of relative weakness; these submicroscopic particles act as keys and help to prevent easy slip (Fig. 13.5). The result is much higher
strength
and hardness, accompanied, however, by increased
brittleness.
lowering of the transformation temperature to about 480F. (250C.) and the increased hardness and strength are accompanied by the formation of a structural constituent known as martensite,
characterized by an angular, needlelike appearance
(Fig.
The sudden
13.6).
The
n
:cc -^CFC^ J3T h =D=
<)
\=Q-r^^^ 6\ Q. -Or 0=
Fie. 13.5.
Schematic representation of a crystal containing

particle,
(A)
no hard panicles.
(B)
one large
and
(C)
many
small particles.
272
needlelike formation, while

of small cross section,
is
common
in rapidly cooled high-carbon steels
constituent;
its
by no means universal. Martensite is a transition composition, hardness, and appearance under the micro-
scope depend primarily upon the

tion,
amount of carbon, the size of the secand the quenching treatment. Depending upon the carbon content, the strength of steels which are chiefly martensitic in structure may vary from 150,000 to more than 350,000 lb. per sq. in., and such steels may be as brittle as glass or may show considerable toughness.
Metallurgists are generally agreed that the primary cause of the hardness of martensite
(and drastically quenched medium- and high-carbon

solid solution
steels)
is
the precipitation of submicroscopic particles of carbon or iron
carbide from the
gamma
and the retention of these
particles
as a supersaturated solution in the tetragonal alpha-iron
lattice,
where
they act as a multidude of keys effectively preventing slip. Some authorities, thinking that this explanation does not account for all the hardness,
have postulated
lattice distortion, internal strain,
and the
fine grain size as
important contributing causes.*
The
internal structure of martensite
and
Fig. 13.6.
Structure of martensite
(B) 3,000x; etched.
in
high-carbon steel quenched in iced
brine.
(A)
500x:
A complete and wholly satisfactory explanation of the hardness of martensite will not be available until more is known about the atomic forces that hold the crystal lattice together and about the nature and magnitude of the strains produced by an
entrapped stranger atom in a
lattice.
Fundamentals of Heat Treatment of

the causes of
its
Steel
273
hardness are of
much
interest to the physical metallurgist
but are
of only passing interest to the engineer

is
who wants a
basic knowl-
edge of heat treatment. Far more important

bility of structure that results
a realization of the insta-
from quenching.
Steels
13.7.
The
Instability of
steel
is
Quenched Carbon
When
carbon
cooled slowly through the transformation temis

,
perature, all
phase changes take place and the carbon
completely
precipitated as large particles of iron carbide (cementite)

structure, laminated pearlite, that
is
is
resulting in a
steel
very stable.
If,
however, the
cooled very rapidly, phase changes are arrested before completion, the
is
carbide
entrapped in the crystal

is
lattice as exceedingly
minute
particles,
and
the lattice
strained, resulting in a structure, martensite,
which
is
very unstable.
As is characteristic of an extremely unstable condition, there is a very strong tendency for quenched steel to become more stable under the
slightest
provocation.
Re-
heating to 500F.
(260C.)
or above will give the atoms
enough mobility so that instability and the strained

structural condition are reless comdepending on the temperature and the time.
lieved
more or
pletely,
The
instability
after
quenching is accompanied by high internal stresses, so

high that frequently a small
piece of
high-carbon
water-quenched steel, though
undisturbed, will crack (Fig.
go with explosive violence hours or even days

to
13.8) or will, occasionally,
pieces
after
quenching.
To
to
relieve
these stresses
at
F.G. 13.7. Quenching cracks in the spline of a shaft, natural size, etched.
and
produce
the same
time a more
condition,
end
Stable
ural
steel is
quenched
always
re-
274
heated.
This
Is
known
as
tempering
or, colloquially
and somewhat
in-
accurately, as
drawing*
13.8. Retained Austenite
and Cold Treatment
When steel is quenched, the cooling must be continued to the a temperature before austenite will start to transform to martensite and before complete conversion takes place the temperature must lower to or
below the
temperature
(Fig.
13.4).
If
cooling stops between these

rise to
temperatures only part of the austenite transforms giving

called retained austenite.
what
is
The
temperature level of the
tion of alloying elements
Chapter 12. If the quenching to room temperature will result in only part of the austenite being transformed and the remainder being retained as austenite. If however the steel is quenched and then cooled by refrigeration well below
f
M, and are both lowered by the addiand increase of carbon content as indicated in temperature is below room temperature then
t
temperature the transformation of the austenite r be made fairly complete.

the
to martensite
can
Since martensite
is
much harder
than austenite the hardness, strength
and wear
be improved by eliminating the retained austenite by cooling the steel down to about minus 100F. This can easily be done by placing dry ice in a container of acetone and using this as the
resistance of steel can
cooling medium.
This kind of cold treatment

ite
is
often used to reduce the retained austen-
particularly in the case of tool steels
retained austenite
and hardness and wear

where dimensional
where alloy content encourages resistance must be especially

stability
is
high or
in steel gages
important.
13.9. Structural
and Other Changes
in
Tempering
steel is reheated, two things happen: The unstable tetragonal crystal structure of the martensite transforms to the more stable body-centered cubic lattice of the ferrite, and
When
a drastically
quenched high-carbon
at the
it
is
same time internal

steels the
stresses are relieved.
To
produce such changes,

(100 to 200C.)
only necessary to reheat to about 200 to 400F.
for
temperature of boiling water is sufficient. Tempering at these low temperatures produces only a very slight mobility of the iron and carbon atoms, and it is likely that the only effect, in addition
to relief of stresses,
lattice as it
is the escape of the carbon atoms from the tetragonal changes to body-centered cubic. As a result low-temperature
some
The terra drawing for tempering originated from the old blacksmith's expression "drawing the temper." Drawing in its correct sense means pulling a wire through a
die to reduce the cross section.
Fundamentals of Heat Treatment

tempering produces no appreciable change
400F.
(200C.) or lower
steels
is,
of Steel
275
at
in hardness.
Tempering
for
high-carbon tool
internal stresses.
quenched which must be very hard but should be free from

therefore,
commonly used
tempering medium and high carbon steels in this low temperait has been established that some sort of transition carbide (not Fe 3 C) is precipitated. The composition of this carbide seems to have the composition approaching Fe 2 C or Fe^C.,. As the tempering temperature goes higher this first carbide is absorbed and reture range of 180 to 480F.,
When
precipitated as cementitc (Fe 3 C)
When
drastically
quenched carbon
steel
is
tempered
at
500F.
(260C.) or higher, the particle size of the iron carbide increases.

far this return to stability proceeds
How
depends upon the tempering temperature and to a lesser extent upon time. Most of the growth of carbide particles at any definite temperature occurs in the first few minutes; the reaction then slows down but continues for some time. In practical heat treatment the time for tempering is rarely less than 30 min. for each inch
of cross section.
As the carbide
ness
particles
grow
larger, it follows that there will

.
of them to act as minute keys to prevent slip (see Fig. 13.4)
be fewer Hence, hard-
and strength decrease, and
ductility, as
measured by elongation and
reduction of area, increases.

larger the carbide particles
Finally,
The
higher the tempering temperature, the

stable the resulting structure.
is
and the more
within a few degrees of the A, transformation temperature, the cementite has grown to particles so
when
the tempering temperature
Fie. 1S.8.
at 575-F.
(300C.)
Structure of high-carbon steel quenched in ice water and tempered and (B) at 1100 o F. (595C); etched 500x-
(A)
276
low magnificaand the properties are practically the same as those of a steel of corresponding carbon content cooled slowly through the A x temperature. Structural changes in tempering can be followed by microscopic examination of polished and etched specimens but not so closely as by dimensional changes and other methods. Martensite which has a structions,
large that they are readily visible with the microscope at
ture similar to that

etches slowly.
shown in Fig. 13.6 is white after etching, that is, Tempering at 575F. (300C.) produces, for the same
of the carbide particles.
degree of etching, a dark, almost black, structure indicating precipitation
and considerable growth

1100F.
(595C.)
,
After tempering at
the particles have increased in size so that they are
visible in the microstrucfure. Tf
These two
stages are
shown
is
in Fig. 13.8.
quenched
steel
contains retained austenite and
not cold treated
tempering is somewhat go through the various stages of tempering just described. However, the retained austenite will, at about 450F. to 500F., transform to a dark etching bainite, %vhich is quite hard,
to transform the retained austenite to martensite,
will
more complex. The martensite
and may
result in a little increase in hardness.
QUESTIONS
1.
What happens
to the structure of a small piece of
.8% carbon
it
steel con-
taining a mixture of large
and
small grains
when
is
subjected to the
following treatments:
(a)
heated slowly to about 1400F., held 80 min.,
2.
3.
and cooled slowly to room temperature; (b) heated slowly to 2000F., held 30 min., and cooled slowly to room temperature; and (c) heated slowly to 2000F., held 2 hr., and cooled slowly to room temperature? Define grain-growth tendency. Compare grain-sue control by submicroscopic particles and by controlling the heating above the critical. Why is the former method preferable? What ,is critical cooling rate? What is its effect on the austenite-pearlite transformation and on the resulting structure of high-carbon steel? Is a cooling rate of 600F. per sec. more or less than the critical cooling rate
for eutectoid steel.
4.
When
is
a high-carbon steel is cooled faster than at the critical rate, what the effect on the crystal structure, the appearance under the microscope, and the properties? What is martensite, and why is it hard?
5.
Why
is
high-carbon steel that
is
drastically
sirable conditions
may accompany
this instability
quenched unstable? What undeand how may they be
6.
7.
avoided? Describe the changes in structure and properties that take place when drastically quenched steel is reheated to (a) 350F.; (b) 600F.; and (c) 1200F. What effects have the alloy elements on the temperature at which austenite transforms to pearlite? How are these effects related to heat-treatment?
Fundamentals
8.
of
Heat Treatment
of Steel
277
variables affecting the hardness of quenched other factors are constant, which will be the harder one as quenched: (a) steel containing 0.30 or 0.60 per cent carbon? (b) steel containing 0.60 or 0.80 per cent carbon? 9. Define hardenability. What is its relation to grain size and to the alloying elements present? Distinguish between shallow-hardening and deep-hardening steels. 10. In what classes of steel is deep hardening important? Why? 11. Describe process annealing.
steel.
If
Name
the three principal
12. 15.
14. 15. 16. 17.
How
What What What
does grain size effect hardenability? factors determine the grain size of steel after process annealing? is the relationship between grain size and toughness?
are two standards for classifying grain size? Describe the effects of hot working on grain size.
What
factors
determine the amount of retained austenite after quenching?
CHAPTER
The Operations of Heat Treatment

Moore, M.S., Associate Professor of Chemical Alabama Polytechnic Institute, Auburn, Alabama Robert E. SHAFFER, M.S., Associate Professor of Engineering, University of Buffalo, Buffalo, New York
C.
14
Omar
Engineering,
1 HE
world's steel tonnage that
is
phasized in previous chapters, has
value of heat treatment to mankind, emlittle relation to the proportion of the
treated.
This tonnage amounts, in the
United States, to possibly two or three million tons annually, certainly less than 5 per cent of the total amount of steel used. Heat treatment is most valuable for tools and dies, which are in turn a very small proportion of heat-treated steel.
Heat treatment is ordinarily an expensive operation, because costly quenching baths, apparatus for controlling the atmosphere in the furnace, and temperature-recording and -controlling equipment are necessary. Some treatments cost as much or more than the steel itself, but this is no criterion of the value of the operation. Moreover, the cost of steel and of treatment is usually a very small part of the cost of the finished article and is even a smaller proportion of the value of the article to industry. One example will indicate this. The steel in a die may cost $2 and the heat treatment may increase this to $4. On this $4 die, the machine work frequently costs $100, but the completed die will turn out thousands of pieces of a finished product at a cost which is a very small fraction per piece of the cost of a similar product turned out, one by
furnaces,
one, by hand.
economic value of a properly heat-treated article and to machine work to prepare this article for use, it is poor economy on the part of the engineer to take chances on the quality of the steel or the heat treatment so that a few cents may be
to the
Owing
the customary expense of the
278
The Operation
saved.
It
is,
of
Heat Treatment
279
furthermore, poor practice for the engineer to design ex-
pensive tools, dies, or other parts without requesting the metallurgist to

advise whether the finished article will or will not survive the heat treat-
ment
tools
satisfactorily.
Thousands of
which
dollars are wasted every year because
ing.
much to machine, crack in quenchSuch waste can usually be prevented by the intelligent selection of the proper steel and by avoiding, in the design, sharp corners or reentrant angles where stresses concentrate. This factor is discussed in some detail
and other
articles,
cost
later in this chapter.
The
operations of heat treatment discussed in this chapter are those

steels,
used for carbon
most alloy
steels,
and some nonferrous
alloys.
Modifications of these operations used for a few high-alloy

certain other iron alloys,
steels, for
and
for a
number
of nonferrous alloys are
described in the chapters where these materials are discussed or in the
chapter on precipitation hardening.
14.1. Heating Cycle
Uniform and
if
consistent results from
any cooling
cycle can be obtained
the proper care has been taken in the heating of the steel prior to the of cooling.
method
The
steel
must be heated slowly
to the proper tem-
perature range and held at this temperature long enough for homogenization of the austenitic structure.
Color Orange-
The
are
temperature used and time required

functions of the chemistry of the
steel, section size
and shape, prior grain
Salmon
Bright-
900
size,
original condition of the steel, prior
Red
Cherry
850 heat treatments, or mechanical working. boo
The
750
usual time requirement at heat for homogenization of the austenite for a

is
Medium\ Cherry ]
TOO forging or casting,
Dork
650 of section thickness.

0.40 0.80
one hour per inch This is not a firm
Cherry )
Percentage
FlC. 14,1.
120 Carbon
1.60
rule
ever,
and
is
frequently neglected.
How-
Temperature
for
the heal,
ranges treatment of carbon
adequate time at heat must be provided for solution of carbides, and

if uniformity of product is to be achieved upon cooling for the diffusion
also,
steels.
(Metah Handbook)
of carbon and alloying elements from areas of high concentration into the lean areas.
Modern heat
treating
equipment should provide some means of
sur-
face protection for the steel during the heating cycle.

trolled atmospheres in heat treating furnaces
is
The
use of conprac-
becoming standard
280
tice.
If
during heating the

it
steel is
exposed
to
combustion gases or air in
the furnace,
will oxidi/e, dccarburize, or both.
An
oxidized surface
is
and can be removed by machining or grinding. Decarburization does not show and will result in low surface hardness and poor
easily detected
mechanical properties if not removed. Protective atmospheres are provided by several different methods and a number of different gases are used, including hydrogen, nitrogen, carbon dioxide, and sulfur dioxide.* With the proper selection and composition
control of the furnace atmosphere
parts free of scale
it is
possible to produce heat treated
and decarburization.
14.2. Annealing
Process annealing is the recrystallization of a cold-worked steel, by heating below the A t transformation temperature, usually in the range between 800 to 1200F., the exact temperature being governed by the
amount
Heating
of cold working, composition, grain

to the
proper temperature
affects
size, and time held at heat. complete recrystallization and
restores the original structure
and
properties.
Too
high a temperature or
too long time at heat
may produce
a coarsening of the grain size with a
subsequent
loss of toughness, hardness, and strength. For full annealing, the steel is heated slowly to from 50 to 100F. above the A 3 transformation (Fig. 14.1) held at this temperature until uniformly heated, and then slow cooled to room temperature. The cooling may be done in the furnace, or in an outside pit covering the steel with
,
asbestos, sand, lime or cinders. 5 to 20F. drop per minute.
The
rate of cooling
is
in the
range of
The
and
objects of annealing are to soften the steel for machining, to re-
fine the grain structure, to relieve stresses
from cooling or machining,

it
to increase ductility.
In hypoeutectoid steels
for castings
produces the poorest
strength and wear resistance of any structure except spheroidizing.
An-
nealing
is
commonly used
and forgings
to reduce the coarse
grain structure prior to machining.
14.3. Normalizing
The
air.
steel
transformation (Fig. 14.1)
The
least 100F. above the A s or A cm proper time, and then cooled in still cooling rate can be varied by changing volume of air or air
is
heated slowly at
for the
Discussion of controlled atmospheres and equipment is outside the scope of this book. For a more complete description see: American Society for Metals, Metals Handbook. The Society Cleveland, 1948.
The Operation
temperature.
of
Heat Treatment
is
281
The normal
rate of cooling
the range of 120 to 200F.
per minute, depending on section size and air conditions. Normalizing of low carbon content steels is usually done for
grain
size
stress relief,
refinement, to improve toughness and to increase strength and
ductility.
Steels containing over

tures,
1%
carbon, slowly cooled from high tempera-
may have
the excess carbides forming in a network around the

is
heating to the annealing and hardening temperatures
and unaffected by re(Fig. 14.1). This carbide formation will increase machining costs and produces an undesirable condition in the heat treated part. By heating above the A cm
grains of pearlite. This carbide network
stable
temperature and normalizing, insufficient time

pearlitic structure.
is
available for the excess
carbide to form a network around the grains or to form large plates in the
Some
finished parts, castings, forgings,
and rolled shapes

section.
to be
used after
a normalizing treatment should be given a temper to relieve cooling

stresses resulting
from non-uniformity of cross
usually give a noticeable

in hardness or strength.
improvement
in ductility with little or
This temper will no change
14.4. Spheroidizing
The
spheroidized structure, ferrite

3 to 8
,
and
carbides,
is
usually produced
by prolonged heating,
hours at a temperature slightly above or
below the A! or
A3
transformation.
The prolonged
heating causes
the carbides to coalesce into spheres, completely destroying the pearlitic
formation and resulting in a matrix of ferrite with the carbon in the form
of spheroidal carbides.
a
The time for spheroidizing normalizing treatment prior to spheroidizing.
is
usually lessened by
In medium and high carbon steels the spheroidized structure has the lowest hardness, strength and wear resistance, but the best machineability,
toughness, and ductility.
ing,
if
Though the spheroidized structure is desirable for machining and formit may cause some difficulty in heat treatment. The carbide material, in large spheres, may not go into solution when a simple heating and
cycle
is
quenching
used, resulting in spotty
and low hardness.
It is desir-
able to give steels of this type a normalizing treatment prior to the
hardening cycle to help break up and to dissolve the excess carbide areas. A similar structure of a ferritic matrix with spheres of undissolved carbides will result if a martensitic structure is tempered at a high temperature 1200 1250F. This method of producing the spheroidized structure is not recommended because of the problems involved in quenching higher carbon steels.
282
14.5.
Quenching for Hardening

sieel is
For hardening, the

range
the
(Fig. 14.1).
slowly heated above the A. t transformation
The hardening
temperature range for carbon
steels is
same as the full annealing range. The steel is usually held at heat long enough to insure uniform heat distribution in all sections. It is then removed from the furnace and immediately quenched in the cooling medium.
In carbon steels
it is
generally true that the faster the heat
is
extracted,
the harder, stronger,
High hardness is quenched high-carbon
and more wear resistant the finished part will be. frequently accompanied by excessive brittleness. Water
steels will often crack or shatter
if
dropped, or
if
allowed to stand overnight before tempering.
The common quenching media

Selection of the proper
of the steel, section size
are air, oil, water, and brine solutions. quenching medium is based on the chemistry and shape, and the final mechanical and physical
properties required. Air has the slowest cooling rate, and brine solutions
the fastest rate. the
The
cooling rate of a quenching
medium
will vary with
at 65F. is considered to have a cooling rate of one; brine solutions have as much as twice the cooling rate of water; oils vary in rate of water.*
amount
of agitation, temperature,
and composition. Water

from 15%
to
50%
of the cool-
maximum
the steel
Hardening of a steel is usually required because of the demand for the of one or more of the mechanical or physical properties that
is
tion in cross section, or
capable of assuming. Sometimes because of size, shape, variasome production problem, a compromise must be
maele. If this must be done, a careful study of the different cooling media should be made in order to select the one best suited to produce the best compromise of mechanical and physical properties.
For lower carbon

steels, oil is
steels,
water
is
usually used because of

In
its
low
cost,
easiness of handling,
and
availability.
it
medium and
high carbon
often used because
cracking than with a water quench.

instead of water,
maximum
less warpagc, distortion, and However, by using an oil quench hardness, strength, and wear resistance may
produces
not be obtained.
When
the heated steel
steps or stages of heat
is quenched in a liquid, there are two distinct removal that are passed through before reaching
the temperature of the quenching
medium.
of the cooling cycle
in contact with the
Step One:
the
The vaporization period. In this period quenching medium will vaporize when it comes
American Society for Metals Handbook. The
Society, Cleveland, 1948. pp. 616-619.
The Operation
steel.
If
of
Heat Treatment
283
the vapor
is
quenched, the cooling rate
allowed to form a film around the part being is slow because the vapor film insulates and
steel.
blocks off contact between the cooling liquid and the
By breaking
vapor film
is
up the vapor film and allowing the liquid to vaporize and be carried away,
the fastest cooling rate
is
achieved.
The
breaking up of
this
accomplished by proper agitation or circulation of the quenching

or by agitation of the parts being quenched, or both.
liquid
Step
Two: The
is
liquid period.
is
cient heat so that the liquid
removal of heat
heat loss
is
now
relatively fast
After the quenched pari has lost suffino longer vaporized upon contact, the simple problem of heat transfer and the rate of as compared with the vapor cycle.
The
ing.
difficult
and
critical
period in quenching
is
the elimination of
the vapor film. Prolonging this step
may
result in unsatisfactory harden-
The
part
may have
areas which arc low in mechanical properties, or
the entire microstructure
may be
unsatisfactory
and
fail to
produce the
required mechanical properties.
The
surface
internal stresses introduced by

(2)
quenching are the
result of
(1)
dimensional changes in cooling,
large temperature gradients between
and
center,
and
to
(3)
the change in
If
volume accompanying the

is
change from
carbon
build
steels
gamma
alpha iron.
the steel
ductile, these changes

stress.
cause slight plastic flow of the grains which relieves the
In high-
where no
in
plastic
deformation takes place these
stresses
may
up
to a high value.
Stress distribution
quenching
it is
is
complex and
difficult
to analyze
accurately.
stress
steel.
In
many
instances,
certain that the
sum
of the induced
and the working stress is near or above the tensile strength of the Thus, it was found* that in hollow cylinders the stress that was introduced by quenching at the inner surface of the hole was about 150,000 lb. per sq. in. As the working stress on these cylinders was 100,000 lb. per sq. in., the total stress was 250,000 lb. per sq. in. or close to the actual
tensile strength of the steel.
Internal stresses
may
affect the strength
and
ductility
and frequently
is
cause warping and cracking.
The magnitude
of these stresses
de-
and shape of the piece, the kind of steel, the quenching temperature, and the coolant. When the stress builds up to a value higher than the tensile strength, the steel cracks. There are two types of such defects: (1) local cracks, which are usually external and start at sharp comers or deep tool marks, and (2) internal cracks, which follow the major axis of the piece. Quenching in water is more likely to
pendent on the
size
O. V. Greene, Trans.
Am
Soc. Steel Treat., v. 18, 1930, pp. 369-403.
284
oil
cause cracking than quenching in
or
air.
Coarse-grained
steels
crack
more
readily than fine-grained material.
Localized heating in grinding
frequently causes cracking, as does increasing the temperature from which
the steel
is
quenched.
fillets
quenching cracks are as follows: (1) where the contour changes and avoid tool marks which may act as a notch; (2) avoid rapid heating, especially through the transformation range, which may cause cracking because of the uneven expansion; (3) temper immediately after quenching; and (4) quench in oil instead of water wherever possible.
use generous
The
best procedures in avoiding
14.6.
Tempering
The previous discussions of the principles underlying quenching included details of structural changes and related changes in properties.
Some
larly
of these changes in physical properties are often desirable, particu-
where hardness and wear-resistance are of importance. However, this and wear-resistance is at the expense of ductility because, in most instances, the brittleness has also increased. The extent of brittleness, coupled with hardness, etc., depends on the severity of quench and the percentage of carbon in the steel. Tempering lowers the hardness and strength and decreases wear-resistance; it also increases
increase in hardness, strength
ductility.
The purpose
restore ductility
of tempering
is
not to decrease hardness but rather to
A way of doing this and at the same time retaining the original hardness and strength would be desirable. However, since tempering does decrease the hardness and strength, but at the same time restores ductility, it would be well to consider what is
and improve toughness.
desirable in the
way
of strength.
it is
Generally a structural part

it is
is
not sub-
jected to deformation until
breaks;
the stress capacity without
permanent deformation which
important.
Tempering should be
comparable to
ness
carried out at the highest temperature that will
insure retention of sufficient strength so that the part can withstand loads
its yield strength. The higher the temperature, the tougher the product, but this will necessarily be at the expense of hard-
and
strength.
For tempering, the hardened steel is reheated in a furnace, in heavy oil, in molten salts, or in molten lead, and held long enough for the
heat to penetrate to the center. For most
steels,
the speed ol cooling after
tempering
pering
is
is
of little consequence, provided the steel was not heated
to the transformation temperature.
In practice, the cooling after tem-
usually in the
air.
The Operation The

ment
of
Heat Treatment
285
dis-
metallographic structure of tempered steel will be further
cussed in Section 14.7,

processes.
where tempering
is
compared
to other heat treat-
14.7. Isothermal Treatments
One
which
result of the study of the subcritical transformation of austenite,

also led to the S. curve,
by Bain and
his associates*
was the
dis-
covery of austempering, a process of interrupted quenching whereby
high-carbon and low-alloy steels of suitable composition and cross section can be hardened without cooling to atmospheric temperature, thus eliminating the possibility of introducing high quenching stresses with possible
distortion or cracking.
tensitic structure, as
The process cannot be used if a very hard marobtained by water quenching high-carbon steels and
tempering at 200 to 300F. (100 to 150C), is desired; but it may be used to obtain a structure corresponding to tempered martensite of any required degree of fineness, such as is usually attained by cooling rapidly
room temperature followed by reheating to 400F. (200C.) or above. At any temperature below the A\ transformation and above the temperatureabout 400F. (200C.) where martensite is formed, the austo
tenite transforms to pearlitej of definite structure at a definite rate.
If,
therefore, small specimens of high-carbon steel are heated above
the
transformation temperature and are quenched very rapidly into a bath maintained at any intermediate temperature, for example, 500 to 800F.
(260 to 425C.)
,
and
if
the specimen
is
held in this bath for a definite
time, the transformation of the retained austenite

ture
and the resulting
struc-
may be
controlled closely. Steels so treated are
similar steels cooled rapidly to
more ductile than room temperature and tempered at a
temperature that produces a corresponding structure.
The
hardness and
strength of the austempered steel are about the same as
if the steel had been quenched and tempered in the usual manner, but elongation, reduction of area, and impact resistance are usually higher. The explanation advanced for the higher ductility in the austempered steel is its freedom
from submicroscopic cracks that are caused by drastic quenching (to form martensite) and not subsequently healed by tempering. A schematic representation of austempering is shown in Fig. 14. 2. t To prevent any transformation of the unstable austenite to pearlite,. the specimen must be small enough to cool past the nose of the S curve very rapidly; for the steel whose diagram is given in Fig. 14.2, it must cool
E. C. Bain and E. S. Davenport, U.S. Patent 1.924,099, Aug. 29, 1933. f Based on diagram by F. J. McMulkin, Iron Age, v. 157, June 27, 1946, p. 58.
% (or Bainite)
286
1400
I30C
1200
MOO
-11000
900,
800".
700
| "
E
600
500 400
300
Mostly \morfensife
I5min.30min.
I
200
Bhr.
Icty
.
Ihr.
I
100
1000
10,000
100.000
Time,
Fig.
14.2.
sec.
curve,
Schematic T-T-T diagram for carbon steel showing critical-cooling-rate temperature, and temperatures for austempering and martcrnpering. (Mc-
Mulkin)
through the temperature range of 900 to 1000F. (480 to 540C.) in about 1 sec. The specimen is therefore quenched rapidly into a bath maintained at the desired temperature-600F. (315C.) in Fig. 14.2-and held in the bath until the transformation to bainite (emulsified ferrite and cementite)
about 45 min. Structural changes are now comat any rate, to room temperature. A process that carries the principles underlying the subcritical decomposition of austenite farther than austempering is martempering, which was developed a few years ago by Shepherd.* In this process the
is
complete, that
is,
for
plete,
and the specimen may be cooled,
Shepherd has described martempering in a number of papers. A lucid which also includes an elementary discussion of the transformation of austenite to martensite in quenching and isothermally, as mapped by the S curve, is contained in two arUcles by Shepherd in Production Eng., July, 1945, p. 438, and Aug.,
F.
* B.
description,
1945, p. 515.
The Operation
steel
is
of
Heat Treatment
it
287
will pass the nose
quenched
at
its
critical rate or fasterso that
of the S curve without any transformation of the austenite into a bath
maintained
just
at a temperature slightly above the s point, in other words above the temperature where martensite starts to form. This temperature varies with carbon content and slightly with the amount of alloying elements present, but for high-carbon and many alloy steels it is ap.
proximately 400F. (200C.) The steel is held in this bath just long for the temperature to become uniform throughout the cross section, after which it is removed and cooled in air. A schematic representation of martempering is shown in Fig. 14.2. The specimen is quenched at the critical cooling rate or faster into a bath maintained at about 450F. (230C.) and held in this bath for a sufficient time to be heated through (about 1 min. for a small specimen of the steel shown
enough
in Fig. 14.2)
It
so long that the line
should be noted that the specimen should not be heated where bainite begins to form is crossed by the time
axis at this tempering.
Martcm|>ering is based on the principle that, if austenite is retained by rapid cooling down to the temperature where martensite begins to
form, the austenite-martensite transformation will proceed, regardless of the cooling rate from this temperature down to atmospheric temperature;
and
that
on cooling
slowly, as in air,
result without the concomitant high internal
are characteristic of drastically
from about 400F. full hardness will quenching stresses which quenched high-carbon or alloy steels. AcThe method can be used for heavy which often crack in the usual
cording to Shepherd,
especially ductility
this
treatment improves the mechanical properties,
and toughness.
sections
and
for pieces of irregular shape
hardening operation.
Martempering resembles austempering only in that the quenching is interrupted at an intermediate temperature; but the steel is not held at
this
to transform.
temperature long enough for any appreciable amount of the austenite In martempering, therefore, the austenite transforms to
hard martensite, while the steel is cooling slowly from this intermediate temperature to atmospheric temperature; in austempering the steel is held at the intermediate temperature long enough for the austenite to
transform to a ferrite-carbide aggregate of desired structure and properties.
Patenting is a very old process used to heat treat medium- and highcarbon rods which are to be cold drawn into high-strength wire. The rods or the wire (if patenting is used as an intermediate stage in drawing coarse wire to finer sizes) are heated to a temperature considerably above
the
A3
transformation temperature, so that some grain growth takes place,
288
in air or
and cooled
850 to 950F. (455 to 510C).
quenched in a bath of molten lead maintained at The object of patenting is to produce a
fairly coarse austenitic grain that transforms in the air or at the lead-bath
temperature to large pearlite grains which are made up of fine ferrite and cementite. Such a combination of controlled overheating and finely dispersed carbide and ferrite in the pearlite is essential for the steel to withstand the cold work to which the wire is subjected in drafting and
is
also essential if satisfactory quality
is
to
be secured.
Patented and cold-drawn wire for use in cables in suspension bridges is fairly high in carbon and has a final strength of around 225,000 lb per sq. in. and an elongation of about 2 to 6 per cent in 10 in. Patented
and cold-drawn wire
is
the only suitable material found thus far for
suspension-bridge cables.
high-carbon wire, cold drawn and then

it
quenched and tempered

is
so that
has the same mechanical properties,

is
unsatisfactory.
The
reason for this
not
clear,
but the
first
attempt
to use heat-treated wire instead of patented
and cold-drawn material
ended
so disastrously that
again." Patented
bridge cables for
it is doubtful whether it will ever be tried and cold-drawn wire has been used for suspensionmany years, and failures are unknown. The most that
can be said
is
that apparently the equiaxed structure of the heat-treated
resist so well as the elongated "fibrous" structure of the cold-drawn material the propagation of minute cracks on the surface, formed when the wire is bent around the anchorage shoes.
wire does not
Some emphasis should be given to the advantages of austempering and martempering as compared to tempering a martensitic steel. A tougher, more shock-resistant steel is obtained in austempering or martempering.
Tempering
involves the decomposition of martensite to granular mix-
and ferrite in which the cementite particles tend to be round rather than lamellar as in pearlite. Temperature and time,, primarily temperature, are important factors, along with the amounts of alloying elements in the case of alloy steel, in determining the size of the separated carbide particles. At very low tempering temperatures the resulting decomposition products are hardly discernible under the microtures of cementite
scope.
Tempering
at progressively higher temperatures results in micro-
structures that can be resolved
under the microscope; the carbide
par-
The wire used in the construction of the Mt. Hope Bridge, at Providence, and the Ambassador Bridge, at Detroit, both ot which were suspension bridges, contained 0.80 per cent carbon and was oil quenched and tempered. Although the mechanical properties were satisfactory, the wires began to fail soon after the cables were spun; the bridges had to be dismantled and rebuilt with the usual patented and cold-drawn
wires in the cables. See E. E. No*. 1, 2, and 3.
Thum, Metal
Progress, v. 21, 1932, No. 6; v. 22, 1932,
The Operation
tides are progressively larger,
of
Heal Treatment
eacli
289
is
and
micro-structure
softer
and
tougher than the preceding one.

cementite,
The
structure in which the divorced
embedded
is
in the ferrite matrix, can be seen with
moderate
magnification
termed spheroidite.
is
In the practice of austempering, the formation of martensite structure avoided by suddenly cooling the heated steel to a predetermined temit
perature at which only bainite forms and by holding
there for sufficient
time to complete the transformation of austentite to bainite. Thus a product having ductility (toughness) comparable to that of a tempered steel is obtained in a single operation and without subjecting it to the quenching necessary to produce martensite.
Martempering, which produces a hard martensitic structure, avoids the high internal quenching stresses produced in a fully hardened steel
by
drastic quenching. Attention should be called to the commercial limitations of austem-
pering and martempering.
In practice, small section sizes (plain steel)
up
to
y
4
inch respond best to the above
method because of the

is
necessity
of suppressing the austenite-to-pearlite transformation.

size that
The maximum
can be effectively treated, though,

characteristic S-curve of the alloy.
determined by the composi-
tion
and
14.8. Case
Hardening Processes
There are many important industrial products, such as gears, camand the like, which should have a hard, wear-resistant surface and a tough core. Carburizing is the most widely used method
shafts, piston pins,
of securing such a combination of properties.
In this process, unalloyed
low-carbon or low-carbon alloy steel is heated in contact with a carbonaceous material, from which the steel absorbs carbon. The depth of
absorption depends on temperature, time, the alloying element present
and the carburizing compound. With a commercial compound, % in. deep is obtained by heating for 8 hr. at 1700F. (925C). Two general methods are in use: pack carburizing and gas carburizing. In the former, the steel article, fully machined and finished except for a small allowance for grinding, is packed, together with the compound, in
(if
any)
a case
a heat-resistant alloy box.
The
carburi/ing
is
compound
is
coke or charcoal
mixed with an
usually barium carbonate. At the carburizing temperature, the barium carbonate dissociates into barium oxide and carbon dioxide; the latter reacts with the carbon in the charcoal to form carbon monoxide gas (CO a + C = 2CX)) This gas reacts with the iron at the surface of the steel to form iron carbide. By diffusion, the carbon then penetrates below the surface. In the other method, used
"energizer," which
.
290
Fie.
in the transition zone

is
Structure of slowly cooled carburized steel (A) at the surface and (B) between surface and core. The structure of the low-carbon core shown at the bottom of B; etched. 100x14.3.
is heated in a retort furnace into which composed of hydrocarbons or carbon monoxide is introduced. This method is more rapid than pack carburizing, and the case depth can be more closely controlled.
chiefly for small articles, the steel

a gas
After carburizing for a sufficient time at the proper temperature (both

of which have been standardized)
,
the carbon at the surface varies from
This grades off uniformly with increasing distance from the surface, until at a depth of >/ or s/ in. the 4 A structure is unaffected. Typical structures of slowly cooled carburized
0.8
about
to about 1.1
per cent.
steel, at
the surface
(A)
and
in the transition
zone (B)
are
shown in
Fig. 14.3.
Carburized
steel is
always heat treated to produce the required hard-
ness of the case
may
usually to improve the ductility of the core, which be too coarse-grained from the long heating at high temperature.*
is
and
After heat treatment, the case of carburized steel articles

structure
martensitic in
and very hard, and the core has the
ductility of low-carbon
Sec Metals Handbook,

Epstein,
The
Company,
1948, pp. 681-G85, for a detailed description. See also S. Alloys of Iron and Carbon, Vol. I, Constitution, McGraw-Hill Book Inc., New York, pp. 335-340, for a discussion of principles.
The Operation
steels.
of
Heat Treatment
resistance,
291
Even greater toughness and shock
combined with a hard

steel, especially
surface, can be secured by carburizing a low-carbon alloy one containing 3 to 5 per cent nickel.
Austenite grain
size is
important
in carburizing steels.
After carburiz-
ing and heat treatment, a coarse-grained material has a uniformly hard surface, but the core may not have such high impact resistance as is
generally desired.
Fine-grained steels, on the contrary, are prone to carburize irregularly and develop soft spots on the surface after heat treatment. These conditions can frequently be avoided by special quenching techniques, most of which use a spray of water under pressure, or
by
the use of alloy steel.
Nitriding, an established process for producing a hard surface on steel, uses nitrogen as the hardening agent instead of carbon. It was in-
Germany about thirty years ago and is now used where widely in applications a superhard surface combined with considerable corrosion resistance and resistance to softening at elevated temperatures is desired. It is used by the automotive and aircraft industries for valve seats and for guides, gears, and piston pins of internal-combustion engines and in a number of applications in steam plants and oil
vented by Adolph Fry
in
refineries.
The
process consists of heating the finish-machined article in a closed
container into which

into nitrogen
ammonia
gas
is
forced under pressure. At a tempera-
ture of 850 to 1000F. (450 to 540G.) the
ammonia
is
mostly dissociated
and hydrogen. The former combines with the iron and other elements in the steel to form complex nitrides which diffuse into the surface layers. This diffusion is slow; a case varying in depth from
0.0005 to 0.02
in. is
obtained after 5 to 25 hr.
Unalloyed carbon steels cannot be nitrided successfully. Some alloying element which forms a stable nitride must be present. The steels used for nitriding, therefore, contain chromium, aluminum, molybdenum, and
vanadium
effective
in various combinations.
in
elements
Aluminum and chromium are the producing high hardness, while molybdenum and
and
also increase the
vanadium
increase the toughness of the steel
depth
of penetration of the nitrogen.
Nitriding steels are usually heat treated

steels
before nitriding to obtain the desired mechanical properties, which are
not affected by the treatment with ammonia, provided that the
were
tempered prior to nitriding at the same or higher temperatures than used during the treatment with ammonia.
The
wear
outstanding advantage of nitriding

to ferrous metallurgy.
It
resistance.
is high surface hardness and This surface hardness cannot be equaled by any other
method known
averages a Vickers hardness
292
of 1200 as
number
steel of
compared with 650

is
to 700 for
quenched high-carbon
maximum
hardness.
Another advantage
as
it
is
for carburized steel.
increase in the size
no subsequent heat treatment is necessary, Nitriding is, however, accompanied by an of the section. This growth is dependent upon the
that
is constant for a given set of averages 0.001 to 0.002 in. for the usual temperatures and for nitriding periods of 15 to 20 hr. To allow for this growth, parts that
time and temperature of the operation but

It
conditions.
are to be nitrided are machined so that they are undersize by the amount of the expected growth. If it is desired to prevent the absorption of nitrogen in certain areas, these are plated with nickel or coated
with
tin.
place, special alloy are necessary; in the second, nitriding equipment is expensive. A nitrided camshaft, for example, costs from 5 to 15 times as much as a comparable article which has been carburized and heat treated. Since the
first
Nitriding
is
a relatively costly process.
In the
steels
cost
in cost
depends largely upon the quantity treated, an appreciable reduction would result if the demand for nitrided steel would permit largeis
scale production.
Cyaniding
process
uses
another method used to produce case hardening. This molten sodium cyanide, sodium chloride, and sodium
carbonate as the bath in which the steel is immersed. The case produced is very thin, seldom over 0.002 of an inch, and the temperature required is from 1300 to 1600F. (700 to 870C).
modification of the cyaniding process

salt
through the molten chapmanizing.
is to bubble ammonia gas bath, thus liberating nitrogen faster and inis
creasing the nitrogen content of the case. This modified process
termed
Carbonitriding involves both carburizing and nitriding in a single by heating the steel (1 200-1 600F) in a carburizing gas (CH 4 GjH 8 etc.) containing ammonia. This process has gained wide acclaim and many steel parts are being case-hardened by this method
operation
, ,
today.
Lower temperature processing
results
in
a case similar
to a
nitrided steel.
steel.
Higher temperatures produce a
case like a carburized
Nitrided cases are very stable; the hardness is unaffected by long heating at temperatures as high as 750 to 850F. (400 to 455C.) and is not affected by heating for short periods at temperatures as high as 1000 to 1 100F. (540 to 595 C C.) The surface is resistant to such corrosive agents as the atmosphere, alkalies, crude oil, tap water, salt water except when
.
it is
moving, ethyl gasoline, and
many
to mineral acids. It has the highest
others. It is, however, not resistant wear resistance of any ferrous material
The Operation
of
Heat Treatment
this
293
property
is
and is finding increasing use in applications where prime importance.

14.9.
of
Flame Hardening and Induction Hardening
There are a number of applications for steel articles that should be hard only in a relatively small area on the surface. For such uses, it is not economical to heat treat a section weighing 100 lb. or more by the usual method of heating in a furnace followed by quenching and tempering, or by carburizing to harden the whole surface. In some cases, heat
treating
complex section by the usual method causes too much

Also,
it is
distortion.
the treatment of a single piece. For heat treatment

as these, flame
recently.
not generally economical to operate a furnace for under such conditions
hardening and induction hardening have been developed
Flame hardening consists of heating above the Aa transformation temperature any desired external spot of the finished steel article, as for example
is
the teeth of a gear (Fig. 14.4),* with an oxyacetylene torch. This adjusted for flame composition so that the steel does not oxidize. The
distance of the torch from the
controlled so that the steel does not
work and the time of heating are also become overheated to the point
is
where grain growth is serious. As soon as the surface area temperature, it is quenched and immediately tempered to
ing
stresses.
at the
relieve
proper quench-
Two
general methods are used. In the
first,
the steel piece
is
fixed
and
the torch moves across the area to be heated at a predetermined rate. This must be controlled carefully as the temperature of the oxyacetylene flame is approximately 6300F. (3500C.) but the piece to be hardened
,
should not be heated higher than 1475 to 1550F. (800 to 850C.) In the second method, the torch is stationary, and the steel piece moves
.
slowly under the flame.

is
The hot
just
area
is
usually
quenched
in water,
which
conveniently conveyed through one tube of the torch and flows out of
orifice
an
under pressure
behind the flame.
In addition to economy under certain conditions, flame hardening has

it has no effect on hardens only at the surface and to a depth of not more than \/ 4 in., and distortion is minimized. Its disadvantages are that it is more costly than the usual methods if large numbers of identical pieces are to be treated, and that high-carbon steels and very coarse grained steels cannot be treated, as they arc likely to crack at the surface.
other advantages.
It
does not scale or pit the surface;

it
the chemical composition;
R. L. Rolf, Trans.
Am.
Soc. Metals, v. 27, 1939, pp. 43-00.
294
Fie. 14.4.
Flame hardening the
teeth of a large gear.
(Rolf)
most suitable for flame hardening are carbon steels containing and low-alloy steels containing 0.25 to 0.50 per cent carbon. Such articles as alloy-steel gears which have been heat treated so that they have optimum strength and toughness can be effectively hardened on the surface of the teeth by this method. Differential hardening by induction is a recently developed method for securing high hardness on a relatively small bearing surface and is especially applicable to heavy-duty crankshafts* and to gear teeth, the ends of shafts, pins, hubs, and similar sections that act as thrust bearings. The surface to be hardened is enclosed in a perforated induction block that surrounds the steel but does not touch it. A high-frequency current of 2,000 to 200,000 cycles (from 25 to 50,000,000 may be used) is passed through the block, inducing eddy currents which rapidly (in to 5 sec.)
Steels
0.35 to 0.60 per cent carbon
The method
is
described in detail by M. A.
Tran and W.
Am.
Soc. Metals, v. 25, 1937, p. 935. Sec also Induction
E. BcnninghofT in Trans. Hardening, American Society
for Metals, Cleveland, 1946, 172 pp. practice.
This
is
a series of lectures covering theory and
The Operation
of
Heat Treatment
295
Fie.
145.
Cross section of a crankshaft showing hardened
(while) bearing surfaces,
etched. (Tran
and BenninghofJ)
heat the surface to be hardened to a temperature above the upper transformation temperature. As soon as this occurs, water under pressure is
sprayed onto the hot surface through the holes in the induction block. The heating and quenching cycle and other conditions are controlled,
so that
if
steel of the
proper composition and grain
size is used, the bear-
ing surface will have a hardness of about 60 Rockwell

to a
(600 Brinell)
dis-
depth of
of the
i/jj
in.
or more,
and decarburization, grain growth, and

in the
tortion will be prevented.
manufacture of incombination of high hardness and wear resistance on the bearing surfaces and ample toughness and relatively easy machinability for the rest of the shaft. This problem has been solved by induction hardening. The shaft can be heat treated by quenching and tempering at a high temperature, or even by
most
difficult
One
problems to solve
is
ternal-combustion engine crankshafts
how
to secure a
normalizing, to obtain a structure of fine pearlite, which has satisfactory toughness and ductility and can be machined fairly easily. Hardening by
induction heating produces a bearing surface with ample hardness and
wear
resistance
and
leaves
the
fillets,
where the
stress
concentrates,
ductile
and
relatively stress-free.
is
An
induction-hardened crankshaft
surfaces are readily apparent.
etched cross section of a heavy-duty shown in Fig. 14.5. The hard bearing
Heat treatment by induction heating has
expanded rapidly in the past few years; at present approximately one third of all the quenched and tempered parts used in the United States are hardened by this method.*
E. L. Cady, Materials and Methods, v. 24, Aug., 1946. pp. 400-410. This excellent summary with emphasis on the economic aspects.
is
an
296
QUESTIONS
1.
2.
is complete Austenization of hypoeutectoid steels essential for full hardening? Why is only partial austenization sufficient for hypereutectoid steel to be hardened? What is process annealing? What is full annealing? Explain the difference between these two annealing processes on the basis of prior processing, temperature required, changes in micro constituents, cooling rates and general usage.
Why
3.
What
4.
are the objects of normalizing low carbon steels? Of normalizing high carbon spheroidized steels? Compare air, oil, water, and brine as quenching media. What is the mass
in quenching? What other conditions proper quenching medium?
effect affect
the selection
of
the
5.
What
6.
quenched steels? Why should these internal be relieved? How is spheroidized structure obtained? What are the reasons for spheroidizing? What problems arise in the heat treatment of a spheroidized structure for full hardness?
causes internal stresses in
stresses
7.
What
is
the overall
objective
tempering
properties.
8.
has
on
the
of tempering? Correlate the effects that hardness, brittleness. strength, and toughness
List the metallographical structures
produced in tempering a
steel
when
9.
martensite decomposes at progressively increased temperatures. Compare the physical properties of these different structures. What is meant by austempering, and what are its advantages and limitations?
10. 11.
Compare martempering with austempering.
Why
is
is carburizing limited to low-carbon or low-carbon alloy carburizing accomplished?
steel,
and how
12.
Compare
the processes: cyaniding, nitriding,
and
carbo-nitriding.
CHAPTER
Carbon Steel Engineering

Arthur
lurgical Engineering,
Illinois
J.
as
an Material
15
C. Forsyth, Ph.D., Associate Professor of Metal-
University of Illinois, Urbana,
cal
Krai.ss, M.S., Head, Department of MechaniTechnology, New York City Community College, Brooklyn, New York
Edward
Jf
tire stock of ferrous
OR
a thousand years before 1850 man's en-
metals consisted of cast iron, wrought iron laboriously
made in small quantities at high cost, and a few high-carbon steel tools made even more laboriously and at still higher cost. These were valuable
materials
and represented a long step forward from the metals of the bronze age, but they were too costly or too low in quality to be used in building railroads, bridges, buildings, and ships. Between 1850 and 1860
Henry Bessemer
discoveries
steel
in England and William Kelly in the United States made which led to the development of a process for making carbon in quantities large enough and at a cost low enough to spark a cen-
tury of industrial progress.
reasonably accurate understanding of this progress can be obtained
from the following production
figures: 800,000 tons in 1870, 28 million tons* in 1900, 119 million tonsf average world production between 1935 and 1939 (42 million tons in the U. S.) and 253 million tonsj between
,
1951 and 1955 (103 million tons in the U. over 100% in the last twenty years. Before
95 per cent of the
steel
This shows an increase of II approximately produced in the world was carbon steel. This perS.)
.
World War
Estimate by Sir Robert Hadfield, The (London) Times Trade and Engineering Supplement, Jan. 28, 1953. f Steel, Jan. 4. 1943. p. 357, Average Production of Steel (1935-1939) for Ingots and Steel for Castings, 119,454,600 toss. Same period for the United States, 42.176,600 tons. t Steel, Vol. 140, No. 1, p. 172, Average World Production of Steel (1951-1955) for Ingots and Steel for Castings, 253,032,163 tons. Same period for the United States,
103,065,068 tons.
297
298
centage has
now dropped
steel is still the
to
but carbon
basis.
about 90.8 per cent (in the United States) , most important metallic material on a tonnage
steel produced annually is poured into form the metal assumed in the mold with no further mechanical treatment. The remaining 98.7 per cent is poured into ingots that are hot worked by rolling, forging, or pressing into a large variety of finished or semifinished products. Most finished wrought sections receive no further treatment, but a few are subjected to some form of heat treatment before use. Some semifinished wrought products
About
-
1.3
per cent of the carbon

in the
castings )-
which are used
are processed further by additional hot working; the rest are fabricated
into the desired

steels
may
or
may
form by cold working. (See Section Cold-worked .9.) not be heat treated before being used.
1 1
There
steel:
are, therefore,
four major classes of finished products of carbon
castings,
hot-worked products, cold-worked products, and heatIt is impossible to decide
treated products.
is
which of these four

life,
classes
the most important in present-day economic

role
for
since each plays a
definite
I
which there
is
no understudy.
Without hot-rolled
beams, there would be no skyscrapers; without heat-treated tools they
could not be built; without cold-drawn wire for elevator cables, they could not be used; and without castings for steam and water
they
lines,
would not be
carbon
its
habitable.
is
It is
the same in most other industries: each

is
class of
steel
indispensable, and the cost or tonnage
no
criterion of
value to man.
15.1. Carbon-Steel Castings as Engineering Materials
Unalloyed
steel castings
have many industrial
uses.
Despite the fact
that their mechanical properties are generally inferior to those of hot-
worked
steel of the
same composition, the proportion of castings to rolled
or forged material remains substantially unchanged year after year.

reasons for this are twofold:
ficult or
(1)
The
Sections that are so complex as to be dif-
duced readily at low

forgings
if
even impossible to fabricate by rolling or forging can be procost by casting; (2) castings are cheaper than
a few pieces of a fairly intricate shape are desired.
is
nomical production of such articles by forging

Steel, Vol. 140, No. 1, p. 174, Average U. and Castings, 9,488,097 tons (1951-1955). + Steel, Vol. 140, Xo. 1, p. 178, Average U.
S.
possible
The ecoonly when a
Alloy Steel Production, Total Ingots
S.
Production of Carbon Steel Castings,
(1951-1955) 1,216,948 tons.
Carbon
Table
15.1.
Steel as an Engineering Material
299
for
Chemical Composition and
Minimum
Mechanical Properties
Medium
* Strength and High Strength Steel Castings
Chemical Composition
(per cent)
Tensile
t
(maximum)
Grade
Strength (lb. per

sq. in.)
Yield Point (lb. per

sq. in.)
Elongation in
Reduction in
in.
Area
(per cent)
(per cent)
Mn
0.75
Si
Nl
N2 N3
U.
60-30 60-30 65-30 65-35 70-36 80-40 80-50 90-60 105-85 120-95 150-125 175-145
0.25 0.35 0.25 0.30 0.30 0.35
0.60
1.00
0.80 0.80
0.80 0.80
0.75 0.60 0.70 0.70
0.80 0.80
60,000 60,000 65,000 65,000 70,000 80,000 80,000 90,000 105,000 120,000 150,000 175,000
30,000 30,000 30,000 35,000 36,000 40,000 50,000 60,000 85,000 95,000 125,000 145,000
22
24
20
J
24
30 35 30 35
22
18
30
30
35 40 35 30
22 20
17 14
9
22
12
A.S.T.M 1955 Standards, Part One, Ferrous Metals, 27-55, and A148-55, pp. 1026 1027 and 1035-1036. f Maximum sulphur 0.06 per cent; maximum phosphorus 0.05 per cent. For each reduction of 0.01 per cent carbon below the maximum specified, an increase of 0.04 per cent manganese above the maximum specified will be permitted to a maximum of 1.00
per cent.
is
X When agreed upon by the manufacturer and the purchaser, and when full annealing required by the purchaser, the yield point value of the 65-35 class shall be 33,000 psi instead of 35,000 psi.
large
number
of pieces of a simple shape are produced thus spreading
thinly the cost of the expensive forging dies.

Steel for castings
in
Table
11.1.
Most of
may be melted by any of the processes enumerated it is made by the basic or acid open -hearth or the
acid electric process.
The
open-hearth process
is
is
used for melting

to its flexibility
steel
for large castings; the acid electric process,

to the high temperatures obtainable,
owing
and
favored for small castings, espe-
used for railroad equipment, especially for underframes of cars, for agricultural and excavating equipment, various parts of machines, electric equipment, and a large
cially those of intricate shape. Steel castings are
variety of small parts
and
fittings.
which specifications have been issued by the American Railway Association, the United States
several grades of steel castings for
There are
300
government, and a number of technical societies. Typical specifications for chemical composition and minimum tensile properties are given in
Table
For
15.1.
80,000 lb per sq. in. tensile with the exception of maximum percentages of sulphur and phosphorus, is not specified; the foundryman is permitted to adjust the percentages of carbon and manganese and to
castings
strength), the chemical composition,
high-strength
(above
use alloying elements,
if
necessary, which,
when combined with
a suit-
able heat treatment, will result in the desired properties. (See Table 15.2.)
15.2. Factors Affecting the Properties of Carbon-Steel Castings

Since the properties of carbon-steel castings are greatly improved by
heat treatment,
many
nealed, or normalized
now annealed, normalized and anand spheroidized. Quenching and tempering of

castings are
is
castings of such shape that distortion
not likely to be serious, are used
more and more frequently.
Table
15.2.
Mechanical Properties of Steel Castings*
Steel castings are generally specified
by mechanical
properties, leaving to the producer
control of the chemistry within certain limits, t
Structural Grades
Carbon Steel
85,000
100,000
Tensile Strength psi
60,000
70,000
Mechanical Properties J
Mod of Blast in Tension, psi: Tensile Strength, 1000 psi: Yield Point, 1000 psi: Elong in 2 in., %: Reduction of Area, %:
Hardness, Bhn: Impact, Izod, Ft-Lb: (70 F) (-50 F) Fatigue Str, (End Limit), 1000
30.1 x 10 60(a)
30
32
55
30.0 x 10 6 70(b) 38
29.9 x 10" 85(c) 50
29.7 xlO6 100(d)
120
30 8 25
28 50 140 30
10
31
24
40 175 20 10 38
70 20 46 200
30
15
Psi:
47
No.
Selected data from "Materials Engineering File Facts." Materials and Methods vol. 38, 4, 1953, pp. 153. Data sheets include current specifications, physical and mechanical
properties, thermal treatment etc. for carbon and alloy steel castings. found in Materials f "Summary of Standard Specifications for Steel Castings" may be and Methods, Vol. 36, No. 1, 1952, pp. 121 and 123. Minimum mechanical properties and
maximum
X
chemical compositions are
listed.
Normally expected values
in the production of steel castings for the tensile strength

(c)
values listed.
(a)
Annealed, (b) Normalized,
Normalized and Tempered,
(d)
Quenched and
Tempered.
Carbon
Steel as
SxSJC
301
^
V
'&N*S?
Fie. 15.1. Photomicrographs of Typical Microstructures o Small Steel Castings containing 054% C, 0.60% Mn., 0.84% Si., 0.032% P. and 0.036% S. Notice the change in grain size due to the following heat treatments. A-as cast, B-normalized 1700F. (926C). C-annealed 1700F. (926C), and D-quenched from 1700'F. (926C.) tempered at 1200F. (651 C). Nital etch lOOx. Courtesy of the Mining and Metallurgy Depart-
ment, University of
Illinois.
Large castings cool so slowly in a sand mold that a very course angular
not too large, simple annealing will refine the grain and improve the properties (Fig. 15.1C) , but such treatment does not effect complete homogenization in large castings.
structure results.
If the casting is
These are subjected

refining treatment.
(Fig.
to high-temperature normalizing followed by a grain-
Quenching and tempering produce the finest structure 15. ID illustrates the structure for small castings) and the best comsize is directly related to the rate
bination of properties.*
Grain
of cooling from the solidifica-
tion temperature to the
A 3 transformation
temperature.
It
follows, there-
Table 152 shows the normally expected values for mechanical properties in the production of steel castings for the tensile strength values listed.
. ,
302
fore, that a
ties
small casting usually has smaller grain size and better properthan a large casting; moreover, if the casting is not heat treated, it is
at the center, f
also true that in large castings the properties are better near the surface
than
is
The
factor of greatest
importance
to the properties of cast
carbon content.
If other things are equal, increasing the
carbon steel carbon inre-
creases the tensile
and the yield strength and decreases elongation,
duction of area, and impact resistance.

