MECH340: Engineering Materials

Lecture 2
Dr. Samir Mustapha

Chapter 3 - 1

Chapter 3: Structures of Metals & Ceramics

ISSUES TO ADDRESS...
What is the difference in atomic arrangement
between crystalline and non-crystalline solids?
What features of a metals/ceramics atomic
structure determine its density?
How do the crystal structures of ceramic
materials differ from those for metals?
Under what circumstances does a material
property vary with the measurement direction?

Chapter 3 - 2

Chapter 3: Structures of Metals & Ceramics

Crystallinity and amorphous
Crystal structures of metals and ceramics
Crystallography
Single crystal and polycrystalline

Chapter 3 - 3

Fundamental Concept
Solid materials may be classified
according to the regularity with which
atoms or ions are arranged with
respect to one another.
A crystalline material is one in which
the atoms are situated in a repeating
or periodic array over large atomic
distances;
During solidification, the atoms will
position themselves in a repetitive
3D pattern, in which each atom is
bonded to its nearest-neighbor
atoms.

Chapter 3 - 4

Fundamental Concept
Absence of the long-range atomic order
referred to as noncrystalline or
amorphous materials.
Some of the properties of crystalline
solids depend on the crystal structure of
the material, the manner in which atoms,
ions, or molecules are spatially arranged.

Amorphous metals resulting

from rapid cooling from the
liquid state
Chapter 3 - 5

Materials and Packing

Crystalline materials...
atoms pack in periodic, 3D arrays
typical of: - metals
- many ceramics
- some polymers

crystalline SiO2
Adapted from Fig. 3.11(a),
Callister & Rethwisch 9e.

Noncrystalline materials...
atoms have no periodic packing
occurs for: - complex structures
- rapid cooling
"Amorphous" = Noncrystalline

Si

Oxygen

noncrystalline SiO2
Adapted from Fig. 3.11(b),
Callister & Rethwisch 9e.
Chapter 3 - 6

Fundamental Concept
Large number of different crystal structures all having long-range
atomic order (main focus):
Body Centered Cubic
Faced Centered Cubic
Hexahgonal packed

Chapter 3 - 7

Fundamental Concept
Atoms (or ions) are thought of as being solid spheres (known
diameter). This is termed the atomic hard-sphere model in which
spheres representing nearest-neighbor atoms touch one another.
The term lattice is used in the context of crystal structures; in this
sense lattice means a three-dimensional array of points coinciding
with atom positions (or sphere centers).
Unit Cell is the smallest repeating unit in the lattice (geometrical
symmetry).
Most crustal structures are parallelepipeds or prisms (three sets
of parallel faces). Corners of the unit cells are taken to coincide
Chapter 3 - 8
with the centers of the solid spheres.

Metallic Crystal Structures

Tend to be densely packed.
Reasons for dense packing:

An array of positive ions

in a sea of electrons

- Typically, only one element is present, so all atomic

radii are the same.
- Metallic bonding is not directional/ metallic bonding.
- Electron cloud shields cores from each other.

Metals have the simplest crystal structures.

We will examine four such structures...
Simple cubic
BCC
FCC
HCP
Chapter 3 - 9

Simple Cubic Structure (SC)

Coordination number: the total number of
nearest neighbors or touching atoms (within a
Important
cubic cell) on a single atom.
characteristics
Atomic packing factor: the volume of atoms as
fraction of the volume of the unit cell.
The number of atoms per unit cell:

Ni = the number of interior atoms

Nf = the number of face atoms
Nc = the number of corner atoms

Chapter 3 - 10

Simple Cubic Structure (SC)

Rare due to low packing density (only polonium - Po has this
structure- it is a semimetal)
Coordination # = 6
(# nearest neighbors)

Fig. 4.2, Callister & Rethwisch 9e.

Chapter 3 - 11

Atomic Packing Factor (APF)

Volume of atoms in unit cell*
APF =
Volume of unit cell
*assume hard spheres
APF for a simple cubic structure = 0.52
atoms
unit cell

a
R = 0.5a

APF =

volume
atom
4
(0.5a) 3
1
3
a3

close-packed directions
contains 8 x 1/8 =
1 atom/unit cell
Adapted from Fig. 4.2 (a),
Callister & Rethwisch 9e.

volume
unit cell
Chapter 3 - 12

Body Centered Cubic Structure (BCC)

Atoms touch each other along cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

ex: chromium, Iron, Tantalum, Molybdenum

Coordination # = 8

Adapted from Fig. 4.1,

Callister & Rethwisch 9e.

