Materials and Metallurgy (ME-209)

Week 4 – The Structure of Crystalline Solids

Course Instructor:
Shehzaib Yousuf Khan
B.Engg, M.Engg in Mechanical Engineering from NEDUET.
M.P.E. in Mechanical Engineering from Sydney University.
Ph.D. (In Progress)
www.digiomnibus.pk
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Chapter 3 : The Structure of Crystalline Solids
Learning Objectives
After studying this chapter, you should be able to do the following:
1. Describe the difference in atomic/molecular structure between crystalline and non-
crystalline materials.
2. Draw unit cells for face-centered cubic, body-centered cubic, and hexagonal close-
packed crystal structures.
3. Derive the relationships between unit cell edge length and atomic radius for face-
centered cubic and body-centered cubic crystal structures.
4. Compute the densities for metals having face-centered cubic and body-centered
cubic crystal structures given their unit cell dimensions.
5. Given three direction index integers, sketch the direction corresponding to these
indices within a unit cell.
6. Specify the Miller indices for a plane that has been drawn within a unit cell.
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Chapter 3 : Mechanical Properties of Metals
Learning Objectives
After studying this chapter, you should be able to do the following:
7. Describe how face-centered cubic and hexagonal close-packed crystal structures may
be generated by the stacking of close-packed planes of atoms.
8. Distinguish between single crystals and polycrystalline materials.
9. Define isotropy and anisotropy with respect to material properties

Issues to Address
• How do atoms assemble into solid structures?
• How does the density of a material depend on its structure?
• When do material properties vary with the sample (i.e., part) orientation?
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WHY STUDY The Structure of Crystalline Solids?
• The properties of some materials are directly related to their crystal structures.
• For example, pure and undeformed magnesium and beryllium, having one crystal
structure, are much more brittle (i.e., fracture at lower degrees of deformation) than are
pure and undeformed metals such as gold and silver that have yet another crystal
structure.

• Furthermore, significant property differences exist between crystalline and non-

crystalline materials having the same composition.
• For example, non-crystalline ceramics and polymers normally are optically transparent;
the same materials in crystalline (or semicrystalline) form tend to be opaque or, at best,
translucent.

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Energy and Packing
• Non dense, random packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

• Dense, ordered packing

Dense, ordered packed structures tend Energy
to have lower energies.
typical neighbor
bond length

typical neighbor r
bond energy
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 Solid materials may be classified according to the regularity with
Materials and Packing which atoms or ions are arranged with respect to one another.

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Materials and Packing
Crystalline materials...
• atoms pack in periodic, 3D arrays • typical of:
➢ metals crystalline SiO2
➢ many ceramics
➢ some polymers
Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing • occurs for:
➢ complex structures
➢ rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2

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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

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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...

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Cubic Crystal Structures

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Simple Cubic Structure (SC)
• Rare due to low packing density (only Po has this structure) • Coordination # = 6
• Close-packed directions are cube edges. (# nearest neighbors)

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Atomic Packing Factor (APF)
volume
atoms atom
Volume of atoms in unit cell* 4
APF = unit cell 1 𝜋 0.5𝑎 3
Volume of unit cell 3
𝐴𝑃𝐹 =
*assume hard spheres
𝑎3 volume
unit cell
• APF for a simple cubic structure = 0.52

a
R=0.5a

close-packed directions
contains 8 x 1/8 =
12
1 atom/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

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

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Atomic Packing Factor: BCC
• APF for a body-centered cubic structure = 0.68

atoms volume
4 3
unit cell 2 𝜋 3𝑎 Τ4 atom
3
𝐴𝑃𝐹 =
volume
𝑎3
unit cell
3a

2a
R
a Close-packed directions:
length = 4R = 3 a
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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

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

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Atomic Packing Factor: FCC
• APF for a face-centered cubic structure = 0.74

atoms volume
4 3
unit cell 4 𝜋 2𝑎 Τ4 atom
3
𝐴𝑃𝐹 =
2a volume
𝑎3
unit cell
maximum achievable APF
a
Close-packed directions:
length = 4R = 2 a

Unit cell contains:

6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell 16
FCC Stacking Sequence
• ABCABC... Stacking Sequence
• 2D Projection
B B
C
C
A
A sites B B B
C
C C
C
B sites B B
C sites

