Symbol Meaning References • 91

n Normalization factor—reduction of directional/planar indices

to integers NA Avogadro’s number (6.022 × 1023 atoms/mol)
Px Lattice position coordinate
R Atomic radius
VC Unit cell volume
x1 Vector tail coordinate
x2 Vector head coordinate
�� X-ray wavelength
�� Density; theoretical density

Important Terms and Concepts

allotropy REFERENCES hexagonal close-packed (HCP)
amorphous crystal structure isotropic
anisotropy crystal system lattice
atomic packing factor (APF) diffraction lattice parameters Miller
body-centered cubic (BCC) face-centered cubic (FCC) indices noncrystalline
Bragg’s law grain polycrystalline polymorphism
coordination number grain boundary single crystal
crystalline unit cell

Buerger, M. J., Elementary Crystallography, John Hammond, C., The Basics of Crystallography and
Wiley & Sons, New York, NY, 1956. Diffraction, 4th edition, Oxford University Press,
Cullity, B. D., and S. R. Stock, Elements of X-Ray New York, NY, 2014. Julian, M. M., Foundations of
Diffraction, 3rd edition, Pearson Education, Upper Crystallography with Computer Applications, 2nd
Saddle River, NJ, 2001. DeGraef, M., and M. E. edition, CRC Press, Boca Raton FL, 2014. Massa,
McHenry, Structure of Materials: An Introduction W., Crystal Structure Determination, Springer, New
to Crystallography, Diffraction, and Symmetry, 2nd York, NY, 2010.
edition, Cambridge University Press, New York, Sands, D. E., Introduction to Crystallography,
NY, 2014. Dover, Mineola, NY, 1975.

Chapter 4 Imperfections in Solids

(a) Schematic Stainless Steel converter.
Body
diagram showing
the location of the
catalytic converter
in an automobile’s (b) Schematic
(a)
exhaust system. diagram
of a catalytic
Insulation Water automobile’s
Packaging Carbon Dioxide
Nitrogen exhaust system.
Molecules of
pollutant gases
become attached
to surface defects
of crystalline
metallic materials
found in the
catalytic converter.
(b) While attached to
Catalyst
Substrate these sites, the

A
molecules
experience
tomic defects
chemical
are
responsible for reactions that
reductions of gas convert them into
pollutant other, non-
emissions from polluting or less-
today’s polluting
automobile substances. The
engines. A Materials of
catalytic Importance box in
Section 4.6
converter is the
contains a detailed
pollutant reducing
description of this
device that is
Tail Pipe Emissions: process.
located in the

Exhaust Gases: Hydrocarbons (c)

Carbon Monoxide Nitrogen Oxides

(d) High-resolution transmission electron

micrograph that shows surface defects on
single crystals of one
material that is used in catalytic converters.

(d)

[Figure (d) from W. J. Stark, L. Mädler, M.

Maciejewski, S. E. Pratsinis, and A. Baiker, “Flame-
92 • Synthesis of Nanocrystalline Ceria/Zirconia: Effect of
(c) Ceramic monolith on Carrier Liquid,” Chem. Comm., 588–589 (2003).
which the metallic catalyst Reproduced by permission of The Royal Society of
Chemistry.]
substrate is deposited.
WHY STUDY Imperfections in Learning Objectives
Solids?

The properties of some materials are is much harder and stronger than
profoundly influenced by the pure copper (Section 7.9).
presence of imperfections. Also, integrated-circuit
Consequently, it is important to have a microelectronic devices found in
knowledge about the types of our computers, calculators, and
imperfections that exist and the roles home appliances function because
they play in affecting the behavior of of highly controlled concentrations
materials. For example, the of specific impurities that are
mechanical properties of pure metals incorporated into small, localized
experience significant alterations regions of semiconducting materials
when the metals are alloyed (i.e., (Sections 18.11 and 18.15).
when impurity atoms are added)—for
example, brass (70% copper–30%
zinc)

After studying this chapter, you should be able to do the following:

1. Describe both vacancy and imperfection point defect
self-interstitial crystalline
defects.
2. Calculate the equilibrium number of
vacancies in a material at some
specified temperature, given the
relevant constants.
3. Name the two types of solid
solutions and provide a Thus far it has been tacitly assumed that
perfect order exists throughout crystalline ma
brief written definition and/or
terials on an atomic scale. However, such an
schematic sketch of each.
idealized solid does not exist; all contain large
4. Given the masses and atomic
numbers of various defects or imperfections.
weights of two or more As a matter of fact, many of the prop erties of
elements in a metal alloy, materials are profoundly sensitive to
calculate deviations from crystalline perfection; the
influence is not always adverse, and often
specific characteristics are deliberately
4.1 INTRODUCTION fashioned by the introduction of controlled
the weight percent and atom amounts or numbers of particular defects, as
percent for each element. detailed in succeeding chapters.
5. For each of edge, screw, and A crystalline defect refers to a lattice
mixed dislocations: (a) describe irregularity having one or more of its dimen
and make a drawing of the sions on the order of an atomic diameter.
dislocation, Classification of crystalline imperfections is
(b) note the location of the frequently made according to the geometry or
dislocation line, and (c) indicate dimensionality of the defect. Several different
the direction along which the imperfections are discussed in this chapter,
dislocation line extends. including point defects (those as sociated with
6. Describe the atomic structure one or two atomic positions); linear (or one-
within the vicinity of (a) a grain dimensional) defects; and in terfacial defects,
or boundaries, which are two-dimensional.
boundary and (b) a twin boundary.
Impurities in solids are also discussed,
because impurity atoms may exist as point
defects. Finally, techniques for the
microscopic examination of defects and the structure of materials are briefly described.

Point Defects
4.2 VACANCIES AND SELF-INTERSTITIALS
vacancy material that is free of these
The simplest of the point defects is a vacancy,
or vacant lattice site, one normally oc cupied
but from which an atom is missing (Figure
4.1). All crystalline solids contain vacancies,
and, in fact, it is not possible to create such a
• 93
94 • Chapter 4 / Imperfections in Solids

Vacancy Self-interstitial

Figure 4.1 Two-dimensional representations of a

vacancy and a self-interstitial.
(Adapted from W. G. Moffatt, G. W. Pearsall, and
J. Wulff, The Structure and Properties of Materials, Vol. I,
Scanning probe defects. The necessity of the existence of
micrograph that shows a vacancy on a (111)- vacancies is explained using principles of
type surface plane for silicon. Approximately thermodynamics; in essence, the presence of
7,000,000×. vacancies increases the entropy (i.e., the
(Micrograph courtesy of D. Huang, Stanford randomness) of the crystal.
University.) The equilibrium number of vacancies N�� for
a given quantity of material (usually per meter
cubed) depends on and increases with
Temperature temperature according to
dependence of the equilibrium number of
vacancies

Boltzmann’s constant

N exp
self-interstitial N�� = (− Q��
kT) (4.1)

Tutorial Video:
Computation of the Equilibrium In this expression, N is the total number of
atomic sites (most commonly per cubic
Number of
meter), Q�� is the energy required for the
Vacancies formation of a vacancy (J/mol or eV/atom), T
Structure, John Wiley & Sons, 1964. Reproduced with
is the absolute temperature in kelvins,1 and k is
permission of Janet M. Moffatt.)
the gas or Boltzmann’s constant. The value
of k is 1.38 × 10−23 J/atom∙K, or 8.62 × 10−5 A self-interstitial is an atom from the crystal
eV/atom∙K, depending on the units of Q��.2 that is crowded into an interstitial site—a
Thus, the number of vacancies increases small void space that under ordinary
exponentially with temperature—that is, as T circumstances is not occupied. This kind of
in Equation 4.1 increases, so also does the defect is also represented in Figure 4.1. In
term exp(−Q��/kT). For most metals, the metals, a self-interstitial introduces relatively
fraction of vacancies N��/N just below the large distortions in the surrounding lattice
melting temperature is on the order of 10−4—
because the atom is substantially larger than
that is, one lattice site out of 10,000 will be
empty. As ensuing discussions indicate, a the interstitial position in which it is situated.
number of other material parameters have an Consequently, the formation of this defect is
exponential dependence on temperature not highly probable, and it exists in very small
similar to that in Equation 4.1. concentrations that are significantly lower
than for vacancies.