2 atoms/unit cell: 1 center + 8 corners x 1/8

Chapter 3 - 13

VMSE Screenshot BCC Unit Cell

Chapter 3 - 14

Atomic Packing Factor: BCC

APF for a body-centered cubic structure = 0.68
3a

a
2a
Adapted from
Fig. 4.1(a), Callister &
Rethwisch 9e.

Close-packed directions:
length = 4R = 3 a

atoms
volume
4
( 3a/4 ) 3
2
unit cell
atom
3
APF =
volume
3
a
unit cell

Chapter 3 - 15

Face Centered Cubic Structure (FCC)

Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

ex: Al, Cu, Au, Pb, Ni, Pt & Ag

Adapted from Fig. 3.1, Callister & Rethwisch 9e.

MANY FCC UNIT CELLS

Coordination # = 12
4 atoms/unit cell: 6 face x 1/2 + Chapter
8 corners
x 1/8
3 - 16

Atomic Packing Factor: FCC

APF for a face-centered cubic structure = 0.74
maximum achievable APF
Close-packed directions:
length = 4R = 2 a
2a

Unit cell contains:

6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell

Adapted from
Fig. 3.1(a),
Callister &
Rethwisch 9e.

atoms
volume
4
3
( 2a/4 )
4
unit cell
atom
3
APF =
volume
3
Spheres/Ions
a
touch each other
unit cell
Chapter 3 - 17

Hexagonal Close-Packed Structure

(HCP)
ABAB... Stacking Sequence (Titanium and Zinc)
3D Projection

2D Projection
A sites

Top layer

B sites

Middle layer

A sites

Bottom layer

Adapted from Fig. 4.3(a),

Callister & Rethwisch 9e.

Coordination # = 12

6 atoms/unit cell

APF = 0.74

ex: Cd (cadmium),
Mg, Ti, Zn

c/a = 1.633

Chapter 3 - 18

FCC Stacking Sequence

ABCABC... Stacking Sequence
2D Projection
B
B
C
A
B
B
B
A sites
C
C
B sites
B
B
C sites

FCC Unit Cell

A
B
C

Chapter 3 - 19

Theoretical Density,
Density = =

where

Mass of Atoms in Unit Cell

Total Volume of Unit Cell

nA
VC NA

n = number of atoms/unit cell

A = atomic weight (g/mol)
VC = Volume of unit cell = a3 for cubic
NA = Avogadros number
= 6.022 x 1023 atoms/mol
Chapter 3 - 20

Theoretical Density,
Ex: Cr- Cromium (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
Adapted from
Fig. 4.1(a), Callister &
Rethwisch 9e.

atoms
unit cell

=
volume
unit cell

a
2 52.00

a 3 6.022 x 1023

a = 4R/ 3 = 0.2887 nm
g
mol

theoretical = 7.18 g/cm3

actual

atoms
mol

= 7.19 g/cm3

Chapter 3 - 21

Atomic Bonding in Ceramics

Ceramics comes from the greek work keramikos which means
burnt stuff properties obtained from heat treatment.
Most ceramics are compound between metallic and nonmetallic
(MgO, NaCl).
The crystals structure of ceramics is more complex than metals
(composed of at least two element).
The atomic bonding ranges from purely ionic to totally covalent,
many ceramics exhibit a combination of both.
The ionic character depend on the electronegativities of the
atoms.
Chapter 3 - 22

Ionic bond metal

nonmetal

donates
electrons
ex: MgO

Mg

1s2 2s2 2p6 3s2

[Ne] 3s2

Mg2+ 1s2 2s2 2p6

[Ne]

accepts
electrons
O

1s2 2s2 2p4

O2- 1s2 2s2 2p6

[Ne]

The metallic ions (cations) are positively charged, they given up their valence
electrons to the nonmetallic ions ( anions-negatively charged).
The crystal structures may be thought of as being composed of electrically
charged ions instead of atoms (where bonding is predominantly
ionic).
Chapter 3 - 23

Atomic Bonding in Ceramics

Bonding:
-- Can be ionic and/or covalent (difference in electronegativity) in
character.
-- % ionic character increases with difference in electronegativity
of atoms.

