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that it has been imported without the approval of the Publisher or Author.
James F. Shackelford’s Introduction to Materials Science for Engineers presents comprehensive and
in-depth coverage of the fundamental principles of materials science and engineering. Starting with
Introduction to Materials
chapters on applied physics and chemistry to cover the foundations of materials science, the text
Science for Engineers

then discusses a wide variety of materials—traditional as well as modern—and their applications
in engineering. This edition contains extensive discussions on new materials that are playing a key
role in the economy of the twenty-first century, materials like “high tech” ceramics for advanced
structural applications, advanced composites for aerospace applications, fullerene carbons,
graphene, engineered biomaterials, and biological materials.
Introduction to Materials
Key Features
• End-of-chapter conceptual problems encourage students to check their understanding of
basic concepts.
Science for Engineers

• Updated discussions on the role of materials used in smartphones, tablets, and optical fibers and
an emphasis on the role of sustainability enhance engagement with contemporary developments in
the field.
• Computer-generated crystal structure illustrations give students the most accurate and
visually realistic images available. Ninth Edition
• A “Powers of Ten” feature emphasizes the fact that the behavior of materials in engineering
designs can be understood by looking at mechanisms that occur at various finer scales. James F. Shackelford
EDITION
NINTH
• “The Material World” boxes offer interesting insights into the world of natural and engineered
materials.
• Images have been upgraded to full color where appropriate to add to the visual appeal.
Available separately for purchase, Mastering Engineering for Introduction to Materials Science for Engineers
now includes all end-of-chapter problems. This teaching and learning platform empowers instructors
Shackelford
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NINTH EDITION
GLOBAL EDITION
Introduction to
MATERIALS SCIENCE
FOR ENGINEERS
University of California, Davis
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Contents
Preface 9 3.4 Polymeric Structures 93

3.5 Semiconductor Structures 94
About the Author 16 3.6 Lattice Positions, Directions, and Planes 98
3.7 X-Ray Diffraction 110
1 Materials for Engineering 17
4 rystal Defects and Noncrystalline
C
1.1 The Material World 17
Structure—Imperfection 120
1.2 Materials Science and Engineering 19
1.3 Six Materials That Changed Your World 19 4.1 The Solid Solution—Chemical Imperfection 121
STEEL BRIDGES—INTRODUCING METALS 19 4.2 Point Defects—Zero-Dimensional
TRANSPARENT OXIDES—INTRODUCING CERAMICS 21 Imperfections 126
SMARTPHONES AND TABLETS—INTRODUCING GLASSES 25
4.3 Linear Defects, or Dislocations—One-Dimensional
NYLON PARACHUTES—INTRODUCING POLYMERS 26
Imperfections 128
KEVLAR®-REINFORCED TIRES—INTRODUCING
COMPOSITES 29 4.4 Planar Defects—Two-Dimensional
SILICON CHIPS—INTRODUCING SEMICONDUCTORS 30 Imperfections 130
1.4 Processing and Selecting Materials 32 4.5 Noncrystalline Solids—Three-Dimensional
Imperfections 134
1.5 Looking at Materials by Powers of Ten 33
5 Diffusion 143
PART I The Fundamentals 5.1 Thermally Activated Processes 144
5.2 Thermal Production of Point Defects 147
2 Atomic Bonding 39
5.3 Point Defects and Solid-State Diffusion 149
2.1 Atomic Structure 40 5.4 Steady-State Diffusion 159
2.2 The Ionic Bond 46 5.5 Alternate Diffusion Paths 163
COORDINATION NUMBER 51
2.3 The Covalent Bond 57 6 Mechanical Behavior 168
2.4 The Metallic Bond 62
6.1 Stress Versus Strain 169
2.5 The Secondary, or van der Waals, Bond 65
METALS 169
2.6 Materials—The Bonding Classification 68
CERAMICS AND GLASSES 181
POLYMERS 185
3 Crystalline Structure—Perfection 75 6.2 Elastic Deformation 189
6.3 Plastic Deformation 191
3.1 Seven Systems and Fourteen Lattices 76
6.4 Hardness 198
3.2 Metal Structures 80
6.5 Creep and Stress Relaxation 201
3.3 Ceramic Structures 84
A01_SHAC0996_09_GE_FM.indd 5 10/10/2022 19:36

6 Contents
6.6 Viscoelastic Deformation 208 RECOVERY 350

INORGANIC GLASSES 210 RECRYSTALLIZATION 351
ORGANIC POLYMERS 212 GRAIN GROWTH 351
ELASTOMERS 215 10.6 The Kinetics of Phase Transformations
for Nonmetals 354
7 Thermal Behavior 226
7.1 Heat Capacity 227 PART II aterials and Their

M
7.2 Thermal Expansion 229 Applications
7.3 Thermal Conductivity 233
7.4 Thermal Shock 238 11 Structural Materials—Metals,
Ceramics, and Glasses 367
8 Failure Analysis and Prevention 244
11.1 Metals 368
8.1 Impact Energy 245 FERROUS ALLOYS 368
8.2 Fracture Toughness 251 NONFERROUS ALLOYS 374
8.3 Fatigue 255 11.2 Ceramics and Glasses 378
8.4 Nondestructive Testing 264 CERAMICS—CRYSTALLINE MATERIALS 378
8.5 Failure Analysis and Prevention 267 GLASSES—NONCRYSTALLINE MATERIALS 380
GLASS-CERAMICS 382
11.3 Processing the Structural Materials 384
9 P
hase Diagrams—Equilibrium
PROCESSING OF METALS 384
Microstructural Development 275
PROCESSING OF CERAMICS AND GLASSES 392
9.1 The Phase Rule 276

9.2 The Phase Diagram 280 12 Structural Materials—Polymers
COMPLETE SOLID SOLUTION 280 and Composites 402
EUTECTIC DIAGRAM WITH NO SOLID SOLUTION 284
EUTECTIC DIAGRAM WITH LIMITED SOLID SOLUTION 286 12.1 Polymers 403
EUTECTOID DIAGRAM 288 POLYMERIZATION 403
PERITECTIC DIAGRAM 292 STRUCTURAL FEATURES OF POLYMERS 408
GENERAL BINARY DIAGRAMS 294 THERMOPLASTIC POLYMERS 412
9.3 The Lever Rule 300 THERMOSETTING POLYMERS 414
ADDITIVES 415
9.4 Microstructural Development During Slow
Cooling 304 12.2 Composites 417
FIBER-REINFORCED COMPOSITES 418
AGGREGATE COMPOSITES 424
10 Kinetics—Heat Treatment 322
PROPERTY AVERAGING 425
MECHANICAL PROPERTIES OF COMPOSITES 431
10.1 Time—The Third Dimension 323
12.3 Processing the Structural Materials 437
10.2 The TTT Diagram 328
PROCESSING OF POLYMERS 437
DIFFUSIONAL TRANSFORMATIONS 329
PROCESSING OF COMPOSITES 440
DIFFUSIONLESS (MARTENSITIC) TRANSFORMATIONS 331
HEAT TREATMENT OF STEEL 335
10.3 Hardenability 342 13 Electronic Materials 449
10.4 Precipitation Hardening 346
13.1 Charge Carriers and Conduction 451
10.5 Annealing 349
13.2 Energy Levels and Energy Bands 455
COLD WORK 349
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Contents 7
13.3 Conductors 461 GLASS FOR SMART PHONE AND TABLET TOUCH
SCREENS 592
THERMOCOUPLES 464
AMORPHOUS METAL FOR ELECTRIC-POWER
SUPERCONDUCTORS 465
DISTRIBUTION 594
13.4 Insulators 473 15.4 Materials and Our Environment 595
FERROELECTRICS 474
ENVIRONMENTAL DEGRADATION OF MATERIALS 595
PIEZOELECTRICS 477
ENVIRONMENTAL ASPECTS OF DESIGN 611
13.5 Semiconductors 481 RECYCLING AND REUSE 615
INTRINSIC, ELEMENTAL SEMICONDUCTORS 482
EXTRINSIC, ELEMENTAL SEMICONDUCTORS 487 APPENDIX 1
COMPOUND SEMICONDUCTORS 498
Physical and Chemical Data
PROCESSING OF SEMICONDUCTORS 502
SEMICONDUCTOR DEVICES 505
for the Elements A-1
13.6 Composites 515 APPENDIX 2
13.7 Electrical Classification of Materials 515 Atomic and Ionic Radii of the Elements A-4
14 Optical and Magnetic Materials 524 APPENDIX 3
Constants and Conversion Factors
14.1 Optical Materials 525 and the Periodic Table of Elements A-7
OPTICAL PROPERTIES 528
OPTICAL SYSTEMS AND DEVICES 538 APPENDIX 4
14.2 Magnetic Materials 547 Properties of the Structural Materials A-9
FERROMAGNETISM 550
FERRIMAGNETISM 557 APPENDIX 5
METALLIC MAGNETS 560 Properties of the Electronic, Optical,
CERAMIC MAGNETS 566
and Magnetic Materials A-18
15 Materials in Engineering Design 578 APPENDIX 6
Glossary A-23
15.1 Material Properties—Engineering Design
Parameters 579 Answers to Practice Problems (PP)
15.2 Selection of Structural Materials—Case and Odd-Numbered Problems AN-1
Studies 584
MATERIALS FOR HIP- AND KNEE-JOINT REPLACEMENT 584 Index I-1
METAL SUBSTITUTION WITH COMPOSITES 588
15.3 Selection of Electronic, Optical, and Magnetic
Materials—Case Studies 589
LIGHT-EMITTING DIODE 589
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A01_SHAC0996_09_GE_FM.indd 8 10/10/2022 19:36

Preface
T his book is designed for a first course in engineering materials. The field that
covers this area of the engineering profession has come to be known as “materi-
als science and engineering.” To me, this label serves two important functions.
First, it is an accurate description of the balance between scientific principles
and practical engineering that is required in selecting the proper materials
for modern technology. Second, it gives us a guide to organizing this book.
After a short introductory chapter, “science” serves as a label for Part I on
“The Fundamentals.” Chapters 2 through 10 cover various topics in applied
physics and chemistry. These are the foundation for understanding the prin-
ciples of “materials science.” I assume that some students take this course at
the freshman or sophomore level and may not yet have taken their required
coursework in chemistry and physics. As a result, Part I is intended to be self-
contained. A previous course in chemistry or physics is certainly helpful, but
should not be necessary. If an entire class has finished freshman chemistry,
Chapter 2 (atomic bonding) could be left as optional reading, but it is impor-
tant not to overlook the role of bonding in defining the fundamental types
of engineering materials. The remaining chapters in Part I are less optional,
as they describe the key topics of materials science. Chapter 3 outlines the
ideal, crystalline structures of important materials. Chapter 4 introduces the
structural imperfections found in real, engineering materials. These structural
defects are the bases of solid-state diffusion (Chapter 5) and plastic deforma-
tion in metals (Chapter 6). Chapter 6 also includes a broad range of mechani-
cal behavior for various engineering materials. Similarly, Chapter 7 covers the
thermal behavior of these materials. Subjecting materials to various mechani-
cal and thermal processes can lead to their failure, the subject of Chapter 8.
In addition, the systematic analysis of material failures can lead to the pre-
vention of future catastrophes. Chapters 9 and 10 are especially important in
providing a bridge between “materials science” and “materials engineering.”
Phase diagrams (Chapter 9) are an effective tool for describing the equilib-
rium microstructures of practical engineering materials. Instructors will note
that this topic is introduced in a descriptive and empirical way. Since some stu-
dents in this course may not have taken a course in thermodynamics, I avoid
the use of the free-energy property. Kinetics (Chapter 10) is the foundation of
the heat treatment of engineering materials.
The words “materials engineering” give us a label for Part II of the book
that deals with “Materials and Their Applications.” First, we discuss the five cat-
egories of structural materials: metals, ceramics, and glasses (Chapter 11) and
A01_SHAC0996_09_GE_FM.indd 9 10/10/2022 19:36

10 Preface
polymers and composites (Chapter 12). In both chapters, we give examples of

each type of structural material and describe their processing, the techniques
used to produce the materials. In Chapter 13, we discuss electronic materials and
discover a sixth category of materials, semiconductors, based on an electrical
rather than bonding classification system. Metals are generally good electrical
conductors, while ceramics, glasses, and polymers are generally good insulators,
and semiconductors are intermediate. The exceptional discovery of supercon-
ductivity in certain ceramic materials at relatively high temperatures augments
the long-standing use of superconductivity in certain metals at very low tem-
peratures. Chapter 14 covers optical behavior that determines the application of
many materials, from traditional glass windows to some of the latest advances in
telecommunications. A wide variety of materials is also discussed in Chapter 14.
Traditional metallic and ceramic magnets are being supplemented by supercon-
ducting metals and ceramics, which can provide some intriguing design appli-
cations based on their magnetic behavior. Finally, in Chapter 15 (Materials in
Engineering Design), we see that our previous discussions of properties have
left us with “design parameters.” Herein lies a final bridge between the princi-
ples of materials science and the use of those materials in modern engineering
designs. We also must note that chemical degradation, radiation damage, wear,
recycling, and reuse must be considered in making a final judgment on a materi-
als application.
I hope that students and instructors alike will find what I have attempted to
produce: a clear and readable textbook organized around the title of this impor-
tant branch of engineering. It is also worth noting that materials play a central
role across the broad spectrum of contemporary science and technology. In the
report Science: The End of the Frontier? from the American Association for the
Advancement of Science, 10 of the 26 technologies identified at the forefront of
economic growth are various types of advanced materials.
In the presentation of this book, I have attempted to be generous with
examples and practice problems within each chapter, and I have tried to be even
more generous with the end-of-chapter homework problems (with the level of
difficulty for the homework problems clearly noted). Problems dealing with the
role of materials in the engineering design process are noted with the use of a
design icon . One of the most enjoyable parts of writing the book was the prep-
aration of biographical footnotes for those cases in which a person’s name has
become intimately associated with a basic concept in materials science and engi-
neering. I suspect that most readers will share my fascination with these great
contributors to science and engineering from the distant and not-so-distant past.
In addition to a substantial set of useful data, the Appendices provide convenient
location of materials properties and key term definitions.
The various editions of this book have been produced during a period of
fundamental change in the field of materials science and engineering. This change
was exemplified by the change of name in the Fall of 1986 for the “American
Society for Metals” to “ASM International”—a society for materials, as opposed
to metals only. An adequate introduction to materials science can no longer be a
traditional treatment of physical metallurgy with supplementary introductions to
nonmetallic materials. The first edition was based on a balanced treatment of the
full spectrum of engineering materials.
A01_SHAC0996_09_GE_FM.indd 10 10/10/2022 19:36