1
Absolute temperature in kelvins (K) is equal to °C + 273.
2
Boltzmann’s constant per mole of atoms becomes the gas constant R; in such a case, R = 8.31
J/mol∙K.

Number of Solution
atoms per This problem may be solved by using
unit volume for a metal Equation 4.1; it is first necessary, however, to
determine the value of NCu—the number of
atomic sites per cubic meter for copper, from
its atomic weight ACu, its density ��, and
Avogadro’s number NA, according to

Tutorial Video NCu = NA ��

4.3 Impurities in Solids • 95 ACu (4.2)

EXAMPLE PROBLEM 4.1 23 3

= (6.022 × 10 atoms/mol)(8.4 g/cm )(10
6

cm3/m3)
Number-of-Vacancies
Computation at a Specified
Temperature
Calculate the equilibrium number of vacancies
per cubic meter for copper at 1000°C. The
energy for vacancy formation is 0.9 eV/atom;
the atomic weight and density (at 1000°C) for
copper are 63.5 g/mol and 8.4 g/cm3,
respectively.
63.5 g/mol
(8.62 × 10−5 eV/K)(1273 K)]
28 3
= 8.0 × 10 atoms/m
= 2.2 × 1025 vacancies/m3
Thus, the number of vacancies at 1000°C
(1273 K) is equal to
N exp
N�� = (−Q��
kT)
) exp
= (8.0 × 1028 atoms/m3 [− (0.9 eV)

4.3 IMPURITIES IN SOLIDS

A pure metal consisting of only one type of atom just isn’t
possible; impurity or foreign atoms are always present, and
some exist as crystalline point defects. In fact, even with
relatively sophisticated techniques, it is difficult to refine
metals to a purity in excess of 99.9999%. At this level, on the
order of 1022 to 1023 impurity atoms are present in 1 m3
alloy highly corrosion resistant, but also very soft.
Alloying with copper significantly enhances
the mechanical strength without re
ducing the corrosion resistance appreciably.
The addition of impurity atoms to a metal
results in the formation of a solid solution
and/or a new second phase, depending on the
solid solution solute, solvent kinds of impurity, their concentrations, and
the temperature of the alloy. The present
discussion is concerned with the notion of a
solid solution; treatment of the formation of a
new phase is deferred to Chapter 9.
of material. Most familiar metals are not Several terms relating to impurities and solid
highly pure; rather, they are alloys, in which solutions deserve mention. With re gard to
impurity atoms have been added intentionally alloys, solute and solvent are terms that are
to impart specific characteristics to the commonly employed. Solvent is the element
material. Ordinarily, alloying is used in metals or compound that is present in the greatest
to improve mechanical strength and amount; on occasion, solvent atoms are also
corrosion resistance. For example, sterling called host atoms. Solute is used to denote an
silver is a 92.5% silver–7.5% copper alloy. In element or compound present in a minor
normal ambient environments, pure silver is concentration.
96 • Chapter 4 / Imperfections in Interstitial
impurity atom
Solids Substitutional impurity atom
substitutional solid solution 4.2). Several features of the solute and solvent
atoms determine the degree to which the
interstitial solid former dissolves in the latter. These are
solution
expressed as four Hume–Rothery rules, as
follows:
1. Atomic size factor. Appreciable quantities
of a solute may be accommodated in this type
of solid solution only when the difference in
atomic radii between the two atom types is
less than about ±15%. Otherwise, the solute
atoms create substantial lattice distortions and
a new phase forms.
2. Crystal structure. For appreciable solid
solubility, the crystal structures for metals of
both atom types must be the same.
3. Electronegativity factor. The more
electropositive one element and the more elec
Tutorial Video: tronegative the other, the greater the likelihood
Defects that they will form an intermetal lic compound
What Are instead of a substitutional solid solution.
the Differences 4. Valences. Other factors being equal, a
between Interstitial and Substitutional Solid metal has more of a tendency to dissolve
Solutions? another metal of higher valency than to
Figure 4.2 Two-dimensional schematic dissolve one of a lower valency.
representations
of substitutional and interstitial impurity atoms. An example of a substitutional solid solution
(Adapted from W. G. Moffatt, G. W. Pearsall, and J. is found for copper and nickel. These two
Wulff, The elements are completely soluble in one another
Structure and Properties of Materials, Vol. I, at all proportions. With regard to the
Structure, John Wiley aforementioned rules that govern degree of
& Sons, 1964. Reproduced with permission of Janet M.
solubility, the atomic radii for copper and
Moffatt.)
nickel are 0.128 and 0.125 nm, respectively;
both have the FCC crystal structure; and their
electronegativities are 1.9 and 1.8 (Figure 2.9).
Solid Solutions Finally, the most common valences are +1 for
A solid solution forms when, as the solute copper (although it sometimes can be +2) and
atoms are added to the host material, the crys +2 for nickel.
tal structure is maintained and no new For interstitial solid solutions, impurity atoms
structures are formed. Perhaps it is useful to fill the voids or interstices among the host
draw an analogy with a liquid solution. If two atoms (see Figure 4.2). For both FCC and
liquids that are soluble in each other (such as BCC crystal structures, there are two types of
water and alcohol) are combined, a liquid interstitial sites—tetrahedral and octahedral;
solution is produced as the molecules these are distinguished by the num ber of
intermix, and its composition is homogeneous nearest neighbor host atoms—that is, the
throughout. A solid solution is also coordination number. Tetrahedral sites
compositionally homogeneous; the impurity
atoms are randomly and uniformly dispersed
within the solid. Figure 4.3 Locations of
Impurity point defects are found in solid 4.3 Impurities in Solids • 97
solutions, of which there are two types:
substitutional and interstitial. For the Octahedral
substitutional type, solute or impurity atoms re 1
place or substitute for the host atoms (Figure
Tetrahedral 1
tetrahedral and octahedral interstitial 21 21
1
sites within (a) FCC Tetrahedral 2 1 4
1
1 and (b) BCC unit
1
2
cells.
2 20 1
2

1 1
 3
1
(a)
4
4
4
Octahedral
1
21 0
(b)

have a coordination number of 4; straight lines drawn from the

centers of the surrounding host atoms form a four-sided
tetrahedron. However, for octahedral sites the coordination
number is 6; an octahedron is produced by joining these six
sphere centers.3 For FCC, there are two types of octahedral
sites with representative point coordinates of 0 12 1 and
12 1
1
2.Representative coordinates for a single 2
1 3 1 4
tetrahedral site type are 4 4 4. Locations of
these sites within the FCC unit cell are noted in Figure 4.3a.
Likewise, for BCC, there are two octahedral and one
tetrahedral types. Representative coordinates for the octahedral
sites are as follows: 12 1 12 and 12 1 0; for BCC tetrahedral, 1 1214
is a representative coordi
nate. Figure 4.3b shows the positions
of these sites within a BCC unit cell.4
Metallic materials have relatively high atomic packing
factors, which means that these interstitial positions are
relatively small. Consequently, the atomic diameter of an
interstitial impurity must be substantially smaller than that of
the host atoms. Normally, the maximum allowable
concentration of interstitial impurity atoms is low (less than
10%). Even very small impurity atoms are ordinarily larger
than the interstitial sites, and as a consequence, they introduce
some lattice strains on the adjacent host atoms. Problems 4.8
and 4.9 call for determination of the radii of impurity atoms r
(in terms of R, the host atom radius) that just fit into
tetrahedral and octahedral interstitial positions of both BCC
and FCC without introducing any lattice strains.
Carbon forms an interstitial solid solution when added to iron; the maximum con
centration of carbon is about 2%. The atomic radius of the
carbon atom is much less than that of iron: 0.071 nm versus
0.124 nm.
Solid solutions are also possible for ceramic materials, as discussed in Section 12.5.

