ASM - Elementary Materials Science-ASM International (2013)

Elementary
Materials
Science
William F. Hosford
ASM International®
Materials Park, Ohio 44073-0002
www.asminternational.org
Copyright © 2013
by
ASM International®
All rights reserved
No part of this book may be reproduced, stored in a retrieval system, or transmitted, in any
form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without
the written permission of the copyright owner.
First printing, August 2013
Great care is taken in the compilation and production of this book, but it should be made clear
that NO WARRANTIES, EXPRESS OR IMPLIED, INCLUDING, WITHOUT LIMITA-
TION, WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR
PURPOSE, ARE GIVEN IN CONNECTION WITH THIS PUBLICATION. Although this
information is believed to be accurate by ASM, ASM cannot guarantee that favorable results
will be obtained from the use of this publication alone. This publication is intended for use
by persons having technical skill, at their sole discretion and risk. Since the conditions of
product or material use are outside of ASM’s control, ASM assumes no liability or obligation
in connection with any use of this information. No claim of any kind, whether as to products
or information in this publication, and whether or not based on negligence, shall be greater
in amount than the purchase price of this product or publication in respect of which damages
are claimed. THE REMEDY HEREBY PROVIDED SHALL BE THE EXCLUSIVE AND
SOLE REMEDY OF BUYER, AND IN NO EVENT SHALL EITHER PARTY BE LIABLE
FOR SPECIAL, INDIRECT OR CONSEQUENTIAL DAMAGES WHETHER OR NOT
CAUSED BY OR RESULTING FROM THE NEGLIGENCE OF SUCH PARTY. As with
any material, evaluation of the material under end-use conditions prior to specification is
essential. Therefore, specific testing under actual conditions is recommended.
Nothing contained in this book shall be construed as a grant of any right of manufacture, sale,
use, or reproduction, in connection with any method, process, apparatus, product, composi-
tion, or system, whether or not covered by letters patent, copyright, or trademark, and nothing
contained in this book shall be construed as a defense against any alleged infringement of
letters patent, copyright, or trademark, or as a defense against liability for such infringement.
Comments, criticisms, and suggestions are invited, and should be forwarded to ASM
International.
Prepared under the direction of the ASM International Technical Book Committee (2012–
2013), Bradley J. Diak, Chair.
ASM International staff who worked on this project include Scott Henry, Senior Manager,
Content Development and Publishing; Karen Marken, Senior Managing Editor; Amy Nolan,
Content Developer; Sue Sellers, Editorial Assistant; Madrid Tramble, Manager of Produc-
tion; and Diane Whitelaw, Production Coordinator.
Library of Congress Control Number: 2013931785
ISBN-13: 978-1-62708-002-6
ISBN-10: 0-62708-002-3
SAN: 204-7586
ASM International®
Materials Park, OH 44073-0002
Printed in the United States of America

Elementary Materials Science Copyright © 2013 ASM International®
William F. Hosford All rights reserved
Preface
This textbook, which covers the subject of materials science with very
few equations, is designed for students who are interested in materials
science. It is assumed they already have had a course in chemistry. A prior
course in physics is not necessary, and the use of mathematics is limited
to algebra. This text also will be useful to nontechnical professionals in
the materials industry.
The book first introduces materials science through the discussion of
the elements, bonding, crystal structures, and amorphous (noncrystalline)
materials; then presents the properties of phase relations, mechanical
behavior, electrical behavior, and magnetic behavior. There is one chapter
each devoted to the following materials: nonferrous metals, ferrous metals,
ceramics, polymers, composites, and wood. To round out this important
basic volume on a growing interdisciplinary scientific field are chapters
on corrosion, forming and shaping, and recycling. There are 14 chapters.
Chapters 3 to 7, and 9 will likely require more time to cover than chapters
1, 2, 8, 10, and 12. Chapters 11, 13, and 14 can be covered in less time than
the others. Chapters end with a Note of Interest and Exercises—all per-
taining to the chapters’ topics of discussion. The Notes of Interest engage
readers with fascinating bits of information about notable people, events,
and developments; the Exercises allow students to explore the world of
materials in a pragmatic, hands-on manner.
vii
Contents
Chapter 1
Chemistry Basics . . . . . . . . . . . . . . . . . . . . . 1
Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Fundamental Particles . . . . . . . . . . . . . . . . . . . . . . 2
Bonding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Crystal Structures . . . . . . . . . . . . . . . . . . . . . . . . 4
Amorphous (Noncrystalline) Materials . . . . . . . . . . . . . 9
Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Chapter 2
Phase Relations . . . . . . . . . . . . . . . . . . . . . . 11
Phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Solid Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Phase Diagrams . . . . . . . . . . . . . . . . . . . . . . . . . 12
Freezing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Segregation during Freezing . . . . . . . . . . . . . . . . . . . 17
Metal Glasses . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Chapter 3
Mechanical Behavior . . . . . . . . . . . . . . . . . . . 23
Stress and Strain . . . . . . . . . . . . . . . . . . . . . . . . . 23
Elasticity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
Plastic Deformation . . . . . . . . . . . . . . . . . . . . . . . 25
Ductility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
Hardness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
Creep . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
Fatigue . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
Fracture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
iii
iv / Contents
Chapter 4
Electrical Behavior . . . . . . . . . . . . . . . . . . . . 37
Conduction . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
Metallic Conduction . . . . . . . . . . . . . . . . . . . . . . . 37
Ionic Conduction . . . . . . . . . . . . . . . . . . . . . . . . 40
Energy Bands . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Intrinsic Semiconduction . . . . . . . . . . . . . . . . . . . . 41
Extrinsic Semiconduction . . . . . . . . . . . . . . . . . . . . 42
III-V Compound Semiconductors . . . . . . . . . . . . . . . . 44
p-n Rectifiers . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Light Emitting Diodes . . . . . . . . . . . . . . . . . . . . . . 46
Transistors . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
Polar Compounds . . . . . . . . . . . . . . . . . . . . . . . . 47
Piezoelectric Behavior . . . . . . . . . . . . . . . . . . . . . . 47
Thermal Conductivity . . . . . . . . . . . . . . . . . . . . . . 49
Exercise . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
Chapter 5
Magnetic Behavior . . . . . . . . . . . . . . . . . . . . 51
Ferromagnetism . . . . . . . . . . . . . . . . . . . . . . . . . 51
Magnetostatic Circuits . . . . . . . . . . . . . . . . . . . . . . 52
Domain Boundaries . . . . . . . . . . . . . . . . . . . . . . . 54
Soft versus Hard Magnetic Materials . . . . . . . . . . . . . . 54
Soft Magnetic Materials . . . . . . . . . . . . . . . . . . . . . 55
Hard Magnetic Materials . . . . . . . . . . . . . . . . . . . . 56
Exercise . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
Chapter 6
Nonferrous Metals . . . . . . . . . . . . . . . . . . . . 59
Cold Work . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
Annealing . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
Copper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
Aluminum . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
Magnesium . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
Titanium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
Zinc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
Lead and Tin . . . . . . . . . . . . . . . . . . . . . . . . . . 66
Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
Chapter 7
Iron and Steel . . . . . . . . . . . . . . . . . . . . . . . 69
Steels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
Hardening . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
Tempering . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
Low-Carbon Steels . . . . . . . . . . . . . . . . . . . . . . . 76
Contents / v
Stainless Steels . . . . . . . . . . . . . . . . . . . . . . . . . 76
Cast Irons . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
Chapter 8
Ceramics . . . . . . . . . . . . . . . . . . . . . . . . . 81
Crystalline Ceramics . . . . . . . . . . . . . . . . . . . . . . 81
Glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
Pottery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
Hydration Reactions . . . . . . . . . . . . . . . . . . . . . . . 91
Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
Exercise . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
Chapter 9
Polymers . . . . . . . . . . . . . . . . . . . . . . . . . 99
Thermoplastics . . . . . . . . . . . . . . . . . . . . . . . . . 100
Thermosetting Polymers . . . . . . . . . . . . . . . . . . . . . 100
Degree of Polymerization and Molecular Weight . . . . . . . . 103
Branching . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
Cross-linking and Stereoisomerism . . . . . . . . . . . . . . . 104
Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
Molecular Configuration . . . . . . . . . . . . . . . . . . . . . 105
Glass Transition . . . . . . . . . . . . . . . . . . . . . . . . . 106
Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
Degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
Properties and Uses of Polymers . . . . . . . . . . . . . . . . 109
Stretching of a Thermoplastic . . . . . . . . . . . . . . . . . . 112
Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
Chapter 10
Composites . . . . . . . . . . . . . . . . . . . . . . . . 115
Fiber-Reinforced Composites . . . . . . . . . . . . . . . . . . 115
Volume Fraction of Fibers . . . . . . . . . . . . . . . . . . . . 117
Fiber Length . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
Particulate Composites . . . . . . . . . . . . . . . . . . . . . 120
Lamellar Composites . . . . . . . . . . . . . . . . . . . . . . 120
Exercise . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
Chapter 11
Wood . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
Structure of Wood . . . . . . . . . . . . . . . . . . . . . . . . 121
Dimensional Changes with Moisture . . . . . . . . . . . . . . 122
Anisotropy of Properties . . . . . . . . . . . . . . . . . . . . 124
Plywood . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
Paper and Cardboard . . . . . . . . . . . . . . . . . . . . . . 125
Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
vi / Contents
Chapter 12
Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . 129
Corrosion in Water Solutions . . . . . . . . . . . . . . . . . . 129
Passivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
Corrosion Control . . . . . . . . . . . . . . . . . . . . . . . . 134
Stress Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . 135
Rust . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
Direct Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . 136
Exercise . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
Chapter 13
Forming and Shaping . . . . . . . . . . . . . . . . . . . 139
Liquid to Solid Processing . . . . . . . . . . . . . . . . . . . . 139
Bulk Forming of Solid Metals . . . . . . . . . . . . . . . . . . 140
Hot Working versus Cold Working . . . . . . . . . . . . . . . 140
Sheet Forming . . . . . . . . . . . . . . . . . . . . . . . . . . 141
Polymer Processing . . . . . . . . . . . . . . . . . . . . . . . 142
Powder Processing . . . . . . . . . . . . . . . . . . . . . . . . 144
Modern Manufacturing Techniques . . . . . . . . . . . . . . . 146
Chapter 14
Recycling . . . . . . . . . . . . . . . . . . . . . . . . . 149
Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
Plastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
Rubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
Glass and Paper . . . . . . . . . . . . . . . . . . . . . . . . . 151
Appendix I
Greek Alphabet . . . . . . . . . . . . . . . . . . . . . . 153
Appendix II
SI Unit System . . . . . . . . . . . . . . . . . . . . . . 155
Appendix III
Conversions and Constants . . . . . . . . . . . . . . . . 157
Appendix IV
Properties of Elements . . . . . . . . . . . . . . . . . . 159
Appendix V
Properties of Materials . . . . . . . . . . . . . . . . . . 161
Appendix VI
Unit Abbreviations . . . . . . . . . . . . . . . . . . . . 163
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
Chapter 1
Chemistry Basics
MATERIALS are so important to civilization that the terms stone age,

bronze age, and iron age have been used to describe periods of history.
Perhaps the present day will be called the silicon age. Without steel, mod-
ern inventions such as the automobile, the bicycle, and railroads would
be impossible. Without aluminum, there would be no airplanes. Without
silicon, there would be no electronic devices like computers, digital cam-
eras, or cell phones.
Advancements in materials have been responsible for most of today’s
prosperity. Two centuries ago the most important materials were wood
and clay. Glass and steel, wrought iron, copper, silver, and pewter were
available, but were very expensive. There were no plastics, processed alu-
minum, modern rubber, and semiconductors. In the mid 1800’s advances
in steelmaking made the production of steel much less expensive. The
technique for economically producing aluminum was developed in the
late 1800’s. The first plastics appeared in the early 1900’s, but only a few
were available until the mid 1900’s. The development of semiconductors
in the last half of the twentieth century made possible the wide variety of
electronic products in common use today.
Elements
Before delving into a discussion of materials, it will be helpful to take
a look at the particles that materials are composed of, and the chemistry
and forces at work behind them. An overview of chemistry is, in fact,
necessary to arrive at an understanding of why and how materials have
the characteristics they do.
The periodic table of the elements (Fig. 1.1) allows one to quickly see
which chemical elements are similar to others. The elements are arranged
in order of increasing atomic number.
The table includes periods (typically horizontal) and groups (typically
vertical). Elements in groups share some similar properties.
2 / Elementary Materials Science
Fig. 1.1 the periodic table of the elements. the atomic numbers are in the upper right corners and the atomic
wts (in amu) at the bottom.
Fundamental Particles
All solid materials are composed of atoms, ions, or molecules. Atoms
are the basic unit of chemical elements. Ions are simply atoms or groups of
atoms that have lost or gained one or more electrons and carry an electric
charge. Molecules are groups of atoms chemically bonded to each other.
Bonding
The study of materials requires an understanding of the forces that hold
atoms together as solids. There are four types of bonds: metallic, ionic,
covalent, and van der Waals. In metallic bonding, individual atoms lose
their valence electrons, which forms a negatively charged “electron gas.”
This electron gas holds together the positively charged atoms. In ionic sol-
ids there is a transfer of valence electrons. Anions (metallic ions) have lost
valence electrons and become positively charged, while cations (nonmetal
ions) are atoms that have accepted extra electrons and become negatively
charged. Electrostatic attraction bonds anions to cations. Figures 1.2(a) and
(b) illustrate metallic and ionic bonding, respectively. In covalent bonding
(Fig. 1.2c), valence electrons are shared so that outer shells can be com-
plete. For example, if a carbon atom with four valence electrons shares one
electron with each of four neighboring carbon atoms, each carbon atom
will have eight outer electrons. Often bonding between atoms is partially
ionic and partially covalent in character. Van der Waals (Fig. 1.2d) bonding
Chapter 1: Chemistry Basics / 3
is much weaker than metallic, ionic, and covalent bonding. It arises from
the electrostatic attraction of molecules. Asymmetric molecules are likely
to have dipole moments (meaning the ends have different charges), and
bonding results from the attraction between the dipoles. Even symmetric
molecules and atoms have statistical dipoles, which results in even weaker
bonding. Hydrogen atoms covalently bonded in water molecules create
strong dipoles. The term hydrogen bonding refers to van der Waals bond-
ing resulting from these dipoles. Figure 1.3 illustrates this schematically.
Fig. 1.2 (a) Metallic bonding results from attraction of positive atoms to elec-
tron gas. (b) Ionic bonding results from mutual attraction of anions
and cations. (c) Covalent bonding involves sharing of electrons to complete outer
shells. (d) Van der Waals bonds are the result of statistical dipoles.
Fig. 1.3 hydrogen bond between adjacent water molecules resulting from
the dipole of the hydrogen atom
Table 1.1 Bond strengths

Bond type Energy (kJ/mol)
Van der Waals 0.0–10

Hydrogen 10–40
Ionic 50–1000
Covalent 200–1000
Metallic 50–1000
Source: Ref 1.1
Table 1.1 gives the approximate ranges of the strengths of the different
types of bonds.
It is useful to think of atoms and ions as hard spheres. In solids and
liquids, these hard spheres are in contact with each other.
Crystal Structures
Solids can be classified into those that are crystalline and those that
are not. A crystal structure is one that repeats itself over long distances.
Most solids are crystal structures, or crystalline. The atoms, ions, or mol-
ecules are arranged in repeating three-dimensional patterns or lattices.
The smallest characteristic piece of the repeating pattern is called the unit
cell. In metal, crystal atoms are in contact with each other. Most crystal
structures are either the densest way of packing spheres or almost the dens-
est. Most metals crystallize in one of three crystal structures.
Face-Centered Cubic Crystal Structure

One of these is called face-centered cubic (fcc) because the unit cell
(Fig. 1.4) is cubic with an atom on each corner of a cube and one in the
center of each face.
The atoms on each corner of the unit cell are shared with eight other unit
cells, so the number of corner atoms is (8 corners) (1/8 atom per corner) =
1 corner atom. There are six faces, and atoms in the centers of each face
are shared with one other unit cell, so there are (6 face-centering atoms)
(1/2 atom per face) = 3 face-centering atoms. Thus there are four atoms
in the unit cell. In an fcc crystal, each atom has 12 nearest neighbors. The
face-centered cubic structure is one of the most densely ways of packing
spheres. Atoms are arranged in close-packed hexagonal planes as shown
in Fig. 1.5. These planes are stacked so that the atoms in one plane are
nested into the valleys of the planes below. There are two sets of valleys.
In the face-centered cubic structure, the planes are stacked so that the third
plane is not directly over the first. Aluminum, copper, nickel, lead, gold,
silver, platinum, as well as iron at elevated temperatures, crystallize in a
face-centered cubic crystal structure.
Fig. 1.4 the unit cell of a face-centered cubic structure
Fig. 1.5 Close packed planes in the face-centered cubic structure
Body-Centered Cubic Crystal Structure

Another common crystal structure of metals is called body-centered
cubic (bcc) because the unit cell is cubic with an atom on each corner of a
cube and one in the middle of the cube (Fig. 1.6). Each of the eight corner
atoms is shared by eight unit cells so there are two atoms per unit cell (one
corner atom and one body-centering atom). Among the metals having a
body-centered cubic crystal structure are chromium, tantalum, vanadium,
niobium, tungsten, molybdenum, iron at room temperature, and both tita-
nium and zirconium at elevated temperatures.
Hexagonal Close Packed Crystal Structure

The third common crystal structure of metals is called hexagonal close
packed (hcp) because the basic structure is a hexagonal prism (Fig. 1.7).
The prism is composed of three layers of atoms, each arranged in a hex-
agonal pattern with an atom in the center of the hexagon. Only three
Fig. 1.6 the unit cell of the body-centered cubic structure
Fig. 1.7 the basic hexagonal cell of the hexagonal close packed structure
Fig. 1.8 Stacking of close packed planes in the hexagonal close packed
structure
atoms of the middle plane are in the basic cell. There are two atoms in
the top and bottom that are shared by two prisms, and 12 corner atoms
shared by six prisms, so there are a total of 3 + 1 + 2 = 6 atoms per prism.
The structure consists of stacked hexagonal planes, as shown from above,
in Fig. 1.8.
Among the metals that crystallize in the hexagonal close packed struc-
ture are beryllium, magnesium, zinc, cadmium, and both titanium and
zirconium at room temperature.
Diamond Cubic Crystal Structure

Aside from the three crystal structures (fcc, bcc, hcp), certain elements,
including carbon, silicon, and germanium, crystallize in another crystal
structure, the diamond cubic crystal structure, which has a repeating pat-
tern of eight atoms.
The periodic table (Fig. 1.9) shows that elements with the same crystal
structure are clustered together.
Sodium Chloride Crystal Structure

There are many different crystal structures of compounds. Figure 1.10
shows the structure of sodium chloride. The chlorine ions are arranged in a
face-centered cubic arrangement, with the sodium ions occupying the loca-
tions where they are in contact with four chlorine ions. This structure also
can be thought of as a face-centered cubic arrangement and the sodium
ions with chlorine ions occupying the locations where they are in contact
with four sodium ions.
Fig. 1.9 the periodic table. Note that neighboring elements share similar crystal structures. Source: ref 1.1
Fig. 1.10 the structure of sodium chloride
Other compounds that crystallize with the sodium chloride structure

include:
barium oxide (BaO) calcium oxide (CaO)

barium selenide (BaSe) calcium sulfide (CaS)
barium sulfide (BaS) cobalt oxide (CoO)
barium telluride (BaTe) ferrous oxide (FeO)
cadmium oxide (CdO) lead sulfide (PbS)
lithium bromide (LiBr) potassium hydride (KH)

lithium chloride (LiCl) potassium iodide (KI)
lithium fluoride (LiF) silver bromide (AgBr)
lithium hydride (LiH) silver chloride (AgCl)
lithium iodide (LiI) sodium iodide (NaI)
magnesium oxide (MgO) tantalum carbide (TaC)
magnesium sulfide (MgS) tantalum oxide (TaO)
manganese oxide (MnO) titanium carbide (TiC)
manganese sulfide (MnS) titanium nitride (TiN)
nickel oxide (NiO) titanium oxide (TiO)
potassium bromide (KBr) vanadium carbide (VC)
potassium chloride (KCl) zirconium carbide (ZrC)
potassium fluoride (KF) zirconium oxide (ZrO)
There are many other crystal structures of compounds. In all com-

pounds, the anions and cations are in contact. In almost every case, the
structure is the one that maximizes the density of the packing of spheres
of different sizes.
Amorphous (Noncrystalline) Materials

Noncrystalline solids are said to be amorphous. An amorphous mate-
rial has a structure like that of a liquid. Atoms, ions, or molecules are in
contact with each other as in a crystal. Often there is short-range order, so
that each atom, ion, or molecule has nearly the same surroundings as oth-
ers, but there is no repeating pattern over long distances. Glass and most
plastics are amorphous. In silicate glasses, silicon atoms are surrounded
by four oxygen atoms forming tetrahedra. Oxygen atoms are shared by two
tetrahedra as sketched in Fig. 1.11.
Fig. 1.11 Structure of a silicate glass consists of tetrahedra with silicon atoms
in the centers and oxygen atoms on the corners. Source: ref 1.2
NoTE oF INTErEST
the seven metals known to antiquity are iron, copper, silver, tin, gold,
mercury, and lead. those that occurred in the native (metallic) state are
gold, silver, copper, and mercury. Metallic iron in the form of meteor-
ites also was probably known early. tin and lead are not found in a
native state, but they probably were first reduced accidentally in a fire.
the first metallic material to be used for tools or weapons likely was
bronze, an alloy of copper and tin.
Exercises
1. Forming hexagonal close packed and face-centered cubic crystal
structures
Construct four rafts of balls arranged in hexagonal patterns with at
least 10 balls in each raft. Then stack the rafts in different patterns. Try
to stack them so they form a hexagonal close packed crystal; restack
them so they form a face-centered cubic crystal.
If the third raft is placed directly over the first raft, the result is hex-
agonal close packing. If it is not, but the fourth raft is placed directly
over the first raft, the result is face-centered cubic.
2. Comparing fcc and bcc crystal structures

Construct a face-centered cubic unit cell and a body-centered cubic
unit cell. Then compare the sizes of the largest holes in each. Which
would accommodate a small carbon atom more easily? Next, try to see
which has the larger passages between holes. Which would allow the
motion of small atoms more easily?
The face-centered cubic cell has the larger hole which allows it to
have the greater solubility for carbon. However, the body-centered
cubic cell has larger passages between holes so the rates of diffusion
in the body-centered cubic lattice are greater.
rEFErENCES
1.1 W.F. Hosford, Physical Metallurgy, 2nd ed., CRC Press, 2010
1.2 W.F. Hosford, Materials for Engineers, Cambridge U. Press, 2008
SElECTEd rEFErENCES
• R.A. Flinn and P.T. Trojan, Engineering Materials and their Applica-
tions, 4th ed. Houghton Mifflin, 1990.
Chapter 2
Phase Relations
Phases
A DISTINCT STATE of aggregation of matter is called a phase. A
phase may be a solid, a liquid, or a gas. A phase may be a pure material
or a solution of several components. A solid phase is either crystalline
or amorphous (noncrystalline). A crystalline phase has a characteristic
crystal structure and a definite composition range. A physical system may
contain more than one phase. A glass of root beer with ice contains three
phases: solid ice, a water-based solution, and bubbles of carbon dioxide. A
material may contain more than one solid phase, each with a different crys-
tal structure, or one or more mutually insoluble liquid phases (for example,
oil and water). All gases are mutually soluble, so only one gaseous phase
is possible in a material.
Single-phase solids include brass (a solid solution of zinc in copper, with
zinc atoms occupying lattice sites), sodium chloride crystals, glass, and
polyethylene. Most plain-carbon steels are two-phase materials, consist-
ing of an iron-rich solid solution containing a small amount of carbon in
solution, and iron carbide.
The composition of a single phase may vary from place to place but
always varies gradually without abrupt changes. In multiple phase systems,
however, there are discontinuities of composition and structure at phase
boundaries. The different compositions on one side of the phase boundary
are in equilibrium with the compositions on the other side of the boundary.
For example, the oxygen concentration changes abruptly between copper
with some oxygen dissolved in it (on one side of the phase boundary), and
copper oxide (on the other side).
Solid Solutions
Solid phases need not be pure materials; they also can be solutions.
Crystalline solids may dissolve other elements. Solution of element B in
(a) (b)
Fig. 2.1 a substitutional solid solution (a) and an interstitial solid solution (b)
crystals of A can occur by atoms of B substituting for A atoms in the

crystal structure. This is called a substitutional solid solution and is illus-
trated in Fig. 2.1(a). If the atoms of element C are very much smaller than
the atoms of A, they may dissolve by occupying the holes between the A
atoms. This is called an interstitial solid solution and is illustrated in Fig.
2.1(b). Only atoms of hydrogen, boron, carbon, and nitrogen are small
enough to dissolve interstitially in metals.
Phase Diagrams
Phase diagrams show the regions of stability of the various phases of a
system at equilibrium. Equilibrium between two phases can be described
by the limits of solubility in the two phases. A phase diagram also may
be thought of as a map of permissible phases. Equilibrium between two
components consists of single-phase regions and two-phase regions.
In a solid alloy of lead and tin, solid lead can dissolve tin, and solid tin
can dissolve lead. Figure 2.2 is a plot of the solubility limits in the lead-tin
system.
If the lead-rich solid solution is designated by a and the tin-rich solid
solution by b, the fields of possible compositions can be labeled as shown in
Fig. 2.3. Any composition in the a + b region between the solubility limits
consists of two-phases, a and b. Both phases are saturated solid solutions.
Their compositions are given by the solubility limits at that temperature.
At higher temperatures tin and lead form a liquid solution. Lead-rich
compositions precipitate crystals of a on cooling, and tin-rich solid
solutions precipitate b crystals on cooling. Above 185 °C (365 °F), the
solubilities of tin (Sn) in the a phase and of lead (Pb) in the b phase
decrease. These solubility limits are plotted in Fig. 2.4. The line from 0%
Sn at 327° to 62% Sn at 183° and the line from 62% Sn at 183° to 100% Sn
at 232° represent the solubilities of lead and tin, respectively, in the liquid.
The line from 0% Sn at 327° to 19% Sn at 183° represents the solubility of
Sn in the a phase, and the line from about 98% Sn at 183° to 100% Sn at
Chapter 2: Phase Relations / 13
Fig. 2.2 Solubility limits in the lead-tin system
Fig. 2.3 phase regions in the lead-tin system
232° represents the solubility of lead in the b phase. These lines complete
the lead-tin phase diagram. This system is called eutectic.
The reaction L Æ a + b on cooling through 183° is a eutectic reaction
that on cooling, a liquid transforms into two solid phases at the same time.
When a liquid containing 62% Sn cools, the a and b phases form a eutec-
tic structure of alternating platelets as sketched schematically in Fig. 2.5.
In another system, copper and nickel are completely soluble in each
other in the liquid state and in the solid state. Figure 2.6 shows the phase
diagram of this system.
The lower line is the solubility limit of copper in the solid; the upper line
is the solubility limit of copper in the liquid.
The copper-tin phase diagram (Fig. 2.7) is more complicated. Above 798
°C (1472 °F), an alloy of 22% Sn consists of two phases, liquid and a. The
Fig. 2.4 the lead-tin phase diagram. Source: ref 2.1
Fig. 2.5 the eutectic structure of a lead-tin alloy consisting of alternating

platelets of lead-rich and tin-rich phases. Source: ref 2.1
reaction L + a Æ b occurs as this alloy is cooled through 798 °C (1472 °F).

