Chapter 3: The Structure of Crystalline Solids

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, ________________ Energy

typical neighbor
bond length

typical neighbor r
bond energy

• Dense, ____________________ Energy

typical neighbor
bond length

typical neighbor r
bond energy

Ordered structures tend to be nearer the

________ in bonding energy and are more stable.
Chapter 3 - 2

Materials and Atomic Arrangments

Crystalline materials...
• atoms arranged in _______, 3D arrays
• typical of: -________
-many ___________
-some ___________ crystalline SiO2
Adapted from Fig. 3.24(a),
Callister & Rethwisch 10e.

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

Chapter 3 - 3

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Chapter 3: The Structure of Crystalline Solids

Metallic Crystal Structures:

Atomic Packing
• Dense atomic packing for crystal structures
of metals.
• Reasons for dense packing:
- Bonds between metal atoms are ____________.
- ________________ distances tend to be small in
order to _______ bond energy.
- High degree of shielding (of ion cores) provided
by ___________________.
• Crystal structures for metals ________ 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 ______________ are cube edges.
ex: Po • Coordination # = ___
(# nearest neighbors)

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

Chapter 3 - 5

Definitions
Coordination Number

Coordination Number = number of ______________

or touching atoms

Atomic Packing Factor (APF)

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

Chapter 3 - 6

2
Chapter 3: The Structure of Crystalline Solids

Atomic Packing Factor (APF)

for Simple Cubic

volume
atoms atom
4
a unit cell 1 π (0.5a) 3
3
R = 0.5a APF = = 0.52
a3 volume
unit cell
close-packed
__________
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 __________ 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, ___ • Coordination # = 8

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

2 atoms/unit cell: 1 center + 8 ______________

Chapter 3 - 8

VMSE Screenshot – BCC Unit Cell

Chapter 3 - 9

3
Chapter 3: The Structure of Crystalline Solids

Atomic Packing Factor: BCC

• APF for the body-centered ___________ structure = 0.68

4R = 3 a

2a

For close-packed ___________

R R = 3 a/4
a
volume
atoms
4 atom
unit cell 2 π ( 3a/4 ) 3 3
3 8 ! 3$
APF = = π ## & = 0.68
3 " 4 &%
volume a3
unit cell Chapter 3 - 10

Face-Centered Cubic Structure (FCC)

• Atoms located at 8 cube corners and at the _______ of the 6 faces.
--Note: All atoms in the animation are __________; the face-centered atoms
are shaded differently for ease of viewing.
ex: Al, Cu, Au, Pb, Ni, Pt, Ag • Coordination # = ___

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

4 atoms/unit cell: 6 __________ + 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 = 2 a ⎜i.e., R = 2a ⎟
2a ⎜ 4 ⎟
⎝ ⎠
Unit cell contains: ______________
a = _________________
atoms volume
4 atom
unit cell _ π ( 2a/4 ) 3
3
APF = = 0.74
__ volume
unit cell Chapter 3 - 12

4
Chapter 3: The Structure of Crystalline Solids

FCC Plane Stacking Sequence

• ABCABC... _________ 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 _____ 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 # = ___ __ atoms/unit cell

• APF = _______ ex: Cd, Mg, Ti, Zn
• Ideal c/a = _________
Chapter 3 - 14

Theoretical Density for Metals, ρ

Mass of Atoms in Unit Cell (nA / NA )

Density = ρ = =
Total Volume of Unit Cell VC
nA
ρ =
VC NA

where n = ____________________________
A = atomic weight
VC = _________________ = ____________
NA = Avogadro’s number
= 6.022 x 1023 atoms/mol

Chapter 3 - 15

5
Chapter 3: The Structure of Crystalline Solids

Theoretical Density Computation for Chromium

• Cr has BCC crystal structure
A = 52.00 g/mol
R = ____________
n = 2 atoms/unit cell
a = 4R/ 3 = 0.2887 nm
R
a VC = a3 = 2.406 x 10-23 cm3
atoms g
unit cell mol
n A _ 52.00
ρ= = = 7.19 g/cm3
VC NA 2.406 x 10-23 6.022 x 1023 atoms
volume mol
unit cell ρactual = 7.15 g/cm3
Chapter 3 - 16

Densities Comparison for Four Material Types

In general Metals/
Graphite/
Composites/
ρ metals > ρ ceramics > ρ polymers Alloys
Ceramics/
Semicond
Polymers
fibers
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 ______ atomic masses Tin, Zinc
Zirconia
ρ (g/cm3 )

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

Composites have... 0.5

Wood
• _____________ densities 0.4
0.3

Chapter 3 - 17

Single Crystals
• When the periodic arrangement of atoms (______ structure)
extends without interruption throughout the entire specimen.
-- diamond single -- single crystal for
crystals for ___________ 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

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Chapter 3: The Structure of Crystalline Solids

Polycrystalline Materials
• Most engineering materials are composed of many small,
single crystals (i.e., are __________________).
______
grain
Courtesy of Paul E. Danielson, Teledyne Wah

1 mm
Chang Albany

______
grain
• Nb-Hf-W plate with an electron beam weld.
• Each ________ 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

________________________ 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 ________________:
properties _____________.
(Epoly iron = 210 GPa)
- If grains ___________ (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

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Chapter 3: The Structure of Crystalline Solids