EXAMPLE PROBLEM 4.2

Computation of Radius of BCC Interstitial Site
Compute the radius r of an impurity atom that just fits into a BCC
octahedral site in terms of the atomic radius R of the host atom
(without introducing lattice strains).

Solution
As Figure 4.3b notes, for BCC, one octahedral interstitial site is
situated at the center of a unit cell edge. In order for an interstitial
atom to be positioned in this site without introducing lattice

3
The geometries of these site types may be observed in Figure 12.7.
4
Other octahedral and tetrahedral interstices are located at positions within the unit cell that
 are equivalent to these representative ones.
98 • Chapter 4 / Imperfections in Solids

strains, the atom just touches the two adjacent host atoms, which
4R
are corner atoms of the unit cell. The drawing shows atoms on
√3
the (100) face of a BCC unit cell; the large circles represent the
host atoms—the small circle represents an interstitial atom that is
R
R
positioned in an octahedral site on the cube edge.
2r
On this drawing is noted the unit cell edge length—the
distance between the centers of the corner atoms—which, from
Equation 3.4, is equal to

Unit cell edge length = 4R

√
3
Also shown is that the unit cell edge length is equal to two times
the sum of host atomic radius 2R plus twice the radius of
the interstitial atom 2r; i.e., Unit cell edge length = 2R + 2r
Now, equating these two unit cell edge length expressions, we get

2R + 2r = 4R
√
3
and solving for r in terms of R

√ = √ 1
3− 2R (2 3− )(2R)
2r = 4R

or

= √ 1
r (2 3− )R = 0.155R

Concept Check 4.1 Is it possible for three or more elements to

form a solid solution? Explain your answer.
[The answer may be found in all digital versions of the text and/or at
www.wiley.com/college/callister (Student Companion Site).]

Concept Check 4.2 Explain why complete solid solubility may

occur for substitutional solid solutions but not for interstitial solid
solutions.
[The answer may be found in all digital versions of the text and/or at
www.wiley.com/college/callister (Student Companion Site).]

4.4 SPECIFICATION OF COMPOSITION

composition weight percent It is often necessary to express the
composition (or concentration)5 of an alloy in are weight (or mass) percent and atom
terms of its constituent elements. The two percent. The basis for weight percent (wt%)
most common ways to specify composition is the weight of a particular element relative
to the total alloy weight. For an alloy that
5
The terms composition and concentration will be assumed to have the same meaning in
this book (i.e., the relative content of a specific element or constituent in an alloy) and
will be used interchangeably.

Computation of weight percent (for a two-

element alloy) C1 = m1
m1 + m2× 100 (4.3a)

where m1 and m2 represent the weight (or

atom percent mass) of elements 1 and 2, respectively. The
concentration of 2 is computed in an
analogous manner.6
The basis for atom percent (at%) calculations
is the number of moles of an element in
relation to the total moles of the elements in
the alloy. The number of moles in some
specified mass of a hypothetical element 1,
nm1, may be computed as follows:

Computation of atom percent (for a two-

element alloy)

nm1 = m1′
A1 (4.4)
Here, m′1 and A1 denote the mass (in grams)
and atomic weight, respectively, for element 1.
Conversion of Concentration in terms of atom percent of
weight percent to atom percent (for a two- element 1 in an alloy containing element 1
element alloy)
and element 2 atoms, C′1 is defined by7
4.4 Specification of Composition • 99

contains two hypothetical atoms denoted by 1

and 2, the concentration of 1 in wt%, C1, is
defined as
 C′1 = nm1 C′1 = C1A2
nm1 + nm2× 100 (4.5a) C1A2 + C2A1× 100 (4.6a)
In like manner, the atom percent of element 2
is determined.8 C′2 = C2A1
Atom percent computations also can be C1A2 + C2A1× 100 (4.6b)
carried out on the basis of the number of
atoms instead of moles, because one mole of
all substances contains the same number of
atoms.

Composition Conversions
Sometimes it is necessary to convert from one
composition scheme to another—for example,
from weight percent to atom percent. We next
present equations for making these
conversions in terms of the two hypothetical
elements 1 and 2. Using the conven tion of the
previous section (i.e., weight percents denoted
by C1 and C2, atom percents by C′1 and C′2,
and atomic weights as A1 and A2), we express
these conversion equations as follows:

6
When an alloy contains more than two (say n) elements,

Equation (4.3a) takes the form C1 = m1

..
m1 + m2 + m3 + . + mn× 100 (4.3b)
7
In order to avoid confusion in notations and symbols being used in this section, we should
point out that the prime (as in C′1 and m′1) is used to designate both composition in atom
percent and mass of material in grams. 8When an alloy contains more than two (say n)
elements, Equation (4.5a) takes the form

C′1 = nm1
..
nm1 + nm2 + nm3 + . + nmn× 100 (4.5b)
hapter 4 / Imperfections in Solids C1 = C′1A1

Conversion of C1 + C2 = 100 (4.8a) C′1 + C′2 = 100 (4.8b)

atom percent to weight percent (for a two-
element alloy) In addition, it sometimes becomes necessary
C′1A1 + C′2A2× 100 (4.7a) to convert concentration from weight percent
to mass of one component per unit volume of
material (i.e., from units of wt% to kg/m3);
C2 = C′2A2 this latter composition scheme is often used in
C′1A1 + C′2A2× 100 (4.7b) diffusion computations (Section 5.3).
Concentrations in terms of this basis are
Because we are considering only two denoted using a double prime (i.e., C1″ and
elements, computations involving the preced C ″), and the relevant equations are as follows:
2
ing equations are simplified when it is realized
that

C1″ = × 103 (4.9a)

��1+C2
C1

Conversion of mass per unit element alloy) ( C″2 =

weight percent to volume (for a two-
C1 C1 ��2) C2 × 103 (4.9b)
( ��1+C2 ��2)

Tutorial Video: Weight Percent and Atom determine the density and atomic weight of a
Percent Calculations binary alloy, given the composition in terms of
For density �� in units of g/cm3, these either weight percent or atom percent. If we
expressions yield C1″ and C2″ in kg/m3. represent alloy density and atomic weight by
Furthermore, on occasion we desire to ��ave and Aave, respectively, then

Computation of density (for a ��2

two element metal alloy) ��ave = 100 C1
(4.10a)
��1+C2

��2
��ave = C′1A1 + C′2A2 C′1A1
(4.10b)
��1+C′2A2

Computation of atomic weight A2

(for a Aave = 100 C1
(4.11a)
A1+C2

two-element metal alloy) It should be noted that Equations 4.9 and 4.11
are not always exact. In their deriva tions, it is
Aave = C′1A1 + C′2A2 assumed that total alloy volume is exactly
equal to the sum of the volumes of the
100 (4.11b) individual elements. This normally is not the
case for most alloys; however, it is a
4.4 Specification of Composition • 101

reasonably valid assumption and does not lead to significant

errors for dilute solutions and over composition ranges where
solid solutions exist.

EXAMPLE PROBLEM 4.3

Derivation of Composition-Conversion Equation
Derive Equation 4.6a.

Solution
To simplify this derivation, we assume that masses are expressed in
units of grams and denoted with a prime (e.g., m′1). Furthermore, the
total alloy mass (in grams) M′ is M′ = m′1 + m′2 (4.12)
Using the definition of C′1 (Equation 4.5a) and incorporating the
expression for nm1, Equation 4.4, and the analogous expression for nm2
yields
 C′1 = nm1
nm1 + nm2× 100
m′1
Tutorial Video A1 × 100 (4.13)
A1+m′2 A2
= m′1

Rearrangement of the mass-in-grams equivalent

of Equation 4.3a leads to m′1 = C1M′

100 (4.14)
Substitution of this expression and its m′2
equivalent into Equation 4.13 gives C1M′
C′1 =
100A1+C2M′
× 100 (4.15) C1M′

Upon simplification, we have 100A2

100A1

C′1 = C1A2
C1A2 + C2A1× 100
which is identical to Equation 4.6a.

EXAMPLE PROBLEM 4.4

Composition Conversion—From Weight Percent to
Atom Percent
Determine the composition, in atom percent, of an alloy that consists
of 97 wt% aluminum and 3 wt% copper.

