Crystal Structure

Chapter 3: The Structure of
Crystalline Solids
ISSUES TO ADDRESS...
How do atoms assemble into solid structures?
(for now, focus on metals)
How does the density of a material depend on
its structure?
When do material properties vary with the
sample (i.e., part) orientation?
Energy
and
Packing
Non dense, random packing
Energy
typical neighbor
bond length
typical neighbor
bond energy
Dense, ordered packing
Energy
typical neighbor
bond length
typical neighbor
bond energy
Dense, ordered packed structures tend to have

lower energies.
Materials and Packing

Crystalline materials...
atoms pack in periodic, 3D arrays
typical of: -metals
-many ceramics
-some polymers
crystalline SiO2
Adapted from Fig. 3.22(a),
Callister 7e.
Noncrystalline materials...
atoms have no periodic packing
occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline
Si
Oxygen
noncrystalline SiO2
Adapted from Fig. 3.22(b),
Callister 7e.
Crystal Systems
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.
7 crystal systems
14 crystal lattices
a, b, and c are the lattice constants

Fig. 3.4, Callister 7e.
Crystal Sytems
The Bravais lattices
Metallic Crystal Structures

How can we stack metal atoms to minimize
empty space?
2-dimensions
vs.
Now stack these 2-D layers to make 3-D structures
Metallic Crystal Structures

Tend to be densely packed.
Reasons for dense packing:
- Typically, only one element is present, so all atomic
radii are the same.
- Metallic bonding is not directional.
- Nearest neighbor distances tend to be small in
order to lower bond energy.
- Electron cloud shields cores from each other
Have the simplest crystal structures.

We will examine three such structures...
Simple Cubic Structure (SC)

Rare due to low packing density (only Po has this structure)
Close-packed directions are cube edges.
Coordination # = 6
(# nearest neighbors)
SC
(Courtesy P.M. Anderson)
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. 3.23,
Callister 7e.
volume
unit cell
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: Cr, W, Fe (), Tantalum, Molybdenum
Coordination # = 8
Adapted from Fig. 3.2,

Callister 7e.
BCC
2 atoms/unit cell: 1 center + 8 corners x 1/8
Atomic Packing Factor: BCC

APF for a body-centered cubic structure = 0.68
3a
a
2a
Adapted from
Fig. 3.2(a), Callister 7e.
Close-packed directions:
length = 4R = 3 a
atoms
volume
4
( 3a/4) 3
2
unit cell
atom
3
APF =
volume
3
a
unit cell
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
Coordination # = 12
Adapted from Fig. 3.1, Callister 7e.
FCC
4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8
Atomic
Packing
Factor:
FCC
APF for a face-centered cubic structure = 0.74
maximum achievable APF
Close-packed directions:
length = 4R = 2 a
2a
a
Adapted from
Fig. 3.1(a),
Callister 7e.
Unit cell contains:

6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
atoms
volume
4
3
( 2a/4)
4
unit cell
atom
3
APF =
volume
3
a
unit cell
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
Compare Between
SC, BCC, FCC
A
B
C
Hexagonal Close-Packed
Structure (HCP)
ABAB... Stacking Sequence
3D Projection
2D Projection
c/a = 1.633
Top
layer
B sites
Middle layer
A sites
Bottom layer
Adapted from Fig. 3.3(a),

Callister 7e.
Coordination # = 12
APF = 0.74
A sites
6 atoms/unit cell
ex: Cd, Mg, Ti, Zn
15
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
VC = Volume of unit cell = a3 for cubic
NA = Avogadros number
= 6.023 x 1023 atoms/mol
Theoretical Density,
Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2
atoms
unit cell
=
volume
unit cell
2 52.00
a3 6.023 x 1023
a = 4R/ 3 = 0.2887 nm
g
mol
theoretical = 7.18 g/cm3

actual
atoms
mol
= 7.19 g/cm3
Densities of Material Classes

In general
metals > ceramics > polymers
30
Why?
Metals have...
Ceramics have...
less dense packing
often lighter elements
Polymers have...
(g/cm3 )
close-packing
(metallic bonding)
often large atomic masses
low packing density