Degree of ionic character may be large or small:

CaF2: large
SiC: small

Chapter 3 - 24
ZnS: small

Mixed Bonding
For example for SiC

XSi = 1.8 and XC = 2.5

X is the electronegativity of each element

~ 89% covalent bonding

For Several Ceramic Materials, Percent Ionic Character of the Interatomic Bonds

Chapter 3 - 25

Ceramic Crystal Structures

Two characteristics of the component ions in crystalline ceramic
materials influence the crystal structure:
A) the magnitude of the electrical charge on each of the
component ions,
B) and the relative sizes of the cations and anions.
A)
the magnitude of the electrical charge
The crystal must be electrically neutral; positive cation must be
balanced by an equal number of negative anion.
The chemical formula of a compound
the ratio of cations to
anions (composition that achieves this charge balance (e.g CaF2
twice F- as Ca2+)).

Chapter 3 - 26

Ceramic Crystal Structures

B) relative sizes of the cations and anions
The metallic elements give up electrons when ionized, cations are
ordinarily smaller than anions, and, consequently, the ratio rC/rA is less
than unity.
Each cation prefers to have as many nearest-neighbor anions as
possible, similarly for anions.
Stable ceramic crystal structures form when those anions surrounding
a cation are all in contact with that cation.
The coordination number (i.e., number of anion nearest neighbors for a
cation) is related to the cationanion radius ratio.

Chapter 3 - 27

Factors that Determine Crystal Structure

1. Relative sizes of ions formation of stable structures:
--maximize the # of oppositely charged ion neighbors.

unstable
2. Maintenance of
Charge Neutrality :

stable

--Net charge in ceramic

should be zero.
--Reflected in chemical
formula:

CaF 2 :

Adapted from Fig. 4.4,

Callister & Rethwisch 9e.

+
-

stable
Ca 2+ +
cation

Fanions
F-

A m Xp
m, p values to achieve
charge neutrality

Chapter 3 - 28

SM1

Coordination Number and Ionic Radii

r cation
Coordination Number increases with r
anion
To form a stable structure, how many anions can
surround around a cation?
r cation
r anion
< 0.155

Coord.
Number
2
linear

0.155 - 0.225

0.225 - 0.414

4 tetrahedral

0.414 - 0.732

6 octahedral

0.732 - 1.0

Adapted from Table 4.3,

Callister & Rethwisch 9e.

triangular

cubic

The bond type

determines the
crystal shape at the
boundary

ZnS
(zinc blende)
Adapted from Fig. 4.7,
Callister & Rethwisch 9e.

NaCl
(sodium
chloride)

Adapted from Fig. 4.5,

Callister & Rethwisch 9e.

CsCl
(cesium
chloride)
Adapted from Fig. 4.6,
Callister & Rethwisch 9e.
Chapter 3 - 29

Slide 29
SM1

Samir Mustapha, 9/14/2015

Computation of Minimum Cation-Anion

Radius Ratio
Determine minimum rcation/ranion for an octahedral site
(C.N. = 6)

a = 2ranion

2ranion + 2rcation = 2 2ranion

ranion + rcation = 2ranion

rcation = ( 2 1)ranion

Chapter 3 - 30

Computation of Minimum Cation-Anion

Radius Ratio
Determine minimum rcation/ranion for an octahedral site
(C.N. = 6)

a = 2ranion

2ranion + 2rcation = 2 2ranion

ranion + rcation = 2ranion

rcation = ( 2 1)ranion

rcation
= 2 1 = 0.414
ranion
Chapter 3 - 31

Example Problem: Predicting the Crystal

Structure of FeO
On the basis of ionic radii, what crystal structure
would you predict for FeO?
Cation Ionic radius (nm)
Al 3+
0.053
Fe 2+
0.077
Fe 3+
0.069
Ca 2+
0.100
Anion
O2Cl F-

0.140
0.181
0.133

Data from Table 4.4,

Callister & Rethwisch 9e.
Chapter 3 - 32

Example Problem: Predicting the Crystal

Structure of FeO
On the basis of ionic radii, what crystal structure
would you predict for FeO?
Answer:
r cation
r anion
< 0.155

Coord.
Number
2
linear

0.155 - 0.225

0.225 - 0.414

4 tetrahedral

0.414 - 0.732

6 octahedral

0.732 - 1.0

triangular

cubic

rcation 0.077
=
ranion 0.140
= 0.550
based on this ratio,
-- coord # = 6 because
0.414 < 0.550 < 0.732
-- crystal structure is
Octahedral
Chapter 3 - 33