Preface 11
Subsequent editions have reinforced that balanced approach with the

timely addition of new materials that are playing key roles in the economy
of the twenty-first century: lightweight metal alloys, “high tech” ceramics for
advanced structural applications, engineering polymers for metal substitu-
tion, advanced composites for aerospace applications, increasingly miniaturized
semiconductor devices, high-temperature ceramic superconductors, fullerene
carbons, g raphene, engineered biomaterials, and biological materials. Since the
debut of the first edition, we have also seen breakthroughs in materials char-
acterization, such as the evolution of the high-resolution transmission electron
microscope (HRTEM), and in materials processing, such as additive manufac-
turing (AM). “Feature boxes” have been introduced in recent editions. These
one- or two-page case studies labeled “The Material World” are located in
each chapter to provide a focus on some fascinating topics in the world of both
engineered and natural materials. Another feature from recent editions is to
emphasize the concept of “Powers of Ten.” In Chapter 1, we point out that an
underlying principle of materials science is that understanding the behavior of
materials in engineering designs (on the human scale) is obtained by looking
at mechanisms that occur at various fine scales, such as the atomic-scale diffu-
sion of carbon atoms involved in the heat treatment of steel. There is a full ten
orders of magnitude difference between the size of typical engineered prod-
ucts and the size of typical atoms. Much of modern engineering practice has
depended on engineering designs based on micrometer-scale structures, such
as the transistors in an integrated circuit. Increasingly, engineers are designing
systems involving the nanometer-scale. At various times throughout the text, a
Powers of Ten icon will be used to highlight discussions that demonstrate this
structure-property relationship.
New to This Edition

As with previous editions, an effort has been made to add the most important
advances in engineering materials, as well as respond to recommendations of
previous users for additional content coverage. The results are:
• The addition of Learning Objectives to each chapter to give students clearer

goals for the knowledge to be acquired.
• The inclusion of end-of-chapter conceptual problems throughout the text.
• The inclusion of all end-of-chapter problems in the MasteringTM platform.
• The upgrade of images to full color where appropriate to provide a more
vibrant presentation of visual information throughout the book.
• Updated discussions of the role of engineering materials in smartphones and
tablets, increasingly ubiquitous parts of our everyday lives.
• Enhanced discussion of the nature of optical fibers in telecommunication.
• The refreshing and updating of all discussions of contemporary materials in
modern engineering design, including an emphasis on the role of sustainability.
A01_SHAC0996_09_GE_FM.indd 11 10/10/2022 19:36

12 Preface
Resources for Instructors

All instructor resources are available for download at www.pearsonglobaleditions
.com. If you are in need of a login and password for this site, please contact your
local Pearson representative.
Instructor’s Solutions Manual

Available to adopters of this textbook, it contains fully worked-out solutions to
the practice and homework problems only. The Solutions Manual is available in
PDF format.
PowerPoint Slides
A complete set of all the figures and tables from the textbook are available in
PowerPoint® format.
Mastering Engineering
This online tutorial and assessment program allows you to integrate dynamic
homework with automated grading of the calculation parts of problems and
personalized feedback. MasteringTM Engineering allows you to easily track
the performance of your entire class on an assignment-by-assignment basis,
or the detailed work of an individual student. For more information visit
www.mlm.pearson.com/global/.
Related Massively Open Online Course (MOOC)

A MOOC based on this book and entitled “MATERIALS SCIENCE: Ten
Things Every Engineer Should Know” is available as open access on coursera.org.
In the course, the author delivers ten short lectures on topics of practical
significance to both students of engineering and practicing professionals.
Acknowledgments
Finally, I want to acknowledge a number of people who have been immensely
helpful in making this book possible. My family has been more than the usual
“patient and understanding.” They are a constant reminder of the rich life beyond
the material plane. Peter Gordon (first edition), David Johnstone (second and
third editions), Bill Stenquist (fourth and fifth editions), Dorothy Marrero (sixth
edition), and Holly Stark (seventh, eighth, and ninth editions) are much appreci
ated in their roles as editors. Erin Ault, Manager of Content Strategy, has been
indispensible in shepherding this edition to completion. Lilian Davila at the
University of California, Merced skillfully produced the computer-generated
crystal structure images. A special appreciation is due to my colleagues at the
University of California, Davis and to the many reviewers of all editions, espe-
cially D. J. Montgomery, John M. Roberts, D. R. Rossington, R. D. Daniels,
R. A. Johnson, D. H. Morris, J. P. Mathers, Richard Fleming, Ralph Graff, Ian W.
Hall, John J. Kramer, Enayat Mahajerin, Carolyn W. Meyers, Ernest F. Nippes,
Richard L. Porter, Eric C. Skaar, E. G. Schwartz, William N. Weins, M. Robert
A01_SHAC0996_09_GE_FM.indd 12 10/10/2022 19:36

Preface 13
Baren, John Botsis, D. L. Douglass, Robert W. Hendricks, J. J. Hren, Sam Hruska,

I. W. Hull, David B. Knoor, Harold Koelling, John McLaughlin, Alvin H. Meyer,
M. Natarajan, Jay Samuel, John R. Schlup, Theodore D. Taylor, Ronald Kander,
Alan Lawley, Joanna McKittrick, Kathleen R. Rohr, James F. Fitz-Gerald. Valery
Bliznyuk, David Bahr, K. Srinagesh, Stacy Gleixner, Raj Vaidyanathan. Jeffrey
Fergus, Christoph Steinbruchel, Wayne Elban, Giovanni Zangari, Guanshui Xu,
Atin Sinha, Yu-Lin Shen, Qiuming Wei, Blair London, and James Chelikowsky.
Davis, California
Acknowledgments for the Global Edition

Pearson would like to acknowledge and thank the following for their work on
the Global Edition:
Contributor
K. S. Vijay Sekar, Sri Sivasubramaniya Nadar College of Engineering
Reviewers
Durul Huda, Swinburne University of Technology
Tanay Karademir, Istanbul Bilgi Üniversitesi
Murat Saribay, Istanbul Bilgi Üniversitesi
A01_SHAC0996_09_GE_FM.indd 13 10/10/2022 19:36

14 Preface
Combine this...
A01_SHAC0996_09_GE_FM.indd 14 10/10/2022 19:36

Preface 15
With the Power of Mastering Engineering for

Introduction to Materials Science for Engineers
MasteringTM is the teaching and learning platform that empowers every student.
By combining trusted authors’ content with digital tools developed to engage students and
emulate the office hours experience, Mastering personalizes learning and improves results for
each student.
Empower each learner

Each student learns at a different pace. Personalized learning, including optional hints and
wrong-answer feedback, pinpoints the precise areas where each student needs practice, giving
all students the support they need — when and where they need it — to be successful.
Learn more at www.mlm.pearson.com/global/
A01_SHAC0996_09_GE_FM.indd 15 10/10/2022 19:36

16 Preface
About the Author

James F. Shackelford has BS and MS degrees in Ceramic Engineering from the
University of Washington and a Ph.D. in Materials Science and Engineering from
the University of California, Berkeley. Following a postdoctoral fellowship at
McMaster University in Canada, he joined the University of California, Davis,
where he is currently Distinguished Professor Emeritus in the Department of
Materials Science and Engineering. For many years, he served as the Associate
Dean for Undergraduate Studies in the College of Engineering and later as the
Director of the University Honors Program that serves students from a wide
spectrum of majors. Dr. Shackelford also served as Associate Director for Educa-
tion for the National Science Foundation (NSF)-funded Center for B iophotonics
Science and Technology (CBST) and as Faculty Assistant to the Director of the
McClellan Nuclear Research Center (MNRC) of UC Davis. He teaches and
conducts research in the structural characterization and processing of materials,
focusing on glasses and biomaterials. His current focus in teaching is doing so
through online technologies. A member of the American Ceramic Society and
ASM International, he was named a Fellow of the American Ceramic Society
in 1992, was named a Fellow of ASM International in 2011, and received the
Outstanding Educator Award of the American Ceramic Society in 1996 and the
Albert Easton White Distinguished Teacher Award from ASM International in
2019. In 2003, he received a Distinguished Teaching Award from the Academic
Senate of the University of California, Davis. In 2012, he received the Outstand-
ing Teaching Award of the College of Engineering at UC Davis, and, in 2014,
received an Outstanding Service Award from UC Davis Extension. In 2016, Pro-
fessor Shackelford received the Inaugural Award for Outstanding Contributions
to Materials Education at the North American Materials Education Symposium
(NAMES) held at the University of California, Berkeley. He has published over
150 archived papers and books including Introduction to Materials Science for
Engineers now in its 9th Edition and which has been translated into Chinese,
German, Italian, Japanese, Korean, Portuguese, and Spanish.
A01_SHAC0996_09_GE_FM.indd 16 10/10/2022 19:36

CHAPTER 1
Materials for Engineering
LEARNING OBJECTIVES
After studying this chapter, you should be
able to:
1. Explain how materials have played
a central role in the development of
human cultures throughout history.
2. Distinguish between the terms materials
science and materials engineering.
3. Identify six categories of engineering
materials, five types of structural
The future of transportation
materials, and semiconductors as one
will include new advances in example of electronic materials.
materials such as this glass road
sign allowing instantaneous 4. (a) Describe how the atomic- and microscopic-scale structure
route changes and updates. of materials help us understand the properties of those
(Courtesy of Corning Glass
Works.)
materials that are used in engineering applications.
(b) Recall the materials tetrahedron that includes the terms
structure and properties as well as their relationship with the
processing of materials and their ultimate performance in an
engineering design.
5. List the wide range of dimensional scales involved in materials
science and engineering:
(a) The atomic scale: 1 : 10−10 meter
(b) The nanoscale: 1 : 10−9 meter
(c) The microscale: 1 : 10−6 meter
(d) The milliscale: 1 : 10−3 meter
(e) The human scale: 1 meter
1.1 The Material World

We live in a world of material possessions that largely define our social rela-
tionships and economic quality of life. The material possessions of our earliest
ancestors were probably their tools and weapons. In fact, the most popular way
of naming the era of early human civilization is in terms of the materials from
which these tools and weapons were made. The Stone Age has been traced as far
back as 2.5 million years ago when human ancestors, or hominids, chipped stones
17
M01_SHAC0996_09_GE_C01.indd 17 10/10/2022 19:40

18 CHAPTER 1 Materials for Engineering
to form weapons for hunting (Figure 1.1). The Bronze Age roughly spanned the
period from 2000 b.c. to 1000 b.c. and represents the foundation of metallurgy,
in which alloys of copper and tin were discovered to produce superior tools and
weapons. (An alloy is a metal composed of more than one element.)
Contemporary archaeologists note that an earlier but less well known
“Copper Age” existed between roughly 4000 b.c. and 3000 b.c. in Europe, in
which relatively pure copper was used before tin became available. The limited
utility of those copper products provided an early lesson in the importance of
proper alloy additions. The Iron Age defines the period from 1000 b.c. to 1 b.c.
By 500 b.c., iron alloys had largely replaced bronze for tool and weapon making
in Europe.
Although archaeologists do not refer to a “pottery age,” the presence of
domestic vessels made from baked clay has provided some of the best descrip-
tions of human cultures for thousands of years. Similarly, glass artifacts have
been traced back to 4000 b.c. in Mesopotamia.
Modern culture in the second half of the 20th century is sometimes referred
to as “plastic,” a not entirely complimentary reference to the lightweight and
economical polymeric materials from which so many products are made. Some
observers have suggested instead that this same time frame should be labeled the
“silicon age,” given the pervasive impact of modern electronics largely based on
silicon technology.
FIGURE 1.1 Stone age tools. (Georg Hergenhan / 123RF.)
M01_SHAC0996_09_GE_C01.indd 18 10/10/2022 19:40

SECTION 1.3 Six Materials That Changed Your World 19
1.2 Materials Science and Engineering

Since the 1960s, the term that has come to label the general branch of engineering
concerned with materials is materials science and engineering. This label is accu-
rate in that this field is a true blend of fundamental scientific studies and practical
engineering. It has grown to include contributions from many traditional fields,
including metallurgy, ceramic engineering, polymer chemistry, condensed matter
physics, and physical chemistry.
The term “materials science and engineering” will serve a special function
in this introductory textbook; it will provide the basis for the text’s organiza-
tion. First, the word science describes the topics covered in Chapters 2 through
10, which deal with the fundamentals of structure, classification, and properties.
Second, the word materials describes Chapters 11 through 13, which deal with
the five types of structural materials (Chapters 11 and 12) and various electronic
materials, especially semiconductors (Chapter 13), along with optical and mag-
netic materials (Chapter 14). Finally, the word engineering describes Chapter 15,
which puts the materials to work with discussions of key aspects of the selection
of the right materials for the right job, along with some caution about the issue of
environmental degradation in those real-world applications.
1.3 Six Materials That Changed Your World