0.50 per cent, the casting
is
When
the carbon
is
higher than
usually so brittle, even after heat treatment,
used only for a few specific applications for example, rolls and dies where hardness and wear resistance are the most important propthat
it is
erties.
In general, carbon-steel castings of satisfactory mechanical properties
made readily by regulating the carbon content and by using a simple annealing or normalizing treatment. The minimum properties
can be
given for
in
medium strength
castings are conservative
and are
easily attained
commercial production (compare properties in Table 15.1 and 15.2) Cast carbon steels containing 0.20 to 0.40 per cent carbon have an
endurance ratio between 0.40 and 0.50. In the cast condition the ratio is usually between 0.40 and 0.43. Heat treatment (that is, annealing, normalizing, or quenching and tempering) improves the ratio, but it is usually somewhat lower than the endurance ratio of a comparable steel that has been hot worked. Heat treatment also improves the yield ratio, elongation, and reduction of area of cast carbon steel and increases the resistance of the material to single-blow impact. The added cost of heat
treatment
is
usually justified
if
castings are to be subjected in service

15.2).
to stresses of considerable
magnitude (Table
15.3.
Hot-Worked Carbon
Most hot-rolled or forged carbon steels contain between 0.05 and 0.30 per cent carbon and are used for sheet, plate, strip, tubes, pipe, various structural sections, tinplate and other coated sheets, and a large number of semifinished sections that are hot or cold worked into bars, wire, sheet, and tubes. Also included in this class is the well-known "machine steel" (containing about 0.20 per cent carbon and 0.40 per cent manganese) which is used for a wide variety of low-stressed machined parts and is the mainstay of every crossroads blacksmith shop in the world. Mediumcarbon steels containing between 0.30 and 0.70 per cent carbon are used for railway materials, especially rails, for a large number of forgings, and
fOwing to the mass elfect and lo segregation, it is frequently a serious to cast a test specimen that has properties truly representative of ihe casting.
problem
Carbon
for high-strength wire.
Steel as an
Engineering Material
303
The
higher carbon grades, containing 0.70 to 1.30
per cent carbon, are used largely for tools and cutlery and to a lesser
extent for springs and wire.
the medium-carbon grades
Low-carbon
or
steels are rarely
heat treated;
may
may
not be heat treated, depending
upon
their use;
the high-carbon steels are almost always used in the
hardened and tempered condition.
The
properties of hot-worked carbon steel are affected by

(2)
(1)
the
(3)
composition,
the several variables present in hot working,
and
the rate of cooling from the rolling temperature. Except for deep-drawing
sheet, this third factor
is
not important for low-carbon

steels,
steels; in
the case
of small sections of
medium- and high-carbon
air cooling
may
cause enough hardening to mask any effect of moderate changes in composition or of variations in the hot-working operation.
The
effect of
composition
is
discussed in the next section.
herent in hot working direction of temperature the first is the most important. In general, specimens cut longitudinally and transversely to the direction of hot working have about the same tensile strength and yield strength, but the elongation, reduction of area, and impact resistance of the transverse specimens are lower than those of the longitudinal specimens. This difference in directional properties is present even in clean steels, but it is accentuated by inclusions which are plastic at hot-working temperatures and which are thus elongated into fibers by the mechanical work.
15.4. Effect of Composition
Of the three variables inwork, amount of work, and finishing
on
Hot-Worked
Carbon
Steels
open-hearth
carbon on the tensile properties of hot-worked basic containing between 0.30 and 0.60 per cent manganese and between 0.02 and 0.04 per cent phosphorus is shown in Fig. 15.2.*
effect of steels
The
The
center line of the hatched area represents the properties to be ex-
pected most frequently.
The
top and bottom boundaries of the hatched
area give the limits of the properties to be expected at least 95 per cent of the time in the testing of commercial rolled or forged basic open-hearth
steel of these carbon percentages. The data used for plotting Fig. were obtained mostly by statistical analysis. It is safe, therefore, to clude that of 1000 specimens of 0.20 percent carbon steel about 700 have a tensile strength of between (53,000 and 65,000 lb. per sq. in.,
15.2
conwill
and
given by F, T. Sisco, in A. anil Include not only laboratory investigations and other data but also the data obtained in Germany by statistical analysis of more than 100,000 individual tests.
The values in Fig. 15.2 are a summary of all the data The Alloys of Iron and Carbon, Vol. II, Properties, Chap. 4,
304
0.1
0.2
0.3
0.4
0.5
Carbon, per cent

Fie. 15.2. Effect of
carbon on
hot-worked carbon
steels.
about 970 will have a tensile strength (60,000 to 68,000 lb. per sq. in.) which falls within the hatched area for steel of this carbon content. There will, however, be about 30 specimens, or 3 per cent of the whole, with a strength falling above or below the limits shown. These proportions should hold for steel of any carbon content between 0.05 and 0.70 per
cent.
The
on
a 2-in.
elongation values used for Fig. 15.2, if not originally determined gage length, were converted to this gage. In connection with
it should be noted that the usual flat specimen for plate, and similar products has a gage length of 8 in.; hence, values
the elongation
sheets,
given in Fig. 15.2 are some 20 to 30 per cent higher than would normally be obtained on an 8-in. gage* The increase in Brinell hardness with inIf standard flat specimens of basic steel of about 60,000 lb. per sq. in. tensile strength and with gage lengths of 2, 4, and 8 in. are tested, the respective elongation values will be approximately 45, 35, and 30 per cent, respectively.
Carbon Steel
as
305
creasing carbon approximately parallels the increase in tensile strength:
each 0.10 per cent carbon raises the hardness 20 numbers, from about
100 for 0.10 per cent carbon steel to 220 for 0.70 per cent carbon
steel.
Although both manganese and phosphorus affect the tensile strength, the influence of the former is unimportant in most carbon steels. For
example,
if
a basic open-hearth steel containing 0.20 per cent carbon
and
0.50 per cent
manganese has a strength of 65,000

in.
lb.
per
sq. in., in-
creasing the manganese to 0.80 will increase the strength only 3,000 to
Phosphorus increases the tensile and the yield per sq. in. for each 0.01 per cent present. In basic open-hearth steels, this element is commonly so low that it has little effect; in acid steels, however, there is usually enough present so that it exerts considerable strengthening action. Thus, acid steel is usually stronger, with lower elongation and reduction of area, than basic steel of the same carbon content.
4,000
lb.
per
sq.
strength about 1,000
lb.
15.5. Effect of Composition
on Other Properties
resist-
Increasing the carbon of hot-rolled steel decreases the impact
ance; low-carbon basic open-hearth steels have an Izod value of 50 to 60

ft.-lb.;
for hot-rolled steels containing 0.50 to 0.80 per cent carbon,

less
it is
usually
than 20
ft.-lb.
Increasing the phosphorus decreases the im-
pact resistance; an acid Bessemer steel is not so tough as basic openhearth steel of otherwise identical composition. The brittleness induced
by phosphorus is discussed in 11.10. In connection with impact resistance it should be emphasized that this property is greatly affected by grain size, direction of hot working, amount and distribution of inclusions, and other factors (aside from chemical composition) related to
the structure.*
These
factors
may have
so
much
influence
on the impact
resistance that
the effect of variations in composition
may
be completely obscured.
limit of hot-worked carbon steels increases with the Owing, however, to the fact that high-carbon steels have less plasticity under load than low-carbon steels, and are more likely to contain internal stresses, the endurance ratio is usually between 0.35 and 0.42, compared with 0.50 to 0.60 for wrought iron, ingot iron, and steels containing less than 0.35 per cent carbon. The modulus of elasticity of carbon steels is between 29 and 30 million lb. per sq. in and is not greatly affected by composition and heat treatment. Some of the other physical constants and most of the electric and magnetic properties are affected, more or less, by changes in composition.
tensile strength.
The endurance
Also see: Temper Kmbrittlement in Plain Carbon Steels, by Powers and G. Bhat, Trans. A.S.M. Vol. 44, 1952, pp. 1058.
J.
F.
Libsch, A. E.
306
Since these properties are not of great importance to most engineers, discussion of them is omitted here.
15.6.
Cold-Worked Carbon

First,
Cold working has two advantages.

nomically by
products, in
this
fact,
sections
of certain
sizes,
shapes, or surface finishes can be produced
more readily and more ecomethod than by any other. Some important industrial
cannot be produced at all except by cold working; it would be economically impracticable to produce by any other method wire small enough to be woven into screens or in quantities large enough for modern telegraph and telephone systems. In addition, cold working is the most effective and the cheapest method of securing a smooth surface and accurate size. Second, certain combinations of properties characteristic
of
cold-worked material
cannot be secured
process; for
in.,
example a tensile strength of 300,000 to 400,000 combined with considerable ductility, can be attained
value of cold-worked carbon steel
is
by any other lb. per sq.

readily.
by the an average year about 3 million tons of wire* 12 million tons of sheet* and strip, and 1.8 million tons of bars* and other cold-worked products are made in the United States. Sheet, strip, tubes, and bars are cold worked primarily to obtain certain sizes, shapes, and surface finishes
attested
fact thai in
The economic
economically.
High
strength
is
usually of secondary importance. Furtherstrip,
more, most cold-rolled sheet and

cially the
and some cold-drawn wire, espelines,
low-carbon grades which are used for screens, fences, barbed
wire, nails, screws
and
nuts, telegraph
and telephone
and for many
other
common
applications, are annealed before use.

effect of cold
Because annealing
completely destroys the

terial
work, the properties of such ma-
need not be considered further here.

steels that are cold
Carbon
to
produce special shapes and
worked to secure high strength as well as sizes and are not subsequently annealed
engineering materials.
affects
comprise an important
these steels
class of
The
properties of
and how cold working
them
is
are,
therefore,
worthy
of considerable attention. This class of material includes

sheet, strip,
some low-carbon
and wire, but the most important
wire containing about
and dental instruments, music (piano) wire, springs, rope and cable wire, and numerous other purposes where high quality and reliability combined with high tensile strength and considerable ductility are required.
0.25 to 1.00 per cent carbon used for needles, surgical
Estimated from -Shipments of Steel Products". Steel Vol. 140, No.
1,
1957, pp. 176.
Carbon Steel
as
307
10
20
JO
40
SO
60
70
SO
SO
92
Reduction by cold working, percent

Fig. 15.3. Stress-strain curves of
cold-worked low-carbon steel
(Kenyan and Burns)
15.7.
The Important Properties

static properties ordinarily
of Cold-Worked Steel
determined on cold-worked steels are and elongation, usually with a gage length of 10 in. for wire and of 2 or 8 in. for sheet and strip. Owing to the small cross section of most cold-worked materials, reduction of area, which is a valuable
tensile strength
The
measure of
ductility,
cannot be determined accurately. Yield strength
is
rarely determined
on cold-worked wire and sheet or strip; but for coldrolled bars of large enough cross section so that accurate measurements are possible, yield strength and reduction of area are frequently reported. Cold working increases the yield strength; with reductions in cross section of 30 to 70 per cent
it is
at least
90 per cent of the
tensile strength,
and with higher reductions it may for practical purposes be the same as the tensile strength. As shown by Fig. 15.3,* the stress-strain curve of
severely cold-worked steel
therefore, very low
is
curved from the origin; the elastic limit

zero.
is,
and may be
Several unstandardized tests are used to determine the ductility of
cold-worked wire and sheet. Some of these are crude, but in experienced
hands they give

regularities.
reliable indications of excessive brittleness or local
ir-
The most common

size,
of these
is
the
bend
test in
which a
speci-
men
of definite
clamped
in a vise
and bent 180
deg. over a definite

is
radius,
must not
crack.
S.
In another
Burns, Trans.
test,
a specimen
v.
bent back and
R. L. Kenyan and R.
Am.
Soc. Metals,
21, 1933. p. 595.
308
forth 90 deg. over a mandrel until failure occurs. bends before failure is a measure of the ductility.
The number
of 90-deg.
Another
it fails
able length
of the ductility of wire is the twist. specimen of suittwisted in a machine, which has one revolving head, until by shear. The number of 360-deg. revolutions of the movable head
test
is is
of the machine
the twist
is
the
number
of twists.
Some
metallurgists consider that

its
a good measure of ductility; others believe that
principal
value
is
to detect local irregularities or flaws in the wire.
10
20
30
40
50
60
70
80
90
100
Reduction of area in drafting,percent
Fie. 15.4.
Effect of cold
working on ihe
tensile strength of
carbon
steel,
(l.egge)
15.8. General Effects of Cold
Working on Strength and
Ductility
effect
These particular properties are markedly affected by cold work and the it produces on grain structures. Cold work rapidly increases the tensile strength while decreasing the ductility. The latter is evident by
the decrease in elongation.
The change
in these properties
is
directly
Carbon
Steel as
309
10
20
30
40
50
in
60
70
80
90
100
Reduction of area
drafting .percent
WW.
15.5.
Effect of cold
working on the elongation of carbon
steel.
(Legge)
amount of cold work. Figure 15.4* gives an indication of the effect of cold working on the tensile strength. The effect of cold work
related to the
is
directly related to the
carbon content of the
steel.
increases, the tensile strength increases
more rapidly and
As the carbon content to a greater
degree for each increment in the reduction in area. The converse effect is evident when the elongation is considered. This value reduces sharply with small amounts of cold work and does not vary
greatly with the carbon content (Figure 15.5). As the reduction in area* is increased, the effect on the elongation is very much smaller.
One should bear in mind that the figures referred to only approximate the properties resulting from cold work. While the amount of cold work is the prime varible having an effect on strength and ductility, it is not the
The term reduction of area is used in cold working to signify the amount that the cross section has been reduced by the cold working operation. It should not be confused with the same term used in tensile testing.
310
sole factor.
Composition
is
important, and the structure of the material
medium and high carbon steels. Another factor that causes variation in total effect is the cross-sectional area. Table 15.3 indicates the variations that exist as a result of this
has an
effect,
particularly for
factor.
Obviously a 1" bar
is less
affected at the center than a wire
would
be.
Table
15.3.
Effect of Cold Rolling
on the Tensile
Properties of a Steel Containing
0.14 Per Cent Carbon.
Property
Annealed
Reduced 30 per cent by

cold rolling
Reduced 60 per cent by

cold rolling
58,800 34,040 27,500 41.7

65.8
80,600 75,300 15 600
98,100
t)e>
inn
10 5 43
-ininn
22
58
Since the degree of cold work cannot be equal in

grain shape
is
all directions, the changed, mechanical twinning occurs, and preferred orien-
tation of the grains also results.
same
cal
While cold working generally has the on the properties of sheet and strip as it has on wire, mechanidirectionality shows up in sheet and is usually undesirable.
effect
Tensile
strength,
Yield
strength,
lb.
Condition
lb.
per
per
sq. in.
sq. in.

28
2
Hot-rolled strip Cold rolled 50 per cent
Annealed
40,000 96,000 33,000
38
The
effect
on the properties
varies with the carbon content.
reduc-
tion by cold rolling of 60 per cent has the following effect

Carbon,
per cent
on
strip:
Increase in tensile
strength, per cent
Decrease in
elongation, per cent
0.10 0.20 0.30 0.50
65 63
61
70
70 68 67
57
Carbon Steel
as
311
15.9. Variables Affecting the Properties of
Cold-Worked Wire
variables which affect the properties of cold-drawn Only a few may be referred to at this point. Approximately 85 per cent of all wire used today is drawn from either acid Bessemer or basic open-hearth low-carbon steels. Hard-drawn Bessemer wire is from 10 to 15 per cent stronger than the hard-drawn open-hearth wire. The tensile strength of Bessemer varies from 90,000 to 150,000 lb. per square in. while the open-hearth varies from 80,000 to 125,000 lb per sq. in. for similar sizes. A slightly increased elongation and a greater
are
There
many
carbon
steel wire.
ability to withstand twist
is
characteristic of the basic open-hearth wire.
The
effect of cold
able in wire.
work on the grain structure is particularly noticeThe fragmentation and distortion of the grains occurs
sections.
throughout the material since we are dealing with small cross
The
effect of galvanizing
low-carbon cold-drawn wire

is
in tensile strength, an increase in elongation, but this
a reduction complicated by
is
the induced brittleness as shown in a twist
test.
This
brittleness
is
probably caused by the formation of a brittle iron-zinc compound at the interface between the steel and the zinc coating. Here failure starts
easily
under the torsional
stresses.
High-strength wire for cables, ropes, and springs and for music wire
is
usually
made from
is
high-grade deoxidized
steel.
The steel
is
rolled into rods

ductility
tion of strength
and
medium and high-carbon which are patented. The best combinaresults from drawing a lead-patented rod.
Air patenting
cheaper, but the properties of the wire are not as good.
Wire drawn from either lead- or air-patented rod is, however, much superior to that drawn from a hot-rolled rod. Hard-drawn music and cable wire drawn from lead-patented rod has a strength of 160,000 to 220,000 lb. per sq. in. in sizes of 0.2 to 0.3 in. and of 280,000 to
400,000
lb. per sq. in. in sizes smaller than 0.1 in. in diameter. Despite the high strength and low elongation (0.5 to 1.5 per cent in 10 in.), the wire is very ductile and withstands many 90 bends and can be wrapped
around
itself
or rolled into long springs of small diameter without
cracking.
The wire used for the cables of large suspension bridges is an acid openhearth steel containing about 0.80 per cent carbon, 0.50 percent manganese, and low sulfur and phorphorus. The wire is drawn from patented
rods,
and the usual
size is
6 gage (0.192 in. in diameter)
It
has an average
tensile strength of 215,000 to 225,000 lb.
per
sq. in., a yield strength for a
permanent
set of 0.75 in. in 10 in. of 160,000 to 175,000 lb. per sq. in., an elongation of 3 to 7 percent in 10 in., and a reduction of area of 25 to 30 percent. Rope or cable formed from high-strength wire has, owing to its
312
which
is
construction, a breaking strength
and usually only 70
to 80 per cent, of the
never more than 90 per cent, sum of the breaking strength
of the individual wires.
15.10. Effect of Cold
Working on Dynamic Properties
As has been pointed out previously the transition temperature has an effect on these properties. Although cold working increases the endurance limit by about the same percentage as it increases the tensile strength, this means relatively little because most cold-worked material has such a
small cross section that standard highly polished specimens usually can-
not be
tested. For specimens of wire tested with the surface produced by the die, the endurance ratio varies from about 0.50, for material containing 0.05 per cent carbon, to 0.25 to 0.35, for high-carbon wire having a
tensile strength of 275,000 to 350,000 lb. per sq. in.
hard-drawn high-carbon wire

reheating the wire to effect
grains raises the ratio.
The low value for due to high internal stresses as a partial or complete recrystallization of the
is
largely
Cold working also decreases the resistance of carbon steel to impact. of this decrease depends primarily upon the amount of cold work and the carbon content high-carbon steels are embrittled to a greater degree than low-carbon materialsand upon other variables.
The magnitude
actual Izod impact value may be as low as 5 to 10 ft. -lb. In general, however, notched-bar impact resistance is not an important property of cold-worked material.
The
15.11. Heat-Treated Carbon Steels as Engineering Materials
As we approach the problem of heat treatment, it would be well to The two treatments that we are particularly concerned about are annealing and normalizing. Annealing is a process involving heating and cooling, usually applied to induce softening. Normalizing is a process in which steel is heated to a suitable temperature above the transformation range and is cooled in still air at room
review a few definitions.
temperature.
With
the
exception of carburizing and annealing of cold-worked
material, low-carbon steels are seldom heat treated.
Quenching generally
improves the properties but hardly enough to justify the cost. Mediumcarbon steels are frequently heat treated; the general improvement in
and ductility, in machinability, or in some other property due to thermal treatment is usually well worth while. Since high-carbon steels are used primarily for tools where high hardness is the chief requirement, these materials are always quenched and tempered. Frequently they are
strength
Carbon
Steel as an Engineering Material
313
also annealed or normalized to
improve machinability or the structural

steels
condition prior to quenching.
The
effect of heat
treatment on the properties of cast
having
been treated earlier in this chapter and carbon steels being more easily presented in the chapter on tool steels, it remains only necessary to briefly cover the properties of medium-carbon
steels after
the characteristics of treated high-
heat treatment.
it is
Referrring to our definitions as a basis,
easy to point out that
annealing
used primarily to improve the machinability of mediumcarbon steels. Comparing steel in the 0.30-0.60 per cent carbon range, we
is
find very small differences in the physical properties.

yield strengths are 6,000 to 10,000
lb.
The
is
tensile
and
per
sq. in.
lower while the elongaeffect
tion
and reduction
in area are a bit higher.
While no
evident on
the endurance ratio, slight increases in impact strength are apparent.
Hot-rolled
the
same
tensile properties.
carbon
steels
and normalized medium-carbon steels have practically This can be attributed to the fact that most after hot working are air cooled from temperatures very
structure,
it
Since normalizing produces a can be justified, economically, for large cross sections after forging or rolling. In addition to producing a finely divided evenly distributed carbide, it eliminates directionality due to mechanical
close to the normalizing temperatures.
homogeneous
fibering of inclusions such as oxide, slag, etc.
Owing to
steels are
the residual stresses introduced by quenching, medium-carbon seldom used in the quenched and untempered condition. The
little interest.
If,
properties of such materials are therefore of
however,
the internal stresses are relieved by tempering,

steels
If
quenched medium-carbon
become valuable
quenched
steel is
structural materials.
tempered
at a
temperature high enough so that
the particle size of the carbide changes, strength and hardness decreases
and
ductility increases almost uniformly as the
tempering temperature
in-
creases.
This
is
shown
in Fig. 15.6,
which
gives the ranges of properties
(included within the hatched bands) that result 95 per cent of the time
from tempering water- and oil-quenched 0.40

at increasing temperatures.
to 0.50 per cent carbon steels
Charts showing the quenched carbon and
effect of
tempering on the
alloy steels of varying carbon content are widely
number of handbooks. It should be emphasized, however, that these charts, while undoubtedly of value in
available in the literature and in a
indicating the properties to be expected most of the time, should never be used for specification purposes as individual specimens frequently vary
considerably from the average shown on the chart.
314
Tempering temperature, deg.

600
_l_
F.
800
1000
1200
600
800
500
600
700
300
400
500
600
700
Tempering temperature, deg. C.

Fic. 15.6. Effect of tempering on the properties of 05 in. bars of water-and oil-quenched 0.40 to 0.50 per cent carbon steel (S.A.E. 1045). (Sisco, The Alloys of Iron and Carbon, Vol. II, Properties, McGraw-Hill Book Company, Inc., New York,
1937, p. 200.)
Carbon
steel
per cent) are shallow hardening.

result that
containing the usual amounts of manganese (0.30 to 0.90 The time available to quench a carbon past the nose of the S-curve is usually less than a second, with the
steels
pieces or
even on severe quenching martensite forms only in very small on the surface of larger sections. Consequently, the structure of
a carbon steel
little
quenched in oil or even in water generally consists of a mixed with a relatively large amount of a ferritecementite transition structure. It will be shown in the chapters on hardenability that the mechanical properties of a quenched and tempered steel
martensite
are in general better
if
the structure before tempering was almost wholly
martensite rather than a mixture of martensite and one or more transition

constituents.
The primary reason why low-alloy steels are favored for quenched and tempered parts is that the alloying elements increase hardenability and thus increase the likelihood that martensite will be formed in large quantities when the steel is quenched in oil.
Carbon
Steed as an
315
15.12. Effect of Section Size on the Properties of Heat-Treated
Medium-Carbon
It is
Steels
well
known
by metallurgists generally, but by surprisingly few
engineers, that the properties of steel determined
on a small heat-treated
is
bar of
steel
may
not be representative of the average properties on a
large bar similarly treated.
The
effect of
mass on properties
important.
it
Since in
many
the
is
industrial applications large sections are used,
may be
more some
essential for the engineer to

cases,
know
the average properties or, in
surface. It
minimum properties than to know the properties at the not always practicable to test full-sized I beams or locomo-
tive axles; hence, data that indicate the effect of increasing size of section
are of considerable value.
heavy section cannot be cooled
as rapidly as a thin section; the in-
surface, transforms not only at a later time but at a higher temperature and therefore to a softer product than the surface. This results in differences in properties
terior of a heavy section, cooling
more slowly than the
between the exterior and the interior, possible distortion, residual stresses, etc. If we were to heat and quench a series of bars of SAE 1045 steel of " to 5", the smallest piece would cool most different diameters from \/ 2 rapidly and each succeeding piece more slowly
Size of
Bar
Surface Hardness
0.5"
1.0
59 58
41 35
2.0
3.0 4.0
30
5.0
24
study of the surface micros tructu re reveals that for the hardest
is
material the microstructure

ness decreases, the
predominately martensitc, and
as hard-
amount
of martensite decreases rapidly and pearlite in
survey taken of the cross section,

rate
varying degrees of coarseness appears. If the bars are cut and a hardness it would show the variation in cooling
from outside edge
to center by the variation in hardness. (Fig. 15.7).
In most large sections the cooling rate upon quenching decreases as if other variables do not enter importantly, hardness and strength decrease and ductility increases
the distance from the surface increases and,
Data for medium-carbon steel are given in Fig. 15.7. The effect is more pronounced in water-quenched than in oil-quenched material, and for the same quenching treatment the effect of mass is less pronounced with high tempering temperatures than with lower
slightly.
of mass
temperatures.
316
Diameter
Fie. 15.7.
Hardness of
series of
SAE
1045 steel bars heated
and quenched.
quenched and tempered carbon steels is 0.50 quenching treatment has introduced stresses which were not wholly relieved by tempering. When such stresses are present the ratio may be as low as 0.30 or 0.40. Quenching and tempering usually have a favorable effect on impact resistance, which, in general, is much
ratio of
The endurance
0.05 unless the
higher than that of a rolled steel of corresponding composition. Tempering increases the impact resistance of a quenched steel: if the Izod value
of a water-quenched 0.30 per cent carbon steel to 25
ft.-lb.
is
10
ft.-lb., it
will be 20
after
tempering at 700F. (400C.) and 45

.
to 65 ft-lb. after
elasticity
tempering at 1100 to 1200F. (595 to 650C.) The modulus of is, of course, unaffected by thermal treatment.*
QUESTIONS
1.
By what per cent has

the last twenty years?
the steel production in the United States increased in

steel in the
2.
Why
less
now
should the per cent production of carbon than it was before World War II?
United States be
* Sec footnote, p. 305.
Carbon
3.
Steel as an
steel
is
317
Give two reasons why a large tonnage of

castings every year.
melted and poured into
4.
melted? What is the general relation between structure, heat treatment, and properties of cast carbon steel? Does carbon steel have a low or high hardenability? How does the per cent of carbon in steel castings affect the hardness of the
How
is
steel for castings usually
5.
martensite produced when the castings are quenched? content in steel castings would be most likely to cause cracking during the quenching cycle? If cracking during quenching were a real possibility, what heat-treating cycle could be used to prevent cracking?
What carbon
6.
How
would the
rate of cooling
from die rolling temperature
affect
the
7.
properties of hot worked carbon steel? Name the three general classes of hot-worked carbon steel, and give the principal industrial uses of each class. Which of these three classes leads in
tonnage?
8.
List the principal variables that affect the properties of hot-rolled carbon steel. What tensile properties would be expected 95 per cent of the time
from hot-rolled
carbon
9.
steel
do manganese and phosphorus

steel?
is
containing 0.15 per cent, 0.30 per cent carbon? How affect the tensile strength of hot-rolled
50.
11.
the effect of carbon on notched-bar impact resistance? on endurance limit? on modulus of elasticity? Why are steels cold worked? What properties are ordinarily determined on cold-drawn wire and on cold-rolled bars? What is the effect of cold working on the yield point? How is the ductility of cold-worked wire usually determined? What is the general efTect of cold working on tensile strength and elongation? If a hot-rolled rod containing 0.15% carbon has a tensile strength of 60,000 lb. per sq. in. and an elongation of 25% in 10 in., what strength and elongation would be expected in drawing to wire with (a) a reduction
What
12.
40%? (b) a reduction of 70%? What percentage increase in tensile

of
strength can normally be expected
if
automobile fender
tion
steel
is
cold rolled
50%? What
is
the effect of this reduc(a) of
on the elongation? Give

(b) of
is
typcial tensile properties
small
sizes of
music wire, and

13.
wire for suspension bridges.
What
the general effect of cold working
on the impact
resistance
and on
the endurance limit of carbon steel?

14.
What
general classes of carbon steel arc heat-treated? What is the advantage of either annealing, or normalizing, or quenching and tempering such steels? What is the general effect of tempering on the tensile properties? For a tempering temperature of about 1000F., what would be the expected properties of a 1-in. round bar of 0.45% carbon steel (a) when quenched in water? (b) when quenched in oil?
If
15.
a small specimen of hot-rolled carbon steel containing 0.45% carbon has lb. per sq. in., a yield strength of 54,000 lb, per sq. in. an elongation of 20% in 2 in., and a reduction of area of 85%. what treatment can be used to increase these values to 103,000: 70,000; 25; and
a tensile strength of 93,000
60; respectively?
section,
With
these latter tensile properties for a heat-treated small

at the center of a 4-in.
what would be the corresponding properties
bar?
Low A Hoy
-
Steels as
CHAPTER
Robert E. Bannon, S.M., Professor of Metallurgy, Newark College of Engineering, Newark, New Jersey
Sic>fUND Lever.v Smith, M.Met.E., Professor of Metallurgy, College of Mines, University of Arizona, Tucson,
16
Arizona
Al.I.OY
steels are
about seventy years
old.
The
pioneer investigations of the effect of the various alloying elements on carbon steel were made between 1875 and 1890 in England, Germany,
France, and, to a lesser extent, the United States. Owing to the high price of alloying metals, the only use for these materials on a relatively
large scale was in armor plate. By 1910, alloying metals were much cheaper, and from then on industrial applications multiplied rapidly,
between 1915 and 1918 when there was an abnormal demand war materials. This demand, together with the approximately simultaneous development of the first "stainless" steel, stimulated metallurgists all over the world to investigate the effect on carbon steel of all possible combinations of many alloying elements. The result has been alloy steels by the hundreds steels containing one alloying element in addition to carbon, and steels containing half a dozen. Before World War II much of the research work on alloy steels was of the hit-or-miss type or was carried out to develop a steel that would
especially
for high-quality alloy steel for
duplicate the properties of a patented composition without actual infringement. One result of this frenzied research between 1910 and 1950
was a phenomenal growth of metallurgical literature; another was the development of many unnecessary alloy steels which, with slightly different compositions, duplicate the characteristics of
some of the older and better-known steels. However, some remarkable developments have resulted from this mass of hit-or-miss research, including several new steels and special ferrous alloys with splendid properties and of much
value to industry.
It
has also shown to engineers that alloy
steels
make
318
Low-Alloy
Steels as
319
possible the design of certain structures that
would be impossible with unalloyed carbon steels and cast irons. Without alloy steels the modern airplane, the streamlined railroad train, the modern automobile, and many other important developments would never have been brought to
their present efficiency.
The most
steels to
characteristic indication of the increasing value of alloy

is
the engineering professions
that their production has increased
in 1910 was was more than 3,000,000 tons, or about (i per cent of the total output of the steel industry. During 1944, when total steel production in the United States reached 89,642,000 net tons of ingots, alloy-steel ingot production was 10,630,000 net tons, which is 12 per cent of the total. The demand for alloy steels in the average prosperous postwar year, for example 1960, cannot be foreseen now; probably it will average about 8 or 10 per cent of the total. The amount of published data on alloy steels and cast irons is so large at a greater rate than total steel production.
The output
600,000 tons, or 2 per cent of the total; in 1939
it
that
it is
now
impossible for a metallurgist to

it is
know
everything that
is
going on
in this field;
a hard job even to keep
up with developments
in a single branch.*
To
present status of knowledge of alloy steels

of course, quite impossible to give
summarize adequately, in a single book, the is a difficult task, and it is,
many
details of their properties in
three short chapters. Consequently, the discussion in this
and the next

fundamentals
steels.
two chapters
is
restricted to a brief description of the characteristics of
these materials
and
to a concise outline of the metallurgical
in the relation of the
common
alloying elements to carbon
16.1. Balanced Compositions in Low-Alloy Steels
workable definition of alloy
steels
and a general
including
classification of
these materials into low-
and high-alloy
steels,
sitions for the low-alloy grades, are given in

steels,
Chap.
11.
common compoMany low-alloy
under specifications that give desired ranges for the various alloying elements and for carbon and manganese and usually maximum percentages for sulphur and phosphorus. Widely available in the literature and in handbooks are charts
especially the S.A.E. grades, are purchased
of average, typical, or
steels after definite
minimum
mechanical properties of the various
heat treatments.
Such
specifications
and charts
are
the result of long experience and arc of unquestioned value to engineers.

Alloys of Iron Research, founded in 1930 by The Engineering Foundation of New York, is reviewing this literature and correlating and summarizing the most important of the world's research on alloy steels and cast irons. Results are published in a series
of
monographs.
320
In the past few years, however, there has been a trend toward making use of steels of "balanced composition" or of definite hardenability rather than attaching too much importance to rigidly specified compositions and the necessity of accepting the data in mechanical-property charts. Steels of "balanced composition" are those in which the percentages of carbon and alloying elements, as well as the heat treatment (if any)
are varied to produce a desired combination of properties for a particular
application. Assume, for example, that for a structural application a steel
must have a minimum yield strength of 50,000 lb. per sq. must weld readily, and must not air harden after welding.
cent of alloy metal
in.
as rolled,
steel
con-
taining 0.30 per cent carbon, 0.75 per cent of alloy metal A,
per has the required strength and welds readily, but it

0.5
and
air hardens unless specially treated during or after welding. Because this composition is not balanced for this particular application, the carbon
is
reduced to 0.15 per cent, and the amounts of the alloying metals are
increased to 1.0
still
and
0.75 percent, respectively.
The
yield strength
is
well above the required

a better
minimum,
the material
still
welds readily,
the steel
but owing to
balance of the carbon and metals

a definite hardenability
A and B
does not harden in air after welding.
Producing
steel
with
is
primarily a problem in
balancing the composition correctly.

curacy (this
The
is
effect of
carbon and of the

considerable ac,
various alloying metals on hardenability

is
known with
two chapters) with the result that steels having a definite response to quenching can be readily produced by balancing the amounts of carbon and of the one or more alloying metals which are readily available.
discussed in detail in the next
an alloy steel for a specific applieconomy. Any alloy steel is more costly than plain steel of corresponding carbon content and should not be used for a structure or a machine merely because it contains one or more special metals, or because the steelmaker says it is better than some other steel. Alloy steel should be used only if considerable weight can be saved, or if the design can be materially simplified, and only if its total cost meaning the cost of the steel, of its treatment (if any) and of fabrication is less, when spread over the expected life, than the total cost of any competing
final criterion in the selection of
The
cation
is
material.
16.2. General Effects of the Alloying Elements
on Carbon
Steel
The
general effects of the
common
alloying, elements
on the structure and the next
and, consequently, on the properties of carbon steel are discussed in
Chaps. 12 and
13. It is
the purpose of the discussion in this
Low-Alloy Steels as Engineering Materials
321
two chapters to expand this and to show how these alloying elements are used to produce steels which are more satisfactory for certain applications than the unalloyed carbon steels. Hot-rolled carbon steel is low in cost and has excellent properties, and with certain carbon percentages these properties can be still further improved by heat treatment. Carbon steel also has several disadvantages as an engineering material. An important disadvantage is the rapid decrease of ductility as the carbon (and the strength) increases. Another
is
that,
because
it
is
shallow hardening,
optimum combinations
of prop-
can usually be attained only in small sections. A third disadvantage is that carbon steels, whether hot rolled or heat treated, suffer marked deterioration of properties when used at temperatures considerably below or above normal. Alloying elements are added to carbon steels to overcome, partly at least, these disadvantages.
erties in heat-treated material
The
principal effect of the alloying elements in low-alloy steels
is
to
increase hardcnability by heat treatment.
In addition,
all
the
common
alloying elements dissolve in the ferrite
and strengthen
it
to
Five of these elements also form carbides, but of these only
some extent. molybdenum,
vanadium, and tungsten have a strong carbide-forming tendency. Changing the properties of carbon steel materially by the formation of such carbides is important chiefly in the high-alloy and the tool steels, which
are discussed in later chapters.
The ferrite-hardening (and -strengthening) potency of the elements forming solid solutions with iron varies (increasing from chromium to
10
12
It
16
IB
20
22
Alloying
element
in alpha iron,
per cent
Fie. 16.1.
Effect of the
common
alloying elements,
when
dissolved in iron,
on
its
hardness. (Bain)
322
phosphorus),
ing effect
as
shown
in Fig. 16.1.*
is
None
of these, with the possible
exception of phosphorus,
is
so potent as carbon.
In
fact,
the strengthen-
small, provided that the carbon content

is
and the structure are

is
held constant. This
shown by the curves

If,
for the furnace-cooled speci-
mens plotted
240
in Fig. 16.2.f
however, the structure
altered by changis,
ing the treatment, that

230
220
210
by taking advantage of the effect of the element on hardenability,

*/
ft
o\
200
190 180
f
V
y
c
i
of
as
amounts an alloying clement may, shown in Fig. 16.2, have

small
0/
a great effect.
16.2
In
fact. Fig.
shows that chromium

so that high tensile-
4 no
I
160
1
increases the hardenability
f>
V
enough
1
/
150
140
/ /
( *
strength values result from
moderately
cooling.
slow
(air)
/
.
8
.130
-n
/
tiro10tr< / curn wee xjicg c
16.3. Effects of Phosphorus, Manganese,
1ri2o
"no J
100
and Silicon
Of the alloying elements which dissolve in the fer__ __ __
0.30
90
80
%c
rite,
phosphorus,
is
as
just
-- ~OJ0
noted,
its
the most potent in
70
strengthening
16.1)
.
action
60
50
12
(Fig.
The
addition
3 4 5 Chromium, percent
of 0.01 per cent of phos-
phorus increases the
tensile
and the
Fie. 165. Effect of carbon, chromium, and cooling rate on the tensile strength of carbon steels.
yield strength ap1,000

is,
proximately
sq. in., that
(Wright and Mumtna)
lb. per by about as
E. C. Bain, Functions of the Alloying Elements in Steel, American Society for Metals, Cleveland, 1939, p. 66. Data reported by C. R. Austin (Trans. Am. Soc. Metals,
v. 31,
is slightly less, than those Bain's data in Fig. 16.1. Neither Bain's nor Austin's data arc very precise, because the iron used was not of high purity and the slope of the curves shown in Fig. 16.1 may be altered by future work. The ferrite-strengthening cirect of the alloying
in small
1943, p. 331) indicate that the strengthening effect of percentages is greater, and that of chromium
manganese and molybdenum
shown by
elements
is,
however, not of great importance.
t Plotted from data by E. C. Wright and P. F. Met. Engrs., v. 105, 1933, pp. 77-87.
Mumma,
Trans.
Am.
Inst.
Mining
Low- A Hoy
Steels as
323
much
by carbon. This strengthening is, elongation and reduction of area than in the case of carbon addition. f Another advantage is that phosphorus, either alone or more intensely if copper is present, increases the resistance of the steel to atmospheric corrosion. Phosphorus is favored as an alloying element chiefly in low-carbon steels that are used in the
as these properties are increased
moreover, attained with
less sacrifice of
rolled or normalized condition.
Manganese, added to steel in amounts in excess of that necessary to combine with the sulphur and to deoxidize the metal 0.1 to 0.25 per cent for most steels partly dissolves in the ferrite and partly replaces iron in iron carbide (Fe a C) to form a carbide that may be represented by (Fe,Mn) 3 C. If the manganese is below 2 per cent, the amount of this carbide formed is small. Moreover, this substance is so much like iron carbide that it has in itself no appreciable effect on structure and properties. The effect of manganese in solid solution is less than that of phosphorus; the amount by which 0.01 per cent manganese increases the tensile strength varies with the carbon content from about 100 to 500 lb. per sq. in.; it increases the yield strength somewhat more than this. A yield strength of at least 50,000 lb. per sq. in., together with good ductility,
0.30 per cent carbon steel by
can be readily attained in hot-rolled structural shapes of 0.20 to adding 1.00 to 1.75 per cent manganese.
effect
Manganese in amounts exceeding about 0.75 per cent has a strong on the hardenability of carbon steel. In steels that are heat treated,
an advantage, since
less
it
this effect is
permits the use of
less
drastic quench-
ing mediums, which means
distortion or cracking. In hot-rolled struc-
tural steel increased hardenability
may
be a disadvantage, unless the
carbon
is
very low, because air hardening
may
occur in cooling from the

In general, manganese
this
is
rolling temperature with serious loss of ductility.
reduces the ductility of untreated carbon the carbon is low.

Silicon in the
Its effect
steel,
but
not serious
if
on
;
tensile strength
it
(Fig.
16.1)
amounts present in low-alloy steels dissolves in the ferrite. is somewhat greater than that of manganese raises the yield strength and yield ratio and does not
Its effect
appreciably reduce ductility.

resistance
so strong as that of manganese. It has
on hardenability is strong but not no appreciable effect on corrosion

In other than the low-alloy
is
when
present in small amounts.

this
structural steels discussed later in
chapter, silicon
used as an
alloying element in one important group of spring steels that contain
about 2 per cent

f
silicon, 0.60 to 0.90
per cent manganese, and 0.50 to

is,
Phosphorus
is
likely to
is
make
steel
cold short, that
brittle
when
cold, unless
the carbon percentage
low.
324
140
70
,Reducfion ofarea_
Tensile strength.,
I
per cent
120
Reduction of area.
percent -
601
^
5?
100
50
=9
80
40 c
a c
c
60
30c
o
40
(with
(A) Nickel carbon 0.20%)

I
(B) Chromium
(with carbon 0.20%)
I
20
3 2 4 Alloying element, per cent 2
3
Fig. 16.S.
Effect
of
(A)
nickel
and
(B)
chromium on
the
tensile
properties of
rolled carbon steels.
(Bain and Llewellyn)

electric apparatus.
(the S.A.E. 9200 series)
and
in certain steels for
16.4. Effects of Nickel
and Chromium
Nickel dissolves in the ferrite of carbon steel and exerts a strengthening effect that is somewhat less than that due to phosphorus, silicon, or
manganese
(Fig. 16.1)
The
is
effect of nickel
on the
tensile properties of a
0.20 per cent carbon steel the hot-worked
plotted in Fig. 16.3A,* which shows that in
(unhardened) condition nickel has little effect on elongation and reduction of area; it does, however, raise tensile and yield
strengths considerably.
In the heat-treated condition, nickel steels are characterized by high impact resistance, which remains high at low
temperatures.
Nickel does not form a carbide.

steels
It increases
the hardenability of carbon
mildly, being less effective in producing deep hardening than molybdenum, manganese, or chromium. It also increases the resistance
Figures 16.3A
and B are based on data quoted by E.
C.
Bain and
F.
T. Llewellyn,
Trans.
Am.
Soc. Civil Engrs., v. 102, 1937, p. 1249.
Low-Alloy Steels
of carbon steel to
as
especially in
325
some forms of corrosion,
combination with
copper.
and also forms carbides if the carbon and 16.2 its ferrite-strengthening effect when in solid solution is weaker than that of any of the common alloying elements, but it increases hardenability greatly, as shown by
dissolves in the ferrite
Figs.
16.1
is
Chromium
high.
As indicated by
the curves for the air-cooled specimens in Fig.
16.2.*
The
effect of
chromium on
the tensile properties of small air-cooled (hot-rolled) secis
tions of a 0.20 per cent carbon steel

sections, the increase in tensile
plotted in Fig. 16. 3B.
In such in
and yield strengths and the decrease
elongation and reduction of area are

ing effects of nickel. Although
much
greater than the correspond-
increases the impact resistance of very
function
is
is a toughening element and low carbon steels, its primary to increase hardenability, decrease the magnitude of the mass if
chromium
effect, and, of course, increase corrosion resistance, especially
3
is
per cent
a
is
present.
Owing
to
its effect
on hardenability,
more than chromium
common
as
addition to the S.A.E. nickel steels in the proportion of
about half
much chromium
is
as nickel.
steels,
Chromium
where
it
used widely as an alloying element in high-carbon
forms a carbide and also dissolves in the ferrite. When these materials are quenched and tempered at a low temperature, they are very
hard and have good wear resistance. They contain about 1.0 per cent carbon and 0.75 to 1.50 per cent chromium and are used for tools, dies, and ball bearings.
16.5. Effects of the
Other
Common
Alloying Elements
The
other alloying elements used in low-alloy steels are copper, molybto a very limited extent, tungsten. Copper, in the
fer-
denum, vanadium, and,

rite,
small amounts added to carbon and low alloy steels dissolves in the
but its effect on tensile and impact properties is small. If more than 0.6 per cent is present, the steels, as noted in another chapter, may be precipitation hardened. Copper is most useful as an alloying clement for
The addition of 0.10 to 0.40 per cent much that a large proportion of lowcarbon sheets, especially when very thin, and many of the new highstrength structural steels now contain copper.
its effect
on atmospheric corrosion.
reduces this variety of corrosion so
low (below 0.08 or 0.09 per ceni), chromium up to approximately on the hardness and strength when steel is air cooled. For example. Franks (R. Franks. Trans, Am. Soc. Metals, v. 35, 1945, p. 616) reported an increase in tensile strength from 55,000 to 70,000 lb. per sq. in. in 0.08 per cent carbon steel when chromium was increased from to 3 per cent. With 6 per cent chromium, the strength was 197,000 lb. per sq. in.
is
* If the carbon
3.0 per cent has only a small effect
326
are strong carbide formers.
Molybdenum, vanadium, and tungsten

the
In
amounts present
in low-alloy steels a portion of these three elements

it moderately on austenite grain
dissolves in
16.1).
the ferrite and probably strengthens

is
(Fig.
size.
Vanadium
valuable chiefly for
its effect
per cent are usually fine-grained and are not so readily coarsened by overheating as some of the other low-alloy steels. Molybdenum, vanadium, and tungsten all contribute to deep hardening, and the first two are very effective in small amounts. Molybdenum
or vanadium
is
Steels containing 0.10 to 0.20
used in a
number
of low-alloy steels,
especially
the
S.A.E. grades, usually together with another alloying element, such as
chromium, ability and

ores
is
nickel, or
manganese. Owing to
its
strong effect on harden-
to the fact that the world's largest deposit of
located in the United States, the use of
molybdenum molybdenum as an alloy-
ing element has increased greatly in the last few years. The most important function of tungsten and, to a lesser extent, of molybdenum is to increase the hardness and stability of the structure of alloy steels, especially at elevated
temperature. For this purpose, relatively large amounts
are required, usually in conjunction with

in a later chapter.
chromium. This
is
discussed
16.6. Low-Alloy Structural Steels as Engineering Materials
ing
As noted previously, there are two broad classes of low-alloy engineersteels: the structural steels and the S.A.E. steels. The structural steels
a
have
fully
higher yield strength than carbon steels; they are usually of carebalanced composition and are used for structural purposes without heat treatment other than natural or controlled cooling after hot rolling.
S.A.E. steels are, in general,
The
much more
costly than the low-alloy
structural steels
and should be heat
treated to obtain
optimum
properties.
In contrast to the structural steels, in which the function of the alloying elements is primarily to strengthen the ferrite and to produce a fine
when the material is air cooled, in the S.A.E. steels the alloying elements also affect the response of the steel to thermal treatment and, in a few cases, harden it by forming carbides.
pearlite
steels of high yield strength are forty years old. One of the contained about 0.25 per cent carbon and 1.50 per cent manganese and was used between 1900 and 1915 to reduce dead loads in long-span
Low-alloy
first
bridges
and steamship construction

later, a
in the
United States and
in
little
deoxidized carbon steel
(misnamed
silicon steel)
England. was
developed in the United States. This material contained 0.25 to 0.35 per cent carbon, 0.70 to 1.00 per cent manganese, and 0.20 to 0.40 per cent silicon. In the hot rolled condition the yield strength of these two steels
Low- Alloy
was 45,000
lb.
Steels as
327
per sq. in. or higher, and a considerable tonnage was used between 1915 and 1928. A steel o similar yield strength, containing 0.12 per cent carbon, 1 per cent silicon, and 0.70 per cent manganese, was developed in Germany in 1925 but, owing to its variable quality, it was not used long. This German steel is important because it was the first attempt to produce a steel that had high yield strength but was low enough in carbon to be welded readily without the troublesome brittleness in and around the weld that frequently results from welding a steel containing more than 0.20 per cent carbon and 0.75 per cent manganese.
for bridges
About
fifteen years ago, the depression
stimulated steel manufacturers
to investigate the possibility of
tailormade
steel
producing a low-cost, easily weldable, that would have strength properties and resistance to
atmospheric corrosion
much
superior to those of ordinary structural
steel.
The
depression also focused the attention of engineers upon the desir-
ability of reducing cost in certain structures
tions of a steel of higher strength,
The
result
was that
by the use of smaller secand by welding instead of riveting. the steelmakers produced the steels and the engineers
structures.
used them for railway rolling stock, streetcars, trucks, buses, cranes, steam
shovels,
and similar
One
of the essential factors in this adis
vance was the realization that tensile strength

sistance to buckling or crumpling,
essential,
not always the best
criterion of the suitability of a steel for certain structural uses, that re-
which is related to yield strength, is and that increased corrosion resistance is an economic necessity
have,
as rolled,
in
many engineering structures. The low-alloy structural steels

and
a resistance to
approximately twice
the yield strength of low-carbon steel,

weldability,
combined with high ductility, easy atmospheric corrosion which is much
higher than that of carbon steel. In tonnage lots, they cost 15 to 50 per cent more than comparable sections of plain carbon steel. Owing primarily to their high yield strength, it is possible to reduce the size of a
section 25 to 35 per cent
ness.
and
still
design a structure that has ample
stiff-
Despite somewhat higher fabricating and machining costs, it is frequently possible to save 10 to 15 per cent of the cost of a structure by
the use of the properly selected low-alloy steel.
16.7. Composition
and Properties of the Low-Alloy Structural

some
thirty of these steels
less
Steels
The
first
of the present crop of
was made in
1929 and contained 0.30 per cent or
carbon, 1.05 to 1.40 per cent

to 0.60 per cent chro-
manganese, 0.60
to 0.90
per cent
trade
silicon,
and 0.30
mium. Known under the
name
of Cromansil, this steel attracted
328
considerable attention, and a number of others followed it quickly under such trade names as Cor-Ten, Man-Ten, Hi-Steel, Jal-Ten, Konik, Yoloy,
and others. As a group, the low-alloy structural steels are characterized by low carbon (to improve ductility and weldability, and to prevent air hardening) and by the presence of at least two, and sometimes as many as six, of the following alloying elements: manganese, silicon, nickel, copper, chromium, molybdenum, phosphorus, boron, and vanadium. During the war titanium was an important minor constituent in these steels. The percentage of alloying elements is usually low. Manganese is 1.70 per cent or less, with an average of about 1.25 per cent. Silicon is per cent or less, the usual amount being between 0.20 and 0.70 per cent. Nickel varies from 0.3 to 2.0 per cent, and copper, owing to its favorable effect on resistance to atmospheric corrosion, is usually at least 0.10 per cent and may be as high as 1.50 per cent. Molybdenum, if present, is less than 0.40 per cent, and chromium is less than .5 per cent. Phosphorus, if used as an alloying element, is between 0.05 and 0.20 per cent, vanadium up to about 0.1, and boron around 0.003 per cent. In all the low-alloy structural steels the composition is balanced to
1 1
Otiscoloy, N-A-X, Tri-Ten, Carilloy T,,
ensure for hot-rolled sections a

sq. in., a tensile strength of
minimum
yield strength of 50,000

lb.
lb.
per
70,000 to 105,000
per
sq. in.,
and an elon-
|>er cent in 8 in., depending upon composition. The impact resistance of most of these steels is satisfactory; usually it is higher than 25 ft. -lb. Claims have been made that the endurance ratio is higher than for carbon steels, but not enough data have accumulated yet to accept this as generally true. As a group, the steels have a resistance to atmospheric corrosion considerably superior to that of carbon steels.
gation of 18 to 30
These
steels are
outstanding in the relation of properties to
cost.
There
be some casualties in the next few years, but it seems certain that some will survive and that the survivors will be widely used as structural materials where a saving in weight is important.
are too of
will
many
them now; probably there
16.8.
The
S.A.E. Low-Alloy Steels
Of
the
the alloying elements in low-alloy steels, nickel and
chromium were
used commercially. Steels containing about 3 per cent nickel were forged into armor plate between 1885 and 1890, causing a revolufirst
tion in naval warfare.
Chromium was
0.60 per cent were installed as
main members
used even earlier: steels containing of the Eads bridge over
the Mississippi River at St. Louis in 1874. Extensive use of the steels included in the S.A.E. grades began about 1910. It has been claimed with
Low-Alloy Steels
as
329
considerable justification that the availability of these steels at a fairly
reasonable cost was the chief factor in the development of the automotive and aircraft industries, and that without them the weight per horse-
power of internal-combustion engines would be efficiency less than half, what it is today.
Nearly
fifty
at least twice,
and the
years ago, the Society of Automotive Engineers proposed
specifications for the composition of a
number
of low-alloy steels that
were being used at that time by the automotive industry. These specifications were adopted in 1911, and since that time the compositions recommended in the S.A.E. specifications have been used widely in all branches of mechanical manufacturing in the United States and abroad. Revision and extension of the specifications have kept pace with progress in the automotive and steel industries, with the result that engineers generally look upon the S.A.E. steels as the most satisfactory low-cost, high-quality steels commercially available for the production of automotive and aircraft equipment and machine tools, and they know that
these steels will give satisfactory service
when
properly treated. and used.
in 1941, the Society of Automotive Engineers in collaboration with the
American Iron and
Steel Institute
made major changes
in the composi-
These changes consisted primarily of adopting narrower ranges for chemical analysis as made on a specimen representing a whole heat, plus an allowance for check analyses on individual specimens from the same heat. At the same time the American Iron and Steel Institute issued standard analysis specifications for lowalloy steels, which are known as A. I.S.I, specifications and which, in general, follow the same system of classification as is used by the S.A.E.
tion ranges of their standard steels.
The
S.A.E. specifications for low-alloy steels for 1956 cover 114 steels
series.
divided into eight

the
These
are
shown
in
Table
16.1.*
The
A. I.S.I,
specifications cover 170 steels divided into 13 classes, eight of
which are
same and have the same
series
numbers
as the S.A.E. grades.

is
The
16.1.
system of classifying these low-alloy steels
evident from Table

steels;
Series 1300 comprises the
medium-manganese
2300 contains
3.50 per cent nickel;

series
and 2500 contains 5.00 per cent nickel. The 3100 contains nickel and chromium but the amounts are different in
In addition to specifications for low-alloy steels, both the Society of Automotive Engineers and the American Iron and Steel Institute have standardized unalloyed carbon steels. The S.A.E. specifications cover 22 carbon steels (series 10XX) ranging from less than 0.10 to 1.05 per cent carbon, and 10 high-sulphur free-machining steels (series 11XX) containing up to 0.15 per cent sulphur and as much as 1.65 per cent manganese. These specifications are given in the S.A.E. Handbook, 1956 edition, pp. 51-55, and in Steel Products Manual, Sec. 2. Carbon Steel, Semi-finished Products, published by the American Iron and Steel Institute, New York, 3d rev., June, 1943.
330
the 3100, and 3300
series.
The 4000
series is
made up
of plain molyb-
denum
chromium-molybdenum, the 4600 and 4800 series are nickel-molybdenum, and the 4300 series which is popular in the aircraft industry contains nickel, chromium, and molybdenum. The last two digits of an S.A.E. or an A. I.S.I, number indicate the middle
steels,
the 4100 series of
of the carbon range; thus, a 2330 steel contains 3.25 to 3.75 per cent
nickel
steels
is
and 0.28 to 0.33 per cent carbon. The larger number of A.I.S.I. due chiefly to more detailed specifications according to carbon
16.1.
Table
A.I.S.I.
Basic
Numbering System and Composition Ranges

*
for
S.A.E.
and
Low-Alloy
Steels
Composition range, per cent

Series
S.A.E.
or A.I.S.I.
Molyb-
Manganese
1300 2300 2500
1.60 to 1.90
Nickel
Chromium
denum
Other
3.25 to 3.75 4.75 to 5.25
3100 3300 4000 4100 4300 4600 4800 5100 5200

6100 8600 8700 9260 9300 9800
0.70 to 1.00
1.10 to 1.40 3.25 to 3.75
0.55 to 0.75 1.40 to 1.75
1.65 to 2.00 1.65 to 2.00 3.25 to 3.75
0.80 to 1.10 0.40 to 0.90
0.20 0.15 0.20 0.20 0.20
to 0.30 to 0.25
to 0.30
to 0.30
to 0.30
0.70 to 0.90
1.20 to 1.50
0.80 to 1.10 0.40 to 0.70 0.40 to 0.70 0.40 to 0.60 0.40 to 0.60 0.15 to 0.25 0.20 to 0.30
0.15 min.
1.80 to 2.00
Si
3.00 to 3.50 0.85 to 1.15 0.40 to 0.70
1.00 to 1.40 0.70 to 0.90
0.08 to 0.1 0.20 to 0.30 0.15 to 0.25
t86BO0
0.40 to 0.60
Boron, .0015 to .0020
'S.A.E.
Steel Products
Handbook, Society of Automotive Engineers, New York, 1956, pp. 50-55; Manual, Sec. 10, Alloy Steels, American Iron and Steel Institute, New York,
3d
rev.,
t xxBxx,
June 1945, pp. 13-30. B denotes Boron Steel.
331
percentage. For example, in the S.A.E. series 4100 there are 10 steels, cov-
ering a carbon range from 0.17 to 0.53 per cent; in the corresponding
A. I.S.I, series there are 18 steels to cover the same range of carbon. In addition to carbon
and alloying elements, these

it
specifications give
ranges for manganese (regardless of whether

silicon, sulphur,
letters that identify the process
is
an alloying element)
and phosphorus. The A.I.S.I. specifications also carry by which the steel was made: A for the basic open-hearth, D for the acid open-hearth, and E for the electric-
furnace process.
Some
steels,
of the low-carbon S.A.E. alloy steels do not conform exactly to
the ranges the

is
shown in Table 16.1. For example, in the low-carbon 4100 chromium is lower (0.40 to 0.60 per cent) and the molybhigher (0.20 to 0.30 per cent)
0.30 per cent carbon.
denum
than in the
steels
containing
more than
The manganese
in most standard S.A.E.
The 2300 series is typical; manganese is 0.40 to 0.60 per cent in the low-carbon grades, and 0.60 to 0.80 or 0.70 to 0.90 per cent in the higher carbon steels.
steels varies widely.
The
standard S.A.E. and

steels
A.I.S.I. steels are
only a small fraction of the
low-alloy
slightly,
used commercially.
but
16.1.
many
of these other steels vary vary greatly, from the standard compositions given in
Some
Table
by the
is
A
X.
slightly, usually in
letter
few of them, which are widely used and which vary only one element, are given S.A.E. numbers prefixed
is
An example
16.2.
X3140, the nominal composition of which
given in Table
In this steel the
chromium
is
0.70 to 0.90 instead
of 0.55 to 0.75 per cent.
16.9. The S.A.E. Low-Alloy Steels as Engineering Materials Composition, series number, and recommended heat treatment for all the S.A.E. steels are given in the S.A.E. Handbook and in many other
and need not be considered here. These steels more expensive than the low-alloy structural steels, and, furthermore, they must be heat treated to be of the greatest value. They are widely used in the construction of automobiles and aircraft especially engines and for machine tools, particularly for highly stressed parts such as crankshafts, camshafts, axle and other shafts, gears, bolts, studs, steerreadily accessible sources
are
ing knuckles, spindels,
collets, and valves. few of the S.A.E. low-alloy steels are used in the rolled and air cooled conditions; there is one series, discontinued as standard by S.A.E. a few years ago, which contained less than 2 per cent nickel, that was widely used for engine bolts and boiler plate and, to a lesser extent, for
The medium-manganese series 1300 is also used occasionally as rolled and air cooled, and a few of the low-alloy
bridge and ship construction.
332
structural steels discussed in

a small
16.7 are essentially S.A.E. 1320 containing
amount
of copper to increase resistance to atmospheric corrosion.
Most of the S.A.E. steels are used in applications, especially in moving where stresses are relatively high, and they must be quenched (usually in oil) and tempered to secure the maximum combination of strength and ductility. When properly heat treated, they combine high ductility with high strength. Compared with carbon steels of the same tensile strength and hardness, heat-treated low-alloy steels have 30 to 40 per cent higher yield strength, 10 to 20 per cent higher elongation, and
parts,
35 to 40 per cent higher reduction of area.