A
• FCC Unit Cell B
C

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Hexagonal Close-packed Structure (HCP)

• ABAB... Stacking Sequence

• 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
• c/a = 1.633 18
Theoretical Density Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
Mass of Atoms in Unit Cell
Density =  = n = 2 atoms/unit cell
Total Volume of Unit Cell

nA a = 4R/ 3 = 0.2887 nm
 =
VC NA

Where n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadro’s number
= 6.022 x 1023 atoms/mol R
a
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Theoretical Density
atoms
g
unit cell 2 52.00
Mass of Atoms in Unit Cell mol
Density =  = =
Total Volume of Unit Cell
a3 6.022 x 1023
nA volume atoms
 =
VC NA unit cell mol

theoretical = 7.18 g/cm3

actual = 7.19 g/cm3

R
a
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Densities of Different Classes Metals/
Alloys
Graphite/
Ceramics/ Polymers
Composites/
fibers
Semicond
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In general Based on data in Table B1, Callister

metals > ceramics > polymers 20 Platinum *GFRE, CFRE, & AFRE are Glass,
Gold, W
Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
Why? 10 Silver, Mo
60% volume fraction of aligned fibers
in an epoxy matrix).
Cu,Ni
Metals have... Steels
Tin, Zinc
Zirconia
• close-packing

 (g/cm3 )
5
Titanium
(metallic bonding) 4 Al oxide
Diamond
3 Si nitride
• often large atomic masses Aluminum Glass -soda Glass fibers
Concrete
Ceramics have... 2
Magnesium
Silicon PTFE GFRE*
Carbon fibers
Graphite CFRE*
• less dense packing Silicone
PVC Aramid fibers
AFRE*
PET
• often lighter elements 1 PC
HDPE, PS
PP, LDPE
Polymers have...
• low packing density 0.5
Wood
(often amorphous) 0.4
• lighter elements (C,H,O) 0.3

Composites have...
• intermediate values
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Crystals as Building Blocks
• Some engineering applications require single crystals:

→ diamond single crystals for abrasives → turbine blades

(Courtesy Martin Deakins, Fig. 8.33(c), Callister &

GE Superabrasives, Rethwisch 8e. (Fig. 8.33(c)
Worthington, OH. Used courtesy of Pratt and
with permission.) Whitney).

• Properties of crystalline materials often related to crystal structure.

Example : Quartz fractures more easily along
some crystal planes than others.

(Courtesy P.M. Anderson)

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Polycrystals • Most engineering materials are polycrystals.

Anisotropic

Adapted from Fig. K,

color inset pages of
Callister 5e.
(Fig. K is courtesy of
Paul E. Danielson,
Teledyne Wah Chang
1 mm Albany)

Isotropic
• 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 typically range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers). 23
Polycrystals E (diagonal) = 273 GPa
Data from Table 3.3,
• Single Crystals Callister & Rethwisch
8e. (Source of data is
- Properties vary with direction: anisotropic. R.W. Hertzberg,
Deformation and
- Example: the modulus of elasticity (E) in BCC iron: Fracture Mechanics of
Engineering Materials,
3rd ed., John Wiley and
Sons, 1989.)
E (edge) = 125 GPa

200 mm Adapted from Fig.

4.14(b), Callister &
• Polycrystals Rethwisch 8e.
(Fig. 4.14(b) is courtesy
- Properties may/may not vary with direction. of L.C. Smith and C.
Brady, the National
- If grains are randomly oriented: isotropic. Bureau of Standards,
Washington, DC [now
(Epoly iron = 210 GPa) the National Institute of
Standards and
- If grains are textured, anisotropic. Technology,
Gaithersburg, MD].)

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Crystal System 7 crystal systems 14 crystal lattices

Unit cell:

Smallest repetitive volume which contains the complete lattice pattern of a crystal.

Fig. 3.4, Callister & Rethwisch 8e.

a, b, and c are the lattice constants
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Crystal System
A crystal is a solid material
with a highly ordered,
repeating pattern of atoms,
ions, or molecules in three
dimensions.

A lattice is the regular,

repeating arrangement of
lattice points that defines
the crystal structure.

Crystal Structure = Lattice + Basis

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 Non-primitive Unit Cell
Crystal System
Primitive Unit Cell:
The smallest repeating unit in a crystal lattice,
containing only one lattice point at its corners.