The most obvious question to be addressed by the engineering student entering
an introductory course on materials is, “What materials are available to me?”
Various classification systems are possible for the wide-ranging answer to this
question. In this book, we distinguish six categories that encompass the materi-
als available to practicing engineers: metals, ceramics, glasses, polymers, compos-
ites, and semiconductors. We will introduce each of these categories with a single
example.
STEEL BRIDGES—INTRODUCING METALS

If there is a “typical” material associated in the public’s mind with modern engi-
neering practice, it is structural steel. This versatile construction material has sev-
eral properties that we consider metallic: First, it is strong and can be readily
formed into practical shapes. Second, its extensive, permanent deformability, or
ductility, is an important asset in permitting small amounts of yielding to sud-
den and severe loads. For example, many Californians have been able to observe
moderate earthquake activity that leaves windows of glass, which is relatively
brittle (i.e., lacking in ductility), cracked, while steel-support framing still func-
tions normally. Third, a freshly cut steel surface has a characteristic metallic lus-
ter; and fourth, a steel bar shares a fundamental characteristic with other metals:
It is a good conductor of electrical current.
Among the most familiar uses of structural steel are bridges, and one of the
most famous and beautiful examples is the Golden Gate Bridge connecting San
Francisco, California with Marin County to the north (Figure 1.2). The opening
on May 27, 1937, allowed 200,000 local residents to stroll across the impressive
M01_SHAC0996_09_GE_C01.indd 19 10/10/2022 19:40

FIGURE 1.2 The Golden Gate Bridge north of San Francisco, California, is one of the
most famous and most beautiful examples of a steel bridge. (© LOOK Die Bildagentur
der Fotografen GmbH / Alamy.)
new structure. The following day, a ribbon cutting ceremony inaugurated auto-
mobile traffic that has continued to be an important part of the fabric of life in
the San Francisco Bay area for more than 80 years. For many years, the Golden
Gate held the title of “longest suspension bridge” in the world (2,737 meters).
Although new bridge technologies have provided newer holders of that title, the
Golden Gate is still, in the words of a local historian, a “symphony in steel.”
Steel bridges continue to provide a combination of function and beauty with
the Sundial Bridge in Redding, California being a stunning example (Figure 1.3).
The Redding Bridge is a 66-meter pedestrian walkway designed by the famous
Spanish architect Santiago Calatrava. It connects a walking trail system with the
Turtle Bay Exploration Park. New bridges like this one are not merely serving as
sculptural art projects. The aging infrastructure, including many bridges built as
long as a century ago, also provides a challenge to engineers and the requirement
for both maintenance and replacement of these important structures.
In Chapter 2, the nature of metals will be defined and placed in perspec-
tive relative to the other categories. It is useful to consider the extent of metallic
behavior in the currently known range of chemical elements. Figure 1.4 highlights
the chemical elements in the periodic table that are inherently metallic. This is a
large family indeed. The shaded elements are the bases of the various engineer-
ing alloys, including the irons and steels (from Fe), aluminum alloys (Al), mag-
nesium alloys (Mg), titanium alloys (Ti), nickel alloys (Ni), zinc alloys (Zn), and
copper alloys (Cu) [including the brasses (Cu, Zn)].
M01_SHAC0996_09_GE_C01.indd 20 10/10/2022 19:40

FIGURE 1.3 The Sundial Bridge in Redding, California is a modern masterpiece of bridge
design.
IA 0
1 2
H II A III A IV A V A VI A VII A He
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
11 12 VIII 13 14 15 16 17 18
Na Mg III B IV B V B VI B VII B IB II B Al Si P S Cl Ar
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
87 88 89 104 105 106
Fr Ra Ac Rf Db Sg
58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
90 91 92 93 94 95 96 97 98 99 100 101 102 103
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lw
FIGURE 1.4 Periodic table of the elements. Those elements that are inherently metallic in
nature are shown in color.
TRANSPARENT OXIDES—INTRODUCING CERAMICS

Aluminum (Al) is a common metal, but aluminum oxide, a compound of alumi-
num and oxygen such as Al2O3, is typical of a fundamentally different family of
engineering materials, ceramics. Aluminum oxide has two principal advantages
M01_SHAC0996_09_GE_C01.indd 21 10/10/2022 19:40

FIGURE 1.5 A variety of alumina ceramic products are available for high-temperature
(refractory) applications. (Courtesy of AdValue Technology.)
over metallic aluminum. First, Al2O3 is chemically stable in a wide variety of

severe environments, whereas metallic aluminum would be oxidized (a term
discussed further in Chapter 15). In fact, a common reaction product in the
chemical degradation of aluminum is the more chemically stable oxide. Second,
the ceramic Al2O3 has a significantly higher melting point (2020°C) than does
the metallic Al (660°C), which makes Al2O3 a popular refractory (i.e., a high-
temperature-resistant material of wide use in industrial furnace construction). A
variety of engineered alumina products are shown in Figure 1.5.
With its superior chemical and temperature-resistant properties, why isn’t
Al2O3 used for applications such as automotive engines in place of metallic alumi-
num? The answer to this question lies in the most limiting property of ceramics—
brittleness. Aluminum and other metals have high ductility, a desirable property
that permits them to undergo relatively severe impact loading without fracture,
whereas aluminum oxide and other ceramics lack this property. Thus, ceramics
are eliminated from many structural applications because they are brittle.
A significant achievement in materials technology is the development
of transparent ceramics, which has made possible new products and substantial
improvements in others (e.g., commercial lighting). To make traditionally opaque
ceramics, such as aluminum oxide (Al2O3), into optically transparent materials
required a fundamental change in manufacturing technology. Commercial ceram-
ics are frequently produced by heating crystalline powders to high temperatures
until a relatively strong and dense product results. Traditional ceramics made in
this way contained a substantial amount of residual porosity (see also the Feature
Box, “Structure Leads to Properties”), corresponding to the open space between
the original powder particles prior to high-temperature processing. A significant
reduction in porosity resulted from a relatively simple invention* that involved
*R. L. Coble, U.S. Patent 3,026,210, March 20, 1962.
M01_SHAC0996_09_GE_C01.indd 22 10/10/2022 19:40

THE MATERIAL WORLD
Structure Leads to Properties
To understand the properties or observable char- and a nearly transparent material with an important
acteristics of engineering materials, it is necessary additional property—excellent resistance to chemi-
to understand their structure. Virtually every major cal attack by high-temperature sodium vapor.
property of the six materials’ categories outlined in The example of translucent ceramics shows a
this chapter will be shown to result directly from typical and important demonstration of how prop-
mechanisms occurring on a small scale (usually erties of engineering materials follow directly from
either the atomic or the microscopic level). structure. Throughout this book, we shall be alert to
The dramatic effect that fine-scale structure the continuous demonstration of this interrelation-
has on large-scale properties is well illustrated by ship for all the materials of importance to engineers.
the development of transparent ceramics, just dis- A contemporary example is given in the images
cussed in the introduction to ceramic materials. The below, a microstructure and the resulting translu-
microscopic-scale residual porosity in a traditional cent disc of hydroxyapatite ceramic developed for
aluminum oxide leads to loss of visible light trans- biomedical applications. By using the Field-Assisted
mission (i.e., a loss in transparency) by providing a Sintering Technique (FAST) as highlighted in the
light-scattering mechanism. Each Al2O3—air inter- Feature Box in Chapter 10, researchers were able to
face at a pore surface is a source of light refraction produce a material with minimal porosity (note the
(change of direction). Only about 0.3% porosity can densely packed nano-scale grain structure in part a)
cause Al2O3 to be translucent (capable of transmit- and the resulting ability to transmit a visual image
ting a diffuse image), and 3% porosity can cause the (part b). The effect of porosity on light transmission is
material to be completely opaque. The elimination discussed further in Chapter 14 (e.g., Figures 14.8 and
of porosity provided by the Lucalox patent (adding 14.9), and the importance of hydroxyapatite in ortho-
0.1 wt % MgO) produced a pore-free microstructure pedic prostheses is discussed further in Chapter 15.
(a) (b)
(Courtesy of T. B. Tran and J. R. Groza, University of California, Davis.)
adding a small amount of impurity (0.1 wt % MgO), which caused the high-tem-
perature densification process for the Al2O3 powder to go to completion. Cylinders
of translucent Al2O3 became the heart of the design of high-temperature (1000°C)
sodium vapor lamps, which provide substantially higher illumination than do con-
ventional lightbulbs (100 lumens/W compared to 15 lumens/W).
M01_SHAC0996_09_GE_C01.indd 23 10/10/2022 19:41

After the invention of transparent aluminum oxide and the result-

ing advancement in lighting technology, ceramic scientists and engineers
have applied a similar approach to a wide range of compositions, includ-
ing the development of ceramics for laser technology, a topic covered
more fully in Chapter 14. A prime example is yttrium-aluminum-oxide
(Y3Al5O12 or YAG), typically with a small amount of neodymium (Nd)
in a solution to provide the lasing property. These Nd:YAG lasers are
used in a wide range of medical and engineering applications, including
manufacturing technologies. It is also important to note that these trans-
parent laser materials are also made by a more traditional technique, viz.
growing large single crystals from a melt as shown in Figure 1.6.
Aluminum oxide is typical of the traditional ceramics, with mag-
nesium oxide (MgO) and silica (SiO2) being other good examples. In
addition, SiO2 is the basis of a large and complex family of silicates,
which includes clays and claylike minerals. Silicon nitride (Si3N4) is an
important nonoxide ceramic used in a variety of structural applications.
The vast majority of commercially important ceramics are chemical
compounds made up of at least one metallic element (see Figure 1.4)
and one of five nonmetallic elements (C, N, O, P, or S). Figure 1.7 illus-
trates the various metals (in light color) and the five key nonmetals (in
dark color) that can be combined to form an enormous range of ceramic
materials. Bear in mind that many commercial ceramics include com-
FIGURE 1.6 An yttrium-aluminum-oxide
pounds and solutions of many more than two elements, just as commer-
(Y3Al5O12 or YAG) crystal grown over
a period of 21 days for use in laser rods. cial metal alloys are composed of many elements.
(James L. Amos / Science Source.)
IA 0
1 2
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
11 12 VIII 13 14 15 16 17 18
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
87 88 89 104 105 106
Fr Ra Ac Rf Db Sg
58 59 60 61 62 63 64 65 66 67 68 69 70 71
90 91 92 93 94 95 96 97 98 99 100 101 102 103
FIGURE 1.7 Periodic table with ceramic compounds indicated by a combination of one or
more metallic elements (in light color) with one or more nonmetallic elements (in dark color).
Note that elements silicon (Si) and germanium (Ge) are included with the metals in this
figure but were not included in the periodic table shown in Figure 1.4. They are included here
because, in elemental form, Si and Ge behave as semiconductors (Figure 1.16). Elemental tin
(Sn) can be either a metal or a semiconductor, depending on its crystalline structure.
M01_SHAC0996_09_GE_C01.indd 24 10/10/2022 19:41

SMARTPHONES AND TABLETS—INTRODUCING GLASSES

The metals and ceramics just introduced have a similar structural feature on the
atomic scale: They are crystalline, which means that their constituent atoms are
stacked together in a regular, repeating pattern. A distinction between metallic-
and ceramic-type materials is that, by fairly simple processing techniques, many
ceramics can be made in a noncrystalline form (i.e., their atoms are stacked in
irregular, random patterns), which is illustrated in Figure 1.8. The general term
for noncrystalline solids with compositions comparable to those of crystal-
line ceramics is glass (Figure 1.9). Most common glasses are silicates; ordinary
(a) (b)
FIGURE 1.8 Schematic comparison of the atomic-scale structure of (a) a ceramic

(crystalline) and (b) a glass (noncrystalline). The yellow circles represent a nonmetallic
atom, and the green circles represent a metal atom.
FIGURE 1.9 Some common silicate glasses for engineering applications. These materials
combine the important qualities of transmitting clear visual images and resisting
chemically aggressive environments. (Courtesy of Corning Glass Works.)
M01_SHAC0996_09_GE_C01.indd 25 10/10/2022 19:41

window glass is approximately 72% silica (SiO2) by weight, with the balance of
the material being primarily sodium oxide (Na2O) and calcium oxide (CaO).
Glasses share the property of brittleness with crystalline ceramics. Glasses are
important engineering materials because of other properties, such as their ability
to transmit visible light (as well as ultraviolet and infrared radiation) and chemi-
cal inertness.
In the decade following the introduction of the Apple iPhone in 2007, the
annual sales of smartphones increased from 122 million to 1.5 billion in 2017.
By 2025, there will be an estimated 6 billion mobile subscribers, roughly 70%
of the earth’s population. The introduction of the Apple iPad in 2010 led to the
similarly expanding role of tablet devices in our daily lives. The cover glass in
these increasingly ubiquitous devices is one of the most common state-of-the-
art glass materials used by the general public. As such device users are painfully
aware, a major criterion for the cover glass, beyond the obvious optical transpar-
ency, is resistance to mechanical damage (scratching and breakage). A practical
technique to provide improved mechanical performance is “chemical strengthen-
ing,” as discussed in Section 6.6 in which the chemical substitution of some rela-
tively large potassium ions for the smaller sodium ions in the silicate glass creates
a compressive surface state that effectively resists such damage. Figure 1.10 shows
some contemporary examples.
NYLON PARACHUTES—INTRODUCING POLYMERS