S.A.E. steels
strength.
is
The impact
resistance of the
frequently twice that of a carbon steel of the same tensile

steels as
The most
class
is
important characteristic of the S.A.E. low-alloy

smaller.
It is
is
that they are deeper hardening than carbon steels; in other words,
is
harden large sections of lowMoreover, as the critical cooling rate is much lower, oil quenching can be used to attain high strength and hardness with less possibility of distortion or the introduction of high internal stresses.
the mass effect
easier to
alloy steels throughout than
the case with carbon steels.
Tempering temperature, deg. C.
700
Fig. 16.4.
900
1I0O
1300
800
1000
1200
1400
Tempenng temperature, deg. F.

Elfect of
chromium (S.A.E. {S.AM. Handbook,
3140) and 1941)
tempering on the tensile properties of oil-quenched (A) nickel(B) nickcl-chroniium-molybdenum (S.A.E. 4S40) steels.
Low-Alloy
16.10.
Steels as
Steels
333
The New Metallurgy of Low-Alloy
hardness
For many years charts of average or minimum tensile properties and (occasionally impact resistance as well) of S.A.E. and other low-alloy steels, as quenched and tempered at various temperatures, were
published in the S.A.E.
in other readily available sources. by these charts were, moreover, commonly used by engineers in the design of machines and other important equipment. Figure 16.4 shows two such charts.
Handbook and
The
properties indicated
These charts of properties were considered invaluable because of the that each alloy steel had a set of mechanical properties after heat treatment that was characteristic of, and due to, its chemical composition, and that, in general, these properties could be reproduced at will by subjecting any steel of the same specified composition range to the same thermal treatment. This assumption is statistically valid, but the accompanying and widely held assumption that certain low-alloy steels have inherently a better combination of strength and
commonly held assumption
ductility than others
(Fig. 16.4)
is
not valid, at least insofar as the
as-
sumption
is
based on charts of mechanical properties.
Table
16.2.
Per Cent Carbon) Quenched in Oil and
Typical Tensile Properties of S.A.E. Low-Alloy Steels (0.35 to 0.45 Tempered at 1000 F. (540 C.) *
Nominal chemical
Steel
composition, per cent
No.
Tensile strength, lb. per

sq. in.
Yield
strength,
lb.
Elongation
in
Reduction
of
area,
per
in.,
sq. in.
C
1340 2340 3140
0.40 0.40 0.40 0.40 0.40 0.40 0.40
Mn
1.75 0.75 0.75 0.75 0.75 0.65 0.65
!
Ni
Cr
Mo
141,000 137,000 143,000 155,000 170,000 184,000 151,000 120,000 120,000 119,000 1 30,000 147,000 160,000 131,000
per cent 18
21
per
cent
3.50
1.25 1.25 1.75
52 60
57 55 56
X3140
4140 4340 4640
0.60 0.75
1.00
0.65
1.80
0.20 0.35 0.25
17 17 16
15
52
56
19
Data obtained on standard
test
specimens machined from bars
less
than
.5
in.
in diameter.
Some
(540C.)
typical tensile properties of S.A.E. low-alloy steels containing
0.35 to 0.45 per cent carbon as
quenched in oil and tempered at 1000F. Table 16.2. These properties were collected by Hoyt* and are undoubtedly representative. For a definite heat treatment.
are given in
334
tensile
and
yield strengths vary as
much
as 40,000 lb.
per
sq. in.,
and the
is
variation in ductility as measured by elongation
and reduction
of area
considerable.
The
existence of such
lists
of properties
(and published
charts of properties)
makes
it
understandable that engineers designing
a crankshaft for an internal-combustion engine, for instance, believed that there

is
a marked inherent difference in the mechanical properties

in
of heat-treated low-alloy steels.
Two
relatively recent events
ferrous metallurgy were mainly re-
sponsible for the development of what might be called a

of low-alloy steels
new philosophy
our ideas about the relation between composition and properties. They were also primarily responsible for the disappearance of mechanical-property charts from the S.A.E. Handbook (in 1942) and from many other publications and for the almost overnight development during World War II of the National Emergency steels, an accomplishment in which American metallurgists can take much justifiable pride. These two events were the work of Janitzky and Baeyertzf on the similarity in mechanical properties of heat-
and
for changing greatly
treated low-alloy steels,
and the
practical application of the principles
underlying the relation of carbon, alloying metals, and hardenability. The relation among carbon percentage, the amount of alloying ele-
ments present, hardenability and other variables, and the properties of steel is discussed in detail in the next two chapters. In brief, this relation is as follows: If per cent of nickel and N per cent of chromium pro duce a structure of 50 per cent martensite at the center of an oil-quenched 2-in. bar of steel containing 0.45 per cent carbon; and if X per cent of manganese and Y per cent of molybdenum produce the same structure in an oil-quenched bar of the same size and approximately the same carbon content, the tensile properties of the two steels after tempering to the same hardness will for all practical purposes be identical.
16.11. Similarity of Properties of Heat-Treated S.A.E. Low-Alloy

Steels
Some
of the data obtained by Janitzky
in Figs. 16.5
and
16.6.
and Baeyertz are reproduced These investigators quenched 1-in. round bars of
S. I.. Hoyt, Metals and Alloys Data Book, Reinhold Publishing Corporation, New York, 1943, 334 pp. + E. J. Janitzky and M. Baeyertz, in Metals Handbook, American Society for Metals, Cleveland, 1939, pp. 515-518. The work of Janitzky and Baeyertz on the similarity of properties of heat-treated low-alloy steels was antedated by several years by work done but not published by the metallurgical laboratory of General Motors Corporation which resulted in the removal of the old-style property chart from General Motors Standards several years previously. The first publication of a part of this
work was by A.
L. Boegehold,
Metal Progress, Feb., 1937, pp. 147-152.
Low-Alloy
260
Steels as
335
240
y.
^
|220
b
9
"7
200
Yields* -en -jtn- ,
A
G
180
7
t*~
1*160
7
1
Wc ter quenched
1
140
&
&
120
&9
S. A. .1330
2330.
3130
v
a
4130
5130
613
A
240
100
80
120
160
200
Yield strength
thousand lb.pcrsq.in.
40 60 20 Elongation and reduction of area, per cent
Fig.
steels
165. Tensile properties of water-quenched and tempered S.A.E. containing about 0.30 per cent carbon. (Janitzky and Baeyertz)
low-alloy
and oil and tempered them at recommendations given in the S.A.E. Handbook. Yield strength, elongation, and reduction of area were plotted against tensile strength with the result shown in Figs. 16.5 and
a of S.A.E. alloy steels in water
number
various
temperatures in accord with
is little
For tensile-strength values of less than 200,000 lb. per sq. in., there difference in the steels. At high strength values considerable scatter is evident; this is undoubtedly due to internal stresses caused by quenching rather than to any inherent difference in the steels.
16.6.
The data reported by Janiuky and Baeyertz in 1939 have been confirmed since by a number of other investigators. Patton,* for example,
plotted tensile properties heats of 37 grades of carbon
and Izod impact resistance for 409 tests on 180 and low-alloy steels. The steels used were
mostly N.E. and S.A.E. grades, but a considerable number of others were included; all of the steels, however, were of such a composition that it was reasonably certain that the test specimen hardened completely in
quenching. For tensile-strength values of 100,000 to 200,000
lb.
per
sq.
W.
G. Patton, Metal Progress,
v. 43,
1943, pp. 726-733.
336
280 260
-r
r
1 9
*H
1
j
j-240
a.
09
n
Yiela'strength>.
A
6*
*
A
//I
_220
"2
A
PI
200
3
_._L--_ (* 3
-a-
?/n
l80
c
Oil quenched
I "160
.s
/
r
* S.AE.234S 3115 3240

.
L
,
140
f-
43104fi-
J
120
^Reduction ow Of area -> .
1/ '
S/15
1 1
h
[a
1
80
120 160
200 240 Yield strength, thousand lb. per sq. in.
40 60 Elongation and reduction of area, per cent 20
tempered S.A.E. low-alloy steels Fie. 16.6. Tensile properties of oil-quenched and containing about 0.40 to 0.45 per cent carbon. (Janitzky and Baeyertz)
in.,
yield-strength, elongation
(in
in.),
and
reduction-of-area values
at least two-thirds of fell close to a line representing expected values in within a band that varied values fell the tests, and 90 per cent of the values. expected not more than 5 per cent from the Of the values that varied more than 5 per cent from the expected
steels values the variation was such that no single steel and no group of steels. It was of or group could be considered superior to any other steel above 200,000 tensile strength evident that steels heat treated to a
also
lb.
were responsible for conwas more erratic than siderable scatter in properties. Impact more from the line of excent or other property values, varying 20 per
per
sq. in.
contained internal
stresses that
resistance
pected values.
recent correlation of mechanical properties, for low-alloy 16.7.* steels containing 0.30 to 0.50 per cent carbon, is shown in Fig.
The most
Courtesy
American Society
for Metals.
337
100
120
140
160
180
200
Tensile Strength,
1000 psi
Normally expected mechanical properties (heavy line) and average variaquenched and tempered low-alloy steels containing 0.30 to 0.50 per cent carbon (Metals Handbook, 1948, page 458).
FlC. 16.7.
tion (hatched band) of
16.12.
The Engineering
Properties of the S.A.E. Low-Alloy Steels
Some
typical tensile properties of S.A.E.
carbon and low-alloy
steels,
including a few triple-alloy (N.E.)

are given in
steels, collected
from various sources

are given in this
lb.
Table
16.3.
All the steels
whose properties
300)
.
tabulation were heat treated to a tensile strength of 150,000

(Brinell hardness
ties of
number approximately
is
The similiarity
is
per sq. in. in proper-
the low-alloy steels
evident; also evident
the inferior yield
338
strength and ductility of the carbon steels which are inherently shallow hardening in the sizes treated, namely, 1- to li^-in. bars.
The
effect of
tempering on the
tensile properties of 1-in.
of S.A.E. low-alloy steels containing 0.30 to 0.35
carbon is shown by the charts of Fig. 16.8. that can be expected 90 per cent of the time if of a size that will harden with a structure of approximately 50 per cent martensite at the center when quenched in oil is tempered at the temperatures shown.
round and 0.40 to 0.45 per These are the properties an S.A.E. low-alloy steel
bars cent
Table
Steels
16.3.
Heat Treated
Typical Tensile Properties of S.A.E. and N.E. Carbon and Low-Alloy to a Tensile Strength of 150,000 lb. per sq. in. *
Nominal chemica
Steel
Tempering
temperature
composition, per cent
No.
Yield strength, lb. per

sq. in,
C
1045 1060 1080 1340 2340 3130 3140
0.45
Mn
0.75 0.75
N1
Cr
Mo
F.
c.
Elon- Reducgation tion in 2 of in., area. per per cent cent
0.60
0.80
0.40
1.75
0.75 0.65 0.75
600 750 950
315
400 510 510 510 455 510 540

595 565
114,000 113,000 111,000 128,000 132,000 128,000 127,000 130,000 130,000 131,000 130,000 131,000 130,000 131,000 130,000 135,000
10
15 16
35
45
47
X3140
4065 4130
0.40 0.40 0.30 0.40 0.40

0.65
0.75 0.80 0.65 0.50 0.75 0.65 0.65 0.75 0.75
3.50 1.25 1.25 1.25
0.60 0.60 0.75
950 950 850 950 1000

0.20 0.20 0.20 0.20 0.35 0.25
0.18
16
20
17 17 17 16
50 59
57 56 55 47 61 57
0.30 0.30 0.40 0.40 0.40 0.40 0.50
0.65 0.95 1.00

1.75 1.80
1100 1050
20
20
18 19 19
X4130
4140 4340 4640 5140 6150
0.65 1.00 1.00
1050 1100 1200 1000 1000 1200
565
595 650 540 540
60
57
56 55
18
18
650
54
8640 8740 8750 8950 9440
0.40 0.40 0.50 0.50 0.40
0.90 0.90 0.90 1.00 1.10
0.50 0.50 0.50 0.50 0.45
0.50 0.50 0.50 0.50 0.40
0.20 0.25 0.25 0.40
1050 1100 1200

il200
0.12
1050
565 595 650 650 565
133,000 130,000 129,000 133,000 130,000
17
18 18 18
53
56 54
57
18
57
All test data obtained
in diameter. All
quenched
in oil except 1045,
on standard specimens machined from bars 0.75 which was quenched in water.
to 1.5 in.
Low-Alloy Steels
as
339
Tempering temperature .deg.C.

400
500
600
300
400
600
800
1000
1200
60O
800
1000
Tempering temperature, deg.F.

Fie. 16.8. Effect of tempering on the normally expected tensile properties of lowalloy steels containing (A) 0.30 to 0.35 per cent carbon, and (B) 0.40 to 0.45 per cent
carbon.
160 ISO
140 E
130
It"
||II0
|
3100
J -6 90
A. X3I40
'
,
Carbon 0.407. Manganese 015V

Nickel
B. 8b30" Carbon 0.30,
"6
Mawnese 0.807.
Nickel.
0.657.
1.25%
0.157.-
if TO
1.1 so
Chromium
Chromium 0.507. Molybdenum 0.257."
e<fccf/on ofarea
Reduction ofarea
si
||40
ûj
* 30
zo
fjrnaation in
2in.
^pn0jonin2in.
2 3 Diameier of section, in.

I
I 2 3 Diameter of section.in.
Fig.
16.9.
Effect of
oil
through-hardening
quenched in
mass on the normally expected tensile properties of (A) a steel, and (B) a semithrough-hardening (8630) steel, and tempered at 1000F.
(X3140)
340
mechanical properties of heavy sections o heat-treated low-alloy depend on how deeply the material hardens in quenching and upon several other variables such as grain size, quenching tenqjerature, and quenching medium. The higher the carbon (up to about 0.60 per cent) the harder and stronger is the material at and near the surface; and, in general, the higher the percentage of alloying metals promoting hardenability, the harder and stronger is the steel both at the surface and throughout the cross section. The effect of section size on two low-alloy steels is shown in Fig. 16.9.* The nickel-chromium steel X3140 could be classed as a through-hardening material, and the triple alloy steel 8630 is undoubtedly semithroughhardening material. Both steels have a relatively high strength (after oil quenching and tempering at 1000F.) in small sections; and in both
steels
,
The
steels
the strength decreases as
the size of section increases,
but the
tensile
and
yield strengths of 8630 decreases to a greater extent
and more
rapidly with increasing section size than those of X3140.
The impact
variables
others.
resistance of the low-alloy steels
including
composition,
grain
size,
depends on a number of thermal treatment, and
Patton, whose data were discussed in the previous section, plotted
and found that the normal expected value decreased from 85 or 90 ft.-lb. for steels with 100,000 to 120,000 lb. per sq. in. to about 20 or 25 ft.-lb. for steels or
the Izod impact values given for the 400 specimens
200,000 lb. per sq. in., leveling off at this value for higher tensile strengths. Because impact resistance is very sensitive to slight variations in structure, Patton
found much more

as,
scatter than in
any of the other properties.

is
The endurance
steels.
ratio of polished specimens of low-alloy steels
ap-
proximately the same
or perhaps slightly lower than, for carbon
Available data in the literature give ratios of 45 to 50 per cent with the average a little below 50. Because of internal stresses, the endurance limits of heat-treated low-alloy steels with a tensile strength of 250,000 lb. per sq. in. or higher do not exceed approximately 100,000
lb.
per sq. in.
QUESTIONS
1.
Why
2.
should low-alloy steels be balanced? Give as many advantages as you can as to why low-alloy
effects of
steels arc
becoming
so popular.
8.
4.
Explain the Explain the
effects of
adding small amounts of nickel to steels. adding small amounts of chromium to steels.
2,
1934; data
Data on X3140 from International Nickel Co., Handbook on Nickel Steels, on 8630 from Republic Steel Corp., Handbook on N. Steels, 1943.

5. 6. 7. 8.
9.
341
to steels.
Explain Explain Explain Explain
the effects of adding small amounts of

the effects of adding small
molybdenum
the effects
amounts of vanadium of adding small amounts of tungsten

steels.
to steels. to steels.
the effects of adding phosphorus to
10. 11. 12.
What Name
arc the disadvantages of adding phosphorus to steels? three alloying elements that arc carbide formers.
Why
is
the carbon content low for low -alloy steels?

steels
IS. 14.
What advantages do low-alloy when quenched? Name twenty specific uses for
Compare
have compared
to plain
carbon
steels
low-alloy steels.
in chart form the physical properties of low-alloy steels containing

silicon is
0.40 per cent to a plain carbon steel containing 0.4 per cent carbon.
15.
16.
Explain why
obtained.
List various sources
not used to any great extent in low-alloy steels. where physical properties of low-alloy steels may be
17.
18.
What do What do
the letters S.A.E. stand for?
the letters A.I.S.I. stand for?
Hardenability
CHAPTER
17
Walter M. Hirthe,
M.S.M.E., Assistant Professor of
Mechanical Engineering, College of Engineering Marquette University, Milwaukee, Wisconsin
Richard O. Powell, College of Engineering, Tulane

University,
New
Orleans, Louisiana
more than a thousand years, hardness has been the most highly valued attribute of iron-carbon alloys; in fact,
the
bility,
r OR
word "steel" has long been an accepted synonym for hardness, duraand reliability. This is natural; to early social groups, with limited
knowledge of the properties of the metals then available, unhardenable wrought iron was no better, and in many instances worse, than properly made and fabricated bronze. When wrought iron was carburized and heat treated, however, the resulting steel was far superior to anything previously available, not only for weapons, but also for plowshares and other tools essential to an agricultural and pastoral society. It is not surprising, therefore, that hardness became a supreme and lasting virtue in metals, and the medieval metal worker who knew how to produce hardened steel was for centuries considered something of a magician. Today, as well as a thousand years ago, no one questions the importance of hardness and its accompanying high strength; in fact, the ease with which hardness and its related properties can be controlled by thermal treatment makes steel man's most important metallic material. Owing, however, to inherent limitations in our present methods of thermal treatment, hardness may be only superficial. Metallurgists have realized for many years that hardenability, which, briefly, is the depth to which martensite will form in definite sections under definite cooling conditions, is often as important as actual hardness, and there are many applications for which steel should be practically as hard and strong at
or near the center as at the surface. Surface-hardened steels are valuable
for
many
engineering uses, but
if
weight
is
to
be saved and high
stresses
342
Hardenability
343
withstood, steels hardened throughout are necessary. In addition and this is equally important a steel hardened throughout by quenching has
properties, as
properties of a steel tempered to the
tempered to a definite hardness, that are superior to the same hardness but not hardened
throughout.
17.1.
Hardness and Hardenability in Carbon Steels
Among engineers who use heat-treated steel there is considerable confusion concerning the difference between hardness and hardenability, that is, between the maximum hardness that a steel attains in quenching
to which it hardens. There is no direct and close relation between the two, despite the fact that hardness is used to measure hardenability. An example or two should make this clear. Suppose that two 1-in. bars of carbon steel containing, respectively, 0.30 and 0.70 per cent carbon are quenched from above the transformation temperature into ice water or iced brine. The surface hardness of the first will be approximately 55 Rockwell C and that of the other one about 65 Rockwell C. Both bars will harden to a depth of about \/ in. A The hardness values of the two steels differ (at the surface), but the
is the same. specimens of either carbon or low-alloy steels are cooled from the proper quenching temperature at the critical cooling rate or faster, so that no transformation occurs before martensite begins to form, the
and the depth
hardenability
If small
0.40
0.5O
0.60
0.70
0.80
0.90
Carbon, percent
Fjc. 17.1. Relation between carbon content and maximum martensitic hardness (upper curve), and maximum hardness usually attained (hatched band). {Based on data by Burns, Moore, and Archer, and by Boegehold)
344
hardness attainable depends on the carbon content. This
Fig. 17.1.*
It
is
maximum
shown by
the
should be emphasized that the upper curve shows
maximum
hardness obtained
when
the specimen
is
entirely marten-
sitic in structure.
In the commercial heat treatment of carbon and lowrarely realized, except with very small sections.
is
alloy steels this
is
Ordi-
contaminated by varying small amounts of transition structures that reduce the hardness appreciably. In consequence, many metallurgists put the highest practical hardness obtainable in the commercial quenching of these steels at 5 to 10 Rockwell C numbers
narily the martensite
below the maximum, as

17.2. Hardness
is
shown by
the hatched area in Fig. 17.1.
and Hardenability
in Low-Alloy Steels
illus-
The
difference between hardness
trated by Fig. 17.2,*
and hardenability is also well shows hardness values over the entire which
cross
quenched bars of various diameters of S.A.E. 1045 (0.45 per and S.A.E. 4140 (0.40 per cent carbon, 1.0 per cent chromium, 0.20 per cent molybdenum) steels. If 1-in. bars of these two steels are quenched in water from above the transformation temperature
section of
cent carbon)
(Fig. 17.2), their
hardness at the surface
is
practically the same; at the
center, however, S.A.E. 4140 has a hardness of 59
Rockwell C, whereas
S.A.E. 1045 has a hardness of only 34 Rockwell C.
This
content
illustration
shows
clearly that
two
steels of
about the same carbon
may have the same hardness at the surface but a different hardenability. They may also have a very different hardness at the surface and a different hardenability, depending primarily upon the relation of the
cooling rate to the location of the nose of the S curve and, consequently,
upon whether
the rate of cooling
is
sufficient to
prevent
much
pearlite
from being formed during quenching.

17.3. Cooling Rate
and Hardenability
gives
In
these
many ways
may
be.
steel is a very
to the treatments
man
like
it
it,
cooperative metal and responds readily no matter how unreasonable or illogical
In other ways, however, or not,
army mule, and,

is
we can do
typical of this characteristic.
We
stubborn as the traditional about it. Heat extraction can put heat into a piece of steel by
it is
as
little
The upper curve of Fig. 17.1 is based on data collected by J. I.. Burns, T. L. Moore, and R. S. Archer, Trans. Am. Soc. Metals, v. 26, 1938, pp. 1-36. The hatched band is based primarily on data given by A. L. Boegehold, S. A. E. Trans., v. 52,
1944, pp. 472-485.
* Based on diagrams published in U. Corporation. Pittsburgh., 1938, 214 pp. S.
S.
Carillory Steels, Carnegie-Illinois Steel
Hardenability
345
S.A.E. 04!
,QUEN :hed
i
in
WA id
1
1 I
/
-
\
V
\ \ s \
\
S
/ J)
'
/ /
-::
;>
*
H : *-- "::z. A ^
~*
--
--H
Diameter of bar.in.
Diameter of bar, in.
Fig.
17.2.
S.A.E.
1045
and
Hardness over entire cross section of bars of various diameters of S.A.E. 4140 steels quenched in water. (U. S. S. Carilloy Steels)
electrical or other
extract the heat

will permit.
methods at almost any rate we choose, but we cannot from the interior any faster than thermal conductivity
No
matter
how
fast
we
chill the surface, the
heat will flow
which is by the composition of the material. This process is complicated by the fact that during quenching the steel conforms approximately with Newton's law of cooling that heat loss is proportional to the temperature difference between the bar and the quenching medium and also by the fact that, quenching mediums vary greatly in their ability to extract heat from the surface of hot steel. And it must be remembered that it is not always desirable to quench steels drastically in water, as this treatment is likely to result in high internal stresses which may cause severe warping, cracking, or some other
largely unaffected
from the center
to the surface of a large section at a slow rate,
unhappy consequence.
346
17.4.
Time Delay and Hardenability

relatively slow heat transfer
1
from the center to the surface of a or larger severely limits our ability to cool steel rapidly enough to secure deep hardening, if the critical cooling rate is high. There is consequently only one method of securing deep hardening:
section
in.
The
reduce the critical cooling rate. In other words, what we do is to decrease the tendency of austenite to transform to pearlite in the temperature range of the nose of the S curve, or to bainite at lower temperatures;
this is another way of saying that we push the line of the S curve that marks the beginning of austenite transformation below the critical tem-
perature to the right so that more time is available for the steel to cool to 600F. (315C.) or below without such transformation.
stable;
Below the A t transformation temperature, austenite and the more the temperature is lowered, the
is,
of course, un-
greater
becomes
the instability.
tendency of unstable austenite to transform increases with lowered temperatures; but this is counteracted to a degree by the
fact that as the steel gets colder
it
The
gets
more
rigid; that
is,
its
ability to
transform decreases.
The
forces involved in the tendency of unstable austenite to transform
to pearlite, bainite, or martensite are complex,
and
is
at present they are
not well understood.

is
The
net result, however,

as
that in all steels there
a time interval,
commonly known
upon
the unstable austenite begins to decompose. short or very long, depending a
time delay, which elapses before This interval may be very

of factors in addition to
number
temperature, which
is
most important that include among others homosize,
geneity of austenite, grain
and chemical composition.
Small differences in time delay are important in hardenability; but even so, all carbon steels and many low-alloy steels have a time delay at the nose of the S curve that is rarely more than 3 to 5 sec. (for continuous cooling), which means that few of them harden to the center In other words, changes in the S curve in the heat treatment of a razor blade or a small tool but not of a 2-in. shaft or a 55-mm. gun tube.
except in very small sections.
to continuous cooling
due
may be important
17.5. Variables Affecting Hardenability
There are a number of variables that affect time delay and thus affect Homogeneity of the austenite increases its sluggishness and thus increases time delay. Heating long enough or at a high enough temperature to ensure homogeneity is also likely to change the grain size, and since grain size greatly affects hardenability it is difficult to untangle the two variables. It is, however, a fact that, if one or more areas in the
hardenability.
Hardenability
347
austenite are high or low in carbon or in alloying elements, transformation during cooling will be accelerated. Premature transformation in a
segregated area has a "trigger action" that sets off transformation over the whole section, thus decreasing time delay and hardenability.
Since homogeneity depends on diffusion and diffusion takes time, one common but insufficiently recognized causes of a variation in hardenability in steels of the same composition is insufficient time at the
of the
quenching temperature
is
for the austenite to become homogeneous. This the hardenability of a steel as determined in the laboratory, where the homogeneity factor is likely to be taken care of, may differ from the hardenability of the same steel heat treated in large
also the reason
why
lots in the plant.
Another and even more important factor
is
austenite grain
size.
Trans-
formation begins principally at the grain boundaries; hence, as the number of grains increases, the likelihood that transformation will start quickly is increased. Small grain size thus decreases time delay and lowers hardenability. On the other hand, increasing grain size decreases the chances for transformation to begin quickly; it lengthens the total
time for the reaction to
start
and increases hardenability.

field,
Much work
briefly
has been done in this

other factors
which can be summarized
enter, increasing the grain by stating that if (A.S.T.M. rating) to 5 or 6 will double the time size from about 8 without transcool a low temperature available for the austenite to to 2 or 3 will more increasing the grain size to forming to pearlite; and even triple it. than double the time and it may
do not
is relatively simple; it would, therebe easy to increase the hardenability of shallow-hardening grades by using a steel that would be coarse grained just before quenching. Unfortunately, however, the consequences might not be pleasant. Coarsegrained steels frequently crack if cooling is drastic, and they are likely to be sadly lacking in toughness (impact resistance) at room temperature and below. In fact, this lack of toughness is usually so dangerous that
Grain-size control during melting
fore,
most
steels that are to
be used
in highly stressed parts are deliberately

is
made
fine grained,
and deep hardening
secured by the use of alloying
elements.
By a proper balance of carbon content and the various alloying elements, the critical cooling rate can be lowered so much (that is, the time delay is greatly increased) that the steel will harden deeply when large sections are quenched in oil or even on cooling in air. This, and the methods used for measuring hardenability, are the subjects covered
in the following sections.
348
17.6.
Methods of Determining Hardenability

first
The
is
of several tests proposed to measure hardenability directly
the penetration-fracture (P-F) test developed by Shepherd.* This involves quenching short bars, in. in diameter, in a brine solution after
homogenizing for 30 min. at 1450, 1500, 1550, and 1600F. (790, 815, 845, and 870C). The bars are fractured and the fracture is compared with a standard. One half is polished on the end and etched with acid to determine the depth of hardening. The steel is rated according to the numerical values of the fracture (grain size) and the penetration (hard-
The test demands considerable skill and experience. It has never been used widely except by companies making or using large quantities of high-carbon tool steel. It is possible by this test to classify
enability).
tool steels as sensitive or insensitive to grain growth with increasing quenching temperature and as deep or shallow hardening.
Unquestionably, the most reliable test for hardenability is made simply by quenching bars of varying sizes from the proper temperature, cutting the bars in half, and determining Rockwell C hardness from center to surface. These values are then plotted as a U-shaped diagram similar
For a study of the hardenability complete is necessary to prepare, quench under controlled conditions, and measure the hardness of, the transverse sections of five to eight or more bars varying in diameter from i/, to 4 in. or more, which takes 15 to 20 hr. This is the only disadvantage of the test, but it is a major one.
Fig. 17.2.
to that
shown in
enough
to rate a steel accurately it
Twenty
years ago,
when
hardenability was attracting wide attention,
field was to devise a simple, readily reproducible, comparatively accurate test to determine the relative response of the commonly used medium-carbon and low-alloy steels to
one of the important problems in the
quenching.
It
had been apparent
for
some time
that, if the
hardness values at the
center of quenched bars are plotted against the diameter, depth-harden-
ing curves result. Four such curves are shown in Fig. 17.3. The two curves in Fig. 17.3A are plotted from the data given in Fig. 17.2, and the
difference between the shallow-hardening carbon steel
(1045)
and the
deep-hardening chromium-molybdenum steel is clear. The curves plotted in Fig. 17.3B are from hardness data on two low-alloy steels which differ slightly in response to quenching. The hardenability of these two steels is practically the same for \/ and s^-in. bars and for bars larger than H/ r in., but it varies considerably with intermediate sizes.
B. F. Shepherd, Trans.
Am.
Soc. Metals, v. 22, 1934, pp. 979-1016.
Hardenability
349
'h
V4
in.
Diameter
of bar.
Fig. 17.3.
and deep-hardening
Depth-hardening curves for (A) water-quenched shallow-hardening (1045) (4140) steels and (B) two low-alloy steels differing in hardenability
in intermediate sizes.
It was, of course, immediately recognized that any test that could be used to determine hardenability rapidly and cheaply must distinguish not only between deep- and shallow-hardening steels where differences are great (Fig. 17.3A) but also between the hardenability of two steels
whose depth-hardenability curves resemble those plotted in Fig. 17.3B. Such a test was developed by Jominy and his coworkers at the research laboratory of General Motors Corporation and has now been standardized and is used for specification and control purposes.*
17.7.
The Jominy End-Quench Hardenability Test
The Jominy test consists of quenching the end of a 1-in. round bar under controlled conditions and determining the hardness (Rockwell C) at intervals along the bar, beginning with the quenched end. The fixture and the test bar are shown in Fig. 7.4. The test bar is rough-machined and normalized by heating to approximately 150F. (85C.) above the
1
A 3 transformation.
is
After holding at this temperature for 30 min. the bar cooled in air and finish-machined to the dimensions shown in Fig. 14.6. It is then heated in a nonscaling atmosphere to about 75F. (40C.) above A z and held 20 min., after which it is rapidly withdrawn from the furnace by the collar, placed in the fixture, and a column of cold
The method has been tentatively standardized by American Society for Testing Materials (A. S. T. M. Standards, Part 1A, 1955, A255-48T, pp. 636-642) and by Society of Automotive Engineers (Handbook, 1953, pp. 112-120).
350
water passing through a
i/-in.
pipe
and under pressure

2i/ in.
sufficient to rise
is
above the opening

the
is
directed
against
red-hot
cold.
1
end
until
the
specimen
45'-.
\Unimpe<kdwaterjti
-/*-
r l-in.
round specimen
80 deg. apart and deep are ground longitudinally on the bar, and Rockwell C hardness measurements are taken at % 6 -in. intervals, beginning at the quenched end and extending for about 2 in. The hardness values are plotted against distance from the quenched end, which results in curves 0.015
in.
Two flat surfaces
+
From quick.._'
Water at 7tttS'
'i-in. inside diam orifice
similar to those in Fig. 17.5.
Owing to the method of quenching and to the laws of heat flow, the opening valve Jominy bar when cold has a structure and hardness that result from cooling Fig. 17.4. The Jominy standard rates which vary from about 600F. end-quench hardcnability test. 8 (335 C.) per sec. on the quenched face and about 420F. (235C.) per sec. at % e in. from the quenched end to less than 10F. (5C.) per sec. at the other end of the bar. These are equivalent to the center cooling rate of a i/g-in round bar quenched in agitated cold water as one extreme and a 4-in. round bar quenched in oil
as the other.
arc reproduced in from the quenched end; in many curves it is shown as the number of sixteenths of an inch. The horizontal hardness value indicated by the short dashed lines is the average maxima obtained by quenching unalloyed steels of the median carbon content indicated.
test
Some
typical curves obtained
by the Jominy
is
Fig. 17.5.* In these the distance
shown
as inches
End-Quench Test to Actual Cooling Rates and the Selection of Steel by Hardenability
Jominy and a number of others, including a Society of Automotive Engineers' committee on hardenability tests/ have done much work in
W.
K.
Jominy, Metal Progress,
v.
38. 940. pp. 685-690.
fS. A. E.
Handbook,
1953,
"Recommended
Practice
for
Determining
Harden-
ability," pp. 112-120
Hardenability
Rate of cooling at I300R,
F.
351
per sec.
420190
100
75
55
45
'/4 '/ 5/ 3/8 2 8 Distance from water cooled end,
3/ 4
in.
Fig.
175.
Jominy end-quench curves

(Jominy)
for
carbon and low-alloy
sleels
containing
Jominy distance and hardness with cooling Such a correlation is shown in Fig. 17.6, in which is plotted the cooling rate at center and surface and at various radii, bar size, and the position on the Jominy bar. By using the values given in Fig. 17.6, we can readily tell what the hardness should be at the center, at one-half radius, at three-fourths radius, and at the surface of any steel whose endquench curve has been determined. Suppose, for example, that we want to select a steel for a li^-in. round shaft that should be quenched in oil and tempered at a fairly high temperature and that should have a minimum Rockwell C hardness of about 35 at the center and 40 at the surface. Tempering at 1000F. (540C.) causes an average reduction in hardness of 15 to 20 numbers at the surface and 7 to 10 numbers at the center; so the hardness of the steel as quenched in oil should be 55 to 60 Rockwell C at the surface and 42 to 45 Rockwell C at the center. According to Fig. 17.6, the center cooling rate in oil for a li^j-in. round bar is 25F. per sec. and the corresponding distance on the Jominy bar is % 6 in.; the surface cooling rate is about 90F. per sec, and the Jominy distance is slightly more than % 6 in. It is evident from the curves shown in Fig. 17.5 that our requirements can readily be met by S.A.E. X3140 but not by the other four 0.40 per cent carbon steels whose curves arc reproduced in Fig. 17.5. There are,
recent years in correlating
rates.
of course,
many
other low-alloy steels that will serve equally well for this
application.
352
Goolinq rate.deg.
4
F.
per sec. at 1300'F.
lllll 1
i i
i i i i
ssssa ^350=93^3355*
/
/
/
3
.c
i/r
/ /
\1
/
/
A
/..,
42
12
f î
Ml
m
1
Water -quenched rounds
14 16 4 5 6 1 8 9 10 12 2 J Distance from quenched end, sixteenths of on inch
18
20
24
32
48
FlG.
17.6.
Correlation of surface, center, and intermediate cooling rates, bar

of
sizes,
and distance from quenched end

bars.
Jominy
bar, for oil
and water quenching round
(Boegehold)
17.9. Virtues
and Shortcomings of the Jominy End-Quench Test

test
The Jominy
closely
can be
made
relatively quickly
and cheaply, and the
curves for a particular lot of steel obtained in one laboratory check
with results from other laboratories. This agreement is fortunate because even before a tentative standard was worked out by the American Society for Testing Materials in 1942, it was put to good use in the wartime development of the low triple-alloy steels. In brief, the method used when the common alloying elements became short and had to be conserved, and when insufficient time was available for extensive mechanical and service testing, was to make up experimental heats of the new triple-alloy steels, adjusting the composition according to the expected effects of carbon and the alloying elements, and to determine the end-quench hardness characteristics. If the end-quench curve of
Hardenability
353
the new steel coincided closely with that of one or more of the standard higher alloy steels, it was reasonably certain that the new steel could be substituted for these standard steels with considerable assurance that it would have the mechanical properties desired after heat treating to obtain
a definite hardness at a definite distance on the Jominy bar. The Jominy test will tell with accuracy whether the nose of the S
curve has been missed in quenching and that there is no pearlite in the microstructure of quenched bars of certain diameters. It will not tell, however, whether the structure as quenched is contaminated by bainite.
There
and that of acicular but there is a marked temperature, above the bainite which forms just R of tempered martensite and those properties of tempered difference in the
is little
difference in the hardness of martensite
bainite of about the
same hardness.
Consequently, because the endthat
quench test does not make this distinction, there is no guarantee structure and properties will be exactly what is required.
There are other shortcomings of the end-quench
test.
These are not
inherent in the test itself; rather, they arc precautions that should be observed in applying the results too widely. If a steel is segregated or otherwise heterogeneous (and many large heals are), Jominy curves of a specimen cut from a segregated bar will be different from the curves
of specimens cut from a bar that
not segregated, even though the two bars were rolled from the same heat. Another shortcoming is that the hardentest tells only the hardenability of a round bar. To determine
is
and especially of odd-shaped sections, such as a gear blank, a rather complicated procedure must be used.
ability of other shapes,
17.10. Hardenability Bands
About
ten years ago, the steel industry, represented by the
American
Iron and Steel Institute, and the major consumers of heat-treatable carbon and low-alloy steels, represented by the Society of Automotive Engineers, worked out hardenability bands for a few steels, to be used for specification purposes. The composition limits of three of these steels, (Table 17.1), are somewhat wider than designated by the letter
for the steels given in Table 17.1 steelmaker must produce a material whose hardenability is within the specified limits, and he is, therefore, given slightly more latitude in chemical composition so that he can make ad-
ordinarily permitted.
Three such bands
are shown in Fig.
17.7.
The
justments of the analysis while the steel

the
is still
in the furnace.
Thus,
if
on the low side and cannot be increased readily, he can keep manganese, or molybdenum, high to ensure that the harden-
chromium
is
ability will
be within the required
limits.
354
for
Table 17.1 Composition Limits (1955) Hardcnabihty (H) Is and Is Not Specified
Three Low-Alloy
Steels
for
Which
Chemical composition, per cent

Steel
No.
C
4140
Mn
0.75-1.00 0.65-1.10
Si
Ni
Cr
0.80-1.10 0.75-1.20
Mo
0.15-0.25 0.15-0.25
4140H
8640
0.38-0.43 0.37-0.44 0.38-0.43 0.37-0.44 0.38-0.43 0.37-0.44
0.20-0.35 0.20-0.35
8640H
8740
0.75-1.00 0.70-1.05
0.75-1.00 0.70-1.05
0.20-0.35 0.20-0.35
0.20-0.35 0.20-0.35
0.40-0.70 0.35-0.75
0.40-0.60 0.35-0.65
0.40-0.60 0.35-0.65
0.15-0.25 0.15-0.25 0.20-0.30 0.20-0.30
8740H
0.40-0.70 0.35-0.75
Incidentally all
steels are
made by
is
a practice that ensures fine grain,
which means that the hardenability

chemical composition.
obtained solely by adjusting the
17.11. Relation of Hardenability to Engineering Properties

If two steels are treated so that their structure is the same, their important engineering properties will be the same most of the time.
The work
tion,
number of investigators has established this beyond quesuniversally accepted as fundamental in ferrous metallurgy. For steels used in highly stressed engineering structures and machines, the primary object of heat treatment is to produce optimum properties
of a
and
it is
by controlling the
size, character, and distribution of the carbide, and the chemical composition is the principal variable by which this control
can be exercised. Thus, the amount of carbon is controlled to ensure that the martensite or other phase formed by thermal ueatment-and the structure resulting from a change in these constituents by temperingwill have the required
hardness and strength; and one or several alloying elements are added, if necessary, to ensure that the desired structure and properties will be attained at the depth beneath the surface that is required for a specific
application. Optimum properties result from a structure that martensitic before tempering.
is
mostly
Theoretically two steels having the same structure should have the same propThis, however, is an ideal to he approached but hardly attained. There are a number of factors other than structure that may affect properties. The principal one is internal stress, which may be produced by any of a number of
erties all the time.
manufacturing operations.
refining, or fabrication.
Another is gas, taken up by the metal during melting, These, and possibly others, are undoubtedly responsible for the fact that the properties of steels having the same structure vary considerably
from the normal in about one case in ten.
Hardcnability
355
24 28 16 20 12 8 Distance from quenched end of specimen.sixteenths of an inch
32
Fig.
17.7.
(Society of
Hardenability bands for three 0.40 per cent carbon low-alloy Automotive Engineers and American Iron and Steel Institute)
steels.
In ordinary heat treatment

before tempering and,
if
it
is
therefore desirable to have martensite
possible, to avoid
cooling at a rate slightly
lower than the

case
all
(commonly known as slack quenching), in which bainite or a mixture of martensite and bainite will be formed. In
critical
steels, it is relatively
less
easy to obtain than about 1 in. in cross section; but if optimum properties are required in heavy sections, a steel with high hardenability should be used. Slack quenching results in a low yield ratio (low yield strength as compared with tensile strength) and frequently lower elongation, reduction of area, and impact resistance than
martensite
but the very shallow-hardening upon quenching sections
are desired.
In general, a deep-hardening steel in which martensite will form in quantity even in large sections will, after tempering, have a yield ratio of 92 to 88 per cent; a shallow-hardening steel in which the structure is mostly bainite will, after tempering to the same hardness, have a ratio of 85 to 75 per cent or even lower, depending on how much bainite is formed. The effects of slack quenching are especially apparent in the notch toughness of low-alloy steel at or below room temperature. Frequently the impact resistance of a steel containing pearlite or bainite as quenched is only a fraction of the impact value of the same steel when
356
tempered to the same hardness but quenched to ensure a structure that was almost entirely martensitic before tempering.
Tempering naturally reduces hardness and strength, but for a given degree of tempering the reduction is greater if the quenched structure contains much bainite than if it is primarily martensite. As a result, the
center portion of heat-treated heavy sections
may
be too
soft
and weak.
17.12. Relation of
Tempering
to Hardenability
Fundamentally, tempering accomplishes two objectives: First, it redangerous internal stresses, which may cause brittleness or even warping or cracking; and second, it improves ductility and toughness
lieves
by causing transformation of any hard, brittle martensite present to a ductile aggregate of ferrite and cementite. Concomitantly with the increase in ductility, hardness and strength are decreased. Since quenched steel is almost never used in engineering structures and machines without tempering, it may be justifiably asked why endquench data are obtained on a quenched specimen instead of on one that is quenched and tempered. The answer is that, if the Jominy bar were quenched and tempered, we would not get the information we want and, further, that such information as we would get might be misleading. The final structure and properties of a quenched and tempered carbon or low-alloy steel depend to a large degree on the quenched structure, and the end-quench test gives a fairly accurate picture of the hardness and its accompanying structure (and the corresponding cooling rates) for sections of various sizes quenched in various mediums. For that reason it is the as-quenched structure that is the essential variable in determining the final properties of a heat-treated steel, and it is very important that we know how this structure may be controlled.
more
17.13. Fundamentals of Calculated Hardenability In 1942 Grossmann, a pioneer for many years in exploring the fundamentals ol quenching and tempering, presented his classic paper on calculated hardenability.* The data reported in this paper showed that the hardenability of most carbon and low-allow steels could be predicted within a limit of error of 15 to 20 per cent, provided the complete
chemical composition and grain size were

before quenching was
known and
thai the austenite
homogeneous and free from undissolved carbides. The work was based on the concept that "pure" steel has a fundamental hardenability due to carbon alone, and that the final hardenability can
M.
A. Grossmann, Trans.
Am.
Inst.
Mining Met.
Engrs., v. 150, 1942. pp. 227-259.
Hardenability
357
"0
0.10
0.20
0.30
0.40
0.50
0.60
0.10
0.80
0.90
1.00
Carbon, per cent

Fie.
17.8.
Relation
among
ideal
diameter,
carbon
content,
and grain
size.
(Grossmann)
be calculated by multiplying this basic hardenability by a factor for each chemical element present. Grain size may be taken into account either in the fundamental hardenability of "pure" steel or in the final product
of multiplication.
In working out his method Grossmann had to make another and, as turned out later, considerably more questionable assumption. This was that the hardenability should be based on a bar of ideal diameter (Di), defined as the diameter (in inches) of a bar that would show no unhardened core in an ideal quench, which was in turn defined as a quench in which the outside of the bar is instantly cooled to a temperature of
it
the quenching medium. This, of course, is a condition that is never attained in practice, but Grossmann believed that it could be used as a
reference point.
358
3.80
i
8.80
3.60
3.40
**"/
r
/ /
Cr
j
1
8.40 8.00
3.20 3.00
/
/
7.60
7.20
*.
J
\i
2.80
^
/
/
/
g2-60
,
/
S<
Mn
right,
e*2.40
k
/
scale
6
1.2.20
"I"
2.00
1.80 1.60 1.40 1.20 1.00
ji I ai
/S
,'
'
00 c
a* -
/
/
560
520^
4 4
M
u
c.
0.! 10
1."
l.i
80
40
/e x tension
/of
Mn
i
curve
i
00
3.60
0.80 1.20
i
1.60 2.00
3.20
2. )0
2.40
2.80
3.20
3.60
mi- nt, pei
cent
live
FlG.
17.9.
Multiplying factors Cor the
common
alloying elements.
(Boyd and
Field)
Using the assumption of ideal diameter and ideal quench, Grossmann determined experimentally the hardenability factors for all of the elements commonly found in
steel either as residuals or
purposely added.
(D,) of
By using
correction
these factors
it
is
easy to calculate the ideal diameter
a bar that will just harden in an ideal quench,
and by applying the proper
it is easy to calculate the diameter (/)) of a bar Uiat will just harden in any of the commonly used quenching mediums. Basic data for the hardenability in terms of D, of "pure" steel, as dependent on carbon content and grain size, are given in Fig. 17.8. The multiplying factors for a variety of chemical elements are given in Fig. 17.9.* The factors shown in Fig. 17.9 arc those determined by Grossmann, modified in some cases by later data.f Using the factors in Fig. 17.9, the ideal diameter D, can be readily calculated as indicated by the data in Table 17.2. It is important to remember that all elements present (except the gases) should be determined and taken into account in making the calculation. Thus, if only carbon, manganese, and silicon were considered for steel 1040 in Table 17.2, the ideal diameter would be 0.81 in., instead
L. H. Boyd and J. Held. "Calculation of the Standard End-Quench Hardenability Curve from Chemical Composition and Grain Size," Contributions to the Metallurgy of Steel, No. 12, American Iron and Steel Institute, New York, Feb., 1946, 25 pp.
See, for instance, Trans. Am. Inst. Mining Met. Engrs., "Symposium on Calculated Hardenability," ibid., v. 158, posium on Hardenability," ibid., v. 167, 1946, pp. 559-734.
|-
v. 154, 1943, pp. 386-394: or 1944, pp. 125-182; or "Sym-
Hardenability
359
_ o V
SSd .5-
o cm
o"
o o CO CO
If,
CJ
CM
lO
|
q
o 05
la
re
S.S
tr
S 3
m in o
00
in
i--_
>r.
t-i
CO fi
o in
in
_.c
Q sir aE
3 C
Crt
'J
ss
-r,
c;
o b 2
B
sO
r-#
(H
o CN
tf*
o MSO
OS so
in
-
c o
*"
r*
_>.
'J~,
CM
"o
oo
<
| <
3
a c
re
o
ON o **
CM
d
CM
o O
to CM
d
NO
CO
c-i
b
1
u
.a
be
E
3
b 3
65
CM CM
pi CM
in
CO
1 u G
(J
c
c
re
"* o d
m o
CO
f-
d
in so
-O
U
3 O
fe
t-
_C
">-
b 1 2
in
s
&s
eg
c>
a.
3
E
"0
0 O m -r d d
p*
to
t""
>-
q re
c
re
V
"2 S3
8 o o
a.
o g
CO
b s
6
X o
"
CN
CO
CM
* s d
CM to
r~
m CM
d
to
d
c-
d
r 00 tO
3 u o
CM
t-i -
re
1 a
8
IS
b 2
cm to CO
*
*
ON
*
b 2
fiS
SO
00
d
to CM
d d d
o CM o
CM in
CO SO
X X
X
Bl
<
c o
CM
O o
d d
c>
CM CM
1
CJ
c> o
* O
CM
to
d
r~
cc
r-
I*
t
1
CO
>.
o
o
to
c T
o
g (0
2
U
a-
o O z
2
360
of 0.98
in.,
of residual nickel,
an error of 17 per cent, which would increase if the amounts chromium, and molybdenum were higher than shown in the table. Sulphur and phosphorus need not be considered if these impurities are low, and no factors are given for them in Fig. 17.9. The factor for 0.02 per cent phosphorus is 1.05 and the factor for about 0.03 per cent sulphur is 0.97 (sulphur decreases hardenability); consequently, in most high-grade carbon and low-alloy steels the effects of these two
elements cancel out.
17.14.
The Accuracy of Calculated Hardenability
Continued work over the past ten years has demonstrated that attempts to calculate hardenability by the use of multiplying factors represent an
oversimplification of the problem.
We
now know
that additional variNevertheless,
ables are involved, variables that are difficult to determine. in practice
the calculation of hardenability has been used with considerable success
where
its
limitations are understood.
Recent work indicates that there probably are two hardenabilities, one affecting the transformation of austenite to i>earlite and the other the transformation of austenite to bainite, but there are few data which make it possible to differentiate the two. For example, it has been shown
that nickel has
more
effect
on the austenite-bainite than on the austenite-
pearlite transformation, so that the curve for the multiplying factor for
nickel may have a different location from that shoivn in Fig. 17.9, depending on the structure that results from the transformation. This undoubtedly explains the discrepancies found by several investigators in
attempting to confirm Grossmann's multiplying factors for nickel and for some of the other alloying elements.
The most important fact 'that was unrecognized by Grossmann and some of the other early workers in the field of calculated hardenability is the intensifying effect that one alloying element may have upon another. For example, if manganese, chromium, or molybdenum is present, the effect of nickel on hardenability is much greater than its effect as a single alloying element. Similarly molybdenum is more effective in increasing hardenability in a steel containing nickel than in one containing
chromium
as the
second alloying element.

it
As
a result of these recent discoveries

(see Fig.
either curved or straight
17.9),
can be concluded that no line, can be drawn that will show
precisely the effect of an alloying clement
on hardenability
in all types of
low-alloy
steels.
The
calculation of hardenability can be used most

steels
successfully
and reliably on alloy
containing only one alloying
element.
Hardenability
361
Distance from quenched end,

l'"ic.
in.'
17.10.
Kffect of
low-alloy steels.
boron on the end-quench characteristics of some carbon and (American Iron and Steel Institute)
17.15.
The Effect of Boron on Hardenability

of the most intriguing metallurgical discoveries of the past ten
is
One
years or so
ability in
that very small
amounts
of
boron greatly increase harden-
some carbon and
low-alloy steels.
The
increase results
from the
addition of Q.002 to 0.003 per cent, as ferroboron, or as a complex alloy containing 0.5 to 10 per cent boron and iron, aluminum, silicon, titanium,
and other elements

borax.
in various combinations, or even as boric acid or
Some
steels are
end-quench curves for untreated and boron-treated reproduced in Fig. 17.10.*

typical
American Iron and Steel Institute. "Report on Special Alloy Addition Agents," Contributions to the Metallurgy of Steel, No. 9, The Institute, New York, 1942, 30 pp.
362
The steel to which boron is added should be fine-grained and thoroughly deoxidized as boron is an efficient deoxidizer, and trouble is occasionally encountered in assuring that the boron is uniformly distributed in the metal. Very small amounts of boron are difficult to determine by chemical analysis, and it is not certain what residual percentage is the most effective, nor have we any definite knowledge of the mechanism by which this element affects hardenability. We do know, however, that
if
an addition of
less
than 0.001 per cent

is
more than
0.003 or 0.004 per cent
is ineffective, and that added there may be a decided
decrease in hardenability.
only definite knowledge to date is that boron increases hardenby increasing the time available for the steel to cool past the nose of the S curve it pushes the nose to the right but even here its effect may not be enough to increase the hardenability of shallow-hardening
ability
steels materially as Fig. 17.10
The
shows.
Why
it
ability of 4023 but not of 4042 (Fig. 17.10)
is
should increase the hardennot easily explained.
Data on the effect of boron on mechanical properties are erratic and no definite conclusions can be drawn yet. It has no perceptible effect on the properties of the steel as rolled, normalized, or annealed, nor on the
maximum
is
hardness after quenching. In heat-treated
steels it
frequently
responsible for improved yield ratio

its
a direct effect or a by-product of

to
and ductility, but whether this is effect on hardenability is impossible
judge at present.
QUESTIONS
1.
Explain the difference between "hardenability" and of a steel.
"maximum
hardness"
2.
Why
is the "maximum hardness" of a steel less than the hardness usually obtained in commercial quenching for a given carbon content?
3.
Compare
the hardness at the center of a 5 in. round of S.A.E. 4140 with the hardness at the center of a 1 in. round of S.A.E. 1045 when both are
quenched
4.
in water.
does the "delay time" vary with temperature in the isothermal transformation of austenite?
How
5. 6. 7.
Define "critical cooling rate."
What What
is is
the effect of a variation of grain size
on hardenability? on
the effect of a variation in the homogeniety of the austenite formation diagram and hardenability?
8. 9.
How
What
does deoxidation practice influence hardenability?

is
the relationship between the "C-curves" of an isothermal trans-
formation diagram and hardenability?