AX Crystal Structures
Equal numbers of cations and anions most common.
There are several different crystal structures for AX compounds;
each is normally named after a common material:
Rock Salt Structure (NaCl)
Cesium Chloride (CsCl)
Zinc Blende Structure (Sphalerite) ZnS

Chapter 3 - 34

AX type - Rock Salt Structure

Example: NaCl (rock salt) structure
rNa = 0.102 nm
rCl = 0.181 nm
rNa/rCl = 0.564
cations (Na+) prefer octahedral sites
Coordination # for both cations and
anions is 6, therefore cationanion
radius ratio is between approximately
0.414 and 0.732.
Adapted from Fig. 4.5,
Callister & Rethwisch 9e.

Others MgO, MnS, LiF, and FeO

FCC arrangement of anions with one

cation situated at the cube center and
one at the center of each of the 12 cube
Chapter 3 - 35
edges - Interpenetrating.

AX type Cesium Chloride

Cesium Chloride structure:

Since 0.732 < 0.939 < 1.0,

cubic sites preferred
Fig. 4.6, Callister & Rethwisch 9e.

So each Cs+ has 8 neighbor Cl-

This is not a BCC crystal structure because ions of two

different kinds are involved.
Chapter 3 - 36

AX type Zinc Blende Structure

Zinc Blende structure (ZnS, ZnC or ZnTe):
Coordination # is 4; all ions
are tetrahedrally coordinated.
All corner and face positions of the cubic
cell are occupied by S atoms, whereas the
Zn atoms fill interior tetrahedral positions.
An equivalent structure results if Zn and S
atom positions are reversed.
Fig. 4.7, Callister & Rethwisch 9e.

The atomic bonding is highly covalent in

compounds exhibiting this crystal
Chapter 3 - 37
structure.

Atomic Bonding in Ceramics

ZnS: small ionic

components

Chapter 3 - 38

AX2 Crystal Structures

Fluorite structure

Fig. 4.8, Callister & Rethwisch 9e.

AmXp, where m and/or p1 (due

to the change in the charges).
Calcium Fluorite (CaF2)
Cations in cubic sites
rC/rA for CaF2 is about 0.8,
Other e.g. UO2, ThO2,
ZrO2, CeO2
Antifluorite structure
positions of cations and
anions reversed
Coordination # 8
Crystal structure Cubic
Chapter 3 - 39

ABX3 Crystal Structures

Perovskite structure(BaTiO3)
Ex: complex oxide
BaTiO3
Piezoelectric material
Fig. 4.9, Callister &
Rethwisch 9e.

Ceramic compounds to have more than one type of cation; for two types of
cations (represented by A and B), their chemical formula may be designated
as AmBnXp.
Ba2+ ions are situated at all eight corners of the cube and a single
Ti4+ is at the cube center, with O2- ions located at the center of each
Chapter 3 - 40
of the six faces.

Density Computations for Ceramics

Number of formula units/unit cell

n(AC + AA )
=
VC N A

Avogadros number

Volume of unit cell

n = the number of formula units within the unit cell
VC = the unit cell volume
NA = Avogadros number, 6.022x1023 units/mol
= sum of atomic weights of all cations in formula unit
= sum of atomic weights of all anions in formula unit
Chapter 3 - 41

Crystal Systems
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.
Unit cells for most crystal structures are
parallelepipeds or prisms having three sets of
parallel faces.
Crystal structures are divided into two groups
according to:
Unit cell configuration
Atomic arrangement
Chapter 3 - 42

Crystal Systems
Unit cell configurations: based on the unit cell
geometry.
Shape (Parallelepiped) of the unit cell without
regard to the atomic positions within the cell.
The crystal system (cell configuration) is
defined by:

Setting a coordinate system at the corner of a unit

cell
Six parameter are used to describe the system
(length edge a, b and c; also three interaxial angles
, and ).
The six parameters referred to as Lattice parameters.
Chapter 3 - 43

Crystal Systems
7 crystal systems

Cubic system Highest degree of Symmetry

Triclinic system Least degree of Symmetry

Chapter 3 - 44

Crystal Systems

Chapter 3 - 45

Metallic Crystall Structures

The atomic bonding in this group of materials is

metallic and thus non-directional in nature.