A major impact of modern engineering technology on everyday life has been
made by the class of materials known as polymers. An alternative name for this
(a) (b)
FIGURE 1.10 (a) The smartphone and tablet have joined the laptop computer as integral
parts of our personal and business lives. (© wavebreakmedia / Shutterstock) (b) Damage-
resistant cover glass is a central component of the design of iPhone 11. (Courtesy of
Apple Inc.)
M01_SHAC0996_09_GE_C01.indd 26 10/10/2022 19:41

category is plastics, which describes the extensive formability of many poly-

mers during fabrication. These synthetic, or human-made, materials represent a
special branch of organic chemistry. Examples of inexpensive, functional poly-
mer products are readily available to each of us (Figure 1.11). The “mer” in a
polymer is a single hydrocarbon molecule such as ethylene (C2H4). Polymers
are long-chain molecules composed of many mers bonded together. The most
common commercial polymer is polyethylene -(C2H4)-n where n can range from
approximately 100 to 1,000. Figure 1.12 shows the relatively limited portion of
the periodic table that is associated with commercial polymers. Many important
polymers, including polyethylene, are simply compounds of hydrogen and car-
bon. Others contain oxygen (e.g., acrylics), nitrogen (nylons), fluorine (fluoro-
plastics), and silicon (silicones).
Nylon is an especially familiar example. Polyhexamethylene adipamide, or
nylon, is a member of the family of synthetic polymers known as polyamides
invented in 1935 at the DuPont Company. Nylon was the first commercially suc-
cessful polymer and was initially used as bristles in toothbrushes (1938) followed
by the highly popular use as an alternative to silk stockings (1940). Developed as
a synthetic alternative to silk, nylon became the focus of an intensive effort dur-
ing the early stages of World War II to replace the diminishing supply of Asian
silk for parachutes and other military supplies. At the beginning of World War II,
the fiber industry was dominated by the natural materials cotton and wool. By
the end, synthetic fibers accounted for 25% of the market share. A contemporary
example of a nylon parachute is shown in Figure 1.13. Today, nylon remains a
FIGURE 1.11 Polymers are the basis of a wide range of common consumer products,
often available for recycling. (PBWPIX / Alamy.)
M01_SHAC0996_09_GE_C01.indd 27 10/10/2022 19:41

IA 0
1 2
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
11 12 VIII 13 14 15 16 17 18
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
87 88 89 104 105 106
Fr Ra Ac Rf Db Sg
58 59 60 61 62 63 64 65 66 67 68 69 70 71
90 91 92 93 94 95 96 97 98 99 100 101 102 103
FIGURE 1.12 Periodic table with the elements associated with commercial polymers
in color.
FIGURE 1.13 Since its development during World War II, nylon fabric remains the most
popular material of choice for parachute designs. (Courtesy of Stringer/Agence France
Presse/Getty Images.)
M01_SHAC0996_09_GE_C01.indd 28 10/10/2022 19:41

popular fiber material, but it is also widely used in solid form for applications
such as gears and bearings.
As the descriptive title implies, plastics commonly share with metals the
desirable mechanical property of ductility. Unlike brittle ceramics, polymers
are frequently lightweight, low-cost alternatives to metals in structural design
applications. The nature of chemical bonding in polymeric materials will be
explored in Chapter 2. Important bonding-related properties include lower
strength compared with metals and lower melting point and higher chemical
reactivity compared with ceramics and glasses. In spite of their limitations,
polymers are highly versatile and useful materials. Substantial progress has
been made in recent decades in the development of engineering polymers with
sufficiently high strength and stiffness to permit substitution for traditional
structural metals.
KEVLAR®-REINFORCED TIRES—INTRODUCING COMPOSITES

The structural engineering materials we have discussed so far—metals, c eramics/
glasses, and polymers—contain various elements and compounds that can be
classified by their chemical bonding. Metals are associated with metallic bond-
ing, ceramics/glasses with ionic bonding, and polymers with covalent bonding.
Such classifications are described further in Chapter 2. Another important set
of materials is made up of some combinations of individual materials from the
previous categories. This fourth group is composites, and an excellent example is
fiberglass. This composite of glass fibers embedded in a polymer matrix is com-
monplace (Figure 1.14). Characteristic of good composites, fiberglass has the best
FIGURE 1.14 Example of a fiberglass composite composed of microscopic-scale

reinforcing glass fibers in a polymer matrix. (Courtesy of Owens-Corning Fiberglas
Corporation.)
M01_SHAC0996_09_GE_C01.indd 29 10/10/2022 19:41

FIGURE 1.15 Kevlar reinforcement is a popular application in modern high-performance

tires. In this case, an automobile is subjected to aquaplaning at a test track. (© Culture-
images GmbH / Alamy.)
properties of each component, producing a product that is superior to either of

the components separately. The high strength of the small-diameter glass fibers is
combined with the ductility of the polymer matrix to produce a strong m aterial
capable of withstanding the normal loading required of a structural material.
There is no need to illustrate a region of the periodic table as characteristic of
composites, since they involve virtually the entire table except for the noble
gases (column 0), equivalent to an overlay of the periodic table coverage for met-
als, ceramics, and polymers combined.
Kevlar fiber reinforcements provide significant advances over traditional
glass fibers for polymer–matrix composites. Kevlar is a DuPont trade name for
poly p-phenyleneterephthalamide (PPD-T), a para-aramid. Substantial progress
has been made in developing new polymer matrices, such as polyetherether-
ketone (PEEK) and polyphenylene sulfide (PPS). These materials have the
advantages of increased toughness and recyclability. Kevlar-reinforced polymers
are used in pressure vessels, and Kevlar reinforcement is widely used in tires
(Figure 1.15). Kevlar was developed in 1965 and has been used commercially
since the early 1970s. It is especially popular for demanding applications given
that its strength-to-weight ratio is five times that of structural steel. The modern
automobile tire is an especially good example.
SILICON CHIPS—INTRODUCING SEMICONDUCTORS

Although polymers are highly visible engineering materials that have had a major
impact on contemporary society, semiconductors are relatively invisible but have
M01_SHAC0996_09_GE_C01.indd 30 10/10/2022 19:41

had a comparable social impact. Technology has clearly revolutionized society,

but solid-state electronics has revolutionized technology itself. A relatively small
group of elements and compounds has an important electrical property, semicon-
duction, in which they are neither good electrical conductors nor good electri-
cal insulators. Instead, their ability to conduct electricity is intermediate. These
materials are called semiconductors, and in general they do not fit into any of
the structural materials categories based on atomic bonding. As discussed earlier,
metals are inherently good electrical conductors. Ceramics and polymers (non-
metals) are generally poor conductors, but good insulators. An important section
of the periodic table is shown in dark color in Figure 1.16. These three semicon-
ducting elements (Si, Ge, and Sn) from column IV A serve as a kind of boundary
between metallic and nonmetallic elements. Silicon (Si) and germanium (Ge),
widely used elemental semiconductors, are excellent examples of this class of
materials. Precise control of chemical purity allows precise control of electronic
properties. As techniques have been developed to produce variations in chemical
purity over small regions, sophisticated electronic circuitry has been produced
in exceptionally small areas (Figure 1.17). Such microcircuitry is the basis of the
current revolution in technology.
The elements shaded in light color in Figure 1.16 form compounds that are
semiconducting. Examples include gallium arsenide (GaAs), which is used as
a high-temperature rectifier and a laser material, and cadmium sulfide (CdS),
which is used as a relatively low-cost solar cell for conversion of solar energy to
useful electrical energy. The various compounds formed by these elements show
similarities to many of the ceramic compounds.
IA 0
1 2
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
11 12 VIII 13 14 15 16 17 18
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
87 88 89 104 105 106
Fr Ra Ac Rf Db Sg
58 59 60 61 62 63 64 65 66 67 68 69 70 71
90 91 92 93 94 95 96 97 98 99 100 101 102 103
FIGURE 1.16 Periodic table with the elemental semiconductors in dark color and
those elements that form semiconducting compounds in light color. The semiconducting
compounds are composed of pairs of elements from columns III and V (e.g., GaAs) or
from columns II and VI (e.g., CdS).
M01_SHAC0996_09_GE_C01.indd 31 10/10/2022 19:41

(a) (b)
FIGURE 1.17 (a) Typical microcircuit containing a complex array of semiconducting

regions. (Michael W. Davidson / Science Source.) (b) State-of-the-art microcircuitry has
gone beyond the micro-scale into the nano-scale, as shown by this cross section of an
“8 nm generation” device. The 8 nm “gates” are at the top of the pointed silicon fins, seen
here in cross-section. (Micrograph courtesy of TechInsights.)
1.4 Processing and Selecting Materials

Our use of materials in modern technology ultimately depends on our ability to
make those materials. In Chapters 11 through 13, we will discuss how each of the
six types of materials is produced. The topic of materials processing serves two
functions. First, it provides a fuller understanding of the nature of each type of
material. Second, and more importantly, it provides an appreciation of the effects
of processing history on properties.
We shall find that processing technology ranges from traditional methods
such as metal casting to the most contemporary techniques of electronic micro-
circuit fabrication (Figure 1.18). In Section 1.3, we answered the question, “What
materials are available to me?” We must next face a new and obvious question:
“Which material do I now select for a particular application?” Materials selection
is the final practical decision in the engineering design process and can deter-
mine that design’s ultimate success or failure. Figure 1.19 illustrates a simple and
popular visual summary of the overall nature of the field of materials science and
engineering—the materials tetrahedron. While the concept of “structure leads to
FIGURE 1.18 The modern integrated circuit

fabrication laboratory represents the state of
the art in materials processing. (Courtesy of the
College of Engineering, University of California,
Davis.)
M01_SHAC0996_09_GE_C01.indd 32 10/10/2022 19:42

SECTION 1.5 Looking at Materials by Powers of Ten 33
Properties
Performance
Processing
Structure
FIGURE 1.19 The materials tetrahedron represents the fundamental relationship between
“structure” and “properties” introduced in the Feature Box in this chapter as well as
how “processing” technologies affect the properties and how the “performance” of an
engineering design ultimately follows from those relationships.
properties,” introduced in the Feature Box in this chapter, is a fundamental con-

cept, “structure” and “properties” are only two of the corners of this tetrahedron.
As just discussed, “processing” technologies can also have a profound effect on
the properties of the material. Finally, “performance” indicates that the appropri-
ate selection of a material contributes to a successful engineering design.
1.5 Looking at Materials by Powers of Ten

In this chapter, we have seen that an underlying principle in materials science and
engineering is that “structure leads to properties,” that is, we explain the behav-
ior of the materials that we use in engineering designs (on the human scale) by
looking at mechanisms that involve the structure of the materials on some fine
scale. This important concept is reminiscent of the delightful short documentary
film Powers of Ten produced by the designers Charles and Ray Eames in 1977
and narrated by the physicist Philip Morrison. That film popularized the concept
that human experience occurs several orders of magnitude below the scale of the
This icon will appear throughout universe and several orders of magnitude above the scale of the atom. For more
the book to highlight discussions details, see: https://www.eamesoffice.com/the-work/powers-of-ten/.
involving the relationship between Throughout the next several chapters, we will see many examples of the
fine-scale structure and material
properties.
relationship of materials properties on the human scale to fine-scale structural
mechanisms. Some mechanisms involve the structure of the materials at the
atomic scale (such as point defects explaining diffusion in Chapter 5), the micro-
scopic scale (such as dislocations explaining plastic deformation in Chapter 6),
or the millimeter scale (such as structural flaws that cause catastrophic failures
as discussed in Chapter 8). For the past two decades, the significance of the
nanoscale has become widely emphasized. For example, the continuing miniatur-
ization of electronic circuits from the microscale to the nanoscale as illustrated in
M01_SHAC0996_09_GE_C01.indd 33 10/10/2022 19:42

Figure 1.17 is making possible faster, smaller, and more portable electronic sys-
tems. So, the appropriate range of “powers of ten” that we discuss in the book is
the human scale: 1 meter

the milliscale: 1 * 10-3 meter
the microscale: 1 * 10-6 meter
the nanoscale: 1 * 10-9 meter
the atomic scale: 1 * 10-10 meter.
The milli-, micro-, and nanoscales follow the SI unit system. The human
scale and atomic scale are practical end points above and below the three SI
scales. It is interesting to note that a typical atomic bond length (about 2 * 10-10
meter) is a full ten orders of magnitude smaller than the height of an average
person (about 2 meters).
Summary
The wide range of materials available to engineers of transparent ceramics has required careful control
can be divided into six categories: metals, ceramics, of a microscopic-scale architecture. Once the prop-
glasses, polymers, composites, and semiconductors. erties of materials are understood, the appropriate
The first four categories can be associated with three material for a given application can be processed and
distinct types of atomic bonding. Composites involve selected. We now move on to the body of the text,
combinations of two or more materials from the previ- with the term materials science and engineering serv-
ous four categories. The first five categories comprise ing to define this branch of engineering. This term
the structural materials. Semiconductors comprise a also provides the key words that describe the various
separate category of electronic materials that is distin- parts of the text: science S the fundamentals covered
guished by its unique, intermediate electrical conduc- in Chapters 2 through 10, materials S the structural
tivity. Understanding the human-scale properties of and electronic, optical, and magnetic materials of
these various materials requires examination of struc- Chapters 11 through 14, and engineering S materials
ture at some fine scale. For example, the development in engineering design as discussed in Chapter 15.
Key Terms
Many technical journals now include a set of key terms with each article. These words serve the practical purpose of infor-
mation retrieval but also provide a convenient summary of important concepts in that publication. In this spirit, a list of key
terms will be given at the end of each chapter. Students can use this list as a convenient guide to the major concepts that they
should be learning from that chapter. A comprehensive glossary provided in Appendix 6 gives definitions of the key terms
from all chapters.
alloy (18) Iron Age (18) polyethylene (27)

brittle (19) Kevlar (30) polymer (26)
Bronze Age (18) materials selection (32) polymer–matrix composite (30)
ceramic (21) metallic (19) processing (32)
composite (29) microcircuitry (31) refractory (22)
crystalline (25) noncrystalline (25) semiconductor (31)
ductility (19) nonmetallic (24) silica (24)
fiberglass (29) nylon (27) silicate (24)
glass (25) plastic (27) Stone Age (17)
M01_SHAC0996_09_GE_C01.indd 34 10/10/2022 19:42