Polymorphism/Allotropy
• Two or more distinct _______ structures for the same
material (allotropy/polymorphism)
Iron system
Titanium: α or β forms T
liquid
1538°C
Carbon:

Temperature
δ -Fe BCC
___________, graphite
1394°C
γ -Fe FCC
912°C
α -Fe BCC

Chapter 3 - 22

Point Coordinates
A point coordinate is a _____________ in a unit cell
Determined as fractional multiples of a, b, and c unit
cell edge lengths
Example: Unit cell upper corner
z 1. Lattice position is
a, b, c a, b, c
c
2. Divide by unit cell edge
lengths (a, b, and c) and
remove commas
y
a b a b c
= 111
x a b c

3. Point coordinates for unit cell corner are 111

Chapter 3 - 23

Crystallographic Directions I.
Example Problem I Algorithm – determine direction indices
z 1. Determine __________ 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.
pt. 2
3. Normalize coordinate differences in terms
pt. 1: of lattice parameters a, b, and c:
head y
tail
x 2 − x1 y 2 − y1 z2 − z1
a b c
x 4. Reduce to _________ integer
values
5. Enclose indices in square brackets, no
ex: commas [uvw]
pt. 1 x1 = 0, y1 = 0, z1 = 0
pt. 2 x2 = a, y2 = 0, z2 = c/2
=> 1, 0, 1/2 => 2, 0, 1
a−0 0−0 c 2−0
a b c => [ 201 ]
Chapter 3 - 24

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Chapter 3: The Structure of Crystalline Solids

Crystallographic Directions II:

Example Problem 2
z pt. 2
head 1. Point coordinates of tail and head
tail pt. 1 x1 = a, y1 = b/2, z1 = 0
head pt. 2 x2 = -a, y2 = b, z2 = c
2 & 3. Subtract and normalize
y −a − a
= −2;
b−b 2
= 1/ 2;
c −0
=1
a b c
pt. 1:
x tail => __________
4 & 5. Multiply by 2 to eliminate the fraction, then place in
square brackets (no commas)
__________________ where the overbar represents a
negative index
__________________ – 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 - 25

Common Crystallographic Directions

Adapted from Fig. 3.7, Callister

& Rethwisch 10e.

Chapter 3 - 26

Linear Density of Atoms (LD)

number of atoms centered on direction vector
LD =
length of direction vector

ex: linear _____ of Al in [110] direction

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

# atoms

2
LD = = = 3.5 nm-1
a 2a 2 (0.405 nm)
length
a = 0.405 nm
Chapter 3 - 27

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Chapter 3: The Structure of Crystalline Solids

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) with x, y, and z axes in terms of a, b, c
3. Take reciprocals of intercepts
4. Normalize reciprocals of intercepts by multiplying
by lattice parameters a, b, and c
5. Reduce to smallest integer values
6. Enclose resulting Miller Indices in parentheses, no
commas i.e., (hkl)

Chapter 3 - 28

Crystallographic Planes
Example Problem I

x y z
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 - 29

Crystallographic Planes
Example Problem II

x y z
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 - 30

10
Chapter 3: The Structure of Crystalline Solids

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 - 31

Common Crystallographic Planes

Adapted from Fig. 3.11,

Callister & Rethwisch 9e.

Chapter 3 - 32

VMSE Screenshot – Crystallographic Planes

Additional practice on indexing crystallographic planes

Chapter 3 - 33

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Chapter 3: The Structure of Crystalline Solids

Crystallographic Planes (HCP)

• For hexagonal unit cells a similar procedure is used
– Determine the intercepts with the a1, a2, and z axes, then
determine the _________ Indices h, k, i, and l z

example a1 a2 c
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 (1011)

Chapter 3 - 34

Planar Density of Atoms (PD)

number of atoms centered on a plane
PD =
area of plane

2D repeat unit
ex: ___________ of (100) plane of BCC Fe
There are __________ atoms
4
a= R = 1 atom centered on plane
3
4 4
a= R = (0.1241 nm) = 0.287 nm
3 3

# atoms
________ of iron, 1 atom atoms
R = 0.1241 nm PD = = = ____
a2 (0.287 nm)2 nm2
area
Chapter 3 - 35

VMSE Screenshot – Atomic Packing –

(111) Plane for FCC

FCC Unit Cell

Chapter 3 - 36

12
Chapter 3: The Structure of Crystalline Solids

X-Ray Diffraction

• To _________ light, the diffraction grating spacing must be

comparable to the light _______________.
• X-rays are ____________ by planes of atoms.
• Interplanar spacing is the distance between _______ planes
of atoms.

Chapter 3 - 37

X-Rays to Determine Crystal Structure

• Crystallographic planes _________d incoming X-rays
et
ec
to
”

r
“1
in -ray

ys
co s
X

reflections must
ra
m

be in phase for
X-
”
in

“2
“1
g

a detectable signal,
ed
”

extra ct λ nλ = 2d sinθ
“2

a
distance
θ ffr θ
”

travelled di
by wave “2” spacing
= 2 (d sinθ) d between
planes

Measurement of X-ray
intensity nλ
______________, θc, d=
(measured 2 sin θc
allows computation of
By detector)
interplanar spacing, d.
___________ occurs when θ = θc
θ
θc
Chapter 3 - 38

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 - 39

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Chapter 3: The Structure of Crystalline Solids

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 - 40

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 - 41

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