This reaction, in which a solid phase and liquid phase will form a differ-
ent solid phase on cooling, is called a peritectic reaction. Note that in the
Cu-Sn diagram, there is another peritectic reaction: L + b Æ g.
Another important reaction occurs in the iron-carbon phase diagram
(Fig. 2.8). Above 727 °C (1340 °F) iron containing 0.77% carbon has a
Fig. 2.6 the copper-nickel phase diagram. Source: ref 2.2
Fig. 2.7 the copper-tin phase diagram. Source: ref 2.3
face-centered cubic structure (g) called austenite. On cooling through 727

°C (1340 °F), austenite transforms to ferrite and iron carbide, g Æ a +
Fe3C. This reaction of one solid transforming into two others on cooling
is called a eutectoid reaction.
For an overall composition in a two-phase region, simple mass balance
can be used to find the relative amounts of each phase. For example, at
600°C, an alloy containing 80% copper and 20 % silver consists of two-
phases: a silver-rich solid solution, a, containing 0.03% copper and a
copper-rich solid solution, b, containing 0.975% copper.
Fig. 2.8 the iron-carbon phase diagram. Source: ref 2.3
In one gram of alloy, there is 0.8 gram of copper, divided between the
two phases. If we designate the fraction of the microstructure, that is a
by fa, the amount of copper in the a-phase is 0.03fa. Likewise there will
be 0.975(1-fa) gram of copper in (1-fa) grams of b-phase. A mass balance
gives
0.8 = 0.03fa+ 0.975(1 – fa) or

fa = (0.8 – 0.03)/(0.975 – 0.03) = 81.5%.
This procedure can be generalized as the lever law
fa = (cav – ca)/(c b – ca), (Eq 1)
where ca and cb are the compositions of the a and b-phases and cav is the
overall composition of the alloy.
Freezing
Almost all solid metals and alloys are produced from liquids by freez-
ing (vapor deposition and electrodeposition are exceptions.) Often the
Fig. 2.9 typical structure of a cast ingot with many small grains at the surface
and columnar grains extending into the interior. Source: ref 2.1
solidified metal is used in the form of a casting with little or no addi-

tional shaping. On the other hand, most metals are produced in the form
of wrought products. These are solidified as ingots or continuously cast
billets before being shaped into plate, sheet, rod, etc. For both castings and
wrought products, what happens during freezing has a major influence
on the microstructure and properties of the final product. Of particular
importance are porosity and segregation of alloying elements.
The liquid state is intermediate between a gas and a crystal. Liquids do
not have the high degree of order of crystals or the complete disorder of
gases. For most materials, freezing causes a volume decrease of 1 to 6%.
However, there are a few materials (water, silicon, germanium, bismuth,
gallium, etc.) that have packing in the solid state that is not dense and that
actually expands when they solidify.
Freezing starts at the outside of a casting, where the temperature is low-
est. Many crystals may start to form on the outside surface, but the ones
more favorably oriented for growth tend to dominate and cut off less favor-
ably oriented crystals. This results in a columnar structure in the interior
with finer grains at the surface, as shown in Fig. 2.9.
Segregation during Freezing

Solutes become segregated during the freezing of an alloy. Figure 2.10
shows that the first solid to form will be purer than the overall composition.
As the system is cooled, newly formed solid will contain ever-increasing
amounts of B. An unrealistically slow cooling rate (years or centuries per
Fig. 2.10 Schematic drawing showing a binary phase diagram (a) and con-
tours of concentration in a region that has frozen (b). Source:
ref 2.1
degree) would be required to allow enough time for diffusion to eliminate

these concentration gradients.
This enrichment of the liquid near the solid-liquid interface causes the
formation of a boundary layer in which liquid near the solid-liquid inter-
face contains more solute than the liquid further away from the boundary
(Fig. 2.11a). In the liquid there is a variation of the freezing temperature
(liquidus temperature) just ahead of the interface, as shown in Fig. 2.11(b).
These temperatures are determined by comparing the local composition
with the phase diagram (Fig. 2.11c). The liquidus temperature and the
actual temperature are plotted in Fig. 2.11 (b). At the interface, the actual
temperature must equal the liquidus temperature according to the concept
of local equilibrium. Just ahead of the interface, the actual temperature
is lower than the liquidus temperature for the local composition. Such a
condition is called constitutional supercooling because it results from
compositional (constitutional) variations. This situation is not stable. If any
area of the liquid interface happens to extend slightly ahead of the other
areas, it will freeze faster and grow rapidly into the undercooled liquid,
and dendrites will form with arms reaching out into the liquid.
Figure 2.12 shows two-dimensional dendrites forming in a polymer
solution.
With dendrite formation, segregation occurs between the centers of
the dendrite arms and the region between the dendrites. The liquid-solid
shrinkage will cause inter-dendritic porosity rather than large cavities.
Fig. 2.11 Constitutional supercooling resulting from boundary layer forma-

tion. Source: ref 2.1
Fig. 2.12 two-dimensional dendrites formed during the freezing of a poly-

mer solution. Source: ref 2.4
Metal Glasses
Materials that would form complex structures or several phases if they
crystallized may not crystallize on freezing but instead may freeze as
glasses. This is particularly true of polymers and complex silicates. There
also are some metal compositions which freeze to glass structures if
cooled fast enough. Most of the metal early compositions to form glasses
included appreciable amounts of small atoms including phosphorus, sili-

con, beryllium, and germanium. Cooling rates of 103K/s to 105K/s were
necessary to prevent crystallization. This limited glass formation in alloys
to thin ribbons or wires. More recently magnesium-base, iron-base and
zirconium-titanium-base alloys have been developed that do not require
such rapid cooling. The first such commercial alloy available in bulk form
is Vitreloy 1, which contains 41.2% Zr, 13.8% Ti, 2.5% Cu, 10% Ni, 22.5%
Be. Because the critical cooling rate is about 1K/s, glassy parts can be
made with dimensions of several centimeters. Metallic glasses can store
a great deal of energy elastically. This accounts for their use in golf club
heads as shown in Fig. 2.13.
Fig. 2.13 Golf clubs made from metallic glass. Courtesy of: Otis Buchanan,
Liquidmetal technology, Lake Forrest, Ca
NotE oF INtERESt
Josiah Willard Gibbs (1839–1903) was an american theoretical chemist
and physicist. he spent his entire professional career at Yale University,
which awarded him the first american phD in engineering in 1863. his
paper, “On the equilibrium of heterogeneous Substances,” published
in 1876, formed the basis for the development of phase diagrams. as
one of the greatest american scientists of the nineteenth century, his
work laid much of the theoretical foundation for chemical thermo-
dynamics. he invented vector analysis. although his work was little
known in america during his life, it was widely recognized abroad. his
work inspired James Clerk Maxwell, a Scottish mathematical physicist
and Gibbs’ most enthusiastic supporter, to personally make a plaster
cast illustrating Gibbs’ construction that Yale University still owns.
Fig. 2.14 Water is turning to ice during the horizontal hold
Exercises
1. Density of Different Phases
Pour melted wax into a cup and allow it to freeze. Note the shape of
the cavity that forms because solid wax is denser than liquid wax and
therefore occupies less volume.
One should see a cavity that is larger at the top than at the bottom.
2. Temperature versus Time during Freezing of Water

Put a thermometer into a half pint of water and put it into a freezer.
Record the temperature at intervals of five minutes and plot the tem-
perature as a function of time. What is happening during the horizontal
hold?
A plot of temperature versus time should look like the diagram in Fig.
2.14.
REFERENCES
2.2 D.S. Clark and W.R. Varney, Physical Metallurgy for Engineers 2nd
ed., Van Nostrand Reinholt, 1962
2.3 Metals Handbook, Vol. 8, 8th ed., ASM International, 1973
2.4 K.A. Jackson, Solidification, ASM International, 1971
Chapter 3
Mechanical Behavior
MECHANICAL BEHAVIOR of a material is how it deforms or breaks

when it is stressed. When a force is applied to a solid material, there are
three possible responses. The material may deform elastically which
means it will regain its original shape when the force is removed. Springs
and rubber bands deform elastically. If the force is high enough, the mate-
rial will not regain its original shape and the result is permanent or plastic
deformation. Dents in fenders of cars are examples of plastic deformation.
A still greater force may cause the material to fracture.
Stress and Strain

Stress is defined as the intensity of force, F, per area. True stress, s, is
defined in terms of the current area, A,
s = F/A.
Nominal or engineering stress, S, in a tension or a compression test is

defined in terms of the original area, Ao,
S = F/Ao.
Strain describes the amount of deformation a material has undergone.

Engineering or nominal strain, e, is defined simply as
e = DL/L o.
Elasticity
If a low stress is applied to a material, it will deform elastically and
when the stress is removed the material will return to its original shape.
Although stretching of a rubber band is a familiar example, most materi-
als can undergo much less elastic deformation than rubber. The maximum
elastic strain in crystalline materials usually is less than 0.2 %. For most
materials (not rubber) it is safe to assume that the strain is proportional to
the stress. The amount of elastic deformation is proportional to the stress,
and can be described by
e = S/E,
where E is called the elastic modulus or Young’s modulus.

When a material is stretched elastically, the bonds between neighboring
atom, ions, or molecules are stretched. Bonding is strong in materials with
high melting points. This strong bonding also is reflected in the elastic
stiffness of a material; therefore, materials with high melting points tend
to have high elastic moduli, as shown in Fig. 3.1.
Table 3.1 lists values of Young’s moduli for several materials.
Fig. 3.1 Correlation of elastic moduli with melting points. Metals having a
high melting point generally have a high elastic modulus. Source:
ref 3.1.
Table 3.1 Young’s moduli at 20 °C (70 °F)

Material Young’s modulus GPa (10 6 psi)
Aluminum 70 (10)
Iron and steel 205 (29.5)
Copper 110 (16)
Magnesium 45 (6.5)
Titanium 116 (19)
Glass 70 (10)
Polystyrene 2.8 (0.5)
Nylon 2.8 (0.5)
LD polyethylene 0.1 – 0.35 (0.05 – 0.1)
Urea formaldehyde 10.3 (1.5)
Chapter 3: Mechanical Behavior / 25
Fig. 3.2 Use of the fingers to sense the elastic and plastic response of a wire.
With a low force (top) the deformation is entirely elastic and the
bending disappears when the force is removed. With greater force (bottom) the
elastic portion of the bending disappears when the force is removed but some
plastic deformation remains. Source: ref 3.2.
Plastic Deformation
If the amount of deformation exceeds a critical amount, atoms slide over
one another and the material will not return to its original shape. In this
case, the material is said to have yielded and deformed plastically. This is
illustrated schematically in Fig. 3.2. Plastic behavior often is characterized
by the engineering stress-strain curve in tension. Figure 3.3 is an engineer-
ing stress-strain curve of a ductile material.
It is tempting to define an elastic limit as the stress at which the very
first plastic deformation occurs, and a proportional limit as the stress at
which stress is no longer proportional to strain. However, both of these
quantities depend on how accurately the stress and strain are measured.
Increased accuracy of measurement results in lower values for the elastic
and the proportional limits. To avoid this problem, it is customary to define
an offset yield strength that can be measured reproducibly. The offset yield
strength is found by constructing a straight line parallel to the initial linear
portion of the stress-strain curve but offset from it by a strain of 0.002 or
0.2% as shown in Fig. 3.4. The stress at the intersection of this line with
the stress-strain curve is taken as the 0.2% offset yield strength. Loading
a tensile specimen to this stress and then unloading will result in a plastic
strain of 0.002.
Fig. 3.3 typical engineering stress-strain curve for a ductile material. Source:
ref 3.1.
Fig. 3.4 the first portion of a stress-strain curve illustrating how the 0.2%
offset yield strength is determined. Source: ref 3.1.
For a few materials, an initial drop of stress occurs after the first yield-
ing. Examples include low carbon steel (Fig. 3.5a) and linear polymers
(Fig. 3.5b). For these materials, an upper yield strength is defined as the
stress at the first maximum, and a lower yield strength is defined as the
level of the plateau following initial yielding.
The highest engineering stress is called the tensile strength or ultimate
strength. If a material is ductile, as in Fig. 3.6, its tensile strength is reached
before it breaks. In this case its tensile strength corresponds to the point at
which the deformation begins to localize to form a neck. For less ductile
materials, fracture occurs before necking or even before yielding; there-
fore, the tensile strength is the fracture strength (Fig. 3.7).
Fig. 3.5 Inhomogeneous yielding of low carbon steel (a) and a linear polymer
(b). after the initial stress maximum, the deformation in both materi-
als occurs within a narrow band that propagates the length of the gage section
before the stress rises again.
Fig. 3.6 Necking starts when a maximum engineering stress is reached.

Source: ref 3.1.
Fig. 3.7 the tensile strength is the maximum engineering stress in a ten-
sion test, regardless of whether the specimen necks, fractures before
necking, or fractures before yielding. Source: ref 3.1.
Ductility
The ductility of a material describes the amount of deformation before
fracture in a tension test. There are two common measures of ductility.
One measure is the percent elongation before fracture,
%El = (Lf – L o)/L o ¥ 100%.
The other is the percent reduction of area,
%RA = (Ao – Af )/Ao ¥ 100%.
The percent reduction of area at fracture is a better measure of ductility

because the percent elongation involves both the uniform elongation before
necking and the elongation during necking so that the percent elongation
during necking depends on the ratio of the specimen diameter to its length.
Tensile specimens with large length-to-diameter ratios have lower % elon-
gations than those with low length-to-diameter ratios.
It should be realized that the amount of deformation that a material can
withstand depends on the form of loading. Under compression, as in roll-
ing, the ductility is far higher than that measured in a tension test.
Hardness
The hardness test is a simple way of characterizing a material’s resis-
tance to plastic deformation. In a hardness test, an indenter is pressed into
the surface of a material under a fixed force and the extent of indenta-
tion is measured. In the Brinell, Vickers, and Knoop hardness tests, the
dimensions of the indentation are measured after the load is removed;
the hardness equals the load divided by the area of the indentation. With
the several Rockwell tests, the depth of the indentation is automatically
recorded as the hardness number. Materials with high hardnesses have
high yield strengths.
Creep
At high temperatures, materials under stress may deform slowly. Such
time-dependent deformation is called creep. Figure 3.8 shows that the rate
of creep increases with increasing stress and temperature.
Fatigue
Failures may occur under repeated applications of stress at a level which
would not cause failure if the stress were applied only once. This phenom-
enon is called fatigue. The number of cycles before failure increases as the
stress is lowered, as shown in Fig. 3.9. For steels there is a level of stress
Fig. 3.8 Increased stress and increased temperature cause faster creep
Fig.3.9 Fatigue behavior of steels

Fig. 3.10 Fatigue behavior of aluminum
below which fatigue failure will not occur even after an infinite number
of cycles. This is called the endurance limit or the fatigue strength. For
nonferrous metals there is no such fatigue limit, as shown in Fig. 3.10.
Fracture
The mode in which a fracture occurs may be classified as ductile or brit-
tle, depending on how much deformation precedes the fracture. Fractures
may occur along grain boundaries or, more commonly, through the grains.
The tendency of a material to break in a brittle manner is increased by low
temperatures, high rates of loading, and the presence of notches. These
three factors tend to suppress plastic deformation; therefore, permitting
higher stresses. Molasses candy is a good example of these effects. If one
tries to break it by bending, it just deforms. However, if it is refrigerated,
notched, and rapped sharply, it is likely to break before it deforms. These
effects are illustrated in Fig. 3.11.
A material is regarded as being tough if it absorbs a large amount of
energy in breaking. In a tension test, the energy per volume to cause failure
is the area under the stress-strain curve and is the toughness in a tension
test. However, the toughness under other forms of loading may be very
different because toughness depends also on the degree to which deforma-
tion localizes. The total energy to cause failure depends on the deforming
volume as well as on energy per volume.
Impact tests often are used to assess the toughness of materials. The
most common of these is the Charpy test. A notched bar is broken by
a swinging pendulum. The energy absorbed in the fracture is measured
by recording how high the pendulum swings after the bar breaks. Figure
3.12 gives the details of the test geometry. The standard specimen has a
Fig. 3.11 Increased rates of loading, lower temperatures, and the presence of
notches tend to make materials behave in a brittle manner because
they raise the stresses to a level where fracture can occur
Fig. 3.12 a Charpy testing machine and test bar. a hammer on the pendulum
breaks the bar. the height the pendulum swings after breaking the
bar indicates the energy absorbed. Source: ref 3.3.
cross section 10 by 10 mm (0.5 by 0.5 in.). There is a 2 mm (0.05 in.) deep

V-notch with a radius of 0.25 mm (0.01 in.). The pendulum’s mass and
height are standardized. Sometimes bars with U- or keyhole notches are
employed instead.
The toughness in a Charpy test can be measured easily over a range of
temperatures. A specimen can be heated or cooled to the specified tem-
perature, and then transferred to the Charpy machine and broken quickly
enough so that its temperature change is negligible. For many materials
there is a narrow temperature range, over which there is a large change
of energy absorption and fracture appearance. It is common to define a
transition temperature in this range. At temperatures below the transition
temperature, the fracture is brittle and absorbs little energy in a Charpy
test. Above the transition temperature the fracture is ductile and absorbs a
large amount of energy. Figure 3.13 shows typical results for steel.
The transition temperature does not correspond to any structural change
of the material. The ductile-brittle transition temperature depends greatly
on the type of test being performed. Lower transition temperatures are
measured with less severe notches. With slow bend tests and un-notched
tensile tests, even lower ductile-brittle transitions are observed. In dis-
cussing the ductile-brittle transition temperature of a material, one should
specify not only the type of test, but also the criterion used. Specifications
for ship steels often require a certain Charpy V-notch 15 ft-lb transition
Fig. 3.13 Ductile-brittle transition in a Charpy V-notch specimen of a low-

carbon, low-alloy, hot-rolled steel. Source: ref 3.4.
temperature (the temperature at which the energy absorption in a V-notch

Charpy test is 15 ft-lbs).
In general, bcc metals and many hcp metals exhibit a ductile-brittle tran-
sition, but it is significant that fcc metals do not. For fcc metals, changes
of impact energy with temperature are small. Because austenitic stainless
steels and copper are not embrittled by low temperatures, they frequently
are used in equipment for applications that involve low temperatures.
In the period 1948 to 1951, there were many fractures of natural gas pipe-
lines. Most occurred during testing, and most started at welding defects
but propagated through sound metal. One of the longest cracks was 975
m (3200 ft) long. Once started, such cracks run at speeds greater than the
velocity of sound in the pressurized gas. Therefore, there is no release of
the gas pressure to reduce the stress at the tip of the crack. Figure 3.14 is
a photograph of one of the cracked lines.
During World War II, there was a rapid increase of shipbuilding. The
production of ships by welding together steel plates (in contrast to the ear-
lier process of joining them by riveting) became common during World
War II. As a result, a large number of ships, particularly Liberty ships and
T-2 tankers, failed at sea. More ships sunk as the result of brittle fractures
than by German U-boat attacks. Recovery of some ships and half-ships
allowed the cause of the failures to be investigated. It was found that there
were three main factors: poor welds, bad ship design (cracks often started
at sharp cornered hatchways that created stress concentrations), and high
Fig. 3.14 a natural gas pipeline that failed during field testing. Source:
ref 3.5.
NoTE oF INTErEST
the Great Boston Molasses Flood occurred on January 15, 1919 in
Boston. a large molasses storage tank suddenly burst and a wave of
molasses ran through the streets at an estimated 35 mph, killing 21
and injuring 150. residents claim that on hot summer days the area
still smells of molasses. this was the first brittle fracture failure of a
large structure. Other failures of large engineering structures include
fractures in pipelines and ships.
Fig. 3.15 a ship that fractured while still in port. Source: ref 3.6.
transition temperatures of the steels. Figure 3.15 is a photograph of a ship

that failed in harbor.
Exercises
1. Stress-Strain Curve Differences
Take a piece of iron florists wire and bend it by holding the ends. All
of the bend will occur in a short region.
Now repeat the experiment with a piece of copper wire. You should
see that the bend is distributed over the whole wire.
Note: You may have to anneal each wire before the experiment by put-
ting it in a 230 °C (450 °F) oven for a few minutes.
The different behavior is the result of the differences in the stress-

strain curves of the two metals. With the iron wire, initial yielding
in one region makes that region softer than the other regions, so
the deformation will localize there. The copper wire strain hardens,
causing regions that have yielded to be harder to deform than other
regions, so the deformation will spread over the whole wire.
2. Metal Fatigue
Take a paper clip and bend it. Then unbend it. Note that unbending it
requires more force than bending it. Also note that if the paper clip is
bent back and forth repeatedly, it eventually will break.
This is an example of fatigue.
3. Cardboard Fiber Alignment

Cut a piece of cardboard into a square, orient it so it is parallel to the
floor, and support it at two opposite edges. Place a weight in the cen-
ter and note the deflection. Remove the weight, rotate the cardboard
square 90° so it is supported at the other two edges, replace the weight,
and note the deflection.
The difference in stiffness is caused by the alignment of fibers during

the production of the cardboard.
4. Paper Fiber Alignment

Tear a newspaper vertically and then horizontally.
The fact that one tear is almost straight and the other wanders is
caused by the alignment of fibers during the production of the paper.
5. Effects on Ductility
Take a piece of molasses candy and try to break it slowly. Then try
to break it by rapping it suddenly on a hard surface. Then cool it in a
freezer and try to break it. Finally, scratch a notch into it and try to
break it. What effects do low temperatures, high rates of loading, and
notches have on the ductility?
Applying a high rate of loading (rapping suddenly), cooling, or notch-

ing lowers the ductility of the molasses, causing it to break.
rEFErENCES
3.1 W.F. Hosford, Mechanical Behavior of Materials, 2nd ed. Cambridge
University Press, 2010
3.2 W.F. Hosford in Tensile Testing, ASM International, 1992

3.3 H.W. Hayden, W.G. Moffatt and J. Wulff, Structure and Properties
of Materials, Vol. III Mechanical Behavior, Wiley, 1965.
3.4 R.W. Vanderbeck and M. Gensamer, Welding J. Res. Suppl. p. 37s–
48s, January 1950
3.5 E. Parker, Brittle Fracture of Engineering Structures, Wiley, 1957
3.6 C.F. Tipper, The Brittle Fracture Story, Cambridge University Press,
1963
Chapter 4
Electrical Behavior
Conduction
Electrical conduction through materials occurs by the movement of
charge carriers such as electrons, missing electrons, or ions. The conduc-
tivity, s, of a material is the product of the number of charge carriers per
volume, n, the charge on the carriers, q, and their mobility, m,
s = nmq
Mobility is the ratio of drift velocity to the electric field.
Metallic Conduction
Metals are excellent conductors. Table 4.1 lists the conductivities of some
metals. Temperature and impurities affect the conductivities of metals.
Their effects can be understood in terms of how they influence mobility.
Valence electrons form an electron gas that is free to move throughout a
metal. They are in constant motion. If there is no applied field, their move-
ment is random. However, an electric field accelerates the electrons in the
direction of the field, causing a net drift velocity. Any irregularity in the
lattice will cause a random change in the path. The drift velocity increases
Table 4.1 Electrical conductivities at 20 °C (70 °F)
Metal Conductivity (nWm) –1
Aluminum 37.7
Copper 59.77
Silver 68.0
Nickel 14.6
Iron 10.5
Magnesium 22.47
Zinc 16.9
70/30 brass 16.7
Cupronickel (20% Ni) 3.9
Stainless steel (18% Cr,8% Ni) 13.9
b b
c c
a a
d d
Net effect
(a) (b)
Fig. 4.1 Imposition of an electrical field on the random motion of electrons

creates a drift velocity. random motion (a) and the influence of field
(b). Source: ref 4.1.
Fig. 4.2 the electrical resistivities of copper and aluminum vary linearly with
temperatures above about 100 K. Source: ref 4.2.
with the field and the mean free path between interactions with lattice
irregularities. Therefore, the conductivity and mobility are determined by
the mean free path. Figure 4.1 illustrates this concept.
With increased temperature, atoms vibrate more from their normal lat-
tice positions, making the lattice less regular and decreasing the length of
the mean free path. This decreases the drift velocity. Figure 4.2 shows that
the resistivity, which is the reciprocal of conductivity, varies linearly with
temperature, except at very low temperatures. Figure 4.3 shows the effects
of various solutes on the resistivity of copper.
Chapter 4: Electrical Behavior / 39
Cold working a metal creates lattice defects that raise the resistivity of
the metal. Vacancies are the most important defects. The effect of each
vacant lattice site acts the same way as a solute atom. Therefore, the change
of resistivity caused by cold work, Drcw, is proportional to the number of
vacancies. The effects of cold work, annealing, and temperature on resis-
tivity are shown in Fig. 4.4.
Fig. 4.3 effects of various solutes on the conductivity of copper. Source:

ref 4.3.
Fig. 4.4 effects of annealing and cold work on the resistivity of copper.
Source: ref 4.4
Whereas increased temperature and impurities lower the conductivity

of metals, they have the opposite effect in insulators and semiconductors.
Ionic Conduction
In ionic solids, current is carried by the movement of ions under the
influence of an electric field, just as it can be in liquid solutions. The dif-
ference is that the rate of movement of ions in solids is much slower than
in liquids. Increases of both temperature and impurity content increase
conduction in ionic crystals.
Energy Bands
The difference between metals, semiconductors, and insulators can be
understood in terms of the energy levels of the outer electrons. Electrons in
isolated atoms can exist in only discrete energy levels, with no more than
two electrons occupying any level. However, as a large number of atoms
are brought together to form a crystal, the electric fields of the various
atoms interact, causing permissible energy levels to split into bands. The
number of electrons in each energy band can be no more than twice the
number of atoms.
Because conduction requires the energy of electrons to increase, for any
conduction, there must be available energy levels. With metals, either the
valence band overlaps the conduction band or is only partially filled, thus
there is a very large number of carriers. In semiconductors, the valence
band is filled, but there is only a small energy gap between the valence and
conduction bands. With insulators, the valence band is filled, and there is
a large energy gap between the valence and conduction bands. Figure 4.5
illustrates these possibilities.
Fig. 4.5 the band structures of different classes of materials. Source: ref 4.1.
Intrinsic Semiconduction
In a semiconductor like silicon, the energy gap is so small that thermal
agitation will increase the energy of a small number, n, of electrons enough
to promote them into the conduction band, as sketched in Fig. 4.6. The
missing electron in the valence band is called an electron hole; it also can
move through the lattice causing conduction. For a pure (intrinsic) semi-
conductor, the number of carriers increases with temperature.
Figure 4.7 illustrates this on an atomic level. For every electron pro-
moted to the conduction band, a hole is generated in the valence band.
Fig. 4.6 Band structure of an intrinsic semiconductor. a few electrons are

thermally promoted from the valence band to the conduction band.
Source: ref 4.1.
Fig. 4.7 (a) each atom in silicon shares two electrons with each of four near
neighbors. (b) If an electron is removed from bonding, a conduction
electron and an electron hole are created. Source: ref 4.1.
Fig. 4.8 the conductivity of pure germanium increases exponentially with

temperature. Source: ref 4.1.
Table 4.2 Energy gaps and mobilities in intrinsic semiconductors

Mobility, m2/V-s
Semiconductor Energy gap, eV Electrons Holes
Silicon 1.1 0.19 0.425

Germanium 0.7 0.36 0.23
GaAs 0.7 0.60 0.08
InAs 0.36 2.26 0.26
InP 1.3 0.47 0.015
The electrons in the conduction band are carriers of a negative charge, and
the electron holes in the valence band act as carriers of a positive charge.
Figure 4.8 shows that the conductivity of germanium increases expo-
nentially with temperature. The energy gaps and mobilities in several
semiconductors are listed in Table 4.2.
Extrinsic Semiconduction
The addition of even very small amounts of impurities to a semiconduc-
tor greatly increases its conductivity. For example, impurities of group V
elements (nitrogen, phosphorus, arsenic, antimony, bismuth) add an extra
electron, which can act as a conductor. The extra electron creates a donor
state with an energy level only slightly below the conduction band, as
illustrated in Fig. 4.9, so very little thermal energy (Eg – Ed) is required to
promote an electron from the donor state to the conduction band. At room
temperature, almost all of the donor electrons are promoted. In this case,
the conductivity primarily is by donor electrons; their number is approxi-
mately the number of group V atoms per volume, and the semiconductor is
n-type (negative carriers). Figure 4.10 shows the temperature dependence
in this case.
The effect of group III elements (aluminum, gallium, indium) is similar.
It takes very little thermal energy to promote an electron from the valence
band to the acceptor state. This creates a hole in the valence band (Fig.
4.11). At room temperature the acceptor state is almost filled so the num-
ber of electrons holes is approximately the number of group III atoms per
volume and the semiconductor is p-type (positive carriers).
Fig. 4.9 Group V impurities create donors. (a) the energy level of donors is
close to the conduction band. (b) the extra electron can easily be
promoted to conduction. Source: ref 4.1.
Fig. 4.10 the temperature dependence of conductivity in an extrinsic semi-

conductor. at very low temperatures, conductivity depends on
thermal excitation of donor or acceptor levels. Near room temperature, there is
saturation. at high temperatures, intrinsic conduction prevails. Source: ref 4.1.
In the exhaustion range, the conductivity is approximately proportional

to the impurity concentration.
III-V Compound Semiconductors

Compounds of group III and group V elements are semiconductors.
Examples include aluminum antimonide, gallium phosphide, gallium
arsenide, indium phosphide and indium antimonide. Zinc sulfide (group
II–VI) also is a semiconductor. Either nonstoichiometric compositions or
foreign impurities create n- or p-type semiconductors. Figure 4.12 illus-
Fig. 4.11 Group III impurities create electron holes. (a)the acceptor energy
level is slightly above the valence band. (b)the missing electron is
easily promoted to be an electron hole. Source: ref 4.1.
Fig. 4.12 Structure of a III-V semiconductor. Source: ref 4.1.

trates schematically the structure of these compounds. Table 4.3 lists some
of the properties of semiconductors.
p-n Rectifiers
A rectifier or diode allows current to pass in only one direction. A p-n
junction can act as a rectifier. Figure 4.13 shows that if a forward bias is
applied to the junction, holes in the p-material and electrons in the n-type
material will flow to the junction where they will combine, allowing cur-
rent to flow. More electrons and more holes are created where external
Table 4.3 Properties of some semiconductors

Energy gap, E g Mobility, m2/vs Intrinsic
conductivity Lattice
Material 10 –18
J eV Electrons mn Holes mn (W.m) –1 nm parameter
Silicon 0.176 1.1 0.19 0.0425 5 ¥ 10 –16 0.543

Germanium 0.112 0.7 0.36 0.23 2 0.566
AlSb 0.26 1.6 0.02 0.613
GaP 0.37 2.3 0.019 0.012 0.545
GaAs 0.22 1.4 0.88 0.04 10 –6 0.565
InP 0.21 1.3 0.47 0.015 500 0.587
InAs 0.058 0.36 2.26 0.026 10 –4 0.604
InSb 0.029 0.18 8.2 0.17 0.648
ZnS 0.59 3.7 0.014 0.0005
Fig. 4.13 a p-n junction rectifier has both p- and n-type regions (a). With
a forward bias (B) both electrons and holes move toward the
junction, allowing current to pass. With a negative bias (C) the region near the
junction becomes depleted in carriers so no current can flow. Source: ref 4.1.
leads are connected. With a reverse bias, electrons and holes move away
from the junction creating a zone depleted of carriers.
Light Emitting Diodes

If a forward bias is applied across a p-n junction, electrons and holes
annihilate each other. The energy of this recombination is converted into
light. The wavelengths of the light of such light emitting diodes (LEDs)
depend on the energy gaps. Table 4.4 lists the wavelengths of several com-
pounds. These can be adjusted by varying the ratio of the elements.
Transistors
Junction transistors are either of the n-p-n type or the p-n-p type. In a
p-n-p transistor (Fig. 4.14), the n-type material forms a thin base. Because
the base is so thin, holes in the emitter can cross into the collector. A small
input voltage signal controls the number of such holes as well as the col-
lector current. The voltage drop across the large resistor in the collector
circuit amplifies the smaller input voltage signal.
The other type of transistor is the metal oxide semiconductor field effect
transistor (MOSFET) sketched in Fig. 4.15. The gate, made from polycrys-
Table 4.4 Common Light Emitting Diodes

Compound Wavelength, nm Color
GaP 565 Green

GaAsP 590 Yellow
GaAsP 632 Orange
GaAsP 649 Red
Fig. 4.14 a p-n-p transistor. a small input signal imposed on the emitter
causes holes to penetrate the base and allows current in the col-
lector. Because the voltage across the collector is high, the output signal is at
high voltage. Source: ref 4.1.
talline silicon, is separated from the channel by a layer of SiO2. A small

signal voltage between the source and gate creates an electric field that
penetrates the channel and controls its conductivity. Thus modulating the
field between the source and gate will modulate the conduction between
the source and drain.
Polar Compounds
Some crystals are polarized. This happens if their centers of positive
and negative charge do not coincide. One example is quartz. Another is
barium titanate. Above 120 °C (250 °F), BaTiO3 is cubic with the Ti4+ ion
in the center of a cubic unit cell with O2– ions in face-centering positions
and Ba2+ ions at the corners. However, at lower temperatures, the cell
becomes tetragonal. The Ti4+ ion shifts in one direction and the O2– ions
in the opposite direction relative to the Ba2+ ions at the corners. These
displacements of the centers of positive and negative charge set up a per-
manent dipole. Electrons and the negative ions are attracted to the positive
electrode. There is no voltage in the absence of an external field (Fig. 4.16)
because the accumulated charge just balances the dipole.
Piezoelectric Behavior
Piezoelectricity of some polar crystals generates a voltage in response to
applied stress and conversely to undergo a reversible strain in response to
a voltage. The word piezoelectricity comes from the Greek piezein, which
means to squeeze or press. The effect finds useful applications such as the
production and detection of sound, generation of high voltages, electronic
frequency generation, sonar, and ultra fine focusing of optical assemblies.
Fig. 4.15 a MOSFet transistor. Source: ref 4.1.