CHAPTER 1 References 35
References
At the end of each chapter, a short list of selected references Callister, W.D. and D.G. Rethwisch, Materials Science and
will be cited to indicate some primary sources of related Engineering—An Introduction, 10th ed., John Wiley &
information for the student who wishes to do outside read- Sons, Inc., Hoboken, NJ, 2018.
ing. For Chapter 1, the references are some of the general Smith, W. and J. Hashimi, Foundations of Materials Science
textbooks in the field of materials science and engineering. and Engineering, 6th ed., McGraw-Hill Higher Education,
Askeland, D.R. and W.J. Wright, The Science and Boston, MA, 2019.
Engineering of Materials, 7th ed., Cengage, Independence,
KY, 2016.
M01_SHAC0996_09_GE_C01.indd 35 10/10/2022 19:42

M01_SHAC0996_09_GE_C01.indd 36 10/10/2022 19:42

PART I
The Fundamentals
CHAPTER 2 Atomic Bonding
CHAPTER 3 Crystalline Structure—Perfection
CHAPTER 4 Crystal Defects and Noncrystalline
Structure—Imperfection
CHAPTER 5 Diffusion
CHAPTER 6 Mechanical Behavior
CHAPTER 7 Thermal Behavior
CHAPTER 8 Failure Analysis and Prevention
CHAPTER 9 Phase Diagrams—Equilibrium
Microstructural Development
CHAPTER 10 Kinetics—Heat Treatment
M02_SHAC0996_09_GE_C02.indd 37 10/10/2022 19:54

W e begin our exploration of the field of
materials science and engineering by focus-
ing on materials science. Chapters 2 through
10 cover a variety of fundamental topics from
physics and chemistry. A student may well have
encountered many of the concepts in Chapter 2
(atomic bonding) in previous courses. Of spe-
cial interest to the field of materials science is
A central principle of materials
science is that the properties
the role of atomic bonding in providing a clas-
of materials that permit their sification scheme for materials. Metallic, ionic, and covalent bonding roughly
engineering applications can be correspond to the categories of structural materials: metals, ceramics/glasses,
understood by examining the and polymers. Semiconductors, an important category of electronic materials,
structure of those materials on generally correspond to covalent bonding. Chapter 3 introduces the crystalline
a small scale. The instrument
shown above is a scanning
structures of many engineered materials and includes an introduction to x-ray
electron microscope that can diffraction, an important tool for determining crystal structure. Chapter 4 identi-
provide higher magnifications fies various imperfections that can occur relative to the crystalline structures of
with a greater depth of field than Chapter 3. In Chapter 5, we see that some of these structural defects play a cen-
possible with traditional optical tral role in solid-state diffusion, and, in Chapter 6, we find that other defects are
microscopes. Shown on the facing
page is a micrograph produced
responsible for some of the mechanical behavior of materials. Chapter 7 intro-
using such an instrument. The duces the thermal behavior of materials, and, in Chapter 8, we see that certain
image shows particles trapped on mechanical and thermal processes (such as machining and welding) can lead to
the fibers of an air filter recovered the failure of materials. In Chapter 9, we are introduced to phase diagrams that
from near the World Trade serve as useful tools for predicting the microscopic-scale structures of materials
Center attack of September 11,
2001. Such analyses were used to
that are produced at a relatively slow rate, maintaining equilibrium along the
determine the nature of particulate way. In Chapter 10 on kinetics, we see the effect of more rapid heat treatments
air pollution in the vicinity of the that lead to additional microstructures. Throughout Part I, we will find that fun-
attack and its potential effect on damental principles from physics and chemistry underlie the practical behavior
human health. (Courtesy of the of engineered materials.
Department of Materials Science
and Engineering University of
California, Davis.)
38
M02_SHAC0996_09_GE_C02.indd 38 10/10/2022 19:54

CHAPTER 2
Atomic Bonding
LEARNING OBJECTIVES
After studying this chapter, you should be
able to:
1. (a) Identify the basic structural
components of an atom and
understand the related terminology,
such as amu, energy levels, and
energy orbitals.
(b) Sketch the bonding force and
bonding energy curves and
understand the relationship
between the two curves.
(c) Explain the relationship between
atomic structure and the periodic
table of the elements.
Computer models of the structures of materials on the atomic scale 2. (a) Describe the nature of the ionic
require accurate knowledge of the bonding between adjacent atoms. bond between a cation and an
In this model of a molecule that plays an important role in organic
photovoltaic materials, atoms are shown as spheres joined by anion, including the calculation of
covalent bonds. (Courtesy of Roland Faller, Adam Moule, and Varuni bonding force and bond length.
Dantanarayana, University of California, Davis.)
(b) Calculate the coordination number
and radius ratio for anions
surrounding cations.
3. Describe the nature of the highly directional covalent bond and
its role in forming polymeric molecules.
4. Describe the nature of the nondirectional electron sharing in
the metallic bond that gives metals their characteristically high
electrical conductivity.
5. Describe the nature of secondary, or van der Waals bonding, and
its distinction from primary bonding.
6. Relate the role of the various types of atomic bonding to the
categories of engineering materials.
C hapter 1 introduced the basic types of materials available to engineers. One

basis of that classification system is found in the nature of atomic bonding in
materials. Atomic bonding falls into two general categories. Primary bonding
39
M02_SHAC0996_09_GE_C02.indd 39 10/10/2022 19:54

40 CHAPTER 2 Atomic Bonding
involves the transfer or sharing of electrons and produces a relatively strong join-
ing of adjacent atoms. Ionic, covalent, and metallic bonds are in this category.
Secondary bonding involves a relatively weak attraction between atoms in which
no electron transfer or sharing occurs. Van der Waals bonds are in this category.
Each of the five fundamental types of engineering materials (metals, ceramics,
glasses, polymers, and semiconductors) is associated with a certain type (or types)
of atomic bonding. Composites, of course, are combinations of fundamental
types.
2.1 Atomic Structure

In order to understand bonding between atoms, we must appreciate the structure
within the individual atoms. For this purpose, it is sufficient to use a relatively
simple planetary model of atomic structure—that is, electrons (the planets) orbit
about a nucleus (the sun).
It is not necessary to consider the detailed structure of the nucleus for
Outer orbital which physicists have catalogued a vast number of elementary particles. We need
(with four sp3 hybrid
bonding electrons)
to consider only the number of protons and neutrons in the nucleus as the basis
of the chemical identification of a given atom. Figure 2.1 is a planetary model of
a carbon atom. This illustration is schematic and definitely not to scale. In reality,
the nucleus is much smaller, even though it contains nearly all the mass of the
atom. Each proton and neutron has a mass of approximately 1.66 * 10-24 g. This
value is referred to as an atomic mass unit (amu). It is convenient to express the
mass of elemental materials in these units. For instance, the most common iso-
tope of carbon, 12C (shown in Figure 2.1), contains in its nucleus six protons and
six neutrons, for an atomic mass of 12 amu. It is also convenient to note that there
are 0.6023 * 1024 amu per gram. This large value, known as Avogadro’s* n umber,
Inner orbital Nucleus (with represents the number of protons or neutrons necessary to produce a mass of 1 g.
(with two 1s six protons and Avogadro’s number of atoms of a given element is termed a gram-atom. For a
electrons) six neutrons) compound, the corresponding term is mole; that is, one mole of NaCl contains
Avogadro’s number of Na atoms and Avogadro’s number of Cl atoms.
FIGURE 2.1 Schematic of
the planetary model of a 12C Avogadro’s number of 12C atoms would have a mass of 12.00 g. Naturally
atom. occurring carbon actually has an atomic mass of 12.011 amu because not all
carbon atoms contain six neutrons in their nuclei. Instead, some contain seven.
Different numbers of neutrons (six or seven) identify different isotopes—
various forms of an element that differ in the number of neutrons in the nucleus.
In nature, 1.1% of the carbon atoms are the isotope 13C. However, the nuclei
of all carbon atoms contain six protons. In general, the number of protons in
the nucleus is known as the atomic number of the element. The well-known
*Amadeo Avogadro (1776–1856), Italian physicist, who, among other contributions, coined the word
molecule. Unfortunately, his hypothesis that all gases (at a given temperature and pressure) contain
the same number of molecules per unit volume was not generally acknowledged as correct until after
his death.
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SECTION 2.1 Atomic Structure 41
IA 0
1 2
H He
1.008 II A III A IV A VA VI A VII A 4.003
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
6.941 9.012 10.81 12.01 14.01 16.00 19.00 20.18
11 12 VIII 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
22.99 24.31 III B IV B VB VI B VII B IB II B 26.98 28.09 30.97 32.06 35.45 39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
39.10 40.08 44.96 47.90 50.94 52.00 54.94 55.85 58.93 58.71 63.55 65.38 69.72 72.59 74.92 78.96 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
85.47 87.62 88.91 91.22 92.91 95.94 98.91 101.07 102.91 106.4 107.87 112.4 114.82 118.69 121.75 127.60 126.90 131.30
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
132.91 137.33 138.91 178.49 180.95 183.85 186.2 190.2 192.22 195.09 196.97 200.59 204.37 207.2 208.98 (210) (210) (222)
87 88 89 104 105 106
Fr Ra Ac Rf Db Sg
(223) 226.03 (227) (261) (262) (266)
58 59 60 61 62 63 64 65 66 67 68 69 70 71
140.12 140.91 144.24 (145) 150.4 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.04 174.97
90 91 92 93 94 95 96 97 98 99 100 101 102 103
232.04 231.04 238.03 237.05 (244) (243) (247) (247) (251) (254) (257) (258) (259) (260)
FIGURE 2.2 Periodic table of the elements indicating atomic number and atomic mass
(in amu).
periodicity of chemical elements is based on this system of elemental atomic

numbers and atomic masses arranged in chemically similar groups (vertical col-
umns) in a periodic table (Figure 2.2).
While chemical identification is done relative to the nucleus, atomic
bonding involves electrons and electron orbitals. The electron, with a mass of
0.911 * 10-27 g, makes a negligible contribution to the atomic mass of an ele-
ment. However, this particle has a negative charge of 0.16 * 10-18 coulomb (C),
equal in magnitude to the +0.16 * 10-18 C charge of each proton. (The neutron
is, of course, electrically neutral.)
Electrons are excellent examples of the wave-particle duality; that is, they
are atomic-scale entities exhibiting both wavelike and particlelike behavior. It is
beyond the scope of this book to deal with the principles of quantum mechan-
ics that define the nature of electron orbitals (based on the wavelike charac-
ter of electrons). However, a brief summary of the nature of electron orbitals
is helpful. As shown schematically in Figure 2.1, electrons are grouped at fixed
orbital positions about a nucleus. In addition, each orbital radius is characterized
by an energy level, a fixed binding energy between the electron and its nucleus.
Figure 2.3 shows an energy level diagram for the electrons in a 12C atom. It is
important to note that the electrons around a 12C nucleus occupy these specific
energy levels, with intermediate energies forbidden. The forbidden energies
correspond to unacceptable quantum mechanical conditions; that is, standing
waves cannot be formed.
M02_SHAC0996_09_GE_C02.indd 41 10/10/2022 19:55

