Chapter 3: The Structure of Crystalline Solids

ISSUES TO EXPLORE...
• What is the difference in atomic arrangement
between crystalline and noncrystalline solids?
• What are the crystal structures of metals?
• What are the characteristics of crystal structures?
• How are crystallographic points, directions, and
planes specified?
• What characteristics of a material’s atomic
structure determine its density?

Chapter 3 - 1
 Energy and Packing
• Non dense, random packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

• Dense, ordered packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Ordered structures tend to be nearer the

minimum in bonding energy and are more stable.
Chapter 3 - 2
 Materials and Atomic Arrangments
Crystalline materials...
• atoms arranged in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2
Adapted from Fig. 3.24(a),
Callister & Rethwisch 10e.

Si Oxygen
Noncrystalline materials...
• atoms have no periodic arrangement
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.24(b),
Callister & Rethwisch 10e.

Chapter 3 - 3
 Metallic Crystal Structures:
Atomic Packing
• Dense atomic packing for crystal structures
of metals.
• Reasons for dense packing:
- Bonds between metal atoms are nondirectional.
- Nearest neighbor distances tend to be small in
order to lower bond energy.
- High degree of shielding (of ion cores) provided
by free electron cloud.
• Crystal structures for metals simpler than
structures for ceramics and polymers.
We will examine three such structures for metals...
Chapter 3 - 4
 Simple Cubic (SC) Crystal Structure
• Centers of atoms located at the eight corners of a cube
• Rare due to low packing density (only Po has this structure)
• Close-packed directions are cube edges.
ex: Po • Coordination # = 6
(# nearest neighbors)

Adapted from Fig. 3.3,Callister & Rethwisch 10e.

Chapter 3 - 5
 Definitions
Coordination Number

Coordination Number = number of nearest-neighbor

or touching atoms

Atomic Packing Factor (APF)

Volume of atoms in unit cell*
APF =
Volume of unit cell
*assume hard spheres

Chapter 3 - 6
 Atomic Packing Factor (APF)
for Simple Cubic

volume
atoms 4 atom
a unit cell 1 π (0.5a ) 3
3
R = 0.5a APF = = 0.52
a3 volume
unit cell
close-packed
directions
Unit cell contains 1 atom = 8 x 1/8 = 1 atom/unit cell

Chapter 3 - 7
 Body-Centered Cubic Structure (BCC)
• Atoms located at 8 cube corners with a single atom at cube center.
--Note: All atoms in the animation are identical; the center atom is shaded
differently for ease of viewing.

ex: Cr, W, Fe (α), Ta, Mo • Coordination # = 8

Adapted from Fig. 3.2,Callister & Rethwisch 10e.

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

Chapter 3 - 8
VMSE Screenshot – BCC Unit Cell

Chapter 3 - 9
 Atomic Packing Factor: BCC
• APF for the body-centered cubic structure = 0.68

4R = 3a

2a

For close-packed directions

R R = 3a /4
a
volume
atoms
4 3 atom
unit cell 2 π ( 3a /4)
3
APF =
volume a3
unit cell Chapter 3 - 10
 Face-Centered Cubic Structure (FCC)
• Atoms located at 8 cube corners and at the centers of the 6 faces.
--Note: All atoms in the animation are identical; the face-centered atoms
are shaded differently for ease of viewing.
ex: Al, Cu, Au, Pb, Ni, Pt, Ag • Coordination # = 12

Adapted from Fig. 3.1,Callister & Rethwisch 10e.

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

Chapter 3 - 11
 Atomic Packing Factor: FCC
• APF for the face-centered cubic structure = 0.74
maximum achievable APF
For close-packed directions:

4R = 2a
2a

Unit cell contains: 6 x 1/2 + 8 x 1/8

a = 4 atoms/unit cell
atoms volume
4 atom
unit cell 4 π ( 2a /4)3
3
APF = = 0.74
a3 volume
unit cell Chapter 3 - 12
 FCC Plane Stacking Sequence
• ABCABC... Stacking Sequence–Close-Packed Planes of Atoms
• 2D Projection
B B
C
A
A sites B B B
C C
B sites B B
C sites

A Close-Packed
• Stacking Sequence B
Referenced to an C Plane
FCC Unit Cell.