10.
Discuss several methods of determining hardenability.
Hardenability
11.
363
in.
What
is
the hardness at the

in oil?
is
radius of a 2
round of S.A.E. 4640
quenched
12.
If a steel specification
based on
hardness of 50
Re
for
an equivalent
17.6
Jominy distance of
be acceptable?
13.
six-sixteenths,
which of the
steels in
Fig.
would
What
test?
are the advantages
and disadvantages
of the
Jominy hardenability
14.
15. 16. 17.

18.
What What
are "hardenability bands"

are the advantages
critical
Define "ideal
What
is
the effect of
and "hardenability steels?" and disadvantages of "slack quenching?" diameter" and "ideal quench." a proeutectoid phase on hardenability?
size
Calculate the ideal critical diameter for the following composition:
C = 0.40 Mn = 0.60 Si = 0.30

19.
Grain
No. 5
Calculate the ideal critical diameter for the following
steel:
= Mn =
C
Si
20.
0.40 0.60
Grain
size
No. 8
Cr =
0.50 0.20
0.30
Mo =
What
is
the effect of
boron on hardenability?

CHAPTER
18
Frederick Leo Coonan, D.Sc, Professor and Chairman, Department of Metallurgy and Chemistry, U. S. Naval Postgraduate School, Monterey, California
Jules Washington Lindau, III, M.E., Associate Professor of Mechanical Engineering, University of South
Carolina, Columbia, South Carolina
oOME
unusual properties in metals.
types
of service
in
industry require
Many
of the alloys discussed in the previous
chapters are not entirely satisfactory for these specialized requirements;
many
alloys that are satisfactory
do not conveniently
tools
fall
into the estab-
lished patterns developed in the earlier chapters. Included in this

are alloys particularly suitable for (1)
group
low
and
(4)
dies,
(2)
corrosion and
(5)
heat resistance,
(3)
magnetic applications,
will
wear
resistance,
temperature, and
(6)
ultra high-strength service.
The
alloys in
is
two of these categories
be treated in separate chapters.
Chapter 19
resistance.
concerned with tools and
dies,
and Chapter
21
with wear with alloys
Most
of the discussion here will be concerned with steels

lesser extent,
developed for resistance to corrosion and, to a utilized in service involving magnetic effects.
18.1. Classes of Stainless Steels
The element chromium combines

oxide that
is
readily with oxygen
forming an
protects the
thin, tightly adherent, self-healing,
and that
it
metal
itself
from further
attack.
When
dissolved in iron,
forms an alloy
classes:
that has similar stainless
and oxidation-resisting properties.
The chromium
bearing steels
may be
divided into three
(1)
special purpose steels containing 3.5 to 10 per cent
chromium with or
without 0.5 to 4 per cent

tional
alloying elements; (2)
taining
more than
10.0
molybdenum, or tungsten as addiand heat-resisting steels conper cent chromium and not more than 2 per cent
silicon, nickel,
corrosion-
364

of another alloying element;
365
and heat-resisting steels containing more than 10 per cent chromium and more than 2 per cent of one or more other alloying metals. and
(3)
corrosion-
Chromium
chromium
steels
containing 3.5 to
10% chromium
have better corat elevated
rosion and heat resistance than

(see Fig. 18.3)
the S.A.E. low-alloy steels containing
and have excellent properties
tem-
peratures. Steel with about 0.10 per cent carbon, 4 to 6 per cent chromium, 0.40 to 0.75 per cent silicon, and about 0.50 per cent molybdenum
used widely in oil-refining equipment. Another steel in this class is silchrome, a material commonly used for automobile- and airplane-engine valves and containing about 0.50 per cent carbon, 7 to 10 per cent
is
chromium, and 1.00 to 3.75 per cent silicon. Silchrome is resistant to attack by the exhaust gases of internal-combustion engines and has satisfactory strength and hardness at a dull red heat. Moreover, it costs
considerably
nickel,
less
than the highly alloyed valve materials containing

silicon.
chromium, and
high-alloy steels in which chromium is the only amounts are those included in class 2. These element large alloying in four groups: may be divided into
The most important
2/1.
containing 12 to 18 per cent chromium and

carbon.
Low-carbon, high<hromium steel usually called stainless iron less than about 0.14 per cent
2B. Cutlery steels containing 12 to 16 per cent

chromium and
0.20 to
2C.
Tool and die
steels
containing 12 to 18 percent chromium and
0.70 to 2 per cent carbon.
2D. Heat-resisting steels containing 20 to 30 per cent chromium, with less than 0.50 per cent carbon for hot-worked material, and with 0.50
to 2.5
per cent carbon for castings.

less
than 2 per cent of nickel or other metals are occasionally added to the plain chromium steels. With the exception, however, of 0.15 to 0.50 per cent sulphur to improve machinability, the
Small amounts generally
addition of small percentages of a second alloying element
is
not
common.
is
The
principal corrosion- and heat-resisting steel of class 3
the fa-
miliar low-carbon 18 per cent chromium, 8 per cent nickel alloy

to metallurgists
known
a very important highalloy engineering steel. Despite the cost, the amount of 188 used per year has increased enormously. Most of the 188 steels contain no other alloying element. A few that must have exceptional stability at
and engineers
as 188.
This
is
elevated temperatures contain larger percentages of
chromium
nickel,
366
plus cobalt, tungsten, or molyb-hromium.ato nic per cent
10
20
30
1
40
1
2000
1800
denum, and some contain titanium or columbium, added to stabilize the carbon and prevent
-3200
intergranular
is
corrosion.
This
discussed later.
1600
,w elf
In the past several years

-2800
new
manganese bearing and

tic steels
UJ
cr
disper-
1400
-2400
sion hardening types of austeni-
have been developed.
<->l200
T3
u"
3a.
/*/p/
These
will also be discussed in
1000
nmcfW
h20Q0-
a later section of this chapter.
Up to + gc im
^**
*.
T7
1-
3
!
-1600
18.2. Constitution
of HighSteels
less
I 800 Q. E
V
3fc_
'"Sw
Chromium
Chromium
in
T]
i
600 400
y
^_
-1200
\V
1
1
amounts
than 30 per cent dissolves completely in carbonless iron.

It
i| -800
1 j
has marked effects on the tem-400
4//
ha
1
200
1
h>
perature of the
tion,
/f
transforma-
B
Alpha -0 + Sigma "n
,
1
n *>
-200
if
'
where alpha changes to gamma iron, or vice versa, and on A 4 where gamma changes to the high-temperature modi,
2C
3C
*)
-.f
sc I
Zhr om
Fro.
18.1.
um
pet ce
fication of alpha
(delta) iron,
or vice versa. These effects are

Iron-rich
chromium phase diagram.

receive
portion of (Kinzel
the
ironCrafts)
and
chromium
important in commercial highsteels and should re-
some
attention.
portion of the iron-chromium diagram for alloys containing less than 50 per cent chromium is shown in Fig. 18.1.+ From this diagram it is
chromium to carbonless iron lowers the point slightly and lowers the A 4 point nearly 275F. (15()C.) Further additions of chromium raise /J., and at the same time lower A 4 until, with the addition of about 12 per cent chromium, these two points merge. The result is what is known as the gamma loop and is a characteristic of several binary alloy systems of which iron is one component.
evident that adding 8 per cent
At
The
significance of the
gamma
loop
is
plain. If
is
per cent
chromium and 90 per cent

The
iron
an alloy containing 10 heated slowly, no change in

and Chromium,
Vol.
I,
+ A. B. Kinzel and Walter Crafts,
Alloys of Iron
Inc.,
Low-
Chromium
Alloys,
McGraw-Hill Book Company,
New
York, 1937. p. 43.
Special Purpose
structure occurs until a
Steels
367
(900C.)
is
temperature of 1650F. changes to
reached.
Here the alpha

is
solid solutions
gamma
solid solution. If heating
2350F.
continued, the (1200C.)
solution.
On
remains unchanged until a temperature of (delta) solid it changes to alpha slow cooling, the reverse changes take place. If, now, an
is
gamma
reached, where
alloy containing 15 per cent
chromium and 85 per cent iron is heated, no change (except grain growth) takes place between room temperature and the melting point, and, conversely, no structural change occurs in cooling. Alloys containing more than 12 per cent (and less than 30 per cent) chromium and very little or no carbon have no allotropic transformations.
The concentration limits of the gamma loop are changed by carbon, which moves the extreme limit of the loop to the right and at the same time increases the width of the duplex alpha-plus-gamma field. Thus, the loop, which with negligible carbon extends to 12 per cent chromium, extends to about 18 per cent chromium with 0.40 per cent carbon. These relationships are complicated further by the carbides which are formed by chromium and which together with iron carbide (Fe3 C) form (Cr.Fc) 7 C 3 and (Cr.Fe) 4 C in the commercial high-chromium steels. The iron-chromium carbides are partly soluble in the gamma solid solution but not in the alpha solid solution and may be retained in supersaturated
solid solution by quenching, in a
manner analogous
to the retention of
steel.
iron carbide in the
gamma
iron of unalloyed high-carbon
Constitution of
High-Chromium
Steels
to
Their Heat Treatment
From
the foregoing discussion
it
is
evident that
we should know from
the composition whether high-chromium steels will or will not respond

to heat treatment.
Thus,
a steel
containing 12 to 18 per cent chromium

(class
and
If
less
than 0.13 per cent carbon

the relative
2A,
18.1)
will or will not
harden depending upon
the steel contains 0.12

is
amounts of chromium and carbon. per cent carbon and 13 per cent chromium,
the steel
is
some austenite
formed
if
heated to 180()F. (980C.)
and
upon quenching. If the steel contains 0.06 per cent carbon and 16 per cent chromium, no phase changes take place, and the steel does not harden when quenched from 1800F. (980C). Low-carbon high-chromium steels in which no phase changes take place remain ferritic in structure at all temperatures. They are relatively soft
this transforms to martensite
and
ductile,
and the only change caused by heating

ductility.
is
grain growth
which reduces the
368
of (A) oil-quenched cutlery steel containing 0.30 per cent per cent chromium, and (B) oil-quenched high-carbon chromium steel containing 0.70 per cent carbon and 17.5 per cent chromium; etched. 500 X(Kinzel and Forgeng) Fig. 18.2.
Structure
12.7
carbon and
containing 12 to 16 per cent chromium and 0.20 to 0.60 per cent carbon (class 2B, 18.1) undergo a phase change: when they are heated to about 1800F. (980C.) , the alpha solid solution changes
Cutlery
steels
respond to heat treatment very much like unalloyed high-carbon steels. In a steel containing 12 per cent chromium the structure is entirely pearlitic with
to
gamma and
the carbide goes into solution.
These
steels
only 0.3 per cent carbon

quently, martensitic
cutlery steels differ
when
the steel
is
is
cooled slowly;
it
is,
conse-
when
the steel
cooled rapidly (Fig. 18.2)
.*
These
from unalloyed steel containing 0.80 to 0.85 per cent carbon chiefly in that the chromium lowers the critical cooling rate, that is, they become as hard when quenched in oil, or even in air, as an unalloyed high-carbon steel when quenched in water. Since steels containing 12 to 14 per cent chromium and 0.30 to 0.40 per cent carbon correspond to unalloyed "eutectoid" steels, it follows that high-chromium steels containing about 1 per cent carbon (class 2C, are hypereutectoid and, when quenched and tempered, have 18.1)
numerous excess carbide which increase the wear and dies.
particles in the microstructure
(Fig.
18.2B)
resistance
and make the
steels useful for tools
Courtesy of A. B. Kinzel and
W.
D. Forgeng.
Special Purpose
Steels
369
The
2D,
heat-resisting steels containing 20 to 30 per cent

18.1)
chromium
(class
may
or
the carbon content.

for steels
may not respond to The carbon range for
heat treatment, depending upon

this class
is
0.5
per cent or
less
which are hot or cold worked, and from 0.5 to 2.5 per cent for those which are used in the form of castings. At room temperature the steels containing about 25 per cent chromium and less than 0.70 per
cent carbon are
ferritic;
their structure consists of alpha solid solution
and the carbide (Cr,Fe) 4 C, and no phase changes take place in heating. These steels cannot be hardened; they can, of course, be annealed if
cold worked.
is
higher carbon grades respond to quenching, but this treatment seldom used as no advantage results. High-carbon castings containing 20 to 30 per cent chromium are very hard as cast and must be annealed
The
if
machining
is
necessary.
facture of
chromium) used in the manuhigh-chromium steel varies inversely with the carbon percentage. Ferrochromium containing less than 0.5 per cent carbon, which must be used to produce high-chromium steels with low carbon percentages, is much more costly than ferrochromium containing 4 to 6 per cent carbon. The economic factor is, therefore, important in selecting a
The price
of ferrochromium (70 per cent
high-chromium steel for a certain application; the advantages resulting from the use of a steel containing less than 0.12 per cent carbon, instead of one containing 0.40 per cent, must be balanced against the higher
cost of this material.
18.4. Mechanical Properties of
High-Chromium
(16.4),
Steels
little
As remarked
in
previous chapter
is,
chromium has
it
solid-solution effect, that
when
is
dissolved in alpha iron,
strengthens
18.1 for
the iron relatively

steels.
little.
This
shown by
is
the data in
Table
such that the steel undergoes a annealed chromium is to increase the hardenprincipal effect of phase change, the properties with relatively in marked changes ability, thus producing
If the composition
slow cooling
rates.
high-chromium depend obviously upon how much carbon
The
steels
is
cooled in air or oil
present
and upon what
proportion of the carbides dissolves in the

temperatures.
12 to
18.2.
gamma
solid solution at high
Some typical values for tensile properties of low-carbon 15 per cent chromium steel and for cutlery steel are given in Table The high-chromium steels are more resistant to tempering than
carbon and low-alloy steels. Increasing the tempering temperature has little effect on the properties until a temperature of 950 to 1050F. (510
370
to 565C.)
is
reached
when there is a sudden decrease in tensile strength, and hardness and a moderate increase in ductility. The impact resistance of the quenched and tempered low-carbon and medium-carbon (cutlery) steels is in general satisfactory, except when
yield strength,
the steels are tempered
at, or cooled slowly through, the temperature range 875 to 1000F. (470 to 540C.) For reasons yet unknown this treatment causes brittleness, which is manifested by very low notched.
bar impact resistance.
The endurance
limit of both the hardenable

is
and
about one half of the tensile strength or approximately the same as for carbon and low-alloy steels. The modulus of elasticity, however, seems to be somewhat higher; most available data indicate that it is between 31 and 32 million lb. per sq. in.
18.5. Corrosion
the unhardenable high-chromium steels
and Oxidation Resistance of High-Chromium

steels are
Steels
Although high-chromium
more
resistant to certain kinds of
corrosion than any other ferrous material, they are not corrosion resistant in the broadest sense of the term.
less.
In
fact, to
some forms of
steels.
attack, they are
Neither are they always stainno more resistant than the
unalloyed carbon
Steels containing 10 per cent
or more chromium are resistant
to oxidiz-
ing mediums and to corrosion caused by fruit juices, food products, and
beverages.
The
low-carbon 12 to 18 per cent chromium
steels
are re-
sistant to a large
number
and
to
of organic acids
and
to all concentrations of
nitric acid, except 65 per cent boiling nitric acid.
They
are also resistant
to strong alkalies
many
salt solutions
but are readily attacked by
chlorides
and other halides. Sulphuric acid, except when concentrated and cold or when containing nitric acid, and hydrochloric acid of all
In general, corrosion resistance
is
concentrations attack these steels readily.

a function of the
is
amount
it
of chrore-
mium
dissolved in the iron, but the relation

is
not direct. Corrosion
sistance
not important with low percentages of chromium;

as the
more pronounced
resistance
is
chromium
increases very rapidly with slightly
increases from 4 to more than 10 per cent. The corrosion
becomes 10 per cent and
film of chromium-iron oxide which,
thought to be due to the formation of a thin, tight, adherent if broken, is self-healing unless the corrosive agent (as, for example, hydrochloric acid or chlorides) dissolves the film as rapidly as it is formed. It is generally assumed that in order to produce a self-healing film there should be at least one atom of chromium to seven atoms of iron. Increasing the chromium from 10 to 30 per cent increases the corrosion resistance, but the increase is not
proportional to that of the chromium.
Special Purpose
Table
18.1.
Steels
371
Steels
Effect
of
Chromium on
the Tensile Properties of Annealed
Containing 0.10 Per Cent Carbon*
Chromium,
per cent
Tensile strength,
lb.
Yield strength,
lb.
per sq.
in.
per sq. in.
Brinell
hardness 90 135 140 148 155 160
12
15.5
17
27
50,000 65,000 72,000 75,500 80,000 84,500
38,000 26,000 35,000 42,500 47,000 55,000
44 38 36 33 30 26
Based on E. E.
Thum, Metal
Progress, v. 29, No. 6, 1936, pp. 49-57. 104.
TABU
18.2.
Typical Tensile Properties of High-Chromium Steels*
Composition, per cent
Quenched and
tempered at
F.
Tensile
strength,
lb.
Yield
strength,
lb.
ReducElongation in 2 in., per cent

tion of
per
per
area,
Cr
C.
sq. in.
sq. in.
per cent 38
0.09
12.2
400 600 800 1000 1200 400 600 800 1000 1200 600 800 1000 1200 1400
205 315 425 540 650 205 315 425 540 650 315 425 540 650
146,000 145,000 143,000 135,000 95,000

170,000 168,000 166,000 160,000 90,000
135,000 134,000 134,000 120,000 79,000

160,000 160,000 160,000 148,000 83,000
15
15
40
46 52 60
18
16
20 29
8
10
15 18 21
20
45 46
0.09
50
5
0.30
13.0
760
240,000 245,000 250,000 160,000 140,000
208,000 210,000 195,000 138,000 105,000

i
3
5
7 12
14
20 20
38
45
Based on data by
v. 6,
1).
J.
Giles,
The Book
for Metals, Cleveland,
1935, pp. 267-276;
of Stainless Steels, American Society and O. K. Parmiter, Trans. Am. Soc. Steel
Treat.,
1924, pp. 315-340.
372
Carbides,
sistance.
if
not in solution, have a deleterous effect on corrosion
re-
For
this reason, the cutlery steels
should be heat treated
if
op-
timum corrosion and stain resistance is desired. The alloys containing carbon in excess of that which dissolves in the gamma solid solution at high temperatures are not so resistant to oxidizing mediums as the lower carbon steels.
The high-chromium steels rust slowly when exposed to the atmosphere, but the thin coating can readily be wiped off, leaving the surface underneath unaffected. Steels containing 12 to 14 per cent chromium and less than 0.12 per cent carbon are, therefore, widely used for automobile and building trim. In industrial at45 ~bon
40 usfe ./c e/5
mospheres, especially those con
taining sulphur, the high-chro-
mium
The
steels
may
pit badly.
35
resistance
steels to
of
the
high-
chromium
JO
oxidation at
but,
as
is
elevated
Chro miurr
stee Is
temperatures increases
with
the
chromium
25
shown
in Fig. 18.3, the increase
not important until more than

8 20
10 per cent chromium is With higher chromium

'faint ess sree/s
present.
percent-
ages the increase in oxidation reis fairly uniform until about 20 per cent chromium is
\
\
sistance
present,
when
the resistance
is
Vj
12 16
Chr ome ron

1
very high.
Fig. 18.3
The
data shown in
20
24
28
J2
Ch romi um, per cent
were obtained* by heating 0.5-in. cubes with ground surfaces for 48 hr. at 1830F.
(100()C.)
.
Fie. 18.3.
Effect of
chromium on the
steels to
re-
With
the exception
sistance of
chromium
oxidation at
1830F.
(lOOO-C).
(MacQuigg)
of a few iron-nickel-chromium
and
alloys, steel
containing 20 to 35 per cent chromium
iron-chromium-aluminum is the most resistant
of the ferrous alloys to high-temperature oxidation.
18.6.
The
Constitution of 18-8
Nickel
iron.
(as well as
chromium)
(1)
is
soluble in both alpha
When
in solution it
lowers the
A3
point,
and gamma where alpha iron

for Metals. Cleve-
C. E.
MacQuigg. The Book
oj Stainless Steels,
American Society
land, 1935, pp. 351-368.
373
j-2800uJ
-2400
i
J
-2000 u -1600"
-1200
-800 L
2800
-2400 g -2000
10
150
10
150
10
15
N ickel .per cent

Fig.
18.4.
Effect of
chromium on phase changes
in
iron-nickel alloys.
(Bain and
4 born)
gamma on heating and where gamma transforms to alpha on cooling, and (2) makes these allotropic changes, especially the one on cooling, very sluggish. A small portion of the iron-nickel phase diagram is shown in the upper left corner in Fig. 18.4.+ As noted on a pretransforms to
vious page
(p.
366)
chromium
restricts the
is
temperature-concentration
is,
region where the
gamma
solid solution
stable, that
it
produces a
gamma
loop; nickel,
When
The
first
on the contrary, increases the limits of this area. chromium is added to the iron-nickel solid solution it dissolves.
effect
is
lowering of the delta- (alpha-)
gamma
transforma-
and a widening of the field where delta (alpha) is stable. This is apparent from the sections of Fig. 18.4 showing phase relations for alloys containing S and 6 per cent chromium. As the chrotion temperature
mium
is
increased, the area of the delta
(alpha)
region
is
increased
Handbook, American Society for Metals, f E. C. Bain and R. H. Aborn, in Metals Cleveland, 1939, pp. 418-422.
374
further,
and with 9 per cent or more

stable
is
the low-temperature area
where
alpha
is
also increased.
Increasing the
chromium thus moves
the boundaries of the

to the right.
gamma and
the alpha-plus-gamma phase regions
Consider
now
the small diagram at the lower left in Fig. 18.4 for 18
per cent chromium:
if 3 per cent nickel is added and the alloy is heated, no phase changes take place at any temperature. If, however, 8 per cent nickel is present and the alloy is heated, a phase change occurs at about 660F. (350C.) and some of the alpha solid solution changes to gamma
,
solid solution.
If
the alloy
is
heated
still
further, this allotropic change
continues until at 1200F. (650 C.)
all
the alpha has changed to
gamma.
no further change if the heating is continued almost to the melting point. Now, if the alloy is cooled, the reverse changes should take place, that is, gamma should start to transform to alpha at 1200F. and should be completely transformed at 660F. Owing, however, to the
is
There
sluggishness of the reactions, only a small
amount
of alpha
is
actually
formed
by rapid cooling the formation of any and thus to obtain at room temperature an
in
it is
slow cooling, and
relatively easy to suppress
alloy that
is
entirely austenitic.
and are readily deformed cold For a combination of maximum resistance to corrosion by certain mediums, austenitic structure at room temperature, and other useful properties the most economical composition
ductile
Austenitic steels are strong
and
into a variety of useful products.
is is
18 per cent chromium and 8 per cent nickel, with carbon as low as commercially possible. With this composition it is advisable to guard
against the presence of any alpha by heating the material to 1830 to
2010F. (1000 to 1100C.) and quenching it in water or in an air blast. Increasing the nickel to 10 per cent or more increases the stability of the austenite but also increases the cost.
18.7.
The Role
of Carbon in 18-8
If 188 could be made free from carbon, many of the troubles of the manufacturers and users of this steel would be over. Unfortunately, however, this is difficult, and even if made by the best commercial practice, 188 contains 0.06 and frequently as much as 0.12 per cent of this element. Unfortunately also, only about 0.01 or 0.02 per cent carbon is soluble in the iron-chromium-nickel austenite at room temperature. This solubility increases with increasing temperature as shown in Fig.
Carnegie- Illinois Steel Corporation has produced 18-8 with carbon well under 0.06 per cent by feeding oxygen into the molten bath during refining. See Electric Furnace Steel Proceedings, Am. Inst. Mining Met. Engrs., v. 3, 1945, pp. 107, 108, 127.
375
IOUU
d?.
CL+Ls
-- --
-- ~-
3*y +l^ ,-
-- r^ __
____
,_
-2400
--
-T -- - y+L+carbide
,'
~~ -r
-?fififl
CUUU
LL
Y
I000
H600
' 7 ""! "" i(a;/* A> *''
*?
D
CO
r?
-1200-^
D.
"!
500
a+vtcarb ide
E
-800,"
r
i i
n tea rbi'a e
-400
q
1
0.3
0.4
:cr
pon pe- cen t
Fig. 185.
Effect
of temperature on
the solubility of carbon in iron-chromium-
nickel austenite. (Kinzel
and Franks)
Fig. 18.6. Structure of (A) quenched 18-8 and (B) quenched and reheated 18-8 showing carbide precipitation at grain boundaries; etched. 250 X- (Kinzel and Forgeng)
376
18.5,f until at 1830F.
(1000C.) 0.14 per cent,
and
at 2010F.
(1 is
100C.)
that the
0.22 per cent
is
soluble.
One advantage
if
of quenching 188
at
carbon
is
held in supersaturated solution
room temperature. This

Severe
is
carbon, however, will precipitate

cold working
conditions are favorable.
most high temperature, as in welding or in service in superheaters or other equipment operating at elevated temperatures, some carbon precipitates from solution.
may
cause some precipitation; in addition and this

to a
important on heating
If this were the only thing that happened, it would not be serious. However, when the carbon precipitates, it is apparently thrown out of
solution at the grain boundaries as a
chromium
carbide, thus impover-
chromium and making them susceptible to corrosion. The usual structure of quenched 188 showing the polyhedral grains of austenite is pictured in Fig. 18.6A,* the carbides which have precipitated at the grain boundaries are shown in Fig. 18.6B.
ishing the austenite grains adjacent to the boundaries in
Carbide precipitation occurs frequently

570 to 1470F.
to a
if
188
is
heated in the range

very susceptible
(300 to 800C.)
making the material
form of attack known as intergranular corrosion or intergranular disintegration. It is very hard to detect and was the cause of a number of disastrous failures before a cure was found.
Carbide precipitation can be prevented by reducing the carbon to less, which is not easily attained commercially, and it can be reduced innocuous by adding titanium equivalent to 5 times the carbon content, or columbium equivalent to 10 times the carbon content,
0.02 per cent or
to the steel when it is made. Both of these elements combine with the carbon to form a stable carbide and prevent the carbon from combining with the chromium. When 188 is "stabilized" with titanium or colum-
bium it can be used at elevated temperatures or can be welded without danger of premature failure.
18.8. Properties of 18-8
The
austenitic chromium-nickel steels can readily be cold rolled into
drawn into wire. They can also be riveted, soldered, now commonly used for fabricating 188. Because of its high electric resistivity and low thermal conductivity, spot welding has been especially successful. This method of joining is used in the
sheet or strip or cold
or welded. Welding
is
A..
B. Kinzcl
Chromium
Alloys,
Courtesy of
and R. Franks, The Alloys of Iron and Chromium, McGraw-Hill Book Company, Inc., New York, 1940, A. B. Kinzel and W. D. Forgeng.
Vol.
II,
High-
p. 275.
377
construction of the stainless-steel streamlined trains which have attracted
much
attention recently. Austenitic chromium-nickel steel has, as quenched, a fairly high tensile
strength with high ductility and resistance to impact (Table 18.3). It hardens rapidly by cold work (Table 18.3) The increase in tensile and
.
in yield strength
less
is
greater and the decrease in ductility
is
considerably
than that caused by comparable cold working of low-carbon steel. The endurance ratio of Carbon increases the strength (Table 18.3) quenched 188 is 0.40 to 0.45, that is, somewhat lower than the usual ratio for carbon and low-alloy steels. Peculiarly, the endurance limit is usually
.
higher than the proportional

Table
limit.
18.3.
Typical Mechanical Properties of Austenitic Chromium-Nickel Steel

Condition of specimen
Tensile strength, lb. per

sq. in.
Yield
strength, lb. per
sq. in.
Elonga- Reduction in
2 in.,
tion of
area,
Izod impact.
ft-Ib.
C
0.16 0.17 0.07 0.07 0.07
0.16 0.07
Ct 18.0 18.0
Ni
per cent per cent
8.0 8.0
8.5 8.5
Water-quenched bars Watcr-qucnchcd bars

Cold-rolled bars, Cold-rolled bars,
17.9 17.9
18.0 16.0 18.0 18.0 18.0 18.0
15%
9.5 10.2 8.0 8.0 14.0 14.0
0.16 0.06 0.14 0.14
25.0
20.0
Cold-drawn Cold-drawn Water-quenched Watcr-qucnchcd Watcr-qucnchcd Water-quenched Watcr-qucnchcd
40% wire, 60% wire, 85%

sheet sheet
bars bars
bars
90,000 96,500 142,700 227,600 263,000 273,000 86,400 93,300 80,000 90,000 90,500
37,500 40,000 117,800 201,000
68
65 30
11
78 75
61
Ill
103 88
17
43
33,500 46,600
50,000
4 3 63 57 63 53 47
75
70 63
90
expansion of 18-8 is about 50 per cent higher than and the thermal conductivity at normal temperatures is about 0.04 cal. per sec. per sq. cm. as compared with 0.16 cal. per sec. per sq. cm. for low-carbon steel. The stress-strain curve of 188 is
coefficient of
The
that of carbon steels,
curved from the origin.
This
steel has, therefore, a
low proportional
no modulus varies from 26

limit,
yield point,
and no
true
modulus of
elasticity.
The
secant
to 28 million lb. per sq. in.
The
austenitic chrois
mium-nickel
steels
have exceptionally high resistance to creep. This
discussed in a later chapter.
steels to corrosion
Nickel increases the resistance of low-carbon 18 per cent chromium by nonoxidi/.ing mediums, permitting these materials
steels steels
to be used economically in environments where the high-chromium containing no nickel would be attacked rapidly. These austenitic
378
are resistant to
many
organic acids, organic solvents, and

steels.
oils
which
Their
if
attack the
high-chromium
is is
Their resistance to staining
in the at-
mosphere
also higher than that of the plain
chromium
if
steels.
,
oxidation resistance
high, especially at 1650F.
(900C.)
and
the
chromium and
not highly stressed, be used at temperatures as high as 2010F. (1100C). The corrosion and oxidation resistance and the strength and stability at high temperature can be increased by the addition of silicon, tungsten, molybdenum,
cobalt, or
nickel are both increased, they may,
columbium.
18.9. Recent
Developments
in Stainless Steels
There
are a
number
affect
of elements for example, carbon, nitrogen,
and
the
titanium that
the phase boundaries of the 18 per cent
chromium
result,
section of the ternary iron-chromium-nickel diagram.
As a
188
alloy
may have
a duplex structure of ferrite

it.
and
austenitc unless
precautions are taken to prevent
It
is
also evident that lowering the
nickel slightly (see the 18 per cent
chromium
section in Fig. 18.4)
will
make
it
impossible to produce a structure consisting entirely of austenite

fact,
even by quenching. In
less
the
metallurgists believe that with very low carbon
188 composition is so critical that some and 8 per cent or slightly
nickel, an austenitic structure is possible chiefly because the small percentage of nitrogen introduced during metling prevents normal phase changes. In practice, an austenitic structure is assured by rapid cooling (Sect. 18.6) and by keeping the nickel well over 8 per cent, especially if
the carbon
is
less
than about 0.08 per cent.

steels,
The
ferrite
chromium-nickel
less
which are magnetic, are much
stronger
They have not including corrosion resistance, are not enough better than those of low-carbon 16 to 18 per cent chroductile than the austenitic material.
as their properties,
and
been used industrially,
mium
One
alloys
which are
also ferritic)
to justify the
much
higher
cost.
of the disadvantages of the austenitic chromium-nickel steels is that high strength can be attained only by cold working heat treatment
is used solely to ensure the proper structure. This limits the application of such cold-worked material as sheet, tubes, strip, and wire products. Some years ago, Smith, Wyche, and Gorr* discovered that by adding
0.50 to 1.00 per cent titanium, which is a ferrite former, to a steel containing about 0.07 per cent carbon, 17 per cent chromium, and 7 per cent nickel a ferritic structure can be readily produced; this structure can
v.
R. Smith, E. H. Wyche, and W.

pp. 313-345.
W.
Gorr. Trans.
Am.
Inst.
Mining Met.
Encrs.,
1G7, 1946,
Special Purpose
Steels
379
be hardened by precipitation of a carbide that is retained in supersaturated solution in the ferrite matrix by a suitable heat treatment. The heat treatment consists of heating the alloy to temperatures between about 1400 and 2000F. (760 and 1095C.) to produce a homogeneous austenitic structure, followed by cooling to room temperature The alloy is then reheated (at any rate faster than slow furnace cooling)
.
between 950 and 1050F. (510 and 565C.) to precipitate the hardening constituent. This steel, known as stainless W, has many desirable properties. Representative mechanical properties are given in Table 18.5. In addition to the high tensile strength, it has a high yield strength and a definite
to temperatures
The enis about 28 million lb. per sq. in. lb. per to 90,000 specimens varies from 80,000 durance limit on polished of sheet having a for specimens treatment; sq. in., depending on the
modulus of
elasticity,
which
about 30 per cent of the tensile strength. has much lower ductility than the austenitic material, Stainless which in view of its strength and structure is not unexpected. The steel is readily welded. Its corrosion resistance is apparently the same as that of
normal rolled surface
it is
austenitic 188,
and it is not subject to intergranular embrittlement. This steel has been the forerunner of a group developed to meet a need in industry for austenitic alloys that respond to a hardening heat treatment. Approximate compositions of representative members are given in
the table below.
Table
18.4.
Nominal Composition of Prccipitation-Hardenahle Grades
Designation
Stainless
C
0.07 0.04
0.07 0.07
Cr
17
Ni
7 4 7
Other
0.70Ti, 0.20A1
17-4PH
16.5
17 17 17 16
19
4.0Cu, 0.35Cb
I.IOAI
Ta
17-7PH
AM350
17-10P
17-14
2.75Mo
0.25P
HNM
Cu-Mo
0.12 0.12 0.30
10.25 14 9.5
2.5Mo, 3Cu, 0.45Cb, 0.25Ti 3.5Mn, 0.30P
Data from Roach and
Hall, Materials and Methods, April 1956, p. 144.
The steels, except Am350, noted in the table, contain elements forming compounds that are soluble in austenite at elevated temperatures but that may be retained in a supersaturated condition in the phase existing
380
Table
18.5.
Typical Room-Temperature Mechanical Properties of Precipitation-
Hardcnable Grades
Ten
Str.
Yld.
Str.
Elong. Hardin
ness,
Charpy Endur. ImLimit

pact
Ft-lb
Designation
Condition
1000
psi
1000
psi
in.
Rockwell
1000
psi
%
7 7 8 12 13 30 9
8
Stainless
Annealed Aged 'A hr.
at 950 F.
Aged Vi
17-4PH
Aged
1
hr. at 1050 F.
Annealed
hr. at
900 F.
135 210 190 150 195 130 145 215 186 197 199
95 195 170 110 180
43
25 43 39
19
_
80 90
17-7PH
Annealed
Treated at 1400 F. Aged at 950 F. Annealed Subzero cooled Tempered at 750 F.
AM350
40 100 200 52 110 159

37.5
R b 85
31
6 100
^_
^_
45
22
12
11
R b94
40
41
51
80
78
17-10P
17-14
Annealed
89
137
70
25 45
26.5
Rb82
30
120'
Aged
88 42
110
40'
Cu-Mo
HNM
Annealed at 2250 F. and aged Annealed at 2000 F. aged at 1200 F.
86
153
R b80
34
110'
18
Data from Roach and Hall, Materials and Methods, April 1956,
p.
145.
at
room temperature. Subsequent heating

in hardness
to temperatures in the vicinity
by an increase
is accompanied and strength. The treatments producing this hardened condition have been described for stainless W. Alloy 17-4 PH responds in a similar fashion. Mechanical properties are given in the table. The alloy 17-7 PH on annealing remains austenitic. It is however unstable and may be converted to martensite on cold work or by cold treatment. Subsequent heating to about 1000F. will produce a precipitate in a state of dispersion that will cause a marked increase in hardness and strength.
of 1000F. will produce a finely dispersed precipitate that
The alloys with appreciably higher nickel, 17-10P, 17-14, HNM, will remain austenitic on rapid cooling from about 1900F. and retain dispersion hardening compounds in solution, on aging at about 1300F. the compounds precipitate. The presence of phosphorus will intensify the hardening effect. The continuing expanding use of nickel has led to a shortage of the available supply of this metal. In an effort to alleviate to some extent this

situation, several low-nickel,
381
high-manganese austenitic stainless steels nickel-free, heat-resisting austenitic alloys. well as been developed as have Approximate compositions are given in the table below.
Table
18.6.
Composition of
New
High Manganese Grades
Designation
A1S1' 201 A1S1' 202
C
0.15 max. 0.15 max. 0.65
Mn
5.5/7.5 7.5/10.0
12
Cr
16.0/18.0 17.0/19.0
25
Ni
N
0.25 max. 0.25 max. 0.45 0.30/0.40
3.5/5.5 4.0/6.0
CMN*
G-192 8
0.55/0.65
8.0/9.0
21.25/22.75
Designation of the American Iron Crucible Steel Co. of America. Allegheny Ludlum Steel Corp.
&
Steel Institute.
Data from Roach and Hall,
Material/! arts Methods, April 1956, p. 138.
Table
18.7.
Typical Tensile Properties of High-Manganese Grades
Yld. Str.
Designation
Form
Condition
Test
Ten
Str.
psi
Temp. F
A1S1 201
1000
(0.2%) 1000 psi

55 105 55
Elong.
%
55 25 55 10
11
Sheet Sheet
Annealed
\i Hard
Room Room
Room
1200
115 150 105
A1S1 202
Sheet
Sheet
Annealed Ann.
CMN
G-192
& Aged
76
149
84
Bar
Hot worked
Room
Data from Roach and Hall, Materials and Methods, April 1956,
p. 139.
mechanical properties of types 201 and 202 are essentially the same as A1S1 301 (17 Cr-7Ni) and A1S1 302. Corrosion tests seem to indicate that type 201 is comparable in corrosion resistance to 301, and type 202
The
resembles 304.
18.10. Superstainless Steels
faced
During the early years of World War II, American metallurgists were with an urgent and difficult problem in the metallurgy of
to develop a superstainless steel for use in turbosu-
high-alloy steels:
382
(jet
perchargers and gas turbines
engines)
In addition to
its
great
importance for military aircraft and propelled missiles, solution of the problem would probably have far-reaching peacetime ramifications, because it has been known for some time that a gas turbine has a high
over-all efficiency for
power generation
in
marine and other forms of
transportation.
The problem was to develop an alloy that would have a relatively long and useful life as highly stressed wheels, buckets, and other parts of turbines, when operated at very high temperatures and when exposed to highly corrosive hot gases. Two methods of attack were used: to produce a superstainless steel based on the 188 analysis which has excellent elevated-temperature properties and to develop further existing nickel-rich and cobalt-rich alloys of the Inconel, Stellite, and Hastelloy types, which are extremely heat- and corrosion-resistant. Some of the principal alloys developed and used during the war are given in Table
18.8.
Early in World War II, German engineers were ahead of ours in the design of jet engines, but the lack of suitable alloying elements was responsible for an average life for these power units of much less than 100 hr. After designs were perfected in the United States, the following
typical requirements for alloys for superchargers
were
set
up: they should

(815C.)
withstand a
stress of at least
12,000
lb.
per
sq. in. at
1500F.
without failure and be resistant to exhaust gases containing tetraethyl lead. For gas turbines, temperature and stress conditions were somewhat less severe. It is to the credit of American metalfor at least 1,000 hr.
lurgists that
most of the
alloys listed in
Table
18.8
meet the requirements
satisfactorily.
For industrial gas turbines, economics will be more important than was for military aircraft during the war. Some of the elements used in large quantities during the past three or four years in alloys for turbosuperchargers and jet engines cobalt is an example-will be too scarce
it
or too costly to be used in turbines which must develop power economically; further, the life of the alloys must be much longer, up to at
least
100,000
hr.,
for example, for a
marine turbine. Turbine
efficiency
increases rapidly with

stainless alloys
increasing tempera lure so that postwar super-
must withstand very high temperatures for long periods of the alloys available now will meet this requirement unless stresses are much below those characteristic of superchargers and jet engines. If high stresses must be withstood at very high temperatures and for long periods of time, new alloys must be developed. Tt is to be expected, therefore, that some of the alloys listed in Table 18.8 will
of time.
None
383
Chemical Composition of Supcrstainless Steels and Heavy Nonferrous Table 18.8. Alloys for Turbosuperchargers and Gas Turbines
Nominal composition, per cent

Alloy designation
C
Supcrstainless
steels:
Mn
Si
'
Cr
Ni
Co
Mo
W
1.25 1.26
Cb
Ti
19-9 DL 19-9 W-Mo S 495 S 590
0.30 0.10 0.45 0.45
1.00 0.60 1.00

1.00 0.60
0.55 0.50
0.40 0.08 1 6-25-6 f 0.30 0.40 0.35 0.35 0.10 155 MultimctJ.. 0.15 0.04 0.03 Rcfractalloy 25-20-2 Si 0.10
1.50 0.60 1.00 1.25 4.00 0.75 1.00 0.50 0.70 0.50
0.50 0.60 0.60 0.80 1.00 1.00

1.00
0.50 0.50 0.50 0.50 0.65 2.00
19.00 19.00 14.00 20.00 20.00 16.50 13.00 15.00 15.00 18.50 19.00
20.00 13.00 18.00 25.00
9.00 9.00 20.00 20.00 20.00 25.00 20.00 25.00 27.00 4.50 12.00 20.00 24.50 37.00 20.00
1.25 0.40
20.00 44.00
4.00 4.00
4.00 6.25 0.60 3.00

1.35
4.00 4.00 4.00 2.25
0.40 0.40 4.00 4.00 4.00
0.30
0.35
4.00 4.00
1.35
0.60
1.25
3.25
20.00
20.00
3.00 3.00 3.00
2.00
1.00
2.25 3.00
Heavy
nonferrous alloys:
Inconcl, modified
Stellite Stellite
6059 30-422
Hastelloy Hastelloy
0.15 0.10 0.25 0.40 0.40 0.05 0.15
0.75 0.60 0.60 0.60 0.30 0.75 1.00
0.25
0.60 0.60 0.60 0.25

0.75 1.00
13.00 15.00 27.00
26.00 27.00
16.00
78.00 74.00 2.00 32.00 16.00 65.00 55.00
65.00 35.00 50.00
5.00 5.00 6.00
29.00 17.00
5.00
* Contains only 4 per cent iron. t Contains 0.10 per cent nitrogen.
X
In development stage, contains 0.15 per cent nitrogen.
Contains 0.70 per cent
aluminum.
disappear, except for military use, in the next few years, and that other and more economical or better alloys for industrial gas turbines will take
their place.
The
is,
supcrstainless alloys are important almost wholly for their strength

resistance at elevated temperatures,
and corrosion
therefore, deferred to a later chapter.
The
and further discussion following data give a genduring the

last
eral idea of the overall
improvement
in these alloys
few
years:
is
The
stress
which
causes failure in 1,000 hr. at 1200F.
(650C.)
1,000 lb. per sq. in. for 3 per cent nickel
(S.A.E. 2340) steel; 4,000 lb.
384
l'i
12
ID
O
*I0
*-,
/
1
b
6
"o
/
/
J
4 o
2
\J
C
I
o
9
2( )
30
4( )
60
70
80
between
90
100
Nickel, per cent

Fie. 18.7.
Coefficient
of
expansion
of
iron-nickel
alloys
and 200 F.
{Marsh)
for the silchrome used before the war; 19,000 lb. for
17W
(Table
16.4)
used at the start of the war; 30,000

36,000 lb. for
lb. for
gamma Cb
used in 1944; and
16-256 used
at the
end of the war.
18.11. High-Nickel Steels and Special Iron-Nickel Alloys

Nickel dissolves in
gamma and
in alpha iron
it
and has a strong
effect
atmospheric temperature or A3 below but, in addition, slowing greatly the rate of the phase change and producing some anomalies in properties which are of great value to industry. Alloys of iron with 20 to 30 per cent nickel may easily be made
on the position of
not only lowering
to
nonmagentic (despite the
fact that
both iron and nickel are magnetic).
Alloys of iron with 30 to 60 per cent nickel have variable and controllable
expansion characteristics which were discovered late in the nineteenth century in France. The fact that alloys of iron with 45 to 85 per cent nickel can be treated to produce high magnetic permeability and low hysteresis loss has led to wide use of some of them in telephone, telegraph, and radio equipment. and As shown in. Fig. 18.7,* the coefficient of expansion between 200 F. ( 18 and 100 C C.) decreases to nearly zero as nickel approaches
* Based on data in J. S. Marsh, The Alloys of Iron and Nickel, Vol. I, SpecialPurpose Alloys, McGraw-Hill Book Company, Inc., New York, 1938, p. 160.

36 per cent. Increasing the nickel from 36 to 60 per cent makes
desired coefficient of
it
385
possible
"6
-
expansion between 1 and 12 X 10 to have any have been developed for use in measuralloys As the result, a number of machines and instruments which of ing tapes, watch parts, and parts temperature changes. The despite dimension must remain constant in
use of invar struts in aluminum-alloy pistons is well known. Some of the commercial alloys with controlled expansion characteristics are given in
Table
If
18.9.
chromium and tungsten
are
added
to
an
alloy containing
about 32
per cent nickel, the affect of temperature

perature)
(in the vicinity of
on the modulus of elasticity is zero. This alloy elinvar and is used for hairsprings of watches and for springs of other precision measuring instruments. The invars and other high-nickel alloys have the additional advantage that they have excellent corrosion resistance.
room temis known as
and perminvar are used in applications where their high or constant permeability produces marked economics or increased efficiencies in communication. Because under weak magnetizing forces permalloy has a permeability many times
The
alloys
known
as permalloy, hipernik,
greater than that of all other ferrous materials except iron of the highest purity, permalloy is a commercially feasible high-permeability material.
The development
possible,
of this alloy has
made modern
long-distance telephony
and
its
use in the loading of submarine cables has speeded
up
the transmission of messages several hundred per cent. Hipernik has initial and maximum permeabilities much greater than those of com-
mercial grades of high-purity iron and the advantage of relatively high maximum induction, which makes it valuable for use in radio transformers.
The efficiency of radio loud speakers and other apparatus requiring powerful permanent magnets has been greatly increased by the recent development of the iron-nickel-aluminum-cobalt permanent-magnet maIn addition to alnico, two Japanese alloys are terials (see Table 18.9) noteworthy: the M.K., containing 25 to 30 per cent nickel, 20 per cent cobalt, and 12 per cent aluminum; and the K.S., containing 10 to 25 per
.
cent nickel, 15 to 36 per cent cobalt,
and
8 to 25 per cent titanium.
18.12. Austenitic Manganese Steel
Of
the large
number
in this chapter, austenitic
of high-alloy steels that have not been discussed manganese steel is of sufficient industrial im-
portance to deserve mention. This steel was discovered a number of years
386
Table
18.9.
Commercial High-Nickel Iron-Nickel Alloys
Composition,* per cent
Name
Ni
36
Characteristic properties
Co
Cr
Al
Cu
expansions from to 200 F. (-18 to 100 C.) Zero expansion near room temperature
Low
Supcrinvar
31
32 42
Low
thcrmoclastic
coeffi-
cient
Kovar
Platinilc ....
29 46
78.5
17
Permalloy
For sealing in soft glass For sealing in hard glass Expansion same as platinum High permeability at low
field
strengths
at higher
Hipernik ....
50 45 20 17 25 28 25
5
High permeability
field
strengths
Perminvar
Alnico
I
.
.
12
10
12
Alnico II Alnico III... Alnico IV...

. .
12.5
5
12
Constant permeability over a range of flux densities Permanent magnet of high magnetic hardness Same as above Same as above Same as above
Balance of composition
is
mostly iron.
ago by Hadfield in England during his pioneer researches on alloys of iron with manganese, silicon, nickel, chromium, and other elements. The annual tonnage of high-manganese steel used is small, but, as is the case
with
many
ferrous materials, production
is
no
criterion of
its
usefulness
High-manganese steel contains 1.00 to 1.30 per cent carbon and 11 to 14 per cent manganese and is made by the basic open-hearth, Bessemer, or electric process. It may be poured into ingots and rolled into
to industry.
a variety of sections, or it may be cast in sand molds. Owing to its workhardening capacity when cold, it cannot be machined readily; hence, if shaping is necessary, it usually must be ground. Economically this is
a great disadvantage.
In amounts under 50 per cent, manganese dissolves in alpha and
gamma
Like nickel it lowers the A 3 temperatures where alpha in heating and where the reverse change occurs in cooling, and slows the transformation rate. As noted in a previous chapter, manganese also forms a carbide, (Fe.Mn) 3 C, which is closely allied to Fe 8 C in structure and properties. Alloys containing 1.00 to 1.30 per
iron.
transforms to
gamma
387
cent carbon and 13 per cent manganese, if cooled very slowly so that all phase changes take place, contain at room temperature alpha solid solution plus excess carbide. In the usual cooling after hot working, or in a
mold
in the case of a casting, these
phase changes, owing to the low

consists of the
reaction rates,
do not take
place,
and the structure
gamma
solid solution plus, possibly, a little alpha, plus excess carbide as massive particles or as a network around the grains. With this structure the steel
hard and brittle. If, however, the steel is heated to 1830 to 2010F. (1000 to 1100C), the carbide goes into solution in the gamma, and if the steel is now quenched in water, a structure consisting wholly of austenite with no free carbide is obtained. Unfortunately, tempering to
is
relieve
quenching
stresses
is
impossible because reheating in the tem-
perature range 930 to 1290F. (500 to 700C.) or even lower

precipitation of carbide or change of
may
cause
some
gamma
to alpha
and thus
following
may cause
brittlencss.
steel has the
As water quenched, rolled austenitic manganese

properties:
lb. per sq. in Proportional limit, lb. per sq. in Elongation in 2 in., per cent Reduction o area, per cent
Tensile strength,
130,000 to 160,000
40,000 to
60,000
60 to 40 to
180 to
70 60
Brinell hardness
220
steels
As is characteristic of austenitic alloys, the high-manganese no well-defined yield point and are nonmagnetic.
High-manganese
steel
is
have
important industrially chiefly because of
its
high abrasion resistance.
Although the Brinell hardness of the heattreated steel is low, cold working causes a rapid increase to as much as 550 Brinell. As abrasion consists largely of cold working the surface, this capacity for work hardening has important ramifications. Thus, in steamshovel buckets, in crushers, grinders, and other machines, and in rails, cross-overs, switches, frogs and such sections where pounding, pressure,
or abrasion by rock and sand or by other metals are encountered, highmanganese steel outwears high-carbon steel by several hundred per cent.
QUESTIONS
1.
Name
the three classes of high-alloy steels containing
chromium
as the prin-
2.
Give the approximate composition of six common high-chromium steels, and name the class to which they belong. What is the effect of up to about 15 per cent chromium on the transformation temperatures in high purity iron? Describe the phase changes that take place if an alloy containing (a) 10 per cent chromium and 90 per cent iron,
cipal alloying element.
388
and
(b) 20 per cent chromium and 80 per cent iron, is heated slowly to 2,500F. (1,370C) and cooled again. What is the effect of carbon on the phase changes that take place when alloys of iron and chromium containing up to about 20 per cent chromium
3.
4.
are heated to a high temperature and cooled again? What effect has carbon on the response of these alloys to heat treatment? What structure would be expected if the following steels were quenched
(a) 0.35 per cent carbon and 14.50 per cent chromium? per cent carbon and 16.75 per cent chromium? (c) 0.07 per cent carbon and 15.80 per cent chromium? How does the hardenability of a steel containing 0.35 per cent carbon and 14 per cent chromium compare with the hardenability of an unalloyed high-carbon steel? What is the relation between the tensile properties and the carbon content of heat-treated 14 to 18 per cent chromium steels? Give two peculiarities in tempering quenched cutlery steels and the effect of these on tensile
in
oil
or water:
(b) 0.75
5.
strength and impact resistance. What is the relation between the chromium content and the corrosion (and oxidation) resistance of chromium steels?
What
6.
is
the effect of carbides

to 18
on
corrosion resistance?
To
what corrosive
media are the 12
per cent chromium
steels especially resistant?
Why?
What
in
is
the general effect of nickel
on the alpha-gamma transformations
iron-chromium alloys? What is the effect of adding 5, 8, or 10 per cent on phase changes in alloys containing 18 per cent chromium and approximately 82 per cent iron when they are slowly heated and cooled between room temperature and 2,400F. (1,315C)? Why are alloys containing 18 per cent chromium. 8 per cent nickel, and low carbon usually
nickel
austenitic at
7.
room temperature?
What
lying
is
intergranular corrosion in 18-8?
What
causes
it?
What
is
the under-
mechanism of the phenomenon?
How
is it
prevented?
8.
What
are the characteristic mechanical properties of 18-8, and what effect has heat-treatment on these properties? How does the resistance of 18-8 to corrosion and oxidation compare with that of the high chromium steels?
9.
What What
chromium -nickel steels and what is stainless are superstainless steels? What alloying elements in addition to chromium and nickel are used in these materials? What are the general
are fcrritic
W?
characteristics of superstainless steels,

10.
and what are they used for? Outline the main points of difference between the well-established 18-8 grade of stainless steel and the new group of these materials.
CHAPTER
Tool Steels, Die Steels, and Cemented Hard Carbides

JOSEPH Gi.rland,
Engineering,
Island
Sc.D., Assistant Professor, Division of
19
Brown
University,
Providence,
Rhode
Joseph
Kaufman, Instructor, Metallurgy Department, J. Academy of Aeronautics, Flushing, New York
slow, advance of civilization over the past ten or twelve thousand years has been largely the result of progthey are ress in the design of tools and in the material from which fashioned: from stone to copper, then to bronze, and then to iron,
if
XHE steady,
and after a long period to carburized iron (steel)-which was the most important step of all and finally to high-speed and other alloysteel tools and sintered hard carbides, which made possible great reductions in the cost of finished structures and machines.
All tools can be divided broadly into two general classes:
(1)
cutting
and should and shearing tools (2) forming tools. Requirements differ and cutting Thus, for selected. steel is be considered before the proper
and
shearing, high hardness, ability to withstand wear, stability of structure to withstand the heat generated by the friction of the cutting edge
against the work, and a substantial
amount
of toughness to prevent chip-
ping and breakage are important. For shearing tools, a lack of deformation or warping in heat treatment is usually also important. Forming tools consist chiefly of dies, which are used to transfer their impression
molten metal. In addition to poscutting or shearing tool, forming sessing the qualities necessary in a and to cracking treatment tools must be resistant to distortion in heat
to either hot or cold solid metal, or to
caused by sudden changes in temperature during use.
The representative
fication
is
types of tool steels
and
their principal characteristics
are given in Tables 19.1 and 19.2.

used.
The
recently adopted
AISI-SAE
classi-
As Table 19.2
indicates,
tool steels vary widely in
characteristics.
389
390
selection of the proper tool steel for a certain
The
is
difficult
and
is
problem
is
in the solution of
machining operation which the advice of the

specific tool
tool-steel metallurgist
very helpful.
is
An
accurate evaluation of a steel that
to
be used for a
in a specific
sult, large
machining operation
is
practically impossible,
and
as
re-
quantities of tool steel are,
and always have been, purchased
by brand name.
The only reliable performance test of a tool steel is to use it in actual production and to use enough similar tools of the same steel to make the
results convincing.
Large users of tool
steel
frequently distribute their
of tool-steel manuand keep accurate records of the performance of each brand. At the end of this production test the company whose brand makes the best showing receives 50 per cent or more of the business for the next yearly or half-yearly requirements
facturers
among
number
period.
19.1. High-Carbon Tool Steels
The
steels of class
W, Table
19.1, are the
cheapest and, despite high
distortion in hardening, low resistance to softening at elevated temperature, and shallow hardening, the most widely used of the tool steels. There are four classes, graded according to carbon content as follows: 1. Carbon 0.60 to 0.75 per cent; used for machinery parts, hot-forging dies, rivet sets, battering tools, large chisels, and set screws. 2. Carbon 0.75 to 0.90 per cent; used for forging dies, boilermakers' tools, hammers, sledges, mining tools, and miscellaneous blacksmiths'
tools.
3.
Carbon
0.90 to 1.10 per cent; used for drills, saws, cutters, taps,
small shear blades and dies, anvils, wood- and stone-working tools of various kinds, punches, and axes.
4.
Carbon
1.10 to 1.40 per cent; used for small drills, taps
and lathe
dies, brass-
tools, files, cutlery
and small edge
tools, jewelers'
tools
and
and copper-working tools, wire-drawing dies, and The hardness and toughness of the high-carbon
razors.
tool steels vary with carbon content; they also vary with heat treatment, that is, with tempering temperature. Since high hardness and considerable toughness are incompatible in an unalloyed high-carbon steel, it is necessary to sacrifice part of one or the other depending upon the use for which the tool is intended. Thus, for razors, which must be very hard and which are not ordinarily subjected to shock, a 1.20 per cent carbon steel, treated to give a hardness of 60 to 65 Rockwell C, is used; but for a hammer or a chisel, which must withstand impact, a steel containing 0.70 to 0.90
Tool
Steels,
Die
Steels,
and Cemented Hard Carbides
391
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Tool
Steels,
Die
Steels,
393
Tempering femperature.deg.C.
100
300
500
"As
quenched
200
600 800 1000 400 Tempering temperature, deg.F.
I20C
Fic. 19.1.
Effect of
tempering on the hardness of water-quenched high-carbon
steel.
(GUI)
per cent carbon, treated to about 55 Rockwell C and with more toughness, will be chosen. Wear resistance, which usually is not so high in carbon steels as in some of the alloy steels, is secured by the use of a 1.20 to 1.40 per cent
heat treated so that there will be numerous well-distributed excess carbide particles in a martensitic matrix. Such a structure (Fig. 19.2) is important for cutting tools and wire-drawing dies. Under the
carbon
steel,
quenching conditions necessary to obtain high hardness, high-carbon

steels
warp considerably. In
tools of simple section this
may be
tools
mini-
mized by quenching in special fixtures; for dies and some must be finish-machined before heat treatment and for which stability of dimensions is necessary, special nondeforming alloy steels, which
which
harden in
oil
or
air, are
used.
394
Fig 19.2.
Structure of water-quenched high-carbon tool steel: small carbide particles
in martensitic matrix, etched.
500X-
High-carbon
steels,
even though of practically the same composition,
may
differ in their response to
quenching (hardenability).
temperature,
is it
If
the steel con-
has an inherent tendency to become coarse-grained

siderably above the transformation
when heated
hardens relatively
deeply and uniformly

spots
when quenched but

it is
likely to crack. If it is fine-
grained after such treatment,
on the
surface,
but
it
alloyed high-carbon steels

steels
may have soft not so likely to crack in quenching. Unare all shallow hardening compared with tool
shallow hardening and
is
containing considerable
molybdenum
or chromium, but the harden-
ability can be controlled to
some extent by controlling the grain-growth
tendency during manufacture. The difference in hardenability between two lots of high-carbon steels of identical chemical composition is shown
in. in diameter were quenched in brine from the temperatures noted and were not tempered. The fractures of the "finegrained" bars are shown at the top, and those of the "coarse-grained"
in Fig. 19.3.* Bars
bars at the bottom.
The coarser grain and

steels arc
the greater depth of hardening
for the latter are clearly evident.
Unalloyed high-carbon
response to heat treatment.
Even
steels of the
apt to be inherently erratic in their same composition, made
by the same manufacturer, may differ in their tendency toward grain growth and in depth of hardening. To render the response to quenching
more uniform, small percentages of chromium or vanadium are frequently

*
Shepherd P-F hardenability
test
specimens.
Tool
Steels,
Die
Steels,
395
Fracture of quenched and untempered high-carbon tool Fie. 19.3. hardening. fine-grained, shallow hardening; bottom, coarse-grained, fairly deep
steel.
Top,
(Gill)
added
mium
W. Vanadium inhibits grain growth and chrohardenability; both have a favorable effect which probincreases
to steels of class
ably compensates for the increased cost. As a class, the high-carbon tool steels are characterized by high hardness at the surface and a relatively soft core in all but very small sections.
Owing
to this soft core, Gill* rates these steels as
tough and resistant to
disshock. They are, as previously mentioned, subject to considerable the surface at tortion in quenching due to the formation of martensite and of bainite or pearlite in the center, and to the stresses caused by
differential cooling of surface
and centerwhich means
that they are not
suitable for tools of
complex or irregular shape.
Small amounts of nickel, chromium, molybdenum, or tungsten are added to some varieties to increase hardenability and to permit quenching in
oil
instead of water.
19.2.
Low
Alloy Tool Steels
which include the well-known ball- and per cent carbon and 1.2 to 1.5 used to some extent for dies, rivet are cent chromium (S.A.E. 52100) per sets, small rolls, and for a few cutting and shock-resisting tools. They are relatively cheap, at least as compared with some of the highly alloyed tool steels, and have exceptionally high strength combined with relatively good toughness. They are also much deeper hardening than the highcarbon steels. Whether the steels are water or oil hardening depends
Low
alloy steels of class L,
roller-bearing material containing about

,
chiefly
on the manganese content, which
in the oil-hardening grades
is
0.50 to 0.60 per cent.
Tool
Steels,
American Society for Metals, Cleveland,
1944.
396
carbon content of these steels depends on the service requireif toughness is important as in pneumatic hammer pistons or chisels, it is 0.40 to 0.70 per cent; but if maximum hardness and wear resistance are necessary as in files, drills, and cutlery, it is between 0.90
ments;
The
and
1.10 per cent.
The amount
is
of
chromium
in the steel
depends
pri-
marily on the depth of hardening required, which in turn depends on

the size of the tool that
0.50 to 1.50 per cent to be treated.
Increasing the
chromium from
more than doubles the time available for the steel to cool past the pearlite nose of the S curve without transforming. Also in this class are high-carbon variants of some of the S.A.E. engineering
steels.
medium-carbon S.A.E. nickel-chromium or chromiummolybdenum steels are fairly deep hardening;* increasing the carbon to 0.60 to 0.70 per cent and maintaining the chromium at well over 1.0 per cent and the molybdenum at 0.30 per cent or more increases the quenched hardness and the depth of hardening; at the same time the steel retains considerable toughness. These steels are, therefore, finding relatively wide use in many machine parts and especially in die blocks for hot forging. These steels are generally quenched in oil.
of the
Most
19.3.
Medium
is
Alloy Tool and Die Steels

taken of the effect of manganese or
Advantage
chromium when
and
of in-
dissolved in alpha iron of decreasing the critical cooling rate
creasing deep hardening to produce a valuable and extensively used class
of oil-hardening "nondeforming" tool and die steels

steels are
(class
O)
These
used
when
the design of the tool or die
is
such that distortion or
cracking
steels
is likely to occur in water quenching. In this group there are containing 0.90 to 1.45 per cent carbon. If the manganese is
1.60 per cent, the steel usually contains no other alloying element although the addition of 0.10 to 0.25 per cent vanadium to reduce grain growth is optional. To increase wear resistance the manganese may be
cent tungsten
lowered to 1.20 per cent, and about 0.5 per cent chromium plus 0.5 per may be added; or the manganese may be reduced to 0.25 per cent, and 0.75 per cent chromium and 1.75 per cent tungsten may be
added. These modified steels are not so likely to crack in quenching as the higher manganese steels, but, on the other hand, they do not become
so hard.
The
steels of class
are quenched in
oil
from 1400 to 1500F.