(often amorphous)
lighter elements (C,H,O)
Composites have...
intermediate values
Metals/
Alloys
20
Platinum
Gold, W
Tantalum
10
Silver, Mo
Cu,Ni
Steels
Tin, Zinc
5
4
3
2
Titanium
Aluminum
Magnesium
Graphite/
Ceramics/
Semicond
Polymers
Composites/
fibers
Based on data in Table B1, Callister

*GFRE, CFRE, & AFRE are Glass,
Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
60% volume fraction of aligned fibers
in an epoxy matrix).
Zirconia
Al oxide
Diamond
Si nitride
Glass -soda
Concrete
Silicon
Graphite
Glass fibers
PTFE
Silicone
PVC
PET
PC
HDPE, PS
PP, LDPE
0.5
0.4
0.3
GFRE*
Carbon fibers
CFRE*
Aramid fibers
AFRE*
Wood
Data from Table B1, Callister 7e.
Solidification of polycrystals
Polycrystals
Anisotropic
Most engineering materials are polycrystals.
Adapted from Fig. K,

color inset pages of
Callister 5e.
(Fig. K is courtesy of
Paul E. Danielson,
Teledyne Wah Chang
Albany)
1 mm
Nb-Hf-W plate with an electron beam weld.

Each "grain" is a single crystal.
If grains are randomly oriented,
overall component properties are not directional.
Grain sizes typ. range from 1 nm to 2 cm

(i.e., from a few to millions of atomic layers).
Isotropic
Crystals as Building Blocks

Some engineering applications require single crystals:
--diamond single
crystals for abrasives
(Courtesy Martin Deakins,
GE Superabrasives,
Worthington, OH. Used with
permission.)
--turbine blades
Fig. 8.33(c), Callister 7e.
(Fig. 8.33(c) courtesy
of Pratt and Whitney).
Properties of crystalline materials

often related to crystal structure.
--Ex: Quartz fractures more easily
along some crystal planes than
others.
Single vs Polycrystals
Single Crystals
E (diagonal) = 273 GPa

Data from Table 3.3,
Callister 7e.
(Source of data is R.W.
Hertzberg, Deformation
and Fracture Mechanics
of Engineering
Materials, 3rd ed., John
Wiley and Sons, 1989.)
-Properties vary with

direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
Polycrystals
-Properties may/may not
vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)
-If grains are textured,

anisotropic.
E (edge) = 125 GPa
200 m
Adapted from Fig.

4.14(b), Callister 7e.
(Fig. 4.14(b) is 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].)
Polymorphism
Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
iron system
titanium
liquid
, -Ti
1538C
-Fe
BCC
carbon
1394C
diamond, graphite
-Fe
FCC
912C
BCC
-Fe
Polymorphism or Allotropy
Materials exist in more than one crystalline form. This is

called polymorphism or allotropy.
Temperature and pressure leads to change in crystalline
forms.
Examples: Titanium exists in the form of: , -Ti,
Carbon exists in the form of diamond and graphite

Iron exists in both BCC and FCC form depending on the temperature.
Liquid
Iron
-2730C
9120C
13940C 15390C
Iron
Iron
Iron
Science, BCC
BCC I El Mahallawi; MaterialFCC
BUE
24
Atom Positions in Cubic Unit

Cartesian coordinateCells
system is used to locate atoms.
In a cubic unit cell
y axis is the direction to the right.

x axis is the direction coming out of the paper.
z axis is the direction towards top.
Negative directions are to the opposite of positive
directions.
Atom positions are

located using unit
distances along the
axes.
I El Mahallawi; Material Science,

BUE
Figure 3.10 b25
Directions in Cubic Unit Cells
In cubic crystals, Direction Indices are vector

components of directions resolved along each axes,
resolved to smallest integers.
Direction indices are position coordinates of unit cell
where the direction vector emerges from cell surface,
converted to integers.
Figure 3.11
BUE
26
Procedure to Find Direction