0
2 (sp3)
- 6.5
Energy (eV)
-283.9 1s
In Section 13.2, we shall see that

energy level diagrams like this
FIGURE 2.3 Energy-level diagram for the orbital electrons in a 12C atom. Notice the
are central to the understanding sign convention. An attractive energy is negative. The 1s electrons are closer to the
of energy band gap structures nucleus (see Figure 2.1) and more strongly bound 1binding energy = -283.9 eV2. The
that are, in turn, at the heart of outer orbital electrons have a binding energy of only -6.5 eV. The zero level of binding
semiconductor technology. energy corresponds to an electron completely removed from the attractive potential of
the nucleus.
A detailed list of electronic configurations for the elements of the periodic

table is given in Appendix 1, together with various useful data. The arrangement
of the periodic table (Figure 2.2) is largely a manifestation of the systematic “fill-
ing” of the electron orbitals with electrons, as summarized in Appendix 1. The
notation for labeling electron orbitals is derived from the quantum numbers of
wave mechanics. These integers relate to solutions to the appropriate wave equa-
tions. We do not deal with this numbering system in detail in this book; instead,
it is sufficient to appreciate the basic labeling system. For instance, Appendix 1
tells us that there are two electrons in the 1s orbital. The 1 is a principal quan-
tum number, identifying this energy level as the first one which is closest to the
atomic nucleus. There are also two electrons each associated with the 2s and 2p
orbitals. The s, p, and so on, notation refers to an additional set of quantum num-
bers. The rather cumbersome letter notation is derived from the terminology of
early spectrographers. The six electrons in the 12C atom are then described as a
1s22s22p2 distribution; that is, two electrons in the 1s orbital, two in 2s, and two in
2p. In fact, the four electrons in the outer orbital of 12C redistribute themselves
in a more symmetrical fashion to produce the characteristic geometry of bond-
ing between carbon atoms and adjacent atoms (generally described as 1s22s12p3).
This sp3 configuration in the second energy level of carbon, called hybridization,
is indicated in Figures 2.1 and 2.3 and is discussed in further detail in Section 2.3.
(Note especially Figure 2.19.)
The bonding of adjacent atoms is essentially an electronic process. Strong
primary bonds are formed when outer orbital electrons are transferred or shared
between atoms. Weaker secondary bonds result from a more subtle attraction
between positive and negative charges with no actual transfer or sharing of elec-
trons. In the next section, we will look at the various possibilities of bonding in a
systematic way, beginning with the ionic bond.
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SECTION 2.1 Atomic Structure 43
THE MATERIAL WORLD
Naming a New Chemical Element
The periodic table is generally one of the first record of this important information sometimes
items to which we are introduced as we begin to overshadows the fact that, at some point in time,
seriously explore modern science. This systematic each element had to be given a name. Some names,
arrangement of the chemical elements is, of course, such as iron, simply have evolved from earlier lan-
useful for providing a visual understanding of the guages (the Old High German isarn that led to the
similarities and differences of the various chemical Old English iren, with the chemical symbol Fe com-
elements. The periodic table’s role as a permanent ing from the Latin ferrum).
IA 0
1 2
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
11 12 VIII 13 14 15 16 17 18
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
87 88 89 104 105
Fr Ra Ac Rf Db
106
Sg
58 59 60 61 62 63 64 65 66 67 68 69 70 71
90 91 92 93 94 95 96 97 98 99 100 101 102 103
As some elements were discovered, they were transuranic elements was Dr. Glenn Seaborg (1913–
given names in honor of the country in which they 1999), Professor of Chemistry at the University
were discovered or synthesized (e.g., germanium of California, Berkeley. (It was Seaborg’s idea to
for Germany). The advances in physics and chem- reconfigure Mendeleev’s original periodic table by
istry in the 20th century made possible the synthe- breaking out the actinide series below the main
sis of new elements that are not found in nature table.) Seaborg and his team discovered plutonium
and that have atomic numbers greater than that and nine other transuranic elements, including ele-
of uranium (92). These transuranic elements were ment 106, which was named seaborgium after him.
often named in honor of great scientists of the past Professor Seaborg received the singular honor
(e.g., mendelevium for Dmitri Mendeleev, the 19th- of being the first person ever to have an element
century Russian chemist who devised the periodic named after him while he was still alive. He right-
table). The leading authority in synthesizing the fully viewed this honor as much greater than his
(Continued)
M02_SHAC0996_09_GE_C02.indd 43 10/10/2022 19:55

Nobel Prize in Chemistry awarded in 1951. While

seaborgium has been synthesized only in min-
ute amounts and may not play a significant role
in materials science and engineering, its name-
sake, Professor Seaborg, was a great advocate of
the field. His enthusiasm for materials came in
no small measure from his long term of service
as Chair of the Atomic Energy Commission (the
predecessor of today’s Department of Energy).
He was quoted in the January 1980 issue of ASM
News as saying that “materials science and engi-
neering will be essential for the solution of the
problems attendant with the energy sources of the
future.” Professor Seaborg’s vision is as true today (© The Regents of the University of California,
as it was more than four decades ago. Lawrence Berkeley National Laboratory)
EXAMPLE 2.1
Chemical analysis in materials science laboratories is frequently done by means
of the scanning electron microscope. In this instrument, an electron beam gen-
erates characteristic x-rays that can be used to identify chemical elements. This
instrument samples a roughly cylindrical volume at the surface of a solid mate-
rial. Calculate the number of atoms sampled in a 1@mm-diameter by 1@mm-deep
cylinder in the surface of solid copper.
SOLUTION
From Appendix 1,
density of copper = 8.93 g/cm3

and
atomic mass of copper = 63.55 amu.
The atomic mass indicates that there are

63.55 g Cu .
Avogadros number of Cu atoms
The volume sampled is

1 mm 2
Vsample = a b * 1 mm
2
1 cm 3
= 0.785 mm3 * a b
104mm
= 0.785 * 10-12 cm3.
M02_SHAC0996_09_GE_C02.indd 44 10/10/2022 19:55

Another random document with
no related content on Scribd:
PART FIFTH.
ESTIMATION OF GASES HELD IN SOILS.
276. Relation of Soil Composition to Gases.—The power of a

soil for occluding gases rests primarily on its composition as
determined by silt analysis. The discussion of this part of the subject is
so nearly related to that of the physical properties of the soil that it
might properly have been included in that part of the work. Since,
however, we deal in this part more with the determination of the gas
constituents of the soil, it was deemed preferable to place it after the
silt analysis and as introductory to the general estimation by more
strictly analytical processes of the chemical constituents of the soil.
277. Occurrence of Carbon Dioxid.—The amount of organic
matter in the soil, according to Wollny,[179] is no indication of the
quantity of carbon dioxid when the organic matter is in excess. The
percentage of carbon dioxid is only proportional to the amount of
organic matter when this is in small quantities. Large quantities of
organic matter do increase the amount of carbon dioxid, but the
increase is not a proportional one, since a larger quantity of this gas in
the air of a soil reduces the activity of the organisms which produce
oxidation. Water and temperature have a greater influence on the
oxidation, and act in an opposite direction to that of the organic
matter. The amount of free gas in the soil affords no indication either
of the intensity of the action of oxidation or of the amount of organic
matter.
The addition of liquid manure to the soil results in a reduction of the
decomposition of the organic matter when the quantity of the salts
therein contained is greater than that already present in the soil. But if
the liquid manure is dilute, and the absorptive power of the soil for
salts is great, then the decomposition is promoted.
278. Absorption of Aqueous Vapor.—The power of a soil to
resist drought depends largely upon its coefficient of absorption for
aqueous vapor. Hilgard has shown[180] that at temperatures between 7°
and 21°, the amount of aqueous vapor absorbed by a thin layer of a
clay or soil not unusually rich in humus, in a saturated atmosphere, is
sensibly constant. In general, clay soils are more absorbent than sandy
ones, yet there is no direct connection between the amount of clay
present and the absorbent power of the soil. Evidently the hygroscopic
coefficient is largely controlled by the presence with the clay of the
powdery ingredients which determine its looseness of texture, and it is
found that the finer silts themselves possess a considerable absorbing
power. According to Whitney this is largely dependent upon the extent
of the surface area of the soil grains and upon the size and
arrangement of these grains. Again, the presence of hydrated ferric
oxid materially influences this power, so that the amount of iron
present must always be taken into consideration.
279. Methods of Study.—The study of the deportment of a soil
with vapors or gases may be divided into two general classes. The first
depends on the subjection of a sample of soil to the saturating
influence of a given vapor or gas and measuring the amount thereof
absorbed, either directly by increase of weight, or by the diminution in
the amount of gas originally supplied. The maximum absorbent
capacity of a soil under given conditions for a gas or vapor is in this
way determined.
In the second class the determination consists in accurately
estimating the amount of gas which is absorbed by a soil in natural
conditions or in situ, thus giving the natural percentages of the
gaseous constituents of the soil.
In the first case in general, the principle of the method depends
upon the exposure of the soil for a given time under given conditions,
to an atmosphere of the gas to be absorbed. The principle of the
second class of determinations depends upon the extraction, usually
by means of suction, from a given mass of soil of the gaseous matters
therein contained. The general details of the methods of procedure for
the first class are found in the following directions for manipulation:
280. Determination of the Maximum Hygroscopic
Coefficient.—The fine earth, in Hilgard’s method, is exposed to an
atmosphere saturated with moisture for about twelve hours at the
ordinary temperature (60° F.) of the cellar in which the box should be
kept. The soil is sifted in a layer of about one millimeter thickness
upon glazed paper, on a wooden table, and placed in a small water-
tight covered box, twelve by nine by eight inches, in which there is
about an inch of water; the interior sides and cover of the box should
be lined with blotting paper, kept saturated with water, to insure the
saturation of the air.
Air-dried soil yields results varying from day to day to the extent of
as much as thirty to fifty per cent, nor have we any corrective formula
that would reduce such observations to absolute measure. Knop’s law,
that the absorption varies directly as the temperature, while applicable
to low percentages of saturation, is wide of the truth when saturation is
approached. The ordinary temperature of cellars will serve well in
these determinations without material correction.
After eight to twelve hours the earth is transferred as quickly as
possible, in the cellar, to a weighed drying tube and weighed. The tube
is then placed in a paraffin bath; the temperature gradually raised to
200° C. and kept there twenty to thirty minutes, a current of dry air
passing continually through the tube. It is then weighed again and the
loss in weight gives the hygroscopic moisture in saturated air.
The reason for adopting 200° C. as the temperature for drying
instead of 100° is that water will continue to come off from most soils
at the latter temperature for an indefinite time, a week or more, before
an approach to constancy of weight is attained; and that up to 200°
only an arbitrary limit can be assigned for the expulsion of hygroscopic
moisture. Moreover, the great majority of soils, especially those poor
in humus, will reabsorb moisture from a saturated atmosphere to the
full extent of that driven off at 200° C.
281. Estimation of the Absorption Power of Soils for
Aqueous Vapors.[181]—Method A.—The fine earth, ten to twenty
grams, is spread out on a surface of about twenty-five square
centimeters, and left for several days with the observation of the
temperature of the air and the loss of weight determined from time to
time. This evaporation is continued until the weight remains
practically constant. Afterwards by drying the sample at 100° the
amount of hygroscopic moisture is determined. A similar result can be
reached if the sample is first dried at 100°, or over sulfuric acid at
ordinary temperatures, and then the increase in weight observed
which the sample acquires on being exposed for several days to the
atmosphere under ordinary conditions. Soils with about the same
content of humus show variations in the power to absorb aqueous
vapors which are almost proportional to the amount of clay which they
contain. With the increase of humus substance, the power of the soil
for absorbing moisture is increased, so that a sandy soil which is rich
in humus often will retain as much moisture in an air-dried state as a
clay soil which is poor in humus. If the experiment is carried on by
drying over sulfuric acid instead of at 100°, the sample should be left
from four to seven days in order that a constant weight may be
reached. Even after this time the loss in weight is 0.2 to 1.5 per cent
less than when the sample is dried at 100°.
Method B.—In order to determine the amount of aqueous vapor
which a soil will absorb in an atmosphere saturated with the vapor the
following method is used:
The sample of air-dried soil in a flat dish of given surface; viz., about
twenty grams of soil to twenty-five square centimeters surface is
placed in a vessel over water without contact with the water, and the
whole of the apparatus is covered with a glass bell-jar. The sample is
weighed at intervals of six or eight hours until no appreciable increase
of weight is observed. An empty vessel of the same size and character
as that containing the soil is kept under the bell-jar, also in the same
conditions, so that any increase in weight by the deposition of
moisture on this vessel may be determined. This increase in weight is
to be deducted from the total increase in weight of the vessel and the
soil. Sandy and loamy soils become saturated in this manner in the
course of the first twenty-four hours and remain after that unchanged
in weight. Very clayey soils, and also those which are very rich in
humus, require a much longer time, three or four days even. In this
case it is better to take a smaller sample of the soil; viz., ten grams. The
temperature of the air within the glass vessel, of course, must be taken
into consideration.
Method C.—The same flat dish and the same quantity of soil as in
the other methods are taken in this one. The sample is left out over
night where it can be fully saturated with dew. The amount of dew
which appears on the bushes should be noted and also the temperature
of the air and the percentage of clouds in the sky. An experiment
should also be made on spots of earth which are entirely free from
vegetation in order that the difference in the amount of water
absorbed in places practically devoid of dew and in places where the
dew is abundant may be observed.
Method D.—Deeper flat dishes should be used for this determination
so that the depth of soil contained in them shall be from one to three,
or even six centimeters. The sample of soil should be completely air-
dried and in a state of fine subdivision. The vessels containing the soil
should be placed in a locality saturated with aqueous vapor or in the
open air during the night where they are subjected to the influence of
the cooling of the atmosphere and the deposition of dew. Note should
be made of the different amounts of moisture absorbed by the layers of
earth of different thicknesses in a given time. Observation should also
be made of the depth to which the moisture sinks in the sample of soil
under consideration.
282. Estimation of the Absorption Power of the Soil for
Oxygen and Atmospheric Air.[182]—From fifty to one hundred
grams of air-dried soil are placed in a glass vessel of about 500 cubic
centimeters capacity, and the flask closed with a stopper after the
addition of enough water to make the percentage of moisture in the
soil about twenty. After from eight to fourteen days the air contained
in the vessel is analyzed for oxygen, nitrogen, and carbon dioxid, with
special reference to the determination of how much oxygen has
disappeared and how much the carbon dioxid has been increased. As
an alternative method, twenty-five grams of the soil may be moistened
with tolerably concentrated potash lye in a small glass vessel, which is
itself joined with air-tight connections to an azotometer in which a
known volume of air is confined by quicksilver. The glass vessel is
frequently shaken during the progress of the experiment. The
diminution of the volume of air in the apparatus after from one to four
days gives approximately the quantity of oxygen absorbed.
283. General Method of Determining Absorption.—This
method, due to Freiherrn von Dobeneck,[183] is as follows: The soil, in a
state of fine powder, is dried at 100° to 105° to a constant weight. It is
then placed in an absorption tube of the following construction:
The absorption tube consists of a ᥩ shaped wide glass tube, both
ends of which are supplied with small glass tubes sealed upon the end
of the ᥩ tube, and those are furnished with tightly-ground glass stop-
cocks. Above these stop-cocks these small tubes are bent in opposite
directions at right angles. On the bend of the ᥩ is sealed another tube
which is furnished with a ground glass stopper. Through this opening
the ᥩ tube can be filled with the sample of soil. When the tube is filled,
the glass stopper inserted, and the two stop-cocks on the small tubes
closed, the contents of the tube are completely excluded from the
external atmosphere. Many of these tubes can be used at once so as to
hasten the progress of the work.
The tubes after being filled are placed in a drying oven with the stop-
cocks open. The stop-cocks are then closed before the tubes are
removed, when they are placed in a desiccator for cooling preparatory
to weighing. The weighed tubes are held in a tin box which can be
placed in a water-bath which is kept at a given temperature by means
of a thermostat. The top of the tin box should be hinged and made of a
thick non-conducting material so as to prevent any rapid change of
temperature within. On the inner side of the box a small thin-walled
glass tube is carried around four times. One end of this tube passes
through an opening in the side of the box by means of which it can be
connected with the gas apparatus outside. The other end of it is
connected directly with the absorption tubes.
The absorption tubes are so connected among themselves that when
ammonia or carbon dioxid is employed the gas passes through one of
the tubes before it can reach the next, and so on. For experiments with
water-gas, however, that is, air charged with aqueous vapor, the
arrangement must be different. While in the case of ammonia and
carbon dioxid the composition of the gas is not changed by passing
through the samples of soil, the case is quite different when air
charged with aqueous vapor passes through. In the latter case the
amount of aqueous vapor in the air would be notably lessened in
passing from sample to sample on account of the retention of a part of
the aqueous vapor by the soil. In this case, therefore, the saturated air,
after it has passed through the glass tube around the inside of the box
in order to reach the proper temperature, is conducted into a
receptacle of glass which has a number of connections equal to the
number of absorption tubes so that the saturated air can pass directly
into each one of them.
The gases which are to be used for the experiments are prepared in
proper apparatus and are forced through the samples of soil, either by
pressure as in the case of ammonia or carbon dioxid, or by means of
aspirators as in the case of air saturated with aqueous vapor.
The carbon dioxid employed is purified by passing over sodium
carbonate and calcium chlorid.
The ammonia is prepared by the action of finely powdered lime on
ammonium chlorid, and is dried by passing over lime and sticks of
potassium hydroxid.
The air which is to be saturated with aqueous vapor, in order to
purify it from dust, carbon dioxid, and ammonia, is passed through
two flasks in which are contained respectively, diluted sulfuric acid
and potash lye. It is afterwards thoroughly saturated with aqueous
vapor at the temperature desired.
Various kinds of soil material may be employed as follows:
(1) Pure quartz sand.—Freed from all fine particles by subjection to
silt analysis, afterwards boiled with hydrochloric acid and washed with
water to free it from all clayey materials. The sand prepared in this way
should be passed through different sieves in order to prepare it in
different states of fineness.
(2) Quartz powder.—Prepared from pure quartz crystals by grinding
in an iron mortar.
(3) Kaolin.—Material such as is used in the manufacture of the finest
porcelain which, after being freed of all foreign matter, is rubbed to a
fine powder in a porcelain mortar.
(4) Humus.—Washed with ether and alcohol, boiled with
hydrochloric acid, washed, dried and reduced to a state of fine powder.
(5) Iron oxid.
(6) Calcium carbonate.—Precipitated, washed, and dried.
(7) Soil mixtures.—Prepared artificially by mixing the kaolin, quartz,
and humus, above mentioned.
The quantity of gas absorbed by each of these materials is
determined by filling the tubes, as above mentioned, with the dried
material. The content of each tube is previously determined by filling
with mercury and weighing. Having determined the weight of the
substance to the exclusion of the air contained within its pores, it is
treated with the gas in the apparatus described above and weighed
from time to time until no further increase of weight takes place.
The method of calculating the results is shown in the following
scheme:
V = content of the absorption tube obtained by filling with mercury
and weighing.
P′ = weight of the empty tube filled with air at 100°.
pl = weight of the air in the tube (pl = V × specific gravity of the air
at 100°).
pt′ = weight of the tube (pt′ = P′ − pl).
P² (second weighing) = weight of the tube filled with the substance
with the included air at 100°.
vs = volume of the substance calculated according to the formula
vs = ss − specific
P² − P′
gravity of air.
ss = specific gravity of the substance.