(160 to 260C.)
(765 to 815C.)
and
are tempered at 325 to 500F.
They
and
are used as stamping dies, thread-rolling dies, dies for molding
plastics,
punches, broaches, blanking
dies,
and
especially as master tools
gages.
Kor
example, the
SAE
3100 series and 4100
series.
Tool
Steels,
Die Sleeb, and Cemented Hard Carbides

steel
397
Silicon-manganese
(S.A.E. 9255
and
per cent carbon, 1.80 to manganese is widely used for springs. Recently it has become popular as a tool steel, especially for punches, chisels, and shear blades, owing to its low cost and is fairly high wear resistance and toughness (class S-5) Strictly speaking, silicon-manganese steel is a misnomer, as the amount
of manganese
is
2.20 per cent
silicon,
9260) containing 0.50 to 0.60 and 0.60 to 0.90 per cent
not greater than that present in

steels.
many
is
of the S.A.E.
it is carbon and low-alloy resistance is wear steels, and high-carbon somewhat less than for plain steel and is high-carbon deeply than higher. The steel hardens more chromium cent 0.20 to 0.40 per tougher. To increase deep hardening, or 0.40 to 0.60 per cent molybdenum is occasionally added. Steels of class
Distortion in quenching
high, but
S are usually quenched in water
(or
molybdenum
tempered
at
are present)
from 1575
to
enough chromium and 1625F. (860 to 885C.) and are

oil, if
350 to 600F. (175 to 315C.)

low-tungsten tool and die steels are fairly
The medium-chromium and
or very deep hardening and, generally, can be hardened with little distortion. They have higher resistance to wear than unalloyed high-
carbon
steels
and they have

class S
satisfactory toughness.
and therefore of relatively high toughness, are used for chisels, punches, shear blades, and battering tools and occasionally for dies. These steels do not have high resistance to tempering. According to Gill, chisels of this steel have three times the
Steels of
of low carbon content
life
of unalloyed chisel
steels in class
steel.
The
contain
1.0
per cent carbon and

1
1.0
per cent
molybdenum. Chromium varies from .0 to 5.0 per cent, and manganese varies inversely with the chromium from 3.0 to about 0.50 per cent. These steels are air hardening and are widely used for intricate dies that must
maintain their dimensions accurately after heat treatment. They are used for- blanking and forming dies, rolls, punches, and drawing dies but not for dies that operate at high temperatures.
19.4. High-Alloy Tool
and Die Steels
Dies that are to be used in applications where they are heated to temperatures
(315C.) or above are usually rather highly alloyed, (class H). Steels in these classes are characterized by high hardenability
600F.
(the pearlite nose of the S curve of
some of
these steels
is
far
to the
is
right of the time axis), very low distortion in heat treatment which
natural in view of the fact that most of the steels can be hardened in air high hardness at elevated temperatures, and fairly good toughness. Most
398
Fie. 19.4.
and
(B) oil
Structure of high-chromium die steels (A) forged and annealed, 750X". quenched and tempered at 400F. (200C), 500x: etched. (Kinzel and
Forgeng)
will withstand temperatures of
100F. (595C.) or even slightly higher.

steel in
This
is
to be
expected as some of them approach high-speed
composition and in
many
characteristics.
steels
(class
The
structure pf the
high-chromium die
is
D)
as forged
and
quenched and tempered
shown
in Fig. 19.4. Although, after annealing,

is
200 to 230, they are difficult to machine. Steels of this type harden deeply with little distortion and do not soften appreciably when tempered below about 900F. (480C.) Their wear resistance is high. Despite high cost and difficulty of machining, these steels are among the best as dies for forming and trimming,
the Brinell hardness of these steels
blanking, thread rolling, and wire drawing, as shear blades, bushings, and rolls, and as small machine parts where resistance to abrasive wear
is
important.
They
are seldom used as cutting tools.
19.5.
High Speed
Steels
are
steel.
The majority of today's tool steel cutting tools The principal types are given in Table 19.3.
made
of high speed
Tool
Table
Steels,
Die
Steels,

Steel
399
19.3.
Classification of
High-Speed
by Chemical Composition
AISI-
Nominal chemical composition, per cent
SAE
Class
Type
C
T-1 18-4-1
Mn
0.25 0.25 0.25 0.25
0.25 0.25 0.25 0.25 0.25
Si
W
18.0 18.0 14.0 18.0
Cr
4.0 4.0 4.0 4.0 4.0 4.0 4.5 4.0 4.0
V
1.0 2.0 2.0 3.0 1.0 2.0
1.5 1.0
Mo
Co
0.70
0.85 0.80 1.00
T-2 T-7 T-3

T-4 T-8 T-6
18-4-2 14-4-2
0.25 0.25 0.25 0.25

0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25
M-1 M-10
Co Co 20-4-2 Co Molybdenum Molybdenum

18-4-1 14-4-2
W
. .
0.75 0,80 0.80 0.80 0.85

0.85 0.85 0.85 1.30 0.85
18.0 14.0 20.0

1.5
5.0 5,0 12.0
2.0
1.3 2.0 2.0 4.0 2.0
8.0 8.0
8.0 8.0 5.0 4.5 5.0 5.0 8.0
M-30 M-34 M-2 M-4

M-35
Mo WCo Mo W Co Mo W Mo WV Mo WCo
0.25 0.25 0.25 0.25 0.25
2.0 2.0 6.0 5.5 6.0
4.0 4.0 4.0 4.0 4.0
5.0
But since World War II, molybdenum is replacing tungsten in these alloys. Today, 80% of all shipments of high speed steel are of types M-1, M-2, and M-10;
The
familiar 18-4-1 composition has long been the basic type.
whereas type T-1 represents only
10%
of
all
high speed
steel
being used.
In general, cutting performance increases with tungsten or molybdenum. Vanadium is necessary for satisfactory performance and approxi-
mately 1 per cent or more is always present. Chromium is held constant at about 4 per cent, with carbon varying from 0.50 per cent (if toughness at the expense of some hardness is desired) to as much as 1.50 per cent. Cobalt has been used in the regular grades of high-speed steel with considerable success. It increases red hardness and the efficiency of the tool where temperatures are high as during heavy roughing cuts. High-speed
retains
its
steel
is
hard, strong, and brittle at
hardness and strength at temperatures
room temperature and up to 1100 to 1200F.

which
is
(595 to 650C.)
The
fifty
cutting performance of high-speed
steel,
from three
to
is
times that of unalloyed high-carbon steel of the same hardness,
largely
dependent upon the heat treatment. The optimum quenching temperature depends upon composition, and a variation of 50F. (30C.) from the optimum will affect the performance of the tool.
, ,.
400
Engineers owe a large debt to two Americans, F. W. Taylor and Maunsel White, who, while working at Bethlehem Steel Company in October, 1898, discovered the "weird and novel" heat treatment which gives high tungsten-chromium steel its property of red hardness. Taylor and White found that a steel containing 1.14 per cent carbon, 0.18 per cent manganese, 7.72 per cent tungsten, and 1.83 per cent chromium performed poorly in rapid machining when heat treated in the usual way. After considerable investigation the present-day treatment was
developed. This consists of heating the tool slowly to 1500F. (815C.) then rapidly to a temperature slightly below the melting temperature
with modern high-speed steels this is 2200 to 2350F. (1205 to 1285C.) which would ruin carbon or low-alloy steel and cooling it rapidly in The tool is then tempered immediately by oil, or, sometimes, in air.
reheating to 1000 to 1150F
this
When heat treated in (540 to 620C.) way, high-speed steel machines at high speeds and with such heavy cuts that the point of the tool becomes red hot, without losing any
.
hardness.
Although considerable work has been done on the constitution of iron-tungsten-carbon alloys, little is known about the effect of 4 per cent to 2 per cent vanadium on these alloys. Studies of chromium and microstructure indicate that high-speed steel when annealed consists of
1
matrix and a large number of paris heated to a high temperature, the matrix changes to austenite and some of the carbides go into solution. To produce red hardness and satisfactory cutting performance, the temperature to which the steel is heated must be as high as possible without causing incipient melting. When the steel is quenched from
a relatively soft (probably ferritic)
ticles
of a complex carbide.
When
the steel
such as is shown in Fig. 19.5 A* results. It thought that the polygonal grains of the matrix are composed of austenite plus untempered martensite. Reheating to 1()50F. (565C.)
this temperature, a structure
is
upon
tempers the martensite slightly so that it etches rapidly (Fig. 19.5B), and cooling from the tempering temperature the retained austenite transforms to more martensite. The secondary hardening that results
is
from tempering
shown
in Fig. 19.8
The
steel,
cause of red hardness, the most important property of high-speed has not yet been explained satisfactorily. It is usually considered
to be related to the high stability of the complex carbide particles and to the fact that the most favorable size of the particles for stability of
structure
is
not altered by temperatures as high as 1100F.
(595 C.)
Inc.,
J.
New
I.. Gregg, The Alloys of iron York, 1934, pp. 294, 295.
and Tungsten, McGraw-Hill Book Company,
Tool
Steels,
Die
Steels,
401
&4&&L *3 ,CK-^^^
FIO. 19.5.
L
<8f>*
quenched and
Structure of high-speed tempered; etched. 750x- (Gregg)
steel;
(A)
quenched and
(B)
the substitution recent development in high-speed steels is This was Table 19.3) of molybdenum for most of the tungsten (see who Emmons.t by pioneered by Richie* at Watertown Arsenal and
The most
developed the
steels
commercially.
(1)
Molybdenum
has three advantages
in high-speed steel:
Since
it is
twice as effective as tungsten in pro-
as Table 19.3 ducing red hardness, only 6 to 9 per cent is necessary, and (3) it is tungsten; shows- (2) it is cheaper pound for pound than ores are available. not a strategic material, as ample supplies of domestic molybdenum grades have been Initial difficulties in the heat treatment of between molybdenum solved, so that, at present, there is little difference performance. 1 he inand tungsten base alloys as to fabrication and tool steels is due mainly to creased consumption of molybdenum high-speed
their lower price.
expenCompared to carbon tool steels, the high-speed steels are more kind right used in the sive and arc not as tough. However, properly any from made out-perform tools of equipment, the high-speed steels will up stand will which steel. It is the only type of steel
other type of edge by modern, highto the high temperatures generated at the cuttting speed, production machines.
S.
B. Richie,
fj. V.
Army Ordnance, V. 11, Emmons, Trans. Am. Soc. Steel
July, 1930. Treat., V. 21,
193S, p. 193.
402
Temperinq
temperature
400
deq.C.
'
SOO
soo
60
Tempering temperature,
Fig. 19.6.
deq.
F.
Effect
of.
chromium on the
resistance of 0.35
per cent carbon steel to
tempering.
(Bain)
19.6. Function of Alloy Additions in Tool
and Die
Steels
The
tions
is
structure of tool steels consists essentially of a dispersion of hard
steel. The purpose of small alloy addiimprove the properties of the matrix by increasing the hardenability and refining the grain si/e. The most common alloy additions to low alloy steels are chromium, vanadium and manganese. Chromium increases the depth of hardening and adds some wear-resistance; vanadium increases toughness and limits grain growth; manganese permits oil hardening with much less distortion than water quench. To further reduce the likelihood of cracking during cooling, about 1% molybdenum makes a steel air hardened. Larger amounts of alloy elements, together with increased carbon contents, form hard alloy carbides which are responsible for the superior hot hardness and wear-resistance of alloy tool steels. The amount and the dispersion of the carbide particles determine the hardness; the greater the relative volume of the hard phase, the harder and more brittle the
carbide particles in a matrix of

to
steel.
The
principal function of large alloy additions to tool steels
is
to
increase the
amount
of the carbide phase.
Tool
Steels,
Die
Steels,

C.
403
400
600
600
1000
1200
F.
Fig. 19.7.
Effect of
molybdenum on the
resistance
of 0.35
per cent carbon steel
to tempering.
{Bain)
As
steels,
is
are the most important alloying elements in
evident from Table 19.1, tungsten, molybdenum, and chromium medium and high alloy tool
in high-
and together with vanadium they are more imi>ortant

steel
than in the ordinary tool and die steels. All three are soluble amount in gamma and in alpha iron and, more importa considerable to all three form hard and stable carbides. All three, when dissolved ant,
speed
in
gamma
The
iron, slow the reaction rate for austenite to transform to pearl-
ite chromium and molybdenum strongly and tungsten weakly.

carbides formed by these three metals dissolve to
of carbon
some extent
(depending on the amount and can be retained in supersaturated solution by quenching. This increases hardness and wear resistance. In addition, the carbides in excess
of those dissolved,
if
and
the temperature) in austenite
favorably distributed, greatly increase the resistance
of the steel to abrasive wear.
In contrast to tungsten, which has a minor cflect on hardenability, chromium and molybdenum have a powerful effect. This was discussed in detail in earlier chapters. The most valuable property of tungsten,
molybdenum, and chromium when present
in relatively large
amounts
404
Tempering tempcroture.deg. C. 200 300 400 500 600
'
i
100
'
J
I
'
703
48l
~_
J00
As
quenched
500 700 900 Tempering femperalure^d
UOO
Fic. 19.8.
Effect of
tempering on the hardness of high-speed. (Emmons)
in steel containing sufficient carbon is that they make the steel "red hard"; that is, the steel retains its hardness at elevated temperatures, in some cases so high that the steel becomes red in color.
Tungsten, molybdenum, and chromium also increase the resistance to is shown by Fig. 19.6* for steel with 0.35 per cent carbon and increasing chromium, by Fig. 19.7* for steel with 0.35 per cent carbon and increasing molybdenum, and by Fig. for high-speed
tempering. This
19.8f
steel
containing 0.70 per cent carbon, 18 per cent tungsten, 4 per cent chromium, and 1 per cent vanadium. The increase in hardness of these
steels
is
when tempered between 900 and 1100F. (480 and 595C.) due primarily to the transformation to martensite of some austenite tained by the quenching treatment.
19.7. Cast Alloys
Alloys rich in cobalt,
re-
placed on the market
in
1907 under the
chromium and tungsten were developed and name of Stellite. They contain a
high proportion of a hard constituent (complex chromium-rich carbide) within a cobalt rich matrix phase. Cutting tools of this type usually contain from 45 to 55% cobalt, 25 to 35% chromium, 12 to 17% tungsten, 1 to 3% carbon. The proper-
cannot be varied by heat treatment, but are controlled by the comhaving a higher strength. The tool grades range in hardness from 40 to 64 Rockwell C. Considerable hardness and
ties
position, the softer alloys
E. C. Bain, Functions of the Alloying Elements

Metals. Cleveland, 1939.
in Steel,
American Society fo*
t J. V.
Emmons, Trans. Am.
Soc. Steel Treat., v. 19, 1932, pp. 289-332.
Tool
Steels,
Die
Steels,
405
Tungsten carbide with Fie 19.9. Typical structures of sintered hard carbides. (A) carbides with columbium and tantalum titanium, Tungsten, cobalt. (B) 4 per cent about 8 per cent cobalt. Polished with diamond dust and etched with alkali ferricyanide. 1.500X- (Courtesy Kennametal Inc.)
are maintained at high temperatures, their "red hardness" making these alloys superior to high speed steels in resisting wear at elevated temperatures. At the same time they are appreciably weaker and
strength
somewhat more
brittle.
The
They
alloys are sold
commercially under a variety of trade names.
and wear resisting parts. Since they are expensive and have relatively low strength they are usually cast into small pieces of the desired size and shape which are used as inserts supported by a stronger backing material. Or, thin layers can be welded as
are used as cutting tools
a hard surface coating over steel parts.
19.8.
Cemented Carbide Tools

carbides, are
Cemented carbides, also called sintered for tools and dies. They are the hardest of
amounts
used mainly
in small
all metallic tool materials,
consisting largely of finely divided carbide particles
embedded
19.9)
of a soft ductile metal, usually cobalt
(see Fig.
The
hard, abrasive carbides of tungsten,
molybdenum, titanium,
tanta-
lum, zirconium, and other metals have been

five years,
known
for nearly seventy-
but their use for tools is much more recent. It began about twenty-five years ago in Germany and about twenty years ago in the
tools contain tungsten carbide
United States. All cemented carbide
(WC)
as the es-
sential constituent. The tungsten carbide may be used alone for the machining of cast iron, nonferrous metals and plastics. But steel-cutting
grades, in addition,
must contain titanium carbide. The carbides of titanium and tungsten form a solid solution which has the outstanding characteristic of resisting the abrasion of the steel chip as it glides over
406
the tool. Smaller quantities of tantalum, bides are also added to some grades.
columbium and vanadium
car-
Cemented carbide tools are made by the methods of powder metallurgy. finely ground carbide powder is mixed with cobalt, pressed into the desired shape, and sintered at 2450F (1343C) or above. The sintering
The
temperature is above the liquidus of the alloy system and densification occurs in the presence of a liquid phase. The resulting product is substantially free
from porosity.
properties of sintered carbides vary with composition, particularly with the proportion of cobalt. In general, hardness is increased but
The
toughness or shock resistance
is
decreased by smaller binder contents.
Tungsten and titanium carbides are among the hardest materials known; although less hard than diamond, their hardness is of the same order of magnitude as that of aluminum oxide, boron carbide and silicon carbide. Depending upon the amount of cobalt used (which varies from 3 to
cent), the Rockwell A hardness (diamond indenter, 60 kg. load) ranges from 88 to 93, corresponding approximately to a Rockwell
about 20 per
hardness of 72 to
temperatures
76.
good portion
of this hardness
is
retained at the
during metal cutting, permitting a cutting speed three or four times greater than that of high speed steels. The material has little ductility, strength is determined by a transverse rupture test and varies from 150,000 to 400,000 lb. per sq. in. The cemented carbides have very high compressive strengths (500,000 to
encountered
900,000
lb.
high
per sq. in.)
They
also
have some of the highest
elastic
moduli known (up

truding
to 90,000,000 lb. per sq. in.)
Cemented hard carbides are widely used for wire-drawing dies, exdies, and numerous other dies for burnishing or spinning metal
such as metal radio tubes, shell
others,
cases, projectile jackets, eyelets,
sections,
and many
materials
is
and
also
for gages, thread guides, valve parts for
erosive materials,
in
and the
like.
The most
,
extensive application of these
mass-production machining of cast iron, steel (with Brinell hardness values as high as 500) and most of the other metals, and also
machined nonmetallic materials including plastics, rubber, resins, glass, asbestos, and others. Cemented carbides arc costly and the tool generally consists of a carbide
difficultly
of
many
tip or insert brazed to a steel holder or shank, but great economies frequently result from the use of these tools. The greater machining speeds and increased tool life permit production increases between 30
and several hundred per cent while saving approximately one third of the
production
costs.
Tool
Steels,
Die
Steels,
407
QUESTIONS
1.
Name
2.
3.
main classes of tool steels. What properties are important Give eight essential characteristics that tool steel should have, and rate these in the order of their importance. How are tool steels usually purchased? Why is it difficult to devise a performance test to evaluate tool steels? How important is die cost of the steel from which a tool is made? Give the characteristic properties of high-carbon tool steel. What is the approximate carbon content of the four main classes of high-carbon tool steels, and whv is the carbon percentage adjusted according to the use to which the steel is to be put? What carbon percentage would you specify
the two
in each class?
for the following:
razor blade,
hammer,
drill,
anvil, rivet set, small shear
blade, ax,
4.
and
file?
What
are the outstanding characteristics of the steels of class L?
How
is
the
5.
Compare these steels with the S.A.E. low nickel-chromium and chromium-molybdenum steels. What are the principal alloying elements in the oil-hardening, nondefonning tool steels of class 0? Why are these steels widely used? What are they
hardenability of these steels increased?
used for? Give the important properties of the silicon-manganese steels when used as tools.
6.
What
are the general effect of (a) chromium, (b) molybdenum, and (c) tungsten on hardenability, wear resistance, tempering, and hardness at high temperature?
7.
What
is the chief advantage of the medium-chromium, low-tungsten tool and die steels as compared with high-carbon tool steels, and how do the two groups compare in wear resistance, red hardness, and toughness? What are
the outstanding characteristics of the

8.
high-alloy
tool
and
die materials?
What What
steel?
are the
is
main alloying elements used
in these high-alloy steels?
the approximate composition of the principal types of high-speed
9.
is high-speed steel heat treated? Why is cobalt added to some high-speed steels? What are the advantages and disadvantages of molybdenum high-speed steel as compared with the usual 18-4-1 material? What is the most valuable property of high-speed steel, and what is the usual explanation for this property? What variables affect the cutting per-
How
10.
formance of high-speed steel? What hard carbides are used as tool and die materials? ness of these carbides compare with that of quenched
the structure of these tools.
How
does the hard-
tool steel? Describe
11.
Compare and
discuss the compositions, microstructures
and properties of a
typical stainless steel
Relate the microstructures to the desired properties. (Note particularly the difference in carbon contents.)
a typical tool steel.
and
Cast Iron
CHAPTER
20
CHARLES Arthur Naglkr, Ph.D., Associate Professor, Department of Chemical and Metallurgical Engineering, Wayne State University Detroit, Michigan
Kenneth
E. Rose, M.S., Professor of Metallurgical
En-
gineering, University of Kansas, Lawrence, Kansas
and carbon conOther elements, notably silicon, are generally present also. Metallurgically, cast irons are characterized by (1) an eutectic reaction during freezing, and (2) more carbon than can
irons are alloys of iron
v*AST
taining
more than
2 per cent carbon.
be dissolved
In
steel,
in austenite at
any temperature.
is rarely present in any form other than combined as a However, iron carbide, or cementite, is a metastable compound which can be decomposed to iron and carbon (as graphite) Because of the embrittling effect of cementite, most of the carbon in commercially useful cast iron is converted to graphite unless the hardness and wear resistance of the cementite is of primary importance. Factors tending to encourage the decomposition of cementite are:
carbon
carbide.
1.
High temperature.
2.
3.
Time
4. 5. 6.
(especially at elevated temperature) Slow cooling rates during freezing (a corollary of High carbon content.
and
2)
Presence of graphite. Presence of graphitizing agents (including silicon)
Cast irons
may be
classified
roughly according to the percentage of

is
carbon, but because of the various ways in which the carbon
associated
with the iron, it is usually more convenient to make the classification according to the form of the carbon, rather than the amount. The following outline suggests a procedure for such a classification.
A.
Carbon combined with iron as cementite. White cast iron (usually about 2% carbon). 1.
2.
Chilled cast iron (usually
3% or more carbon)
408
Cast Iron
409
Fie. 20.1A.
ite in
Flake graphgray cast iron.
Fig. 20.1B. Spheroidal graphite in nodular, 01
Fig. 20.2.
Temper
car-
hon
(graphite) in mallc-
ductile cast iron.
able cast iron.
B. Carbon both in combined and elemental (graphite) form.

1.
Mottled
cast
iron a. mixture of white
cast iron with graphite,
generally undesirable.
2.
Gray cast iron graphite as thin, interdendritic flakes which form during freezing. Cementite is present in pearlite in the matrix. Gray cast iron is sometimes described as "steel plus graphite."
(See Fig. 20.1 A.)
3.
Nodular or
ductile cast irongraphite as spherulites which form during freezing of specially treated irons. Massive cementite as well as pearlite may be present in the as-cast condition. (See Fig.
20. IB.)
Pig iron a product of smelting

primarily as a raw material.
essentially gray cast iron.
in the iron blast furnace,
used
is
Large, smooth, star-like flakes of

a
primary graphite or "Kish" are embedded in

C. Graphite formed by heat treatment,
1.
matrix which
some cementite remaining.
iron made by annealing white cast iron to decompose the excess cementite, leaving a matrix of pearlite. D. All carbon present as graphite in a matrix of ferrite. Ferritic gray iron generally undesirable for strength and wear 1.
Pearlitic malleable cast
resistance,
but may be made by annealing ordinary gray iron to
achieve the
2.
maximum
machinability.
of white
3.
iron made by heat treatment iron to decompose both the excess cementite cementite that would otherwise be in pearlite. (See Fig. Ductile cast ironmade by annealing nodular cast iron
Ferritic malleable cast
cast
and the
20.2.)
to attain
is
high degree of ductility. The carbide in such iron posed as in malleable cast iron.
a
decom-
410
20.1.
White Cast Iron

all
as
all
Cast iron containing
or nearly
is
the carbon in the
combined form
Very hard
has a silvery-white fracture and
known
as white cast iron.
and brittle and practically unmachinable, it is important chiefly (1) as an intermediate product in the production of malleable iron castings and (2) when it is produced, by regulating the composition and by cooling rapidly, as a thin, hard layer on the surface of a softer iron casting. The latter product is known as chilled iron and is used where high surface hardness and wear resistance are important.
The microstructure of white cast iron can be predicted from the iron iron-carbide phase diagram used for steel; that is, it consists of cementite
and
pearlite.
20.2. Malleable Cast Iron as
Malleable cast iron is a valuable engineering material and is widely used for machinery, railroad equipment and automobiles, agricultural
machinery, pipe fittings, hardware, household appliances, and in many other applications. Intricate castings are more readily melted and poured with white cast iron than with carbon steel and, despite the cost
of malleablizing, are cheaper than carbon-steel castings.
Malleable cast
iron compares favorably with gray cast iron in machinability
and with
low-carbon
steel in properties.
To
ture
is
produce malleable castings, cast iron solidfying with a white fracpoured into a sand mold; the hard, brittle casting is then annealed
to dissociate the cementite. Malleable cast iron contains per cent carbon, practically all of which is graphite (usually
,
(malleablized)
2.0 to 2.5
temper carbon) 0.7 to 1.2 per cent silicon, 0.40 to 0.60 per cent manganese, less than 0.20 per cent sulfur, and less than 0.10 per cent phosphorus.
called
During the first stage of malleablization, at 1600 to 1700F., cementite which is not soluble in the austenite is converted to ragged loosely formed nodules of "temper carbon." Second-stage malleablization takes place at or slightly below the lower critical (A,) temperature after cooling from the first stage treatment. This causes the remaining cementite, including that which normally would be in pearlite, to gi aphitize. Second-stage malleablization is complete when the structure consists entirely of temper
carbon in a matrix of
ferrite.
20.3. Engineering Properties of Malleable Cast Iron
White
cast iron for malleablizing

is
is
melted chiefly in an
tensile strength
air furnace;
some, however,
melted in a cupola.
The
and elongation
Cast Iron
411
(as
measured on a
test
bar) of cupola malleable iron are lower than those
of air-furnace malleable, but the bursting strength of castings is usually considerably higher. Cupola malleable, therefore, is widely used for pipe
fittings.
Most malleable iron is purchased under specifications issued by the railroads or by the valve- and pipe-fittings industry. Most of these
specifications give the following as
minimum
properties:
Kind
of malleable iron
Tensile strength, lb. per sq. in.
Yield strength, lb. per sq. in.
Elongation in 2 per cent

10
5
in.,
50,000 40,000
32,000 30,000
Reduction of area is usually about 20 per cent and is seldom determined. Malleable cast iron is unique among ferrous materials in that the elongation increases as the tensile strength increases. This is shown by the data for air-furnace malleable given in Table 20.1. Malleable cast iron, with a notched-bar impact resistance of 7 to 9 ft-lb., as compared with
1
ft.-lb.
or
less for
gray cast iron,

is
is
much
lb.
tougher than gray cast iron.

per sq..in., that
is,
The modulus
of elasticity
25,000,000
slightly
lower than that of carbon steel. Malleable cast iron has an endurance ratio of about 0.5, that is, the same as carbon steel. It is considerably
more
sensitive to notches
than gray
cast iron.
Table
20.1.
Tensile Properties of Air- Furnace Malleable Cast Iron*

16.5 17.0 17.6
18.3
in.,

19.0 19.6 20.3 21.0
in.,
51,000 52,000 53,000 54,000
55,000 56,000 57,000 58,000
In malleable iron, as in carbon steel, the tensile strength decreases with increasing size of section; a typical change is from 55,000 lb. per
Proc.
Am.
position
and properties of American malleable
American
Soc. Testing Materials, v. 31. 1931, Part II. p. 317. For ranges of comiron, see Cast Metals Handbook, Foundrymcn's Society, Chicago, 3d ed., 1944, pp. 308-314.
412
thickness to 45,000 lb. per sq. in. for
is
sq. in. for sections 0.25 to 0.50 in. in
sections of 1.25 to 1.50 in.
The
yield strength, however,
practically
In contrast to steel, in which elongation usually increases with mass, the elongation of malleable iron decreases; at the center of a 2- or 3-in. section, for example, the elongation may be only about half what it is at the surface.
size.
unaffected by section
Malleable cast iron has poor wear resistance, but in machinability it as gray cast iron. It is easier to plane, drill, or mill than carbon or alloy steels, including those containing lead or high
ranks about the same
sulphur.
Recently, for a few special applications, the graphitizing operation in the production of malleable has been modified, or alloying elements
have been added and special treatments used so that the annealed
material contains some pearlite.
cast iron
The
properties of pearlitic malleable
depend upon the amount and distribution of the iron carbide; usually it is stronger and less ductile than fully graphitized material. A unique and now well-known example of a specially treated pearlitic alloy malleable cast iron is in the crankshafts of some automotive engines. The alloy is melted and cast under conditions that produce white cast
iron. It is malleablized by a treatment that produces small graphite nodules in a matrix consisting almost entirely of pearlite. This treatment
followed by a complex normalizing and annealing treatment. The composition is approximately as follows: 1.5 per cent carbon, 0.7 per cent manganese, 0.9 per cent silicon, 1.75 per cent copper, and 0.5 per cent
is
chromium.
20.4. Gray Cast Iron as an Engineering Material
Cast iron in which most of the iron carbide has dissociated into iron
and graphite
all
is
usually soft
and readily machinable.
It
has a gray, almost

cent of
black, fracture
and
is
thus
known
as gray iron.
More than 90 per
the iron castings produced are of gray iron.
Gray cast iron is a low-cost material which is easily melted and cast, and is economically machined. These are the primary reasons for its wide use. Of the hundreds of engineering applications for gray cast iron, some of the most important ones, together with the usual compositions, are given in Table 20.2.*
The properties of gray cast iron that determine its suitability for engineering uses are the result of controlling four variables: (1) chemi Trans.
Am.
t'oundrymen's Assoc,
v.
39, 1932. pp. 56-64.
For a complete
list
of
specific applications ot plain
and
alloy cast irons, see Cast Metals

ed., 1944,
Handbook, Ameri-
can Foundrymen's Society, Chicago, 3d
pp. 335-594.
Cast Iron
413
for
Table
20.2.
Recommended
Analyses of Plain Cast Irons
Common
Engineering
Applications
Typical charge,
per cent
Use
CastTotal
Si
Mn
0.65 0.65 0.65 0.65 0.60 0.55
Pig
iron
Steel
C
3.25 3.35 3.40 3.50 3.40 3.50 3.25
3.25 3.23 3.25
scrap
scrap
2.25 2.25 2.60 2.90
0.15 0.15 0.30 0.50
0.10 0.10 0.10 0.06
40 40 50 60
35
40 40 45 40
55
20 20
5
Automobile cylinders Automobile pistons Automobilccas tings, general Automobile piston rings
individually cast
2.10 2.20 2.25

1.75 1.25 1.25
0.50
0.70 0.50
0.10
0.10
0.09
10
Agricultural implements medium sections
40
50
60 50 40 25
25
10
Agricultural
implements
0.50 0.50 0.50 0.65 0.80 0.80 0.80 0.50 0.80 0.90 0.75 0.50 0.50 0.50 0.60 0.55 0.50
0.50 0.50 0.20

0.35 0.35 0.35 0.60 0.10 0.20 0.20 0.80 0.80 0.80 0.35
0.10 0.10 0.10

0.09 0.09 0.09 0.10 0.07 0.07 0.07 0.08 0.08 0.08 0.12
50 50 50
55 55 55 50
25
25 25 25 25 10 10
3.40 3.40 3.40 3.30 3.50 3.50 3.60 3.60 3.40 3.40 3.35
3.60 3.75
1.75 1.50
1.25
20
20 20 40
30
sections not Machinery 1.5-in sections Machinery sections Pressure castings cylinders Gas-engine cylinders
Machinery
over
1
light sections
in.
2-in.
air
Gas-engine cylinders
me-
light
dium
2.00 1.15 1.00 1.00 1.75
1.40 1.40 0.65
1.25 0.85
Gas-engine cylinders heavy Valves and fittings
Firepots and ketUes Ingot molds Pots for caustic soda
5
70 90
60
70
60 70
12.5
40 25
25
15
7.5
30
80
40 40
Light and medium sandcast water pipe Heavy sand-cast water pipe Soil pipe Car wheels (0.90 per cent
combined C)
1
0.40 0.40
0.10 0.10
45
45
15
Chilled plow iron
15
Plow moldboards
cal composition,
(3)
special
(2) rate of cooling from the solidification temperature, methods of melting, including superheating and ladle addi-
tions,
and
(4)
heat treatment.
In addition to low cost and easy machinability, gray cast iron has a
number of properties notably notch insensitivity, high damping capacity, and high compressive strength which make it especially valuable in some applications. In tensile strength, ductility, and toughness, however,
414
it is
much
inferior to steel.
In addition, the absence of a well-defined

elasticity
its
yield point
and modulus of
Despite
is
makes
it
unsuitable for
many
engi-
neering structures.
of gray-iron castings
States.
disadvantages, however, the production

in the
around 5 or 6 million tons a year
United
20.5. Structure of
Gray Cast Iron

cast iron as a
Considering gray
are alpha iron
(graphite).
carbon
steel
containing graphite, the
three primary metallographic constituents present at normal temperatures

(ferrite)
,
iron carbide
is
(cementite)
and
free
carbon
is
The
cementite
usually associated with ferrite as pearlite

distri-
the same constituent found in carbon steel and the graphite
buted through the ground mass as irregularly shaped plates or flakes of varying sizes. However, very rapid cooling from the melt may suppress the formation of graphite and produce chilled iron, a type of white iron. Very slow cooling increases the proportion of ferrite to pearlite. The ferrite of gray cast iron, unlike the ferrite of low-carbon steel which is relatively pure, contains all the silicon and a little of the phosphorus
in solid solution.
Of
the elements in gray cast iron, carbon has the strongest effect
on
depends on the amount of total carbon as well as on the relative amounts of combined carbon and of graphite present. This in turn depends upon the silicon which decreases the stability of the iron carbide, thus promoting graphitization. Next in importance is phosphorus, which combines with the iron to form
structure
and
properties.
This
effect
iron phosphide
(Fe3 P)
small amount of this
compound
dissolves
in the ferrite, the rest forms a eutectic (Fe Fe s P) with iron.
When
the
per cent or above, the eutectic (known as steadite) is The visible as a distinct constituent in the microstructure (Fig. 20.3.) eutectic melts at a temperature of 1750 to 1800F. (955 to 980 C.)
phosphorus
is
0.1
much below
the melting point of gray cast iron. If about 0.5 per cent phosphorus or more is present, there is enough eutectic to make the iron more fluid. High-phosphorus iron is, therefore, used for ornamental
and other thin, intricate sections. Owing to the hardness of the phosphide eutectic, cast irons containing considerable phosphorus may be harder to machine than low-phosphorus material. In the amounts usual for American gray cast irons (Table 20.2) phosphorus has little effect on the strength, but it may increase the brittleness. For cylinders and various kinds of pressure castings 0.5 per cent is, therefore, usually The effect of phosphorus on the maximum permitted (Table 20.2)
castings
.
graphitization
is
negligible.
Cast Iron
415
Phosphide cutcctic in gTay cast iron. (A) 100x; (B) l.OOOx- The cutectic the irregular-shaped light-colored constituent shown in A. At high magnification its duplex character is apparent. (Kunkele, Giesserci, v. IS, 19)1, p. 73)
Fie. 20.3.
is
Commercial gray
cast iron
is
always contains enough manganese to
in-
sure that the sulphur
present as manganese sulphide.
Owing
to the
notch insensitivity of gray cast iron, more sulphur is tolerated than in steel because manganese sulphide inclusions are not so likely to be loci of weakness where failure will start under repeated stress. Manganese in excess of the amount necessary to combine with the sulphur forms ironmanganese carbide. This compound is more stable than iron carbide;
hence, manganese inhibits graphitization. In the amount usually present (less than 1 per cent) the stabilizing effect of manganese is much less
important than the strong graphitizing

20.6. Relation between Properties
effect of silicon.
and Structure of Gray Cast Iron
and structure of gray upon the characteristics of the "steel" matrix and upon the amount and distribution of the graphite. These in turn are dependent upon the variables already menThere
is
a close relation between properties
cast iron.
The
properties are primarily dependent
416
from the solidifimethods of melting, and heat treatment. The amount of iron carbide to be decomposed into iron and graphite or to be left undecomposed depends (if the effect of cooling rate is ignored) upon the amounts of total carbon and silicon. For small specimens cast in sand molds the relation between total carbon, silicon, and structure is shown in Fig. 20.4.*
tioned, namely, chemical composition, rate of cooling
cation temperature, special
?.b
J.O
i.l>
4.0
4.5
5.0
5.5
6.5
7.
Silicon, per cent
Fic. 20.4.
The Maurer cast-iron
diagram.
modification of the Maurer diagram by Coylet
is
shown
in Fig. 20.5
in which approximate tensile strengths are plotted against composition. This diagram shows that for small specimens cooled in sand molds the highest strengths are attained if the total carbon is 2.00 to 3.25 per cent
and
if
the silicon
is
.00 to 2.25
per cent.
20.7. Effect of Cooling Rate
among properties, structure, and composition is affected by varying die rate of cooling from the solidification temperature to the gamma-alpha transformation temperature. As the mass is increased,
The
relation
greatly
the cooling rate

increased.
E.
is if
decreased,
and the
dissociation of the iron carbide is
Thus
a 1-in, sand-cast
bar has a matrix corresponding to a
Maurer, Kruppsche Monatshelte,
+ F. B. Coyle, Trans.
Am.
v. 5, 1924, pp. 115-122. Soc. Steel Treat., v. 12, 1927, pp. 146-465.
Cast Iron
417
Z.50
3.00
3.50
4.0C
"..50
Silicon. per cent
Fie. 20.5. Cast-iron
diagram showing
cltect
of carbon and silicon on tensile strength.
(Coyle)
0.50 per cent carbon steel, the
same iron
if
cast as a 6-in.
bar in sand will

into
ordinarily have
a matrix that corresponds to a 0.10 per cent carbon steel. iron of such composition that,
pearlite, will,
if
On
the other
hand an
it
when poured
mold but
a sand
mold
will
have a matrix of
poured into a castwill
iron mold, form white iron on the surface next to the cold
be pearlitic in the interior of the casting.
Maurer diagram (Fig. 20.4) are moved to the increased, and to the left if the cooling rate is decreased. The approximate relation among structure, cooling rate, and properties is shown in Fig. 20.6.* It is evident from the foregoing that the relation among the composition, cooling rate, structure, and properties of gray cast iron is not simple. Another important factor, which adds to the complexity, is the size and
Thus, the
if
lines of the
right
the cooling rate
is
form
of the graphite flakes.
20.8. Effect of Graphite Size
on Structure and Properties
The
carbon
iron
present.
strength of slowly cooled carbon-steel castings increases as the (cementitc) increases. The strength of slowly cooled gray cast
also increase as the cementite increases if no graphite were Graphite destroys the continuity of the grains of the "steel"
it
would
matrix and makes
weak and brittle. As the si/.e of the graphite particles increases and as they become more flaky and platelike, the iron becomes progressively weaker and more brittle.
* Cast Metals
Handbook. Am. Foundrymen's Soc, Third Edition,
1944, p. 360.
418
Strength increases
350
S
*\hite
r uc
ure
Hard and brittle

iron. Cemenlite andai/stenife
300
Mottlediron. Cementite,grapliile r
andpearlitc
w W V
250
Greatest strength. Hard to machine
|
zoo
4
co 150
Best nigh-
test irons -
Close gray iron. Graphite,
and peartite
/air strength. Easy machining
ndZrf,wl and fair finish
yf, , -^-p^Med^mgroy.ron.eraph,^ peartite ana fernte

,.
.
100 .Low strength. Open grain.

Machines soft
Open gray iron. Graphite and ferrite
"-
sc
FJO. 20.6.
Relation of hardness and
strength
o gray
cast
iron
to structure
and
section
size.
(American Foundrymen's Society)
High-strength cast iron must have a "steel" matrix containing considerable pearlite, and the graphite flakes should be small; there must, howif easy machinability is accomplished by five methods. The first consists of melting an iron of such composition that it would normally solidfy with a white fracture and then treating it by adding a special graphitizer, such as powdered silicon or calcium silicide, just before the castings are poured. The second consists of melting an iron that would normally solidify with a white fracture and mixing with this a definite amount of a soft gray iron melted in another cupola. The third method consists of melting gray cast iron and superheating it considerably above the usual casting temperature. This decreases the size
ever, be 2.0 to 2.5 per cent graphite present
required.
The
control of the graphite size
is
and increases the amount of pearlite in the casting. fourth, used considerably in Europe, consists of pouring a low-silicon iron into a preheated mold. The fifth method consists of adding alloying
of the graphite flakes
The
elements.
To
several variables, including the percentages of carbon
produce high-strength iron by any of these methods the and silicon, must
be controlled carefully.
20.9. Evaluation of Gray Cast Iron for Engineering Applications
The
chines
suitability of gray cast iron for engineering structures

is
and mastrengths.
judged
chiefly
by
tensile, transverse,
and compressive
Cast Iron
419
properties may Hardness, endurance limit, wear resistance, and other Most metalapplications. be valuable criteria of its value for specific test as the transverse the lurgists experienced with cast iron consider
best single source of information
on the quality of cast iron. The transverse test is made by applying a load at the center of a cast (unmachined) round bar, supported at each end, until fracture occurs. The size of the bar depends upon the size of the casting and has been standardized* at 0.875, 1.20, or 2 in. in diameter with a span of 12, 18, 24 in. between supports. The load necessary to fracture the bar and
or
the
of deflection at the center at the moment of fracture are load noted. In the United States transverse strength is reported as the in pounds; in Europe the load is converted by the formula
amount
MR =-u
to a value called
load,
I
Pic
is the breaking the neutral from the distance
modulus
of rupture.
In
this
formula
the distance between supports, c
axis of the bar to the extreme fiber,
and
/ the
moment
of inertia.
modulus of rupture to tensile strength varies with the quality of the iron from 2.5 times the tensile strength for low-strength irons to approximately the same as the tensile strength for high-strength in design if irons. Transverse strength or modulus of rupture is of value to heavy cast iron is used as a beam and especially in pipe subjected
The
relation of
earth loads.
Gray
cast irons are
graded by (minimum)
tensile strength
(in thou-
sands of pounds per square inch) into seven classes: 20, 25, 35, 40, curves of gray 50, and 60. As discussed before, since the stress-strain proportional cast iron are curved from the origin, this material has no limit nor modulus of elasticity. The secant modulus, representing a
point on the stress-strain curve of 25 per cent of the tensile strength, varies between 12 and 20 million lb. per sq. in. In many engineering applications, for example machine beds, columns,
pipes used as structural members, and various other supports, cast iron by subjecting, is used for its strength in compression. This is determined long to a comto in. diameter and 1 3 0.80 in. in sand-cast bars 0.75 to
pressive load until failure occurs.
is
The
stress-strain
curve in compression
is higher than tensile from strength for low-strength tensile times the about 4 strength; it varies from strong irons. strength for tensile the irons to about 3 times The other properties of gray cast iron can be summarized in a series
also curved
the origin.
Compressive strength
of short sentences. Endurance limits are given in

A.
S.
Table 20.2.
The
en-
T.
M.
Standards, Pari
1,
1955, A48-40, pp.
1848-1854.
420
durance
ratio, determined on highly polished specimens, is more erratic than for steel. Values between 0.30 and 0.60 have been reported. A very important characteristic of gray cast iron is the almost negligible effect
of surface
on the endurance
steel as
less
limit;
the
same notch which reduces the
endurance limit of
of soft cast iron
is low and is and drop tests are frequently erratic. The damping capacity of gray cast iron is higher than for any other ferrous material. Gray cast iron is readily machinable unless the surface is chilled; conversely, if the surface is
endurance than 15 per cent. The impact resistance of cast iron usually unimportant. Notched-bar tests are meaningless,
much
as 75 per cent reduces the
chilled, cast iron

ficulty.
is
very wear-resistant and

entirely
It
is
relatively easy to
is
is machined with great difproduce gray-iron castings having a surface
layer in
which the carbon

is,
combined
as cementite.
Chilled
gray cast iron

rolls,
therefore, widely used for large gears, for a variety of
for wheels of railway cars,
surface hardness
face, if
and for many other articles where high and wear resistance are necessary. Machining the surnecessary, is, however, a slow and costly operation.
20.10. Nodular or Ductile Cast Iron as an Engineering Material
The size, shape, and distribution of graphite in cast iron has a pronounced effect upon strength and ductility. This may be illustrated by comparing these properties in malleable cast iron with the same properties The higher ductility in malleable cast iron is related to the rounded, compact form of the graphite (temper carbon) which causes
in gray cast iron.
,
disruption of the matrix than do the long slender flakes of graphite in gray cast iron. Until recently, the rounded graphite form could be achieved only by heat treatment of solid metal, but spherulitic or nodular
less
graphite can
States
now
be
of special treatments
and
in several
made to form during the freezing interval by means and additions developed and patented in the United other countries. High strength and elongation of as
much as 20 to 25 percent are reported in cast iron made by these processes. The total carbon in nodular cast iron is about the same as in gray iron.
Magnesium or cerium are most widely used to promote the formation of nodular graphite. Only a few hundrcths of a percent of these elements is needed, but the addition must be made shortly before the metal is cast,
and the melt must be very low in sulphur. Metallurgists do not clearly understand the mechanism of graphitization in nodular cast iron. The high shrinkage in nodular iron castings
suggests that
little, if any, formation of graphite occurs during freezing. Furthermore, massive cementite is not uncommon in the as-cast metal,
and for
maximum
ductility this
must be eliminated by a separate anneal-
ing heat treatment.
Cast Iron
421
z
1 S3
" rn CM in cm cm mhOr-^soo r-r-fSMNNtn

so
m in o g m cn r- m s
o
^ ^- ^- CM
tj-
L* S .13c
8-2
6 Nl Sim"
m cm in r- o O co ^- ui oo n rr*.
:,
a
O 3
in in fO
.-T e| cm" ofm" rn" to
eg 3 C
C
oo
So If
to
2
*-
w
NO
u-j
0.
a o
r3
s o
O NO Cn CO O U1
so \o so !* co co
'
ifi
in
O O
J* "3.S
Q-5
M
o
g
;=
h
>>
t>
CN NO CM CO -* CM CO cn u*i in \o r*- h*
ss
1
o B
CM
O
en
C
o
rr ,
03VNO co m no o cm co ,-,-, CM CM CM
<*
41
r-^
i o
.2
"8
H omouiowr VnOCOO c-rn ^-~
c 6
O O
O O
c a M""
O O
-
J=
MCN
rOO NO CM
eg
iq a 6S
9 s a
a
mm
J3
o o
S5
a o
c
f2
oo oo o oo o mo oo oo n oo oo oo
a. Go
c u
T3
t
" "
S3
no cm o" oo
Nn* vmh-co
r-^* co
co
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.0-
o oo o o oo o oo oo m O O O NO -* SO CN
Hi
-3 sO -O
>-
|>>
o oo o o mo oo 8
a
a
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bO'1
oo o oooo ooo o ooo

"*
J3 bo
3 1
IP
a
O m
oooooom o * rm r- o CO CN O CM T NO CO
-
t.-
OO oo o o OO
oooo
CO NO CO CN
\ii
" ^< M a p o coo a si & XI "O
li
a
a
,
o"o"in"o"
L
I
o-=
a a
i
5
a p
111
ooo ooo o ooo m o o o o o oo

in in in
'
^ u o
t>
rt
oxx
> tq s s rt t
CnT n6" --T no" <sf CNJ CsT
cm cm en en * in no
o O <5 1
5**1
o
91
"I .3
o o
=i
c
I
om u tn m Oh
6j
fl '"'
SI 5}o
in o m o O O O in no cm cm on to
<*
CJ
O NO o O
(O
Kit!
i 2
in o O no -* m o O in CO NO CO
CUV aa c a. a
IJTJ
Iff
422
Engineering Properties. Specifications of the (A 399-55) recognize two commercial grades designated as 80-60-03 and 60-45-10. The first of these is in the as cast condition; the second is an annealed grade. In each, the first two sets of numbers indicate minimum tensile and yield
strengths in
ASTM
1000
psi,
and the third
set indicates
minimum
percentage
elongation.
hardness.
Nodular iron is more readily machinable than gray irons of similar It is somewhat stiffer than gray cast iron, having a modulus of
25 million
steel.
elasticity of 21 to
psi.
The damping
capacity
is
between that
resistance
is
of gray iron and cast
Nodular iron has somewhat better
to oxidation, but the resistance to atmospheric corrosion
about the
same
as for gray iron.*
20.11. Melting and Casting of Irons