Solution
If we denote the respective weight percent compositions as CAl = 97
and CCu = 3, substitution into Equations 4.6a and 4.6b yields
102 • Chapter 4 / Imperfections in Solids

CAl ′ = CAlACu
CAlACu + CCuAAl× 100
Tutorial Video: How to
CCu′ = CCuAAl
Convert from Atom Percent to Weight
Percent
= (97)(63.55 g/mol)
(97)(63.55 g/mol) + (3)(26.98 g/mol) × 100
= 98.7 at%
and CCuAAl + CAlACu× 100
= (3)(26.98 g/mol) (3)(26.98 g/mol) + (97)(63.55 g/mol) × 100
= 1.30 at%

Miscellaneous Imperfections
4.5 DISLOCATIONS—LINEAR DEFECTS
A dislocation is a linear or one-dimensional defect around
which some of the atoms are misaligned. One type of
dislocation is represented in Figure 4.4: an extra portion of a
plane of atoms, or half-plane, the edge of which terminates
within the crystal. This is termed an
edge dislocation above the dislocation line in Figure 4.4 are
dislocation line squeezed together, and those below are pulled
apart; this is reflected in the slight curvature
for the vertical planes of atoms as they bend
around this extra half-plane. The magnitude
: VMSE of this distortion decreases with distance away
Edge from the dislocation line; at positions far
removed, the crystal lattice is virtually perfect.
Sometimes the edge dislocation in Figure 4.4
is represented by the symbol ⊥, which also
indicates the position of the dislocation line.
screw dislocation An edge dislocation may also be formed by an
edge dislocation; it is a linear defect that extra half plane of atoms that is included in the
centers on the line that is defined along the bottom portion of the crystal; its designation is
end of the extra half-plane of atoms. This is a ⊤.
sometimes termed the dislocation line, which, Another type of dislocation, called a screw
for the edge dislocation in Figure 4.4, is dislocation, may be thought of as being
perpendicular to the plane of the page. Within formed by a shear stress that is applied to
the region around the dislocation line there is produce the distortion shown in Figure 4.5a:
some localized lattice distortion. The atoms The

Figure 4.4 The atom positions around an edge

dislocation; extra half-plane of atoms shown in
perspective.
Burgers vector b

Edge
dislocation line
: VMSE atomic planes of atoms. Sometimes the
Screw symbol is used to designate a screw
dislocation.

Figure 4.5 (a) A screw

dislocation within a crystal.
(b) The screw dislocation in
(a) as viewed from above. The
dislocation line extends along
line AB. Atom positions above
the slip plane are designated
by open circles, those below by
solid circles.
[Figure (b) from W. T. Read, Jr.,
Dislocations in Crystals, McGraw
Hill Book Company, New York,
NY, 1953.]
C

Dislocation
line
A
Burgers vector b
4.5 Dislocations—Linear Defects •
103
D
upper front region of the crystal is shifted one
atomic distance to the right relative to the
bottom portion. The atomic distortion
associated with a screw dislocation is also
linear and along a dislocation line, line AB in
Figure 4.5b. The screw dislocation derives its
name from the spiral or helical path or ramp (a)
that is traced around the dislocation line by the

AB

D C (b)
 104 • Chapter 4 / Imperfections in Solids

mixed dislocation pure screw but exhibit components of both

types; these are termed mixed dislocations.
All three dislocation types are represented
schematically in Figure 4.6; the lattice dis
: VMSE tortion that is produced away from the two
Mixed faces is mixed, having varying degrees of
Most dislocations found in crystalline screw and edge character.
materials are probably neither pure edge nor

Figure 4.6 (a) Schematic A b

McGraw-Hill Book Company,
representation of a dislocation
New York, NY, 1953.]
that has edge, screw, and mixed
character. (b) Top view, where
open circles denote atom
positions above the slip plane, b

and solid circles, atom posi C

tions below. At point A, the
dislocation is pure screw, while
at point B, it is pure edge. For
regions in between where there
is curvature in the dislocation
line, the character is mixed
edge and screw.
[Figure (b) from W. T. Read, (a)
Jr., Dislocations in Crystals, B

B
 C

Ab
(b)

Burgers vector

Tutorial Video: Defects

Screw and Edge
Dislocations
4.6 Interfacial Defects • 105
Figure 4.7 A transmission electron
micrograph of a titanium alloy in which
the dark lines are dislocations, 50,000×.
(Courtesy of M. R. Plichta, Michigan
Technological University.)

The magnitude and direction of the lattice

distortion associated with a dislocation are
expressed in terms of a Burgers vector,
denoted by b. Burgers vectors are indicated in
Figures 4.4 and 4.5 for edge and screw
dislocations, respectively. Furthermore, the
nature of a dislocation (i.e., edge, screw, or
mixed) is defined by the relative orientations
of dislocation line and Burgers vector. For an
edge, they are perpendicular (Figure 4.4),
whereas for a screw, they are parallel (Figure
4.5); they are neither perpendicular nor
parallel for a mixed dislocation. Also, even
though a dislocation changes direction and
nature within a crystal (e.g., from edge to
mixed to screw), the Burgers vector is the
same at all points along its line. For example,
all positions of the curved dislocation in
Figure 4.6 have the Burgers vector shown. techniques. In Figure 4.7, a high-
For metallic materials, the Burgers vector for a magnification transmission electron
disloca tion points in a close-packed micrograph, the dark lines are the
crystallographic direction and is of magnitude dislocations.
equal to the interatomic spacing. Virtually all crystalline materials contain some
As we note in Section 7.2, the permanent dislocations that were introduced during
deformation of most crystalline materials is solidification, during plastic deformation, and
by the motion of dislocations. In addition, the as a consequence of thermal stresses that
Burgers vector is an element of the theory that result from rapid cooling. Dislocations are
has been developed to explain this type of involved in the plastic deforma tion of
deformation. crystalline materials, both metals and
Dislocations can be observed in crystalline ceramics, as discussed in Chapters 7 and 12.
materials using electron-microscopic They have also been observed in polymeric
materials and are discussed in Section 14.13.

4.6 INTERFACIAL DEFECTS

Interfacial defects are boundaries that have two dimensions and
normally separate regions of the materials that have different
crystal structures and/or crystallographic orientations. These
imperfections include external surfaces, grain boundaries,
phase boundaries, twin boundaries, and stacking faults.
106 • Chapter 4 / Imperfections in Solids

External Surfaces
One of the most obvious boundaries is the external surface,
along which the crystal structure terminates. Surface atoms are
not bonded to the maximum number of nearest neighbors and
are therefore in a higher energy state than the atoms at interior
positions. The bonds of these surface atoms that are not
satisfied give rise to a surface energy, expressed in units of
energy per unit area (J/m 2 or erg/cm2). To reduce this energy,
materials tend to minimize, if at all possible, the total surface
area. For example, liquids assume a shape having a minimum
area—the droplets become spherical. Of course, this is not
possible with solids, which are mechanically rigid.