An applied external field distorts the material, as indicated in Fig. 4.17, as

the internal negative charge is attracted to the additional positive voltage.
Conversely, an external force that strains the crystal produces a voltage.
Piezoelectric materials are useful in applications where mechanical
vibrations need to be developed by vibrating fields such as sending units
of sonar, audio speaker systems, and analog watches; and for high fre-
quency sound generators. They also are used where mechanical vibrations
are used to produce electrical signals as in the receiving units of sonar,
microphones, and frequency standards. Above 120 °C (250 °F) (its Curie
temperature), barium titanate has a cubic crystal structure that is not piezo-
electric. Lead zirconate titanate (PZT), [Pb(Zr,Ti)O3] is piezoelectric up
to 480 °C (900 °F). Lead metaniobate has a Curie temperature of 570 °C
(1060 °F). The most widely used piezoelectric material is PZT.
Fig. 4.16 the unit cell of barium titanate. Note the centers of negative
and positive charges are separated, creating a permanent dipole.
Source: ref 4.1.
Fig. 4.17 a piezoelectric crystal (a) is distorted by an electric field (B) and
an external force produces a voltage (C). Source: ref 4.1.
noTE oF InTEREST
Light-emitting diode (LeD) traffic lights are brighter, use less energy,
and have much longer lives than the old incandescent lights. however,
they do have one disadvantage for use in northern states. they are so
efficient that they do not emit enough heat to melt snow.
Vibrating quartz crystals often are used for frequency standards. Their
natural vibrational frequency depends on the crystal dimensions. Once a
crystal is cut to its final dimensions, its frequency is constant to one part
in 108. Piezoelectric crystals are used as pressure sensors.
Thermal Conductivity
Metals have very high thermal conductivities. Most of the heat is trans-
ported by electrons, thus the thermal conductivity is closely related to
the electrical conductivity. The ratio of thermal conductivity to electrical
conductivity is about 7¥10 –6 w-Ohm/(K/m). This is called the Wiedeman-
Franz ratio. In nonmetals, thermal conduction is primarily by lattice
vibrations and correlates with the elastic modulus. Diamond, which has
the highest elastic modulus, also has the highest thermal conductivity of
all materials. Polymers have very low elastic moduli and as a result very
poor thermal conductivity. This makes them useful for pot handles.
Exercise
1. Conductors and Insulators
Using a multimeter to measure the resistance of several materials,
determine which materials are conductors and which are insulators.
You should find that all metals are conductors and almost everything
else is an insulator.
REFEREnCES
4.1 W.F. Hosford, Materials for Engineers, Cambridge U. Press, 2008.
4.2 L.H. Van Vlack, Elements of Materials Science, 6th ed., Addison-
Wesley, 1989.
4.3 W.F. Hosford, Physical Metallurgy, CRC, 2005.
4.4 A. Wert and R.M. Thompson, Physics of Solids, McGraw-Hill, 1970
Chapter 5
Magnetic Behavior
Ferromagnetism
Magnetism seems to be a mysterious phenomenon. The discovery by
ancient people of lodestone (Fe3O4), a naturally magnetized piece of the
mineral magnetite, led to many myths (Fig. 5.1). When “magnetic behav-
ior” is spoken of, it usually means ferromagnetic behavior. Actually there
are two other types of magnetic behavior: diamagnetic behavior, which is
a weak repulsion of a magnetic field, and diamagnetism, which is a weak
attraction of a magnetic field.
Ferromagnetism, in contrast, is a very strong attraction of a magnetic field.
There are only a few ferromagnetic elements, the important ones being iron,
nickel, and cobalt. Several rare-earth elements are ferromagnetic at low
temperatures. Table 5.1 lists all of the ferromagnetic elements and the tem-
perature above which they cease to be ferromagnetic (Curie temperature).
Fig. 5.1 typical legend about lodestone, the first permanent magnet known
to man. Source: ref 5.1
Table 5.1 Ferromagnetic elements and Curie

temperatures
Metal Curie temperature, °C (°F)
Iron 1044 (1910)

Cobalt 1121 (2050)
Nickel 358 (675)
Gadolinium 16 (60)
Terbium –40 (–40)
Dysprosium –181 (–295)
Fig. 5.2 Incomplete magnetostatic circuits raise the energy
Iron, nickel, and cobalt at room temperature always are magnetized,

although they may not behave as magnets. The energy is lowered if the
magnetic spin of each atom is closely aligned with that of its neighbor.
This causes small regions, called domains, in which all of the spins are
aligned. This lowering of energy by the alignment of spins is called the
excha nge energy.
Magnetostatic Circuits
There is a tendency of a material to form complete magnetic circuits,
lowering the magnetostatic energy. The magnetostatic energy is less with
smaller domains (Fig. 5.2). This is the reason why a horseshoe magnet
attracts iron (Fig. 5.3). The net result is that domain structures are formed
like those illustrated in Fig. 5.4.
If a piece of iron is placed in an external magnetic field, those domains
most closely aligned with the field will tend to grow at the expense of those
that are anti-aligned (Fig. 5.4).
Figure 5.5 is a graph showing how the net magnetization of a material,
B, increases with the applied external magnetic field, H, over steps a., b.,
c., and d.
Chapter 5: Magnetic Behavior / 53
Fig. 5.3 horseshoe magnets attract iron to complete magnetostatic circuits
Field
Fig. 5.4 typical domain structures composed of complete magnetostatic

circuits. Source: ref 5.2
d.
c.
b.
a.
Fig. 5.5 Magnetization of a material. Source: ref 5.1

B
Bmax
Br
H
Hc
Fig. 5.6 a typical B-H curve. the magnetization initially increases by growth
of favorably oriented domains. at high magnetic fields, the mag-
netization rotates out of the easy direction of magnetization toward the field.
Source: ref 5.1
A complete B-H curve is illustrated in Fig. 5.6. Initially, the magnetiza-

tion increases with the applied magnetic field. A maximum magnetization,
Bmax, is reached when all of the spins are aligned with the external
magnetic field. If the external field is removed, th ere will be a residual
magnetization, Br. A reverse field, Hc, called a coercive force, is necessary
to demagnetize the material.
Domain Boundaries
The boundaries between domains are regions where there is a gradual
change in the direction of magnetization. In a ferromagnetic material
the direction of magnetization tends to be parallel to a specific crys-
tallographic direction. Magnetization in any other direction raises the
magnetocrystalline energy. The width of these (perhaps 20 atoms) is a
compromise between the magnetocrystalline and exchange energy terms.
A wider boundary would require more atoms to be magnetized in a direc-
tion other than the direction of easy magnetization. The exchange energy
is minimized if the boundary is very wide, thus the direction of magnetiza-
tion changes very little between neighboring atoms. There are two domain
boundary possibilities in iron, 180° and 90° domain walls (Fig. 5.7).
Soft versus Hard Magnetic Materials

There are two main types of magnets: hard and soft. Hard magnetic
materials are permanent magnets. They are difficult to demagnetize. The
hysteresis is very large. The remanence, Br, and coercive force, Hc, are
high. Soft magnetic materials are easily demagnetized. The terms soft and
hard are historic. The best permanent magnets in the 1910s were made of
Fig. 5.7 two domain boundary possibilities in iron, 180° and 90° domain walls. Source: ref 5.1
Fig. 5.8 a hard magnetic material has a much greater hysteresis than a soft
magnetic material. the differences are much greater than shown in
this figure. Source: ref 5.2
martensitic steel, which is very hard, and the best soft magnets were made
from pure annealed iron. The differences of the B-H curves are shown in
Fig. 5.8. The values of Hc range from 0.002 oersteds for a superalloy to
4.300 for a platinum-cobalt alloy.
Soft Magnetic Materials

For a material to be soft magnetically, its domain walls must move eas-
ily. The principal obstacles to domain wall movement are inclusions and
grain boundaries. Low dislocation contents and residual stresses, as well
as a low interstitial content, also are important.
Fig. 5.9 Second quadrant of a B-H curve (left) and the corresponding B ¥
H product (right). the maximum B ¥ H product is a figure of merit.
Source: ref 5.2
Inclusions are important obstacles to domain wall movement because

the energy of the system is lower when a domain wall passes through an
inclusion than when the boundary has separated from the inclusion.
Uses of soft magnetic materials include transformers, motor and gen-
erator cores, solenoids, relays, magnetic shielding, and electromagnets for
handling scrap. Many of these applications employ silicon-iron (usually 3
to 3.5% Si). Alloys containing ≥3% Si are body-centered cubic (bcc) ferrite
at all temperatures up to the melting point (Fig. 5.9). Silicon increases the
electrical resistance of iron. A high electrical resistance is desirable for
transformers because eddy currents are one of the principal power losses
in transformers. The power loss is inversely proportional to resistance,
therefore thin sheets also minimize eddy currents.
Hard Magnetic Materials

A high Hc coercive force is desirable for hard magnets, but most impor-
tant is a high H ¥ B product in the second quadrant of the B-H curve (Fig.
5.9). Often the maximum B ¥ H product is taken as a figure of merit.
Materials made up of small, isolated particles that are single domains
make good hard magnets, particularly if the particles are elongated and
if there is high magnetocrystalline energy. In a microstructure consisting
of small isolated particles surrounded by a nonferromagnetic phase, there
are no domain walls that can move. The direction of magnetization can be
changed only by rotating the magnetization out of the easy direction into
another equivalently easy direction. If there is a great dependence of the
energy on the direction of magnetization, this will require a high magnetic
Fig. 5.10 as the direction of magnetization of an elongated particle is

reversed (a vs. c), the rotation of the direction of magnetization
increases the magnetostatic energy (b). Source: ref 5.1
NoTE oF INTErEST
Lodestone is magnetite, Fe3O4, which is ferromagnetic. It formed
the basis for the first compasses. In the 4th century b.c. the Chinese
recorded that iron was attracted to lodestone. the Chinese used com-
passes with lodestone as early as 1100 a.d. the compass was used
by western europeans in the late 1100s and by arabs in the early
1200s. the first real use of the magnetic phenomenon likely should be
attributed to the Vikings. their development of magnetic compasses
enabled them to travel far at sea, even in foggy conditions.
field. Hexagonal structures are useful here because there are only two easy
directions, both parallel to the hexagonal axis and differing by 180°. When
ferromagnetic particles are elongated, the intermediate stage will have a
high energy (Fig. 5.10).
Inexpensive permanent magnets can be made by aligning fine iron pow-
der in a magnetic field while it is being bonded by rubber or a polymer.
Exercise
1. Magnetic Domains
The following will allow observation of magnetic domains. Make a
very fine slurry of magnetite using the following recipe:
i. Dissolve 2 g of ferrous chloride (Fe2 · 4H2O) and 5.4 g of ferric
chloride (FeCl3 · 6H2O) in 300 cc of hot water in a 500 cc beaker.
ii. While stirring, add a solution of 5 g of sodium hydroxide dissolved
in 50 cc of water. This will form a black precipitate.
iii. After the precipitate has settled to the bottom, pour off the clear
liquid.
iv. Transfer the remainder to a 2-liter beaker and fill with clean water.
After the precipitate has settled to the bottom, pour off the clear
liquid again.
v. Prepare a stabilizing solution by placing 5 g of coconut oil amine
(mostly dodecylamine) into a 1-liter beaker, adding 50 cc of water
and gently warming until the amine has melted. This must be neu-
tralized by adding HCl drop by drop until litmus paper indicates
it is neutral. Next add 300 cc of warm water and combine with the
precipitate, then thoroughly mix in a blender.
vi. Finally, obtain a small piece of silicon-iron sheet (approximately
9.5 mm, or 3/8 in., square). Polish the sheet to approximately 0.05
mm (0.002 in.) thickness, put in a microscope, and place a small
amount of the solution on it. Observe motion of the domains as a
magnet is placed in the vicinity and moved.
Movement of domain boundaries should be visible.
rEFErENCES
5.1 E.A. Nesbitt, Ferromagnetic Domains, Bell Telephone Labs, 1962
Chapter 6
Nonferrous Metals
METALS ARE EASILY recognized by their luster. They are characterized

by their high electrical and thermal conductivities. These properties can be
understood in terms of the nature of metallic bonding. In metals, positively
charged atoms are surrounded by a cloud of valence electrons that are
free to move about the lattice, accounting for high electrical conductivity.
Metals have high thermal conductivities because the free movement of
electrons allows them to transfer heat. Electrical conductivity decreases
with anything that disturbs the periodicity of the lattice, including high
temperatures. Thermal vibrations cause atoms to be displaced from their
normal positions. Atoms in solid solution have the same effect. Because
the valence electrons are mobile, they can absorb energy from photons,
increasing their energy but immediately dropping back to a lower energy
state and emitting photons. This explains the metallic luster.
Most metals are strong and ductile. They deform plastically because
their atomic planes slip over one another, as illustrated in Fig. 6.1. Metals
Fig. 6.1 Deformation of crystals by slip. One plane of atoms slides over
another.
Fig. 6.2 effects of cold work on the hardness, tensile strength, and ductility of copper and iron. here cold work
means the percent reduction of thickness by rolling. Source: ref 6.1
such as copper, aluminum, iron, titanium, magnesium, and nickel are very
ductile. Other metals, including bismuth, manganese, and bronzes, are
brittle and break before they deform very much.
Cold Work
Cold working, which alters the shape of a metal, also strengthens it by
plastic deformation. Plastic deformation leaves defects in crystals, thus
making continued slip more difficult. This is the reason the stress-strain
curves in tension show stress rising with strain. Straining a metal, whether
in a tension test or by rolling or drawing it into thinner sections (in cold
work), causes its hardness, yield strength, and tensile strength to increase,
and its remaining ductility to decrease (Fig. 6.2).
Annealing
When a cold worked material is annealed, or put through a process in
which it is heated and then cooled, changes in properties and structure
occur that can be divided into three stages: recovery, recrystallization,
and grain growth.
During the recovery stage there is a rearrangement and decrease in
the number of defects in the metal. Lattice defects generated during cold
working lower the electrical conductivity, but recovery largely restores the
electrical properties. During recovery there also is a significant decrease in
the residual stresses that were caused by cold working. The hardness does
not change very much during recovery. The effects of recovery in tungsten
are apparent in Fig. 6.3.
At higher annealing temperatures new grains start to form that contain
fewer defects and are much softer. This process, called recrystallization, is
accompanied by a marked decrease in hardness and an increase in ductil-
Chapter 6: Nonferrous Metals / 61
Fig. 6.3 property changes during annealing of tungsten. Only recovery

occurs at temperatures below approximately 400 °C (700 °F).
Source: ref 6.2
Fig. 6.4 progress of recrystallization at 310 °C (590 °F) of aluminum that had been cold worked 5%. Note that a
few new grains are present after 50 h, and these grow bigger as new ones are nucleated, after 70–80 h.
after 100 h, recrystallization is complete. Source: ref 6.3
ity. Figure 6.4 shows new grains forming and growing into old deformed
grains over time.
Figure 6.5 shows there is a large decrease in hardness during recrystal-
lization. It also shows that increasing the amount of cold work tends to
lower the temperature at which recrystallization occurs. Impurities present
as second phases also retard the movement of grain boundaries, thereby
raising the recrystallization temperature.
Fig. 6.5 effect of annealing temperature on cold worked (CW) brass. Note
that the sharp drop in hardness associated with recrystallization
occurs at lower temperatures for material that is more heavily cold worked.
Source: ref 6.1
Fig. 6.6 Large grains tend to be outwardly concave, and, therefore, grow
at the expense of their neighbors. Small grains tend to be inwardly
concave and therefore shrink. Source: ref 6.4
Grain growth, the third stage of annealing, involves the growth of some
recrystallized grains. The equilibrium angle between grain boundaries
is 60°; thus, on average, each grain has six near neighbors. Larger grains
statistically have more neighbors than small grains, thus the grain bound-
aries on large grains are outwardly concave (Fig. 6.6). Grain boundaries
tend to shorten themselves by growing toward their center of curvature.
Thus large grains grow at the expense of smaller grains. A grain that is
smaller than its neighbors has less than six neighbors, so its boundaries
are inwardly concave, and it will shrink until it disappears. The result will
be fewer grains, thus the average grain size will increase.
There is some continued decrease in hardness during grain growth. This
is apparent in Fig. 6.5 for the 60% cold worked material above 280 °C (540
°F), the 40% cold worked material above 300 °C (600 °F), and the 20%
cold worked material above approximately 340 °C (640 °F).
While all metals share important characteristics, metals can be divided
into two main categories: ferrous and nonferrous, the two groups catego-
rized by the presence and absence of iron, respectively. The remainder of
this chapter discusses properties, behavior, and uses of several nonferrous
metals.
Copper
Copper has very high electrical conductivity and therefore it is widely
used for wiring. All alloying additions lower the conductivity of copper.
Copper alloys such as brass, which is an alloy with zinc, and bronze, which
is an alloy with tin, are much stronger than pure copper. This is because
the different size atoms interfere with slip. Brass contains up to 35% Zn
and bronze approximately 5% Sn. Both alloys are often used because of
their color and because of their corrosion resistance in many environments.
Aluminum
The modern process for producing aluminum metal from aluminum
oxide was discovered independently and almost simultaneously in 1886—
in Ohio by Charles Martin Hall and in France by Paul Héroult. Hall opened
the first large-scale aluminum plant in 1888. Until that time, aluminum
was very expensive. In fact, Napoleon had dinnerware made of aluminum
because its expense made it very stylish.
Aluminum also has very high electrical conductivity. It is used for power
transmission because it is less expensive than copper. Many of the uses of
aluminum are due to its low density. These include transportation (bod-
ies, trim, and other parts of autos, trucks, and aircraft). Other uses include
packaging (beverage cans and foil) and building and construction (siding,
roofing, doors, and windows). Its low electrical resistance makes it useful
in electrical wiring and overhead transmission lines, while corrosion resis-
tance makes it useful for cooking utensils. High reflectivity is responsible
for its use in insulation and mirrors. Figure 6.7 indicates relative uses of
aluminum.
An aluminum alloy containing approximately 4% Cu (Fig. 6.8) can be
hardened by a special heat treatment called precipitation or age harden-
ing. This involves heating the alloy to just under its eutectic temperature
to dissolve the copper into the aluminum lattice, followed by quenching
Fig. 6.7 relative uses of aluminum. packaging includes beverage cans. trans-
portation includes cars, trucks, and aircraft.
Fig. 6.8 the aluminum-rich end of the aluminum-copper phase diagram. an

alloy containing 4% Cu can be hardened by heating to 530 °C (990
°F) to dissolve the copper, quenching to room temperature to form a supersatu-
rated solid solution, and finally heating to approximately 200 °C (400 °F) to allow
fine precipitates to form. Source: ref 6.5
to room temperature. This supersaturated solid solution then is reheated

to a lower temperature, at which a copper-rich phase can precipitate. If
the precipitation temperature is properly chosen, the precipitate particles
will be very small, hardening the material by blocking slip. Other pre-
cipitation-hardenable aluminum alloys contain either zinc or Mg2Si in
solution. Other alloys can be strengthened by precipitation hardening. In
fact, even nonmetallic systems are hardened by fine dispersions of hard
particles. Examples include hardening of asphalt by sand, and Bakelite by
fine silica particles.
Most aluminum castings contain silicon because there is little volume
change on freezing due to the expansion of silicon virtually cancelling out
the shrinkage of aluminum. Making sound castings is simplified if there
is little or no shrinkage when liquid metal freezes.
Magnesium
Magnesium is even lighter than aluminum. Because of its low density,
magnesium is finding increasing use in aircraft and automobiles. Because
finely divided magnesium was used in incendiary bombs, magnesium suf-
fered from an unjustifiable fear of fire hazard. It was used for many years
as engine blocks and transmission housings in early Volkswagen automo-
biles without any resulting fires. Some magnesium alloys are precipitation
hardenable. Its room-temperature ductility is limited; thus, most of its
applications are as castings. Other uses include laptop computer cases and
lightweight tool casings.
Titanium
Titanium has a hexagonal close packed (hcp) crystal structure at room
temperature, but titanium transforms to a body-centered cubic (bcc) struc-
ture above 883 °C (1620 °F). Alloying elements either lower or raise this
temperature. This transformation allows heat treatments to be used to
harden some titanium alloys.
The density of titanium is between those of aluminum and steel. It is
stronger than aluminum alloys, thus it offers weight savings over steel
where high strength is required.
The low density of titanium accounts for the majority of its usage. The
aircraft industry uses titanium for airframes and engines. Its low density
also is useful in helmets and armored vests.
A very tenacious surface oxide forms on titanium, giving it excellent
corrosion resistance. Its resistance to corrosion in saltwater is useful in
power plants using salt water, in desalinization plants, and wherever sea-
water corrosion is a problem. Because titanium is inert to human body
fluids, it is an ideal metal for medical replacement structures such as hip
and knee implants. Titanium actually allows bone growth to adhere to

the implants, thus titanium implants are more durable than those made of
other materials.
Zinc
The only major use of zinc-base alloys is for small parts such as locks,
and small automotive parts made by die casting. Die casting is a process
in which liquid metal is forced into a water-cooled metal mold and auto-
matically ejected when it is adequately cool. It is used when a very large
number of parts are to be made. The largest use of zinc is in galvanizing,
which is plating with zinc. Steel sheets often are galvanized with zinc for
corrosion protection. Another major use is for alloying with copper to
form brass.
Lead and Tin

These low-melting metals were used in the past for solder, but because of
the health hazard of lead, modern solders contain no lead. The major use of
lead is in automobile batteries. In the past tin was used to plate steel cans.
However, the high price of tin has almost eliminated this use. It is used as
an alloying element in copper and titanium alloys.
NoTE oF INTErEST
aluminum was chosen for the pyramidal cap of the Washington Monu-
ment. this was many years before the hall-heroult process that made
aluminum relatively inexpensive, so aluminum was very expensive
at the time. aluminum was not the first choice for the cap. It was
selected as an alternative material to copper-base alloys during discus-
sions between Colonel Casey, the engineer in charge of the project,
and William Frishmuth, who was the only U.S. aluminum producer at
that time. Casey sent a request to Frishmuth asking if he could make a
metal pyramidal cap that was to serve as the lightning rod of the monu-
ment. Copper, bronze, and platinum-plated brass were the preferred
materials. Frishmuth proposed that the cap be made of aluminum at a
quoted price of $75, and if he was unsuccessful in casting it in alumi-
num, he would cast it in aluminum bronze and plate it with gold for
a total cost of $50, or, if platinum-plated, for $75. Casey, in accepting
Frishmuth’s proposal, admonished him to keep the costs within the
estimate if possible. Frishmuth’s bill for the aluminum pyramid was for
$256.10. When the bill arrived, Casey sent his assistant, Captain Davis,
to go to philadelphia to investigate the matter. after Davis concluded
his audit, a final price of $225 was agreed upon between Casey and
Frishmuth.
Exercises
1. Annealing Aluminum
Take two pieces of aluminum and bend them back and forth, and note
how they become harder to bend. Then heat one in a flame. After it is
cool, bend it and note that heating softened it.
This is a result of annealing.
2. Dispersion Hardening
Put a handful of peanuts into a jar of peanut butter and note how much
stiffer the peanut butter is than before the peanuts were added.
This is an example of dispersion hardening.
3. Heat Reflection
Place the bulbs of thermometers into two equal weights of food and
wrap each tightly with aluminum foil. Place the shiny side of the foil
out on one, and the dull side out on the other. Heat them together in an
oven. Which heats faster? Why?
It should be found that the one with the dull side out heats faster. This
illustrates that shiny aluminum reflects heat.
rEFErENCES
Wesley, 1989
6.2 A. Guy and J. Hren, Elements of Physical Metallurgy, 3rd ed., Addi-
son-Wesley, 1974
6.3 W.C. Leslie, J.T. Michalak, and F.W. Auk, Iron and its Dilute Solu-
tions, AIME Conference Series, Interscience, 1963
6.5 Metallography, Structures and Phase Diagrams, Vol 8, Metals
Handbook, 8th ed., American Society for Metals, 1973
Chapter 7
Iron and Steel
WHILE THE LAST CHAPTER dealt with nonferrous metals, this chap-
ter focuses on the other main category of metals: ferrous metals, or those
containing iron.
Iron is the most versatile of all metals. It is inexpensive and can be made
very hard or relatively soft and ductile depending on carbon content, alloy-
ing elements, and heat treatment. Its crystal structure at room temperature
is body-centered cubic (bcc). Pure iron transforms to a face-centered cubic
(fcc) structure above 910 °C (1670 °F). Most alloying elements lower this
transformation temperature.
Steels
Most alloys of iron are called steels. Carbon is the most important alloy-
ing element in steel, although not all steels contain carbon. The solubility
of carbon in the fcc form of iron is very much greater than its solubility in
the bcc form. Figure 7.1 shows the iron-rich end of the iron-carbon phase
diagram. The a and d phases are bcc and called ferrite. The g phase is
fcc and called austenite. Iron carbide (Fe3C), also called cementite, forms
from austenite during cooling.
If iron containing 0.77% C is cooled slowly through the eutectoid tem-
perature of 730 °C (1340 °F), the eutectoid reaction, g Æ a + Fe3C, occurs
with both the ferrite (a) and the cementite (Fe3C) precipitating simultane-
ously in the form of alternating platelets (Fig. 7.2). This microstructure is
called pearlite.
When a steel that contains less than the eutectoid composition of 0.77%
C is slowly cooled, ferrite will form before the eutectoid temperature is
reached. As the ferrite forms, the austenite becomes enriched in carbon,
finally reaching 0.77% C at the eutectoid temperature. With further cool-
ing, the austenite transforms to pearlite. Figure 7.3 shows the resulting
microstructure with ferrite in the former austenite grain boundaries. In
steels with more than 0.77% C, cementite will form in the austenite grain
boundaries before pearlite forms.
Fig. 7.1 the iron-rich end of the iron-carbon phase diagram. the phase
region labeled g is face-centered cubic and the phase regions labeled
a and d are body-centered cubic. Iron carbide (Fe3C) contains 6.67% C. Source:
adapted from ref 7.1
Fig. 7.2 Microstructure of pearlite. Note the alternating platelets of ferrite

(white) and iron carbide (dark). Source: ref 7.2
Chapter 7: Iron and Steel / 71
Fig. 7.3 Microstructure of a steel containing 0.45% C after air cooling. the
light regions are ferrite, which formed in the prior austenite grain
boundaries. the black areas are pearlite, in which the spacing between lamellae
is too small to be resolved. Source: ref 7.3
Fig. 7.4 the martensite unit cell. ref 7.4
Hardening
If austenite is rapidly cooled, the carbon atoms do not have enough
time to diffuse away from the growing ferrite to the growing cementite.
Instead, a new phase, martensite, will form. Martensite essentially is a
supersaturated ferrite. Its crystal structure is body-centered tetragonal, or
bct (Fig. 7.4), which is like a distorted bcc structure. The amount of distor-
tion depends on the amount of carbon in the steel. Figure 7.5 shows how
the ratio of the edges of the unit cell depends on the carbon content. With
no carbon the unit cell is bcc.
Martensite is harder than pearlite. Its hardness depends only on the car-
bon content (Fig. 7.6).
Fig. 7.5 the ratio of the c lattice parameter to the a lattice parameter increases
with carbon content. With no carbon, the lattice parameters are the
same so the structure is cubic. Source: ref 7.4
Fig. 7.6 the hardness of martensite increases with carbon content. Note
that the hardness extrapolates to the hardness of ferrite at 0% C. the
hardnesses of pearlitic and spheroidized structures are shown for comparison.
Source: ref 7.5
Alloying elements in austenite slow the transformation to pearlite,

because they must diffuse to either the growing cementite or ferrite
platelets. Neither nickel nor silicon form carbides in steel and, therefore,
segregate to the ferrite. Manganese, chromium, molybdenum, and tungsten
are carbide formers, so they segregate to the cementite. In both cases, the
diffusion of these elements in substitutional solid solution is significantly
slower than the diffusion of carbon, and, therefore, they slow the transfor-
mation of austenite to pearlite.
If parts made from plain carbon steels are too thick, their centers may
not cool fast enough to avoid pearlite formation, and they have insufficient
hardenability. Alloying elements increase the hardenability by allowing
the steels to harden under somewhat slower cooling rates.
The Jominy end-quench test is a simple way to assess the hardenability
of a steel. Water is sprayed on the end of a bar that has been heated to form
austenite (Fig. 7.7). This creates a gradient of cooling rates along the bar,
with the quenched end cooling very rapidly. Hardness measurements then
are made along the length of the bar. Figure 7.8 shows typical results of
the Jominy end-quench test for several steels. The compositions of these
steels are:
Composition, %
Steel C Mn Cr Mo Ni
4340 0.40 0.75 0.77 0.30 1.71