Primitive Unit Cell

Conventional Unit Cell:

A larger repeating unit in a crystal lattice,
containing more than one lattice point, usually at
the corners, face centers, or body centers.

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Point Coordinates
z
111 Point coordinates for unit cell center are
c
𝑎 𝑏 𝑐 1 1 1
→
2 2 2 2 2 2
000
y
a b
Point coordinates for unit cell corner are 111
x •
z 2c
•
Translation: integer multiple of lattice constants
→ identical position in another unit cell
• •
b y
b 28
Crystallographic Directions
z pt. 2
head Example 2:
pt. 1 𝑥1 = 𝑎 , 𝑦1 = 𝑏Τ2 , 𝑧1 = 0
pt. 2 𝑥2 = −𝑎 , 𝑦2 = 𝑏 , 𝑧2 = 𝑐

y 𝑏
−𝑎 − 𝑎 𝑏 − 2 𝑐 − 0 1
, , ⇒ −2 , , 1
pt. 1: 𝑎 𝑏 𝑐 2
x tail

Multiplying by 2 to eliminate the fraction

−4, 1, 2 ⇒ [ 412 ] where the overbar represents a negative index

families of directions <uvw>

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Crystallographic Directions
z Algorithm
1. Vector repositioned (if necessary) to pass through origin.
2. Read off projections in terms of unit cell dimensions a, b, and c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas
y
[uvw]
x

ex: 1, 0, 1/2 ⇒ 2, 0, 1 ⇒ [ 201 ]

-1, 1, 1 ⇒ [ 111 ] where overbar represents a negative index

families of directions <uvw>

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Linear Density
Number of atoms
Linear Density = 𝐿𝐷 =
Unit length of direction vector
[110]

ex: linear density of Al in [110] direction

𝑎 = 0.405 nm

# atoms
a
2
Adapted from
LD = = 3.5 nm-1
Fig. 3.1(a),
Callister & length 2a
Rethwisch 8e.

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HCP Crystallographic Directions
z
Algorithm
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 a2
a2 4. Enclose in square brackets, no commas
a2 -a3
[uvtw]
2
a3
- a3
a1
a1
2
Adapted from Fig. 3.8(a), dashed red lines indicate
Callister & Rethwisch 8e.
projections onto a1 and a2 axes a1

ex: 1/2, 1/2, -1, 0 ⇒ [ 1120 ]

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HCP Crystallographic Directions
z
Miller-Bravais lattice coordinates are used in hexagonal crystal
systems because they reveal hexagonal symmetry more clearly.

4 parameter Miller-Bravais lattice coordinates are related to the

a2 direction indices (i.e., u'v'w') as follows.

a3
- [ u 'v 'w ' ] = [ uvtw ]
a1 1
u = ( 2 u ' - v ')
Fig. 3.8(a), Callister & Rethwisch 8e. 3
1
Hexagonal Crystals v = ( 2 v ' - u ')
3
t = - (u + v )
w = w' 33
Crystallographic Planes

Adapted from Fig. 3.10,

Callister & Rethwisch 8e.
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Crystallographic Planes
z
Miller Indices: c
Reciprocals of the (three) axial intercepts for a plane, cleared
of fractions & common multiples.
y
a b
All parallel planes have same Miller indices. x
z
Algorithm
1. Read off intercepts of plane with axes in terms of a, b, c c
2. Take reciprocals of intercepts
3. Reduce to smallest integer values y
4. Enclose in parentheses, no commas i.e., (hkl) a b
x
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Crystallographic Planes
z
Example a b c
c
1. Intercepts 1 1 ∞
2. Reciprocals 1/1 1/1 1/∞
1 1 0 y
3. Reduction 1 1 0 a b
4. Miller Indices (110) x
z
Example a b c c
1. Intercepts 1/2 ∞ ∞
2. Reciprocals 1/½ 1/∞ 1/∞
2 0 0 y
3. Reduction 2 0 0 a b
4. Miller Indices (200) x
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Crystallographic Planes
Example a b c z

1. Intercepts 1/2 1 3/4 c

•
2. Reciprocals 1/½ 1/1 1/¾
2 1 4/3 • y
•
3. Reduction 6 3 4 a b

4. Miller Indices (634) x

Family of Planes {hkl}

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

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