Grain Boundaries
Another interfacial defect, the grain boundary, was introduced
in Section 3.14 as the boundary separating two small grains or
crystals having different crystallographic orien tations in
polycrystalline materials. A grain boundary is represented
schematically from an atomic perspective in Figure 4.8.
Within the boundary region, which is probably just several
atom distances wide, there is some atomic mismatch in a
transition from the crystalline orientation of one grain to that
of an adjacent one.
Various degrees of crystallographic misalignment between
adjacent grains are possible (Figure 4.8). When this orientation
mismatch is slight, on the order of a few degrees, then the term
small- (or low-) angle grain boundary is used. These
boundaries can be described in terms of dislocation arrays.
One simple small-angle grain boundary is formed when edge
dislocations are aligned in the manner of Figure 4.9. This type
is called a tilt boundary; the angle of misorientation, ��, is
also indicated in the figure. When the angle of misorientation
is parallel to the boundary, a twist boundary results, which can
be described by an array of screw dislocations.
 The atoms are bonded less regularly along a grain
boundary (e.g., bond angles are longer), and consequently
there is an interfacial or grain boundary energy similar to the
surface energy just described. The magnitude of this energy is a
function of the degree of misorientation, being larger for high-
angle boundaries. Grain boundaries are more chemically
reactive than the grains themselves as a consequence of this
boundary energy. Furthermore, impurity atoms often
preferentially segregate along these boundaries because

Figure 4.8 Schematic diagram showing small and high-angle grain boundaries and the adjacent
atom positions.
Angle of misalignment Angle of misalignment

High-angle
grain boundary

Small-angle grain boundary

4.6 Interfacial Defects • 107

Twin plane (boundary)

A
C
Aʹ
Fʹ Eʹ
Cʹ
 E

��
F D
B
Dʹ

Figure 4.9 Demonstration of how a tilt twin plane or boundary and the adjacent atom
boundary having an angle of misorientation positions (colored circles). Atoms labeled with
�� results from an alignment of edge corresponding primed and unprimed letters (e.g.,
dislocations. A and Aʹ) reside in mirror-imaged positions
Figure 4.10 Schematic diagram showing a across the twin boundary.

of their higher energy state. The total interfacial energy is

lower in large or coarse-grained materials than in fine-grained
ones because there is less total boundary area in the former.
Grains grow at elevated temperatures to reduce the total
boundary energy, a phenomenon explained in Section 7.13.
In spite of this disordered arrangement of atoms and lack
of regular bonding along grain boundaries, a polycrystalline
material is still very strong; cohesive forces within and across
the boundary are present. Furthermore, the density of a
polycrystalline speci men is virtually identical to that of a
single crystal of the same material.

Phase Boundaries
Phase boundaries exist in multiphase materials (Section 9.3),
in which a different phase exists on each side of the boundary;
In addition, each of the constituent phases has its own
distinctive physical and/or chemical characteristics. As we
shall see in subsequent chapters, phase boundaries play an
important role in determining the mechanical char
acteristics of some multiphase metal alloys.

Twin Boundaries
A twin boundary is a special type of grain boundary across
which there is a specific mirror lattice symmetry; that is, atoms
on one side of the boundary are located in mirror-image
positions to those of the atoms on the other side (Figure 4.10).
The region
108 • Chapter 4 / Imperfections in Solids

M A T E R I A L S O F I M P O R T A N C E 4.1
Catalysts (and Surface Defects)
in their chemical reactivity rate.
A catalyst is a substance that speeds up the Adsorption sites on a catalyst are
normally sur face defects associated with
rate of planes of atoms; an
a chemical reaction without interatomic/intermolecular bond is formed
participating in the reaction itself (i.e., it is between a defect site and an adsorbed
not consumed). One type of catalyst exists molecular species. The several types of
as a solid; reactant molecules in a gas or surface defects, represented schemati cally
liquid phase are adsorbed9 onto the catalytic in Figure 4.11, include ledges, kinks,
surface, at which point some type of terraces, va cancies, and individual adatoms
interaction occurs that promotes an increase (i.e., atoms adsorbed on the surface).
One important use of catalysts is in catalytic
 con verters on automobiles, which reduce Figure 4.11. These surface defects act as
the emission of exhaust gas pollutants such adsorption sites for the atomic and
as carbon monoxide (CO), nitrogen oxides molecular species noted in the previous
(NOx, where x is variable), and unburned paragraph. Consequently, dissociation,
hydrocarbons. (See the chapter-opening combination, and oxidation reactions
diagrams and photograph for this chapter.) involving these species are facilitated, such
Air is in troduced into the exhaust emissions that the content of pollutant spe cies (CO,
from the auto mobile engine; this mixture of NOx, and unburned hydrocarbons) in the
gases then passes over the catalyst, which exhaust gas stream is reduced significantly.
on its surface adsorbs molecules of CO,
NOx, and O2. The NOx dissociates into N
and O atoms, whereas the O2 dissociates
into its atomic species. Pairs of nitrogen
atoms combine to form N2 molecules, and
carbon monoxide is oxidized to form

Figure 4.11 Schematic representations of

surface defects that are potential adsorption Figure 4.12 High-resolution transmission
sites for catalysis. Individual atom sites are electron micrograph that shows single
represented as cubes. crystals of (Ce0.5Zr0.5)O2; this material is
carbon dioxide (CO2). Furthermore, any used in catalytic converters for auto mobiles.
unburned hydrocarbons are also oxidized to Surface defects represented schematically in
CO2 and H2O. One of the materials used as a Figure 4.11 are noted on the crystals.
[From W. J. Stark, L. Mädler, M. Maciejewski, S.
catalyst in this application is (Ce0.5Zr0.5)O2.
E. Pratsinis, and A. Baiker, “Flame-Synthesis of
Figure 4.12 is a high resolution transmission Nanocrystalline Ceria/ Zirconia: Effect of Carrier
electron micrograph that shows several Liquid,” Chem. Comm., 588–589 (2003).
single crystals of this material. In dividual Reproduced by permission of The Royal Society
atoms are resolved in this micrograph as of Chemistry.]
well as some of the defects presented in

9
Adsorption is the adhesion of molecules of a gas or liquid to a solid surface. It
should not be confused with absorption, which is the assimilation of molecules
into a solid or liquid.

Tutorial Video: Defects crystallographic plane and in a specific

Differences among Point, Linear, and direction, both of which depend on the crystal
Interfacial Defects structure. Annealing twins are typically found
4.8 Atomic Vibrations • 109 in metals that have the FCC crystal structure,
whereas mechanical twins are observed in
of material between these boundaries is BCC and HCP metals. The role of mechanical
appropriately termed a twin. Twins result from twins in the deformation process is dis cussed
atomic displacements that are produced from in Section 7.7. Annealing twins may be
applied mechanical shear forces (mechan ical observed in the photomicrograph of the
twins) and also during annealing heat polycrystalline brass specimen shown in
treatments following deformation (annealing Figure 4.14c. The twins correspond to those
twins). Twinning occurs on a definite regions having relatively straight and parallel
sides and a different visual contrast than the
untwinned regions of the grains within which netic and ferrimagnetic materials, the
they reside. An explanation for the variety of boundary that separates regions having
textural contrasts in this photomicrograph is different directions of magnetization is
provided in Section 4.10. termed a domain wall, which is discussed in
Section 20.7.
Miscellaneous Interfacial Defects
Associated with each of the defects discussed
Other possible interfacial defects include in this section is an interfacial energy, the
stacking faults and ferromagnetic domain magnitude of which depends on boundary
walls. Stacking faults are found in FCC metals type, and which varies from material to
when there is an interruption in the material. Normally, the interfacial energy is
ABCABCABC . . . stacking sequence of close- greatest for external surfaces and least for
packed planes (Section 3.12). For ferromag domain walls.

Concept Check 4.3 The surface energy of a single crystal

depends on crystallographic ori entation. Does this surface energy
increase or decrease with an increase in planar density? Why?
[The answer may be found in all digital versions of the text and/or at
www.wiley.com/college/callister (Student Companion Site).]

4.7 BULK OR VOLUME DEFECTS

Other defects exist in all solid materials that are much larger
than those heretofore discussed. These include pores, cracks,
foreign inclusions, and other phases. They are normally
introduced during processing and fabrication steps. Some of
these defects and their effects on the properties of materials are
discussed in subsequent chapters.