4140 0.38 0.79 1.01 0.22 …
1060 0.62 1.81 … … …
1040 0.39 0.89 … … …
1020 0.20 0.90 … … …
Fig. 7.7 Jominy end-quench test. Source: ref 7.4

Fig. 7.8 Jominy end-quench test curves for several steels. Source: ref 7.5
The 1060(#2) steel in Fig. 7.8 has a larger austenite grain size than the
1060(#8) steel. Several trends are apparent. The hardness at the quenched
end where the structure is 100% martensite depends only on carbon con-
tent. Alloying elements have no effect on the hardness of martensite. The
depth of hardening (hardenability) increases with alloy content, with car-
bon content, and with larger austenite grain size. The grain size effect is
explained by preferential nucleation of pearlite in austenite grain bound-
aries. With a larger austenite grain size, nucleation of pearlite is slower,
allowing more time for martensite to form. The principal use of alloying
elements in steels is to increase their hardenability.
Tempering
Martensite is too brittle for most applications. A hardened steel usu-
ally is heated to some temperature considerably lower than the eutectoid
temperature to temper it. Tempering is the conversion of hard brittle mar-
tensite into products that are more ductile but not as hard as as-quenched
martensite. The amount of tempering increases with higher temperatures
(Fig. 7.9). More tempering is required for hammers, which must be able
to sustain impact loading, than for knives, which must be hard to remain
sharp. Razor blades are tempered even less.
Special steels are used for applications in which a high hardness
must be maintained at a high temperature, such as tools for high-speed
machining. High contents of chromium, molybdenum, and tungsten in
high-speed steels form very hard carbide precipitates when tempered at
a high temperature. Figure 7.10 shows the effect of molybdenum on the
Fig. 7.9 hardness of plain carbon steels after tempering at various tempera-
tures for 30 min. Source: ref 7.4
Fig. 7.10 Secondary hardening in steels containing chromium and molyb-

denum. Source: ref 7.2
tempering response. With 5% Mo, high hardnesses are maintained at 550

°C (1020 °F).
Low-Carbon Steels
Most steels contain 0.10% C or less with no alloying elements except
some manganese and silicon. These steels are classified as either hot
rolled or cold rolled steels. Hot rolled grades are somewhat less expen-
sive because they are finished hot but they have rough surfaces. They are
used where surface appearance is not important, such as for I-beams and
structural plate.
Cold rolled steels are first hot rolled, pickled in acid to remove scale, then
cold rolled, and finally annealed in an inert atmosphere. Automobile bod-
ies, household appliances, and other consumer items are made from cold
rolled steel because of their very smooth surfaces. Formability may be of
concern if the deformation during stamping is severe. For that reason, the
carbon content of steels to be cold formed usually is less than 0.06% and
in some cases is as low as 0.002%. In recent decades, concern over weight
has led to the introduction of steels with somewhat higher yield strengths.
High-strength, low-alloy (HSLA) steels are strengthened by a combina-
tion of precipitation of carbonitrides, finer grain sizes, and solid-solution
effects. The formability of these steels is somewhat lower than plain car-
bon steels of the same carbon content, but adequate for most automobile
parts. Dual-phase steels, which are quenched from the ferrite-austenite
region, contain primarily ferrite with some martensite.
Stainless Steels
Alloying elements have very little effect on the corrosion behavior of
steels. The exception to this is steels having a chromium content of at least
12%. Such stainless steels are very resistant to corrosion in the presence
of oxygen. There are three main types of stainless steels:
• Ferritic stainless steels contain 12 to 18% Cr and very little carbon
(generally less than 0.03%). Even when heated to temperatures just
below their melting points, they maintain a bcc crystal structure.
• Austenitic stainless steels contain enough nickel that they have a fcc
crystal structure at all temperatures below melting. A typical composi-
tion is 18% Cr, 8% Ni with very low carbon. They are more expensive
than ferritic stainless steels and are nonmagnetic.
• Martensitic stainless steels have compositions similar to ferritic stain-
less steels but contain enough carbon so that when heated they transform
to austenite. The hardenability is so high that they form martensite even
with slow cooling. Applications include razor and knife blades.
Cast Irons
Cast irons contain far more carbon than steel. Typical carbon contents
range from 2 to 4% C with 1 to 3% Si. With so much carbon and silicon,
graphite, rather than cementite, tends to form on freezing. With the cooling
rates typical of casting into sand molds, the graphite forms as flakes. Fig-
ure 7.11 shows a typical microstructure of a gray cast iron. The ductility
is limited to a few percent elongation because fracture occurs easily along
the graphite flakes. The name gray cast iron comes from the appearance
of the fracture surfaces, which are almost entirely graphite.
If the sulfur content is kept very low, and magnesium or cerium is added
to the melt just before casting, the graphite will form as spheroids. The
resulting product is called ductile cast iron. Figure 7.12 shows a typical
microstructure. The mechanical behavior of ductile cast iron is similar to
that of steel.
Both gray and ductile cast irons may be reheated to form a structure of
graphite and austenite. The rate of cooling, then, determines whether the
matrix is pearlite, ferrite, or a mixture of pearlite and ferrite. Rapid cooling
can be used to form martensite. Austempering of ductile cast iron produces
many useful products. Gray and ductile cast irons are less expensive than
cast steel because they melt at much lower temperatures than steels and are
easier to cast because there is very little shrinkage on freezing.
White cast iron is a third grade of cast iron. The carbon and silicon
contents of white cast iron are lower than in gray and ductile cast irons,
and the cooling rates are greater. These factors tend to prevent graphite
formation; thus, carbon occurs as iron carbide (cementite). White cast iron
Fig. 7.11 Microstructure of gray cast iron. the black flakes are graphite, the
white areas are ferrite, and the grey areas are pearlite. Source:
ref 7.6
NoTE oF INTErEST
When in about 2000 b.c. the hittites in asia Minor discovered how to
reduce iron ore and make iron weapons, they were able to conquer
the Babylonians, who had a civilization superior to their own, and to
drive the egyptians out of Syria. their success was due to having harder
and more weapons. Iron was far more plentiful than the copper and
tin used for bronze weapons.
Fig. 7.12 Ductile cast iron. the spheroids are graphite and the white areas
are ferrite. Source: ref 7.6
is very hard and brittle and finds applications only where surfaces must
be hard to resist wear.
Exercises
1. Density of Austenite versus Ferrite
Stretch a piece of music wire (piano wire) between two fixed posts
and heat it by passing a current through it. As it is heated it should sag
because its length is changing. However, when it is heated through the
ferrite-to-austenite transformation, it should rise suddenly.
The rise occurs because austenite is denser than ferrite.
2. Graphite Flakes in Gray Cast Iron

Fracture a piece of gray cast iron and compare the color of the surface
with a machined surface.
The fractured surface appears gray like graphite because the fracture
occurred almost entirely through the graphite flakes. The machined
surface looks metallic because it contains only about 10% graphite.
3. Austenitic Stainless Steel

A magnet provides a simple way of distinguishing austenitic stainless
steels from the other grades. Austenitic stainless steel is not magnetic.
Use a magnet on several pieces of stainless steel (i.e., dinnerware, a
sink, hub caps, razor blades) and determine which are austenitic.
If the stainless steel is not attracted to the magnet, then it is not aus-
tenitic stainless steel.
rEFErENCES
7.1 J. Chipman, Met. Trans. Vol 3, 1972
7.2 Making, Shaping and Treating Steels, 9th ed., United States Steel
Corp, 1971
7.3 Atlas of Microstructures of Industrial Alloys, Vol 7, Metals Hand-
book, 8th ed., American Society for Metals, 1972
7.4 W.F. Hosford, Physical Metallurgy, CRC, 2005
Wesley, 1985
7.6 Metallography, Structures and Phase Diagrams, Vol 8, Metals
Handbook, 8th ed., American Society for Metals, 1973
Chapter 8
Ceramics
CERAMICS ARE NONMETALLIC, inorganic materials. Most ceramics

can be grouped into several distinct groups. One group consists of crys-
talline compounds such as magnesium oxide, aluminum oxide, and boron
nitride. Glasses form a second group. There also are materials formed by
reactions involving water. Most ceramics are brittle: they fracture before
they deform very much.
Crystalline Ceramics
Crystalline ceramics are compounds consisting of metal and nonmetal
ions bonded either covalently or ionically. Most have high melting points
and are very hard and brittle. Their tensile strengths are limited by brittle
fracture but their compressive strengths are high. Because they retain high
hardnesses at elevated temperatures, many are used for refractories (mate-
rials having a high heat resistance) such as crucibles and furnace linings.
Oxidation at high temperatures is not a problem with refractory oxides
as it is with refractory metals. Magnesia, alumina, and silica are used as
refractories. (Oxides are named by substituting “a” for “ium” or “um” at
the end of a metal’s name. Thus, alumina is aluminum oxide, and soda
is sodium oxide.) Ceramics also are used as tools for high-speed machin-
ing of metals. The high hardness of ceramics at room temperature leads
to their use as abrasives, either as loose powder or bonded into grinding
tools. The low ductility of ceramics limits the structural use of ceramics
mainly to applications in which the loading is primarily compressive. Iron-
containing ceramics are used as magnets.
The bonding strengths of ionic and covalent compounds depend on the
valences of the metal and nonmetal. Compounds with higher valences (e.g.,
silicon carbide, silicon nitride) tend to be more strongly bonded than those
of lower valences (e.g., sodium chloride, magnesium oxide); thus, they have
higher melting points and higher hardnesses.
Fig. 8.1 Decrease of fracture strength with porosity. From data concern-
ing stainless steel, iron, and plaster of paris. Source: adapted from
ref 8.1
Most crystalline ceramics are prepared by pressing powder into the

desired shape and sintering at a high temperature. The sintering causes
the powder particles to coalesce, which results in some degree of porosity.
Greater porosity causes less strength (Fig. 8.1).
Glasses
Glasses are amorphous materials, meaning they have no long-range
order. However, glasses do have a great deal of short-range order. If crys-
tallization is prevented during cooling, an amorphous glass will form. It
will have short-range order inherited from the liquid. The critical cooling
rate to prevent crystallization varies greatly from one material to another.
Silicate glasses cannot crystallize unless the cooling rates are extremely
slow. On the other hand, extremely rapid cooling is required to prevent
crystallization of metallic glasses.
The basic structural units of silicate glasses are tetrahedra with Si+4
ions in the centers bonded covalently to O –2 ions at each corner. In pure
silica all corner oxygen ions are shared by two tetrahedra (Fig. 8.2), result-
ing in a covalently bonded glass with a very high viscosity at elevated
temperatures.
The compositions of typical commercial glasses are quite complex.
Soda-lime glasses may contain 72% SiO2, 14% Na2O, 11% CaO, and 3%
MgO. The Na+, Ca+2, and Mg+2 ions are bonded ionically to some of the
corner O –2 ions (Fig. 8.3). With these alkali and alkaline earth oxides, not
Chapter 8: Ceramics / 83
Fig. 8.2 Silica glass is composed of tetrahedra with four O –2 ions (shown by
open circles) surrounding Si+4 ions. each O –2 ion is shared by two
tetrahedra. Source: ref 8.2
Fig. 8.3 Commercial glasses contain alkali and alkaline earth ions, which
substitute ionic bonds for the covalent bonds between tetrahedra.
Source: ref 8.2
all of the oxygen ions are covalently bonded to two tetrahedra. This lowers
the viscosity at high temperatures.
Glass Viscosity
The viscosities of glasses increase with the fraction of the number of
oxygen ions that form bridges between two tetrahedra. Figure 8.4 is a plot
of the viscosities of several glass compositions as a function of tempera-
ture. Above the glass transition temperatures, there is a strong temperature
dependence of the viscosity.
Several temperatures are identified in terms of viscosity. In the working
range (103 to 107 Pa◊s), glass can be shaped economically. The softening
point is defined by 4 ¥ 106 Pa◊s. Above this temperature a glass object will
Fig. 8.4 temperature dependence of viscosity for several glasses. the

“working range” is the temperature range in which glasses can be
economically shaped. the straight lines on the semi-log plot do not extend below
the glass transition temperature.
creep under its own weight. Stress relief occurs in the annealing range
(1011.5 to 1012.5 Pa◊s).
Below their glass transition temperatures, glasses should be regarded as
solids rather than supercooled liquids even though they have the structure
of a liquid. It is often said that the glass in the stained glass windows in
European cathedrals is thicker at the bottom than at the top because they
have flowed viscously over the centuries. Observable thickening at the
bottoms by creep under self-weight would make the windows shorter. A
10% thickening at the bottom would be accompanied by approximately
a 5% shortening, which would be much more obvious than the thicken-
ing. There would be a gap at the top of each pane, but there are none. The
other problem with the story is that any creep would be much too small to
produce observable deformation. The stress due to self-weight at the bot-
tom of a pane, and the strain rate to produce 10% deformation over 750
years correspond to a viscosity less than could reasonably be expected by
extrapolation to 20 °C (70 °F).
The true explanation is that the glass varied in thickness when it was
installed. Until the 19th century, sheets of glass were made by spinning hot
viscous globs on a rod. Centrifugal force from the spinning caused the glob
to form into a disc (Fig. 8.5). The disc was thicker near the center than at
the edges, so panes cut from it had a thickness variation. A skilled artisan
naturally would install a pane with the thicker section at the bottom.
Thermally-Induced Stresses
Increased amounts of alkali and alkaline earth oxides in a glass increase
its coefficient of thermal expansion as well as lower its viscosity. Table 8.1
shows coefficients of thermal expansion of several glass compositions, and
Fig. 8.6 shows the relationship between the coefficient of thermal expan-
sion and viscosity.
Fig. 8.5 Until the 19th century, panes of glass were made by spinning a rod
with a glob of glass at the end and letting the centrifugal force form
a disc from which panes could be cut. Source: ref 8.3
Table 8.1 Compositions and coefficients of thermal

expansion of several glasses
Glass Composition, wt%(a) a ¥ 10 –6
Silica 100 SiO2 0.5

Vycor 4 B2O3(b) 0.6
Pyrex 12 B2O3, 4 Na 2O, 4 Al2O3 2.7
Plate glass 13 CaO, 13 Na 2O, 2 MgO, 1 Al2O3 9.0
(a) In each case balance is SiO2. (b) The composition of finished Vycor. The
composition before forming has more of other oxides.
Fig. 8.6 the relation between thermal expansion coefficient and the tem-
perature at which the viscosity is 107 pa◊s (108 poise). Compositions
that promote lower working temperatures have higher coefficients of thermal
expansion.
Glasses, like most ceramics, are susceptible to fracturing under stresses

caused by temperature gradients. When there is a temperature change, two
regions in close contact with each other must undergo the same dimen-
sional change. The thermal expansion or contraction in one region must
be matched by an elastic expansion or contraction in the other. The elastic
dimensional change requires a stress, so internal stresses arise when there
are different temperature changes in adjacent regions. If these stresses are
high enough, fracture will occur.
Differences in resistance to thermal shock between different grades of
glass are related to differences in their coefficients of thermal expansion.
Larger stresses arise in materials with high coefficients of thermal expan-
sion, so they are more susceptible to breaking under thermal shock. The
thermal shock resistance of silica glass is considerably better than that of
plate glass.
Silica-Rich Glass
A very high-silica glass product was developed to circumvent the dif-
ficulty in forming glasses that have a low coefficient of thermal expansion.
The starting composition (62.7% SiO2, 26.9% B2O3, 6.6% Na2O, and 3.5%
Al2O3) has a low enough viscosity at a reasonable temperature for the glass
to be shaped. After the glass is shaped, it is heat treated between 500 and
750 °C (900 and 1380 °F). During this heat treatment a reaction separates
the glass into two phases, one containing 96% SiO2, 4% B2O3 and the other
containing all of the Na2O and Al2O3. The phase rich in soda and alumina
is removed by acid etching, leaving a silica-rich glass with approximately
28% porosity. This can be used either as a filter or reheated to allow sur-
face tension to produce a fully dense product.
Devitrification
If a glass is held for a long period at an elevated temperature, it may start
to crystallize or devitrify. Devitrification of fused quartz (silica glass) to
the crystalline silica is slow. Nucleation usually occurs at a free surface
and often is stimulated by contamination from alkali ions such as sodium.
With surface contamination, devitrification of fused quartz may occur at
temperatures as low as 1000 °C (2000 °F). However, if the surface is clean,
it rarely occurs below 1150 °C (2100 °F).
Some glasses may be intentionally crystallized to produce fine-grained
ceramics. These materials are first formed as a glass into their final shapes
at elevated temperatures, then heat treated at a lower temperature to allow
nucleation of crystals, and finally heated to a somewhat higher temperature
to allow growth of the crystals. Glass forming processes are used to obtain
the final shape while producing a final product that is resistant to thermal
shock because of a very low thermal expansion coefficient.
Photosensitive Glasses
Photosensitive glasses containing microcrystalline silver halides darken
with exposure to ultraviolet light and lighten after the sunlight is removed.
The darkening occurs when silver halides are reduced to metallic silver on
exposure to ultraviolet light.
Other Inorganic Glasses

Borax, B2O3 (boron trioxide), forms a glass in which the basic structural
elements are triangles with boron at the center surrounded by and cova-
lently bonded to three oxygen atoms. Each of the oxygen atoms is shared
by two triangles (Fig. 8.7).
Fig. 8.7 Boron trioxide glass. each boron atom is covalently bonded to three
oxygen atoms, which form a triangle around the boron atom. each
oxygen atom is shared by two triangles. Source: ref 8.2
There also are glasses consisting of long selenium (or tellurium) chains
bonded with germanium or arsenic. In these glasses the basic structural
units are chains that are cross-linked by germanium or arsenic. The struc-
ture of molten pure selenium and pure tellurium consists of long-chain
molecules.
Residual Stresses
The fracture resistance of glass can be improved by inducing a pattern of
residual stress with the surface under compression. The surface compres-
sion is balanced by a residual tension in the center. Residual compression in
the surface increases fracture resistance because fractures almost always
start at the surface, and because the stresses are highest at the surface if
they involve any applied bending or torsion. Furthermore, defects are much
more likely to be present at the surface. With residual compression at the
surface, greater external loads can be tolerated before fracture occurs.
Compressive residual stresses can be induced in the surface either by
cooling rapidly from high temperature or by chemical treatment. In the
former process, called tempering, the glass is cooled by jets of air. During
the cooling, the surface undergoes a thermal contraction before the inte-
rior. The different amounts of thermal contraction are accommodated by
viscous flow of the interior. When the interior finally cools, dimensional
compatibility is maintained by elastic contraction (compression) of the
surface. Glass also may be chemically tempered by ion exchange. Glass
is immersed in a molten salt bath containing potassium ions. Some of the
K+ ions diffuse into the glass, replacing Na+ ions. Because the K+ ions are
larger than the Na+ ions that they replace, the region affected is left in
compression. One important difference between the two processes is the
depth of the compressive layer. The depth of the region under compres-
sion is much less in the chemically tempered glass than in glass tempered
by rapid cooling. The benefits of tempered glass are significant. Not only
is tempered glass more resistant to fracture than untempered glass, but it
also breaks into much smaller pieces, which are less dangerous than the
large shards produced in fracture of untempered glass. Tempered glass is
used for the side and rear windows of automobiles for these reasons. The
windshields of automobiles are made from safety glass produced by lami-
nating two pieces of glass with a polymeric material (polyvinyl butyral,
PVB) that keeps the broken shards from causing injury. Figure 8.8 shows
fracture patterns typical of untempered glass, laminated safety glass, and
tempered glass.
Pottery
Pottery was the first man-made material. The oldest known pottery is
dated between 27,000 and 23,000 b.c. Pottery is made by shaping wet
Fig. 8.8 typical fracture patterns of three grades of glass. (a) annealed
(untempered) glass. (b) Laminated safety glass. (c) tempered glass.
Source: ref 8.4
Fig. 8.9 Schematic of the molecular structure of clay. Source: ref 8.2
clay, drying it, and then firing it at an elevated temperature that changes
its chemical structure.
There are several forms of clay. All are aluminosilicates; many con-
tain other elements. Figure 8.9 shows the platelike structure of kaolinite,
Al2(Si2O5)(OH)4. Water absorbed between platelets allows them to slide
easily over one another so clay can be formed easily when wet.
Typical clay mixtures used for ceramics often contain other materials
including ground quartz (SiO2) and a flux such as a feldspar, which is an
aluminosilicate containing Na+, K+, and Ca+2.
Processing of Clay Products

Clay can be shaped either by pressing into the desired shape or by slip
casting. Slip is a suspension of clay in water made by adding a small
Fig. 8.10 Steps in slip casting. Source: ref 8.2
amount of a deflocculant (often sodium silicate or soda ash), which allows

the clay to be suspended in water. The slip is poured into a plaster-of-paris
mold that absorbs water and causes the clay near the surface of the plaster
to become solid. When this solid skin reaches the desired thickness, the
mold is emptied and the resulting shape removed. Figure 8.10 illustrates
the slip casting process for clay products.
The shaped clay is fired only after it is first air dried. Some shrinkage
occurs during air drying. After air drying, the shape is said to be green
and must be handled with care because it has little strength. Next it is
fired, usually between 900 and 1400 °C (1700 and 2600 °F). Firing drives
off the chemically combined water, with additional shrinkage but a great
increase of strength. For pure kaolinite, the composition after firing is
3(Al2O3)◊2(SiO2)2, which is a mineral called mullite.
3Al2(Si2O5)(OH)4 Æ 3(Al2O3)◊2(SiO2)2 + 6H2O
Figure 8.11 is the SiO2-Al2O3 phase diagram.

Usually silica and feldspar are added to the kaolinite. During firing they
form a silica-rich glass that bonds together the mullite crystals.
Earthenware, ovenware, stoneware, china, and porcelain are various
forms of pottery that differ in composition and firing temperature. Earth-
enware basically is kaolinite with some silica and feldspar fired at lower
temperatures than other clay products. It is relatively weak with porosity
of 5 to 20%. It may be left unglazed as in flowerpots and soil pipe, or it
may be glazed to make it water resistant. Stoneware is fired at higher
temperatures, which reduces the porosity to less than 5%, giving it bet-
ter strength. China is fired at even higher temperatures, which converts
much of the silica, clay, and feldspar mixture into a glass. Increased firing
temperatures lower the thermal expansion coefficient, a. Pottery with a <
4 ¥ 10 –6/K can withstand air cooling after heating in an oven. To be able
to withstand flame contact, the coefficient of thermal expansion should be
less than 2 ¥ 10 –6/K.
Fig. 8.11 the SiO2-al2O3 phase diagram showing mullite as an intermedi-

ate phase
Most pottery is glazed. After firing, a glaze is applied as a suspension of

low-melting-point glass particles. Then the pottery is fired a second time
to allow the glaze to melt and spread over the surface. Glazing has two
functions: earthenware vessels would otherwise be unable to hold liquids
due to porosity, and glazing also is done for decoration. To avoid cracking
on cooling, the glaze should have a lower coefficient of thermal expansion
than the pottery base so it will be left under a residual compressive stress.
Sometimes, however, for aesthetic reasons glazes intentionally are formu-
lated to produce surface cracks.
Hydration Reactions
Several materials react with water to form solids. Among these are
plaster of paris, lime plaster, and Portland cement. Plaster of paris is the
hemi-hydrate of calcium sulfate, CaSO4◊0.5H 2O. It is obtained by heating
gypsum, CaSO4◊4H2O, to approximately 150 °C (300 °F), which releases
some of the hydrated water.
2CaSO4◊4H2O Æ 2CaSO4◊0.5H2O + 7H2O
When dry plaster powder is mixed with water to form a paste, it hydrates
to form hard gypsum by the reverse reaction. The rate of the hydration
reaction depends on the particle size of the plaster of paris because the
reaction product surrounds the unreacted plaster of paris (Fig. 8.12). This
slows the reaction because water must diffuse through the gypsum. Thicker
gypsum layers slow the reaction; thus, hydration occurs more slowly with
large particles.
Fig. 8.12 In a typical hydration reaction, the product separates the reacting
chemicals. here water is separated from the plaster of paris by the
gypsum formed. Source: ref 8.2
Lime plaster is a mixture of calcium hydroxide and sand (or other inert
fillers). Lime is made by heating limestone (calcium carbonate) to above
830 °C (1520 °F) to cause it to decompose into calcium oxide and carbon
dioxide, CaCO3 Æ CaO + CO2. When lime is hydrated with water, it forms
lime plaster, CaO + H2O Æ Ca(OH)2. With long periods of time, plaster
reacts with atmospheric CO2 to form calcium carbonate. Commercial plas-
ters contain both plaster of paris and lime. Lime often is added to plaster
of paris to control the rate of hardening. The rate of the hydration reaction
depends on particle size as well as the fraction of each component.
Portland Cement
Portland cement contains several minerals, the two principal minerals
being tricalcium silicate, (CaO)3◊(SiO2), which is abbreviated as C3S, and
dicalcium silicate (CaO)2◊(SiO2), abbreviated as C2S. There also is some
tricalcium aluminate, (CaO)3◊(Al2O3), abbreviated by C3A.
Dry powdered cement is mixed with water, which forms hydrates by the
reactions:
Ca3Al2O6 + 6H2O Æ Ca3Al2(OH)12

Ca2SiO4 + xH2O Æ Ca2SiO4◊(H2O)x
Ca3SiO5 + (x + 1)H2O Æ Ca2SiO4◊ (H2O)x + Ca(OH)2
Cement also may contain some tricalcium aluminum ferrite,

(CaO)3◊(Al2O3)◊(FeO), abbreviated as C3AF.
Hardening occurs by these hydration reactions in which water is chemi-
cally bound into hard compounds rather than by “drying.” The rate of
hardening is controlled by the composition of the mixture and by the par-
ticle size of the cement powder. Because heat is released during hydration,
large structures must be cooled to slow the curing to prevent thermal gra-
dients that would cause cracking.
Fig. 8.13 Concrete consists of gravel particles (large open circles), sand
(small gray circles), and cement paste filling the remaining space.
Source: ref 8.2
Concrete Mixes
Concrete is a mixture of gravel, sand, and cement paste (Fig. 8.13). There
are two reasons for adding gravel and sand to cement: sand and gravel par-
ticles are stronger than the hydrated cement, and they are significantly less
expensive than cement. If the particles of gravel filled 60% of the space and
sand filled 60% of the remaining space, the volume that the cement paste
must fill would be only (100 – 60)(100 – 40) = 16%. However, because
mixing is not complete, the ratio of sand to cement and the ratio of cement
paste to sand should be higher.
A common concrete mix contains gravel, sand, cement, and water in
the ratio of 3.1 gravel: 2.6 sand: 1.0 cement powder: 0.55 water by volume.
With this mixture there is enough sand to fill the spaces between gravel
particles and enough cement paste to fill the spaces between the sand.
Carbon
Carbon occurs in several forms including diamond, graphite, amorphous
carbon, and fullerenes. None of these forms can be classified as a metal,
ceramic, or polymer. Figure 8.14 shows the equilibrium between graphite,
diamond, and liquid.
Diamond
Each carbon atom in diamond is covalently bonded to four other car-
bon atoms (Fig. 8.15). Very strong bonding makes diamond the hardest
(10,000 kg/mm2) known material. Diamond is used for cutting very hard
materials. Diamond has an extremely high Young’s modulus (1050 GPa,
Fig. 8.14 phase diagram showing the equilibrium phases of carbon. Source:
ref 8.2
Fig. 8.15 the crystal structure of diamond. each carbon atom is covalently
bonded to four others.
or 15 ¥ 104 ksi) and a very low coefficient of thermal expansion (1 ¥

10 –6/K). It has the highest thermal conductivity of all materials (2 kW/
m◊K compared with 401 W/m◊K for copper), making it useful for dissi-
pating heat. Its density (3.52 Mg/m3) is considerably greater than that of
graphite (2.25 g/m).
The first synthetic diamonds were made by subjecting carbon to very

high pressures at high temperatures. Later it was learned that diamond
also can be grown by chemical vapor deposition (CVD) under low pressure
(1 to 27 kPa, or 0.15 to 3.92 psi.) Gasses including a carbon source and
typically hydrogen are heated in a pressurized chamber and broken down,
depositing diamond on exposed surfaces. Large areas (over 150 mm2, or
0.23 in.2) can be coated on a substrate. This allows CVD diamond films to
be used as heat sinks in electronics and wear-resistant surfaces.
Graphite
The structure of graphite consists of sheets of carbon atoms arranged in
a hexagonal pattern (Fig. 8.16). The bonding in the hexagonal sheets is like
that in a benzene ring. Each carbon has two single bonds and one double
bond. The sheets are bound to each other by weak van der Waals bonds. The
ease with which sheets can slide over one another explains the lubricity of
graphite. Because the double bond can move freely, the electrical conductiv-
ity in the plane of the sheet is very high, like that of a metal. The electrical
and thermal conductivities perpendicular to the sheets are very low. The
Young’s modulus is very high in the planes of the sheet and very low per-
pendicular to them. The anisotropy of properties listed in Table 8.2 reflects
the difference in bond strengths parallel and perpendicular to the sheets.
Fig. 8.16 the structure of graphite. Source: ref 8.2
Table 8.2 Directional properties of graphite