There are minimal restrictions as to the number and

position of nearest-neighbor atoms; this leads to
relatively large numbers of nearest neighbors and
dense atomic packings for most metallic crystal
structures.

Chapter 3 - 46

Crystallographic Points, Directions and

Planes
Crystallography: is the process of defining
points, directions and planes within a unit cell.
Three numbers/indices (convention) are used to
used to designate point locations, directions and
planes.
Define an axis system at one of the corners of
the unit cell.
For some crystal systems, the three axis may not
triclinic).
be mutually perpendicular (Rhombo andChapter
3 - 47

Point Coordinates
z

Specify a lattice position within a unit

cell (using q, r and s point
coordinate indices)
Q, r and s are fractional multiples of a,
b and c (edge lengths)
y

111

000

a
x

2c

qa= lattice position referenced to the xaxis

rb= lattice position referenced to the yaxis
sc= lattice position referenced to the zaxis

b
Chapter 3 - 48

Point Coordinates

111

Point coordinates for unit cell

center are

a/2, b/2, c/2

a

000

Point coordinates for unit cell

corner are 111

2c
Note the representation

Translation: integer multiple of

lattice constants
identical
position in another unit cell

b
Chapter 3 - 49

Example

Chapter 3 - 50

Example

Chapter 3 - 51

Example

Chapter 3 - 52

Crystallographic Directions
Algorithm

Define a coordinate
system z

pt. 2
head

pt. 1:
tail

x
example:
pt. 1 x1 = 0, y1 = 0, z1 = 0
pt. 2 x2 = a, y2 = 0, z2 = c/2

1. Determine coordinates of vector tail, pt. 1:

x1, y1, & z1; and vector head, pt. 2: x2, y2, & z2.
2. Tail point coordinates subtracted from head
point coordinates.
3. Normalize coordinate differences in terms
of lattice parameters a, b, and c:

4. Adjust to smallest integer values

5. Enclose in square brackets, no commas

[uvw]
=> 1, 0, 1/2

=> 2, 0, 1

=> [ 201 ]

Note the
Chapter 3 - 53
representation

Crystallographic Directions

Chapter 3 -

Crystallographic Directions

?
?

Chapter 3 -

Crystallographic Directions

Note the
representation

Chapter 3 -

Crystallographic Directions
z

pt. 2
head

y
x

pt. 1:
tail

Chapter 3 - 57

Crystallographic Directions
z

pt. 2
head

Example 2:
pt. 1 x1 = a, y1 = b/2, z1 = 0
pt. 2 x2 = -a, y2 = b, z2 = c

y
x

pt. 1:
tail

=> -2, 1/2, 1

Multiplying by 2 to eliminate the fraction

-4, 1, 2 => [ 412 ]

where the overbar represents a

negative index

Chapter 3 - 58

Determination of HCP Crystallographic Directions (ii)

For crystals having hexagonal
symmetry in that some
crystallographic equivalent directions
will not have the same set of indices.
This is circumvented by utilizing a fouraxis, or MillerBravais coordinate
system.
The three a1, a2, and a3 axes are all
contained within a single plane (called
the basal plane) and are at 120 angles
to one another.
The z axis is perpendicular to this
basal plane.
Chapter 3 - 59

Determination of HCP Crystallographic Directions (ii)

Chapter 3 - 60

Determination of HCP Crystallographic Directions (ii)

Algorithm
1. Determine coordinates of vector tail, pt. 1:
x1, y1, & z1; and vector head, pt. 2: x2, y2, & z2. in
terms of three axis (a1, a2, and z)
2. Tail point coordinates subtracted from head
point coordinates and normalized by unit cell
dimensions a and c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas,
for three-axis coordinates
5. Convert to four-axis Miller-Bravais lattice
coordinates using equations below:

u=

1
1
(2u v ) v = (2v u)
3
3

t = (u +v )

w = w

6. Adjust to smallest integer values and

enclose in brackets [uvtw]
Chapter 3 - 61

Drawing HCP Crystallographic Directions (i)

Algorithm (Miller-Bravais coordinates)

1. Remove brackets
2. Divide by largest integer so all values
are 1
3. Multiply terms by appropriate unit cell
dimension a (for a1, a2, and a3 axes)
or c (for z-axis) to produce
projections
4. Construct vector by placing tail at
origin and stepping off these
projections to locate the head

Chapter 3 - 62

Drawing HCP Crystallographic Directions (ii)

Draw the [1 2 13] direction in a hexagonal unit cell.