4.8 ATOMIC VIBRATIONS

Every atom in a solid material is vibrating very rapidly about its lattice position within
atomic vibration of the average vibrational activity of atoms
the crystal. In a sense, these atomic and molecules. At room temperature, a typical
vibrations may be thought of as imperfections vibrational frequency is on the order of 1013
or de fects. At any instant of time, not all vibrations per second, whereas the ampli tude
atoms vibrate at the same frequency and is a few thousandths of a nanometer.
amplitude or with the same energy. At a given Many properties and processes in solids are
temperature, there exists a distribution of manifestations of this vibrational atomic
energies for the constituent atoms about an motion. For example, melting occurs when the
average energy. Over time, the vibrational vibrations are vigorous enough to rupture
energy of any specific atom also varies in a large numbers of atomic bonds. A more
random manner. With rising temperature, this detailed discussion of atomic vibrations and
average energy increases, and, in fact, the their influence on the properties of materials is
temperature of a solid is really just a measure presented in Chapter 19.
110 • Chapter 4 / Imperfections in Solids

Microscopic Examination
4.9 BASIC CONCEPTS OF MICROSCOPY
On occasion it is necessary or desirable to examine the
structural elements and defects that influence the properties of
materials. Some structural elements are of macroscopic
dimensions; that is, they are large enough to be observed with
the unaided eye. For example, the shape and average size or
diameter of the grains for a polycrystalline specimen are
important structural characteristics. Macroscopic grains are
 often evident on aluminum streetlight posts and also on
highway guardrails. Relatively large grains having different
textures are clearly visible on the surface of the sectioned
copper ingot shown in Figure 4.13. However, in most
materials the constituent grains are of micro
scopic dimensions, having diameters that may be on the order
of microns,10 and their details must be investigated using some
type of microscope. Grain size and shape are
microstructure microscopy copper ingot. The small, needle-shape grains
may be observed, which extend from the
center radially outward.
photomicrograph
only two features of what is termed the
microstructure; these and other
microstructural characteristics are discussed
in subsequent chapters.
Optical, electron, and scanning probe
microscopes are commonly used in
microscopy. These instruments aid in
investigations of the microstructural features
of all material types. Some of these techniques
employ photographic equipment in
conjunction with the microscope; the
photograph on which the image is recorded is
called a photomicrograph. In addition, many
microstructural images are computer
generated and/or enhanced.
Microscopic examination is an extremely
useful tool in the study and characteriza tion
of materials. Several important applications of
microstructural examinations are as follows:
to ensure that the associations between the
properties and structure (and defects) are
properly understood, to predict the properties
of materials once these re lationships have
been established, to design alloys with new
property combinations, to determine whether
a material has been correctly heat-treated, and
to ascertain the mode of mechanical fracture.
Several techniques that are commonly used in © William D. Callister, Jr.
such investiga tions are discussed next.

Figure 4.13 Cross-section of a cylindrical

10
A micron (μm), sometimes called a
micrometer, is 10−6 m.

4.10 MICROSCOPIC
TECHNIQUES Optical
Microscopy
4.10 Microscopic Techniques • 111
With optical microscopy, the light microscope is used to study
the microstructure; opti cal and illumination systems are its
basic elements. For materials that are opaque to visible light
(all metals and many ceramics and polymers), only the surface
is subject to observation, and the light microscope must be
used in a reflecting mode. Contrasts in the image produced
result from differences in reflectivity of the various regions of
the microstructure. Investigations of this type are often termed
metallographic because metals were first examined using this
technique.
Normally, careful and meticulous surface preparations are
necessary to reveal the important details of the microstructure.
The specimen surface must first be ground and polished to a
smooth and mirror-like finish. This is accomplished by using
successively finer abrasive papers and powders. The
microstructure is revealed by a surface treat
ment using an appropriate chemical reagent in a procedure
termed etching. The chemi cal reactivity of the grains of some
single-phase materials depends on crystallographic orientation.
Consequently, in a polycrystalline specimen, etching
characteristics vary from grain to grain. Figure 4.14b shows
how normally incident light is reflected by three etched surface
grains, each having a different orientation. Figure 4.14a depicts
the sur face structure as it might appear when viewed with the
microscope; the luster or texture of each grain depends on its
reflectance properties. A photomicrograph of a polycrystal line
specimen
exhibiting
these

characteristics is shown in Figure 4.14c.

(a)

Microscope
 Polished and
etched surface

(b) (c)

Figure 4.14 (a) Polished and etched grains as they might appear when viewed with an
optical microscope. (b) Section taken through these grains showing how the etching
characteristics and resulting surface texture vary from grain to grain because of differences
in crystallographic orientation. (c) Photomicrograph of a polycrystalline brass specimen, 60×.
[Figure (c) from J. E. Burke, Grain Control in Industrial Metallurgy, in “The Fundamentals of
Recrystallization and Grain Growth,” Thirtieth National Metal Congress and Exposition, American
Society for Metals, 1948. By
permission of ASM International,
Materials Park, OH.
www.asmInternational.org.]
112 • Chapter 4 /
Imperfections in Solids

Microscope

Polished and
etched surface

Surface
groove

Grain boundary
(a)
(b)

Figure 4.15 (a) Section of a grain boundary and its surface groove produced by etching;
the light reflection char acteristics in the vicinity of the groove are also shown. (b)
Photomicrograph of the surface of a polished and etched polycrystalline specimen of an
iron–chromium alloy in which the grain boundaries appear dark, 100×. [Photomicrograph
courtesy of L. C. Smith and C. Brady, the National Bureau of Standards, Washington, DC (now the
National Institute of Standards and Technology, Gaithersburg, MD.)]

Also, small grooves form along grain boundaries as a

 consequence of etching. Because atoms along grain boundary
regions are more chemically active, they dissolve at a greater
rate than those within the grains. These grooves become
discernible when viewed under a microscope because they
reflect light at an angle different from that of the grains
themselves; this effect is displayed in Figure 4.15a. Figure
4.15b is a photomi
crograph of a polycrystalline specimen in which the grain
boundary grooves are clearly visible as dark lines.
When the microstructure of a two-phase alloy is to be
examined, an etchant is often chosen that produces a different
texture for each phase so that the different phases may be
distinguished from each other.

Electron Microscopy
Some structural elements are too fine or small to permit
observation using optical microscopy. The upper limit to the
magnification possible with an optical microscope is
approximately 2000×. Under such circumstances, the electron
microscope, which is capable of much higher magnifications,
may be employed.
An image of the structure under investigation is formed
using beams of electrons instead of light radiation. According
to quantum mechanics, a high-velocity electron becomes
wavelike, having a wavelength that is inversely proportional to
its velocity. When accelerated across large voltages, electrons
can be made to have wavelengths on the order of 0.003 nm (3
pm). High magnifications and resolving powers of these
microscopes are consequences of the short wavelengths of
electron beams. The elec
tron beam is focused and the image formed with magnetic
lenses; otherwise, the ge ometry of the microscope components
is essentially the same as with optical systems. Both
transmission and reflection beam modes of operation are
possible for electron microscopes.

transmission electron microscope (TEM) scanning probe

microscope (SPM)
4.10 Microscopic Techniques • 113

Transmission Electron Microscopy

The image seen with a transmission electron
microscope (TEM) is formed by an electron
beam that passes through the specimen.
Details of internal microstruc tural features are
accessible to observation; contrasts in the
image are produced by differences in beam
scattering or diffraction produced between
scanning electron microscope (SEM) various elements of the microstructure or
defect. Because solid materials are highly
absorptive to elec tron beams, a specimen to
be examined must be prepared in the form of a
very thin foil; this ensures transmission
through the specimen of an appreciable
fraction of the incident beam. The transmitted
beam is projected onto a fluorescent screen or
a photographic film so that the image may be
viewed. Magnifications approaching an atomic scale, that is a representation of
1,000,000× are possible with transmission surface features and characteristics of the
electron microscopy, which is frequently used specimen being examined. Some of the
to study dislocations. features that differentiate the SPM from other
microscopic techniques are as follows:
Scanning Electron Microscopy
• Examination on the nanometer scale is
A more recent and extremely useful possible inasmuch as magnifi cations as high
investigative tool is the scanning electron as 109× are possible; much better resolutions
microscope (SEM). The surface of a are attainable than with other microscopic
specimen to be examined is scanned with an techniques.
electron beam, and the reflected (or back-
scattered) beam of electrons is collected and • Three-dimensional magnifi ed images are
then displayed at the same scanning rate on a generated that provide topographical
cathode ray tube (CRT; similar to a CRT information about features of interest.
television screen). The image on the screen, • Some SPMs may be operated in a variety of
which may be photographed, represents the environments (e.g., vacuum, air, liquid); thus,
surface features of the specimen. The surface a particular specimen may be examined in its
may or may not be polished and etched, but it most suitable environment.
must be electrically conductive; a very thin
metallic surface coating must be applied to Scanning probe microscopes employ a tiny
nonconductive materials. Magnifications probe with a very sharp tip that is brought
ranging from 10× to in excess of 50,000× are into very close proximity (i.e., to within on the
order of a nanometer) of the specimen
possible, as are also very great depths of field.
Accessory equipment permits qualitative and surface. This probe is then raster-scanned
semiquantitative analysis of the elemental across the plane of the surface. During
composition of very localized surface areas. scanning, the probe experiences deflections
perpendicular to this plane in re
Scanning Probe Microscopy sponse to electronic or other interactions
In the past two decades, the field of between the probe and specimen surface. The
microscopy has experienced a revolution with in-surface-plane and out-of-plane motions of
the development of a new family of scanning the probe are controlled by piezoelectric
probe microscopes. The scanning probe (Section 18.25) ceramic components that have
microscope (SPM), of which there are several nanometer resolutions. Furthermore, these
varieties, differs from optical and electron probe movements are monitored electronically
microscopes in that neither light nor electrons and transferred to and stored in a computer,
are used to form an image. Rather, the which then generates the three-dimensional
microscope generates a topographical map, on surface image.
114 • Chapter 4 / Imperfections in Solids