Property Perpendicular to c Parallel to c
Electrical resistivity, ohm◊m 2.5 to 5 ¥ 10 –6 3000 ¥ –6

Thermal conductivity, W/m◊K (Btu◊in/(h◊ft2◊°F) 398 2.2
Thermal expansion at 20 °C (C –1) 25 ¥ 10 –6 Slightly negative °C –1
Elastic modulus, GPa (ksi) 1060 35.5
Source: Ref 8.5
Carbon Fibers
Carbon fibers are thin graphite ribbons. They are made by pyrolizing
polymeric precursors such as polyacrylonitrile (PAN), pitch, rayon, or other
polymers that have carbon-carbon backbones. (Pyrolysis is the heating of
carbonaceous materials in the absence of oxygen to drive off hydrogen.)
Processing consists of several steps: stretching to align molecular chains;
then heating to stabilize the orientation, and pyrolize and graphitize. The
strengths and moduli are very high because they involve stretching car-
bon-carbon bonds. The properties of graphite fibers depend greatly on the
nature of the precursor, its diameter, and the details of processing. Young’s
moduli of commercial carbon fibers vary from 200 to 700 GPa (29 ¥ 103
to 102 ¥ 103 ksi), and tensile strengths from 2 to 7 GPa (290 to 1015 ksi).
Carbon fibers are used in epoxy-bonded composites.
Amorphous Carbon
Although soot and coal often are referred to as being amorphous, they
actually contain small regions that are graphitic or diamond-like. Amor-
phous carbon can be produced by vapor sputter deposition. Some of the
bonding is sp2 (graphite-like) and some is sp3 (diamond-like). (The “s” and
“p” in sp2 and sp3 refer to sigma and pi bonds, respectively.) The ratio of
the two types of bonds may vary considerably. Amorphous carbon con-
tains a high concentration of dangling bonds, causing deviations of the
interatomic spacing of more than 5%, and noticeable variations in bond
angles.
Fullerenes
Until 1985, the only known elemental forms of carbon were diamond,
graphite, and amorphous carbon. Then in 1985, Kroto et al. (Ref 8.6)
announced the discovery of C60, a spherical arrangement of carbon atoms
in hexagons and pentagons (Fig. 8.17). They called this form the Buckmin-
sterfullerene after the architect, Buckminster Fuller, who developed the
geodesic dome. The name for this type of carbon molecule has since been
shortened to fullerene, and the molecules are commonly called Buckyballs.
Since their discovery, it has been found that fullerenes can be made in
quantity from electrical arcs between graphite electrodes. Approximately
75% of the fullerenes produced by arcs are C60, 23% are C80, with the rest
being even larger molecules. Approximately 9000 fullerene compounds
are known.
Nanotubes
Carbon nanotubes are in the family of fullerenes. They can be regarded
as hexagonal sheets of carbon atoms (graphene sheet), rolled up to make
a cylinder and capped at the ends by one-half of a Buckyball (Fig. 8.18).
Fig. 8.17 a C60 Buckyball, which has 60 carbon atoms arranged in hexagons
and pentagons. the arrangement is the same as that on a soccer
ball. Source: ref 8.2
Fig. 8.18 Single-wall nanotubes can be thought of as being made from

rolled-up chicken wire. Source: ref 8.2
Tubes typically have diameters of approximately 1 nm (0.039 min.). The

diameter of the smallest nanotube corresponds to the diameter of the
smallest Buckyball (C60). The length-to-diameter ratio typically is approxi-
mately 104.
Nanotubes can be made by arc discharge, laser ablation, or chemical
vapor deposition (CVP). There are a number of potential uses of fullerenes,
including using nanotubes for field effect transistors. Nanotubes decorated
with metal atoms have a great potential for hydrogen storage in fuel cells.
NoTES oF INTEREST
• photosensitive glass was first developed by Donald Stookey at
Corning Glass in 1937. a U.S. patent was issued in 1950.
• portland cement was developed in england. Its name comes from
its similarity to the stones on the Isle of portland. a British patent
on its composition was issued in 1824.
In another potential use of fullerenes, A3C60 compounds in which A is an

alkali (potassium, rubidium, cesium, sodium) are superconductors. Lastly,
sieves made of fullerenes have been suggested that allow biological com-
pounds to pass through but do not permit entrance of larger viruses.
Exercise
1. Changes during Processing of Clay
Make an object out of clay. Weigh it. Weigh it again after a day. Then
heat it to 400 °C (750 °F) for one hour and let it cool. Weigh it again.
Explain the differences in weight.
The weight decreases during the day after forming because of the
evaporation of water. The weight decreases further when heated to
400 °C as more water is driven off. Hydration levels decrease both
times.
REFERENCES
8.1 R.L. Coble and W.D. Kingery, J. Am. Ceram. Soc., Vol 29, 1956
8.2 W.F. Hosford, Materials for Engineers, Cambridge U. Press, 2008
8.3 Diderot Pictorial Encyclopedia of Trades and Industries, Plate 245,
1758
8.4 Engineering Materials Handbook Volume 4: Ceramics and Glasses,
ASM International, 1991
8.5 H.O. Pierson, Handbook of Carbon, Graphite, Diamond and Fuller-
enes, Knovel, 2001
8.6 H. Kroto, J. Heath, S. O’Brien, R. Curl, and R. Smalley, Nature, Vol
318, 1985
Chapter 9
Polymers
THE WORD polymer is the scientific name for what is commonly called
a plastic. The word polymer comes from the Greek poly (meaning many)
and mer (meaning parts). Polymers are very large molecules with many
repeating parts, or mers. For example, polyethylene is composed of many
repeating ethylene mers. It is formed by the reaction:
nCH2 = CH2 Æ |-CH2-CH2-|n
where n is a very large number. This reaction is called an addition reac-

tion. It must be initiated by breaking the double carbon-carbon bond in
the ethylene monomer. This may be broken by stimulation of an initiator
such as a radical, R–, which produces another radical that can stimulate yet
another ethylene molecule in the reaction:
R– + CH2+CH2 Æ R– (+ CH2-CH2) –
Another type of polymerization reaction involves two different mono-

mers and produces a small byproduct. An example is the reaction between
adipic acid, H–O–C= O–(CH2)4 –O+C–O–H, and hexamethylenediamine,
NH2–(CH2)6NH2:
H 2O
] [ ´ ´
H H O O
N– (CH2)6 – N H–O– C(CH2)4 – C –O–H

[ ]
H H
that produces nylon with a water molecule as a byproduct. This is repeated

many times to make a long molecule. This type of reaction is called a
condensation reaction because in the laboratory the resulting water con-

denses in a cool part of the apparatus.
Thermoplastics
The two examples above produce linear molecules. Such polymers are
said to be thermoplastic because they soften on heating. Table 9.1 gives a
number of examples of linear thermoplastics.
Other thermoplastics have more complex backbones. Among these are
nylon, polyester (PET), polycarbonate, cellulose, and poly paraphenylene ter-
phthalamide (PPTA). Figure 9.1 illustrates the molecular structure of these.
Silicones are polymers with -Si-O-Si-O- backbones.
Elastomers are rubberlike polymers. They have carbon backbones that
include carbon-carbon double bonds. Figure 9.2 shows the repeating unit.
The radicals, R, are listed in Table 9.2.
In all cases there is weak van der Waals bonding between neighboring
chains. This allows heating to melt thermoplastics.
Thermosetting Polymers
In contrast to thermoplastics, some polymers form three-dimensional
structures that cannot be melted, and where all mers are tied together by
covalent bonds. Such polymers are said to be thermosetting. Once formed,
their shape cannot be changed. Figure 9.3 is a schematic sketch of such
a network. The open circles represent monomers that are tri-functional.
Some have reacted with three smaller monomers (black) while others have
reacted with only two.
ı 1 3 ı
ı fi fi ı
ıß Cß C ß ı
ı fi fi ı
Table 9.1 Polymers of the general form ı 2 4 ı
Polymer name 1 2 3 4 Abbreviation
Polyethylene H H H H PE
Polyvinyl chloride H H H Cl PVC
Polyvinyl alcohol H H H OH PVA
Polypropylene H H H CH3 PP
Polyvinyl acetate H H H O PVAc
´
O–C–C–H3
Polystyrene H H H PS
Polyacrylonitrile H H H N PAN
Polyvinylidene H H Cl Cl PVDC
Polyethylene methacrylate H H CH3 … PMMA
Polyisobutylene H H CH3 CH3 PIB
Polytetrafluoroethylene F F F F PTFE
symbolizes a benzene ring.

Chapter 9: Polymers / 101
Fig. 9.1 Structure of several linear polymers. Kevlar is a registered tradename

of e.I. du pont de Nemours and Company. Source: ref 9.1
Fig. 9.2 Basic structure of rubbers. the filled circles are hydrogen atoms and
R stands for a radical. Source: ref 9.1
Table 9.2 Several rubbers
R Rubber
H Polybutadiene (buta-rubber)
Cl Polychloroprene
CH3 Polyisoprene (natural rubber)
Among common thermosetting polymers are phenol formaldehyde

(Fig. 9.4) and urea formaldehyde (Fig. 9.5). Polyesters and epoxies also
are thermosetting.
Fig. 9.3 Schematic illustration of a three-dimensional network formed by

two types of monomers. the open circles represent a large mono-
mer, and the black circles another smaller monomer. Source: ref 9.1
Fig. 9.4 the structure of phenol formaldehyde. Source: ref 9.1

Degree of Polymerization and Molecular Weight

The degree of polymerization is the average number of mer units per mol-
ecule. It is the molecular weight of the polymer divided by the molecular
weight of the mer.
Both strength and melting temperature increase with molecular weight.
Figure 9.6 shows this effect for the paraffin series, CxH2x+2.
Branching
Linear polymers may form branches, as illustrated in Fig. 9.7.
Fig. 9.5 the structure of urea formaldehyde. Black dots are hydrogen atoms.
Source: ref 9.1
Fig. 9.6 Melting point increase of paraffin series with molecular weight.
Source: ref 9.1
Cross-linking and Stereoisomerism

Cross-links may be formed between molecular chains. Rubber is vulca-
nized with sulfur to form cross-links between polyisoprene molecules (Fig.
9.8). The hardness of the rubber increases with the number of cross-links.
Sometimes there is more than one distinguishable arrangement of side
groups around the carbon-carbon chains in molecules of the same chemi-
cal formula. Rotation around the carbon-carbon bond cannot change these
distinguishable arrangements. One example is polypropylene. If all of the
CH3 groups are on the same side of the chain, the polymer is said to be
isotactic, whereas if they are on opposite sides, the polymer is said to be
syndiotactic (Fig. 9.9). If the position of the CH3 groups is random, the
polymer is atactic.
Fig. 9.7 Branched polyethylene. Source: ref 9.1
Fig. 9.8 Cross-linking of rubber molecules by sulfur. Source: ref 9.1

Fig. 9.9 tacticity of linear polymers. ref 9.1
Copolymers
Many commercial plastics are copolymers, or polymers in which two or
more monomers are polymerized together. Acrylonitrile butadiene sty-
rene (ABS) is a copolymer of acrylonitrile, butadiene, and styrene that
incorporates some of the rubberlike properties of buta-rubber. What is
commercially called “vinyl” is a copolymer of polyvinyl acetate and poly-
vinyl chloride (PVC). The properties of vinyls depend on the proportions
of vinyl acetate and vinyl chloride. Pure PVC is rigid and brittle. Its use is
limited to pipes and siding. With increasing amounts of vinyl acetate, it is
used for insulating wires, molded parts, and as a lacquer.
Molecular Configuration
Linear polymers may be either amorphous or crystalline, or may contain
both amorphous and crystalline regions. One may think of the molecules
in amorphous regions of a polymer as being like cooked spaghetti. In crys-
talline regions, the molecules are parallel and fit closely together. Figure
9.10 illustrates these two possibilities.
The crystalline regions have a higher density and are stiffer than the
amorphous regions. The factors that tend to prevent crystallinity are those
that decrease the order of the polymer chains such as side branching, cross-
linking, large side groups, irregular spacing of side groups (being atactic),
and copolymerization. As a linear polymer is stretched, the molecules
tend to become aligned with the direction of stretching. This increases
the crystallinity and stiffness. Some polymers are highly crystalline but
others have little or no crystallinity. Branching, large side groups, and
copolymerization all tend to suppress crystallinity. There is no branch-
ing in high-density polyethylene, but low-density polyethylene is highly
branched.
Fig. 9.10 In amorphous regions (left) the molecules are randomly oriented,
while in crystalline regions (right) the molecules are aligned.
Source: ref 9.1
Glass Transition
The bonds between neighboring molecular chains are weak van der Waals
bonds. Therefore, most polymers do not readily crystallize. Instead, on
cooling they form an amorphous glass at a glass transition temperature.
The relative positions of molecules are frozen so the amorphous glass is
not a liquid. The change of specific volume on cooling is schematically
illustrated in Fig. 9.11.
The glass transition temperatures of several polymers are given in Table
9.3.
At temperatures below their glass transition temperature, polymers tend
to have a high Young’s modulus and be brittle. Figure 9.12 shows the sharp
drop of Young’s modulus for PVC near its glass transition temperature.
Clearly the glass transition temperature is near 80 °C (180 °F) and depends
slightly on the time of loading.
The reason that the modulus is time dependent is illustrated by Fig. 9.13.
For the same stress, the strain increases with the time of loading so the
modulus drops.
Additives
Because the carbon-carbon bonds of polymers can be broken by ultra-
violet radiation; carbon black, titanium dioxide, and other pigments often
are added to block sunlight. Dyes do not perform this function. Other
examples of additives are fillers such as wood flour and silica, which often
are used to decrease price; and hard particles such as silica, which increase
wear resistance. Lastly, small molecules called plasticizers are added to
polymers to decrease the glass transition temperature and elastic modulus.
In the past, halogen-containing compounds were used for flame retardants,

but because of toxicity and environmental concerns these compounds are
being replaced by phosphorous-, nitrogen-, and silicon-containing organic
compounds, inorganic compounds, and nanomaterials.
Degradation
There is a spectrum of interactions between plastics and solvents. There
is no interaction of polyethylene or polyethylene terephthalate with water.
Fig. 9.11 Change of the specific volume of polyethylene with temperature.

If it does not crystallize at the melting temperature, polyethylene
will remain a supercooled liquid until it reaches its glass transition temperature.
Source: ref 9.1
Table 9.3 Glass transition (Tg ) and melting (Tm)

temperatures of several polymers
Polymer Tg, °C (°F) Tm, °C (°F)
Polyethylene (high density) –120 (–184) 140 (284)

Polybutadiene –70, (–94) (a)
Polypropylene –15 (5) 175 (347)
Nylon 6/6 50 (122) 265 (59)
Polyvinyl chloride 85 (185) 210 (410)(a)
Polystyrene 100 (212) 240 (464)(a)
(a) Difficult to crystallize
Other plastics will absorb a solvent and swell. Examples include nylon in
water and PVC in ketones. Some solvents may dissolve certain polymers.
Polyvinyl alcohol dissolves in water. Polyvinyl chloride pipes are joined
together with solvents that evaporate to form welds. Gasoline will cause
hydrocarbon rubbers to swell. Alcohol attacks polyurethanes.
Fig. 9.12 Young’s modulus of polyvinyl chloride (pVC) is approximately three

orders of magnitude below the glass transition temperature rather
than above it. It depends only slightly on the rate of loading. Source: ref 9.1
Fig. 9.13 at constant stress, the strain increases so the modulus, σ/ε,
decreases with time of loading. Source: ref 9.2
The double bonds of vulcanized rubber are susceptible to attack by

ozone. The scission reaction involves reaction with ozone:
H H H H
–
–
–
–
–
– R– C = C – R + O3 Æ –R– C= O + –R– C= O + O
A combination of stress and environments containing some chemicals may

lead to stress cracking.
Properties and Uses of Polymers

Polyethylene Terephthalate (PET)—Often Simply Called ‘Polyester.’
The density of PET is 1.35 to 1.38 g/cm3 (84.27 to 86.15 lb/ft3), melting
temperature (Tm) = 260 °C (500 °F), and glass transition (Tg) = 75 °C (167
°F). It is tough, provides a barrier to water and gases, and finds uses as
beverage bottles and food containers, yarns and polyfill, and film that is
used for its dielectric properties.
High-Density Polyethylene (HDPE). The density of HDPE is 0.94 to

0.96 g/cm3 (58.68 to 59.93 lb/ft3), Tm = 130 °C (270 °F), and Tg = –90 °C
(–130 °F). It is highly crystalline, giving it a high modulus of elasticity and
making it translucent. It is tough, strong, easy to process, and resistant to
water and chemical attack. It finds uses as bottles for milk, bleach, and
motor oil.
Low-density polyethylene (LDPE) contains many branches that inhibit

crystallization. Its density is 0.92 to 0.94 g/cm3 (57.43 to 58.68 lb/ft3), Tm
= 170 °C (340 °F), and Tg = –110 °C (–170 °F). It is tough, flexible, and
transparent, and finds wide usage in wire insulation, squeezable bottles,
furniture, and carpets.
Polyvinyl Chloride (PVC)—Often Simply Called ‘Vinyl.’ The den-

sity of PVC is 1.32 to 1.42 g/cm3 (82.40 to 88.64 lb/ft3), Tm = 212 °C (414
°F), and Tg = 87 °C (189 °F). In unplasticized forms it is hard and brittle. It
is used for building materials such as siding, window frames, and piping
systems. As plasticized and copolymerized with polyvinyl acetate, it is
used for clothing, upholstery, flexible tubing, and nonfood containers. Its
flexibility depends on how much polyvinyl acetate has been copolymerized
with it. It has stable electrical properties, is easy to blend and process, and
is suitable for injection molding. Polyvinyl chloride is flame resistant but
the chlorine in it produces HCl when PVC is burned.
Polystyrene (PS)—Contains a Benzene Ring. The density of PS is

1.05 g/cm3 (65.54 lb/ft3), Tm = 240 °C (460 °F), and Tg = 95 °C (203 °F). It
is brittle and hard. It is molded into rigid objects, but the greatest use is as
foam for insulation in construction and cups, and for packaging (“peanuts”
and rigid shapes).
Polypropylene (PP). The density of PP varies from 0.85 g/cm3 (53.06

lb/ft3) for amorphous PP to 0.95 g/cm3 (59.30 lb/ft3) for crystalline PP; Tm
= 165 °C (329 °F); and Tg = –10 °C (14 °F). Its resistance to chemical attack
makes it suitable for linings that must be resistant to chemicals, sinks,
ducts, barrels, tanks, pump components, and prosthetic devices. As a fiber
it is used in “polypro” clothing.
Polymethyl Methacrylate (PMMA). The density of PMMA is 1.19 g/

cm3 (74.28 lb/ft3), Tm = 130 to 140 °C (270 to 280 °F), and Tg = 105 °C (221
°F). It is highly transparent. It has a higher impact strength than glass but
is softer and is used wherever toughness and transparency are required.
Applications include shields for hockey, aircraft windows, colored glasses,
and eyeglass lenses.
Nylon 6/6. There are a number of nylon compounds, which vary in

the length of the monomers. The most common is nylon 6/6, which is
made from two monomers, hexamethylenediamine and adipic acid, each
of which contains six carbon atoms. The density of nylon 6/6 is 1.13 to 1.15
g/cm3 (70.54 to 71.79 lb/ft3), Tm = 265 °C (509 °F), and Tg = 57 °C (135 °F).
It is used as a fiber in clothing and rope, as well as molded into gears and
other objects that require strength and low friction.
Polycarbonate. The density of polycarbonate is 1.20 to 1.22 g/cm3

(74.91 to 76.16 lb/ft3), Tm = 267 °C (513 °F), and Tg = 150 °C (300 °F). It is
very tough and transparent. It is used in applications requiring toughness
and heat resistance such as bulletproof glass, injected molded and extruded
shapes, film, signs, and football helmets.
Polyvinylidene Chloride. The density of polyvinylidene chloride is

1.7 g/cm3 (106.12 lb/ft3), Tm = 169 °C (336 °F), and Tg = –17 °C (1.4 °F). Its
principal use is as plastic food wrap.
Aramids. There are three common grades of aramids. The density of

aramids is 1.44 g/cm3 (89.89 lb/ft3), Tm = 640 °C (1180 °F), and Tg = 375
°C (707 °F).
Aramids are an aromatic polyamide. One of the grades typically is used
for reinforcements in tires and other rubber mechanical goods. Another
of the grades of aramids is used in industrial applications such as cables,
replacement for asbestos, brake linings, and body armor. A third grade,
considered to have the greatest tensile strength of all the aramids, is used
in applications such as plastic reinforcement for boat hulls, airplanes, bicy-
cles, bulletproof vests, trampolines, and tennis rackets.
Polytetrafluoroethylene (PTFE). The density of PTFE is 2.2 g/cm3

(137.34 lb/ft3), Tm = 327 °C (621 °F), and Tg = –110 °C (–166 °F). It decom-
poses at 350 °C (662 °F), so it cannot be molded. Because of its extremely
low coefficient of friction it is used for coating armor-piercing bullets,
bushings, bearings, and frying pans. A breathable PTFE fabric variant
with micropores is used for raingear.
Phenol Formaldehyde. Although its use has declined because of cost,

phenol formaldehyde is still used for small parts such as disc cylinders,
electric plugs, and switches.
Urea formaldehyde is commonly used for electrical appliance casings

such as desk lamps. It largely has replaced phenol formaldehyde.
Polyurethanes are used as both flexible and rigid foams. Flexible foam,
often referred to as “foam rubber,” is used for auto seats, chairs, and mat-
tresses; rigid foam is used in surfboards. Solid polyurethanes are used
for roller blade wheels, tables, and furniture, and for encasing electronic
components. Polyurethanes also are the basis of some varnishes.
Acrylonitrile butadiene styrene (ABS) combines the strength and

stiffness of acrylonitrile and styrene with the flexibility of butadiene
rubber. It is used for keyboards. Because of its toughness and impact resis-
tance, it is used in canoe hulls.
Epoxies. An epoxy is a thermosetting resin that polymerizes when

mixed with a catalyst or hardener. Most common resins are produced from
a reaction between epichlorohydrin and bisphenol-A. Epoxy materials tend
to harden somewhat more gradually than polyesters. Epoxies are widely
used as adhesives.
Silicones are analogous to linear polymers. They have a Si-O backbone

with organic radicals or hydrogen attached to the silicon atoms (Fig. 9.14).
Silicones are stable up to 250 °C (480 °F) and are resistant to sunlight,
Fig. 9.14 Structure of silicones. the small open circles represent either Ch3
groups or other hydrocarbons. Source: ref 9.1.
oxidation, and chemical attack. They have low toxicity. The uses of sili-
cones include body implants, sealants for joints in construction, O-rings,
and spatulas for cooking. Silicone greases for lubrication withstand higher
temperatures than hydrocarbons.
Stretching of a Thermoplastic
When a linear polymer is stretched, the yielding occurs first in some region
with the molecules becoming aligned with the direction of stretching. This
results in a drop in stress (Fig. 9.15). Continued stretching occurs by propa-
gation of the deformed region only after the whole specimen has yielded
(Fig. 9.16).
NOTE OF INTEREST
Celluloid was the first synthetic plastic material. It was developed by
John Wesley hyatt in the late 1860s. he reacted a dispersion of cel-
lulose nitrate and camphor. Celluloid is a tough material, with great
tensile strength and resistance to water, oils, and dilute acids; it is
capable of low-cost production in a variety of colors. Its uses included
combs, collars, toys, film, and many other consumer goods. although
its flammability led to its replacement by newer synthetic polymers in
many of these uses, celluloid has continued to be manufactured and
widely used in europe, the United States, Japan, and elsewhere.
Stress
Elongation
Fig. 9.15 Stress-strain curve for polyethylene. Note the formation and propa-
gation of a necked region along the gage section. Source: ref 9.2
Fig. 9.16 Stages of neck formation and propagation in high-density poly-

ethylene. Source: ref 9.3
Exercises
1. Expansion of Yielded Region of Plastic
Take the piece of plastic that holds a six-pack of beverage cans together
and try to stretch the ligaments.
This will require a high force at first, but then the force required will
decrease as the yielded region expands. See Fig. 9.6.
2. Decrease of Strength in 90° Stretching

After the plastic is stretched, try to stretch it at 90° to the original
direction of stretching. Why does it come apart so easily?
During the initial stretching, the molecules become aligned. This

decreases the strength at 90° because only van der Waals bonds hold
together the molecules.
3. Shrinkage of Rubber Band

Stretch a rubber band by hanging a weight from it. Then heat the rub-
ber band with a hot air blower. The weight will rise.
The rubber band is shrinking as it is heated because the segments of

chain between cross-links are vibrating. As they vibrate they shorten.
4. Increasing Entropy in Rubber Band

Stretch a rubber band, then quickly release the tension and place it to
your lips.
It should feel cool because entropy (disorganization) increases and

heat is now absorbed from your lips by the rubber band.
5. Recycling Codes
The type of plastic often is identified by a recycling code. Identify as
many of these as you can.
Look on the bottom of polystyrene foam insulated cups, plastic soft

drink bottles, and so forth.
REFERENCES
9.1 W.F. Hosford, Materials for Engineers, Cambridge University Press,
2008
9.2 W.F. Hosford, Mechanical Behavior of Materials, 2nd ed., Cam-
bridge University Press, 2010
9.3 F.W. McClintock and A.S. Argon, Mechanical Behavior of Materi-
als, Addison-Wesley, 1966
Chapter 10
Composites
WITH COMPOSITE MATERIALS, combinations of properties can be

achieved that could not be achieved with individual materials because of
the inclusion of reinforcing material. Some examples of composites are
concrete, which is a composite of cement, sand, and gravel; steel-belted
tires; plywood with alternating directions of fibers; carbon or glass fiber-
reinforced polyester; and epoxy used for furniture, boats, and sporting
goods. The reinforcing material of composites may be in the form of fibers,
particles, or sheet laminates.
Fiber-Reinforced Composites
In fiber-reinforced composites, the reinforcing material is stronger and
stiffer than the matrix material. Different geometric arrangements of the
fibers are possible. The fibers may be unidirectionally aligned, aligned at
90° to one another in a woven fabric, or randomly oriented (Fig. 10.1). The
fibers may be very long or chopped into short segments for easy fabrica-
tion. In thick sections, it is possible to have three-dimensional composites
with randomly oriented short fibers. Fiber reinforcement is used to impart
Fig. 10.1 Several geometric arrangements of fiber reinforcements. Source: ref 10.1
stiffness (increased modulus of elasticity) or strength to the matrix. Fiber

reinforcement also increases toughness.
The strains parallel to long parallel fibers must be the same in both the
matrix and the fiber, ef = em = e. For loading parallel to unidirectionally
aligned fibers, the elastic modulus is:
E = Ef Vf + EmVm
where Ef and Em are the moduli of the fiber material and the matrix, and
where Vf and Vm are the volume fractions of fiber and matrix. This often is
called the rule of mixtures. It is an upper boundary to the elastic modulus
of a composite. The modulus is very much lower for loading perpendicu-
lar to the fibers. Cross-plies or randomly oriented fibers give stiffening in
other directions. A useful engineering approximation for randomly aligned
fibers is:
E ≈ (3/8)E⊥ + (5/8)E//
where E⊥ and E// are the moduli perpendicular and parallel, respectively,
to unidirectional fibers.
The rule of mixtures cannot be used to predict the strengths of com-
posites with uniaxially aligned fibers. The reason can be appreciated by
considering the stress-strain behavior of both materials as shown sche-
matically in Fig. 10.2. The strains in the matrix and fibers are equal, thus
Fig. 10.2 Stress-strain curves for the matrix, the fibers, and the composite.
Source: ref 10.1
Chapter 10: Composites / 117
the fibers reach their breaking strengths long before the matrix reaches its
tensile strength. Thus, the strength of the composite is UTS < VmUTSm +
Vf UTSf.
Usually the load carried by the fibers is greater than the breaking load of
the matrix, so the composite will fail when the fibers break. The composite
strength is given by:
UTS = Vmsm + Vf (UTS)f
where sm = (Em/Ef)(UTS)f is the stress carried by the matrix when the fiber
fractures.
For composites with low-volume-fraction fibers, the fibers may break at
a load less than the failure load of the matrix. In this case, after the fibers
break, the whole load must be carried by the matrix, thus the predicted
strength is UTS = Vm(UTS)m.
Volume Fraction of Fibers