vl = volume of the air in the flask filled with the substance (vl = V −
s
v ).
pl′ (weight of this included air) = vl × specific gravity.
ps = weight of the substance (pl = p² − pt′ − pl)
P³ = weight of the apparatus at the end of the experiment.
sg = specific gravity of the gas employed for saturation.
pg (weight of the gas remaining over the substance) = vl × sg.
pa (weight of the absorbed gas) = P³ − pt′ − ps − pg.
ps gram of substance absorbs pa gram of the gas and 100 grams of
substance would absorb 100ps× pa grams.
The specific gravities of the gases employed are calculated from the
tables given by Landolt and Börnstein in “Physical and Chemical
Tables,” page 5.
The specific gravity of the quartz sand employed was 2.639; of the
quartz powder, 2.622; of the kaolin, 2.503; of the humus, 1.462; of the
iron hydroxid, 3.728; and of the calcium carbonate, 2.678.
One liter of ammonia, at a pressure of 760 millimeters of mercury
and a temperature of 0°, weighs 0.7616 gram; one liter of carbon
dioxid, 1.9781 grams; one liter of aqueous vapor, 0.8064 gram; and
one liter of dried air, 1.2931 grams.
At a pressure of 720 millimeters, and at 20° temperature, a liter of
air saturated with aqueous vapor at 0° weighs 1.1383 grams; saturated
at 8.6°, 1.1362 grams; saturated at 10°, 1.1358 grams; saturated at 14°,
1.1340 grams; saturated at 18.2°, 1.1330 grams; saturated at 20°,
1.1321 grams; saturated at 30°, 1.1313 grams.
The general results of the experiments are as follows:
Absorption at 0°.
Aqueous vapor Ammonia. Carbon dioxid.

from saturated
air.
Grams. Cubic Grams. Cubic Grams. Cubic
cm.[H] cm.[H] cm.[H]
100 quartz 0.159 197 0.107 145 0.023 12
grams
„„ kaolin 2.558 3,172 0.721 947 0.329 166
„„ humus 15.904 19,722 18.452 24,228 2.501 1,263
„„ Fe₂(OH)₆ 15.512 19,236 4.004 5,275 6.975 3,526
„„ CaCO₃ 0.224 278 0.256 320 0.028 14
H. Reduced to 0° and 760 millimeters pressure mercury.