Indices
Produce the direction vector
till it
z
emerges from surface of cubic cell
(1,1/2,1)
Determine the coordinates of point

of emergence and origin
Subtract coordinates of point of
Emergence by that of origin
Are all are
integers?
YES
Are any of the direction
vectors negative?
NO
(1,1/2,1) - (0,0,0)
= (1,1/2,1)
y
(0,0,0)
2 x (1,1/2,1)
= (2,1,2)
The direction indices are [212]

Convert them to
smallest possible
integer by multiplying
by an integer.
NO
YES
Represent the indices in a square
Represent the indices in a square
bracket without comas with a
bracket without comas (Eg: [212] )
over negative index (Eg:I El[121])
Mahallawi; Material Science,
27
BUE
Direction
Indices
Example
Determine direction indices of the given vector.
Origin coordinates are (3/4 , 0 , 1/4).

Emergence coordinates are (1/4, 1/2, 1/2).
Subtracting origin coordinates
from emergence coordinates,
(1/4, 1/2, 1/2)-(3/4 , 0 , 1/4)
= (-1/2, 1/2, 1/4)
(note the correction)
Multiply by 4 to convert all
fractions to integers
4 x (-1/2, 1/2, 1/4) = (-2, 2, 1)
Therefore, the direction indices are [ 2 2 1 ]
families of directions <uvw>, ex <100>,<111> & <110>

Figure EP3.6
BUE
28
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
LD =
length
= 3.5 nm 1
2a
29
HCP Crystallographic Directions

z
Algorithm
a2
a3
1. Vector repositioned (if necessary) to pass

through origin.
2. Read off projections in terms of unit
cell dimensions a1, a2, a3, or c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas
[uvtw]
a2
a1
ex:
, , -1, 0
=>
-a3
a2
2
Adapted from Fig. 3.8(a), Callister 7e.
[ 1120 ]
a3
dashed red lines indicate

projections onto a1 and a2 axes
a1
2
a1
30
HCP Crystallographic Directions

Hexagonal Crystals
4 parameter Miller-Bravais lattice coordinates are
related to the direction indices (i.e., u'v'w') as
follows.
z
[ u ' v ' w ' ] [ uvtw ]

u =
( 2 u ' - v ')
3
a2
v =
-
a3
a1
( 2 v ' - u ')
3
t = - (u + v )
w = w '
Fig. 3.8(a), Callister 7e.
31
Crystallographic Planes
32
Miller
Indices
Miller Indices are are used to refer to specific lattice
planes of atoms.
They are reciprocals of the fractional intercepts (with
fractions cleared) that the plane makes with the
crystallographic x,y and z axes of three nonparallel
edges of the cubic unit cell.
z
Miller Indices =(111)
y
x
BUE
33
Miller Indices - Procedure

Choose a plane that does not pass
through origin
Determine the x,y and z intercepts
of the plane
Find the reciprocals of the intercepts
Fractions?
Place a bar over the
Negative indices
Clear fractions by
multiplying by an integer
to determine smallest set
of whole numbers
Enclose in parenthesis (hkl)where h,k,l

are miller indicesof cubic crystal plane
forx,y and z axes. Eg: (111)
3-20

BUE
34
Miller Indices - Examples

z
(100)
x
x
Intercepts of the plane at x,y &

z axes are 1, and
Taking reciprocals we get
(1,0,0).
Miller indices are (100).
*******************
Intercepts are 1/3, 2/3 & 1.
taking reciprocals we get (3,
3/2, 1).
Multiplying by 2 to clear
fractions, we get (6,3,2).
Miller indices are (632).
Figure
I El3.14
Mahallawi; Material Science,
3-21
BUE
35
Miller Indices - Examples
Plot the plane (101)

Taking reciprocals of the indices
we get (1 1).
The intercepts of the plane are
x=1, y= (parallel to y) and z=1.
******************************
Plot the plane (2 2 1)
Taking reciprocals of the indices
we get (1/2 1/2 1).
The intercepts of the plane are
x=1/2, y= 1/2 and z=1.

BUE
Figure EP3.7 a
Figure EP3.7 c
36
Miller Indices - Example
Plot the plane (110)

The reciprocals are (1,-1, )
The intercepts are x=1, y=-1 and z= (parallel to z axis)
(110)
To show this plane in a

single unit cell, the origin
is moved along the
positive direction of y
axis by 1 unit.