The stiffness and strength of reinforced composites should increase with
the volume fraction of fibers, but there are practical limitations on the
volume fraction. Fibers must be separated from one another. Fibers often
are precoated to ensure this separation, and to control the bonding between
fibers and matrix. Variability in fiber spacing (Fig. 10.3) may result during
the infiltration of fiber arrangements by liquid resins. Approximately 55 to
60% is the practical upper limit for volume fraction fibers in unidirectional
alignments. It is even lower in woven or cross-ply reinforcement.
Fig. 10.3 Glass fibers in a polyester matrix. Note the variability in fiber spac-
ing. Source: ref 10.2
Fiber Length
Fabrication is much simplified if the reinforcement is in the form of
chopped fibers. These can be blown onto a surface to form a mat. Shapes
can be made with chopped fibers that are impossible with continuous
fibers. Examples are extrusions, injection moldings, and transfer mold-
ings. The disadvantage of chopped fibers is that some of the reinforcing
effect of the fibers is sacrificed because the average axial stress carried by
fibers is less for short ones than long ones. The average axial stress in a
fiber depends on its aspect ratio, D/L, where D and L are the diameter and
length of the fiber, respectively.
Failure may occur either by the fracture of fibers or by the fibers pulling
out of the matrix. Both possibilities are shown in Fig. 10.4. Pullout will
occur if the plane of the crack is near the end of the fiber. If it is not near
the end, the fiber will fracture. Figure 10.5 is a picture showing the pullout
of silicon carbide fibers in a titanium matrix.
More energy is absorbed if fibers pull out than if they break. The energy
expended in fiber pullout increases with fiber length up to a critical length
and then decreases with further length increase. Often greater tough-
ness can be achieved with shorter fibers and lower fiber-matrix interface
strength.
Epoxies and polyesters are common polymer matrices. Most of the poly-
mers used for matrix materials have moduli of 2 to 3 GPa (290 to 435 ksi)
and tensile strengths in the range of 35 to 70 MPa (5 to 10 ksi). Fiber rein-
Fig. 10.4 Sketch showing some fibers fracturing at a crack and others pulling
out. Source: ref 10.1
Chapter 10: Composites / 119
forcements include glass, boron, aramid fiber, and carbon. Properties of

some epoxy matrix composite systems are given in Table 10.1. Properties
of some commonly used fibers are given in Table 10.2.
Other fiber composites include ceramics reinforced with metal or
ceramic fibers. Metals such as aluminum-base alloys may be reinforced
with ceramic fibers to increase their stiffness. In some eutectic systems,
Fig. 10.5 photograph of SiC fibers pulling out of a titanium matrix. Source:
ref 10.3
Table 10.1 Properties of epoxy matrix composites

Young’s modulus, GPa (ksi) Tensile strength, MPa (ksi)
Fiber Fiber, vol% Longitudinal Transverse Longitudinal Transverse
E-glass (unidirectional) 60 40 (5,801) 10 (1,450) 780 (113) 28 (4)

E-glass (bidirectional) 35 16.5 (2,393) 16.5 (2,393) 280 (40) 280 (40)
E-glass (chopped matte) 20 7 (1,015) 7 (1,015) 100 (14) 100 (14)
Boron (unidirectional) 60 215 (31,183) 24 (3,480) 1400 (203) 65 (9)
Kevlar29 (unidirectional) 60 50 (7,251) 5 (725) 1350 (195) …
Kevlar49 (unidirectional) 60 76 (11,022) 6 (870) 1350 (195) 30 (4)
Carbon 62 145 (21,030) … 1850 (268) …
Kevlar is a registered tradename of E.I. du Pont de Nemours and Company.
Table 10.2 Typical fiber properties

Fiber Young’s modulus, GPa (ksi) Tensile strength, MPa (ksi) Elongation, %
Carbon (PAN* HS) 250 (36,259) 2.7 (0.39) 1.0

Carbon (PAN* HM) 390 (56,564) 2.2 (0.32) 0.5
SiC 70 (10,152) … …
Steel 210 (30,457) 2.5 (0.36) …
E-glass 70 (10,152) 1.75 (0.25) …
Boron 390 (56,564) 2.0–6.0 (0.29–0.87) …
Kevlar29 65 (9,427) 2.8 (0.41) 4.0
Kevlar49 125 (18,129) 2.8 (0.41) 2.3
Al 2O3 379 (54,969) 1.4 (0.20) …
b-SiC 430 (62,366) 3.5 (0.51) …
Kevlar is a registered tradename of E.I. du Pont de Nemours and Company.
NoTES oF INTEREST
the use of composites dates back to biblical times. exodus chapter 5
describes how the pharaoh forced the Israelites to use straw in making
bricks.
the first use of reinforced concrete usually is attributed to Joseph-
Louis Lambot in 1448. In 1868 Joseph Monier, a French gardener,
patented a design for reinforced garden tubs and later patented rein-
forced concrete beams and posts for railway and road guardrails.
directional solidification can lead to rods of one phase reinforcing the

matrix.
Particulate Composites
Composites reinforced by particles rather than long fibers are called par-
ticulate composites and include such diverse materials as concrete (cement
matrix with sand and gravel particles) and “carbide tools” with a cobalt-
base matrix alloy hardened by tungsten carbide particles.
Lamellar Composites
Two or more sheets of materials bonded together can be considered lamel-
lar composites. Examples of lamellar composites include safety glass,
plywood, plated metals, and glazed ceramics. The properties of plywood,
such as stiffness and water expansion, are much less anisotropic (depen-
dent on direction) than those of the wood itself.
Exercise
1. Fractured Surface of Fiberglass
Break a piece of fiberglass and note the appearance of the fractured
surface.
Some glass fibers that have pulled out of the other surface should be
visible, like those in Fig. 10.4.
REFERENCES
10.1 W.F. Hosford, Mechanical Behavior of Materials, Cambridge, 2005
10.2 Composites, Vol 1, Engineered Materials Handbook, ASM Interna-
tional, 1987
10.3 T.W. Clyne and P.J. Withers, An Introduction to Metal Matrix Com-
posites, Cambridge University Press, 1993
Chapter 11
Wood
WOOD IS ONE OF THE FIRST MATERIALS used by man. Trees often

are described as being either coniferous (cone bearing) or deciduous (los-
ing leaves in the winter.) However, these descriptions are not mutually
exclusive. Larch trees are both deciduous and coniferous, and holly trees
are neither deciduous nor coniferous. Softwoods come from conifers, such
as pine, spruce, and fir, and hardwoods come from deciduous trees, such as
oak, maple, hickory, poplar, and willow. Most hardwoods are denser and
harder than softwoods but there are exceptions. Douglas fir and eastern
red cedar are harder and denser than willow and poplar.
Structure of Wood
Wood is composed of hollow cells, which trees use to transport sap.
Annual growth rings are evident in the cross section of a tree trunk (Fig.
Fig. 11.1 Cross sections of typical softwood (red pine, left) and hardwood
(red oak, right). Source: ref 11.1
Fig. 11.2 Growth rings in typical softwood (red pine, left) and hardwood
(red oak, right). Source: ref 11.1
11.1). They are easily seen because faster growth in the spring results in
larger cells (Fig. 11.2). The percentage of growth rings in the sapwood,
the portion of the trunk though which sap is conducted, is between 20
and 40% for most hardwoods. Heartwood is dead sapwood and usually is
darker in color.
Dimensional Changes with Moisture

Bone-dry wood consists mainly of three compounds: cellulose (40 to
50%), hemicellulose (15 to 25%) in the cell walls, and lignin (15 to 30%),
which holds together the cells. In a living tree, wood usually contains
approximately 30% moisture, thus wood shrinks as it dries. The shrinkage
on drying varies with direction. Table 11.1 lists the shrinkage of several
woods on drying to 6% moisture.
Because the shrinkage is greater in the tangential direction than in the
radial direction, there is a strong tendency for radial cracks to form when
a log is dried (Fig. 11.3). This tendency to split is aggravated because the
outside dries before the inside does. To prevent this, lumber usually is cut
from logs before oven drying to approximately 6% moisture.
Even after being sawn into board, the directional dependence of shrink-
age causes warping, as illustrated in Fig. 11.4.
After drying, the moisture content of wood will approach equilibrium
with the atmosphere. At 20 °C (70 °F), the moisture content may vary
Chapter 11: Wood / 123
Table 11.1 Percent shrinkage of woods on drying

Shrinkage, %
Wood Radial direction Tangential direction
White pine 2.1 6.1

Douglas fir 4.8 7.6
Western cedar 2.2 4.9
Yellow birch 7.3 9.5
Hickory 4.9 8.9
Maple 3.7 7.1
White oak 5.6 10.5
Note: In all cases the longitudinal shrinkage is less than 0.25%.
Fig. 11.3 Splitting of a red oak log on drying. Source: ref 11.1
from 4.5% if the humidity is 20%, to 16% if the humidity is 80%. The
dimensional changes that result from a change in moisture content vary
with direction, as listed in Table 11.2.
It is interesting to note that one often can tell whether a picture frame
was made in the winter or the summer (Fig. 11.5). In the winter, the 45°
angles at the corners will have decreased in angle if the frame was made
in more humid weather (summer), thus the corners will open on the inside
(Fig. 11.5A). On the other hand, if the frame was made in the winter (low
humidity), the 45° angles at the corners will open on the outside in the
summer (Figure 11.5B).
Fig. 11.4 elm board warped because the shrinkage in the tangential direc-
tion is greater than in the radial direction (bottom). Splitting when
a warped board is flattened (top). Source: ref 11.1
Table 11.2 Dimensional change in wood with change of

moisture content
Direction Dimensional change per 1% moisture change
Radial 0.15%
Tangential 0.25%
Longitudinal 0.01%
Fig. 11.5 a picture frame made in the summer will open on the inside during
the winter (a), while a picture frame made in the winter will open
on the outside during the summer (B). Source: ref 11.2
Anisotropy of Properties
Table 11.3 shows that the elastic modulus and tensile and compressive
strengths vary with direction.
Plywood
The orientation dependence of properties can be largely circumvented by
the use of plywood, composed of plies oriented with their grain at 90° to
one another. The plies are cut from rotating logs that have been softened
with moisture (Fig. 11.6). The number of plies is always an odd number to
prevent warping as changes occur in moisture content.
Paper and Cardboard

The earliest paper was papyrus made from reeds by the ancient Egyp-
tians. Today, paper is made from pulp consisting of ground up wood in
water. Often chemicals are added to help decompose the wood. The pulp
is heated to soften the fibers. Some clay or cloth may be added. Clay is
used to produce shiny paper used in magazines. Newsprint and cardboard
Table 11.3 Properties of common woods at 12%

moisture content
Property White oak Douglas fir
Densit y, Mg/m3 0.68 5.0

Young’s modulus, GPa (ksi) 6.0 (0.87) 2.9 (0.42)
Tensile strength (a) (a)
Radial, MPa (ksi) 5.4 (0.8) 2.4 (0.3)
Compressive strengths, MPa (ksi)
Longitudinal 51 (36) 51 (36)
Radial 7.4 (1.1) 5.2 (0.8)
(a) The longitudinal tensile strengths are approximately 20 times the radial tensile
strengths.
Fig. 11.6 Cutting a log for plywood and veneer. Source: ref 11.2
NoTE oF INTErEST
the plywood industry began in 1907, when the portland Manufactur-
ing Company installed an automatic glue spreader and a hand press
to produce plywood. they made 420 panels a day. Initially the market
was primarily for door panels. automobile running boards were made
from plywood but this stopped because of water damage. In 1934,
Dr. James Nevin, a chemist at harbor plywood Corporation in aber-
deen, Washington, finally developed a fully waterproof adhesive for
plywood. this technological advancement had the potential to open
up significant new markets. after World War II, the industry produced
1.4 billion square feet of plywood. By 1954, the industry approached
4 billion square feet. By 1975, U.S. production alone exceeded 16 bil-
lion square feet.
contain no clay. Water is removed by squeezing—often by rolling, which

tends to align the fibers, making the properties very anisotropic.
Exercises
1. Dimensional Increases of Wood upon Hydration
Take a small piece of wood and measure its dimensions. Immerse it
in water for a day, then remove the wood and measure the dimensions
again. Which dimension increased the most? Which the least? Why?
The greatest dimensional increase will be in the direction that is

perpendicular to the grain (the direction that was parallel to the
circumference of the tree.) The least dimensional increase will be
parallel to the grain.
2. Paper Fiber Alignment

Take a piece of newspaper and try to make a straight tear down the
page. Then try to make a straight tear across the page. Explain the dif-
ference and deduce the direction in which the paper was rolled.
Rolling during the manufacture of the paper aligns the fibers. Paper
will tear most easily in this direction.
3. Cardboard Fiber Alignment

Cut a square piece of cardboard (20 ¥ 20 cm, or 8 ¥ 8 in.) from the
back of a pad of paper. Suspend it as shown in Fig. 11.7 and place a
small weight on it. Note how much the cardboard deflects. Then turn
the cardboard 90° and repeat. Explain the difference and deduce the
direction in which the cardboard was rolled.
Fig. 11.7 Setup for exercise 3
The cardboard will deflect least when the direction it was rolled is the
direction between the supports.
rEFErENCES
11.1 R.B. Hoadley, Understanding Wood, The Taunton Press, 1980
2008
Chapter 12
Corrosion
THE COST OF CORROSION in the United States is estimated to be $1

trillion annually. Approximately 40% of this cost can be avoided by well-
known practices. Much of this loss is due to the corrosion of iron and steel,
although many other metals also corrode. There are two principal types
of corrosion: aqueous corrosion (corrosion in water) and direct corrosion
(attack in air).
Corrosion in Water Solutions

Aqueous corrosion always involves an electrolytic cell with a cathode and
an anode (Fig. 12.1). It is the opposite of electroplating. The anode is where
ions go into solution M → M+n + ne –. The cathode is where electrons are
consumed. Possible cathode reactions are:
M+n + ne– → M (This can occur only if there is a high concentration of M+n ions.)
2H+ + 2e – → H2 (This can occur only if the solution is acid.)
O2 + 2H2O + 4e – → 4(OH) – (There must be O2 in solution. This is the most
common cathode reaction.)
O2 + 4H+ + 4e – → 2H2O (There must be O2 in an acid solution.)
Table 12.1 shows the electromotive series. It gives the electrode potentials
for various possible half reactions for solutions with 1 molar concentration.
The voltages for the various reactions are measured against a hydrogen
electrode 2H+ + 2e– → H2, which is defined as zero (Fig. 12.2).
The electrode potentials are different in other aqueous solutions. Seawa-
ter is a common corrosive environment. The galvanic series ranks alloys
according to their cathode potential in seawater (Table 12.2).
The potential depends on the concentration. Often cells arise as a result
of different concentrations in different places. Oxygen concentration cells
are very common. Figure 12.3 illustrates some sources of oxygen concen-
Fig. 12.1 Corrosion cell. the anode is where electrons are generated in the
external circuit, and the cathode is where they are consumed.
Source: ref 12.1
Table 12.1 Electromotive series

Anode half-cell reaction Electrode potential used
(the arrows are reversed for by electrochemists and
the cathode half-cell reaction) corrosion engineers, volts
Au → Au3+ + 3e – +1.50
−−−−−−−−−−−−−→
2H 2O → O2 + 4H+ + 4e – +1.23
Pt → Pt4+ + 4e –
Cathodic
+1.20
(noble)
Ag → Ag+ + e – +0.80
Fe2+ → Fe3+ + e – +0.77
4(OH) – → O2 + 2H 2O + 2e – +0.40
Cu → Cu2+ + 2e – +0.34
H 2 → 2H+ + 2e – 0.000 Reference
Pb → Pb2+ + 2e – –0.13
Sn → Sn 2+ + 2e – –0.14
←−−−−−−−−−−−−−−−−
Ni → Ni2+ + 2e – –0.25
Fe → Fe2+ + 2e – –0.44
Anodic
(active)
Cr → Cr2+ + 2e – –0.74
Zn → Zn 2+ + 2e – –0.76
Al → Al3+ + 3e – –1.66
Mg → Mg2+ + 2e – –2.36
Na → Na+ + e – –2.71
K → K+ + e – –2.92
Li → Li+ + e – –2.96
Source: Ref 12.2
Chapter 12: Corrosion / 131
Fig. 12.2 the hydrogen cathode
Table 12.2 The galvanic series of common alloys
Graphite Cathodic Nickel—A

|
Silver ↑ |
| Tin
| |
| |
12% Ni, 18% Cr, 3% Mo steel—P | | Lead
| |
| |
20% Ni, 25% Cr steel—P | | Lead–tin solder
| |
23 to 30% Cr steel—P | | 12% Ni, 18% Cr, 3% Mo steel—A
| |
| |
14% Ni, 23% Cr steel—P | | 20% Ni, 25% Cr steel—A
| |
8% Ni, 18% Cr steel—P | | 14% Ni, 23% Cr steel—A
| |
| |
7% Ni, 17% Cr, steel—P | | 8% Ni, 18% Cr steel—A
| |
16 to 18% Cr steel—P | | 7% Ni, 17% Cr steel—A
| |
| |
12 to 14% Cr steel—P | | Ni-resist
| |
| |
80% Ni, 20% Cr—P | | 23 to 30% Cr steel—A
| |
Inconel—P | | 16 to 18% Cr steel—A
| |
| |
60% Ni, 15% Cr—P | | 12 to 14% Cr steel—A
| |
Nickel—P | | 4 to 6% Cr steel—A
| |
| |
Monel metal | | Cast iron
| |
Copper–nickel | | Copper steel
| |
| |
Nickel–silver | | Carbon steel
| |
Bronzes |
| |
|
Aluminum alloy 2017-T
| |
Copper | | Cadmium
| |
| |
Brasses | | Aluminum, 1100
| |
80% Ni, 20% Cr—A | | Zinc
| |
| |
Inconel—A | | Magnesium alloys
|
60% Ni, 15% Cr—A | ↓ Magnesium
|
| Anodic
Note: A, active state; P, passive state. Source: Ref 12.2
tration cells. The role of oxygen in corrosion at times can seem anomalous.
Oxygen normally is required for corrosion. However, the metal loss does
not occur where the oxygen concentration is the greatest.
Corrosion cells can arise from two-phase microstructures, from cold
work (Fig. 12.4), and from grain boundaries (Fig. 12.5).
Accumulation of positive ions near the anode and negative ions near
the cathode (Fig. 12.6) will polarize the cell, decreasing the voltage. With
polarization, the corrosion current decreases, as indicated in Fig. 12.7.
Passivation
With some materials, when the anode potential reaches a critical value, the
corrosion current drops abruptly to a very low rate (Fig. 12.8). This condi-
tion is called passivation. A very thin oxygen layer on stainless steels is
Fig. 12.3 Oxygen concentration cells. the regions that are shielded from oxygen are the anodes, while
the cathode reaction occurs where oxygen is plentiful.
Fig. 12.4 regions that have been cold worked are anodic to regions that
have not.
Fig. 12.5 Because atoms at grain boundaries are in a higher energy state,
the grain boundaries become anodic.
Fig. 12.6 polarization is caused by an accumulation of positive ions near the

anode and negative ions near the cathode.
sufficient to cause passivation. Oxygen and a very small amount of corro-

sion are required to maintain the passive state. In Table 12.2 (the galvanic
series of common alloys) stainless steels occupy two places, depending
on whether they are passive or not. Titanium alloys may be passive under
special conditions.
If conditions are oxidizing enough, even carbon steel can become pas-
sive. Concentrated nitric acid can be shipped in mild steel containers.
However, the containers would corrode extremely rapidly if filled with
dilute nitric acid.
Oxygen is required for passivity of stainless steels. In one case, simply
identifying stainless steel pipes by attaching transparent adhesive tape to
the outside of the pipes was responsible for corrosion when moisture con-
densed on them. The tape prevented the access of oxygen so the regions
under the pipe lost their passivity.
Fig. 12.7 polarization at the cathode decreases the cell potential. Increased
convection decreases the polarization. the effects of anode polar-
ization are similar.
Fig. 12.8 above a critical anode potential, certain materials become pas-
sive. their corrosion rate drops abruptly. Note the current density
is plotted on a logarithmic scale.
Corrosion Control
The means of controlling corrosion are means of disrupting or changing
the corrosion cell. One way is to remove the electrolyte, because corrosion
will not occur in the absence of water. Inert coatings such as paint serve
this function. Another is to break the circuit. Cells caused by electrical
contact of dissimilar metals can be interrupted by placing an insulator
between the metals. Reversing the voltage by imposing opposite voltage

with external circuit or sacrificial corrosion (Fig. 12.9) are other means.
With galvanized steel, the zinc is anodic to iron and hence protects the
steel by sacrificial corrosion versus inert coatings (Fig. 12.10).
Stress Corrosion
Stress corrosion can occur in some metals when loaded in tension in a
specific environment. Cracks run through grains and along grain bound-
aries. Brass is susceptible to stress corrosion in the presence of ammonia.
Chloride ions form an environment that leads to stress corrosion of many
metals.
Fig. 12.9 Corrosion protection by sacrificial corrosion of zinc (left) and mag-
nesium (right)
Fig. 12.10 aqueous solution. (a) plating steel with zinc (galvanizing) offers
cathodic protection to steel if the plating is scratched. (b) tin
plating offers no cathodic protection so the steel will corrode if the plating is
scratched.
Rust
Rust is ferric oxide, Fe2O3, and ferric hydroxide, Fe(OH)3. Ferrous ion,
Fe2+, is soluble, but further oxidation produces ferric ions, 3Fe2+ + 6OH–
→ 3Fe(OH)3 + 3H2O. Ferric hydroxide is insoluble and precipitates as
rust. If dried, the ferric hydroxide turns into an oxide, 2Fe(OH)3 → Fe2O3
+ 3H2O. Often, the rust-producing reaction occurs at some distance from
where the anode reaction occurs, so rust deposits may not be directly over
the corroded region. This is illustrated in Fig. 12.11.
Special steels containing small amounts of copper and nickel form more
protective rusts. These steels do rust, but more slowly than ordinary steels.
This has led to their use in architecture and sculpture.
Direct Oxidation
Direct oxidation of most metals in the absence of water occurs only at
high temperature. It might seem that high-temperature oxidation would not
involve an electrolytic cell. However, there is an anode and cathode. The
anode reaction is M → Mn+ + ne–, and the cathode reaction is O2 + 4e– →
2O2–. Either O2– ions or Mn+ ions and e – must diffuse through the oxide.
The Mn+ ions are smaller than O2– ions and therefore diffuse faster. Hence,
their diffusion is rate controlling. Figure 12.12 illustrates the reactions and
transport in direct oxidation.
Diffusion and electron transport through Al2O3 and Cr2O3 are very slow
because they are very free of defects. Hence, they are very protective. For
an oxide to be protective, it must cover the surface. Hence, volume of oxide
≥ volume of metal oxidized. If nM + mO → ρMnOm, protection occurs if:
( MW)oxide § roxide ≥ n ( AW)M § rM
The equation is not satisfied for sodium, potassium, alkali, and the
alkaline earth metals, so they oxidize rapidly in air. If the ratio
⎡⎣( MW )oxide/ρoxide ⎤⎦ / ⎡⎣ n ( AW )M /ρM ⎤⎦ is too high, the compressive stresses in
the oxide may cause it to spall off. This is the case for Fe2O3. Another
necessary condition for a protective oxide is that it must be solid. Tung-
Fig. 12.11 rust formation away from corroded sites where the oxygen
concentration is higher
sten and molybdenum oxidize very rapidly at high temperatures because

their oxides are volatile. Because vanadium pentoxide (V2O5) forms a
low-melting eutectic with Fe2O3, which flows off of the surface, fuels
containing a small amount of vanadium have caused serious problems in
power-generating turbines.
Fig. 12.12 Direct oxidation. Oxide forms by diffusion of anions and elec-
trons to the oxide-air surface.
NOTES OF INTEREST
Francis Wollaston in about 1815 first suggested that acid corrosion was
electrochemical. Sir humphrey Davy in 1824 showed that there was a
voltage between two different metals when connected and immersed
in water. From this work he showed that a voltage was set up between
them and suggested that the copper bottoms of ships could be protected
by attaching iron or zinc plates to them. In about 1830, theodore Stur-
geon showed that there could be potentials between different regions
on the same metal surface. he found that differences of electrolyte
concentration and temperature caused potential differences.
at the time of WWI, the U.S. army did not specify that brass car-
tridge cases be given stress-relief anneals. this caused a problem when
cow barns in France were used to store ammunition. as anyone who
has changed diapers knows, ammonia is one of the decomposition
products of urine. ammonia from cow urine caused stress-corrosion
cracking of the brass cartridge cases that contained residual tensile
stresses in the hoop direction. Since then, the army has specified stress
relief annealing.
Exercise
1. Corrosion of Steel Wool
Put pads of steel wool into two jars of water. Boil one jar and securely
cap it. Leave the other open to the air. Compare the two jars after two
days. Explain the difference.
Corrosion of the steel wool will be observed in the open jar but not
in the capped jar. The boiling removes dissolved oxygen. There can
be no corrosion without oxygen, thus no corrosion can occur in the
capped jar. Oxygen from the air will dissolve in the open jar, allowing
corrosion.
REFERENCES
12.1 W.F. Hosford. Physical Metallurgy, 2nd ed., CRC Press, 2010
12.2 L.H. Van Vlack, Elements of Materials Science and Engineering, 3rd
ed., Addison-Wesley, 1974
Chapter 13
Forming and Shaping
Liquid to Solid Processing

Metals usually are cast into molds of sand, another refractory material, or
another metal. Steel and iron are cast into sand or refractory molds. Gold, sil-
ver, and refractory metals are cast into molds of high-temperature ceramics.
Aluminum may be cast into sand or iron molds. Low-melting-point metals
(aluminum, magnesium, and zinc) may be die ca st. In die casting, metal
is forced into a metal mold that automatically opens and ejects the part as
soon as it is frozen. The production rate is high but so are capital costs. In
recent variations of this process, called thixotropic or rheocasting, the melt
is approximately half solid-half liquid when it is injected into the mold.
Injection molding of thermoplastics is very much like injection molding
of metals. Thermoplastics also can be extruded or blow molded.
Single crystals may be grown by directional solidification. With the
Bridgman technique, a mold is slowly removed from a furnace (Fig. 13.1).
Freezing starts at one end and slowly progresses to the other. Because
Fig. 13.1 Bridgman and Czochralski methods of growing single crystals.