Chapter 3 - 63

Drawing HCP Crystallographic Directions (ii)

Draw the [1 2 13] direction in a hexagonal unit cell.

Algorithm

a1

a2

a3

1. Remove brackets

-1

-2

2
3

1
3

2. Divide by 3

[1213]

1
3

3. Projections
4. Construct Vector

p
r

start at point o
proceed a/3 units along a1 axis to point p
2a/3 units parallel to a2 axis to point q
a/3 units parallel to a3 axis to point r
c units parallel to z axis to point s

[1213] direction represented by vector from point o to point s

Chapter 3 - 64

Determination of HCP Crystallographic Directions (i)

Chapter 3 - 65

Determination of HCP Crystallographic Directions (i)

Determine indices for green vector
Example
1. Tail location
Head location
2. Normalized
3. Reduction
4.

a1
0
a

a2
0
a

z
0
0c

1
1

1
1

0
0

Brackets

[110]

5.

6.

Convert to 4-axis parameters

1
1
1
1
u = [(2)(1) (1)] =
v = [(2)(1) (1)] =
3
3
3
3
1 1
2
w =0
t = ( + ) =
3 3
3
Reduction & Brackets

1/3, 1/3, -2/3, 0

=>

1, 1, -2, 0

=>

[ 1120 ]
Chapter 3 - 66

Crystallographic Planes
The orientation of planes for a crystal structure are represented in a
similar fashion.
The miller indices are used except for the hexagonal crystal system.

Adapted from Fig. 3.7, Callister

& Rethwisch 9e.

Chapter 3 - 67

Crystallographic Planes
If the plane passes through the selected origin,
either another parallel plane must be constructed
within the unit cell by an appropriate translation,
or a new origin must be established at the corner
of another unit cell.
Algorithm
1. Read off intercepts of plane with axes in
terms of a, b, c
2. Take reciprocals of intercepts
3. Reduce to smallest integer values
4. Enclose in parentheses, no
commas i.e., (hkl)
All parallel planes have same Miller indices.
Chapter 3 - 68

Crystallographic Planes
z

a
x

z
c

x
Chapter 3 - 69

Crystallographic Planes
z

example
1. Intercepts
2. Reciprocals
3.

Reduction

a
1
1/1
1
1

4.

Miller Indices

(110)

example
1. Intercepts
2. Reciprocals
3.

Reduction

a
1/2
1/
2
2

4.

Miller Indices

(100)

b
1
1/1
1
1

1/
0
0

a
x

1/
0
0

1/
0
0

x
Chapter 3 - 70

Crystallographic Planes
z
example
1. Intercepts
2. Reciprocals
3.

Reduction

4.

Miller Indices

a
1/2
1/
2
6

b
1
1/1
1
3

(634)

c
c
3/4

1/
4/3

4 a
x

Family of Planes {hkl}

Ex: {100} = (100), (010), (001), (100), (010), (001)
Chapter 3 - 71

Crystallographic Planes (HCP)

In hexagonal unit cells the same idea is used
z

example
1. Intercepts
2. Reciprocals
3.

Reduction

a1
1
1
1
1

a2

1/
0
0

a3
-1
-1
-1
-1

c
1
1
1
1

a2

a3

4.

Miller-Bravais Indices

(1011)

(hkil)

a1
Adapted from Fig. 3.8,
Callister & Rethwisch 9e.

(Where i=-(h+k))
Chapter 3 - 72

Equations used to determine Crystallographic

points, directions and planes

Chapter 3 - 73

Linear Density
Linear Density of Atoms LD =

Number of atoms
Unit length of direction vector

[110]
ex: linear density of Al in [110]
direction
a = 0.405 nm

# atoms
a
Adapted from
Fig. 3.1(a),
Callister &
Rethwisch 9e.

LD =
length

= 3.5 nm1

2a

Number of atoms per unit length whose centers lie on the direction vector
Chapter 3 - 74
for a specific crystallographic direction.

Planar Density of (100) Iron

Solution: At T < 912C iron has the BCC structure.
2D repeat unit

(100)

4 3
R
3
4
a=
R
3

a=

Fig. 4.2(c), Callister & Rethwisch 9e [from W. G. Moffatt, G. W.