Chapter 3 - 13
 Hexagonal Close-Packed Structure
(HCP)
• ABAB... Stacking Sequence–Close-Packed Planes of Atoms
• 3D Projection • 2D Projection

A sites Top layer

c
B sites Middle layer

A sites Bottom layer

a

• Coordination # = 12 6 atoms/unit cell

• APF = 0.74 ex: Cd, Mg, Ti, Zn
• Idealc /a = 1.633
Chapter 3 - 14
 Theoretical Density for Metals,

Mass of Atoms in Unit Cell

Density =   
Total Volume of Unit Cell

nA
 
VC
N A

where n = number of atoms/unit cell

A = atomic weight
VC = Vol
u m eofun itcell
=a 3for cu b i
c

NA
Av
o
g
ad
r
o
’
sn
u
mb
e
r
 6.022 x 1023 atoms/mol

Chapter 3 - 15
 Theoretical Density Computation for
Chromium
• Cr has BCC crystal structure
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
a = 4R / 3 = 0.2887 nm
R
a VC =a 3
=
2
.4
06 x-
2
3
1
0c
m3
atoms g
unit cell mol
n A 2 52.00
 = =  7.19 g/cm3
VC
N A 2.406 x 10-23 6.022 x 1023 atoms
volume mol
unit cell ρa
l  7.15 g/cm3
c
t
u
a
Chapter 3 - 16
 Densities Comparison for Four Material Types
In general Graphite/
ρ metals > ρ ceramics >ρ polymers Metals/
Alloys
Ceramics/ Polymers
Composites/
fibers
Semicond
30
Why? Platinum
B ased on data in Table B1, Callister
*GFRE, CFRE, & AFRE are Glass,
20 Gold, W
Metals have... Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
• close-packing 60% volume fraction of aligned fibers
10 Silver, Mo in an epoxy matrix).
(metallic bonding) Cu,Ni
Steels
• often large atomic masses Tin, Zinc
Zirconia

ρ (g/cm3 )
Ceramics have... 5
4
Titanium
Al oxide
• often lighter elements 3
Diamond
Si nitride
Aluminum Glass -soda Glass fibers
Polymers have... 2
Concrete
Silicon PTFE GFRE*
Magnesium Carbon fibers
• low packing density G raphite
Silicone CFRE *
Aramid fibers
PVC
(often amorphous) PET AFRE *
1 PS
• lighter elements (C,H,O) PE

Composites have... 0.5

• moderate to low densities 0.4
Wood

0.3

Chapter 3 - 17
 Single Crystals
• When the periodic arrangement of atoms (crystal structure)
extends without interruption throughout the entire specimen.
-- diamond single -- single crystal for
crystals for abrasives turbine blade
(Courtesy Martin
Deakins, GE
Superabrasives,
Worthington, OH.
Used with permission.)

-- Quartz single crystal

(Courtesy P.M. Anderson)

Fig. 8.35(c),Callister &

Rethwisch 10e.
(courtesy of Pratt and Whitney)
Chapter 3 - 18
 Polycrystalline Materials
• Most engineering materials are composed of many small,
single crystals (i.e., are polycrystalline ).
large
Courtesy of Paul E. Danielson, Teledyne Wah Chang

grain

1 mm

small
Albany

grain
• Nb-Hf-W plate with an electron beam weld.
• Each "grain" is a single crystal.
• Grain sizes typically range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).
Chapter 3 - 19
 Anisotropy

• Anisotropy — Property value depends on

crystallographic direction of measurement.
- Observed in single crystals. E (diagonal) = 273 GPa
- Example: modulus
of elasticity (E ) in BCC iron

E (edge) ≠E (diagonal)

E (edge) = 125 GPa

Unit cell of BCC iron

Chapter 3 - 20
 Isotropy
• Polycrystals
200 μm
- Properties may/may not
vary with direction.
- If grains randomly oriented:
properties isotropic.
(E pol
yi
ron= 21 0G Pa )
- If grains textured (e.g.,
deformed grains have
preferential crystallographic
orientation):
Fig. 4.15(b),Callister & Rethwisch 10e .
properties anisotropic. [Fig. 4.15(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).]