Dimensions of structural feature (m)

6 4 2 8 10 12
10 ̶ 10 ̶ 10 10 ̶ 10 ̶ 10 ̶ 10 ̶ 1̶ 4

Subatomic particles

Atom/ion diameters

Unit cell edge lengths

Dislocations (width)

Second phase particles

Grains

Macrostructural features
(porosity, voids, cracks)
10 1 102 104 106 108 6̶ 10 4̶ 10 ̶2 Dimensions of structural
feature (nm)
(a)

Useful resolution ranges (m)

 10 6̶ 10 4̶ 10 ̶2
8 10 12
10 10 ̶ 10 ̶ ̶ 1

Scanning probe microscopes

Transmission electron microscopes

Scanning electron microscopes

Optical microscopes

Naked eye

(b)
10 ̶2
1 102 104 106 108 Useful resolution ranges (nm)

Figure 4.16 (a) Bar chart showing size ranges for several structural features found in
materials. (b) Bar chart showing the useful resolution ranges for four microscopic
techniques discussed in this chapter, in addition to the naked eye.
(Courtesy of Prof. Sidnei Paciornik, DCMM PUC-Rio, Rio de Janeiro, Brazil, and Prof.
Carlos Pérez Bergmann, Federal University of Rio Grande do Sul, Porto Alegre, Brazil.)

These new SPMs, which allow examination of the surface

of materials at the atomic and molecular level, have provided a
wealth of information about a host of materials, from
integrated circuit chips to biological molecules. Indeed, the
advent of the SPMs has helped to usher in the era of
nanomaterials—materials whose properties are designed by
engineering atomic and molecular structures.

Figure 4.16a is a bar chart showing dimensional size ranges for

several types of structures found in materials (note that the
axes are scaled logarithmically). The use ful dimensional
resolution ranges for the several microscopic techniques
discussed in this chapter (plus the naked eye) are presented in
the bar chart of Figure 4.16b. For three of these techniques
(SPM, TEM, and SEM), an upper resolution value is not
imposed by the characteristics of the microscope and,
therefore, is somewhat arbitrary and not well defined.
Furthermore, by comparing Figures 4.16a and 4.16b, it is
possible
4.11 Grain-Size Determination • 115

to decide which microscopic technique(s) is (are) best suited

for examination of each of the structure types.

4.11 GRAIN-SIZE DETERMINATION

grain size Relationship
between ASTM grain size number and number
of grains per square inch (at 100×)
The grain size is often determined when the
properties of polycrystalline and single phase
materials are under consideration. In this
regard, it is important to realize that for each
material, the constituent grains have a variety
of shapes and a distribution of sizes. Grain
size may be specified in terms of average or
mean grain diameter, and a number of
techniques have been developed to measure
this parameter. determination was devised by the American
Before the advent of the digital age, grain-size Society for Testing and Materials (ASTM).11
determinations were performed manually The ASTM has prepared several stand ard
using photomicrographs. However, today, comparison charts, all having different average
most techniques are automated and use digital grain sizes and referenced to pho
images and image analyzers with the capacity tomicrographs taken at a magnification of
to record, detect, and measure accurately 100×. To each chart is assigned a number
features of the grain structure (i.e., grain ranging from 1 to 10, which is termed the
intercept counts, grain boundary lengths, and grain-size number. A specimen must be
grain areas). prepared properly to reveal the grain structure,
We now briefly describe two common grain- which is then photographed. Grain size is
size determination techniques: (1) linear expressed as the grain-size number of the chart
intercept—counting numbers of grain that most nearly matches the grains in the
boundary intersections by straight test lines; micrograph. Thus, a relatively simple and
and (2) comparison—comparing grain convenient visual determina tion of grain-size
structures with standardized charts, which are number is possible. Grain-size number is used
based upon grain areas (i.e., number of grains extensively in the specification of steels.
per unit area). Discussions of these techniques The rationale behind the assignment of the
is from the manual perspective (using grain-size number to these various charts is as
photomicrographs). follows: Let G represent the grain-size
For the linear intercept method, lines are number, and let n be the average number of
drawn randomly through several grains per square inch at a magnification of
photomicrographs that show the grain 100×. These two parameters are related to
12
structure (all taken at the same magnification). each other through the expression
Grain boundaries intersected by all the line
segments are counted. Let us represent the
sum of the total number of intersections as P
and the total length of all the lines by LT. The
mean intercept length ℓ [in real space (at 1×—
i.e., not magnified)], a measure of grain
diameter, may be determined by the following
expression:

ℓ = LT

PM (4.16)
where M is the magnification.
The comparison method of grain-size
n = 2G−1 (4.17)

11
ASTM Standard E112, “Standard Test Methods for Determining Average Grain Size.”
12
Please note that in this edition, the symbol n replaces N from previous editions; also, G in
Equation 4.17 is used in place of the previous n. Equation 4.17 is the standard notation
currently used in the literature.
116 • Chapter 4 / Imperfections in Solids

For photomicrographs taken at magnifications other than 100×,

use of the following modified form of Equation 4.17 is
necessary:
2
M
n (M 100) = 2G−1 (4.18)

In this expression, nM is the number of grains per square inch at

magnification M. In ad 100)2term
makes use of the fact that,
whereas magnification
dition, the inclusion of the
(M
is a length parameter, area is expressed in terms of units of
length squared. As a conse quence, the number of grains per
unit area increases with the square of the increase in
magnification.
Relationships have been developed that relate mean
intercept length to ASTM grain-size number; these are as
follows:

G = −6.6457 log ℓ − 3.298 (for ℓ in mm) (4.19a) G = −6.6353

log ℓ − 12.6 (for ℓ in in.) (4.19b)

At this point, it is worthwhile to discuss the representation

of magnification (i.e., linear magnification) for a micrograph.
Sometimes magnification is specified in the micrograph
legend (e.g., “60×” for Figure 4.14b); this means the
micrograph repre sents a 60 times enlargement of the specimen
in real space. Scale bars are also used to express degree of
magnification. A scale bar is a straight line (typically
horizontal), either superimposed on or located near the
micrograph image. Associated with the bar is a length,
typically expressed in microns; this value represents the
distance in magnified space corresponding to the scale line
length. For example, in Figure 4.15b, a scale bar is located
below the bottom right-hand corner of the micrograph; its
“100 μm” notation indicates that 100 μm correlates with the
scale bar length.
To compute magnification from a scale bar, the
following procedure may be used: 1. Measure the length of
the scale bar in millimeters using a ruler.
2. Convert this length into microns [i.e., multiply the
value in step (1) by 1000 because there are 1000
microns in a millimeter].
3. Magnification M is equal to
 M = measured scale length (converted to microns)

the number appearing by the scale bar (in microns) (4.20)

For example, for Figure 4.15b, the measured scale length

is approximately 10 mm, which is equivalent to (10 mm)(1000
μm/mm) = 10,000 μm. Inasmuch as the scale bar length is 100
μm, the magnification is equal to

M = 10,000 μm

100 μm = 100×

This is the value given in the figure legend.