Source: ref 13.1
freezing starts at a point, only one crystal is nucleated. The Czochralski

method involves lowering a seed crystal into the melt so that it partially
melts, and then withdrawing it slowly upward. The growing crystal is
rotated about a vertical axis to help stir the liquid. The lack of a mold
eliminates contamination from mold walls but makes it impossible to con-
trol the exterior shapes of the crystals. This is the method used to grow
silicon crystals for the semiconductor industry.
Bulk Forming of Solid Metals

Bulk forming of cast ingots can be accomplished by rolling, extrusion,
forging, and drawing. The important forces are compressive. Figure 13.2
illustrates several bulk forming processes.
Hot Working versus Cold Working

Many bulk forming processes are done hot. At high temperatures lower
tool forces are required. Consequently, equipment size and power require-
ments are decreased. Hot working often is defined as working above the
recrystallization temperature so that the work metal recrystallizes as it
deforms in the time period between repeated operations, as in forging and
Fig. 13.2 Several bulk forming processes

Chapter 13: Forming and Shaping / 141
multiple-stand rolling, or while the material is cooling to room tempera-

ture after the deformation is complete. High temperatures lower the flow
stress, whether recrystallization occurs during the deformation or not. Hot
rolled products are in an annealed state.
The elevated temperatures during hot working have several undesirable
effects. Among them are:
• Lubrication is more difficult. Although viscous glasses often are used
in hot extrusions, most hot working is done without any lubrication.
• The work metal tends to oxidize. Scaling of steel and copper alloys
causes loss of metal and roughened surfaces. Although processing
under inert atmosphere is possible, it is prohibitively expensive and is
avoided except in the case of very reactive metals, such as titanium.
• Tool life is shortened because of heating, the presence of abrasive
scales, and the lack of lubrication.
• Poor surface finish and loss of precise gage control result from the lack
of adequate lubrication, oxide scales, and roughened tools.
• The lack of work hardening is undesirable where the strength level of
a cold worked product is needed.
Because of these limitations, it is common to hot roll steel to a thick-

ness of approximately 2 mm (0.08 in.) to take advantage of the decreased
flow stress at high temperature. The hot rolled product then is pickled to
remove scale. Further rolling is done cold to ensure good surface finish and
optimal mechanical properties. The cold rolled steel sheet almost always
is sold in an annealed state. Annealing is done in a controlled atmosphere
after cold rolling. The principal advantage of cold rolled sheet steel over
hot rolled sheet is a much better surface finish.
Sheet Forming
In sheet forming processes the important stresses are tensile. Sheets can
be formed into complex shapes by stamping. In stampings the sheets are
clamped at their edges and stretched to a final shape by a shaped punch
(Fig. 13.3). Draw beads control how much material from the flange is
drawn into the die. Wrinkling of the finished part results if too much
material is allowed to flow into the die. It should be emphasized that in
stamping processes the sheet is not squeezed between the die and punch.
Rather, tensile forces in the sheet cause it to deform by stretching. If too
much stretching occurs, the sheet may suffer a tensile failure in the die.
Cups can be formed by deep drawing discs cut from sheets (Fig. 13.4).
Cups and cans are made by deep drawing. The maximum diameter
reduction is limited by failure of the cup walls. This usually limits the
height-to-diameter ratio to approximately 0.75. Deeper cups can be made
by redrawing and ironing (thinning of the walls).
Polymer Processing
Thin sheets and films to form bags are made from thermoplastics by blow-
ing air into an extruded tube. The air expands the tube, which then is
collapsed by nip rollers. The thickness and size of the film is controlled
by the volume of air inside the bubble, the speed of the nip rollers, and the
output rate of the extruder.
Fig. 13.3 Stamping of a sheet metal part. Note that the restraint from the
draw beads in the blank holder promotes more stretching of the
sheet. Source: ref 13.2
Fig. 13.4 Schematic illustration of forming a cup from sheet metal. (a) a descending punch forces the sheet through
a circular hole in the die. a hold-down plate prevents buckling. (b) the major deformation is the circum-
ferential contraction of the flange so that it can pass over the die lip. (c) By focusing on a pie-shaped segment, it can be
seen that the flange is under hoop compression and the wall under tension. Source: ref 13.1
Plastic bottles are made by blow molding. The process begins with the
conventional extrusion of a parison or closed-end tube. The parison then
is clamped inside a hollow mold and inflated. The air pressure forces the
parison against the mold surface until it cools in the shape of the interior of
the mold cavity. The mold then is opened and the plastic bottle is ejected.
Blow molding is used with many different plastics, including high-density
polyethylene (HDPE), polyvinyl chloride (PVC), polycarbonate (PC), poly-
propylene (PP), and polyethylene terephthalate (polyester, or PET). The
largest use is the PET beverage bottle. The same process of blow molding
is used to make containers of glass.
When fibers of thermoplastics are stretched, the molecules become
aligned and the fibers become very strong and resist being stretched any
further. Once the fibers have been stretched, or drawn, they are strong
enough for use in textiles and rope. Drawn fibers of nylon and polyesters
are used for their strength.
Sheets of polymethylmethacrylate (PMMA), polycarbonate (PC), poly-
ethylene (PE), polystyrene (PS), nylon, acrylics, and other polymers are
produced by rolling. The process is similar to the rolling of metals.
Sheets of thermoplastics are thermoformed. This involves heating them
enough to soften them and form them by drawing them into a mold with
vacuum (Fig. 13.5).
Compression molding is a widely used molding process for thermoset-
ting plastics. This consists of loading a precise charge in the bottom half
of a heated mold, closing the mold halves to compress the charge, forcing
it to flow and conform to the shape of the cavity, and heating the charge to
polymerize it into a solidified part (Fig. 13.6).
Foams may be created by mechanical stirring or by gases formed by
a chemical reaction that forms a gas or releases dissolved gases. Poly-
styrene foam is formed by the release of dissolved pentane on heating.
Fig. 13.5 thermoforming of a thermoplastic sheet. Source: ref 13.1

Fig. 13.6 Compression molding. Source: ref 13.1
Polyurethane foam is formed by the release of water vapor produced as a

byproduct of the polymerization reaction. In all cases the foam is formed
into the desired shape by molding.
Powder Processing
Many products are made by pressing and sintering powders. Most ceramics
are consolidated this way. Refractory oxides ceramics cannot be fabricated
by melting and freezing. Sintering also is used to produce parts of metals
that are difficult to melt. Examples include carbide tools and tungsten for
lamp filaments. Mixed powders are sintered to make composites that are
not otherwise possible, such as friction materials for brakes and clutches.
Porous parts for filters or oil-less bearings are made by incomplete sinter-
ing. Teflon cannot be melted without decomposing so it also is processed
as a powder. Pharmaceutical pills are made from powder. Powder process-
ing is a simple and inexpensive way of fabricating large numbers of parts.
Figure 13.7 illustrates schematically how a part is pressed from pow-
der. The process is highly automated with many parts being pressed per
second.
There are limitations on the shape of the die: it must be prismatic so the
compact can be ejected. The ratio of height-to-diameter must not be too
great. Otherwise, friction on the sidewalls of the die will not allow suf-
ficient compaction pressure in the center.
The sintering of pressed powders at elevated temperature bonds together
the small powder particles without melting them. The driving force for
sintering is the reduction surface area and the associated energy. In the
initial stages of sintering, adjacent particles adhere to each other and form
a neck where they are in contact. Figure 13.8 is a micrograph of such a
neck formed between two nickel spheres.
Fig. 13.7 powder compaction. (a) a die is filled with powder. (b) the powder
is compacted. (c) the compact is ejected. (d) the die is refilled as
the part is pushed away. Source: ref 13.1
Fig. 13.8 partially sintered nickel spheres. Source: ref 13.3

As sintering progresses, the amount of surface area and the energy asso-
ciated with the surfaces decrease. The density increases and the porosity
decreases. The decrease in porosity is accompanied by an increase in
strength.
Modern Manufacturing Techniques

The intricate circuits formed on semiconductor chips are patterned by
photolithography. A photosensitive material (photoresist) is applied to a
semiconductor surface and baked at a low temperature. The surface then
is exposed to intense ultraviolet light, which makes the exposed regions
of the photoresist become soluble in a developer. After these areas are
removed, the surface is baked at a somewhat higher temperature to harden
the remaining photoresist. The exposed regions then are acid etched.
The etched regions then may be treated differently from the rest of the
surface. They may be doped by exposure to plasma containing n- or p-type
impurities, or they may be plated to form conducting circuits. Integrated
circuits are composed of many overlapping layers (Fig. 13.9), each defined
by photolithography. Dopants are diffused into the substrate; additional
ions are implanted into some layers. Metal and polycrystalline silicon are
deposited on others to form conductive circuits.
Transistors can be formed where there are n-p-n or p-n-p diffusion
layers. Resistors are formed by creating long narrow strips of a resistive
conductor. Capacitors are formed by parallel conductors separated by insu-
lating material.
Fig. 13.9 Integrated circuit with many layers. Source: ref 13.4
NoTES oF INTEREST
aluminum foil is produced by simultaneously rolling two sheets of alu-
minum. When the sheets are separated, the sides that were in contact
with each other have a matte finish, the roughness of which reflects
the grain size. the other sides are shiny because of sliding on the pol-
ished steel rolls.
Many consumer goods are shrink-wrapped. Shrink-wrapping uses
films of pVC or low-density pe that have been stretched biaxially dur-
ing manufacture. On heating they tend to contract, so if wrapped
around an object and heated with hot air, they shrink to form a tight
package. the same phenomenon is used to make tubes that serve
as electrical insulators. prestretched tubes placed over a wire joint
decrease their diameters, forming a tight insulation when heated.
Three-dimensional parts can be made by photostereolithography or 3-D

printing using a liquid that polymerizes on exposure to ultraviolet light.
A substrate platform is lowered into a bath and a desired portion of the
surface of the liquid is exposed to a beam of ultraviolet light, causing it
to polymerize. A computer data file controls the area to be exposed to the
scanning beam. After the surface is scanned, the substrate is lowered,
allowing an additional thin layer of liquid to flow over the surface. The
process is repeated until a three-dimensional structure is polymerized.
Finally, the liquid that has not polymerized is drained off, leaving a solid
part.
Dense sintered parts of inorganic materials can be formed by adding sin-
terable ceramics or metals to the liquid and firing the polymerized shape to
drive off the organics. Typically the liquid may contain 40 to 70% sinter-
able ceramic and/or metallic particles, 10 to 35 % photocurable monomer,
and 1 to 10% photoinitiators and dispersants.
This process has been used to make scaffolds for bone growth that can
be implanted where bones are missing, for internal cores to allow air pas-
sages in cast turbine blades, and other parts that require intricate ceramic
shapes.
REFERENCES
2008
13.2 W.F. Hosford and R.M. Caddell, Metal Forming: M echanics a nd
Metallurgy, 4th ed., Cambridge University Press, 2010
13.3 R.M. German, Powder Metallurgy Science, Metal Powder Industries
Federation, Princeton, NJ, 1984
13.4 http://en.wikipedia.org/wiki/Integrated_circuit, accessed 2007
Chapter 14
Recycling
Metals
More than 80% of steel is made from recycled material. Steel and iron
can easily be separated magnetically from other scrap. The scrap is either
remelted in an electric arc furnace or added to pig iron in a basic oxygen
furnace. All grades of steel can be recycled because most alloying ele-
ments are oxidized during processing. Tin and copper are the exceptions,
and there is concern in the steel industry about the gradual buildup of these
tramp elements in steel.
Recycling of nonferrous metals involves two types of scrap. One is the
offal, or waste, from a manufacturing plant. It consists of trimmings from
sheets, parts rejected for failure to meet standards, and other sources where
the composition of the material is well known. Because the composition
of new scrap metal is well known, it can be remelted to make more of the
same alloy. This is much more valuable than old scrap of unknown com-
position. For most nonferrous metals, alloying elements cannot be removed
during melting. Therefore, old scrap must be used to produce alloys with
less critical compositions.
A substantial amount of aluminum is recycled. It was estimated that in
1998, 40% of the world’s aluminum was produced by recycling. Aluminum
scrap is shredded, and any lacquer is removed from cans before remelting.
Remelting aluminum requires only 5% of the energy that is required to
produce virgin aluminum from bauxite, and emits only 5% of the CO2.
The energy saving is 14 kwh/kg. In the United States, nearly half of all
aluminum beverage cans are recycled; the rest go into landfills. The recycle
rate in Europe is approximately 40%. Almost 90% of the aluminum cans
are recycled in Norway, Sweden, and Switzerland. The rate of recycling in
Brazil and Japan is over 90%.
Recycled copper accounts for approximately 40% of the U.S. consump-
tion of copper. Recycling uses approximately 15% of the amount of energy
that is used to produce copper from ore. In general, the value of recycled
copper is approximately 90% that of virgin copper. The primary sources

are electrical wiring, plumbing pipes, and fixtures. Control of the scrap
is important. To produce new wire, only high-conductivity (highly pure)
scrap can be used. Some impurities may cause hot s hortness (cracking
during hot working). Copper and copper alloy scrap must be carefully
segregated. Pure copper, not contaminated by other metals, can be used to
produce high-quality products. Alloy scrap that is segregated can be used
for products of similar composition. Copper that is mixed with other met-
als, perhaps by having been tinned or soldered, or alloys to which lead has
been added for machinability, can be used in alloys—such as bronze—that
contain these metals.
At present, approximately 70% of the zinc produced originates from
mined ores, and 30% from recycled zinc. The level of recycling is increas-
ing in step with progress in zinc production technology and zinc recycling
technology.
The supply of zinc-coated steel scrap increases annually as more auto
body steel is galvanized. Approximately half of the world’s steel is pro-
duced in electric arc furnaces. In the process, flue dust with high zinc
contents is treated to recover zinc.
Lead battery plates are melted, refined, and recycled. The plastic case
is shredded and recycled. The U.S. Environmental Protection Agency
(EPA) estimates that approximately 80% of all lead-acid car batteries cur-
rently are recycled. Most battery recycling facilities will accept lead-acid
batteries.
Different solder alloys contain different combinations of metal elements.
The most common metals used in lead-free solder are tin, copper, silver,
and sometimes zinc-antimony and bismuth. Recycling these materials,
the user can reduce the environmental impact and save reprocessing and
disposal costs.
Photographic film, plates, and paper; electrical and electronic parts; jew-
elry; and spent catalysts are sources of silver for recycling. It is estimated
that 26% of the annual usage of silver comes from recycling.
Plastics
Thermoplastics account for 80% of all plastics and these can be recycled.
Heating of thermosetting polymers will cause them to decompose with-
out melting, so they can be used only as landfill. The American Plastics
Council has established a system of symbols (Fig. 14.1) to identify several
of the more common plastics for recycling.
Resins that already have been recycled are identified by an R before the
previous designation. For example, RHDPE means recycled high-density
polyethylene.
Recycling polyethylene uses only one-third of the energy that is used to
produce new polyethylene. According to the EPA, recycling of 0.45 kg (1
Chapter 14: Recycling / 151
Fig. 14.1 recycling symbols for polymers. (1) polyethylene terephthal-

ate, also indicated by pet and called polyester. (2) high-density
polyethylene (also pe-hD). (3) polyvinyl chloride, or pVC. (4) Low-density poly-
ethylene (pe-LD), or LLDpe for very-low-density polyethylene. (5) polypropylene.
(6) polystyrene. (7) Other resins or a combination of resins.
lb) of polyethylene terephthalate (PET) saves approximately 12.5 MJ of

energy. Generally, recycled polymers are less desirable to manufacturers
than new resins and are used in less critical applications. For example,
virgin PET is used for bottles, and recycled PET is used mainly for fibers
for carpets and fiberfill. New high-density polyethylene (HDPE) also is
used for bottles, but recycled HDPE is used for drainage pipes, laundry
detergent bottles, floor tile, and picnic furniture. New polyvinyl chloride
(PVC) finds uses as squeezable bottles, frozen food bags, clothing, and car-
pets, while recycled PVC is used for floor tile, garbage can liners, furniture,
trash cans, and lumber. Polypropylene (PP) is used in food and medicine
packaging, but recycled PP is used for brooms, battery cases, ice scrapers,
trays, and pallets. Virgin polystyrene (PS) is used for rigid and foamed
products including coffee cups; among the recycled applications are foam
packaging, thermal insulation, egg cartons, carryout containers, and rulers.
Rubber
Because most rubber products have been cross-linked by vulcanization,
recycled rubber cannot be molded into new shapes. However, shredded
rubber often is added to concrete or used in mats.
Glass and Paper

It is estimated that recycling of glass saves 50% of the energy that is used
to make new glass from sand and limestone, and generates 20% less air
pollution and 50% less water pollution. Recycling of paper uses only 40%
of the energy that is used to make paper from wood and causes only 5%
as much air pollution.
Many products that claim to be biodegradable should more properly be

called oxi-degradable. Plastarch material (PSMpolyactide) and polyac-
tide (PLA) do degrade by composting. Products made from petrochemical
compounds generally do not biodegrade. Tree leaves are biodegradable.
They are made in the spring, used by the plant during the summer, drop
to the ground in autumn, and are assimilated into the soil. There are no
microorganisms that can similarly break down most man-made products.
NotE oF INtERESt
recycling has been practiced throughout human history. even before
the industrial revolution, scrap bronze, tin, and other precious metals
were collected and melted down for reuse because recycled met-
als were cheaper than virgin metals. the shortage of materials during
World War II greatly encouraged recycling. Governments in every
country involved in the war urged citizens to donate metals. recycling
programs established during the war were continued in some coun-
tries, such as Japan, after the war ended.
Appendix I
Greek Alphabet
Name Greek use or letter Meaning Name Greek use or letter Meaning
alpha A nu N
a angle n
beta B xi Ξ
b angle ξ
gamma Γ omnicron O
g angle, shear strain, surface energy o
delta D difference pi P multiplicative series
δ difference p 3.14159…
epsilon E rho R
e true strain r
zeta Z sigma S summation
z s stress, conductivity
eta H tau T
h viscosity, efficiency τ shear stress
theta Q upsilon U
q angle u
iota I phi F
i f angle
kappa K chi C
k c
lambda Λ psi Ψ
λ y pi
mu M omega W ohm, the end
m w angular frequency
INDEX
Index Terms Links
II-IV semiconductors 44
III-V compound semiconductors 44–45(F,T)
3-D printing 147
ABS. See acrylonitrile butadiene styrene (ABS)

acid etching 86–87 146
acrylonitrile 105
acrylonitrile butadiene styrene (ABS) 105 111
addition reaction 99
additives (polymers) 106–107 108(F)
age hardening 63 64(F) 65
aluminosilicates 89
aluminum 63–65(F)
aluminum-base alloys 119
aluminum-copper phase diagram 64(F)
applications 63 64(F)
casting 139
corrosion resistance 63
crystallizing 4
ductility 60
electrical conductivity 63
electrical resistance 63
electrical resistivity 38 38(F)
fatigue 30 30(F)
historical development 1
properties 159 161
This page has been reformatted by Knovel to provide easier navigation.

Index Terms Links
aluminum (Cont.)
recycling 149
recycling rates (by country) 149–150
reflectivity 63
aluminum alloys 63 64(F) 65
aluminum castings 65
aluminum foil 67 147
American Plastics Council 150
amorphous (noncrystalline) materials 9 9(F)
amorphous, defined 9
amorphous carbon 96
anions 2 3(F) 9
137(F)
anisotropic 120 126
annealing 60–63(F)
annealing range 84
cold rolling 141
grain boundaries 62–63
grain growth stage 62 62(F) 63
grain size 62–63 62(F)
recovery stage 60 61(F)
recrystallization stage 60–61 61(F) 62(F)
stress relief annealing 137
tungsten 61(F)
annual growth rings 121–122 121(F) 122(F)
anode 129 130(F) 132
136
aqueous corrosion. See corrosion in water
solutions
aramids 110
aromatic polyamide 110
atactic 104 105 105(F)

Index Terms Links
atoms
amorphous (noncrystalline) materials 9
bcc crystal structure 5 6(F)
borax 87 87(F)
brass 11
carbon 93
copper 63
crystal structures 4
defined 2
diamond cubic crystal structure 7
domain boundaries 54
elasticity 24
energy bands 40
extrinsic semiconduction 43
fee structure 4 5(F)
ferromagnetism 52
fullerenes 96
as hard spheres 4
hcp crystal structure 6–7 6(F) 7(F)
hydrogen atoms 3 3(F) 103(F)
metal glasses 20
metallic conduction 38 39
nanotubes 97
nonferrous metals 59
oxygen 9 9(F)
silicon 9 9(F) 41
41(F)
solid solutions 12 12(F)
solute 39
austempering 77
austenite
cast irons 77
grain size 74
grain size effect 74

Index Terms Links
austenite (Cont.)
hardening 71 73
Jominy end-quench test 73
low-carbon steels 76
martensitic stainless steels 76
overview 69
phase diagrams 15
steels 69 70(F) 71(F)
transformation to pearlite 73
austenitic stainless steels 33 76 79
backbones 96 100 101(F)

barium titanate 47 48 48(F)
bauxite 149
bcc. See body-centered cubic (bcc)
benzene ring 95 100(T) 109
beryllium 7 20 59(T)
biodegradable 152
bismuth 17 42 60
150
blow molding 143
body-centered cubic (bcc) 5 6(F) 69
bonding
bond strengths 4(T)
covalent bonding 2 3 3(F)
hard spheres 4
hydrogen bond 3(F)
hydrogen bonding 3
ionic bonding 2 3(F)
metallic bonding 2 3(F)
van der Waals bonding 2–3 3(F)
borax, B2O3 (boron trioxide) 87 87(F)
branching 103 104(F) 105

Index Terms Links
brass 11 63 66
135 161
Bridgman method of growing single crystals 139–140 139(F)
Brinell hardness test 28
brittle fracture 30 31(F)
bronze 10 60 63
150 161
bronze age 1
Buckminsterfullerene 96
Buckyballs 96 97(F)
bulk forming (solid metals) 140 140(F)
butadiene 105
butadiene rubber 111
cadmium 7 131(T)
capacitors 146
carbon 93–98(F,T)
amorphous carbon 96
carbon fibers 96
diamond 93–95(F)
fullerenes 96 97(F) 98
graphite 95(F,T)
iron-carbon phase diagram 69 70(F)
nanotubes 96–97(F)
(see also nanotubes)
overview 93
phase diagram showing the equilibrium
phases 94(F)
properties 159
in steels 69
carbon black 106
carbon content 71 72(F) 77
carbon fibers 96

Index Terms Links
carbon steels
low-carbon steels 27 27(F) 76
passivation 133
plain-carbon steels 11 73 75(F)
cardboard 125–126
cardboard fiber alignment 126–127 127(F)
cast ingot 17(F) 140
cast irons 77–78(F)
austempering 77
carbon content 77
ductile cast iron 77 78(F)
ferrite 77 77(F)
graphite formation 77
gray cast iron 77 77(F)
properties 161
white cast iron 77–78
casting
aluminum 65 139
cast irons 77
die casting 66 139
freezing 17
gold 139
iron 139
magnesium 65
silver 139
slip casting 89 90(F)
steels 139
zinc 66
cathode 129 130(F) 132
136
cations 2 3(F) 9
celluloid 112
cellulose 100 101(F) 122

Index Terms Links
cementite 69 71 73
77
ceramics
carbon 93–98(F,T)
crystalline ceramics 81–82(F)
fine-grained 87
glasses 82–88(F,T)
hydration reactions 91–93(F)
overview 81
pottery 88–91(F)
powder processing 144
Charpy test 30–33(F)
ductile-brittle transition in a Charpy V-notch
specimen 32(F)
low-carbon, low-alloy, hot-rolled steel 32–33 32(F)
ship steels 32–33
testing machine and test bar 30–32 31(F)
toughness, measuring 32
transition temperature 32 32(F)
Charpy V-notch 15 ft-lb transition temperature 32–33
chemical vapor deposition (CVD) 95
chemistry basics
amorphous (noncrystalline) materials 9 9(F)
bonding 2–4(F,T)
crystal structures 4–9(F)
elements 1
fundamental particles 2
historical development 1
periodic table 1 2(F)
chromium 5 73 159
clay 88–89 89(F) 125–126
See also pottery
cobalt 51 52 52(T)
120 159

Index Terms Links
coercive force 54 54(F) 56

cold rolled steel 76 141
cold rolling
advantage of 141
annealing 141
versus hot working 140–141
steel 141
cold work 60 60(F)
compasses 57
composites
fiber length 118–120(F,T)
fiber-reinforced composites 115–117(F,T)
lamellar composites 120
overview 115
particulate composites 120
reinforced concrete 120
use of 120
volume fraction of fibers 117(F)
compression molding 143 144(F)
concrete, properties of 161
concrete mixes 93 93(F)
condensation reaction 99–100
conduction 37
conduction band 41–42 41(F)
coniferous (cone bearing) 121
constants 157
conversions 157
copolymers 105
copper
aluminum-copper phase diagram 64(F)
applications 63
brass 63
cold work 60(F)

Index Terms Links
copper (Cont.)
crystallizing 4
ductility 60
electrical resistivity 38 38(F)
fracture 33
as known to antiquity 10
properties 159 161
recycling 149–150
resistivity, effects of solutes on 38 39(F)
copper alloys 63
Corning Glass 98
corrosion
acid corrosion 137
brass cartridge cases 137
control 134–135(F)
cost of (United States) 129
direct oxidation 136–137(F)
overview 129
passivation 131(T) 132–133 134(F)
rust 136 136(F)
sacrificial corrosion 135 135(F)
stress corrosion 135
in water solutions (see corrosion in water solutions)
corrosion control 134–135(F)
corrosion in water solutions 129–132(F,T) 133(F) 134(F)
anode 129 130(F)
cathode 129 130(F)
cathode reactions 129
corrosion cell 130(F)
electromotive series 129 130(T)
galvanic series of common alloys 129(F) 131(T)
grain boundaries 132 133(F)
hydrogen cathode 129 131(F)

Index Terms Links
corrosion in water solutions (Cont.)

oxygen concentration cells 129 132 132(F)
polarization 132 133(F) 134(F)
regions that have been cold worked 132(F)
seawater 129 131(T)
corrosion resistance
aluminum 63
copper 63
stainless steels 76
titanium 65
covalent bonding 2 3 3(F)
100
cracking
copper 149
polymers 109
Portland cement 92
pottery 91
stress-corrosion cracking 137
creep 29 29(F) 84
cross-linking and stereoisomerism 104 104(F) 105(F)
cross-links 104
crystal structures
defined 4
fcc crystal structure 4 5(F)
hcp crystal structure 6–7 6(F) 7(F)
introduction 4
periodic table 8(F)
sodium chloride crystal structure 7–9 8(F)
unit cell 4
crystalline
devitrification 87
HDPE 109

Index Terms Links
crystalline (Cont.)
linear polymers 105 106(F)
materials, elastic strains in 24
phases 11
PP 110
solids 4 11
(see also crystal structures)
crystalline ceramics 81–82(F)
applications 81
porosity 82 82(F)
preparation 82
properties 81
cups 141 142(F)
Curie temperature 48 52(T)
CVD. See chemical vapor deposition (CVD)
CVD diamond films 95
Czochralski method of growing single crystals 139(F) 140
Davy, Sir Humphrey 137

deciduous (losing leaves in the winter.) 121
deep drawing 141 142(F)
deflocculant 90
degradation 107–109
degree of polymerization 103 103(F)
dendrites 18 19(F)
devitrification 87
devitrify 87
diamagnetic behavior 51
diamagnetism 51
diamond 93–95 94(F)
coefficient of thermal expansion 94
CVD diamond films 95
density 94

Index Terms Links
diamond (Cont.)
properties 161
synthetic diamonds 95
thermal conductivity 94
Young's modulus 93–94
die casting 66 139
diodes 45
See also p-n rectifiers
direct corrosion 129
direct oxidation 136–137(F)
directional solidification 139
domain boundaries 54 54(F) 55(F)
domains 52 54 54(F)
56
dopants 146
doped 146
draw beads 141
drawn fibers 143
drift velocity 37–38 38(F)
dual-phase steels 76
ductility
ceramics 81
cold working, effects of 60 60(F)
defined 28
magnesium 65
overview 28
earthenware 90 91
eddy currents 56
elastic deformation 23–24

Index Terms Links
elastic limit 25
elastic modulus. See also Young's modulus
diamond 49
elastic moduli with melting points
correlation of 24(F)
fiber-reinforced composites 116
graphite 95(T)
polymers 106
properties of common woods at 12%
moisture content 124 125(T)
rule of mixtures 116
elasticity 23–25 24(F,T)
electric arc furnaces 150
electrical behavior
III-V compound semiconductors 44–45(F,T)
conduction 37
energy bands 40 40(F)
extrinsic semiconduction 42–44(F)
intrinsic semiconduction 41–42(F,T)
ionic conduction 40
LED traffic lights 49
LEDs 46 46(T)
metallic conduction 37–40(F,T)
piezoelectric behavior 47–49(F)
p-n rectifiers 45–46(F)
polar compounds 47 47(F)
transistors 46–47(F)
electrical insulators 147
electrolyte 134
electron gas 2 3(F) 37–38
electron holes 41 43 44(F)
45–46 45(F)

Index Terms Links
electrons
energy bands 40
extrinsic semiconduction 42–43 43(F)
intrinsic semiconduction 41
p-n rectifiers 45–46 45(F)
polar compounds 47
electrostatic attraction 2 3
elements
periodic table 1 2(F)
properties of 159
endurance limit 30
energy bands 40 40(F)
EPA. See U.S. Environmental Protection
Agency (EPA)
epoxies 111
eutectic
eutectic structure of a lead-tin alloy 14(F)
lead-tin phase diagram 13 14(F)
phase diagrams 13
eutectic reaction 13 14(F)
eutectic systems 119–120
eutectoid reaction 15 69 70(F)
exchange energy 52 54
extrinsic semiconduction 42–44(F)
donors 42–43 43(F)
electron hole 43 44(F)
exhaustion range 44
group III elements, effects of 43 44(F)
group V impurities 43(F)
impurities, effect of 42–43
p-type semiconductor 43
temperature dependence of conductivity 43(F)

Index Terms Links
face-centered cubic (fcc) 4 5(F) 69

fatigue
aluminum 30(F)
cycles before failure 29 29(F) 30(F)
defined 29
endurance limit 30
fatigue strength 30
nonferrous metals 30 30(F)
steels 29–30 29(F)
fatigue strength 30
fcc. See face-centered cubic (fcc)
feldspar 89 90
ferrite
cast irons 77
ductile cast iron 78(F)
gray cast iron 77(F)
martensite 71 72(F)
microstructure 71(F)
microstructure of pearlite 70(F)
microstructure of steel 71(F)
overview 69
Portland cement 92
soft magnetic materials 56
steels 69
transformation to austenite 15 71
ferritic stainless steels 76
ferromagnetic elements 51 52(T)
ferromagnetism 51–52(F,T)
direction of magnetization 54
domains 52
exchange energy 52

Index Terms Links
ferromagnetism (Cont.)
lodestone 51(F)
rare-earth elements 51
ferrous metals 69
See also iron
fiber
length 118–120(F,T)
Nylon 6/6 110
polypropylene (PP) 110
volume fraction of 117 117(F)
fiber-reinforced composites 115–117(F,T)
composite strength 117
elastic modulus 116
geometric arrangements of fiber
reinforcements 115(F)
predicted strength 117
stress-strain curve for the composite 116(F)
stress-strain curve for the fibers 116–117 116(F)
stress-strain curve for the matrix 116–117 116(F)
fibers
average axial stress 118
chopped fibers 118
epoxies 118–119 119(T)
epoxy matrix composites, properties of 119(T)
eutectic systems 119–120
fiber length 118–120(F,T)
fracture 118 118(F)
polyesters 118–119 119(T)
polymer matrices 118–119 119(T)
properties 119(T)
pullout 118 118(F) 119(F)
thermoplastics 143
volume fraction of fibers 117 117(F)

Index Terms Links
flame retardants 106

flexible foam 111
flue dust 150
flux 89 155
foams 143–144
forming and shaping
bulk forming of solid metals 140 140(F)
bulk forming processes 140(F)
hot working versus cold working 140–141
liquid to solid processing 139–140(F)
modern manufacturing techniques 146–147(F)
polymer processing 142–144(F)
powder processing 144–146(F)
sheet forming 141 142(F)
single crystals 139 139(F)
fracture 30–34(F)
bcc metals 33
brittle fracture 30 31(F)
Charpy test 30–33(F)
classification 30
fcc metals 33
fibers 118 118(F)
glasses 86 88 89(F)
grain boundaries 30
grains 30
hcp metals 33
impact tests 30
mechanical behavior 23
natural gas pipelines 33 33(F)
ships 33–34 34(F)
tension test 30
toughness 30

Index Terms Links
freezing 16–17(F)
cast ingot 17 17(F)
exceptions 16
liquid state 17
materials that expand when solidifying 17
process 17
volume decrease 17
wrought products 17
freezing, segregation during 17–19(F)
actual temperature 18 19(F)
binary phase diagram 18(F)
boundary layer formation 18(F)
constitutional supercooling 18 19(F)
contours of concentration 18(F)
dendrite formation 18 19(F)
freezing temperature 18 19(F)
inter-dendritic porosity 18
liquidus temperature 18 19(F)
fuel cells 97
Fuller, Buckminster 96
fullerenes 96 97(F)
galvanizing 66 135(F)
gases 11 17 109
143
gasoline 108
germanium
conductivity of 42 42(F)
energy gaps 42(T)
freezing 17
glasses 88
metal glasses 20

Index Terms Links
germanium (Cont.)
mobilities, intrinsic semiconductors 42(T)
properties 45(T) 159
Gibbs, Josiah Willard 20
glass recycling 151
glass transition
change of specific volume on cooling 107(F)
glass transition temperatures 107(F)
melting temperatures 107(T)
overview 106
Young's modulus 106 108(F)
Young's modulus of PVC 108(F)
glass viscosity 83–85(F)
annealing range 84
creep 84
glass transition temperature 83 84(F)
spinning glass 85 85(F)
stained glass windows 84–85
stress relief 84
temperature dependence of viscosity 83–84 84(F)
glasses 82–88(F,F)
borax 87 87(F)
chemically tempered 88
compositions and coefficients of thermal
expansion 85(F)
devitrification 87
fracturing 86
glass transition temperature 106 107(F) 108(F)
glass viscosity 83–85(F)
inorganic glasses 87–88(F)
other inorganic glasses 87–88
overview 82–83(F)
photosensitive glasses 87 98
residual stresses 88