Chapter 3 - 21
 Polymorphism/Allotropy
• Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
  Iron system
Titanium:α orβ forms
T liquid
Carbon: 1538°C

Temperature
diamond, graphite δ -Fe BCC
1394°C
• Some metals, as well as
nonmetals, may have γ -Fe FCC
more than one crystal 912°C
structure, a phenomenon
α -Fe BCC
known as polymorphism
• When found in elemental solids, the condition
is often termed allotropy. Chapter 3 - 22
 Crystal Systems
• Because there are many
different possible crystal
structures, it is sometimes
convenient to divide them
into groups according to
unit cell configurations and/
or atomic arrangements.

Chapter 3 - 23
 Point Coordinates
A point coordinate is a lattice position in a unit cell
Determined as fractional multiples ofa , b , and c unit
cell edge lengths
Example: Unit cell upper corner
z • Lattice position is
a, b, c a, b, c
c 111
2. Divide by unit cell edge
lengths (a , b , and c ) and
remove commas
y
a b
x
3. Point coordinates for unit cell corner are 111
Chapter 3 - 24
 Crystallographic Directions I.
Example Problem I Algorithm – determine direction indices
z 1. Determine coordinates of vector tail, pt. 1:
x 1y
, ,&
1 z 1 ; and vector head, pt. 2:x 2
y
,,
2& z 2.
2. Tail point coordinates subtracted from
head point coordinates.
pt. 2
3. Normalize coordinate differences in terms
pt. 1: of lattice parametersa b, , andc :
head
tail y

x
4. Reduce to smallest integer values
5. Enclose indices in square brackets, no
ex: commas uvw
[ ]
pt. 1 x 1
=
0y
,
1=z
0
,
1=0
a
pt. 2 x 2
=y
,=
2z
0
,=
2c
/
2
=> 1, 0, 1/2 => 2, 0, 1
=> [ 201 ]
Chapter 3 - 25
 Crystallographic Directions II:
Example Problem 2
z pt. 2
head 1. Point coordinates of tail and head
tail pt. 1 x 1
=
ay
,1b
/
2
=
,z=
0
1
head pt. 2 x 2
=
-
ay
,2b
=
,z
2c
=
2 & 3. Subtract and normalize
y
pt. 1:
x tail => -2, 1/2, 1
4 & 5. Multiply by 2 to eliminate the fraction, then place in
square brackets (no commas)
-4, 1, 2 => [ 412 ] where the overbar represents a
negative index
Family of directions – all directions that are crystallographically equivalent
(have the same atomic spacing) – indicated by indices in angle brackets
Ex: <100> = [100], [010], [001], [100], [010], [001]
Chapter 3 - 26
Common Crystallographic Directions

Adapted from Fig. 3.7,Callister

& Rethwisch 10e.

Chapter 3 - 27
 Linear Density of Atoms (LD)
number of atoms centered on direction vector
LD = 
length of direction vector

ex: linear density of Al in [110]

direction 
There are 2 half atoms and 1 full atom
= 2 atoms centered on vector

# atoms

2 2 1
LD    3.5 nm
a 2a 2 (0.405 nm)
length
a = 0.405 nm
Chapter 3 - 28
 Crystallographic Planes
Algorithm for determining the Miller Indices of a
plane 
1. If plane passes through selected origin, establish a
new origin in another unit cell
2. Read off values of intercepts of plane (designated
A , B , C ) withx , y , and z axes in terms ofa , b , c
3. Take reciprocals of intercepts
4. Normalize reciprocals of intercepts by multiplying
by lattice parametersa , b , and c
5. Reduce to smallest integer values
6. Enclose resulting Miller Indices in parentheses, no
commas i.e., (hkl )

Chapter 3 - 29
 Crystallographic Planes
Example Problem I

z
x y z
1. Relocate origin – not needed c
2. Intercepts a b ∞c
3. Reciprocals 1/a 1/b 1/∞c
4. Normalize a /a b /b c /∞c
y
a b
1 1 0
5. Reduction 1 1 0 x
6. Miller Indices (110)

Chapter 3 - 30
 Crystallographic Planes
Example Problem II

z
x y z
1. Relocate origin – not needed c
2. Intercepts a /2 ∞b ∞c
3. Reciprocals 2/a 1/∞b 1/∞c
4. Normalize 2a /a b /∞b c /∞c
y
a b
2 0 0
5. Reduction 2 0 0 x
6. Miller Indices (200)

Chapter 3 - 31
 Crystallographic Planes
Example Problem III
x y z z
1. Relocate origin – not needed
c
2. Intercepts a /2 b 3c /4 
3. Reciprocals 2/a 1/b 4/3c
4. Normalize 2a /a b /b 4c /3c  y

2 1 4/3 a b
5. Reduction (x3) 6 3 4 x
6. Miller Indices (634)

Family of planes – all planes that are crystallographically equivalent (have

the same atomic packing) – indicated by indices in braces
Ex: {100} = (100), (010), (001), (100), (010), (001)

Chapter 3 - 32
 Common Crystallographic Planes

Adapted from Fig. 3.11,

Callister & Rethwisch 9e.