Different methods of melting are used in order and microstructure of cast iron.
to control the chemistry
The
greatest tonnage of iron
is
melted in a cupola furnace, Fig. 20.7, a
cylindrical type of furnace
refractory brick.
vertically on legs and lined with Depending on the type of foundry operated, the furnaces
mounted
can be lined with either basic or acid brick. The lining of the cupola with basic brick is a relatively new innovation. Cupolas are charged some distance above the floor of the furnace, and depending on the
above the tuyeres. group of tuyeres attached to a wind box that supplies the necessary oxygen for combustion. The area below the tuyeres makes up the molten metal reservoir, which is periodically tapped. Above the metal tap hole and usually on the opposite side
is
capacity, the charging
door
located
15 to 30 feet
On
the lower portion of the furnace
is
is
iron or
the slap tap hole. Materials charged to the cupola are pig iron, scrap steel, coke, and flux. The materials are weighed accurately and
layers. The function of the cupola furnace is to melt the various components of the charge, and the molten mass of metal becomes carburized by being in contact with the hot coke. The carbon
charged in alternate
solubility in the iron will
depend on the temperature of operation of the

solubility will reach an equilibrium value
cupola furnace.
The carbon
Cupola furnaces are not operated under equilibrium conditions. However, the time that the molten metal is allowed to remain in contact with the coke is carefully controlled. When
the metal
A. S. 1954.
is
after a given length of time.
tapped from the cupola furnace, the
air is shut off,

66,
and
15,
M. Metals Handbook. Supplement-Metal Progress Vol.
No. 1-A, July
Cast Iron
423
FlG.
20.7.
Section through a cupola furnace.
(Whiting Corp.)
opened to allow the molten metal to flow from the bottom of the cylindrical shaft furnace. After the tap is completed, the tap hole is plugged and the air is again turned on and
the tap hole
is
reservoir in the
melting continues until the next tap. Raw materials that are charged into the cupola furnace ultimately determine the chemistry of the melt that will be cast. The size of scrap
and pig charged depends on the size of the cupola furnace. Coke, which is the fuel, is carefully selected on the basis of size, heating value, chemistry, porosity, and strength, and must necessarily be low in sulfur and phosphorus content. The molten iron in the cupola furnace has a high affinity for sulfur and phosphorus, and invariably the sulfur
424
and phosphorus that are charged with the raw materials will be totally accounted for in the molten iron. The slag produced in a silica bricklined cupola will not effect the removal of sulfur or phosphorus. In the case of the basic lined cupola, the product will show a considerable decrease in sulfur content due to the molten iron being in contact with the basic slag. By far the best method of producing a low sulfur and phosphorus iron is to minimize initially the charging of the two elements
into the cupola.
The
melting rate in the cupola furnace
is
controlled
admitted through the wind box into the tuyeres. The air causes the combustion of the coke which in turn supplies the heat for fusion. In controlling closely the operation of the cupola with respect to air, it is not uncommon to find that the air is conditioned to a constant humidity. Research work on the effect of moisture
air that is
by the amount of
on quality of iron has indicated the need

to insure constant quality of iron.
for the control of moisture
study on the effect of moisture in
the air feed of a cupola furnace has indicated a definite relationship be-
tween hard spots in cast iron and a critical amount of moisture in the air. The cupola furnace is considered to be an intermittent type of furnace.
On
the basis of 24 hours of foundry operation, the cupola
may be
con-
sidered to operate 18 hours, and the remaining time allotted to repair of the lining
and
to general
maintenance on the furnace.

is
The
melting of malleable iron
usually carried out in a reverberatory
or air furnace, Fig. 20.8.

furnaces.
relatively small
tonnage
is
is
melted in electric
usually powdered
The
fuel used in the reverberatory furnace
coal or fuel
oil.
The raw
flux.
materials added to the air furnace are scrap iron,
pig iron, and
Iron of various analyses are selected so that

is
when
fusion and oxidation are completed the resulting melt

desired analysis.
close to the
Some adjustments
are
made
in final analysis
by addition
of ferro alloys containing desired elements.
It is
well to
mention that the
carbon content of the metal melted in the air furnace is considerably lower than that produced in the cupola furnace and necessarily has a higher melting and casting temperature. The feature that differentiates the product of the cupola furnace from that of the air furnace is that the
fracture of the latter
fracture
is
is
white and that of the former
is
gray.
The
gray
caused by free carbon being in the form of graphite, and the white fracture is caused by carbon being in solution. The molten iron is
cast into suitable
molds
for ultimate solidification into the desired
shape
tests
of ultization.
Prior to the casting of the metal from the melting furnace, various
are carried out
on
the molten metal to determine
its
suitability
and
quality for casting.
chill
test is carried
out on gray
cast iron to de-
425
Flo. 20.8.
Section through a reverberator^ or air furnace.
[Whiting Corp.)
be free from a white cast-iron outer layer. The test block is fractured and the depth of white layer measured. A fluidity test is carried out to determine the flow characteristics of the metal under certain standardized conditions. The test is carried out in a termine
if
the metal
when
cast will
mold, the flow of the metal in filling the spiral being a measure of the viscosity and tendency to produce useful casting. To determine the quality of the iron after casting, physical tests such as tensile strength, transverse breaking strength, and hardness tests are carried out. The alloys are studied to determine the chemical analysis with specific interest in such elements as carbon, silicon, manganese, phosphorus, sulfur and others that may be present. Tests on iron that
spiral fluidity
are cast from the air or reverbratory furnace are as follows: study of
fracture to determine
how much white
cast iron
is
formed; chemical
such as carbon,
analysis to determine the presence of such elements

silicon,
manganese, sulphur, phosphorus, and others. In the case of white cast iron the chemical analysis will predetermine whether the alloy will satisfactorily be annealed to malleable iron. On a tonnage basis the
largest
amount
of iron cast as white cast iron
is
ultimately annealed into
malleable iron.
20.12. Ternary System of Iron, Carbon, and Silicon

Cast irons can be considered on a simplified basis as alloys of iron, and silicon. In reality, the alloys contain, in addition to the
carbon,
elements mentioned, small amounts of phosphorus, sulfur, manganese, and other elements. In order that we be able to interpret the various changes that take place in the cooling of a cast iron from its liquidus temperature to room temperature, it is imperative that we bealloying
come familiar with the ternary system of
iron, carbon,
and
silicon.
The
ternary system allows the plotting of die composition on the basal
temperature plane in three dimensions of carbon, silicon, and iron; the vertical axis is temperature. Drawn in Fig. 20.9 is a corner of the
ternary system iron-carbon-silicon.
The
familiar iron-graphite constitu-
426
Fie. 20.9. Iron-rich
corner of the ternary system of iron, carbon, and silicon.
tion system
is
recognized; the other section
is
for the iron-rich corner of
the iron-silicon system.
The
iron-silicon system contains a
gamma
loop,
which terminates at the transformation temperature from alpha to gamma, and gamma to delta iron. A section taken through the system at constant amounts of silicon illustrates the effect of silicon on the temperature and composition of the eutectic and eutectoid of the system. In Fig. 20.10 is illustrated sections taken through the system at constant silicon content of per cent, 2 per cent, 3.8 per cent and (i.5 per cent. It is readily noted in Fig. 20.10 that the transformation which takes place at the solidus temperature line for the 2 per cent carbon alloy in
the
iron-carbon
system
is
simply a transformation of austenite-plusIn the case of the 2 per cent silicon
liquid to austenite-plus-cementite.
section of the iron, carbon,
and
silicon system, the transformation at 2
per cent carbon involves a three-phase region changing from liquid-plusaustenite to austenite-plus-graphite.
region of austenite, cementite,
Cast Iron
1600
427
a-
i 1200
o
1000
# \^
7*0
OX Si
7' L
J>
rv
-^
/IsCa
r+Ca
-/
.^
a+
ca
3.0
800
600
V>
0.5
1.0
1.5
2.0
2.5
3.5
4.0
4.5
5.0
Carbon, percent
600
0.5
1.0
1.5
2.0
2.5
3.0
35
4.0
45
5.0
Carbon, per cent
600
05
1.0
15
2.0
2.5
3.0
3.5
4.0
4.5
5.0
Carbon, per cent
1400
o
.I200
a\
'
6.5% Si
a- 3
1000
-
^Sfcs^p t \L-a?
71
-a
2.0
^p ^
a*L a
2.5
zl
"-^/ *Ca
*tc*L >Ca
\ 800
600
0.6
1,0 1.5
3.0
3.5
4.0
4.5
5.0
Carbon, per cent
per cent silicon, Fig. 20.10. Sections through the iron, carbon, and silicon system at Iron and 2 per cent silicon, 3.8 per cent silicon, and 6.5 per cent silicon. {Alloys of Book Co., 1935. Silicon, Greiner, Marsh, and Stoughton, New York: McGraw-Hill
428
3% Total Carbon. 2% Si
Liquid
A*L
c
L.Liquid A, Austenite
P, Pearlite
A*C
-A,Pt
A+C+G
A+G
G A r P-,G
A.t>+$+F
C .Cementite
G, Graphite F. Ferrite
C AiP,C*G
P*C*G
(Mottled
Iron)
P*C
(Whili
Iron)
P*G
P.G* C
F.G
K
Foil
Cooling
Moderately
Foil Cooling
Moderate
Cooling
Moderate',
Siow Cooing
S'o*
Co:'-ng
Fie. 20.11. cast iron.
Transformation occurring during the
solidification
and the cooling
of
(Lorig)
and graphite is passed through prior to the formation of the solid phase. This region is used in explanation of the formation of graphite from the
The explanation of the freezing of iron, carbon, complicated by the presence of two systems the stable system of iron and graphite and the metastable system of iron and cementite. In both systems prior to reaching the liquids temperature, the carbon is in solution in the iron. Considerable changes occur during the
melt on solidification.
and
silicon alloys
is
solidification of alloys according to the stable
and metastable system. Al-
loys that freeze according to the stable system will give structures that contain graphite plus transformation products of austenite upon cooling. In the case of the metastable system, the products of transformation on cooling contain iron carbide (cementite) plus transformation products of
the austenite. Hence,

stituents formed,
it is
evident that an alloy has different microconrate
depending on the
Fig.
of cooling
from above the

the
rela-
liquidus to
room temperature.
20.11
above
illustrates
tionship of cooling to microstructure for a 3 percent carbon, 2 percent

is noted that on fast cooling the microstructure is and cementite, and on slow cooling the microstructure is ferrite and graphite. At an intermediate cooling rate, it is possible to form a structure of cementite, pearlite, and graphite which is referred to
silicon cast iron. It
basically pearlite
as
mottled iron. In Fig. 20.11 notice that the rate of cooling determines
is
whether the stable or metastable constitution system

considering the process of freezing.
applicable in
When
alloys of iron, carbon,
and
Cast Iron
429
(Tentative recommended Fig. 20.12. Types of graphite flakes in gray cast iron. ASTM designation practice for evaluating the microslructure of graphite in gray iron,
A247-41T).
silicon solidify according to the stable system, the
carbon
is
present in the
uncombined form of graphite. Depending on the conditions of cooling, of sizes nucleation, and other factors, the graphite will assume a variety
and shapes. The flake-type chart for graphite is reproduced in Fig. 20.12. Depending on the mode of formation, any one of five different types of graphite patterns can be formed, namely, uniform distribution random
orientation, rosette grouping random orientation, superimposed flake orientation, size random orientation, interdenderitic segregation random
and
interdendritic segregation preferred orientation.

is
The
at
size
of graphite
flakes
tions.
usually rated
on the
basis of length
measured
100 magnifica-
gray iron
may be present in a section of with the exception of the superimposed flake size, which is found typically in hypereutectic irons. It is generally agreed that the flake type of graphite forms directly from the melt on cooling below the
All types of graphite flake patterns
cast,
region of austenite plus liquid or austenite plus carbide of the stable system of iron and carbon. The formation of graphite from the melt is
explained on the basis of the binary system of iron and carbon for simplification purposes only. In explanation of the formation of the
interdendritic graphite pattern,
which contains
fine graphite, it is as-
sumed that the eutectic transformation takes place at a lower temperature than that of the large graphite flakes. This tends to indicate that
formed during the undercooling of the melt (and the absence of residual nuclei in the melt to initiate the formation of the graphite) It can be generally concluded that all forms of graphite found in cast irons form directly from the melt on solidification. The
the fine graphite structure
is
.
innoculation of cast irons is practiced in many foundries to control the size of graphite flake formed in the cooling of various section sizes. The
amount
graphite
as
of innoculant added will control the size

flakes.
and distribution of the
Any one
calcium
of a
number
of innoculants can be used, such
ferrosilicon,
silicide,
combinations of titanium, aluminum
430
and
iron
silicon, mill scale,
it is
and others. In specially controlled heats of cast possible by innoculation to alter the shape of the graphite. The
graphite formed on cooling after innoculation assumes the shape of spheres. The chemical composition of the cast iron must be carefully
controlled with respect to sulfur, which must be present in an
less
than 0.02 per cent.
The
spheriodizing additive
amount may be cerium or
magnesium
in alloyed forms.
The
addition of the innoculants results in
exothermic reactions, and care must be taken in making the alloy addition. The mechanism of the formation of the nodular graphite particle
on the cooling of
the cast iron takes place in the following manner. The addition of the cerium or magnesium to the cast iron, low in sulphur, causes the graphite to crystallize in the form of nodules.
and 2 per cent silicon can formation of temper graphite during the longtime annealing of white cast iron to form malleable cast iron. The formation of temper carbon takes place in two stages during the malleablizing of white cast iron. The first stage is carried out at a relatively high temperature of 1600 to 1700F. by slowly heating to this temperabe used
to explain the
The
constitution diagram of iron, carbon,
decomposed into gamma iron and temper carbon. The gamma iron dissolves in the austenite and the carbon will be uncombined. The amount of carbon that remains in solution can be determined from the solubility of carbon in iron as determined in the constitution system of iron, carbon, and 2 per cent silicon.
Prior to the second stage of malleablization the alloy is slowly cooled from 1600 - 1700F. to 1200 - 1300F. and held at this temperature until the austenite that had transformed on cooling into pearlite decomposes into ferrite and temper carbon.
line.
ture and holding until the cementite has
The amount
of carbon that the

solubility
austenite will yield can be determined again
from the carbon
At approximately 1200F. the solubility of carbon in iron is less than 0.10 per cent. The alpha iron formed dissolves in the ferrite, and the uncombined carbon deposits on the temper carbon that was initially rejected during first stage of malleablization.
20.13. Heat Treatment of Cast Iron
There are a number of methods whereby the heat treatment of cast we can summarize the various type of heat treatment under the headings of stress relief and growth, annealing and normalizing, hardening and tempering, isothermal heat treatment, flame hardening and induction hardening. Stress Relief and Growth. Cast irons unless given a stabilizing heat treatment are susceptible to growth on remaining at room temperature
iron can be carried out. Briefly
Cast Iron
for extended lengths of time.
It is
431
practice
common
when time permits
to store gray cast-iron parts for a length of time of six months or more to allow the natural growth to occur on aging at room temperature.
be accelerated by heat treatment, but the heat-treating temperature is kept at a minimum to lessen graphitization of the ccmentite phase. Cementite is unstable in the presence of silicon and when held at slightly elevated temperatures, tends to break down into graphite and ferrite. The breakdown results in a decrease in mechanical
Growth
in cast irons can
properties of the iron.

is
The room
temperature aging of the gray cast iron
most desirable in that no conditions are offered for the graphitizing action. The temperature range used for the aging to promote growth is between 700 and 1300F. It is well to mention that all gray cast irons do not show growth on aging, and this problem has been investigated by metallurgists for a number of years. There has evolved no acceptable answer as to why some compositions of irons show the growth phenomena and others do not. Suggestions have been made as to mechanism of growth, and they embody some of the following concepts: due to graphitization of some of the cementite, a volume expansion takes place; penetration of oxygen at the grain boundaries and internal oxidation occurs with an increase in volume; thermal gradients and volume changes during heating and cooling. Depending on the type of heat treatment cycle given the gray cast iron for dimensional stabilization, any or all of the mentioned factors may apply. Oxidation is a growth factor from room temperature up to about 800F. Cementite break-down is a factor in temperature ranges from 800 to 1300F. Thermal gradients and volume
changes occur over
all
of the heat-treating ranges.
Annealing and Normalizing.
The
heat treatments of annealing and
normalizing are usually applied to gray cast irons for the purpose of increasing machinability. The cooling rate from above the critical
temperature will
affect the coarseness
or fineness of the pearlite ferrite
cementite aggregate associated with the graphite.
As the coarseness of
During machining
the pearlite of the gray cast iron increases, the hardness of the material
decreases. It
is
possible to over-anneal a gray cast iron.
of such material, tearing takes place, resulting in a poor surface finish.
During the annealing or normalizing cycles, graphitization may take place with a lowering of the combined carbon content of the cast iron,
resulting in a decrease in strength. In determining the temperature above
which the
cast irons
must be heated to promote austenization, the usual
iron, iron-carbide
diagram cannot be used.
The
proper section through

should be consulted.
the ternary diagram of iron, carbon,
and
silicon
432
Hardening and Tempering. The gray cast iron, the pearlitic malleable and the pearlitic nodular cast irons respond to heat treatment much in the same manner as do plain carbon steels. The ability to respond to heat treatment stems from the presence of carbon in the combined state. The carbon present in the combined state causes the formation of
irons,
austenite
critical
when
the ferrite-carbide aggregate
is
heated above the upper

the
temperature.
Some
graphitization
heating to the austenitizing temperature. the proper austenizing temperature until the desired degree of solubility of carbon has taken place, and the alloy is then quenched. The usual precautions taken in the heat treatment of cast iron are the same as those for steels. To cause the formation of a completely martensitic matrix from the austenite, it is necessary that the section be quenched
at,
may take place during The cast iron is held at
or faster than, the critical
cooling rate. If the cooling
is
some-
what slower than the critical cooling rate, some of the soft pearlitic constituents are formed and associated with the martensite. When conditions of service require properties other than high hardness, the irons
are given a tempering treatment.
It is quite common to give the heat treated cast iron, to be used in the martensitic condition, a stress-relief
heat treatment to minimize cracking during grinding and to minimize

the brittleness of the martensite.
The
tempering curves of hardness versus

for
steels.
time are similar to that obtained
The
is
hardness of the
increased.
martensite decreases as the tempering temperature

similar to those produced in hardening
The
is
resulting microstructure formed by the tempering of the martensite
and tempering of steels. In studying the hardenability response of cast iron, the Jominy hardcnability
type of bar can be used, the hardness being determined along the edge
of the bar in a
carbon
steels.
manner similar to that for low alloy steels and As one may anticipate, the hardness of the fully
quenched
steel of the
plain
heat-
treated cast iron
at
or
faster
than the
critical
rate
is
someto the
what
less
than a
same combined carbon content, due
presence of graphite.
The
presence of graphite in the martensite matrix
decreases the hardness considerably.

tester will verify the fact that the
The
use of a light-load hardness
hardness of the martensite between

a lull heat-treated
the graphite flakes

steel.
is
as great as the martensite in
The
presence of graphite in the matrix of the cast iron during
heat treatment to full hardness acts as a cushion and tends to minimize
quench cracks that many occur during the considerable volume changes that accompany the transformation of austenite to
the formation of
martensite.

Cast Iron
433
7.--"
T ^
00M1
IIIT
tiktiuti
If
it no in
1
noo
\ J
* too
1
JOOH
MM
Ui
s.ai
^ZUC
^s.
I LTNI
oo
GRAY CAST IRON
^1
riao
- 3.
14
M 5 TOO I 000 p
ioo
Mn P
S
Si
- 0. 81 - 0.219
- 0. - 2.
NN
064
15
f,
if *N
iac
"s
400
rl , n ,
IOO
too
Fig. 20.13.
Time. Temperature. Transformation (TTT) diagram
for a cast iron.
(Nagler and Dondelt).
Isothermal Heat Treatment. The various types of cast irons such as gray cast iron, pearlitic malleable iron, and nodular cast irons can be heat treated by any of the known isothermal transformation methods. The
TTT
curve for cast irons does not differ greatly from that of low alloy, diagram high alloy, or plain carbon steels. Fig. 20.13 is a typical influencing iron is an the cast for a cast iron. The combined carbon in diagram. factor in determing the position of the upper nose of the
TTT
As the carbon content
increases, the
upper nose of the
TTT TTT diagram
is
shifted to the right. The maximum shift to the right is produced by a eutectoid composition of combined carbon. Amounts of carbon above
or below the euctectoid composition tend to shift the nose of the curve to the left. The cementite or the ferrite, whatever the excess proeutectoid constituent may be, nucleates the transformation of austenite to pearlite at the position of the upper nose of the curve. The products
of transformation produced isothermally are identical to those produced
TTT
434
below the lower
critical
in steels. Starting at a temperature just
tempera-
ture (Aij), coarse pearlite
nose of the
TTT
formed at the upper curve; below the upper nose the upper bainite is
is
formed;
fine pearlite is
formed; at the lower range the lower bainites are formed; at the M, temperature manensite is formed from the austenite on cooling to room temperature. The isothermal method of heat treating cast irons produces
increased toughness of the matrix of cast irons.
Flame Hardening and Induction Hardening. The gray cast iron, pearlmalleable cast irons, and the nodular cast irons respond to induction and flame hardening. The principle of this process of hardening is to heat rapidly above the upper critical temperature the surface of the parts to the desired depth and immediately quench. The heated portion of the iron is changed to an austenitic condition initially, and when quenched, the austenite is converted to a martensite. Depending on the thickness of the section size, there may be no alteration in the properties of the core. The intent of this form of heat treatment is to produce a marked increase in hardness on the surface of the part with retention of unitic
altered core properties.
The hardened
portion of the cast irons illustrates
the presence of a martensite matrix with graphite. This heat treatment
produces a hard-wearing case on the tough shock-damping core of the

cast iron,
and the depth of hardening can be controlled very

in Cast
closely.
20.14.
Normal and Alloy Elements
Iron
sili-
The normal
elements in cast iron include such elements as carbon,
con, manganese, phosphorus,
and sulfur. The commonly used alloying elements include copper, chromium, molybdenum, vanadium, and nickel.
Carbon. Carbon in cast iron is present in the uncombined and combined forms. In the uncombined form the carbon can assume the shape of flakes or nodules. In the combined form the carbon can be present as a simple iron carbide (cementite) binary carbide, and other complex alloy iron carbide forms- The presence of the carbon in the uncombined state is controlled by such factors as chemical analysis of the iron and the cooling rate from the casting temperature. In the malleablizing of white cast iron, an additional type of carbon is formed called tempered carbon.
,
Silicon.
Silicon
is
generally considered as a graphitizing element.
The
amount
is
of silicon present in a cast iron determines
whether the carbon
present in the combined or
dition.
The
uncombined state for a given cooling congraphitizing effect of the silicon can be somewhat offset
fer-
by the addition of carbide forming elements. Silicon dissolves in the rite and acts to toughen the iron.
Cast Iron
435
Manganese. Manganese combines with the sulfur and forms manganese inclusions. Some sulfide, which is insoluble in iron and forms non-metallic present in the iron also silicate, of the manganese may form manganese dissolved in the is remaining as a nonmetallic inclusion. The manganese
ferrite
and
acts as a ferrite toughener.
Phosphorus. Phosphorus is present in cast iron in the form of steadite, a ternary eutectic of iron, carbon, and phosphorus. Steadite is a low melting constituent contributing to the fluidity of cast iron. The steadite melts at about 1750F. The presence of phosphorus adds to the brittleness of cast iron
Sulfur.
and tends
is
to lower the
impact strength of
it.
combined form of manganese sulphide or iron sulphide. Iron sulphide, when form usually occurs in the grain boundaries and reduces the impact toughness of the
Sulfur
present in cast iron in the
iron.
Chromium. Chromium has a two-fold effect on cast iron: it dissolves in the ferrite and is a carbide former. The chromium that dissolves in the ferrite acts as a toughener. Chromium that is present in an amount over
that necessary to saturate the ferrite occurs in the pearlite as a massive iron-chromium carbide. Chromium has a tendency to produce a uni-
form
cast
fine-fracture grain size.
As the per cent of chromium added
to the
in a
iron is increased, there is a tendency for the carbon to remain combined form, and the fracture will be white. Chromium in the amounts of from 0.15 to 2.00 per cent may be added to cast iron and still
provide gray fractures
if
suitable
graphitizing elements are present.
Additions of
chromium
hardness, wear
tion resistance.
to the cast iron will increase tensile strength, resistance and depth of chill, and corrosion and oxidiza-
Chromium
will delay the isothermal transformation of
cast iron during heat treatment.
Molybdenum.
degree,
agent.
Molybdenum dissolves in the ferrite is a carbide former. Molybdenum does not act The addition of molybdenum to cast iron
and
and, to a limited
as a graphitizing
increases
tensile
strength, hardness, transverse strength,
resistance to deflection to cast iron
on
cast
transverse loading.
The
addition of
molybdenum
when
into large section sizes tends to promote uniform structures. This results in an iron of uniform strength, hardness, and density throughout the
Molybdenum additions to cast iron promote machinfrom structural uniformity and a minimum occurrence of large carbides. Molybdenum has little or no effect on retarding
large section
size.
ability resulting
isothermal transformation over the range of baintic transformation products. The isothermal transformation to pearlite products is retarded by
the addition of
molybdenum.
436
Copper.
Copper dissolves to a limited degree in the ferrite and acts and is a mild promoter of the formation of graphite. Copper tends to increase strength, hardness, wear resistance, and corroas a toughener,
The addition of copper to cast iron reduces the tendency form a chill layer, hence increases machinability. Copper is not used as an individual additive element but is usually added with such elements as chromium, molybdenum, nickel, and vanadium. Nickel. Nickel dissolves in ferrite and is a graphitizer. Nickel additions reduce depth of chill and tend to refine the grain size. Nickel is effective in retarding the transformation of austenite over the whole
sion resistance.
to
range of transformation.
nickel
is
If
the graphitizing effect of nickel
is
disregarded,
considered to increase the strength, hardness, resistance to de-
flection, toughness, corrosion resistance,
and machinability. In addition

utilized in martensitic cast iron
to using the nickel in gray cast iron,
it is
containing comparatively large percentages of nickel and chromium. The alloy has superior wear and corrosion resistance. A grade of cast iron
termed austenitic
is
cast
with the addition of nickel and chromium for
wexpansion and stainless qualities. Vanadium. Vanadium when added to cast iron performs the role of a strong carbide former. Vanadium retards graphitization and stabilizes cementite and has a high affinity for carbon and combines to form vanadium carbides. The addition of vanadium to cast iron tends to produce small uniformly distributed graphite flakes and decreases fracture grain size and increases the tensile strength, transverse strength, hardness, and machinability. Vanadium is alloyed in cast iron with elements such as nickel, copper, chromium, and molybdenum. Vanadium, when added to cast iron, acts as an effective deoxidizing agent in the removal of dissolved oxygen from the iron. Little to no effect can be found on the
service conditions requiring lo
isothermal transformation of cast irons because at ausieniting temperatures the
vanadium carbide
is
quite stable.
QUESTIONS
1.
What
the general appearance of the fracture of gray, mottled, and white cast iron? What is responsible for the different fractures of these three
is
classes of cast iron?

2.
What
is
their relative industrial importance?
What
the relation of gray cast iron to steel? In what respects are the properties of gray cast iron inferior to those of steel? Give die variables that affect the properties of gray cast iron. What characteristics make gray cast
is
iron a valuable engineering material?

3.
How
is
a gray cast iron
the desired composition attained?
melted, and what raw materials are used? How is How much carbon, silicon, and phos-
phorus are usually present?
Cast Iron
437
4.
Name
the role played by carbon
Describe the primary metallographic constituents in gray cast iron? and silicon in iniluencing the structure as seen
with the microscope.

5.
What
is
steadite? Describe
its
appearance.
What is the general relation between carbon and silicon, and the structure and appearance of the fracture? If a small specimen of cast iron, poured the structure of the in a sand mold, contains 3.5 per cent carbon, what is
cent? matrix if the silicon is (a) 1.0 per cent? (b) 1.5 per cent? (c) 2.25 per would you silicon carbon and total percentages of For small castings, what 38,000 specify to obtain a tensile strength of (a) 33,000 lb. per sq. in.? (6)
lb.
per
sq. in.?
is
6.
What
the effect of cooling rate on the structure of gray cast iron? If to a steel the matrix of a small sand-cast bar has a structure corresponding correspond to if matrix the would carbon, what containing 0.60 per cent effect of the the casting was a block 6 to 8 in. square? What is the general control of graphitesize of the graphite flakes on the properties? How is
flake size
accomplished?
are
Why
is
cast iron frequently
annealed?
7.
What
tests
applications?
commonly used to evaluate gray cast iron for engineering Which is the best of these tests, and how is it made? How are
results reported?
What
is
the approximate secant
modulus of gray
cast iron,
8.
the average compressive strength? and how is it determined? What properties would you consider to be representative of (a) a highgray test gray cast iron? (b) a low-strength iron? (c) an average American
is
What
How do the endurance limits, impact resistance, and capacity of gray cast iron compare with those of carbon steel?
cast iron?
9.
damping
Why How
tional
die addiare alloying elements added to gray cast iron, and when is cost of these elements justified? What are the general effects of
(b)
(a) nickel? 10.

is
chromium?
(c)
molybdenum?
malleable cast iron produced? What is it used for? Give the approximate tensile strength and elongation of American malleable cast iron. What the relation between the two? Compare endurance ratio, impact reis sistance, and machinability of malleable cast iron with those of gray cast
iron.
are the significant differences between pig iron and gray cast iron? In what way are they similar? In what respect does mottled iron resemble un-annealed, nodular iron? gray cast iron 12. How does the development, or formation, of graphite in reason for using one Give at least malleable cast iron? that in differ from a lower carbon content in malleable iron than in gray iron.
11.
What
13.
14.
In Table 20.2, study the percentages of carbon and silicon recommended for various types of castings and satisfy yourself why these analyses arc good for the particular application. Why is closer control of chemical composition necessary in producing high
strength gray iron?
15. 16. 17.
Draw
List the requirements of
Why
a section through a cupola and label the operating parts. coke that would be suitable for use in a cupola. are large amounts of sulfur and phosphorus undesirable in cast iron?
18. 19.
Differentiate between a graphitizing element
20.
What What
and a carbide-forming element. performed by alloying elements when added to cast irons? different types of graphite patterns are formed in gray cast iron.
roles are
CHAPTER
Mach inability, We ar Resistance and Deep D rawing Properties

-
21
Irvinc
J.
gineering,
Lkvinson, M.S., Professor of Mechanical EnLawrence Institute of Technology, Detroit,
Michigan
oINCE
complex metallurgical, mechanical, and
environmental factors are involved, a precise evaluation of machinability, wear resistance, and deep-drawing is extremely difficult. This problem of evaluation has been attacked from many fronts, but to date only generalities
have been formulated no hard and
fast rules exist.
21.1. Variables Affecting Machinability
To remove
surface.
metal by machining, the tool must

ease with
first
penetrate the
The
which
this occurs
is
a function of the static- and
dynamic hardness of the cutter and the metal to be machined, the rate of penetration, the depth of penetration, the frictional and shear forces involved, and the relative rigidity of the system.
readily break.
has penetrated the surface the chip formed should coiled chip is not the desired one. Breaking the chip mechanically involves a loss of power and thus is not the most desirable answer. The ideal method of breaking the chip
tool
Once the
While spectacular, the long
is
to provide a built-in breaker in the

It is
wrong machine. Toughness

stituent.
to
is
form of a weak and assume that because a metal is soft
brittle conit
is
easy to
usually a corollary of softness, and, as a con-
sequence, the chips formed separate only with difficulty. In steel, a completely spheroidized structure is considered the easiest to machine, although the presence of some small pearlite islands does promote chip breakage.
21.2. Evaluation of Metallic Materials for Machinability
Experience has shown that a correlation

physical properties of the metals
exists
between the basic
and 438
their machinability. Figure 21.1,

439
140
Machinability,
)
i
Wear
Resistance
80
70
Tensile strength, thousand lb.persg.in. 100 120 80 60 40 20 i_ _l

1 ,
\
Feed S *lmm.
60
50
\
V/oy. t/eeb truck irali feels
per revolution
Depth
t=2mm.
.40 c
o asts feels
~X^
hfc^
'-'ft;
'E30
.20 E
10
20 >
O
.
Heeds
Depth
-I mm.
per revolution
t-4mm.
>
o-50 c
4<
15
V
*s.
,
30
zo
10
|0
20
30
40
50
60
10
60
90
100
Tensile strength, kg. per
sq.mm.
cuts
tool life of 1 hr. to tensile strength for Fig. 21.1. Relation of cutting speed for a Dabringhaus, Maschmenbau, v. 9, of 0.08 and 0.16 in. (A. Wallichs and H.
1910, p. 251)
for example,
shows that machinability decreases with increasing tensile probably a good strength. This property, together with hardness, is controlled condicriterion of machinability. It is also true that, under of cast and hottions, there is very little difference in the machinability
rolled steels, of carbon and low-alloy steels, or of acid provided tensile strength and hardness are the same.
and basic
steels,
machine Cast steels and nonferrous alloys may be more difficult to structure if the composition and same of the material wrought than the sand skin of the casting has cooled rapidly enough to harden it, or if
has not been removed thoroughly from the surface. Many efforts have been made to devise a laboratory test to indicate been accurately relative machinability in service. Recent attempts have
440
concerned with the work-hardening capacity of the material cut, ihe object being to use the maximum hardness so induced as a measure of
machinability.
21.3. Free Machining Steels

Despite the impossibility of evaluating machinability accurately, exshown that the machinability of some materials can be im-
perience has
proved by certain treatments and, further, that there are alloys of certain compositions which can be machined more easily at high speed than other alloys of the same general type. Such materials are, therefore, used
widely in automatic machines for mass production of machined parts. The machinability of those low-carbon steels which arc too soft and
tough to machine easily is improved by heat treatment and, especially by cold working. Quenching a low-carbon steel to increase the Brinell hardness number from 90 or 100 to 170 to 210 improves its machinability (provided, of course, that no martensite is formed by quenching) Cold working is even more effective in increasing the hardness and at the same time decreasing the toughness; hence, most low-carbon steels that must be machined economically are cold drawn or cold rolled. This operation also has the advantage of producing a smooth surface. The best and cheapest method of improving the machinability of lowcarbon steels is to add sulfur, or lead, or both. However, owing to the
.
Table
21.1.
Relative Machinability Rating of Cold- Worked Free-Cutting Steels

S.A.E.
Machinability rating,
No.
per cent
C
X1112
1112L*
1112
0.08 0.08 0.08 0.10 0.10 0.10 0.15 0.25 0.30 0.35 0.15 0.35
to 0.16 to 0.16 to 0.16 to 0.20 to 0.20 to 0.20 to 0.25 to 0.35
to 0.40
Mn
0.60 to 0.90 0.20
S
to 0.30
P
0.09 to 0.13 0.09 to 0.13
X1314 XI 31
1115 1120
XI 330
X1335
XI 340
1020 1040 1010
to 0.45 to 0.25
to 0.45
0.05 to 0.15
0.60 to 0.90 0.60 to 0.90 1.00 to 1.30 1.30 to 1.60 0.75 to 1.00 0.60 to 0.90 1.35 to 1.65 1.35 to 1.65 1.35 to 1.65 0.30 to 0.60 0.60 to 0.90 0.30 to 0.60
0.10 0.10 0.075 0.075 0.075
to 0.20 to 0.20 to 0.150 to 0.150 to 0.150 to 0.150 to 0.150 to 0.150
0.09 to 0.13 0.045 max.
140 140 100
90
87
81
0.075 0.075 0.075 0.075 0.055 0.055 0.055
to 0.150
max. max. max.
0.045 0.045 0.045 0.045 0.045 0.045 0.045 0.045 0.045
max. max. max. max. max. max. max. max. max.
78
76
72 70
63 60 53
* Contains 0.20 to 0.25 per cent lead.
Machinability,
Wear
Resistance
441
high sulfur (plus high phosphorus for some of the steels), these "freemachining" or "free-cutting" steels have much lower impact resistance than low-sulfur steels of the same carbon content and should be employed, therefore, only where low impact resistance is not a handicap.
Leaded
steel is a
development of the past few
years.
The
addition of
lead improves the machinability of low- as well as of high-sulphur steel. Leaded steel is also more resistant to impact than high-sulphur material. A somewhat similar effect is obtained in stainless steel with the addition of Selenium.
The
relative machinability of the free-machining steels

steels
is
com-
pared with three low-sulphur

Iron carbide particles,
if
given in Table 21.1.*
favorably located
and
as chip breakers; thus, unalloyed
carbon
steels
of favorable shape, act containing 0.20 to 0.40
when properly annealed, machine much more easily than those containing carbon below 0.15 per cent (Table 21.1). The In high-sulphur steel, inbest chip breaker is manganese sulphide (MnS) small particles, break up the when well distributed as clusions of MnS, 21.1 shows, greatly improve maeffectively and, as Table chips very
per cent carbon,
.
chinability.
Despite their low impact resistance large tonnages of high-
sulphur
steels are used.
21,4. Relative Machinability of Steel
and Nonferrous Alloys
An approximate evaluation of the relative machinability of some common ferrous and nonferrous materials can be made by averaging the data
by Bostont for drilling, milling, and planning tests. They were reported as the horsepower required to remove one cubic inch of metal per minute. The order is as follows:
re|>orted
Horsepower per
Material
cu. in.
per min.
0.30
0.35
Magnesium
alloys
Bearing bronze
Aluminum
alloy,
8% Cu
0.35
Free-cutting brass
0.38 0.60
0.60 0.75 0.85
Manganese bronze Hard cast iron

Malleable iron Yellow brass, unleaded
Free-cutting, steel, cold
drawn
0.90
1.12
1
Forged carbon steel, 020% C Nickel steel, 0.40% C Annealed copper Tool steel, high carbon Low-carbon, high-chromium steel Monel metal
.20
.35 .60
1
1
.70
1.70
Adapted from a tabulation by H. W. Graham, Metal Progress, July,

Boston, Proc.
tO. W.
Am.
1939, p. 53. Soc. Testing Materials, v. 31, 1931, part II, pp. 388-421.
442
This is not an infallible evaluation, and the order might be changed for some of the alloys if the conditions of the tests were changed slightly. It does, however, show that it requires much more power to machine the free-cutting steels than is needed for some of the magnesium and aluminum alloys, some of the free-cutting brasses and bronzes, or cast or
malleable iron.
Soft gray cast iron, containing
particles,
no hard excess carbide or phosphide and malleable iron are the most readily machinable of all fersteel.
rous materials, usually ranking higher than high-sulphur
The
ease
with which these materials are cut

ferrite plus the
is
due primarily
to the softness of the
numerous small
particles of graphite
which
act as
chip
breakers and as a lubricant.
In general, copper- and aluminum-base alloys are easy to machine.
There
is,
however, enough difficulty with these alloys so that special

is
compositions are used for material that

Free-cutting brass
chinability
is
cut in automatic machines.
and bronze contain 1 to 4 per cent lead; their ma70 to 100 as compared to 20 to 30 for the same alloys con-
taining
no
lead.
21.5.
Types of Wear
importance of wear resistance needs no amplification.
The
Wear
oc-
when pistons and valves operate; when a gear meshes and drives another; when steel or cast-iron wheels start, run, or stop on rails; when brakes are set; when excavating, concurs in machines
shafts rotate;
when
veying, crushing, or mixing machines handle sand, clay, rock, coal, or
other engineering applications.
implements arc used; and in a multitude of Some of the most destructive wear of metals is caused by rapidly moving soft materials; for example, the wearing of hardened steel parts by cotton or silk thread in textile machinery and the wear of turbine blades by high-velocity gases. The wear of metals may be divided broadly into metal-to-metal wear and abrasive wear. Another division is possible: into wear under rolling friction or under sliding friction and, further, according to whether lubrication can or cannot be used. The latter is, of course, most important in the metal-to-metal contact of machine parts. Lubrication may be omitted from detailed consideration because, although it greatly influences the rate of wear, it probably has little or no effect on the type of wear. Wear resistance is an important property of metals used in maminerals;
when
agricultural
chines even
if
lubrication
is
of the best, because perfect lubrication
is
more
of an ideal than a reality.

it
Moreover, even
it
if
lubrication
is
so
thorough that
prevents a metal-to-metal wear,
frequently happens
Machinabiiity,
Wear
Resistance
443
that extraneous grit in the lubricant causes severe abraisive wear. Another important factor entering into the wear of machines is corrosion of the
wearing surfaces caused by condensed moisture or acids in gases and

lubricants.
Wear
involving a single type

occur.
is
rare; in
is
most machinery, both abrasive
and metal-to-metal wear
This
the case in such parts as shafts
revolving in bearings, where abrasive wear occurs until the shaft and
bearing are "run in" and worn to a mirror
finish, after
metal wear predominates. Since in such service avoided completely, even with the best lubrication,
which metal-towear can rarely be

it is
common
to
use
a hard metal and a relatively soft one together, the softer material being
used (as in a bearing) for the part which is most economical to replace. In some kinds of excavating and material-handling equipment, abrasive
wear
is
the principal type involved.
21.6. Variables Affecting
Wear
Resistance
Like machinabiiity, wear resistance depends upon two factors, the metallurgical and the mechanical. The latter has been discussed briefly in the previous paragraphs and may, consequently, be dismissed with
the statement that wear of metal depends as much, or even more, on
the conditions of service as
From
ness.
the
upon the metal used. metallurgical standpoint, wear resistance

is
is
inversely pro-
portional to machinabiiity and, in general, directly proportional to hard-
Hardness, however,
not the only metallurgical factor of im-
portance.
Wear by
abrasion, like machinabiiity, involves tearing off small
particles of the metal.
Consequently, strength and toughness are im-
portant factors in resisting wear,
The wear
resistance of the various carbon

it
and
alloy steels receives
attention elsewhere;
can be dismissed here with a brief mention of the general types of ferrous material used for wear resistance. The first and most common, especially for metal-to-metal wear, is a cast iron or a steel with a surface of high hardness. Usually, in an application requireing high surface hardness, considerable toughness, especially of the core,
is
also required.
and tempering an
or alloy steel bined with considerable ductility in the core. For abrasion resistance, two kinds of materials are used: (1) an austenitic steel, which is relatively soft but which, under the severe cold working of the abrasion, transforms to martensitic; and (2) a carbon or alloy steel, on which a hard surface layer of some special alloy is deposited by electric arc or other method.
This combination of properties is attained by quenching alloy steel or by case carburizing or nitriding a carbon and heat treating to produce high surface hardness com-
444
80
130 120
70
.*60
{ ocw/C" c
3
r.
110
:;.:
?S0
B
a a
=3
f
_x--""
X"*
_ U-^x-f
]
'
< -
'/,-
-i
S*
*20
tt
io
90
1
|30 !
O
at
60
70
50
Jr k^
\.
yj r~
s ' y* psf^
4
B scale
50
o
0.16
0.15
o Hardened Normalized
d
g.gO.14
D Annealed
l| an
%.%
0.12
\ jS
k
\
X
)
>x
^n
S.,
^r~
|1 a"
a
^.
.-
(,_
""
*x.
0.10
\
\,
H
X
f-8*
0.09
S" 0.08
0.07 0.06
0.2.
\>
0.4
V
0.6
-o
-'
^
1.0
1.2 1.4
0.8
Carbon, per cent
Fig. 21.2. Effect
of
carbon
content
and
heat-treatment
on
metal-to-metal
wear
of carbon steels. (Rosenberg)
21.7. Evaluation of Steel for
Wear
Resistance
The
cult
evaluation of the wear resistance of steels is one of the most diffiproblems a metallurgist is called upon to solve. Simulating actual
service conditions by a laboratory test the
most important phase of
this
problem can be accomplished only rarely and then only if wear in service occurs rapidly and if it is possible to design a machine which
duplicates service conditions exactly.
Wear
is
usually a slow process.
Shidle* notes that,
when
a 5-ton truck has finally
worn
out,
it
has lost
only 5 lb. of metal. The useful life of the average automobile engine is probably 100,000 miles; hence the difficulty of devising a test which will simulate such service conditions accurately.
Several types of laboratory machines have been developed that deter-
mine
the wear resistance of a material fairly rapidly and under relatively
closely controlled conditions.
For determining metal-to-metal wear, the

19, 1932, p. 449.
N. G. Shidle, Automotive Ind., v. 66, Mar.
Machinability,
Wear
Resistance
445
most common is the Amsler machine, which tests a specimen under pure sliding or pure rolling friction, or a combination of the two. Pressures can be varied at will, and wear can be determined at any temperature, with or without lubrication. Some data on metal-to-metal wear at room temperature of carbon steels, together with Rockwell hardness, are shown
in Fig. 21.2.*
For the determination of abrasive wear, two machines are commonly employed: the Brinell and the Spindel (used widely in Germany) which use sand or emery as the abrasive. Much care is necessary in the selection of the abrasives as these may not be uniform. The order of merit of a series of steels and alloys with one abrasive may change completely if
,
another abrasive or a different lot of the same abrasive
is
used.
It
has
been said with considerable justification that machines for determining resistance to abrasive wear are a better test of the abrasive than of the
metal.
The important fact to be recognized is that any wear-testing machine determines the relative resistance of a series of metals or alloys under a few carefully regulated conditions, but that the results obtained, while
valuable for comparing the materials, cannot be translated quantitatively into probable life in service unless the test used duplicates in all respects,
including time, the conditions of service.
21.8.
Importance of Deep-Drawing Properties
Practically all steels and most of the nonferrous alloys can be deformed cold, but how much deformation they will withstand without failure, or without annealing to restore ductility, varies greatly, depending upon composition, structure, and other factors. In general, the higher the ductility as shown by the tensile test, and the lower the hardness, the more a material can be deformed without fracture. Thus, low-carbon wire can be drawn through a die to a smaller size than high-carbon wire without intermediate annealing to restore the original ductility and softness.
As cold forming by pressing or stamping
is
cheap and readily adapted
to large-scale production, this method is used widely, especially by those industries producing automobile fenders and bodies and a variety of
small stamped utensils for domestic

of
and other
uses.
With
the exception
aluminum and
stainless steels,
practically all
deep-drawn products
are coatedgalvanized, tinned, painted, enameled, lacquered, or plated.
High
tensile strength
is
usually not important; consequently, the
ma-
S. 1366, 1367. J. Rosenberg, Iron Age, v. 128, 1931, pp.
446
terials
most widely used are those with the least tendency to harden when cold worked. The principal ferrous materials are, therefore, ingot
iron,
unalloyed basic open-hearth
steels
containing 0.04 to 0.10 per cent

the form of thin-annealed or
carbon, and the soft stainless
steels, all in
annealed and slightly cold-worked
sheets.
As the manufacture of deep-drawn products, such as of fenders and

bodies by the automotive industry,
it
is
is
a continuous low-cost operation,
common
practice for fabricators of the grade of sheet to arrange

is
their various operations so that the material
worked
until
it
strain
hardens almost to the breaking point before annealing is necessary. Steel with a ductility just slightly below the standard will, therefore, show
excessive breakage.
Consumers' requirements have become more severe year by year.

only necessary to compare the automobile fender of the last
five
It is
years
with those of fifteen years ago to prove how the steel industry has kept up with this demand by raising the quality of its deep-drawing stock. There is still much room for improvement, both on the part of the steel maker and on the part of the consumer of deep-drawing sheets. What is needed most urgently is a test giving a reliable indication of drawability and, even more importantly, a standardization of consumers' requirements.
21.9. Evaluation of Steel for
Deep Drawing
and
yield ratio in tension, hardness,
Drawability
including,
is
weighted average of a large number of components,
among
others, yield point
elongation, reduction of area,
and
possibly impact.
Drawing
correctly,
different
if
shapes involves a different relation of the components; hence, even

the components were known and could be weighted
it
all
would
change the weighting for different drawing operations. The difficulty of weighing even the known components accurately is increased by the virtual impossibility of determining accurately reduction
be necessary
to
of area probably the most important
component on
thin
test
speci-
mens Some
users of deep-drawing stock have arrived at certain combina-
tions of tensile strength, elongation,
and hardness
for different thicknesses
of sheet to indicate satisfactory drawing properties, but such correlation

is
worthless to others
who draw
their product
under
slightly different
conditions.
To overcome these difficulties, and in the hope that a single test could be devised to measure drawability, much time and effort have been devoted to the cupping test. Several varieties have been developed, chief of which arc the Erichsen, used in Europe, and the Olsen, used in
Machinability,
Wear
Resistance
447
';</
Erichsen Fie. 21.8. Structure and coarse-grained low-carbon sheet steel.
(F.
cupping tests o[ (A) fine-grained and (B) Kbrber, Stahl u. Eisen, v. 47, 1927, p. 1158)
the United States.* Essentially, the test consists of supporting a speciof the sheet between two dies, while a ball or a plunger is brought down against the specimen forcing it into the shape of a cup. The flow
men
of the metal can be followed in a mirror,
and the
first
fracture can be
observed. The depth of the cup, or the pressure necessary to cause failure, is measured. The test gives some information on how the material
deforms but not enough invariably to predict how it will deform in service. Metallurgical opinion on the value of cupping tests is divided; some metallurgists consider them not only unreliable, but actually misleading.
Because the structure and the hardness of steel are important factors in deep drawing, great care is exercised in the melting, rolling, annealing, and finishing of the sheet so that the grain size will be controlled ac
Cupping
tests
in
The
Alloys of Iron
and their significance are discussed by S. Epstein and F. T. Sisco. and Carbon, Vol. I, pp. 272-278, and Vol. II, pp. 646-650 re-
spectively.
448
Strainlow-carbon deep-drawing steel showing upper yield point A, lower yield point B, and yield-point elongation E. Slight cold rolling reduces the amount of yield-point elongation (second curve from right), and further cold working eliminates it entirely (right).
Fic. 21.4. Stress-strain curves of
curately
steel
and the hardness will be within certain limits. A fine-grained can be deformed to a greater extent and has a much better surface after deforming than coarse-grained material. This is shown in Fig. 21.3.
The
surface of the fine-grained steel is smooth after cupping; the coarsegrained material, on the contrary, has a crinkled "orange peel" surface.
21.10. Yield-Point Elongation, Stretcher Strains, and Deep-Drawing Properties
Most annealed low-carbon

yield point
steel
used for deep drawing (0.04 to 0.10 per
cent carbon) has two yield points, an upper and a lower one.
(A in Fig. 21.4.)
is
The upper
its
the stress at which yield begins, and
dependent to a considerable extent upon testing conditions. The lower yield point (B in Fig. 2 .4) represents the lowest stress to which the applied load sinks during stretching; this value is probably more characteristic of the material than the upper point. The distance that the material stretches while passing through the yield point is known as the yield-point elongation (E in Fig. 21.4) and this value is an important one in determining whether the sheet will have satisfactory deep-drawing properties. When annealed low-carbon sheet is deep drawn, strain linesknown as stretcher strains frequently appear on the surface (Fig. 21.5). This
location
is
1
,
defect
(Fig.
is
analogous to the orange-peel surface caused by large grains
These same stretcher strains appear on the surface of a specimen which has a double yield point and considerable yield-point elongation, and the severity of the defect apparently is related
21.3).
tensile-test
directly to the
amount
that the specimen stretches between the
upper
Machinability,
Wear
Resistance
449
Fie. 21.5. Stretcher strains in
cold-drawn low-carbon sheet.
(J.
Winlock and G. L.
Keltey, Trans.
Am.
Soc. Steel Treat., v. 18, 1930, p. 241)
and lower yield points. By subjecting deep-drawing sheet to a slight amount (0.5 to 2 per cent) of cold rolling on a "temper mill," the yieldpoint elongation is eliminated and stretcher straining is prevented. The stress-strain curve for a steel in this structural condition is shown at the
right in Fig. 21.4.
There is still much to be learned about deep-drawing steels and their behavior under extreme cold deformation. In general, microscopic examination, Rockwell
ability as
hardness, yield ratio,

test,
and yield-point elongation,
plus some form of cupping
give about as
much information on draw-
can be secured
at present.
21.11. Deep-Drawing Properties of INonferrous Alloys

In general, the working of metals and alloys of suitable properties by deep drawing is an economical operation, and a considerable tonnage
of nonfcrrous materials
cles
is
fabricated into finished and semifinished arti-
by this process. Second only to deep-drawing low-carbon steel in tonnage is alpha brass, containing more than 62 per cent copper and less than about 38 per cent /inc. The variables affecting the deep-drawing properties of alpha brass are very important and have, as a result, been subjected to more study than similar properties for any other deepdrawing material with the possible exception of steel for automotive
fender and body stock.
The
principal variables that affect the cold-working characteristics of

size.
alpha brass are composition, hardness, and grain
Ductility
is
lowered
450
by small amounts of tin, lead, and iron, and the presence of much beta constituent should be avoided. Beta is a hard constituent that is likely
to occur if the copper is less than 62 or 63 per cent and may be present even if the copper is 65 or 66 per cent. Considerable brass of this composition is deep drawn. To be readily subjected to a large amount of cold deformation, the grain size should be small; the optimum size depends on the nature of the drawing operation and to some extent on the degree of smoothness desired on the surface. An average grain size of from 0.035 to 0.10
mm.
is
about
if
right.
Brass strain hardens readily and must be anis
nealed at intervals
the cold working
severe.
The
and
annealing temperacare
is
ture varies from 900 to 1100F.
(480 to 590C.)
exercised to
prevent grain growth during annealing.

to that
Deep-drawn found
size.
is
brass will occasionally have
an orange-peel
surface, similar
in
deep-drawn
steel
(Fig. 21.3),
caused usually by large

is is
grain
The
principal defect to which deep-drawn alpha brass
subject
season cracking, a variety of stress-corrosion cracking that
encountered in a large number of nonferrous alloys and in some steels, especially the stainless grades. Season cracking is due to a combination of high internal stress and some forms of corrosion and has been especially troublesome in deep-drawn cartridge cases. It can be prevented by annealing to relieve residual stresses.
Most
nickel,
of the other soft metals, especially
and
zinc,
and some
into a variety of useful
aluminum, copper, lead, tin, deep drawn commercially shapes. In most cases, special techniques and
of their alloys are
equipment for example, impact extrusion for collapsible tubes used widely for drugs, cosmetics, and toilet articles must be used, and for
many of which are one of the principal problems in deep drawing aluminum is to prevent the abnormal grain growth which is likely to occur in annealing, and which may cause a rough surface and premature breakage of the deep-drawn part. In deep drawing high-purity copper, abnormal grain growth is also a problem.
each metal there are special problems to be solved,
metallurgical. For example,
QUESTIONS
1.
Calculate the theoretical horsepower required to machine a hollow monel metal shaft having an outside diameter of 3.250 inches, an inside diameter of 1.625 inches, and a length of 36.00 inches, from a blank 36>/j inches
long, having a outside diameter of 3% inches. Design a dynamometer to determine the power required to turn
a
2.
given
material in a lathe.
obtained.
Make
use of the spring characteristic
of the tool holder,

basis of the data
and show how the power could be calculated on the
Machinability,
Wear
Resistance
451
re-
3.
Compare
sistance.
What
wear the variables affecting machineability with those affecting conclusions can you draw?
4.
5.
Discuss the effect of wear on fatigue life. Differentiate between erosion, galling, and corrosion as a
mode
of wear.
as
6.
some examples of cadi. Discuss the difference between rolling friction

List
and sliding
friction
mode
7.
of wear.
rate of Discuss the possibility of using radioactive materials to study the
wear.
8.
9.
List the environmental factors that effect wear resistance. as important as the physical properties of the material itself? Describe the cupping test and discuss its limitations.
Why
are these
10.
What What
which
is
meant by "double-yield point" and how does
it
effect
the deep-
drawability?
11.
benefits are obtained in having a

is
homogeneous
structure in a material
properties.
to
undergo deep drawing?
12.
Discuss the effects of lattice configuration
on deep drawing

CHAPTER
Mars G. Fontana,
22
Ph.D., Professor and Chairman, Department of Metallurgical Engineering, The Ohio State University, Columbus, Ohio
Richard Edward Grace, Ph.D., Associate Professor of Metallurgical Engineering, Purdue University, Lafayette,
Indiana
L4ORROSION
tion of metals
causes destruction or deteriora-
and
alloys because of electrochemical or chemical reaction
with the environment.

reverse.
Corrosion can be considered as metallurgy in example, For iron and steel are made from iron-oxide ores, and
they revert to oxides
when
rusting occurs.
at 6 gases,
The annual
billion.
oils,
cost of corrosion in the
Practically all
United States is estimated environments water, soils, acids, alkalies,
etc.are corrosive to
some
degree.
Corrosion of fuel systems in
automobiles alone costs $100 million per year. One plant spends $2 million annually for painting to prevent external rusting of steel equipment. Some of the results of corrosion are poor appearance, high operation
loss
and maintenance
costs,
plant shutdowns, contamination of products,
of valuable products, and safety hazards.

classified in two general ways, namely (1) wet and combination and electrochemical. Wet corrosion occurs
Corrosion can be
dry or
(2)
direct
when
liquids are present, usually electrolytes.

is
Dry corrosion occurs

is
in.
vapors and gases: a liquid phase
not present. Dry corrosion
usually
associated with high temperatures.
Direct combination usually involves reaction between a metal and nonmetallic elements or compounds such as steam, oxygen, sulfur dioxide, and chlorine at high temperatures similar to dry corrosion. This subject
is
discussed later
under high-temperature oxidation.
22.1. Electrochemical Corrosion
The
electrochemical theory of corrosion

(1)
are two basic requirements:
is the accepted theory. There anodes and cathodes must be present to
452
453
form a
cell,
and
(2)
direct current
must
flow.
may
be very close together
(local cells)
or they
example, two sections of pipe. The current be impressed on the system from an outside source. The anode, or anodic area, is where corrosion occurs and where current leaves the metal. The cathode, or cathodic area, does not corrode; cursingle rent enters the metal here. Anodes or cathodes can form on a environthe metal or in in the local differences piece of metal because of
ment. The metal at the anode becomes an ion. This situation
dissolves, loses electrons,
is is
The anodes and cathodes may be far apart, for may be self-induced or it may
oxidized,
Fig. 22.1.
and
shown schematically in
The
Fie. 22.1.
Formation of Ferrous Ions in the Corrosion of Iron.
through it to the cathode. Current flows in the opposite direction. Immersion or contact with an electrolyte is required to complete the circuit or to carry current from
electrons
(e)
are left
on
the metal
and
travel
the anode to the cathode.
Corrosion in pure water (or acids) occurs as follows:
Fe
2e = Fe++
2e
is:
(Anode
reaction)
2H+ +
The overall
reaction
= H2
(Reduction at cathode)
Fe + 2H+ = Fe+++ H 2 The quantity of current which passes through this cell is directly proportional to the amount of metal that corrodes. For example, one ampere per year is equal to about 20 lbs. of steel. Anything that changes these
.
reactions or the cell circuit could reduce or increase corrosion.
If the
454
hydrogen bubbles
on the cathode and thus form an insulating reduced and corrosion is practically stopped. called polarization and, in this case, cathodic polarization
collect
is
blanket, current flow
This
is
it occurs on the cathode. Most waters contain dissolved oxygen which combines with the hydrogen as shown in Fig. 22.2. This is cathodic depolarization and corrosion proceeds. This is the basis for one of the earliest forms of corrosion con-
because
trol,
namely deaeration of boiler water.