Index Terms Links
glasses (Cont.)
silica-rich glass 86–87
silicate glasses 82 83(F)
soda-lime glasses 82–83 83(F)
tempered glass 88
tempering 88
tetrahedra 82 83 83(F)
thermally-induced stresses 85–86(F,T)
transition temperature 84
glazing 91
gold 4 139 159
golf club heads 20 20(F)
grain boundaries 30 62–63
grain size 63 74 76
147
grains
annealing 60 61(F) 62(F)
cast ingot 17(F)
columnar grains 17(F)
cracks 135
fracture 30
freezing, during 17
grain growth 62–63
graphene sheet 96–97 97(F)
graphite
carbon fibers 96
cast irons 77 78(F)
density 94
directional properties 95(T)
elastic modulus 95(T)
fullerenes 96
galvanic series of common alloys 131(T)

Index Terms Links
graphite (Cont.)
overview 95(F,T)
phase diagram, equilibrium phases of
carbon 94(F)
properties 161(T)
as spheroids 77 78(F)
structure 95 95(F)
graphite fibers. See carbon fibers
graphite flakes 77 77(F)
Great Boston Molasses Flood 34
Greek alphabet 153
green (pottery) 90
Hall, Charles Martin 63

Hall-Heroult process 66
hardenability 73 74 76
hardening 71–74(F)
See also martensite; steels
alloying elements 73
Jominy end-quench test 73 73(F) 74(F)
martensite 71 72(F)
plain carbon steels 73
hardness tests
Brinell hardness test 28
indenter 28
Knoop hardness test 28
Rockwell hardness tests 28
Vickers hardness test 28
hcp. See hexagonal close packed (hcp)
structure
HDPE. See high-density polyethylene (HDPE)
heartwood 122

Index Terms Links
hemicellulose 122
Heroult, Paul 63
hexagonal close packed (hcp) structure
crystal structures 6–7 6(F) 7(F)
ductile-brittle transition 33
elements, properties of 159
titanium 65
hexagonal planes 4 5(F) 7
hexagonal prism 6–7 6(F)
high-density polyethylene (HDPE) 109 143 151
high-speed steels 74–76 75(F)
high-strength, low-alloy (HSLA) steels 76
Hittites, the 78
horseshoe magnets 52 53(F)
hot rolled steel 32(F) 76 141
hot shortness 150
hot working 140–141
Hyatt, John Wesley 112
hydration reactions
concrete mixes 93 93(F)
hydration reaction 91 92(F)
lime plaster 91 92
overview 91–92(F)
plaster of paris 91 92(F)
Portland cement 92
hydrogen properties of 159
hydrogen atoms 3 101(F) 103(F)
hydrogen bond 3(F)
hydrogen bonding 3
impact tests 30
inclusions 55 56
indenter 28

Index Terms Links
ingots 17 17(F) 140

injection molding 109 118 139
inorganic materials 147
See also ceramics
insulators 40 134–135
integrated circuits 146 146(F)
interstitial solid solution 12 12(F)
intrinsic semiconduction 41–42(F,T)
band structure, intrinsic semiconductor 41(F)
conduction band 41–42 41(F)
electron hole 41
energy gaps, intrinsic semiconductors 42(T)
germanium 42 42(F)
mobilities, intrinsic semiconductors 42(T)
silicon 41
valence band 41 42
intrinsic semiconductors 41
band structure 41(F)
energy gaps 42(T)
mobilities 42(T)
ionic bonding 2 3(F)
ionic conduction 40
ions
chemically tempered (glasses) 88
chloride 135
chlorine 7
corrosion in water solutions 132
defined 2
devitrification 87
elasticity 24
ion exchange 88
ionic conduction 40

Index Terms Links
ions (Cont.)
polar compounds 47
potassium 88
sodium 7
iron
bcc crystal structure (room temperature) 5
casting 139
cold work 60(F)
corrosion 129
crystal structure 69
crystallizing 4
domain boundaries 54 55(F)
ferromagnetic element 51
magnetostatic circuits 52 53(F)
overview 69
properties 159
pure iron 69
recycling 149
soft magnets 55
transformation temperature 69
iron age 1
ironing 142(F)
isotactic 104 105(F)
kaolinite 89 89(F) 90
91(F)
ketones 108
Kevlar 101(F) 119(T)

Index Terms Links
Knoop hardness test 28
Lambot, Joseph-Louis 120

laminated safety glass 88 89(F)
lattices
aluminum 63
cold working 39 60
intrinsic semiconduction 41
martensite 72
metallic conduction 37–38 39
nonferrous metals 59
semiconductors 45(T)
single-phase solids 4
LDPE. See low-density polyethylene (LDPE)
lead 4 10 66
159
lead battery plates 150
lead metaniobate 48
lead zirconate titanate (PZT) 48
lead-tin system 12–13(F) 14(F)
lever law 16
Liberty ships 33–34 34(F)
light emitting diodes (LEDs) 46 46(T) 49
lime 92
lime plaster 91 92
linear polymers
branching 103 104(F)
molecular configuration 105
plastic deformation 27 27(F)

Index Terms Links
linear polymers (Cont.)

structure 101(F)
tacticity of 105(F)
liquid state 17
liquidus temperature 18 19(F)
lodestone 51(F) 57
long-chain molecules 88
low-carbon steels 27 27(F) 76
low-density polyethylene (LDPE) 109
lower yield strength 27
luster 59
magnesium
applications 65
density 65
ductility 60
hcp crystal structure 7
properties 159 161
room-temperature ductility 65
magnesium alloys 65 131(T)
magnetic behavior
diamagnetic behavior 51
diamagnetism 51
domain boundaries 54 54(F)
ferromagnetism 51–52(F,T)
hard magnetic materials 56–57(F)
magnetic materials, soft versus hard 54–55(F)
magnetostatic circuits 52–54(F)
soft magnetic materials 55–56(F)
magnetic materials
B-H curves 55 55(F) 56(F)
direction of magnetization 56–57

Index Terms Links
magnetic materials (Cont.)

elongated 57 57(F)
hard magnetic materials 56–57(F)
inexpensive permanent magnets 57
soft versus hard 54–55(F)
magnetization
direction of 54 54(F) 56–57
57(F)
domain boundaries 54
magnetization 53(F)
magnetostatic circuits 53 54(F)
magnetocrystalline energy 54
magnetostatic circuits 52–54(F)
B-H curve 54 54(F)
coercive force 54 54(F)
domain structures 52 53(F)
horseshoe magnets 52 53(F)
iron 52 53(F)
magnetization of a material 53(F)
magnetostatic energy 52 52(F)
net magnetization of a material 52
manganese 60 73 159
manufacturing techniques (forming and shaping) 146–147(F)
3-D printing 147
capacitors 146
dopants 146
inorganic materials, dense sintered parts of 147
integrated circuits 146 146(F)
photolithography 146
photostereolithography 147
plated 146
resistors 146

Index Terms Links
manufacturing techniques (forming and shaping) (Cont.)

three-dimensional parts 147
transistors 146
martensite
alloying elements, effect on hardness 74
carbon content 71 72(F)
crystal structure 71(F)
ferrite 71 72(F)
formation of 71
hardenability 74
hardening 71–72 72(F)
martensite unit cell 71 (F)
transformation to pearlite 73
martensitic stainless steels 76
martensitic steel 55
mass balance 15–16
materials, properties of 161
Maxwell, James Clerk 20
mean free path 38 38(F)
mechanical behavior
creep 29 29(F)
ductility 28
elasticity 23–25(F,T)
fatigue 29–30(F)
fracture 23 30–34(F)
Great Boston Molasses Flood 34
hardness tests 28
nominal or engineering strain 23
nominal or engineering stress 23
overview 23
permanent deformation 23
plastic deformation 23 25–27(F) 28(F)

Index Terms Links
mechanical behavior (Cont.)

strain 23
stress 23
true stress 23
medical replacement structures 65–66
mer (meaning parts) 99
metal glasses 19–20
complex silicates 19
golf club heads 20 20(F)
metal early compositions 19–20
polymers 19
temperature versus time, freezing of water 21 21(F)
Vitreloy 1 20
water turning to ice 21(F)
metal oxide semiconductor field effect
transistor (MOSFET) 46–47 47(F)
metallic bonding 2 3(F)
metallic conduction 37–40(F,T)
annealing, copper 39 39(F)
cold working, copper 39 39(F)
drift velocity 37–38 38(F)
electrical conductivities at 20 °C (70 °F) 37(T)
electrical resistivity, aluminum 38 38(F)
electrical resistivity, copper 38 38(F)
electron gas 37
impurities, effect of 40
increased temperature, effect of 40
mean free path 38 38(F)
valence electrons 37
metals
crystal atoms 4
known to antiquity 10
native (metallic) state, occurring in 10
recycling 149–150

Index Terms Links
meteorites 10
mobility (defined) 37
molding
blow molding 143
injection moldings 109 118 139
polyurethane foam 144
transfer moldings 118
molecules
Buckyballs 96
defined 2
elasticity 24
glasses 88
linear 100
plasticizers 106
polyisoprene molecules 104 104(F)
polymers 99 105 106(F)
rubber 104 104(F)
molten salt bath 88
molybdenum 5 73 137
159
Monier, Joseph 120
monomers 100 102(F)
MOSFET. See metal oxide semiconductor field
effect transistor (MOSFET)
mullite 90 91(F)
nanotubes
applications 97–98
diameters 97
graphene sheet 96–97 97(F)

Index Terms Links
nanotubes (Cont.)
length-to-diameter ratio 97
overview 96–97(F)
production processes 97
sieves 98
neck 27
necking
plastic deformation 27 27(F)
polyethylene 112(F)
sintering pressed powders 144 145(F)
Nevin, James 126
nickel
crystallizing 4
ductility 60
ferromagnetic element 51
partially sintered nickel spheres 145(F)
properties 159
in steels 73
niobium 5 159
nitric acid 133
nonferrous metals
aluminum 63–65(F)
annealing 60–63(F)
cold work 60 60(F)
copper 63
deformation of crystals by slip 59 59(F)
ductility 59–60
lead 66
magnesium 65
overview 59–60(F)
recycling 149
thermal vibrations 59
tin 66

Index Terms Links
nonferrous metals (Cont.)

titanium 65–66
zinc 66
n-type semiconductors 44
nylon
drawn fibers 143
formation of 99
properties 161
structure 101(F)
Nylon 6/6 110
offal 149
offset yield strength 25 26(F)
old scrap 149
oxi-degradable 152
oxygen 132 133 159
ozone 109
paper 125–126 151

papyrus 125
paraffin series 103 103(F)
particulate composites 120
passivation 131(T) 132–133 134(F)
pearlite 69 70(F)
pentane 143
periodic table 8(F)
permanent deformation 23
permanent magnets 54–55 57
PET. See polyethylene terephthalate (PET)
petrochemical compounds 152
pharmaceutical pills 144

Index Terms Links
phase 11
phase diagrams
austenite 15
copper-nickel phase diagram 13 15(F)
copper-tin phase diagram 13–14 15(F)
eutectoid reaction 15
iron-carbon phase diagram 14–15 16(F)
lead-tin phase diagram 14(F)
lever law 16
limits of solubility 12
mass balance 15–16
peritectic reaction 14 15(F)
phase regions in lead-tin system 12 13(F)
solubility limits in the lead-tin system 12–13 13(F) 14(F)
phase relations
freezing 16–17(F)
freezing, segregation during 17–19(F)
metal glasses 19–20(F) 21(F)
phase diagrams 12–16(F)
solid solutions 1–2 12(F)
phases 11
phenol formaldehyde 102 102(F) 111
photolithography 146
photons 59
photoresist 146
photosensitive glasses 87 98
photostereolithography 147
pickled 141
picture frames 123 124(F)
piezoelectric behavior 47–49(F)
applications 47 48 49
barium titanate 48
lead metaniobate 48
piezoelectric crystal 48 48(F)

Index Terms Links
piezoelectric behavior (Cont.)

PZT 48
vibrating quartz crystals 48–49
piezoelectric crystals 49
See also piezoelectric behavior
piezoelectricity 47–49(F)
plain-carbon steels 11 73 75(F)
plastarch material (PSMpolyactide) 152
plastic bottles 143
plastic deformation 25–27(F) 28(F)
elastic limit 25
engineering stress-strain curve for a ductile
material 25 26(F)
example 23
linear polymers 27 27(F)
low-carbon steels 27 27(F)
lower yield strength 27
necking 27 27(F)
offset yield strength 25 26(F)
overview 23
proportional limit 25
tensile strength 27 28(F)
ultimate strength 27
upper yield strength 27
yielded and deformed plastically 25 25(F)
plasticizers 106
plastics
blow molding 143
commercial plastics 105
compression molding 143

Index Terms Links
plastics (Cont.)
first appearance 1
recycling 150–151(F)
plated 66 120 146
platinum 4 55 66
plies 125 125(F)
plywood 124(F) 125 125(F)
126
PMMA. See polymethyl methacrylate
(PMMA)
p-n junction rectifier 45(F)
p-n rectifiers 45–46(F)
polar compounds 47 48(F)
polarized 47
poly paraphenylene terphthalamide (PPTA) 100 101(F)
polyacrylonitrile (PAN) 96
polyactide (PLA) 152
polycarbonate (PC)
blow molding 143
properties and uses 110
structure 100 101(F)
polyester. See polyethylene terephthalate (PET)
polyethylene
branched polyethylene 104(F)
branching 105
formation of 99
necked region 112(F)
properties 161
recycling 150–151
stress-strain curve 112(F)
polyethylene terephthalate (PET)
blow molding 143
fibers 118–119 119(T)
properties and uses 109

Index Terms Links
polyethylene terephthalate (PET) (Cont.)

recycling 150–151
structure 100 101(F)
polymer, description of 99
polymer processing
blow molding 143
foams 143–144
overview 142
parison 143
plastic bottles 143
polystyrene foam 143–144
polymers
additives 106–107
branching 103 104(F)
copolymers 105
cross-linking and stereoisomerism 104 104(F) 105(F)
degree of polymerization 103 103(F)
elastic modulus 106
freeze as glass 19
glass transition 106 107(F,T) 108(F)
molecular configuration 105 106(F)
molecular weight 103 103(F)
overview 99–100
polymer processing 142–144(F)
properties and uses of 109–112(F)
recycling 151
stress cracking 109
thermoplastic, stretching of a 112 113(F)
thermoplastics 100 101(F,T)
thermosetting polymers 100 102(F) 103(F)
ultra-violet radiation 106

Index Terms Links
polymethyl methacrylate (PMMA) 110

polypropylene (PP) 110 143 151
polystyrene (PS) 109–110 151 161
polystyrene foam 114 143–144
polytetrafluoroethylene (PTFE) 110
polyurethanes 108 111
polyvinyl alcohol 108
polyvinyl butyral (PVB) 88
polyvinyl chloride (PVC) 105 108 109
143 151 161
polyvinylidene chloride 110
porosity
crystalline ceramics 82 82(F)
earthenware 90 91
freezing 17
glazing 91
inter-dendritic porosity 18
powder processing 146
silica-rich glass 87
sintering pressed powders 146
stoneware 90
Portland cement 92 98
pottery 88–91(F)
aluminosilicates 89
china 90
clay mixtures 89
clay products, processing 89–91(F)
coefficient of thermal expansion 90
earthenware 90
firing 90
flame contact 90
flux 89
glazing 91

Index Terms Links
pottery (Cont.)
green 90
kaolinite 89 89(F)
making 88–89
molecular structure of clay 89(F)
ovenware 90
overview 88–89(F)
porcelain 90
SiO2-Al2O3 phase diagram 91(F)
slip casting 89–90 90(F)
stoneware 90
powder processing 144–146(F)
ceramics 144
die shape limitations 144
pharmaceutical pills 144
porosity 146
powder compaction 144 145(F)
refractor oxides ceramics 144
sintering 144–146 145(F)
Teflon 144
PP. See polypropylene (PP)
PPTA. See poly paraphenylene terphthalamide
(PPTA)
precipitation hardening 63 64(F) 65
pressure sensors 49
proportional limit 25
PS. See polystyrene (PS)
PTFE. See polytetrafluoroethylene (PTFE)
p-type semiconductors 43 44
pure iron 69
PVC. See polyvinyl chloride (PVC)
pyrolysis 96
PZT. See Lead zirconate titanate (PZT)

Index Terms Links
quartz 47
quartz crystals, vibrating 48–49
rare-earth elements 51
recrystallization 60–61 61(F) 62(F)
140 141
rectifiers 45
See also p-n rectifiers
recycling
aluminum 149
biodegradable 152
copper 149–150
glass 151
HDPE 151
lead battery plates 150
metals 149–150
old scrap 149
oxi-degradable 152
paper 151
PET 150–151
plastics 150–151(F)
polystyrene (PS) 151
PP 151
PS 151
PVC 151
rates (by country) 149
rubber 151
scrap 149
silver 150
solder alloys 150
throughout human history 152

Index Terms Links
recycling (Cont.)
tramp elements 149
World War Two 152
zinc-coated steel scrap 150
refractory oxides ceramics 144
reinforced concrete 120
residual stresses 88
resins 111 117 150
151 151(F)
resistors 146
rheocasting 139
Rockwell hardness tests 28
rubber
aramids 110
buta-rubber 101
cross-linking 104
cross-linking with sulfur 104 104(F)
elastic deformation 23
foam rubber 111
gasoline, effect of 108
hardness 104
inexpensive permanent magnets 57
mechanical behavior 23
recycling 151
several runners 101(T)
structure 101(F)
vulcanized rubber 109
rust 136 136(F)

salt water 65
See also seawater

Index Terms Links
sap 122
sapwood 122
scaffolds for bone growth 147
scission reaction 109
scrap 149
seawater 65 129 131(T)
semiconductors 40 140
shaping. See forming and shaping
sheet forming. See also cold rolling
cups 141 142(F)
deep drawing 141 142(F)
draw beads 141
ironing 141
stamping 141
tensile stresses 141
wrinkling 141
ship steels 32–33
shrink-wrapping 147
SI unit system 155
sieves 98
silica
aluminum 65
china 90
clay products 90
coefficient of thermal expansion 85(T)
compositions 85(T)
crystalline ceramics 81
mullite 90
polymers 106
tetrahedra 82 83(F)
silica glass 83(F) 86
See also silica-rich glass
silica-rich glass 86–87

Index Terms Links
silicon
aluminum castings 65
intrinsic semiconduction 41 41(F)
properties 159 161
in steels 73
silicon age 1
silicon crystals 140
silicones
backbones 100
properties and uses 111–112
structure 111(F)
silver
casting 139
crystallizing 4
properties 159 161
recycling 150
sintering
crystalline ceramics 82
partially sintered nickel spheres 144 145
powder processing 144–146 145(F)
pressed powders 146
slip 89–90 90(F)
slip casting 89 90 90(F)
sodium chloride 7–9 8(F) 11
81
solid solutions 11–12 12(F)
solvents 107–108
spheroids 77 78(F)
stained glass windows 84–85
stainless steels
corrosion behavior 76

Index Terms Links
stainless steels (Cont.)

passivation 131(T) 132–133
types 76
stamping 76 141 142(F)
steels
alloying elements, principle use of 74
carbon as alloying element 69
casting 139
cold rolling 141
corrosion 129
eutectoid reaction 69 70(F)
hardening 71–74(F)
high-speed steels 74–76 75(F)
high-strength, low-alloy (HSLA) steels 76
hot rolling 141
iron-carbon phase diagram 69 70(F)
low-carbon steels 76
overview 69–71(F)
recycling 149
solubility of carbon in 69 70(F)
stainless steels 76
tempering 74–76(F)
tramp elements 149
stone age 1
stoneware 90
strain 23
stress 23
stress cracking 109
stress relief annealing 137
stress-corrosion cracking 137
Sturgeon, Theodore 137

Index Terms Links
styrene 105
substitutional solid solution 12 12(F)
sulfur 104 104(F) 159
superconductors 98
syndiotactic 104
synthetic diamonds 95
T-2 tankers 33–34 34(F)

tantalum 5
Teflon 144
tempered glass 88 89(F)
tempering
carbide precipitates 74
chemically tempered (glasses) 88
glasses 88
hammers 74
hardness of plain carbon steels after
tempering 75(F)
knives 74
overview 74–76(F)
razor blades 74
secondary hardening in steels containing
chromium 75(F)
secondary hardening in steels containing
molybdenum 74–76 75(F)
tensile strength 27 28(F)
tensile stresses 137 141
tension test 28 28(F) 30
60
tetrahedra 9 9(F) 82
83 83(F)
thermal conductivity 49 94 95
161

Index Terms Links
thermally-induced stresses 85–86(F,T)

coefficient of thermal expansion 85–86 85(T)
coefficient of thermal expansion and
viscosity, relationship between 85–86 86(F)
thermoformed thermoplastics 143 143(F)
thermoplastics
backbones 100 101(F)
cellulose 100 101(F)
drawn fibers 143
elastomers 100 101(F,T)
forming and shaping 139
Kevlar 101(F) 119(T)
linear thermoplastics 100(T)
nylon 101(F)
overview 100 100(T) 101(F,T)
polycarbonate 100 101(F)
polyester (PET) 100 101(F)
polymers of the general form 100(T)
PPTA 100 101(F)
recycling 150
silicones 100
stretching 112 112(F) 113(F)
thermoformed 143 143(F)
van der Waals bonding 100
thermosetting 100
thermosetting polymers 100 102(F) 103(F)
thixo tropic 139
three-dimensional parts 147
tin
as alloying element 66
applications 66
bronze 63
as known to antiquity 10

Index Terms Links
tin (Cont.)
plating 135(F)
properties 159
titanium
applications 65–66
bcc crystal structure (elevated temperature) 5
crystal structure 65
density 65
ductility 60
hep crystal structure (room temperature) 7
medical replacement structures 65–66
properties 159
strength 65
titanium alloys 65 66 133
titanium dioxide 106
tough, defined 30
toughness
ABS 111
Charpy test 32
fiber length 118
fiber reinforcement 116
fracture 30
impact tests 30
PC 110
PMMA 110
tension test 30
traffic lights LEDs 49
tramp elements 149
transistors 46–47(F)
forming 146
junction transistors 46 46(F)
MOSFET 46–47 47(F)

Index Terms Links
transistors (Cont.)
n-p-n type 46
p-n-p type 46 46(F)
transition temperature
Charpy test 32
Charpy V-notch 15 fit-lb transition
temperature 32–33
defined 32
ductile-brittle transition temperature 32
glass transition temperature 106 107(F) 108(F)
glass viscosity 83 84(F)
glasses 84
ship steels 33–34
trees 121
tungsten
annealing 61(F)
bcc crystal structure 5
direct oxidation 136–137
properties 159
in steels 73
ultimate strength, defined 27

ultraviolet light 84 146 147
ultraviolet radiation 106
unit abbreviations 163
unit cell 4 5(F)
barium titanate 48(F)
defined 5
fcc crystal structure 4 5(F)
martensite 71 71(F)
untempered glass 88 89(F)
upper yield strength 27

Index Terms Links
urea formaldehyde 102 103(F) 111

U.S. Environmental Protection Agency (EPA) 150–151
vacancies 39
valence band
energy bands 40
extrinsic semiconduction 43 44(F)
intrinsic semiconduction 41 42
valence electrons 2 37–38 59
valences 81
valleys 4
van der Waals bonding 2–3 3(F) 95
100
vanadium 5 137 159
vanadium pentoxide (V2O5) 137
vapor sputter deposition 96
vector analysis 20
veneer 125(F)
Vickers hardness test 28
vinyl. See polyvinyl chloride (PVC)
vinyl acetate 105
viscosity. See also glass viscosity
softening point 83–84
working range 83
Vitreloy 1 20
volume fraction of fibers 117 117(F)
vulcanized rubber 109
Washington Monument, pyramidal cap 66

Index Terms Links
water
bonding 3
cardboard 125–126
celluloid 112
ceramics 81
clay 89 89(F)
concrete mixes 93
condensation reaction 99–100
corrosion 129–132(F,T)
corrosion control 134
die casting 66
direct oxidation 136
firing 90
freezing 17 21 21(F)
glazing 90
HDPE 109
hydration reactions 91 92(F)
hydrogen bonding 3(F)
Jominy end-quench test 73 73(F)
kaolinite 89 89(F)
lime plaster 92
newsprint 125–126
nylon 108
paper 125
PET 109
phase relations 11
plywood 120
pollution 151
polymers 99–100
Portland cement 92

Index Terms Links
water (Cont.)
PVC 108
slip 89–90
white cast iron 77–78
Wollaston Francis 137
wood
anisotropy of properties 124 125(T)
annual growth rings 121–122 121(F) 122(F)
cardboard 125–126
dimensional change with moisture
(see wood dimensional changes with moisture)
hardwood 121 121(F) 122(F)
heartwood 122
overview 121
paper 125–126
plywood 125 125(F)
sap 122
sapwood 122
softwood 121 121(F) 122(F)
structure 121–122(F)
veneer 125(F)
wood, dimensional changes with moisture 122–123(F,T) 124(F,T)
change of moisture content 124(T)
directional dependence of shrinkage 122 124(F)
moisture content 122–123
percent shrinkage of woods on drying 122 123(T)
picture frames 123 124(F)
splitting 123
splitting of a red oak log on drying 123(F)
warping 122 124(F)
wood flour 106
World War Two 33–34 34(F) 152
wrinkling 141
wrought products 17

Index Terms Links
Young's modulus
carbon fibers 96
diamond 93–94
epoxy matrix composites 119(T)
fiber properties 119(T)
glass transition 106 108(F)
graphite 95
materials, properties of 161
polymers 106
PVC 106 108(F)
woods at 12% moisture content 125(T)
Young's moduli at 20 °C (70 °F) 24(T)
zinc 7 63 66
135 135(F) 159
zirconium 5 7 159

ASM - Elementary Materials Science-ASM International (2013)

Uploaded by

Copyright:

Available Formats

ASM - Elementary Materials Science-ASM International (2013)

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

ASM - Elementary Materials Science-ASM International (2013)

Uploaded by

Copyright:

Available Formats

Elementary

First printing, August 2013

Library of Congress Control Number: 2013931785

Printed in the United States of America

MATERIALS are so important to civilization that the terms stone age,

Table 1.1 Bond strengths

Van der Waals 0.0–10

Face-Centered Cubic Crystal Structure

Fig. 1.4 the unit cell of a face-centered cubic structure

Fig. 1.5 Close packed planes in the face-centered cubic structure

Body-Centered Cubic Crystal Structure

Hexagonal Close Packed Crystal Structure

Fig. 1.6 the unit cell of the body-centered cubic structure

Diamond Cubic Crystal Structure

Sodium Chloride Crystal Structure

Fig. 1.10 the structure of sodium chloride

Other compounds that crystallize with the sodium chloride structure

barium oxide (BaO) calcium oxide (CaO)

lithium bromide (LiBr) potassium hydride (KH)

There are many other crystal structures of compounds. In all com-

Amorphous (Noncrystalline) Materials

2. Comparing fcc and bcc crystal structures

crystals of A can occur by atoms of B substituting for A atoms in the

Fig. 2.2 Solubility limits in the lead-tin system

Fig. 2.3 phase regions in the lead-tin system

Fig. 2.4 the lead-tin phase diagram. Source: ref 2.1

Fig. 2.5 the eutectic structure of a lead-tin alloy consisting of alternating

reaction L + a Æ b occurs as this alloy is cooled through 798 °C (1472 °F).

Fig. 2.6 the copper-nickel phase diagram. Source: ref 2.2

Fig. 2.7 the copper-tin phase diagram. Source: ref 2.3

face-centered cubic structure (g) called austenite. On cooling through 727

Fig. 2.8 the iron-carbon phase diagram. Source: ref 2.3

0.8 = 0.03fa+ 0.975(1 – fa) or

This procedure can be generalized as the lever law

fa = (cav – ca)/(c b – ca), (Eq 1)

solidified metal is used in the form of a casting with little or no addi-

Segregation during Freezing

degree) would be required to allow enough time for diffusion to eliminate

Fig. 2.11 Constitutional supercooling resulting from boundary layer forma-

Fig. 2.12 two-dimensional dendrites formed during the freezing of a poly-

included appreciable amounts of small atoms including phosphorus, sili-

Fig. 2.14 Water is turning to ice during the horizontal hold

2. Temperature versus Time during Freezing of Water

MECHANICAL BEHAVIOR of a material is how it deforms or breaks

Stress and Strain

Nominal or engineering stress, S, in a tension or a compression test is

Strain describes the amount of deformation a material has undergone.

where E is called the elastic modulus or Young’s modulus.

Table 3.1 Young’s moduli at 20 °C (70 °F)

Fig. 3.6 Necking starts when a maximum engineering stress is reached.

%El = (Lf – L o)/L o ¥ 100%.

The other is the percent reduction of area,

%RA = (Ao – Af )/Ao ¥ 100%.

The percent reduction of area at fracture is a better measure of ductility

Fig.3.9 Fatigue behavior of steels

Fig. 3.10 Fatigue behavior of aluminum

cross section 10 by 10 mm (0.5 by 0.5 in.). There is a 2 mm (0.05 in.) deep

Fig. 3.13 Ductile-brittle transition in a Charpy V-notch specimen of a low-

temperature (the temperature at which the energy absorption in a V-notch

transition temperatures of the steels. Figure 3.15 is a photograph of a ship