Chapter 3 - 33
VMSE Screenshot – Crystallographic Planes

Additional practice on indexing crystallographic planes

Chapter 3 - 34
 Crystallographic Planes (HCP)
• For hexagonal unit cells a similar procedure is used
– Determine the intercepts with thea 1
a
,
2,
an
dza
x
e
s
,t
h e
n
determine the M il
ler-
Brav ai
s In di
cesh
k
,i
,,
a
nl z
d
example a1a
2c
1. Relocate origin – not needed
2. Intercepts a ∞a c
3. Reciprocals 1 /a 1/∞a 1/c a2
4. Normalize a /a a /∞a c /c
1 0 1 a3
5. Reduction h= 1 k =0 l =1
a1
6. Determine index i = -(h +k ) i = -(1 + 0) = -1
7. Miller-Bravais Indices

Chapter 3 - 35
 Planar Density of Atoms (PD)
number of atoms centered on a plane
PD = 
area of plane

ex: planar density of (100) plane of BCC Fe 

2D repeat unit
There are 4 quarter atoms
4 = 1 atom centered on plane
a  R
3
4 4
a  R  (0.1241 nm) = 0.287 nm
3 3

# atoms
Radius of iron, 1 1 atom atoms
R = 0.1241 nm PD    12.1
a2 (0.287 nm)2 nm2
area
Chapter 3 - 36
VMSE Screenshot – Atomic Packing –
(111) Plane for FCC

FCC Unit Cell

Chapter 3 - 37
 X-Ray Diffraction

• To diffract light, the diffraction grating spacing must be

comparable to the light wavelength.
• X-rays are diffracted by planes of atoms.
• Interplanar spacing is the distance between parallel planes
of atoms.  

Chapter 3 - 38
 X-Rays to Determine Crystal Structure
• Crystallographic planes diffract incoming
d X-rays
et
ec
t or

”
“1
in ray
ys

co s
X-
reflections must
-r a

m
be in phase for
X

in

”
“2
“1
a detectable signal,

g
d
te

”
extra
ac λ nλ = 2d sinθ
distance
θ “2 ff r
θ
travelled ” di
by wave “2” spacing
= 2 (d sinθ ) d between
planes

Measurement of X-ray
nλ
, intensity
diffraction angle,θ c d 
(measured 2 sinθ c
allow s com put
a tion
ofBy detector)
i
n terplan arspac ind
g,
.
Diffraction occurs whenθ =θ c
θ
θc
Chapter 3 - 39
 X-Ray Diffraction Pattern
z z z
c c c
(110)
y plane y y
a b a b a b
Intensity (relative)

x x x (211)
plane

(200)
plane

Diffraction angle 2θ
Diffraction pattern for polycrystalline α-iron (BCC)

Chapter 3 - 40
 Summary
• Atoms may assemble into crystalline (ordered) or
amorphous (disordered) 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 calculate the theoretical density of a metal, given
its crystal structure, atomic weight, and unit cell lattice
parameters.
• Crystallographic points, directions and planes may be
specified in terms of indexing schemes.
• Atomic and planar densities are related to
crystallographic directions and planes, respectively.

Chapter 3 - 41
 Summary (continued)

• Materials can exist as single crystals or polycrystalline.

• For most single crystals, properties vary with crystallographic
orientation (i.e., are anisotropic).
• For polycrystalline materials having randomly oriented
grains, properties are independent of crystallographic
orientation (i.e., they are isotropic).
• Some materials can have more than one crystal
structure. This is referred to as polymorphism (or
allotropy).
• X-ray diffraction is used for crystal structure and
interplanar spacing determinations.

Chapter 3 - 42
 ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 3 - 43