Pearsall, and J. Wulff, The Structure and Properties of Materials, Vol. I,
Structure, p. 51. Copyright 1964 by John Wiley & Sons, New York.
Reprinted by permission of John Wiley & Sons, Inc.]

atoms
2D repeat unit

Planar Density =
area
2D repeat unit

1
a2

Radius of iron R = 0.1241 nm

atoms
atoms
19
= 1.2 x 10
2 = 12.1
2
nm
m2

4 3
R
3
the number of atoms per unit area that
are3 -centered
Chapter
75
on a particular crystallographic plane

Planar Density of (111) Iron

Solution (cont): (111) plane

1 atom in plane/ unit surface cell

2a

atoms in plane
atoms above plane
atoms below plane

3
a
2

h=
2

area = 2 ah = 3 a 2 = 3
atoms
2D repeat unit

atoms =
= 7.0
2

Planar Density =
area
2D repeat unit

16 3
3

nm

4 3
R
3

16 3 2
R
3

0.70 x 1019

atoms
m2

Chapter 3 - 76

Single Crystal
For crystalline solid, when the periodic and repeated
arrangement of atoms is perfect or extends throughout the
entirety of the specimen without interruption, the result is a
single crystal.

All unit cells interlock in the same way and have the same
orientation.

Single crystals are ordinarily difficult

to grow, because the environment
must be carefully controlled.
Single Crystal --- Electronic
microcircuits

Garnet

Chapter 3 - 77

Polycrystalline materials
Most crystalline solids are composed of a collection of many
small crystals or grains; such materials are termed
polycrystalline.
The crystallographic orientation varies from grain to grain. Also,
there exists some atomic mismatch within the region where two
grains meet; this area, called a grain boundary.

Chapter 3 - 78
Fig_03_10

Chapter 3 - 79

Chapter 3 - 80

Anisotropy/ Isotropy
The physical properties of single crystals of some substances
depend on the crystallographic direction in which measurements
are taken.
The elastic modulus, the electrical conductivity, and the index of
refraction may have different values in the [100] and [111]
directions.
This directionality of properties is termed anisotropy.
The extent and magnitude of anisotropic effects in crystalline
materials are functions of the symmetry of the crystal structure.
Anisotropy increases with decreasing structural symmetry
(triclinic structures).
Substances in which measured properties are independent of
the direction of measurement are isotropic.
Chapter 3 - 81

Anisotropy/ Isotropy
For many polycrystalline materials, the crystallographic
orientations of the individual grains are totally random. Under
these circumstances, even though each grain may be
anisotropic, a specimen composed of the grain aggregate
behaves isotropically.
The magnitude of a measured property represents some
average of the directional values.

Chapter 3 - 82

Non-crystalline solids
Noncrystalline solids lack a systematic and regular arrangement of
atoms, also called amorphous.
Rapid cooling through the freezing temperature favors the formation
of a noncrystalline solid, because little time is allowed for the
ordering process.
Polymers may be completely noncrystalline and semicrystalline
consisting of varying degrees of crystallinity.

Chapter 3 - 83

Non-crystalline solids

Fig_03_11

Chapter 3 - 84

SUMMARY
Atoms may assemble into crystalline or amorphous structures.
Common metallic crystal structures are FCC, BCC, and HCP.
Coordination number and atomic packing factor are the same
for both FCC and HCP crystal structures.
We can predict the density of a material, provided we know the
atomic weight, atomic radius, and crystal geometry (e.g., FCC,
BCC, HCP).
Interatomic bonding in ceramics is ionic and/or covalent.
Ceramic crystal structures are based on:
-- maintaining charge neutrality
-- cation-anion radii ratios.
Crystallographic points, directions and planes are specified in
terms of indexing schemes. Crystallographic directions and
planes are related to atomic linear densities and planar densities.
Chapter 3 - 85

SUMMARY
Materials can be single crystals or polycrystalline.
Material properties generally vary with single crystal
orientation (i.e., they are anisotropic), but are generally
non-directional (i.e., they are isotropic) in polycrystals
with randomly oriented grains.
Some materials can have more than one crystal
structure. This is referred to as polymorphism (or
allotropy).

Chapter 3 - 86

Recommended problems
Reading:
3.1- 3.2-3.5-3.7-3.8-3.12-3.16-3.18-3.21-3.25-3.26-3.293.43-3.46-3.29-3.51-3.54-3.57-3.61-3.73-3.75-3.78-

Core Problems:

Self-help Problems:

Chapter 3 - 87