The foregoing methods will suffice to show the procedures to be
followed in estimating the maximum amount of any common gas or
vapor a given quantity of soil may be made to absorb. We pass next to
consider the quantities of gases or vapor soils in situ may hold.
284. Method of Boussingault and Lewey.[184]—This method is
the oldest and most simple procedure for estimating the nature of the
gases held in a soil in situ.
For the purpose of collecting the sample of gas from the soil a hole,
thirty to forty centimeters in depth, is dug, and a tube placed in it in a
vertical position, having on its lower extremity a bulb perforated with
fine holes. The hole is filled and the earth closely packed around the
tube which is left for twenty-four hours. At the end of that time the
tube is slowly aspirated until a volume of gas approaching from five to
ten liters is obtained.
Estimation of Carbon Dioxid.—The carbon dioxid in the sample of
gas is estimated by allowing it to bubble through a solution of barium
hydroxid.
Estimation of the Oxygen.—The oxygen is estimated in a separate
sample of the gas by means of potassium pyrogallate.
The chief objection to this simple process is the uncertainty of being
able to obtain an average sample of the occluded gas. In digging the
hole and refilling, there must evidently be a considerable disturbance
of the original distribution of the gas or vapor.
The methods of Pettenkofer[185] and Aubry[186] are essentially like
that just described. Pettenkofer found the largest quantities of carbon
dioxid in the earth gases in July, August, and September, and the
smallest quantities in the winter months.
No greater detail concerning these methods of the direct aspiration
of the air is considered necessary inasmuch as the methods about to be
described, while more elaborate, are superior in accuracy to the older
methods mentioned. In general, in these experiments, it is deemed
sufficient to determine the carbon dioxid only.
285. Method of Schloesing.—The apparatus
used by Schloesing[187] in the collection of the soil gases
consists of a steel tube (Fig. 62) a little over one meter
in length, ten millimeters in external diameter, and
one and one-half to two millimeters in internal
diameter. The end which penetrates the soil is made
slightly conical for a distance of twenty-five to thirty
centimeters. By reason of the shape of the tube, when
it is driven into the soil all connection between the
orifice in the point of the tube and the external air is
prevented. The obstruction of the internal canal of the
tube is prevented by introducing a thread of steel
which penetrates the whole length of the tube. This
Figure 62.
thread, represented by A, B, C, D, is flush with the
Schloesing’s interior extremity of the tube at D. It extends for about
Soil-Tube for three centimeters above the upper end of the tube in
Collecting order to be easily handled when it is to be removed.
Gases. For the purpose of driving the tube into the soil its
upper part is covered with a cylindrical piece of steel,
EF, in the interior of which are freely engaged H and A. This head
piece rests upon a ring of steel, K. This ring is fastened solidly into the
tube. On striking the piece EF the tube and the steel wire in the center
are driven together into the soil. The tube is flattened at L and L′ in
order to be embraced by the key MM, the employment of which is
necessary in order to revolve the tube around its axis when it is being
driven into the soil. When the tube has been driven to the depth
desired, the steel wire is withdrawn and it is immediately connected at
H with the rubber tube N (Fig. 63) belonging to the system PQT, and
furnished with a pinch-cock X. The system PQT comprises the
following elements: PQT made of a capillary glass tube in the form of a
T. The lower end of the tube P is closed by the larger glass tube O,
sealing the end of P with a little mercury. O is held to P by the cork S,
which is attached firmly enough to prevent O from dropping off, but is
furnished with a canal in order to allow the air to flow in or out freely.
This system is connected with the system UV by the rubber connection
T. U is a glass vessel having the constrictions as indicated in its stem
above and below the bulb. V is a glass vessel of convenient size
connected with U by the rubber tubing as indicated. The capacity of
the cylindrical portion of U should be from fifteen to eighteen cubic
centimeters.
To take a sample of soil gas, V is lifted above U.
The air is driven from U and escapes through O,
which acts as a true valve. When the mercury has
completely filled U the pinch-cock X is opened and
V depressed gradually. The gas coming from the soil
is thus collected in U. A few cubic centimeters of the
soil gas are collected in this way, the pinch-cock X is
again closed and V is raised in order to drive the
whole of the contents of U again through O. In this
way the whole of the air which the capillary vessel
originally contained is removed and all parts of it
remain filled with soil gas. Two or three operations,
using from five to ten centimeters of soil gas in all,
will be sufficient to completely free the apparatus Figure 63.
from its original content of air. U is then entirely Schloesing’s
filled by depressing V, and it is then hermetically Apparatus for
sealed at the two constricted points by means of an Collecting Gases
alcohol lamp. The sealed tube can then be from Soil.
transported to the laboratory and its contents
subjected to eudiometric analysis.
Without displacing the tube from the soil, several samples of gas can
be taken from the same spot. A sufficient number of the bulbs V
should be at hand to hold the required number of samples. Instead of
submitting the sample to eudiometric analysis it is usually sufficient to
determine the quantity of carbon dioxid which it contains, inasmuch
as numerous experiments have shown that in 100 parts of soil gas the
oxygen and carbon dioxid together constitute twenty-one parts. No
appreciable trace of marsh gas, or other combustible gas, has yet been
detected in ordinary arable soils. These gases have only been found in
special soils from marshes, in the neighborhood of gas wells, etc., and
not in arable soils.
286. Apparatus for Estimating the
Carbon Dioxid.—The apparatus used for
determining the carbon dioxid in
Schloesing’s work consists of the apparatus
shown in Fig. 64. A represents a glass vessel
surrounded by a jacket of glass, full of
water, and sealed on its lower part to the
tube BC of about six millimeters internal
diameter. On its upper part it is sealed to
the capillary tube D. The tube BC is
graduated from C in hundredths of the
Figure 64. volume of DAC, which volume is about
twelve cubic centimeters. On its lower part
Schloesing’s Apparatus for it is connected by a rubber tube with a
Determination of Carbon
Dioxid. reservoir F which is capable of being raised
or lowered. GHK are capillary tubes
connected together by the rubber tubes L
and M, which are furnished with pinch-cocks. The tube G is connected
to a vacuum by the rubber tube N. The rubber tube should be of very
small internal diameter and from forty to fifty centimeters in length.
To the tube H are sealed, at right angles, the branch D and another
branch O. This last dips into a little mercury which the tube P contains.
It serves as a valve, permitting the exit of the gases but not their
entrance. The tube K carries some lines engraved on its inferior part
and is sealed to the system of the two bulbs Q and R. The bulb Q
contains a concentrated solution of potash. It carries a number of
pieces of glass tubing for the purpose of increasing the surface of the
potash solution.
All the parts of the apparatus are fixed upon a rectangular board,
nineteen centimeters broad by twenty centimeters long. This forms
one of the faces of a wooden box to which it is hinged and which serves
for the transportation of the apparatus in a vertical position. The
graduation of the tube BC is recorded behind this tube upon a card
fixed upon the board. By means of these two graduations, the height of
the mercury in the tube BC is most easily read, even when the tube is
not perfectly vertical. Each one of the pinch-cocks L and M, on its
upper part is fixed in a sort of guard which prevents it from being
displaced laterally during the processes of the manipulation, thus
avoiding all danger of breakage.
After the operation is finished a little air is sent into Q in such a
manner as to sensibly lower the level of the solution of potash, and the
upper extremity of R is closed with a rubber stopper. Afterward, the
apparatus can be transported without any danger of the potash
becoming engaged in the tube K and reaching the measuring tank A.
To proceed to the analysis, a stake is driven into the soil to which all
of the apparatus can be fixed. At the side of the stake the apparatus for
taking the sample, already described, is driven into the soil and this
apparatus is connected by the tube N with the apparatus for
determining the carbon dioxid. The pinch-cocks L and M being closed,
F is lifted until the mercury which runs from it fills A and approaches
D. During this time the air which the apparatus contains has been
driven out through O. The tube NGD is freed from air by opening the
pinch-cock L, lowering F and drawing into A the gas coming from the
soil; afterward closing L and driving out the gas through O. After two
or three rinsings of this kind, which employ altogether only ten to
twelve cubic centimeters, the gas which is to be analyzed is sucked into
A. For this purpose F is lowered until the mercury in the tube BC is
very near C. The pinch-cock L is closed and M opened. The reservoir F
is displaced little by little by pressing lightly against the rectangular
board in order to give it greater firmness in such a way as to fix the
level of the mercury exactly at C, and the line is noticed where the
solution of potash in K stands. The gas contained in the apparatus is
under a pressure, the difference of which from the external pressure is
represented by the column of the potash solution between the mark
just noticed and the level of the same solution in the bulb R. In order
to absorb the carbon dioxid, F is lifted until the mercury stands
between D and E. The gas thus passes from A into Q. It gives up
immediately its carbon dioxid to the potash solution. It is then made to
come again into A, and afterward a second time into Q in order to free
it from the last trace of dioxid. Finally it is made to return to A and F is
kept at such a height that the potash solution maintains in the tube K
the same level as at the commencement of the operation. The gas is
then at the same pressure to which it was subjected before absorption.
The level of the mercury is then read on BC. At the time the apparatus
is used, the measuring tube A should be slightly moist. If it is not so, a
small quantity of water should be introduced which is afterward
rejected, but which leaves a sufficient quantity of moisture upon the
internal walls of A. In this way the gas will always, before or after
absorption of carbon dioxid, be saturated with vapor of water, and the
figure read in the last place upon the tube BC represents the
percentage of carbon dioxid in 100 parts of the gas extracted from the
soil supposed to be saturated with vapor at the temperature of the
experiment.
During the course of the analysis, the temperature of the measuring
flask, which is almost entirely surrounded with water, does not vary
sensibly, but in a series of experiments which are executed at different
times, the temperature of the measuring apparatus, which is that of
the ambient air, may change much. It may oscillate between 10° to 25°,
and exceptionally between 0° and 30°, whence there are notable
variations in the tension of the vapor of the gas measured. If it should
be desired to calculate to 100 parts of dry gas the observations made at
30° upon 100 parts of saturated gas, it would be necessary to increase
the percentage of carbon dioxid by about ¹⁄₂₅ of its value. It is noticed
that with the apparatus described above, the gas upon which the
estimation is really conducted comprises not only that which the
measuring apparatus contains from E to C before the absorption of the
carbon dioxid, but also the small quantity which remains in the
capillary tube KME at the moment when closing the pinch-cock M,
after the second rinsing, the gas from the soil is aspired into EAC. On
the other hand, there is left in the same tube KME, when the final
reading is made, some gas which belongs to that which has been
measured at the end. These two small gaseous portions which we
consider in the tube KME to be sensibly equal, do not contain any
carbon dioxid and may be left out of consideration. That is why the
volume of the measuring apparatus is limited to E and the graduation
of the tube BC is in hundredths of the volume comprised from E to C.
In reality the two portions are not absolutely equal because the two
successive levels of the potash solution, which limit them in the tube K,
are not absolutely identical. These two levels can differ in such a
manner as to correspond to a volume of about ¹⁄₁₀₀₀ of the measuring
apparatus. Thus the estimation is really made upon a volume of gas
which may be greater or less by ¹⁄₁₀₀₀ than the volume of EAC; whence
there might result an error of ¹⁄₁₀₀₀ in the estimation of the carbon
dioxid, an error which is wholly negligible.
As a result of numerous analyses it is concluded, first, that the
oxygen exists normally in the atmosphere of soils in large proportion;
second, very probably the gaseous atmosphere of arable soils, to a
depth of sixty centimeters, contains scarcely one per cent of carbon
dioxid and about twenty per cent of oxygen; third, the highest
percentages of carbon dioxid correspond to epochs of highest
temperature and periods of greatest calm; fourth, the proportion of
carbon dioxid increases ordinarily with the depth at which the samples
are taken. This disposition of the carbon dioxid would appear almost
necessary, since near the surface the internal atmosphere is almost
constantly diluted by external air by virtue of diffusion. Fifth, from one
epoch to another the composition of the atmosphere of the soil can
undergo considerable variation.
287. Determination of Diffusion of Carbon Dioxid in Soil.—
The method proposed by Hannén[188] is a convenient one to use in
studying the rate of diffusion of carbon dioxid in soils. A large Woulff’s
bottle with three necks serves for the reception of the gas. The two
smaller outer necks of the bottle carry two glass tubes bent outwards
and provided with stop-cocks. One of these passes to near the bottom
of the bottle and the other just through the stopper. The middle tubule
of the bottle is of a size to give in section an area of about twenty-two
square centimeters. It is made with a heavy rim two centimeters wide
and plane ground. This rim carries a plane-ground glass plate with a
circular perforation in one-half of it, of the size of the opening in the
central tubule of the bottle. A glass cylinder, carrying a fine wire-gauze
diaphragm near the lower end, fits with a ground-glass edge air-tight,
over this aperture, being held in position by a brass clamp. The
ground-glass plate moves air-tight between the cylinder and the bottle,
so that the cylinder can be brought into connection with the bottle or
cut off therefrom without in any way opening the bottle to the air. The
plate and all ground movable surfaces should be well lubricated with
vaseline.
The experiment is carried on as follows: The glass cylinder is filled
with the soil to be tested, closed above with a rubber stopper carrying a
gas tube, and then by moving the perforated-glass plate brought into
connection with the bottle. The side tube, with short arm inside the
bottle, is then closed, and carbon dioxid introduced through the other
lateral tube until the gas passing from the tube at the top of the
cylinder is pure carbon dioxid.
The lateral tube is then closed and the bottle is placed in a water-
bath and kept at a constant temperature of 20°. When the temperature
within and without the apparatus is the same the reading of the
barometer is made, the stopper removed from the top of the cylinder,
and the process of diffusion allowed to begin. After from six to ten
hours the glass plate is moved so as to break the connection between
the cylinder and bottle. The carbon dioxid remaining in the bottle is
driven out by a stream of dry, pure air. The air is allowed to pass
through the apparatus for about ten hours. The carbon dioxid driven
out is collected in an absorption apparatus and weighed. The
absorption apparatus should consist of a series of Geissler potash
absorption bulbs and finally a ᥩ form soda-lime tube. In front of the
absorption apparatus is placed a drying bulb containing sulfuric acid.
Inasmuch as the temperature and pressure can be readily determined,
the weight of carbon dioxid obtained is easily calculated to volume.
The weight of 1,000 cubic centimeters of carbon dioxid at 0° and
760 millimeters pressure is 1.96503 grams. Therefore one milligram is
equivalent to 0.5089 cubic centimeter of the gas. The volume of the
bottle should be carefully determined by calibration with water. The
results should be calculated to cubic centimeters per square centimeter
of exposed surface in ten hours. The depth of the soil layer is
conveniently taken at twenty centimeters.
288. Statement of Results.—
The Soil Packed Loosely in the Diffusion Tube.
Diffusion Time, Ten Hours.
Diameter of Weight Pure carbon Carbon Cubic

soil of soil dioxid at dioxid at centimeters of
particles, taken, beginning of end of carbon dioxid
millimeters. grams. experiment, experiment, diffused for
cubic cm. cubic cm. each square
cm.
0.01–0.071 520 2549.4 1230.3 59.9
0.071–0.114 550 2545.9 1269.2 58.0
0.114–0.171 590 2556.4 1354.2 54.6
0.171–0.250 620 2538.9 1336.1 54.6
0.250–0.500 660 2532.0 1374.5 52.6
0.500–1.000 680 2528.2 1440.2 49.5
1.000–2.000 690 2496.6 1396.9 50.0
Mixture of the 720 2514.3 1572.5 42.8
above
In greater detail the calculation and statement of the results may be

illustrated by the following data:
In the first experiment given in the above table the diameter of the
soil particles varied from 0.010 to 0.071 millimeter. The weight of soil
in the diffusion tube was 520 grams. The volume of gas, at 0° and 760
millimeters, before the diffusion began was 2549.4 cubic centimeters.
The volume of carbon dioxid under standard conditions remaining
after ten hours of diffusion was 1230.3 cubic centimeters. This volume
is calculated from the weight of carbon dioxid obtained in the potash
bulbs, each milligram being equal to 0.5089 cubic centimeter of
carbon dioxid. The volume of carbon dioxid diffused is therefore
2549.4 − 1230.3 = 1319.1 cubic centimeters. The per cent of carbon
dioxid diffused is 1319.1 ÷ 2549.4 = 51.74. The volume of carbon dioxid
diffused for each square centimeter of cross section of the diffusion
tube is 1319.1 ÷ 22 = 59.9 cubic centimeters.
The carbon dioxid should be passed long enough to secure complete
expulsion of the air before the determination is commenced.
289. General Conclusions.—The general results of the
experiments with the diffusion apparatus to determine the effect of the
physical condition of the soil upon the rate of diffusion are as follows:
1. The diffusion of carbon dioxid through the soil is, at a constant
temperature, chiefly dependent upon the pores in the cross section of
the column of soil. Therefore, the absolute quantity of the diffused gas
is greater the larger the total volume of the pores and vice versa.
2. Every diminution of the volume of the pores, whether secured by
pressure of the soil or by an increase in the moisture thereof, is
followed by a decrease in the volume of diffused gas. The giving up of
the carbon dioxid present in the soil atmosphere to the upper
atmosphere by the method of diffusion is therefore the less the finer
the soil is, the more compressed the soil particles are, and the larger
the water capacity of the sample and vice versa.
3. The quantity of diffused carbon dioxid is diminished according to
the measure of compression to which the soil is subjected but is not
strictly proportional to the height of the soil layer.
4. In soils in which rain water percolates slowly the diffusion of the
carbon dioxid on account of this property is depressed to a greater or
less extent.
AUTHORITIES CITED IN PART FIFTH.
179. Proceedings of the American Association for the Advancement of Science,
1872, p. 328.
180. Die Landwirtschaftlichen Versuchs-Stationen, 1889, S. 197.
181. König, Untersuchung Landwirtschaftlich und Gewerblich Wichtiger Stoffe,
Ss. 64–66.
182. König, op cit. supra.
183. Forschungen auf dem Gebiete der Agricultur-Physik, Band 15, S. 190.
184. Annales de Chimie et de Physique, Tome 37, 1853; Encyclopedie Chimique,
Tome 4, p. 154.
185. Zeitschrift für Biologie, Band 7, S. 395 and Band 9, S. 250.
186. Jahresbericht für Agriculturchemie, Band 1, S. 160.
187. Annales de Chimie et de Physique, 1891, Sixième Série, Tome 23, pp. 362, et
seq.
188. Op. cit. 5, 1892, Ss. 8, et seq.
PART SIXTH.
290. Preliminary Considerations.—The sample of soil intended for

chemical analysis should consist of the fine earth which has passed at least a
one-millimeter mesh sieve and subsequently been completely air-dried.
According to Petermann the air-drying of a soil should continue for about four
days for an ordinary arable soil, and about six days for one very rich in organic
matter. With peat and muck soils I have found that ten or twelve days with
frequent stirring, even when in thin layers, are necessary to attain approximately
a constant weight.
The soil is conveniently spread on a zinc or other metal sheet of sufficient area
so that the layer will be only one or two centimeters in thickness. The weight
before and after desiccation will give the percentage of moisture lost on air-
drying, which, of course, will depend chiefly on the degree of saturation of the
sample when taken and the atmospheric conditions prevailing during drying.
If samples of soil are taken in very dry times it is often necessary to moisten
them with distilled water in order to prepare them properly for air-drying.
The quantity of hygroscopic water which the sample loses at 100°–105° should
be determined, and all subsequent calculations of the percentages of the various
constituents be based on the water-free material. When a soil which has been
dried at 100°–105° to a constant weight is heated to 140°–150° it loses
additional weight not due to loss of water of constitution. A part of this loss may
be due to hygroscopic moisture which is not given off at 100°–105°, and a part
may be hydrocarbons, or other easily volatile organic or inorganic bodies. Before
estimating the total loss on ignition it is recommended by most chemists to dry
at 140°–150°. The samples of soil, however, intended for chemical examination
should never be dried beyond the point which is reached by exposure in thin
layers at ordinary room temperatures. The state of aggregation, degree of
solubility, and general properties of a soil, may be so changed by absolute
desiccation as to render the subsequent results of chemical investigation
misleading. In the methods which follow the actual processes employed have
been given, which in some instances transgress the general principle stated
above, but in all cases standard and approved methods are given in detail, even
if some of their provisions seem unnecessary or imperfect.
291. Order of Examination.—First of all in a chemical study of the soil
should be determined, its reaction (with litmus), its water-holding power in the
air-dried state (hygroscopicity), its content of combined water (giving hydrous

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Preface 9 3.4 Polymeric Structures 93

7.1 Heat Capacity 227 PART II aterials and Their