Steel
Wafer
+ 2 -<-2H2
Fig 22.2. Corrosion of Steel by Ordinary Water Containing Oxygen. Depolarization.
In neutral or alkaline waters the anode reaction cathode reaction is:
is
the same, but the
H
The
overall reaction
is
i/ 2
+ 2e = 2 OH-.
.
Fe + 2 + i/ 2 = Fe (OH) 2 ? Fig 22.3 is a basic diagram which summarizes the requirements for corrosion of metals by electrolytes. Differences in the metal surface, or lack of homogeneity, may be due to
impurities, grain boundaries, orientation of grains, differences in composition of the microstructure, differences in stress, scratches, nicks,
and
holes.
It might be said that nature abhors a vacuumcorrosion abhors homo-
geneity.
22.2.
EMF
Series
and Passivity
shown
in
Different metals have different tendencies to corrode or vary in reactivity.
The
familiar Electromotive Force Series,
Table
22.1,

lists
455
elements in order of decreasing corrosion activity. Hydrogen is and shown as zero because a hydrogen electrode is used as the reference electrode or half cell to measure the electrode potentials of the other elements. The more negative the potential of an element is, the
listed
greater the tendency to corrode.
Table
22.1
Electromotive Force Series

Cation
Volts
Galvanic Series
Sea Water
alloys*
Magnesium and magnesium

Zinc 2S Al (Comm. pure)
Na +
Mg+ + A1 + + + Be + + U++++ Mn + + Zn + + Cr + + Cr+ + + Fe + + Cd + + Co + + Ni + + Sn + + Pb+ +
-2.71* -2.40 -1.70 -1.69 -1.40 -1.10 -0.76 -0.56 -0.50 -0.44 -0.40 -0.28 -0.23 -0.14 -0.12
0.00
Cadmium 24 ST Al (4.5%
or iron [Cast iron
( Steel
Cu, 1.5%
Mg, 0.6% Mn)
13% Cr
iron (active) Ni-Resist (High Ni cast iron)
(l8-8 (active)
U8-8-M0
Lead Tin
(active)
Lead-tin solders
[Nickel (active) llnconcl(active)

fHastelloy
Brasses
B (60%
H+
Bi
Ichlorimct 2
13% Cr, 7% Fe) 30% Mo, 6% Fe, 1% Mn) (66% Ni, 32% Mo, 1% Fe)
(80%
Ni,
Ni,
Sb+ + +
Cu + + Cu + Ag +
Pt
+++
Pb+ + + +
Au + + + Au +
++++
+0.10 +0.23 +0.34 +0.47 +0.80 +0.80 +0.86 +1.36
(Cu-Zn)
Copper
Bronzes (Cu-Sn)
Cupro-nickcU (60-90% Cu, 40-10%Ni) Moncl (707c Ni, 30% Cu)

Silver solder (Nickel (passive)
l,Inconel (passive)
+ 1.50t
rChromium
steel (passive) (11 to
30%
Cr)
18-8 (passive) 18-8-Mo (passive)
fHastelloy
Silver
ichlorimct 3
(62% Ni, 17% Cr, 15% Mo) (62% Ni, 18% Cr, 18% Mo)
Titanium
Graphite Gold Platinum t
* t
Anodic end Cathodic end
456
According to the
is
EMF Series,
the addition of
chromium
to iron should
increase corrosion; yet this mixture results in stainless steels.

active hut
it
is
Aluminum
This effective increase in nobility or corrosion resistance is due to passivity, which can be simply defined as "a condition that causes the metal not to corrode when it should." Passivity is generally due to surface films which act as barriers between the metal and its environment. These films could be absorbed gases or adherent corrosion products. A series for commercial metals and alloys in a given environment could show different positions than indicated by the EMF Series. Table 22.1 gives the order for Chromium, aluminum, and silicon the Galvanic Series (sea water) alloy additions to steel are the three most important as elements or as
widely used for corrosion resistance.
.
from the
passivity standpoint.
WET CORROSION
The
Corrosion
itself.
Eight Forms of Corrosion

it
may
be classified into the eight forms in which
manifests
metal.
The basis for this classification is the appearance of the corroded Some of these forms are unique, but all are interrelated. This
is
classification
arbitrary, but
it
covers practically
(1)
all
corrosion failures
(2)
(4)
and
(5) (8)
problems.
The
eight forms are

(3)
uniform corrosion,
cell corrosion,
galvanic or
pitting,
two-metal corrosion,
erosion-corrosion.
concentration
intergranular corrosion, (6) stress corrosion, (7) dezincification,
and
22.3.
Uniform Corrosion Uniform corrosion or overall general attack occurs when anodic and cathodic areas keep shifting, and corrosion takes place more or less uni-
The metal becomes thinner and This form of corrosion accounts for most of the destruction of metals on a tonnage basis. From the technical standpoint, however, uniform attack causes the least concern largely because service life can often be quite accurately estimated on the basis of relatively simple corrosion tests. It is the localized form of corrosion that often results in an unexpected failure.
formly over the entire exposed surface.
eventually
fails.
22.4. Galvanic or Two-Metal Corrosion
two dissimilar metals are in contact, or otherwise connected electrically, and exposed to a corrosive electrolyte, coirosion of the less resistant metal is increased and corrosion of the more corrosion-resistant metal is decreased. All of the former usually becomes the anode, and the latter the cathode. Current flows here similar to the situation shown
When
Corrosion and Oxidatio7i
457
Environment
Current enters
Current leaves ./y
Fie. 22.3. Basic
Diagram Showing Requirements
for
the Corrosion
of Metals by
Electrolytes.
in Fig. 22.3.
The
driving force for the current

is
is
the potential generated
by the electrodes. This, of course,

battery.
the principle of the so-called dry
Table
22.1
shows a practical galvanic
series for
metals and alloys ex-
posed to actual sea water.
series the greater the potential
The when
farther apart two metals are in this
they are coupled.
The
material
higher in the series becomes anodic to one below it. Magnesium and copper would form a bad galvanic couple as far as corrosion is concerned. In many cases, the accelerated attack occurs on the anodic metal near the
junction with the cathode.
as the conductivity of the
The
effect
spreads farther in a linear direction

increases.
environment
An
is
important
effect that is often
overlooked, and rapid failures result,
large the area effect, or the ratio of cathodic area to anodic area. anode. attack on the cathode and small anode accelerate further the
For example, a metal by
itself in a
mils per year; the rate

it
but
may may be 1000X when the

Note that the
corrode at metal; noble be lOx when coupled to a more

area ratio
is
given environment
may
large. Fig. 22.4 illustrates this
effect.
steel rivets
(small anodic area)
are completely
still
corroded; whereas, the other specimen with a large anodic area

represents a strong joint.
An
excellent practical
example
of rapid failure because of an unfavor-
able area ratio concerns large tanks handling a solution mildly corrosive
458
*V
*&*:
'
-&&COPPER RIVETS IN STEEL PLATE LARGE ANODE SMALL CATHODE

Fie. 22.4. Effect of
STEEL RIVETS IN COPPER PLATE LARGE CATHODE
SMALL ANODE
(15
Months). [Courtesy
The
Area Relationship on Corrosion of Rivets in Sea Water International Nickel Co.)
to steel. The bottoms were made of 18-8 stainless steel, and they were welded to ordinary carbon steel sides. The steel was covered with a baked coating. Small defects in the coating exposed tiny anodic areas which were in electrical contact through the welds with the larger bottom area of stainless steel. The steel in the sidewalls near the welds failed by perforation in several weeks.
22.5. Concentration Cell Corrosion
Anodes and cathodes can form because of differences in the environment. For example, a potential difference can be measured between two identical copper electrodes immersed in different concentrations of hydrochloric acid. The cells formed because of differences in the environment are called concentration cells. This form of corrosion is also designated
crevice corrosion, gasket corrosion,
and deposit corrosion, and
is
usually
associated with stagnant conditions.
459
Low Metal
Ion Concentration
High Metal Ion Concentration

Joint Metal Ion Concentration Cell Riveted Lap
High Oxygen Concentration
Low Oxygen Concentration

Oxygen Concentration
Cell
Fig. 22.5.
Typical Examples of Concentration Cell Corrosion.
(Courtesy
The
Inter-
national Nickel Co.)
forms of concentration cells are oxygen cells in Fig. 22.5. Fig. 22.6 shows attack on the face of the flange of a pipe because of concentration cell corrosion. The inside
The most common

cells as
and ion
shown
is
surface of the pipe
in
good condition.
22.6. Pitting
This and one of the hardest to is corrosion progresses instationary and predict. The anodic area remains wardly on one spot. Pitting can be considered as the intermediate situation between no corrosion (complete passivity) and uniform corrosion (entirely active) in that the surface breaks down and corrodes only in
Pitting corrosion
is
readily recognized because of pits or holes.
one of the most vicious forms of corrosion
relatively small areas.
460
Fig. 22.6.
Gasket Corrosion Caused by Concentration
Cells.
a permeable deposit.
Pitting often starts because of concentration cell effects such as under The environment under the deposit becomes ex-
hausted of oxygen, or increases in ion concentration; whereas, the surrounding metal away from the deposit is exposed to essentially a constant
concentration of oxygen or ions.
tion cell effect.
The
rate of penetration often acceler-
ates because the pit acts as a crevice
and thereby
increases the concentraexists.
An
unfavorable ratio of cathode to anode also
This is one reason why the stainless steels often show severe pitting in some environments with most of the surface showing no attack.
22.7. Intergranular Corrosion
Intergranular corrosion consists of selective or localized attack at the
grain boundaries of a metal or alloy. In some cases, complete disintegration of the metal results even though a relatively small portion of the total weight is dissolved. The austenitic stainless steels, such as 18-8, are
they are not properly heat treated. If this steel is heated in the range of about 950 to 1400F. for an appreciable time, it becomes sensitized or susceptible to intergranular attack in
particularly susceptible
when
461
environments where high chromium content is needed for corrosion resistance. The commonly accepted explanation for this phenomenon is that chromium carbides (Cr 23 C) precipitate in grain boundaries. This
mium
removes chromium from solid solution and lowers or depletes the chroin areas adjacent to the grain boundaries. This lowers the corrosion resistance of these areas, and corrosion proceeds aided by galvanic
corrosion
cathodic.
and
a large cathode area represented by the grains,
which are
as
it is
Fig. 22.7
shows intergranular attack, or weld decay
often called.
Fife 22.7. Intergranular
Corrosion of Welded 18-8 Stainless Steel.
The
plate to the left of the weld in Fig. 22.7 contains about
0.60%
titanium.
These
steels
are
stabilized
with
niobium
(columbium),
titanium, and tantalum, which are strong carbide formers and thus preferentially tie up the carbon so that chromium carbides cannot form.
new, very low carbon steels (0.03% max.) can stand much more abuse from this standpoint. Another procedure to minimize intergranular corrosion is to finally heat the part or equipment to about 1950F. at which point the chromium carbides dissolve, and then rapidly cool by quenching through the sensitizing temperature zone. Sometimes the stabilizing element fails to do its duty, as shown by Fig. 22.8. In this case, intergranular corrosion occurs in a narrow zone
The
relatively
in the parent metal immediately adjacent to the
weld or melted metal.
462
I"ic.
22.8.
Knife-Line Attack of Stabilized 18-8 Stainless
Steel.
The
attacked zone
is
usually a few grains wide
and hence has been
christened knife line attack.
The mechanism
is
briefly as follows.
The
heated to a very high temperature, and when rapidly cooled, the niobium stays in solution because niobium carbide does not have time to form. If this material is then heated in the sensitiz-
metal next to the weld
is
ing zone,
present.
chromium carbides form as if no stabilizing element were Experiments have shown the niobium carbides dissolve at
temperatures over 2250F.
One recommended
cure for this situation
is
to
heat the material to around 1950F, where
chromium carbides
dissolve
and niobium carbides form. Other alloys are also sometimes attacked intergranularly, as shown in Figure 22.9, which is typical of attack on nickel and high-nickel alloys
when exposed
to sulfur-bearing
atmospheres
at high temperatures.
22.8. Stress Corrosion

Stress corrosion could
of corrosion by
stress.
be defined in a general way as the acceleration In some cases, more or less over-all corrosion is
increased because of stresses in the metal. Stress corrosion is more generally interpreted as the type of attack that causes cracking, and it is this
form of failure that is under discussion here. In most cases, the magnitude of the stresses required to cause stress corrosion is high. These stresses could be due to applied loads or to residual stresses, although failures because of the former are relatively rare because most structures are over-designed. The most common of the residual stresses that cause stress corrosion are those resulting from cold working or cold forming and also the "locked-in" stresses resulting from
Corrosion and Oxidalion
463
Fig. 22.9.
Intcrgranular
Corrosion
of
Nickel
at
High
Temperatures.
Top
SOX.
Bottom 500X.
In a few cases, plant failures have occurred because of severe thermal gradients in the metal, which cause high stresses. Tensile stresses are required for cracking.
welding.
Stress corrosion usually occurs
when
over-all or
uniform corrosion
is
low and often negligible.

in that
It is
is
somewhat
similar to pitting in this respect
most
of the metal
passive but active sites develop.
The
presence
of stress often accelerates this localized attack.
crack
is
initiated
and
propagates to failure.
Two
of the earliest
and
classic
examples of
stress
corrosion arc the "season cracking" of brass cartridge cases and the
"caustic embrittlement" of riveted steel locomotive steam boilers.
Am-
munition became worthless during the wet seasons. Boilers exploded because of cracks starting near the rivets or stressed areas. Statements have been made to the effect that all metals and alloys could be made to crack under selected conditions of stress and corrosion. Fortunately stress corrosion happens much less frequently than other forms of corrosion but cracking failures are often serious and unexpected. Table 22.2 lists a number of metals and alloys and the environments in which stress corrosion may occur. This does not mean that failure would always develop in these combinations, but one should be aware of the possibilities. For example, nickel is widely used in caustic services, and cracking is difficult to develop unless severely cold-worked metal is used. On the other hand, brass cracks readily in ammonia, and "as welded"
464
2 50
.200
>
g
150
100
10
20
30
40
50
As-Welded
% CONCENTRATION
Fig. 22.10. Effect!
Steel
Equipment
in
of Temperatures and Concentration on Cracking Sodium Hydroxide Based on Service Experience.
of
steel will fail
quite readily in strong sodium hydroxide at elevated tem-
peratures.
Fig. 22.10
shows the relation between temperatures and consteel.
centration of caustic on the cracking of as-welded
These data are
based on actual service performance.*
A number
corrosion.
of theories have been proposed for the mechanisms of stress

calls for susceptibility to selective
The Electrochemical Theory

more or
less
continuous paths and a high stress tending to pull the metal apart along these paths. These continuous paths could be along grain boundaries where a precipitated anodic phase, or an anodic depleted zone resulting from precipitation, may exist. Trenching or
corrosion along
pitting results causing stress raisers or notches where cracks begin
to
form and then propagate because of corrosion and stress at the point of the crack. Differences in potential between the grain boundary area and the grains have been observed. This theory explains the intergranular cracking observed in some systems. The Mechanical Theory states briefly that localized corrosion forms the notch or stress raiser, but the propagation of the crack is then due to mechanical effects, and corrosion docs not play a continuous role. According to the Strain Accelerated Decomposition Theory an anodic phase is formed because of the presence of stress. In other words a site that is not susceptible to attack becomes susceptible because of a phase decomposition or formation caused by stress.
'Corrosion,
7,
295-302 (1951), H.
Vv".
Schmidt,
P. J.
Gegner, G. Heincman.

Tabu: 222. Environments That May Cause
Stress Corrosion of Metals
465
and
Alloy's
Material
Environment
alloys
Aluminum
NaCl-HjOj solutions NaCl solutions

Sea water Air, water vapor
Copper
alloys
Ammonia
Amines
vapors and solutions
Water, water vapor
Cold
alloys
FeCh solutions
Acetic acid salt solutions Caustic soda solutions Lead acetate solutions NaCl-KsCrO-i solutions
Inconel
Lead Magnesium
alloys
Monel
Rural and coastal atmospheres Distilled water Fused caustic soda

Hydrofluoric acid
Hydrofluosilicic acid
Nickel
Fused caustic soda

steels
Ordinary
NaOH solutions
NaOH-NaaSiO* solutions Calcium, ammonium, and sodium Mixed acids (HsSOi-HNOs)
nitrate solutions
HCN solutions
Acidic HiS solutions Sea water Molten Na-PI alloys Acid chloride solutions such as MgClz and NaCl-H202 solutions
Sea water
Stainless steels
BaCh
HjS
Titanium
NaOH-H2S solutions Red fuming nitric acid
The Anodic Shift Theory explains the propagation of the crack by by corstating that when a certain stress concentration is brought about
some plastic deformation takes place metal is shifted in an anodic direction and the electrode potential of the produced by the deformaenergy at the crack base because of the latent
rosive attack (pitting or trenching)
,
anodic area produced in this manner is attacked, and the crack behavior. This again produces stress concentration sufficient for plastic and simulpotential in shifting process can be visualized as a continuous
tion.
The
taneous metal removal.
another form of the electrochemical theory of than composition stress corrosion but suggests a different driving force electrochemical the usual Stress corrosion is started by differences.
The Film Theory
is
466
attack,
and
stress
concentration at the base of the incipient crack
is
sufficient to tear
or break any protective film that
may be
present.
The
is propagated by the simultaneous corrosion of the exposed metal and tearing of any film that may form. The fact that potential differences do exist between filmed and film-free metal surfaces has been confirmed many times. In one case, the potential at the base of notches in alloys subject to tensile stretching was found to be as much as 0.7 volt anodic to the remainder of the specimen. Attack in these bare areas becomes permanently faster than on the filmed surface, and preferential corrosion
crack
occurs.
One of the
in
mysteries of stress corrosion concerns an explanation of why,
some
cases, intergranular
cracking occurs while in others the cracks
are transgranular or across the grains.
The work of Priest, Beck, and Fontana* shows that corrosion and stress must be present simultaneously for cracking to occur. Motion pictures of crack propagation at actual speed show that cracking stops when cathodic protection is applied, and propagation resumes when it is removed. This
indicates that the mechanical theory
is
not correct.
cyclic stresses are involved.
Failure
is
called corrosion fatigue
when
22.9. Dezinci fixation
term implies, the phenomenon of dezincification was first obThe zinc is selectively leached out of the alloy leaving a brittle, weak, porous mass consisting predominantly of copper plus copper oxides. The obvious mechanism is solution or corrosion of the
this
As
served on brasses.
then the zinc stays in solution, and the copper plates back on. Dezincification can be readily observed because the attacked areas show the color of copper as compared to the yellow brass. Brasses with 15 per
brass;
cent or
less
zinc are practically
immune, and additions
of tin, arsenic,
dezincifi-
phosphorous, and antimony increase the resistance of brasses to

cation.
De/incification can occur uniformly, as shown in Fig. 22.11, or as the plug type, or attack in spots. Fig. 22.12 shows a section through a dezincified plug and also the porous nature of a dezincified area.
The selective removal of one of the constituents of any alloy falls into the category described here. The so-called graphitization of cast iron is a misnomer. What actually occurs is the removal or corrosion of iron
alloys,
leaving the graphite network. Selective removal of cobalt in high-cobalt and silicon in copper-silicon alloys have been observed.
Trans.
ASM.
47, 473-492 (1955).
467
:-.'..
..
Fie. 22.12. Section
Through
Dezincified Plug.
Fie. 22.11.
Uniform Dezincification
of Brass.
5000
45
50
55
DEGREES CENTIGRADE
ErosionFie. 22.13. Inhibiting Effect of Copper Ion in a Sulfuric Acid Slurry on Corrosion of I8-8SM0 Stainless Steel.
468
22.10. Erosion-Corrosion
Many
metals
and
alloys
depend upon surface

If these
films
or
corrosion
removed and rapid corrosion occurs. Erosioncorrosion is often encountered under conditions of high velocity, turbulence, impingement, and solids in suspension. Valves, pumps, elbows, centrifugals, agitators, and heat exchange tubes often fail because of
surface
layers are
products for corrosion resistance.

effects, active
by mechanical wear
erosion-corrosion.
shows the effect of high velocity on corrosion of I8-8SM0 by a sulfuric acid slurry. The x on the abscissa shows no attack under static conditions. The curve marked "no copper" shows the rapid increase in corrosion with temperature under high velocity conFig. 22.13
stainless steel
ditions.
The
addition of cupric sulfate
conditions. Fig. 22.14 shows the typical

corrosion.
reduced attack under these wavy appearance due to erosion-
Fig. 22.14.
Erosion-Corrosion of a
Pump
Impeller.
Cavitation may be considered as one form of erosion-corrosion. Roughened surfaces or deep craters are often found on the trailing faces of ship propellers and pump impellers. This is cavitation and is largely due to the mechanical effect or pounding caused by the formation and collapse of air or vapor bubbles in the liquid on the metal surface.
Fretting corrosion is the attack that occurs at contact areas between metals under load and subject to vibration and actual slip at these surfaces.
It is
false Brinelling.
sometimes called chafing corrosion, friction oxidation, and The latter because the attacked areas often look like
mechanical indentations.
The
corrosion product on steel
is
usually a
469
oxide debris. Two proposed mechanisms involve tearing away of metal particles because of seizing or galling and then oxidation of these Fretting particles, or oxidation first and then wearing away of the oxides.
ferric
could be considered as one type of erosion-corrosion.
22.11. Methods for Combating Corrosion

corrosion problems can be solved by more than one method or means. Sometimes a combination is used. In any case, the most economical solution to the problem is usually adopted. Methods for
Many
combating corrosion are
arbitrarily classified into eight general categories
that cover essentially all corrosion problems.
Alloying, or better corrosion resistance, involves using materials with better resistance to corrosion. If steel corrodes, copper, stainless steel,
or high-silicon iron
corrosion resistance
may do
is
the job. Proper heat treatment for
optimum
also in this classification.
Cathodic protection involves making the structure to be protected namely, the cathode of a cell. This can be done by two general methods known widely most currents. The use of sacrificial anodes or impressed is the coating zinc where the sacrificial anode system is galvanized steel and Zinc steel. the anode and corrodes preferentially, thereby protecting have is to point magnesium anodes are also widely used. The important direct current entering the entire surface of the structure to be protected. Impressed currents involve passing a direct current from an external source through an anode, through the corrosive environment, and then
to the structure.
In
this case, a very corrosion-resistant or
"permanent"
needed. Carbon and 14.5% silicon iron (Duriron) are used for impressed current anodes. Underground pipe lines, water tanks, sea-going vessels and piers are examples of structures using cathodic protection.
anode
is
Metallic
tin
and inorganic coatings are typified by nickel, chromium, and electroplates, and glass and enamels. The principle here is to install
a barrier to separate the metal from the environment.
Organic coatings involve paint-type materials, which act as a barrier. Proper metal surface preparation, such as sandblasting, is the most important factor, followed by a proper primer for good adhesion and compatability with over-coats, and then by good top coats themselves. The will use of an expensive paint does not guarantee that good protection
obtain.
Metal purification is not often utilized, but it does solve some problems. High-purity aluminum, which is available at reasonable cost, is a good example. Contamination and catalytic effects are sometimes involved.
470
^.-4.3-rs--?
Fig. 22.15.
Pump
Casing Lined with F.puxy Resin.
(Courtesy,
The Duriron
Co., Inc.)
Alteration of the environment often concerns addition or removal of an ingredient in the environment. Deaeration is an example of the former and inhibitors of the latter. An inhibitor is anything added to an environment to decrease corrosion. In many cases, reduction of temperature or concentration, without substantially affecting the process, solves a corrosion problem or permits the use of less expensive materials such
as steel.
471
Nonmetallic materials involve integral or monolithic construction or thick coverings such as sheet linings. These materials can be classed into stonefive general types: (a) carbon and graphite; (b) ceramics, such as ware, porcelain, fused silica, glass, brick, mortars, and cement; (c) plastics,
such as phenolics, vinyls, polyethylenes, acrylics, epoxies, styrenes, nylon, silicones, and fluorinatcd polymers (d) natural and synthetic rubbers; and (e) wood. Fig. 22.15 shows a cast iron pump casing lined with a
plastic.
Design involves the shape of a structure. Equipment life can be prolonged or corrosion costs reduced through the use of bottom outlets designed to drain completely, readily replaceable or interchangeable parts, standard lengths of tubing, increased thickness in more vulnerable areas, designing to prevent crevices or stagnant areas, and the use of butt-welded
instead of riveted joints.
22.12. Corrosion Testing

Corrosion testing
is
conducted to evaluate or
select
a metal or alloy for
a specific environment or definite application, to evaluate a given material to determine environments where it is suitable or attacked, for controlling corrosion resistance of a material or corrosiveness of an environment, or
for corrosion research purposes.
These
tests
include laboratory, pilot
plant, large scale plant, or field tests.
The most important
point in corrosion testing
is
to duplicate as closely
as possible the actual conditions to be encountered. Factors such as temperature, concentration, velocity, aeration, time, galvanic effects, stress, and intermittent or continuous operation must be considered. Chemical and metallurgical history of the specimens must be known and the
speciments identified.
A clean metal surface
is
preferred.
Most corrosion tests involve determination of loss in weight of the specimen and conversion to a rate of linear penetration for prediction
of
life
expectancy.
is
An
expression for corrosion rates that

its
is
widely used
by engineers
"mils per year," and
formula
is
as follows:
534
mils per year
W
milligrams
DAT
loss in
W = Weight
D = Density in grams per cubic centimeter A = Area in square inches
T = Time in hours.
472
22.13. Liquid-Metal Corrosion*
The
use of atomic energy for commercial power has increased interest
in liquid metals such as sodium, lead,
and lithium, as heat-transfer media. In addition to the usual forms of corrosion, another important factor
is mass transfer or the solution of the equipment and deposition of this metal or alloy in a colder area. This is due to marked change in solubility of one metal in another with change in temperature. In addition, a more careful selection of materials of construction must be made because equipment is not as readily accessible for repair as in more conventional systems.
enters the picture. This

in a hot zone
HIGH-TEMPERATURE OXIDATION
22.14. High-Temperature Oxidation
High-temperature oxidation of metals and alloys, commonly called dry corrosion, can be described as the chemical reaction of a metal or alloy
sulfur, nitrogen or any halogen. Generally, however, the agents involved are solid alloys and oxygen gas. The resulting oxide is generally less dense than the metal from which it was formed, and it has
with oxygen,
poor light reflectivity, electrical conductivity, and mechanical strength. While the term oxidation can apply to many different kinds of reactions, the common chemical change is the valence increase of the metal involved to a higher positive value. In the subsequent paragraphs, the effects of oxygen pressure, temperature, and substrate material are discussed to
point out the salient features of all oxidation processes. Reference to different metals and alloys will be made, but much practical information can be gained from the metallurgical literature.
is known about the nuclcation of oxide phases on metal surfaces. the other hand, the growth of oxides has been studied extensively; various theories and experimental techniques have progressed well enough so that theoretical predictions can often be checked quite accurately.
Little
On
Unlike simple diffusion studies

call for
in solid solutions, oxidation

fulfilled at
measurements
boundary conditions
is
interphase interfaces.
The
gas-
solid oxide interface
metal interface is growth it is usually desirable to know the oxygen pressure in the gas phase and the oxygen solubility in the metal phase. These quantities fix
the concentration gradient of cations and anions in the oxide phase, but
Certain of the material presented in Sections 21.1 to 21.13 of this chapter appeared monthly column on Corrosion by M. G. Fontana for Industrial and Engineering
the external boundary while the solid-oxide, solidthe usual internal boundary. In rate studies of oxide
in a
Chemistry,
who gave
permission to reproduce
it
in this textbook.

they
473
Oxygen presdo not give information about the growth mechanism. but the effect is sure is known to influence the rate of oxide growth,
rather small. Increased temperature generally increases
the oxidation
yield ambiguous rerate; however, the criterion of oxidation rate may simply grams of oxidation were for sults. For example, if the criterion
and the oxide gained per unit area and unit time on a metal substrate result could increases temperature oxide had a very high vapor pressure, rapidly. proceed vaporization or loss of oxide, yet oxidation would
in
An example
alloys
of this behavior
above 600C. Internal
Mo, Mo() 3 O, system at temperatures oxidation occurs in many copper and silver-base
is
the
and
in certain steels.
This kind of oxidation
is
characterized by the
the formation of small particles of oxides of the alloying elements below

external scale.
primarily a deleterious effect, engineers used may be are concerned with design problems in which the part to be design important may be retention subject to hot gases. Size and shape of the properties optical and requirements, but frequently the electrical relays, in example for contacts, oxide phase are considered. In electrical because the the choice of an oxidation-resistant alloy is imperative, conelectrical prevent can formation of a poorly conducting oxide scale
Since scaling or oxidation
is
alloys from being made. The choice of stainless steels and aluminum when it is evident for kitchen utensils which should have eye appeal is and do known that the oxides of these alloys are nearly transparent
tact
temperatures. not materially affect the light reflectivity of surfaces at low area of any Lastly, it is obvious that through oxidation the reduction in part unfit structural member designed to carry a given load may make the magnified when parts are used for service. This effect on strength can be cracked off and in fatigue-loaded operations where the oxide is continually
fresh oxide forms at the expense of base metal.
22.15. Formation of Oxides
The most common method

on metals and
at the cool
alloys
is
for obtaining quantitative oxidation data
by measuring the weight gain per unit time and
condensation reaction unit area. In vapor-deposition processes such as the in the gas phase is which exists species retort, the a zinc end of
reaction frequently the same species that exists on the substrate and the in metal Similarly, is cold. material substrate the progresses because atomic: different vapor may be a deposition, the vapor-phase cladding by
species than the substrate,
but intermetallic compound formation is not the rate of the condensation reaction. The determining important in is a supersaturation brought about by a reactions driving force for these
474
temperature distribution. Furthermore, the nucleation of new grains in these deposition processes occurs in the same way that nucleus formation proceeds in the water-to-ice transformation, the growth of rock candy,
the freezing of metals, and the electrodeposition of metals.
The problem
strate
of nucleation of an oxide
on
metal substrate
is
com-
plicated by the fact that the gas species chemically reacts with the sub-
form a structure of the type The following single steps may xOv occur to a greater or lesser extent in the formation of any oxide. As is evident from the listing, most of the steps are likely to affect the nucleation
.
rate
and the growth

is
reaction
1.
rate of an oxide grain. The rate of any oxidation governed by the single slowest step of the type listed below:
Surface adsorption of an
Dissociation of
2
Ot
molecule on metal.
2.
3.
to
atoms.
x
Ionization of
to
0=.
4.
5.
Ionization of
M to M+
Surface migration of O,
Diffusion of
and 0,
electrons.
M or M+
6.
7.
in the metal phase until the solubility limit
is
reached.
Nucleation of the oxide phase. Once an initial oxide layer has been formed, several other possible
steps
1.
may occur. There are:

Diffusion of
2
gas within cracks in oxide film.

2
2. 3.
Surface adsorption of an
Dissociation of Diffusion of
2
molecule on metal oxide.

layer.
to
atoms.
x
4.
5.
0=
through oxide
to
Ionization of
Diffusion of
M+
and
electrons at the metal-metal oxide
surface.
6.
M+ x
through oxide
layer.
shows a sequence of microscopic steps that may be operative when a bare metal surface is oxidized. Since the view has been taken
Fig. 22.16
that the rate of oxidation is governed by the single slowest step, any experimental work necessitates the reduction of a system of many factors to a system in which a single variable can be studied to yield meaningful
results.
22.16. Dependence of Oxide Growth on Gas Pressure
The
effect of pressure
on oxidation rate has been successfully
investi-
gated for very few metals. Among these are iron, copper, zinc, zirconium, titanium, vanadium, and cobalt, reacting with oxygen. At various pressures the dependence of a reaction rate of a solid with
oxygen
is
intimately
related to the
mechanism of the
reaction.
The
conditions for growth are
related to the nonstoichiometry of the oxide phases developed,
and the
475
J~ LINES Of
postulation of oxidation mechanism, a-adsorbed oxygen crystals, d-uniform b-fine mosaic structure of crystals, c-nucleation of large and K. F. Andrew, oxide layer appears. Taken from E. Gulbransen, W. R. McMillian
Fic. 22.16. Gulbransen's
film,
Trans. A.
I.
M.
E. 200, 1027 (1954).
mechanism
for
growth
is
assumed to be diffusion controlled within the
copper oxide phase. Two metals which have been studied extensively are which information present the paragraphs and zinc. The following oxidation observed of the dependence pressure supports the
predicts
rate.
1.
and
The
electrical conductivity of
Cm 2
was observed to increase with
oxygen pressure according to the relation.^

a
J.
Vs = constant PQ
Gunderman, K. Hauffe. and
C.
Wagner,
Zeit. phys.
Chem., B37
(1937). 148.
conductivity are Since the three variables that make up electrical species, varying conducting of the mobility concentration, valence, and to account for variables of the more one or oxygen pressure must change as cation viewed oxide is of the structure the the pressure dependence. If of Cu 2 0. structure represent the could deficient, the following model
Cu"
Cu->
Cu*
O
Cu*
oCu^ Cu<
0=
o-
Of
of
Then, one oxygen molecule may form two molecules

following relationship.
Cu t O by
the
Ot
4-
-*
4Cu +
D+
4*"D
c"*
476
Applying the law of mass action and realizing that the concentrations of Cu+ vacancies and Cu++ions are identical, one finds
C8
defects
is
constant
If the
oxidation rate of copper
determined by the concentration of
defects operative in the oxide phase near the gas-oxide interface, then
oxidation rate
a C defects
cc
PjJ
Oj
report that the oxidation rate of copper at a linear function of the seventh root of the oxygen pressure. This agreement supports the theory reasonably well because such measure-
Wagner and Grunewald*

1000C.
is
ments are difficult to make when the pressure dependence is so small. Oxides which behave similarly are FeO, NiO, CoO, and AgÔ. 2. On the other hand, a class of oxides exists in which the electrical conductivity decreases with increasing oxygen pressure. A typical example of this type of oxide is ZnO. The following structure shows a
typical cation excess oxide.
Zn* +
0Z" ++
&++
o-
0-
Z"*+
0fir*
0-
Zn * +
o-
Zn + *
0Zn ++
Zn **
0-
dB>0Z"
Zn+ *
*
0Z"* +
0If
CD +
0-
the
number
of interstitial ion
and electron defects were decreased by

to the reaction,
an increased oxygen pressure according
i/aO,
+
or
<^f)
(P) -> ZnO
Electrical conductivity
Oxidation rate
a C defects a ô
B40
Vt
C. Wagner, and K. Grunewald, Zeit. phys. Chem.,
(1938), 455.
477
from O. Kubachewski and B. FIG. 22.17. The oxidation-time relationships. Taken Publications, London Hopkins. Oxidation of Metals and Alloys. Butterworth's Scientific
(1953).
Various measurements have shown that electrical conductivity varies with the negative fifth root of the oxygen pressure, and the agreement with theory is relatively good. Other oxides which possess cation excess
structures are
BeO, Fe t O s
MoO
and SnO t
22.17. Dependence of Oxide Growth
Upon Time
Various weight change versus time relationships exist for oxidation oxidation-time relationrates. Fig. 22.17 shows a composite graph of the relations are the linear empirical these important of most ships. The two
and parabolic equations.
The
linear relationship
is
to express experimental data.
the simplest equation that has been found kt The equation
Am =
linear relates the change in mass per unit area with time; k, is called the equation linear this necessary in constant is rate constant. No other because at t= o, [\m = o. Another form of this relationship is
Ax
k,*
where Ax is the change in thickness of the oxide layer. These relations have been found to apply when the molar volume of the oxide phase is less than the molar volume of the parent metal which reacted. Physically,
these oxides cannot cover the entire metal surface; fresh metal surface
is
478
continually exposed and the oxidation rate is quite constant. Common metals which conform to this type of oxidation are lithium, sodium
and magnesium. Pilling and Bedworth expressed their oxidation rate by the following relation:
criterion of linear vs parabolic
Mi
where
Dm <h
>.
M = molecular weight of oxide phase,

D = density of oxide phase, m = atomic weight of metal d = density of metal phase.
phase,
When
but
for.
the above ratio the ratio

is
is
less
than unity, the linear rate law
is
obeyed;
is
when
greater than unity, the parabolic rate law
called
That is to say, if the molar volume of the oxide is greater than the metal which reacted (but not too great to crack off under stress during growth), a protective film would be expected. simple statement of this
situation
would be inversely proportional to the actual film thickness at any time. For example, if the following equation were integrated
that the increase in film thickness
would be
d(Ax)
dt
k p 1_
Ax
to
Ax*
2k p t
we have
a statement of the parabolic expression for rate of oxidation.
This "law" was enuciated by Pilling and Bedworth and frequently bears their name. A similar expression for the change of mass of an oxide film can be written by substituting for Ax and changing the units k p accordingly. Fig. 22.18 shows typical oxidation data which follows the parabolic equations. Protective films are found on many metals and alloys and are highly desirable. Examples of these are aluminum, chromium, copper, beryllium, titanium, and iron. Lastly, some oxidation rates have been observed that are faster than the parabolic rate at first but tend to protect the parent metal very well. Examples of these rates are the cubic and logarithmic expressions which
Am
follow:
(Ax) 3
kc t
t -+-
(cubic)
and
Ax
A'log
(logarithmic)
479
16-
* 6
00'
10
12
Fig. 22.18.
Spilners
and 0.
Oxidation of oxygen-saturated titanium. Katz, Trans. A. I. M. E. 203, 645 (1955).
Taken from M. Simnad, Aija
These expressions are commonly used to represent data on very thin oxide film formation at relatively low temperatures. At intermediate temperatures most metals tend to behave parabolically, and at high
temperatures the linear rate is often observed. Engineering choices of metals for a particular operation often necessitate the gathering of data on oxidation resistance in the temperature interval desired and under
the exact service conditions of gas composition, moisture, pressure, and
surface preparation.
22.18. Dependence of Oxide Growth
Upon Temperature
is
The temperature dependence

form
as that for diffusion
of oxidation rate
generally the same
and
ionic conductivity.
The
following ex-
ponential relation applies for a single oxide in a given temperature interval.
k
In this expression, k
cubic, etc.)
is
l-^r'l
k.
the experimental rate constant (linear, parabolic,
and C
is
a constant having the same units as
term called
480
is
the experimental activation energy
given by
A,
while
is
the gas
constant
(1.986
calories/mole
.
absolute units (Kelvin)
and T is the temperature in Information about the mechanism of oxidation

degree)
and
can often be gained by comparing the experimental activation energy for diffusion of a known species with the activa-
electrical conductivity
tion energies for oxidation or electrical conduction. If the values for A are identical, one may generally assume that a diffusing species accounts for a given oxidation rate or an experimental specific conductivity. Many accurate data are needed in this particular method of deducing the mechanism of metallurgical reactions.
On
the other hand,
some metals and

temperatures.
alloys tend to oxidize very rapidly
It has been observed that the temperature at which "catastrophic" oxidation occurs frequently coincides with the formation of liquid oxide phase, generally a binary or
upon reaching
certain
ternary eutectic.
weight
loss
Severe attack of this type may actually result in a of the oxidized specimen, because the oxide may volatilize
appreciably.
22.19. Oxidation Prevention
Gold and platinum are the only metals which will not form oxides in room temperature. Silver, palladium and rhodium oxides thermally decompose to the metals and oxygen gas at 190, 800 and" 100C, respectively. In some instances it is possible to use one of the noble metals at a temperature where its oxide simply cannot form. However, high costs
air at
1
prohibit such applications. Cladding base metals with precious metals has been attempted, but oxygen diffusion through the precious metal coating is fast enough at elevated temperatures to oxidize the base metal internally. This kind of oxidation results in an oxide layer formed between the base and the precious metal.
One way
low-alloy steels
to retard elevated-temperature oxidation of carbon steels and is to heat them in a neutral or reducing gas. Such pre-
cautions, although expensive, are used in annealing low-carbon sheet and wire to prevent discoloration or the formation of an oxide coating of
it is necessary to prevent oxidation of mediumby heating in a neutral or reducing atmosphere as is sometimes the case in heating treating tools precautions must be taken to prevent decarburization of the surface layers. Removal of carbon from the surface with the production of a soft outer layer is sometimes
appreciable thickness. If
steels
and high-carbon
more of an
evil
than scale formation.

of protection of a metal or alloy
film
is
The common method
by the
for-
mation of a protective oxide
which inhibits further oxidation. In

designing a part for a particular operation
a particular material that will protect formed. The classic example of this
is
481
possible to select
it
may be
itself after
a thin film of oxide has

6.5 tons,
the Delhi pillar of India.
mass of wrought iron, some 24 ft. A.D. 300. made by hand welding small blooms. It was erected about it had atmosphere, pure, dry a Owing to a "tight" oxide coating and Hadbut when years, 1600 about resisted corrosion remarkably well for surface, the moistened England and field brought a piece of the pillar to
it
high and weighing about
This was
rusted badly overnight.
structure and Oxides formed on pure metals are relatively simple in have composition when compared with the oxides formed on alloys which many elements in solid solution or have several phases in their microstructure.
When
several oxide phases form, as
on
iron, the oxide closest
while the oxide to the metal, has the highest per cent of the metal per cent of metal. lowest the surface has external at the
forms
when
layer iron oxidizes at elevated temperatures, an innermost of Fe layer outermost an 2 3 appear. and and intermediate layer of Fe 3 4 , separately appear their oxides may present, When alloying elements are
which Thus, of FeO,
denote metals and or as special oxides of the type AB,0, where A and B of a pure metal resistance Oxidation numbers. x, y and z are small whole elements. alloying addition of the can be increased or decreased by
Additions of chromium, nickel, aluminum, and silicon to iron and steel protect the serve to increase the oxidation resistance, because the oxides parabolic. be to rate tends base metal. In these cases the oxidation resistance oxidation decrease Boron, molybdenum, and vanadium markely copper In dilute nonprotective. because the resulting oxides are
of steels
aluminum, magnesium, and silicon increase resistance to have oxidation while titanium, cobalt, nickel, and manganese seem to
alloys beryllium,
little effect.
High chromium, usually together with high
nickel or high cobalt,
is
Typical necessary for resistance to oxidation at elevated temperatures. nickel per cent chromium, cent 8 per low-carbon 18 include costly alloys
steel;
chromium steel; 35 per cent nickel, 15 per cent cent nickel, 20 per cent chromium alloy; a 62 per chromium steel; an 80 chromium, 23 per cent iron alloy; the cent per per cent nickel, 15 Hastelloy type; the cobalt-chromium the alloys of nickel-molybdenum number of others. All have long life at a type, and alloys of the Stellite
10 to 35 per cent
or even higher and chemical plants. and are used 22.19. Type shown in Fig. results the study yielded oxidation A typical Cr, were cent 16 per cent and 11 per having steels, 410and 430 stainless
temperatures of 1300 to 1800F.

in oil refineries,
(700 to 980C.)
power
plants, furnaces,
482
too TME M HOURS

Fig. 22.19.
moist and dry

(1952).
Oxidation of types 410 and 430 stainless (electropolishcd) at 1600"F in air. Taken from D. Caplan and M. Cohen, Trans. A. I. M. E. 194 1057
oxidized at 1600F. in wet and dry
air.
The wet
air caused rapid attack
on both steels in comparison with the dry air, and in both cases the oxide formed on the 16 per cent Cr steel was more protective than that on the per cent Cr steel.
1 1
One general feature in tailor-making an oxidation-resistant alloy is to add an alloying element which has a very high affinity for oxygen and whose oxide has very low electrical conductivity. Such oxides either have
few ions free or able to migrate or have structures which hinder diffusion. In either case, the oxides formed tend to be protective. Another way of protecting a base metal is by cladding it with another metal which oxidizes very slowly. Cladding techniques include:
1.
Metal spraying.
2. 3.
Hot
dipping.
Roll cladding.
Casting.
Electroplating.
4.
5. 6.
Cementation.
483
of these methods are not generally suitable for the application are of a single metal on a base metal substrate, frequently two or more mirrorin almost used with success. The use of nickel clad steel results
While
all
like surface finishes after a year or
longer of operation near
room
tem-
Studies on the oxidation of nickel-clad steel showed oxide formed was invisible to the naked eye. Chromium plating is as chromium effective as nickel, which is generally used as an undercoat for plated objects. Aluminum-coated irons have been shown to be 30
perature.
that the
is times more resistant to oxidation than noncoated irons, and aluminum one of the most versatile metals to clad with. Every clading technique is used to a greater or lesser extent with aluminum-clad products. Copper,
zinc, lead, brass, bronze,
palladium, and rhodium are
all
used extensively
for cladding to hinder surface reactions.
QUESTIONS
1.
Why do
What
is
metals corrode in electrolytes?

of combating corrosion
2. 3.
meant by anodic polarization? Describe an example where two of the eight methods
arc used simultaneously.
4.
A common
shell.
piece of equipment used for heating water in a plant consists the of a shell-and-tube exchanger with water inside the tubes and steam in In many cases copper tubes with thick cast iron tube sheets are used.
Why?
5.
Describe in detail procedures and equipment needed to prevent intergranular corrosion of a large tank (for a railroad tank car) fabricated by
welding 18%
6.
Cr-8%
Describe a
test
Ni stainless steel (not stabilized). you would devise to determine whether or not a given
(cracking) in a given en-
material would be susceptible to stress-corrosion vironment.

7.
Sketch a heat exchange system using liquid sodium indicating a that may arise because of "mass transfer."
difficulty
8.
Why
are the stainless steels often used for applications involving heat
and
oxidation resistance?
9.
Based on the electrochemical theory of corrosion, why docs "graphitiation"

of grey cast iron occur?
10.
Describe the mechanism of knife-line" attack of the stabilized stainless

steels.
11.
Describe a defect lattice which

excess structure.
is
a (a) cation deficient structure, (b) cation
12.
following data arc given for several metals and their oxides. metals oxidize linearly or parabolically?
The
Do
these
484
(A)
Metal Al
Atomic Weight
26.97 9.02
Density,
g/rm 3 25C
,
2.70
4. SO
Be
Cu
Pl>
63.57
207.21 24.32 22.99 65.38
8.92
11.34
1.75
Mg
Na
Zn
(B) Metal
0.97
7.H
Density, g/cmS,
3.7
Oxide A1 L ,0 3
Molecular Weight
101.94
25C
BeO
CiigO
25.02
143.14 79.57
223.21
3.0
6.0
6.4 9.5 3.7 2.3
CuO
PbO
MgO
Na,0 ZnO
13.
40.32
61.99 81.38
5.5
Calculate the mobility of electrons in a mole of pure solid copper at 25C, if the specific conductivity cze^, where a 10 ohm-' cm-*, c a concentration of carriers, z valence of carriers, e electronic charge and
/i
electron mobility.
14.
Test the following data for "fit" to the parabolic, linear, or cubic rate laws for the oxidation of metal A.
Oxide Thickness,
500 1000
time, minutes
10
40
160
2000
15. If the
experimental activation energy for oxidation of Zn to ZnO is 28.5 Kcal/mole and the frequency factor, C, is 2.8 x 10- cmVsec, what is the value of the oxidation rate constant at 400C?
16. 17.
own words the Pilling and Bedworth rule of oxidation. Are metal oxides better or poorer electrical conductors than metals? Explain your reasoning.
Describe in your
18. 19.
What
If
is
catastrophic oxidation?
tool
order interference color of yellow is seen on a slightly oxidized estimate the oxide thickness. Assume a representative blue radiation of 4700 A, and that first order extinction of blue occurs when
first
steel,
A" =
-.
when A
is
the
wave length being destroyed and v

(^
is
the index
of refraction of the oxide film
3).
Effect of Temperature on MechanicalProperties of Metals

CHAPTER
23
James R. Macdonai.d, Ph.D., Chairman, Department of Mechanical Engineering, School of Engineering, The
University of Mississippi, University, Mississippi George V. Smith, Ph.D., Assistant Director for Metallurgical Engineering, School of Chemical and Metallurgical Engineering, College of Engineering, Cornell
University, Ithaca,
New
York
only interest in the reactions of metals to stresses at elevated temperatures was related to the reactions of the metals to stresses used to form them into usable shapes. He learned that at elevated temperatures metals could be subjected to repeated instantaneous stresses of forging, rolling, or drawing without
fracturing easily.
its Interest in metals for extended service at elevated temperatures had shortto confined were most studies that time Prior to in 1924. beginning
FOR centuries man's
time high-temperature tests, for at that time there was no need to study increased the effects of long-time stress at high temperatures. But with the generating steam-power in the employed pressures being and temperatures industry, problems that were not understood began to develop. Equipment operating at high temperatures and presumably designed conserva-
with an ample factor of safety warped and even failed; the carbon and low-alloy steels being used, instead of exhibiting only elastic deformation as well-behaved steels should, deformed plastically under surprisingly
tively
low loads. At normal temperatures, most high-melting point metals and alloys deform elastically under working loads. There is no appreciable plastic deformation (permanent set) so long as the applied load does not exceed at the elastic limit. Furthermore, most metals and alloys when subjected working cold limit as in elastic above the stresses to normal temperature distorts the strain harden; in other words, permanent deformation
at elegrains and increases strength and hardness. This also holds true at which below that is temperature the long as temperatures so vated
rapid recrystallization takes place.
485
486
As is evident from this introduction, the problem facing the metallurgist and engineer was a phenomenon involving small amounts of plastic deformation over long periods of time at elevated temperatures. This is called creep. Entering importantly into the problem of creep is strain hardening, which is opposed to the softening that occurs during recovery and recrystallization. Recovery and recrystallization de-
phenomenon
pend upon
ture ranges
time, temperature, prior plastic strain
and
the previous struc-
tural condition of the material.
For
steel,
the recrystallization temperacritical
from about 700F.
to the
lower
temperature.
23.1,
The Importance of Creep
Dickinson demonstrated in 1922 that steel deformed slowly at a red heat under stresses which were much lower than the values used in what
was then considered good design. The connection between this slow deformation at high temperature and the failure of certain powergenerating equipment was established, and the importance of creep was recognized. As a result, the American Society of Mechanical Engineers and the American Society for Testing Materials set up a joint committee
in 1924 to study the phenomenon, to devise a method for determining slow deformation, and to accumulate useful data on slow deformation of
industrially important metallic materials. This work has spread from metals to ceramics and has develoj>ed considerable interest in a new series of materials which are produced from mixtures of metals and
ceramics
known
as cermets.
Laboratories are continuing to study creep, and although many data have been accumulated, much more needs to be done.
23.2.
The Engineering
Significance of Creep
In the selection of a steel or other alloy for high-temperature use the mechanical properties of the material as determined at room temperature are of little importance. The requirements for metallic material which is to be used in various kinds of equipment operating at high tem[>eratures vary widely, but in general the following are important: (1) The metal should be resistant to oxidation or other attack by the hot gases (including air) which are present; (2) it should have a stable structure which will remain relatively unchanged under the stress and temperature conditions
imposed; (3) it should withstand the stress imposed with a negligible or at least with a harmless amount of distortion for the useful life of the equipment; and (4) it should withstand momentary overloads at the usual
operating temperature, or short periods of fluctuating temperature at
Effect of
Temperature
all
487
these
normal
loads.
There are few metallic materials which meet

It
is,
requirements.
therefore, not easy for the metallurgist to supply
the engineer with materials suitable for equipment operating at high
temperatures and fairly high loads.

the exact temperatures in the
This
difficulty
is
not lessened by
use.
the fact that engineers are usually uncertain about the exact loads and
equipment they design and

is
The steam-power
generating industry
an excellent example of the

In 1905, the initial
trend to higher temperatures during the past years.
temperature of commercially used steam turbines was only 500F. In a two-year period from 1906 to 1908 it was raised 100F. and it remained at 600F. for nine years. In the next three years (1917 to 1920) it was
raised another 100F., but
it
was not until 1926 that the temperature
attained 750F.
Making
use of the accumulated high-temperature data
manufacturers increased the steam temperature to 950 by 1938. During World War II there was no change because of the scarcity of critical materials, but shortly thereafter the temperature was increased to 100F.
1
Certain units in the petroleum industry have always been operated

at metal temperatures in excess of those
industry.
The
ability to
shorter operating cycles,
employed by the steampower do this is based on shorter expected metal life, and more frequent inspection, with opportunities
of replacement prior to fracture of the parts operating at the higher
temperatures.
In
fact,
prior to 1930, operation of the thermal cracking
units was generally of the intermittent-coking type, so that the cycles were very short, often only 40 to 50 hours. Today the length of the operating
cycle is often measured in months, or years, rather than in hours. Developments in high-temperature alloys have contributed to this ability to use longer operating-time periods, which in turn have greatly increased production because of less down-time of the units.
General conclusions with respect to temperature trends within the chemical industry cannot be drawn because of the wide variety of products manufactured by the different companies, and often within
the same organization. The requirements of this industry do extend from moderate temperatures and extremely high pressures to very high metal temperatures (1800 to 2000F. (980 to 1095C.)) with low pressures.
During World War II there was an ever-increasing demand for stronger and stronger alloys that could be used at higher and higher temperatures.
The
pertures
exhaust turbosupercharger for aircraft engines involved rotor temup to 1350F. (730C.) and blade temperatures to 1500F.
(815C.) or even higher.
planes are somewhat lower.
The requirements for engines in The expected life in these
present-day jet
applications
is
488
which helps
to simplify the metallurgical
currently relatively short, a fact

asjjects of
temperatures in gas turbines for central station power generation are somewhat lower and the expected life very
longer.
the problem.
The
much
may
Another application,
just beginning to acquire importance, that require alloys that can be employed at very high temperatures is the
commercial use of nuclear energy for generating power.
,s
z
D <
r
/\
ELEVAT ED EMPERJ TURE
Uip
/
/ ^Xi
/
TE
1
J_
ROOM
F
1 1
(
A
0-B ELASTIC DEFORMATION AT A-C PLASTIC DEFORMATION. A-0+ CREEP CURVE A-D FIRST-STAGE CREEP
-
EM 'ERATURE
'
OR CREEP
FRACTURE
1 1
1
D-E
E-F
i
SECOND-STAG-E CREEP THIRD-STAGE CREEP

i
i
TIME OF STRESS APPLICATION
Fic. 23.1.
Diagrammatic sketch of
elastic versus plastic properties.
23.3.
The Creep
to
Rupture Curve
complete creep curve under constant temperature
seen to consist of three stages.
first
From
curve
Fig. 23.1 the

is
and constant load
The
portion of the
AD, known
as the
stage, represents a condition of continually
decreasing creep rate; section

increasing creep rate
DE,
the second stage,
is
constant creep rate; and EF, called the third stage,

tion to fracture in this case
is
.
one of substantially one of continually
and ends in fracture (rupture) The total deformawould be represented by OA, the elastic deconstant)
formation, plus
When
tests
are
AC, the plastic deformation. made at other loads (holding temperature