Concept Check 4.4 Does the grain-size number (G of Equation

4.17) increase or decrease with decreasing grain size? Why?
[The answer may be found in all digital versions of the text and/or at
www.wiley.com/college/callister (Student Companion Site).]
4.11 Grain-Size Determination • 117

EXAMPLE PROBLEM 4.5

Grain-Size Computations Using ASTM and Intercept
Methods
The following is a schematic micrograph that represents the
microstructure of some hypothetical metal.
Determine the following:
(a) Mean intercept length
(b) ASTM grain-size number, G using Equation
4.19a

Solution
(a) We first determine the magnification of the
micrograph using Equation 4.20. The scale bar
length is measured and found to be 16 mm,
which is equal to 16,000 μm; and because the
scale bar number is 100 μm, the magnification
is

M = 16,000 μm

100 μm = 160×
The following sketch is the same micrograph
on which have been drawn seven straight lines
(in red), which have been numbered. The Line Number Boundary Intersections 1 8
length of each line is 50 mm, and thus the 28
total line length (LT in Equation 4.16) is
38
(7 lines)(50 mm/line) = 350 mm 49
Tabulated next is the number of grain- 59
boundary intersections for each line: 69
77
Number of Grain Total 58
2 6
31

4
7
5

Thus, inasmuch as LT = 350 mm, P = 58 grain-boundary

intersections, and the magnification M = 160×, the mean intercept
length ℓ (in millimeters in real space), Equation 4.16, is equal to

ℓ = LT
PM

= 350 mm
(58 grain boundary intersections)(160× ) = 0.0377 mm
118 • Chapter 4 / Imperfections in Solids

(b) The value of G is determined by substitution of this value for ℓ into

Equation 4.19a; therefore,
G = −6.6457 log ℓ − 3.298
= (−6.6457) log(0.0377) − 3.298
= 6.16

SUMMARY
Vacancies and Interfacial Defects
Self-Interstitials Impurities in Solids • Point defects are those associated with one or
two atomic positions; these include vacancies
(or vacant lattice sites) and self-interstitials
(host atoms that occupy inter stitial sites).
• The equilibrium number of vacancies
depends on temperature according to Equation
4.1.

• An alloy is a metallic substance that is

composed of two or more elements. • A solid
Specification of Composition solution may form when impurity atoms are
added to a solid, in which case the original
crystal structure is retained and no new phases
are formed. • For substitutional solid solutions,
impurity atoms substitute for host atoms. •
Dislocations—Linear Defects Interstitial solid solutions form for relatively
small impurity atoms that occupy inter stitial
sites among the host atoms. Grain-Size
• A high degree of substitutional solid Determination
solubility of one atom type in another is Summary • 119
possible when the Hume-Rothery rules are
obeyed. • The microstructure of a material consists of
defects and structural elements that are of
• Composition of an alloy may be specified in microscopic dimensions. Microscopy is the
weight percent (on the basis of mass frac tion, observation of microstructure using some
Equations 4.3a and 4.3b) or atom percent (on type of microscope.
the basis of mole or atom fraction, Equations • Both optical and electron microscopes are
4.5a and 4.5b). employed, usually in conjunction with
• Expressions were provided that allow photographic equipment.
conversion of weight percent to atom percent • Transmissive and reflective modes are
(Equation 4.6a) and vice versa (Equation possible for each microscope type; preference
4.7a). is dictated by the nature of the specimen as
well as the structural element or defect to be
• Dislocations are one-dimensional crystalline examined.
defects of which there are two pure types: • The two types of electron microscopes are
edge and screw. transmission (TEM) and scanning (SEM). For
An edge may be thought of in terms of the TEM, an image is formed from an electron
lattice distortion along the end of an extra beam that, although passing through the
half-plane of atoms. specimen, is scattered and/or diffracted.
A screw is as a helical planar ramp. SEM employs an electron beam that raster-
For mixed dislocations, components of both scans the specimen surface; an image is
pure edge and screw are found. • The produced from back-scattered or reflected
magnitude and direction of lattice distortion electrons.
associated with a dislocation are specified by • A scanning probe microscope employs a
its Burgers vector. small and sharp-tipped probe that raster scans
• The relative orientations of Burgers vector the specimen surface. A computer-generated
and dislocation line are (1) perpendicu lar for and three-dimensional image of the surface
edge, (2) parallel for screw, and (3) neither results having nanometer resolution.
perpendicular nor parallel for mixed.
• With the intercept method used to measure
grain size, a series of straight-line seg ments
• Within the vicinity of a grain boundary
are drawn on the photomicrograph. The
(which is several atomic distances wide), there
number of grain boundaries that are
is some atomic mismatch between two
intersected by these lines are counted, and the
adjacent grains that have different crystallo
mean intercept length (a measure of grain
graphic orientations.
diameter) is computed using Equation 4.16.
• Across a twin boundary, atoms on one side
• Comparison of a photomicrograph (taken at a
reside in mirror-image positions of atoms on
magnification of 100×) with ASTM standard
the other side.
comparison charts may be used to specify
grain size in terms of a grain-size number.

Microscopic Techniques

Equation Summary
Equation
Number Equation Solving For
N exp
4.1 N�� = (−Q��
kT) Number of vacancies per unit volume

4.2 N = NA��

A Number of atomic sites per unit volume

4.3a C1 = m1
 m1 + m2× 100 Composition in weight percent
4.5a C1′ = nm1
nm1 + nm2× 100 Composition in atom percent

4.6a C1′ = C1A2

C1A2 + C2A1× 100 Conversion from weight

percent to atom percent 4.7a C1 = C1′A1

C1′A1 + C2′A2× 100 Conversion from atom percent to weight percent

4.9a C1″ = ( C1 × 103Conversion from weight

C1 percent to mass per unit volume
��1+C2 ��2)

Average density of a two-component alloy

4.10a ��ave = 100 C1

��1+C2
(continued)
��2
120 • Chapter 4 / Imperfections in Solids

Equation
Number Equation Solving For

4.11a Aave = 100 C1 4.16 ℓ = LT

A1+C2 Average atomic weight of a two-component

A2 alloy

PM Mean intercept length (measure of average grain diameter)

4.17 n = 2G−1 Number of grains per square inch at a magnification of 100×
2
) Number of grains per square inch at a
4.18 nM = (2G−1 (100
magnification other
than 100×
M)

List of Symbols
Symbol Meaning
A Atomic weight
G ASTM grain-size number
k Boltzmann’s constant (1.38 × 10−23 J/atom·K, 8.62 × 10−5
eV/atom·K) LT Total line length (intercept technique)
M Magnification
m1, m2 Masses of elements 1 and 2 in an alloy
NA Avogadro’s number (6.022 × 1023 atoms/mol)
nm1, nm2 Number of moles of elements 1 and 2 in an alloy
P Number of grain boundary intersections
Q�� Energy required for the formation of a vacancy
�� Density

Important Terms and Concepts

alloy REFERENCES microscope (SPM)
atomic vibration atom percent imperfection screw dislocation
Boltzmann’s constant Burgers interstitial solid solution self-interstitial
vector microscopy solid solution
composition microstructure solute
dislocation line mixed dislocation solvent
edge dislocation photomicrograph substitutional solid solution
grain size point defect transmission electron
scanning electron microscope microscope (TEM) vacancy
(SEM) scanning probe weight percent

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Brandon, D., and W. D. Kaplan, Microstructural
Characterization of Materials, 2nd edition,
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Clarke, A. R., and C. N. Eberhardt, Microscopy
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Publishing, Cambridge, UK, 2002.
Kelly, A., G. W. Groves, and P. Kidd,
Crystallography and Crystal Defects, John Wiley &
Sons, Hoboken, NJ, 2000. Tilley, R. J. D., Defects
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Van Bueren, H. G., Imperfections in Crystals,
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