BUE
37
Miller Indices Important Relationship
Direction indices of a direction perpendicular to a

crystal plane are same as miller indices of the plane.
z
Example:-
(110)
[110]
Figure EP3.7b
Interplanar spacing between parallel closest planes

with same miller indices is given by
hkl
+k +l
h
2
BUE
38
Planar Density of (100) Iron

Solution: At T < 912C iron has the BCC structure.
2D repeat unit
(100)
Planar Density =
area
2D repeat unit
1
a2
4 3
R
3
Radius of iron R = 0.1241 nm
Adapted from Fig. 3.2(c), Callister 7e.
atoms
2D repeat unit
a=
1
4 3
R
3
atoms
atoms
19
12.1
= 1.2 x 10
2
nm
m2
39
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
h=
3
a
2
atoms
2D repeat unit
4 3 16 3 2
2
=
area = 2 ah = 3 a = 3
R
R
3
3
1
=
Planar Density =
area
2D repeat unit
16 3
3
R2
7.0
atoms =
nm2
0.70 x 1019
atoms
m2
40
The following are more

examples on crystallographic
planes and directions

BUE
41

BUE
42
z
example
1. Intercepts
2. Reciprocals
3.
Reduction
a
1
1/1
1
1
4.
Miller Indices
(110)
b
1
1/1
1
1
1/
0
0
y
b
a
x
z
example
1. Intercepts
2. Reciprocals
3.
Reduction
a
1/2
1/
2
2
4.
Miller Indices
(100)
1/
0
0
1/
0
0
y
a
x
BUE
43
z
example
1.
Intercepts
a
1/2
2.
Reciprocals
1/
3.
Reduction
4.
Miller Indices
b
1
c
3/4
1/1
1/
4/3
(634)
Family of Planes {hkl}

Ex: {100} = (100),
(010),
(001),
(100),

BUE
(010),
(001)
44

Crystal Structure

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Chapter 3: The Structure of

Dense, ordered packing

Dense, ordered packed structures tend to have

Materials and Packing

a, b, and c are the lattice constants

The Bravais lattices

Metallic Crystal Structures

Now stack these 2-D layers to make 3-D structures

Metallic Crystal Structures

Have the simplest crystal structures.

Simple Cubic Structure (SC)

Atomic Packing Factor (APF)

Body Centered Cubic Structure

ex: Cr, W, Fe (), Tantalum, Molybdenum

Adapted from Fig. 3.2,

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

Atomic Packing Factor: BCC

Face Centered Cubic Structure

Atoms touch each other along face diagonals.

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

Adapted from Fig. 3.1, Callister 7e.

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

Unit cell contains:

FCC Stacking Sequence

FCC Unit Cell

Adapted from Fig. 3.3(a),

Mass of Atoms in Unit Cell

n = number of atoms/unit cell

theoretical = 7.18 g/cm3

Densities of Material Classes

low packing density

Based on data in Table B1, Callister

Data from Table B1, Callister 7e.

Most engineering materials are polycrystals.

Adapted from Fig. K,

Nb-Hf-W plate with an electron beam weld.

Grain sizes typ. range from 1 nm to 2 cm

Crystals as Building Blocks

Properties of crystalline materials

E (diagonal) = 273 GPa

-Properties vary with

-If grains are textured,

E (edge) = 125 GPa

Adapted from Fig.

Materials exist in more than one crystalline form. This is

Carbon exists in the form of diamond and graphite

Atom Positions in Cubic Unit

In a cubic unit cell

y axis is the direction to the right.

Atom positions are

I El Mahallawi; Material Science,

Figure 3.10 b25

Directions in Cubic Unit Cells

In cubic crystals, Direction Indices are vector

Procedure to Find Direction

Determine the coordinates of point

The direction indices are [212]

Origin coordinates are (3/4 , 0 , 1/4).

families of directions <uvw>, ex <100>,<111> & <110>

Unit length of direction vector

HCP Crystallographic Directions

1. Vector repositioned (if necessary) to pass

Adapted from Fig. 3.8(a), Callister 7e.