,
or at other temperatures (holding load constant) picted schematically in Fig. 23.2, is obtained.
a family of curves, de-
At relatively high temperature and load, the period of first-stage primary creep may be virtually absent; whereas, at relatively low temperature and load, creep
may
cease, for practical purposes. (Fig. 23.1)
The
characteristic
tigators to
form of the creep curve suggest an interplay between the
led early inves-
forces of strain
hardening
Effect of
Temperature
489
Increasing temperature (constant load) Increasing load (constant temperature)
Time
Fic.
235. Schematic illustration of creep
at
low and high temperatures and loads.
strain softening, the latter arising from crystal recovery or in occasional instances from recrystallization. According to this view, hardening predominates during first stage or primary creep, and the creep rate
and
diminishes with time; whereas, during second stage creep, the forces of hardening and softening balance one another, and the rate of creep is
essentially constant.
This conception of the creep curve

flow processes
is,
in principle, still currently ac-
cepted, with refinements, however, as regards the nature of the plastic
and
crystal recovery.
The
tertiary period of accelerating creep
(third stage)
is
clearly as-
sociated with
impending
fracture.
The mode
of fracture at elevated teminteris is
peratures granular,
may
i.e.,
be either transgranular, i.e., through the grains, or between the grains. Transgranular fracture, which
of fracture of metals at ordinary temperatures,
the
less
predominant mode
likely to occur, the higher the test
temperature and the slower the rate

.
of deformation (or the longer the time for rupture)
The
intergranular
mode
of fracture
is
characterized by equiaxed rather than elongated

fracis
grains, by intensive intergranular voiding, by a minimization of local
"necking" deformation, and often by relatively low over-all strain at

ture.
Hence,
little
or no advance warning of impending fracture
afforded.
23.4. Determination of Creep
The knowledge
of what a metal might do over a short period of time
cannot be projected to cover a long period of time. Much effort was wasted in the early work on determining the reactions of alloys to stresses at elevated temperatures for longer periods by attempts to find a rapid method. It took considerable time and effort to discover there was no easy short cut. However, determination of short-time, high-tempcrature
490
Kir.. 23.3. Modern creep-testing equipment. The electric furnaces for heating the specimens arc shown at the left (white): the lever system for loading the specimens is above the furnaces. (Batlelle Memorial Institute)
which is a simpler test than the creep test, and of the time to rupture in relatively short times, as determined in creep to ruptensile strength,
ture tests at high stresses are usually undertaken, for the data are useful
in deciding whether an alloy
is
suitable for parts, as in rockets,
that
would that would be under maximum
be subjected to high temperatures for short periods, or for parts

stress or
temperature only during the event of failure of other parts. Such data also point out which alloys justify further investigation where the maintaining of stresses for
longer periods at elevated temperatures
is
maximum
required.
The
American Society for Testing Materials has adopted
recommended
practices for conducting creep tests, E22-41, and time for rupture tests, E85-50T. These standards place restrictions on temperature distribution and variation, on the sensitivity of the extensometer system, and on the accuracy of the loading mechanism. Specimens are usually maintained un-
der constant load for at least 1000 hours, and the amount of creep is determined periodically during the test. The difference in deformation between any two points divided by the difference in time of the two points represents the creep rate at the
Effect of
Temperature
stress that will result
is
491
in an average
average of the periods of time.
The
creep rate equal to an assigned creep rate
known as the creep strength for the alloy at the specified temperature. The stress causing rupture at a given temperature in a specific time is known as the rupture strength.
necessary consists of an electric furnace capable of temperature control and a suitable device for holding the specimen close in exact alignment in the furnace. The load is applied by dead weights
The equipment
through a system of
levers.
battery of
is
modern
in Fig.
creep-testing furnaces
23.3.
and
their auxiliary
in.
equipment
shown
are usually 0.505
in diameter
(cross section 0.2 sq. in.)
Test specimens and have a
gage length of
at least 2 in.
From
tion of
different stresses
the data accumlated in a series of creep and rupture tests at and temperatures, the information necessary for selecstresses
is
working
obtained. Fig. 23.4 shows the temperature
variation of the stresses necessary for

vals in
1 per cent creep at several time intercomparison with the temperature variation of the yield and tensile strengths determined in short-time tensile tests.
23.5. Effect of Variables
on Creep
is,
one of the most structure-sensitive properties of metals and many factors that have little or no influence on the other characteristics. For example, a series of steels having
Creep
is
therefore, greatly influenced by
practically the
same
tensile properties
and hardness
their creep
at
room temperaat
ture
may
shoiv wide
differences
in
resistance
higher
temperatures.
Owing
yet,
to
the complexity of the subject, information

all
is
not avail-
able concerning
the possible variables and
it
is is
not
all
of these are
known. Certain information
probable that, as available regarding
many of them and among

heat treatment, grain
size,
those to be considered are chemical composition,
method
of manufacture, previous deformation,
and
structural instability.
Chemical composition. In general, creep and rupture strengths of metals increase with increase of the melting point. Thus, lead creeps significantly at room temperature, iron at perhaps 800F., and molyb-
denum
at perhaps 1500F. In
further strengthening a metal.
any base, alloying additions are effective in The specific effect of an alloying addition
depends on whether it enters into solid solution or results in the appearance of an additional phase. In general, greater strengthening can be effected by dispersed secondary phases than by formation of a solid
solution.
492
Temperature, deg. C.
POO
800
1000 1100 900 Temperature, deg. F.
isoo
Fig. 23.1. Effect

stress of cast
of
temperature
(Kanter)
on
short-time
tensile
properties
and on
creep
carbon
steel.
Low
alloy steels,
when
appropriately heat treated, are in general most
effectively strengthened
forming elements, like two of which are extensively used for this purpose. Chromium is widely employed to improve scaling resistance, but it is deleterious to creep strength beyond about 1.5 per cent. Molybdenum is also an effective strengthener of the austenitic chromium-nickel stainless steels. The ultrahigh strength alloys currently in use for high-temperature applications often comprise a solid-solution base composition, containing, for example, cobalt, nickel, chromium, and perhaps iron, with a dispersal phase or phases resulting from alloying additions of such elements as columbium,
by alloying additions of so-called strong carbidemolybdenum, vanadium, and tungsten, the first
vanadium, molybdenum, and tungsten. Heat Treatment and Microstructure. The effects of alloying additions cannot be considered without reference to heat treatment, whereby control is exercised over the grain size and the nature and dispersion of the precipitate phases. At the more elevated temperatures, creep and rupture strengths are greater, the coarser the structural grain size. However, there
some evidence that an optimum grain size exists for each temperature and strain rate or rupture time, and it seems unwise to generalize too
is
broadly. Similarly, fine dispersions generally appear stronger at relatively low temperature, and coarser dispersions stronger at higher teni]>eratures,
but exceptions
exist.
Effect of
Temperature
493
70
000
60 000
10'
10"
-
Stress Cycles
Fig. 23.5. Effect of
temperature on fatigue of 12 Cr
steel.
(Welch and Wilson)
Other Variables.
The methods employed
in manufacturing a metal
exercise indirect but important effects. Included in this category are melting process, deoxidation practice, casting temperatures, etc., varia-
may
which result in variations of chemical composition and microstructure. For example, a higher casting temperature is conducive to
tions of
coarser grain
size.
Strain hardening by prior cold useful for increasing creep
working or by warm working may be

for service temperatures
and rupture strengths

recrystalli/ation.
below the temperature range of
microstructure of metals and alloys used at elevated temperatures often changes during service with consequent effect on properties and be-
The
havior (see Section 23.7)
23.6. Fatigue
and Combined Fatigue and Creep
In general, as temperature increases, fatigue strength progressively decreases. At the same time, the slope of the curve of stress vs. number of cycles becomes steeper, and, even for metals like steel, the curve does not
exhibit a horizontal portion corresponding to the "endurance limit," Fig. 23.5. Moreover, all environments, including air, become corrosive for the usual structural metals and lower the fatigue strength accordingly.
occur to the general rule of decrease in fatigue strength with increasing temperature when the temperature range is one in which metallurgical changes occur that strengthen the metal. Such may be the case for certain steels which undergo strain-aging at tempera-
An
exception
may
494
Sites* to
Mean
Stress
5
Mean
Fie. 23.6. Stress
10
Stress.
15
20
25
1000 psi 24S-T4
aluminum
combinations Tor 0.2% and .5% creep and for rupture of at 500F.; cycle stress applied at 3600 times per minute. (ASM Metals
Hand-
bonk, 1955 Supplement, p. 184.)
tures
up
to 600-700F., so that the fatigue strength of such steels in this

is
temperature range
not
much
different than at
room temperature.
At temperatures sufficiently high that creep occurs under static loads, superimposed cyclic stressing results in complex behavior involving
both creep and fatigue phenomena. Whereas there is an apparent absence of plastic deformation in fatigue fractures at ordinary temperatures, fracture at elevated temperatures under cyclic stress may show both creep deformation and the conchoidal markings that characterize
fatigue.
Behavior under combined fatigue and creep conditions cannot be predicted other than approximately from separately obtained creep and
and fatigue properties vary differently under combined conditions cannot be predicted for other temperatures from data obtained at one temperature. Hence, it is necessary to conduct tests involving combined fatigue and
fatigue data. Moreover, since creep
with
temperature,
behavior
creep).
Owing
to the elevated temperatures of testing, certain variables

in fatigue at
become more important than

clude the
effect of corrosive
low temperatures. These

,
in-
agents in the environment, the changes in

{see Sect. 23.8)
microstructure that
may occur
and since creep
is
time-
dependent, the frequency of cycling. Typical results of combined fatigue-creep

23.6 for the
tests,
are illustrated in Fig.
aluminum
alloy
24S-T4 tested
at
500F.
The
ordinate scale
Effect of
Temperature
495
charts the alternating stress in completely reversed loading, that is for zero mean stress, whereas the abscissae axis corresponds to static loading,
Within the quadrant, there are both a steady stress and a superimposed cycling or fatigue stress. At relatively low mean stress, fatigue conditions predominate and fatigue failure will
that
is,
for zero alternating stress.
tend to determine working
stress,
whereas
at
low alternating
stress, be-
havior corresponds more to creep conditions, and working stress will be prescribed by excessive creep or creep-rupture. Fig. 28.6 indicates by the
perpendicular approach of the data curves to the axes that the superimposition of a small alternating stress on a given mean stress or of a small steady stress on an alternating stress does not appreciably lower
the stress that can be supported.
23.7. Structural Changes During
Creep
changes cause changes in properties,
Most metals and
alloys
undergo changes in microstructure during heat-
ing at elevated temperatures.
The
'
"
'
v v
AS POLLED
AFTER JQOOOHR. SERVICE

C-A40 STEEL IOOOX
Fig. 23.7. Carbide spheroidizalion Corp. Research Laboratory.)
in steel
containing
05%
molybdenum,
(U.S. Steel
496
ORIGINAL
'
m?m m
HOOF
jgOOF
I500F
'
i
XIOOO
'
i:
ORIGINAL
Fig. 23.8. Microstrucniral
HOOF
I300F
I500F
ty\
changes in Cr-Ni-Mo austenitic siainless
steel
during 3000
hours creep
tcsi.
(U.
S.
Steel Corp.)
and hence, the material has

being put in
service.
different properties at different times after
which the changes develop is principally dependent upon the temperature and the time, but may also be influenced by the imposed stress and the resulting strain. Large stresses and plastic strains may greatly accelerate microstructural changes, whereas small stresses and strains may not cause detectable differences from unstressed
rate at
The
material.
The
kinds of readily observable changes in microstructurc which

grain
may
occur are varied, and include carbide spheroidization or graphiti/ation in

steels, recrystallization,
processes of various kinds.
embrittlement of steels, steels are not readily, if

In ferritic
steels,
growth and transformation or precipitation Other changes such as strain-aging, temper 885F. embrittlement of high-chromium ferritic
at all, detectable in the microstructure.
carbide spherodization during service is widespread as the temperature exceeds perhaps 900 F. A well-advanced example is
shown
in
Fig.
23.7
representing the microstructures of
i/
per cent
molybdenum 0.15 per

of service at
cent carbon steel before and after 30,000 hours
about
of the steel before the carbide phase

iron.
and
100F. in a petroleum refinery. Clearly the properties after service would be different. In some steels
to elemental carbon
(graphite)
may break down
and
Microstructural changes during creep

stainless steel are
test
of an austenitic Cr-Ni-Mo
shown
in Fig. 23.8.
In this material carbide and chi

precipitate.
phases,
not
differentiated
in
the
illustration,
In
other
Effect of
Temperature
497
Fie. 23.9.
Thermal
conductivity of various metals temperature dependence.
(Hay-
thorne)
COEFFICIENTS OF THERMAL EXPANSION
COEFFICIENTS ARE
.
MEAN
.000012
VALUES FROM 70T TO INOICATEO TEMPERATURE
.00000;
0O0OOT
.000004
.000005
JOO
400
800
MO O0
-
BOO
1400
TEwpepaTum -f
Fie. 23.10. Coefficients of
thermal expansion-temperature dependence. (Michel)
austenitic stainless steels, or in high
chromium
ferritic steels,
sigma phase
may precipitate. The microstructural
changes that occur during exposure at elevated temperatures generally, but not necessarily, cause a deterioration in strength as measured at elevated temperatures. Often the most profound
498
effects are
observed in
loss of
and
as a result the material
may
toughness at room or lower temperature, fail during shut-down periods rather
than at elevated temperatures. In a particularly severe instance the notched-bar impact energy absorption of austenitic stainless steel exposed at 1500F. (Fig. 23.8) , was lowered to 10-15 foot lbs.
23.8. Variation of Other Properties with
Temperature
A number of properties of metals other

in the design
tures.
than strength
may
be of interest
and operation
of
equipment
for service at elevated tempera-
Among
pansivity, clastic
such properties are thermal conductivity, thermal exmodulus and thermal shock or thermal fatigue.
AUSTENITIC STEELS leCi-BNI 13041 l8Cr-8Ni-Mo<3l6> iec-aNi.Ti (321)
0.10
1,
CARBON
00 CARBON 0.SM0
0.8C'-0.3MO ICr-0.5Me 2Cr-0.M0 2 25Cr-IMo
FERRITIC STEELS 3CY-0.5Mo-l.5S 3Cf-0.5Mp-l.5Si
I8C'-8N1-CM347]
25Cr-l2NI 13091
25O-20NU3I0)
5Cr-0.5Mo-Cb 5C'-0.SMO-TI 9Cr -IMo

l2Cf (410) ITCr (430)
AOSTEMTiC STEELS"
600 800 1000 TEMPERATURE - F
1200
Fig. 23.11.
Young's
modulus
of
various
materials temperature
dependence.
(Michel)
Although thermal conductivity and expansivity vary with variation in chemical composition, they are relatively unaffected by other metallurgical variables such as heat treatment and microstructure. The variation with temperature of thermal conductivity of a representative group of metals
alloys is shown in Fig. 23.9. Fig. 23.10 shows a corresponding chart thermal expansivity. Of particular interest from the practical point of view is the disparity between the expansion coefficients of carbon steel and austenitic stainless steel, which leads to "thermal" stresses when the materials are joined and heated, as they sometimes are. The austenitic
and
for
steels also
have significantly poorer thermal conductivity
at relatively
low
Effect of
Temperature
499
steels possess ap-
temperature; at relatively high temperatures different
proximately the same conductivity. The elastic moduli at elevated temperatures are sometimes needed for computing elastic strains. These constants may change gradually with
composition, but are relatively insensitive to metallurgical structure. With increasing temperature, both the tensile modulus (Young's) and shear modulus decrease. The temperature variation of Young's modulus
for a representative
group of metals
is
shown
in Fig. 23.11.
The
rate of
decrease
is
approximately linear up to
a certain
temperature level which
depends upon the material, beyond which a more rapid decrease occurs. Poisson's ratio does not change significantly with temperature. Thermal shock and thermal fatigue represent a common mode of failure in applications involving relatively rapid changes in temperature. Thermal shock and thermal fatigue may be differentiated depending
on whether
of heating
failure occurs after relatively few or
many
cycles, respectively,
tests
and
cooling.
There are no standardized

is
measure these properties, and resort
had
to special tests
stresses
by which to which attempt

thermal
to simulate actual service conditions.
The
giving
rise to
shock or fatigue are influenced by such properties as thermal expansivity, thermal conductivity, strength and toughness and by the rate of change
of temperature
and the geometrical shape of
the part.
23.9. Design for Elevated
Temperature Service
Although a number of properties will be of interest in the design of equipment for successful operation at elevated temperatures, the governing criteria, at least where corrosive conditions are not severe, will generally be the strength. Owing to creep phenomena, however, strength
From the very fact is not a simple property. occurring, the design engineer recognizes that in time, equipment will either distort beyond a tolerable limit or will fracture or both. It is necessary therefore to choose working stresses such that neither of
at elevated
temperatures
that creep
is
The amount of deformation that may be tolerated depends on the specific application; in a steam turbine it may be only a fraction of one per cent in 100,000 hours, whereas in steam piping, several per cent deformation in the same interval may be tolerated. In all applications, of course, the working stress must not be large enough to cause
these events occurs.
fracture.
necessary to design for a specific
operate under creep conditions it is not for unlimited life. The basic information relating to the amount of deformation as a function of lime comes from creep tests, which must be made under dynamic conditions if
In
all
equipment designed
to
life,
500
l*S
K>
00
2*6
* 6
iooo
oooo
Tim9.hr
Fic. 23.12.
1200F.
(ASM Handbook,
Design data for alloy containing 20 Cr-20 Ni-20 Co-3 Mo-2W-l Cb-Bal. 1955 Supplement)
le,
service involves
superimposed cyclic
stresses.
The
tests,
basic data for design
against fracture comes from creep to rupture

sible to chart time for
rupture as a function of
stress.
a general relation between the

certain time
stress for a specific
from which it is posAlthough there is amount of creep in a

always
and the
stress for
rupture
in a specific time, it is not
possible to insure against fracture by insuring against excessive deformation,
tures
because the amount of deformation at fracture at elevated temperamay be less than that which the designer may be willing to accept in
a specific application.
Moreover, design of equipment for long-life service

or accelerating-rate
state.
necessarily involves extrapolations, with attendant uncertainties as to
when creep
will enter the third
which to summarize creep and rupture data for the A design engineer is in the form of "design charts," an example of which is given in Fig. 23.12. Such charts show the variation with stress of the time for several specific amounts of creep, the time for transition to accelerating-rate creep and the time for fracture, and from them it should be possible to select the working stress for specific applications. For certain general classes of construction, permissable working stresses may be set by Code bodies, an important one of which is the Boiler and Pressure Vessel Code Committee of the American Society for Mechanical
useful form in
Engineers.
23.10. Variation in Mechanical Properties at Reduced Temperatures

In addition to
knowing
the properties of metallic materials at elevated
temperatures, the metallurgist
and engineer should know something of
the
Effect of
Temperature
501
northern behavior o metals and alloys at reduced temperatures. In automobiles equipment, latitudes, the metals used for rails and railroad to and other machines are subject at times to temperatures as low as 50 ships merchant 60F below zero. During World War II a number of
split into
temperatures. two sections while subject to low sea or air low encounter also Aircraft or guided missies operating at high altitudes also importance temperatures, and low temperatures are of increasing
in the chemical process industry.
In a number of fields, therefore, it is necessary to know the metals at these temperaof metals at reduced temperatures. The testing of and techniques equipment tures involves experimental difficulties, but refrigerants using data, have been developed for obtaining reliable test
properties
such as ice, dry liquid helium.

Tensile
erature and at
ice
(solid
carbon dioxide)
liquid nitrogen, liquid air or
test properties of a
number of metals and

504.
alloys at
room tempthat
-300F are given on page
These data show
temperature decreases. The tensile and yield strengths increase as the depends upon the nature however, effect of temperature on ductility, others it increases. The decreases, for of the metal. For some, ductility and the 16% Cr iron steels nickel decrease in ductility of the carbon and of ferritic characteristic general are noteworthy and a manifestation of a in the transition a decreasing temperature,
steels
to
undergo, with
character of the fracture from one that

relatively brittle.
is
relatively ductile to
one that
is
The
occurs
temperature range over which the ductile to

for a specific ferritic steel
brittle
transition
the speed of testing. reference plane) the ence plane) relative to the shear stress (acting in the Consequently, in occurs. transition higher the temperature at which the test, have a high tension the to notched bar specimens which, compared of the notch, sharpness the with increasing ratio of normal to shear stress, than temperature higher appreciably low ductility will be experienced at brittle behavior ductile to from transition in the tension test and, in fact, speed of testmay occur at room or higher temperature. With increased higher temat occurs behavior brittle ductile to
,
depends upon the state of stress and normal stress (acting across a refergreater the The
ing, the transition
from
perature.
speed of testing, "impactIn line with the effects of stress state and notches has come into testing of specimens having "keyhole" or "vee"
metals. Fig. 23.13 widespread use for evaluating the "toughness" of notched-bar impact energy to shows the variation with temperature of for an austenitic chromiumfracture for a number of ferritic steels and
502
nickel steel
fracture.
which does not exhibit
a transition
from ductile
to brittle
23.11. Effects of Metallurgical Variables
The
transition
from ductile
to brittle fracture
of metallurgical variables.
The
effects of these variables
depends upon a number moreover may
not be revealed by the simple tension test unless made at extremely low temperatures. It is possible therefore to have two heats of steel which are nominally identical as judged by chemical analysis or by tensile properties, in tests at room temperature, but one of which is tough in notch-bar impact test at room temperature, the other brittle. It is also
possible to have two heats
which exhibit similar notched-bar toughness

It
at
room temperature, one of which undergoes

at 50F, the
transition to brittle behavior

this charac-
other at
50F.
-125
should be clear therefore that
I7S
50
70
ii
Temperature, deg.C.
-100
-75
i
-50
i
-25
i
+25
jA__
f>0
By
.
50
"/
c/j f
"6
40 o HU
J
30
a
5
20
1/
10
A
-250
.D.
E/
// //
^F
-300
-200
-ISO
-100 -50 Temperature, deg.F.
+50
+100
Fir. 23.13. Effect of low temperatures on the impact resistance of (A) water-quenched low-carbon 8 per cent chromium, 8 per cent nickel steel; (B) annealed low-carbon 3.5 per cent nickel; (C) annealed low-carbon 13 per cent chromium steel; (D) normalized 0.35 per cent carbon, 1.5 per cent nickel, 0.0 per cent chromium steel; (K) annealed 0.35 per cent carbon steel; and (!') normalized 0.35 per cent carbon steel. Specimens for steels B and E had keyhole notch; others had V notch. (The International Nickel
Company)
Effect of
teristic
Temperature
503
can be of metals and the effects of metallurgical variables thereon temperatures. range of over a properly studied only if tests are made
The
specific metallurgical variables
that affect the ductile to brittle
transition in ferritic steels include chemical composition, deoxidation and the practice, finishing temperature of hot working, heat treatment strainand work, degree of cold resulting grain size and microstructurc, same, being the Other factors aging or teni|>er embrittlement, if any.
detransition temperature of steels increases with carbon content and generally Nickel is more. creases with manganese up to one per cent or
low-carbon credited with being beneficial to low-temperature toughness of (Fig. 23.13), steel; commercial steels are available containing 3.5%
5%
and
9%
lower the of nickel with transition temperatures progressively

("killed")
steels
is is
greater the nickel.
The
transition temperature of deoxidized
lower
effective of the
than for undeoxidized (rimmed or capped). elements usually used for deoxidation, but silicon is hot working, the lower beneficial. The lower the finishing temperature of working is benethe transition temperature, and normalizing after hot grain size. Cold in Transition temperature decreases with decrease
ficial.
Aluminum
the most
which may detrimental in itself and may also induce strain-aging microvarious Of the raise the transition temperature substantially. tempered of that structures which may be imparted to ferritic steel, tempering treatmartensite exhibits optimum toughness, provided the has a deleterious such as to avoid temper embrittlement, which
work
is
ment
is
prominent role in on toughness. Since alloying elements play a be obdetermining to what extent the fully martensitic structure can on toughness. 'tained, they thus may exercise an indirect effect
effect
by no means a nealed, wrought austenitic
temperature is Transition from ductile to brittle fracture with lowered the anAlthough characteristic solely of ferritic steels.
steels
toughness at -300F subdo a number of other stantially equivalent to that at room temperature, as
exhibit
structure, metals having the face-centered-cubic crystal
it
is
now
recog-
having nized that most and perhaps all metals not tungsten do exhibit transition and molybdenum, titanium, zinc, including
behavior.
this crystal structure,
23.12. Design for Low-Temperature Service for The problem of design for service at reduced temperatures, except
essentially one applications in which corrosive conditions are severe, is other propthat not to say of insuring against brittle fracture. This is in some cases and interest, not of erties, such as thermal expansivity, are
controlling factors.
504
S I
COlftCOOtOOOJNt^t-'^C^fto in in -i
oi t- oq to
p-iiM
ay
13 CC
coi^tocosot^co-t~t-tf>cip (DrtlftHOqiONlfl HOICI
=
60
Jri.
1
o
03
ml*
ff>M
Pppppoo opooooooopooo W CO HCOMNCO<HOMCON

lO
"*t
X iH of Q CC of O CO of HCOr-c0^03Tt-"^-*MOo]
i-*
in"
Jfr*
1 si
iccooicqcoimocom
ira-*c3-fl"cocct-co-H-*
00 999SS22 ooooooooo o p
t-_
cc in
-<r
cB t-_ oi_
t-lCOJC001t-t-0>t~ fl-coaSoicocDoicD'rinr-0,
J%1
2-fl 8
lncocOrtcorj'c-i-'j'raeoco-Tin
pi.
E
i c
PS
SaLa
t-^
Mcot-^H gb in ^ v> t-*of cc"r~ -<f-ciooicooico'<r--m'}'Tj<m
822222220COOO ppOOOOOOOOOC 3
i-_
cB in
fh cc
cc_
co
| ac
co in * o oi-4ioco^ t"-~-03 of in" in co-*coinci-t~t-o

) I
iOoooo CO
) >
ooo
<
in
t*-"
Effect of
Temperature
505
at Since metals are stronger at reduced temperatures than
room
tem-
perature, working stresses based
on room temperature
if
test
data are
readily supported at low temperatures,
the material possesses adequate
concentoughness to preclude brittle behavior in the presence of stress

trations
and
fast
speeds of loading.
tensile stresses, Bi iuie behavior in metals depends on the presence of with the concerned not be designer need the negligible, and if these are
problem of toughness. If, however, the tensile stresses are significant, from and the material of construction is one that undergoes transition its that designed so should be equipment the ductile to brittle behavior, service lowest below the is loads service transition temperature under
since the transitemperature. This is more easily specified than effected and the range of metal, of a property tion behavior is not a simple geometry and size of upon the depends temperature over which it occurs on obtained data Consequently, the test specimen and speed of loading. engiapplication to questionable small, laboratory test specimens are of fracture has neering structures and the problem of design against brittle economical most choosing the not been satisfactorily resolved insofar as consideraimportant an material for a specific application. If cost is not
can be easily guarded against by selecting high-nickel, ferrous group, or ferritic steel or chromium-nickel austenitic steel in the assuming adequate one of the face-centered cubic non-ferrous metals,
tion, brittle fracture
strength.
QUESTIONS
1.
What
2.
to engineers? What are the principal is creep, and why is it important equipment requirements for a metallic material to be used satisfactorily in temperatures? to high exposed How is creep determined? What are the most important variables in creep testing? How much time is necessary for a creep test?
3.
than the maximum allowis the creep stress, which produces no more determined? How able distortion of the material over the expected life, to other mechanirelation of creep accurate is such a procedure? What is the
How
cal properties?
4.
Describe what happens during the three stages of creep. What creep? of strain hardening and recrystallization on second-stage
-
is
the effect
5.
What
deoxidation? is the effect on creep of (a) grain size? (b) tion hardening? (d) condition of the iron carbide?
is
(c)
precipita-
6.
What
plain
the relative creep strength
(at
constant temperature) of carbon,

aus-
molybdenum, chromium-molybdenum, plain high-chromium, and
7.
chromium-nickel steels? How does the creep strength of these steels compare with the creep strength of the supcrstainless steeb? Compare the suitability of carbon steel, brass, admiralty metal, bronze, Monel at temperatures o metal, duralumin, and the magnesium-base alloys for use
tenitic
506
500 to 800F. (260 to 425C), Compare the creep strength of nickel and Monel with Inconel and with the Hastclloy- and Stellite-type alloys.
8.
What
is
the general effect of elevated temperature on the tensile strength,
yield strength, elongation, reduction of area,
and endurance
lb.
limit of metallic
sq. in. at
materials? If a steel has a tensile strength of 120,000
per
room
temperature, what will be the approximate strength at I200F. at I100F. (760C.)?

9.
(G50C.)?
are stress-rupture tests? What is the significance of these tests? How does the rupture strength at I200F. (fi50C.) of austenitic chromium-nickel steel compare with that of superstainless steel and of the cobalt-rich non-
What
ferrous alloys?
10.
Why
is it
important
to
of metallic materials?
know the What is
effect of
the usual effect of these
low temperatures on the properties temperatures on
tensile and impact properties? What is primarily responsible for low-temperature brittleness in carbon steels, and what alloys reduce this brittleness?
Index
Acid
process,
216,
217,
225
Activation energy for oxidation, 480, 484 Afterblow, 219 Ag-Cu system, 106
and hot working, 147 cold working vs. heat treatment, 147 composition, 138, 142 corrosion resistance, 150
cold
Age hardening,
51,
52,
111
free-machining,
Aging, 107 Air cooling, 254 Air furnace, 424 Allotropic transformation, Alloy
steels,
29,
51-52
classification,
241
function of alloy, joining, 152 number code, 136, precipitation heat protection against riveting, 155
136 143-147
137 treatment,
149
corrosion, 155
composition, 242 high-quality production of, 226-227 low-alloy composition, 319-326 low-alloy production, 319 low-alloy S. A. E., 328-332 low-alloy similarity of properties, 332-339
326-328 precipitation hardening, 126-127 Alloys, controlled expansion, 385-386 Alloys, for high temperatures, 198-202
low-alloy structural,
sand, mold and die castings, solution heat treatment, 149 tensile properties, 138
141
welding,
wrought,
153 136
Steel
American Iron and

specifications,
Institute steel
329-331
Amslcr test, 445 Annealing of cast Anodes and anodic
iron,
areas,
431 453
Alloying effects, 47-51 Alloying elements, effect on carbon 320-322

Alnico, 201
Anode
steel.
reactions, 453-454
151
Anodization,
Area
effect.
457
Annealing, alter cold work, 42-44 Alpha Stabilizers, 256
Aluminum.
chemical properties. 134 deoxidation agent, 135 economics. 130
history,
A.S.M.E. boiler and pressure vessel code committee, 500 A.S.T.M. standards, 299, 300, carbon steel castings, 299, 300
Atomic imperfections, Atomic structure, 5

Aiistempering,
14,
15
129
commercial limitations, 289

critical
manufacture, 132
nitriding
ores,
cooling rate curve. 286
agent,
135
defined. 285
131
outstanding properties, 131

physical properties, purification, 133
vs.
133
thermite welding, 135

steel,
130,
alloys,
132
1
Aluminum
17-123,
hardness and strength of austempercd steel, 285 process. 285 to obtain greater ductility, 285 Austenite, defined, 246 Austenitic manganese steel, 385 Austcnilic stainless steel. 256
Austenitic steel, 374,
alloying elements,
135
annealing, 1-18 brazing, 152 casting, 140
expansion mechanical
of,
377
377
properties.
sensitization, 376
507
508
Babbit. 192
Bainitc, 253. 289,
Index
Carlion
in
(Cont.)
cast iron, 408.
109
in steel, 237-238
hardcnability, 257
Bars, carbon steel cold worked, 306
solubility in
iron, 216
Basic process, 216, 219
Carbon monoxide, Carbon steel,

castings, 298, 302
Bayer process, 131 Bearing metals, 191

composition, 193 mechanical properties, 192, 194 Beginning of transformation, 252
composition, 233-242 effect of alloying elements, clfect of carbon, 247-250

elFect
318-326
of
chromium and
copper, 325
nickel, 323
Bend
tests,
low alloy
117,
124,
steels,
77
elfect of effect of
Beryllium,
copper,
physical
toxicity,
125,
127
effect
elfect
of
molybdenum. 325 manganese and

phosphorous,
silicon,
322
manufacture. 157
properties,
158
159
use,
159
Bessemer process, 217 Binary equilibrium diagrams, 102 Binary system, 101
Blast
322 effect of section si/c on, 315 effect of tempering, 338 cutectoid, 247 heat treated, 312 hypercutectoid, 247 hypocutcctoid, 247
of
silicon in,
furnace,
239
chemistry, 214 description, 212

efficiency,
tensile properties, 322, 324
214
of,
products
213
steel,
tonnage production, 297, 306 Carbontriding, 292 Carburizing, defined, 289

237-238
Cast iron,
definition. -108
effect
Blow
holes, in
effect
Boron,
on hardenabilily, 361
to.
Brasses, 160, 168, 178, 179,
of
section
size,
415-417
additions
cartridge,
178-180
178
170,
high, 168, 178 leaded, 178-179
machinabiliiy, 409, 412, 418, 420 relation of properties to cooling rate, 416-417
low, 170
Muni/, metal,
naval,
180
169, 178
red. 170, special
phase diagram. 178

180-181
169,
165
yellow,
178
Brinel] hardness, 70, conversion tables 75,

Brittle fracture, 32, 82
76
Cast tool alloy, 404, 405 Casting process, 25-28 Catastrophic oxidation, 480 Cathodes and cathodic areas, 453 Calhodic protection, 409 Cathode reactions, 453, 454 Cavitation, 468 Cemented carbide tools, 405, 406 Ccmentitc, defined, 245 Ccmcntitc. stability in cast iron, 408 Cermets. 198
Building-up principle, 9
Chapmani/ing, 292
Charging. 222
Charpy
Calculated hardenabilily, 356, accuracy, 360
table,
test,
83
Chemical interaction
in metal solutions, 18 Chilled iron, 408, 410, 420
S59
process,
Campbell
230 Carbide formers, 257 Carbide, precipitation, Carbide stabilizing, 257 Carbide tools, 405, 406
Chromium, elfccl on
ferritcs,
37(5,
tensile properties, 371
369
461
in
stainless steels, 364
in tool steels, 395, 398, 403
Chromium
in steel, 210-211
steel,
Carbon,
low-chromium,
323,
effect
of
chromium,
amount and importance
325
Index
Chromium
steel
509
(Cont.)
(Cont.)
Corrosion
326-329
testing,
engineering
importance,
471
tensile properties, 371
heat treatment, 367
mechanical properties, 369 resistance to oxidation and corrosion, 370-372 Cladding techniques, 482
Cobalt.
190-191,
alloys of. 201
uses', 201, 201 Coefficient of mass diffnsivity, 99 Coherent precipitate, 21
wet, 452, 456 Covalent Bond, 10 Creep, curve, 488-490 definition, 486 determination of, 489 effect of chemical composition, 491 effect of Cr, Mo, 492 effect of micro-structure, 492
effect
of variables,
of,
491
Cold treatment, 274 Cold-worked carbon steel, 306 Cold- worked wire, 311 Cold-worked bars, sheet. 306 Cold working. 28, 40-42, 259, 306, effects on strength and ductility, 308
effect
486 intergranular, 489 rale, 490 significance of, 486 stages, 488
importance
strength,
491-493
transgranular, 489
Critical cooling rate, 255 Crucible process, 230
on dynamic
232
properties,
312
purpose,
Columnar grains, 27 Combating corrosion, 469

Completion of transformation, 252
Composition, effect of, 303-305 Compression tests, 77 Concentration cell corrosion, 458 Continuous cooling, 254 Cooling curve, 98 Cooling rate, 344. 350 Cupola- furnace, 422 Copper, 162-164, 178-9,
arsenical, lake,
Crystal systems, 11 Crystallographic fibering, 38, 39
Cubic system, 12 Cu-Al system, 108
Cu-Mo,
'379-380
102
Cu-N'i system,
Cupola, use, 215 Cupping test, 447 Curie temperature, 59 Cutlery steel. 365, 368 Cyaniding, 292
Cvclic stresses, at elevated
178
temperatures,
163
494
leaded,
178
163
OFHC,
phosphorized, 178 production, 162 properties and uses, silver-bearing, 178 tellurium, 178
Damping
164
capacity, 94, of cast iron, 420. 122 DeBtoglie'a equation, 6 Decarburi/ation, 91
Deep drawing.
to
Copper
alloys.
165-189,
constitution,
165-178
181
117,
nomenclature,
precipitation
127
167 hardening,
124-125
evaluation of steel for, 446 properties of nonferrous alloys, 449 Defect lattice, 475 Defects in crystals, 14, atomic imperfections, 14, 15
constitution. 165, 178-182 phase diagram, 165
importance of defects,
line
15
Corrosion,
cost,
imperfections, 14 surface imperfections, 14
452
definition.
452
452
Deformation, 32 elastic, 488

of
dry, 452 electrochemical, fatigue, 92

rate, 471
polycrystallinc metal, 37-42
488 Degrees of freedom. 100, Dendrites, 26

plastic,
510
Design. 471
Index
Fatigue, 493,
chan, 500
for
combined with
temperatures
service,
failure, Eerrite,
creep,
493-495
elevated 499-500
86
for
low temperature
406
397
396,
service, 504-505
Dczincification,
defined, 246 strengthen, 256

Kick's
Die
steels,
law, 99
293,
Differential
hardening, 294
Flame hardening,
Diffusion. 99
of cast iron, 434
Dislocations 14, 15, 23
Fleming, Sir Ambrose, 3 Free-machining steels, 440

Fretting, 91
Dispersion hardening. 111
Domain, 58 Double yield point, 448

Ductile cast iron, 409, 420, 421
Fretting corrosion, 468

Ftigacity,
Duplex process, 229 Duplex Talbot process, 230 Dynamic Properties, 81
98 annealing of steels. 280 Furnace cooling, 254

Full
Effect,
carbon
in cast iron,
434
Chromium
in
cast iron, 435
composition, 302, 303 copper in cast iron, 436

gTain
nickel
size,
301
in
cast
molybdenum
iron, 435
in cast iron,
430
phosphorus in
cast iron, 435
silicon in cast iron, 434
sulphur in cast iron, 435 vanadium in cast iron, 436 Elastic limit 63, 64, 485 Elastic Modulus, 498, 499
Electrical conductivity of oxides, 475 Electrical resistivity, 58
Galvanic corrosion, 456 Galvanic series, 455 Gamma loop, 256, 366 Gamma rays, source materials, 204 Gamma stabilizers, 256 Gas carburizing, 289 Gibbs, J. Willard, 100 Gold, 190-191, 202 Grain boundaries, 17 Grain growth. 44, and hot working, 267 control of, 265 in steel, above critical temperature, 264 soaking time and grain growth, 264 tendency for, 265 Grain refining, 257 Grain size, 15,
and
In
properties, 29-31
relation relation
to hardenability, 270 to toughness and macliin-
control, 24-29
Electromotive force series, 454, 455 Electric furnace, 226-227 Electron cloud diagrams, 6 Electron compounds, 21 Elongation 67, 68,
in
ability,
266
of,
size,
measurement
process
266 annealing and grain
264
method
of
measuring, 67
elongation,
yield-point
63
Energy level diagrams, 7
End-quench test, 349, 350, 352 Endurance limit, 87 Endurance strength, 88

Engineering, relation to metallurgy, Epoxy resin, 470 Equi-axed grains, 27 Equilibrium, 97 Erichscn test, 446 Erosion-corrosion, 468 Eutetic, 105 Eutcctoid, iron-carbon, defined, 247
3,
Grains in metals, 15 Graphite, comparison of forms 408-409
in
cast
irons,
control in gray cast iron, 418

in malleable cast iron, 410
in in
gray cast iron, 412, 417
ductile or nodular cast iron, 420 Graphite flake size, 429 Graphite precipitation, 257 Graphitizing agents in cast iron, 408
Gray
cast iron, 409, 412-420, properties, 412-415, 417-421
structure, 409, 414, 415. 418
Index
Grossman, 356
256 Hall process, 132 Hansgirg process, 156 Hardenabilily, and alloying elements, 269 and cooling rate, 344
Hadfielcl
steel,
511
Inconel, 199-200 Indices of direction,
13
and engineering properties, 354 and tempering, 356 and time delay, 346
bands, 353
calculated, 356
Induction hardening, 293 of cast iron, 434 Ingot iron, definition, 211 Inhibitors, 470 Inoculants in cast iron, 429 Inoculation agents, 28
Insulators,
II
Interference colors, 484 Intergranular corrosion, 151, 376, 460 Intermediate phases in alloy systems, 20,
electron compounds, 21 intermediate solid solutions, 20
interstitial
determining, 348
effect
of boron on, 361 factors affecting, 346 in carbon steels, 343 in low-alloy steels, 320. 344 in relation to grain size, 269 in relation to
compounds, 21
phase, 21 normal intermetallic

laves
compounds,
21
quenching medium, 270
sigma phases, 21 Intermediate solid solution, 20

Intermetallic
Interstitial
Hardness, conversion scales, 75, 76 conversion to tensile strength, 75 definition, 69 determination, 69-77
compound,
107
Internal stresses, 283
compound, 21
solid
Interstitial
solution, 20,
101
Interstitial solutes,
20
nonferrous alloys, 76 numbers. 75 tests compared, 72 tool steels, 392, 399
Ionic bond, 10
Iron,
allotropy,
244-45
Hardening of cast iron, 432 Hardening spheroidized steel, 281

Hastelloy, 199-200 Heat treatment, 300-302
alpha, 244 cooling curve, 244, 245 Iron-carbon alloys, critical temperature, 247 phase changes, slowly cooled
alloys,
Heat treating carburized

Heisenberg's uncertainly Hexagonal system, 12
steel,
289 6
247-250
principle,
phase diagram, 245-247 Iron-chromium phase diagram,

Iron-nickel alloys, 384
Ironal, 201
Irreversibility.
366
High manganese steel, High nickel steels, 384 High speed steels,
399 composition, 399 heat treatment, 400 structure, 400
classification,
381
Isothermal
99 heat treatment of cast iron,
433
Isothermal transformation, 251
lzod
test,
83
Homogcnizalion of auslcnite, 279
Hoopes process, 133 Hot metal mixer, 222 Hot rolled, 303 Hot worked carbon steels,
Jominy
test,
349
302,
303
Killed steel, 237-238 Knife-line attack, 462

l.aves phases, 21
Hot working,
purpose, 231
Ideal
28, 38-40,
Lead, 190-191,
357 Ideal quench, 357 Impact specimens, 83
diameter,
alloys
in
193-195 of. type metals, 194

197
uses,
Impact strength.
low-alloy steels,
81,
328. 336,
340
Lever principle, Lime boil, 223
104
512
Line imperfections, 14 Liquid metal corrosion, 472 Liquid solutions, 19 Liquids, 102
Index
Manufacture of steel (Cont.) Talbot process, 230
triplex
process,
230
to austempering,
Martcmpering compared
287,
Low
alloy steels, 257,
A.I.S.I. steels,
329-331
commercial limitations, 289

described. 286
chromium
325
as
an alloying element, 324,
copper in, 325 engineering importance, 318-340 general effects of alloying elements
320-322
underlying principle, 287 Martens. 2 Marlensite. 255 Mass transfer, 99 Mechanical fibering, 39
manganese and
326
nickel
molybdenum
in,
in,
322,
Mechanical properties, 299-300

in cast irons, 41
1,
421
324 prosphorus as an alloying clement, 322 properties, heat treated, 332, 340 S.A.E. steels, 328-332
323,
and
silicon
structural, composition
and
properties,
Mechanical working, 28-29, and engineering properties 32-47 Melting the charge, 223 Metal purification, 469 Metallic bond, 1
Metallurgy,
as a science, 2 as
326-328 tungsten and vanadium in, 325, 326
Low
carbon
steel,
125-126,
strain
aging,
126
an art, importance to engineers,

1
3,
Low Temperature,
Machinability, evaluation of
138, 441
84
Metals,
static
effect
properties, significance, 57-79

of micro-structure,
59
metallic
materials
steels,
for,
Metals in atomic reactors,

control
materials, 20-1 fuel elements, 203
ratings
relation
for
free-cutting
440
tensile
of
cutting
speed
to
strength, 438 variables affecting, 438 Malleable cast iron, 409-412, 421
gamma-ray source, 204 structural materials, 203 Mg-Ca system, 107

Mg-I.i system, 109 Miller indices, 13
Miscibility of metals,
18
Magnesium,
manufacture, 156
properties,
155
vs. aluminum, 156 Magnesium alloys,
casting,
158 treatment, 157 precipitation hardening, 121-124 Magnetic properties, ferromagnetic
158 corrosion resistance,
Modulus of elasticity, 63-65 Modulus of rigidity, 64 Modulus of rupture, in cast iron, 419 Molybdenum in tool and die steels, 396,
399, 403
heat
Molybdenum
ma-
in steel, effect
on properties,
terials, 58,
59
325, 326 Moncl, 199-200,
Mallcablizing cycle, 430 Malleablizing white cast iron, 410 Manufacture of iron, 212-214 Manufacture of steel,
K-Monel, 125
Metal, 102
Process. 230
Campbell
process,
230
S-Monel, 125 Mottled cast iron, 409
crucible process, 231
duplex process, 229 duplex Talbot process, 230

electric- furnace
process,
226-227
Monell process, 230

super-refining process, 230
Newton's law of cooling, Nickel, 190-191, 199, alloys of, 199-200 in cermets, 198
physical
properties, 199
345
Index
Nickel in
effect
steel,
513
Pearlite, 253,
on
properties, 323, 324
defined. 247
Nimonic, 199
Nitriding,
hardcnability, 257
malleable cast
iron,
412
advantages, 291
defined, 291
Perfect crystal, 23 Pcritectic reaction,

steels,
108
limited
to
alloy
291
Pitting.
459
process, 291
Ni-Vee Bronze, 127 Nodular cast iron, 409, 420, 421 Nodular graphite formation, 430 Nodular pearlite, 253 Normalizing of steels, 280, 281 Nose of the curve, 254
Pewter, 191 Phase, 97
Phase diagrams Phase rule, 100 Phosphorus,
in
metal
systems,
19
in gray cast iron, 413-415 in steel elfect on properties, 322
Notch sensitivity in cast iron, 413-420 Nondcforming tool and die steel, 396 Normal intermetallic compounds, 21
Normalizing of cast iron, 431 Notched-bar impact, 502 Notched-bar test, 85
Physical
testing, 59 Pidgeon process, 156 Pig iron,
classed, 409
composition, 211
Pilling
and Bedworth
rule, 478,
484
Notch brittlencss, 81 Notch constraint, 85

Notch
Olsen
89
constant, 6 Plastic constraint, 85 Plastic design, background for, 63 Platinum, 190-191, 202,
Planck's
sensitivity,
Objectives of annealing, 280

test,
446
processes,
metals, 203 Polarization, 454 Polycrystalline metals, 16
Open-hearth
220
Orange peel, 30 Ore boil, 223

Overaging, 52, 116-117, precipitation hardening, 116
Oxidation, high-temperature, 472 internal, 473 of copper, 475 of stainless steel, 482 of titanium, 479
of zinc, 476 prevention, 480
rate,
Polyphase structures, 49-51 Powder metallurgy, 29 Precious metals, 190, 202

Precipitates, 21,
coherent, 21
Precipitation
non-coherent, 21 hardening, 52, 53, alloy requirements. 111 alloy steel, 126-127 aluminum alloys, 117-123
107,
carbon steel, copper base

definition,
125-126
alloys,
117,
124,
125,
127
111
delayed
elfect
precipitation,
113
dislocations, 115-120 of
477 parabolic, 478, 484 cubic, 478 logarithmic, 478 resistant alloys, 481
linear.
temperature, 117
effect of
time, 117 Guinier- Preston zones. 115

lattice
conformity, 112
alloys.
magnesium base
overaging,
116
120-124
Oxide formation, 473 Oxygen pressure, 475

Pack carburizing, 289
Passivity,
process for, 1 12 theory of, 114
time
and
119-120
temperature
effects,
114,
454,
455
Patenting, defined, 287, use of patented wire, 288
Paul!
exclusion
principle,
Prior history elfect in metals, 15 Process annealing of steels, 280 Proeulecloid cementite, 254
514
Procutectoid fcrritc, 254
Properties of a spheroidized steel, 281
Index
Solute atoms, 18, clfcct of solute atoms on properties, 20 formation of intermediate phases, 20
solid solutions, 20 substitutional solid solutions, 20
interstitial
Properties of solid solutions, 20 Proportional limit, 63, 64 Protective atmospheres, 280 Protective oxidation, 478
Pumps, 470 Purpose of hardening, 282

Quality factors, 23, 24
Quantum numbers.
Quench
cracks,
Solution heat treatment, 111, 112, alloy requirements, 112 elfect of quenching, 113 elfect of temperature, 113 Solutions in metal systems, 18, factors controlling extent of solubility,
18
284
270
Quenching,
liquid solutions,
solid
19
mechanism
media, 282
of,
stages, 282, 283
20 Sonic testing, 78, 79 Sorby, 2 Space group, 12
solutions,
Space
lattice,
12
Rate Rate
of growth, 27-28 of nucleation, 27-28
Specific gravity, of the heavy metals, 191
Radiation damage, 53-54 Recovery, 42

Recrystallization,
28, 43,
45-46
Spheroidite, 289 Sphcroidization. 495 Spheroidizing steels, 281 Stabilizing, 123-124

Stainless
Stainless
Reduced temperatures, 500-505

Residual stresses, 93 Retained austenite, 274 Reverberatory furnace, 424 Rockwell hardness, described, 70, 71, relation to other hardness values, 75
iron, 365
Stainless steels, classes of, 364
W.
379-380
properties,
Static
Steel,
mechanical
60
Rotating-beam
test,
87
Rupture strength, 491

S.A.E. steels,
hardening of, early study. 2 mechanical treatment, 231-232 precipitation hardening

alloy steels, 126-127
low carbon
steels,
125-126
low-alloy,
328-332 properties, 333-340

for,
stainless steel, 127
properties, charts, value, 333-334

329, 331
strain aging, 126
specifications
Scaling, 473
world production, 208

Steel
Sensitization of stainless steel, 460
making
processes, classification, 208
Service factors, 54
Shear modulus, 64 Shear tests, 77 Shot pecning, 92 Sigma phase, 21

Silchrome, 365
Silicon
effect
405 Strain aging, 126

Stellite, 404,
Strain hardening, 35-36, 493

Strain rate, 82 Strain softening. 489
in steel,
Strengthening nonferrous metals, precipitation hardening. 111

Stress
Silver,
on properties, 239, 323 190-191, 202 Size factor, in forming metal

18
Slip.
concentration, 89,
locating
solutions.
and magnitude, 60
Stress corrosion, 462, 464, 465

Stress raisers, 60 Stress relief in cast iron,
33-36
S-N diagram, 88
Solid solutions, 20, alloys, 102
effects,
430
Stress-strain curves. 307 Stress-strain curves, cast iron, 65,
47-49
low carbon, cold-worked
steel,
62
Solidus, 102
common
metals,
64
Index
Stretcher strains,
30, 448
515
material,
Tool
Structural changes, 495-498
cast alloys, 404, 405
Structure
of carburized steel, Structure of steel, effect of cold working, 259 Subatmospheric cooling, 258 Substitutional solid solutions, Substitutional solutes, 20 Sulphur in cast iron, 413-415, Super refining process, 230 Super saturated solid solution,
290
Cemented carbides, 405

tool steels,
389-404
389,
391,
Tool
101
steels,
characteristics,
chromium
in, 395, 398,
392 403
classification,
391
420
101
Super
stainless steels, 382-383
composition, 391 high alloy. 397 high carbon, 390 high speed, 398-401
Surface finish, 89, 91 Surface imperfections, 14 Surface protection during
low alloy, 395 manganese in, 396

heating,
279,
280
Surface-rolling,
medium alloy, 396 molybdenum in, 396,

properties,
silicon in,
399, 403
92
System, 97
392 397
structure, 394, 398, 401
Talbot process, 230
tempering, 393, 402, 403 tungsten in. 399, 403
Temper Temper
embrittlement, 305 graphite, 430 Temperature, effects of, 485-506
vanadium
in,
399
Tempered
and
martensile, 285
Torsion tests, 77 Toughness, 502 Transformation on cooling of
cast iron,
Tempering,
hardenability, 356
steel,
change in toughness, 275

effect
on physical properties of method, 284

of
cast
284
132 284 retained austenite and quenching, 274
iron,
of,
purpose
428 Transition elements, 9 Transition temperature, 83, 502 Transverse test, cast iron, 77 Triaxial stress, 85 Triple point, 101 Triplex process, 230
'ITT
curve. 252
399, 403
Tensile strength, metals 61-69, standard specimens, 67, 68

standardization, 61
Ternary-system iron, carbon, 427
silicon, 425,
Tungsten carbide, 405, 406 Tungsten, in tool and die steels, Twinning, 36-37 Two-metal corrosion, 456
Type
Types
Terne plate, 191, 196 Thermal conductivity, 497, 498 Thermal expansivity, 497, 498 Thermal fatigue, 499 Thermal shock, 499 Thermodynamics, second law of, 98
Thermostatics, 97
metals, 191-194 of graphite flakes, 429
Understressing, 93 Uniform corrosion, 456
Unit cell, 12 Uses of carbon
steels.
302
Time
delay, 346 Tin, 190, 191,

alloys of,
Vanadium,
In in
steel,
325
192-193
metals,
tool steel,
399
10
in
type
194-195
Van dcr Waals' bond,

Vicalloy, 201
plating,
Tin
197 bronze, 125

405,
Titanium carbide,
manufacture, 159
properties,
use. 159,
Wave Wear
mechanics, 6
resistance,
159
elfect of
160
carbon content and heat ment, 444
treat-
516
Wear
resistance
of,
Index
(Conl.)
evaluation
444
Yield point, 06, 67 Yield strength, 66

Zinc, 191, 197
variables affecting, 443
Wear-types, 442
White White
cast
iron,
408, 410
crystal
structure,
198
metals,
190-191
Working Wrough t Wrought
Wire, carbon steel cold rolled, 30G stresses, 499 iron, 2 iron, manufacture, 227, 229
1
die castings, 197 fabricating methods, 198 mechanical properties, 198

plating,
uses,
197
198

Engineering Metallurgy

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Engineering Metallurgy

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PITMAN METALLURGY SERIES

THE COMMITTEE ON METALLURGY

collaborative writing group

PITMAN PUBLISHING CORPORATION

No part of this book reproduced in any form without

Pitman & Sons, Ltd. Johannesburg

Pitman & Sons (Canada), Ltd. Toronto /

the United States of America

M.S.M.E., Associate Professor of Mechanical En-

gineering, University of Houston, Houston, Texas; Engineer Associated

with Anderson, Greenwood and Co., Bellaire, Texas

M.S.. Associate Professor of Physical Metallurgy, Uni-

Bannon, S.M., Professor

P. Davis, M.S., Associate Professor,

Wyoming, Laramie, Wyoming

Harold Vincent Fairbanks,

M.S., Professor of Metallurgical Engineering,

Morgantown, West Virginia

Ph.D., Professor and Chairman, Department of Metal-

Arthur R. Foster, M.Eng.,

Associate Professor of Mechanical EngineerNortheastern University, Boston, Massachusetts

neering, University of Illinois, Urbana, Illinois

B. Gulbransen, Ph.D., Associate Professor,

versity, St. Louis,

Joseph Gurland, D.Sc, Assistant Professor, Division of Engineering,

gineering, College of Engineering, Marquette University, Milwaukee,

Abraham Eldred Hostetter,

Ph.D., Professor of Metallurgy, Kansas

State College, Manhattan, Kansas

Kaufman, Metallurgy Department, Academy New York

Levinson, M.S., Professor of Mechanical Engineering, Lawrence

Institute of Technology, Detroit,

James R. MacDonald, Ph.D., Chairman, Department

University of Mississippi, Uni-

Assistant Professor of Mechanical Engineering,

University of Colorado, Boulder, Colorado

Richard O. Powell, College

Pringle, M.S.M.E., Associate Professor of Mechanical En-

gineering, University of Missouri, Columbia, Missouri

Rose, M.S., Professor of Metallurgical Engineering, UniLawrence, Kansas

E. Shaffer, M.S., Associate Professor of Engineering, University

E. Short, M.S.M.E., Associate Professor of Mechanical EngineerBradley University, Peoria, Illinois

Floyd Sheldon Smith, M.S., ing, Alabama Polytechnic

Associate Professor of Mechanical EngineerInstitute,

Rocer Greenleaf Stevens,

Metallurgy, University of Cin-

the principles of ferrous and nonferrous metallurgy

for all engineers student

to obtain a broad understanding of

Keeping up with metallurgical developments in

such a dynamic and diversified art and science,

the preparation of a definitive, up-to-date, authoritative

sive questionnaire techniques,

with the general principles of metallurgy

as they are related to engineering.

of space has been devoted so that com-

plete coverage could be obtained. Chapters

of temperature are fully covered in Chapters 21 to 23.

end of each chapter there

and exercises constructed on the important definitions and

to help the student focus at-

principles presented in the

serve to amplify the discussion. In certain chapters, detailed tables are

Metallurgy and Engineering