Materials Science & Engineering

2023.1 semester

Mechanical Engineering Dep’t

Prof. Suh Wang Byuck

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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?

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 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.
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 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.

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 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...
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 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.

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 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

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 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
directions
Unit cell contains 1 atom = 8 x 1/8 = 1 atom/unit cell

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 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 () • Coordination # = 8

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

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

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

4R = 3 a

2a

For close-packed directions

R R = 3 a/4
a
volume
atoms
4 3 atom
unit cell 2 π ( 3a/4 )
3
APF =
volume a3
unit cell 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, 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

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 Atomic Packing Factor: FCC
• APF for the face-centered cubic structure = 0.74
maximum achievable APF
For close-packed directions:
æ 2a ö
4R = 2 a çi.e., R = ÷
2a ç 4 ÷
è ø
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 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.

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 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
• Ideal c/a = 1.633
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 Theoretical Density for Metals, 

Mass of Atoms in Unit Cell

Density =  = =
Total Volume of Unit Cell

nA
 =
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

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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 = a3 = 2.406 x 10-23 cm3
atoms g
unit cell mol
n A 2 52.00
= = = 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
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 Densities Comparison for Four Material Types
In general Metals/
Graphite/
Composites/
ρ metals > ρ ceramics > ρ polymers Alloys
Ceramics/
Semicond
Polymers
fibers
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Why? Platinum
Based 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 )
5
Ceramics have... 4
Titanium
Al oxide
• often lighter elements 3
Diamond
Si nitride
Aluminum Glass -soda Glass fibers
Polymers have... 2
Concrete
Silicon PTFE GFRE*
Carbon fibers
• low packing density Magnesium Graphite
Silicone CFRE*
Aramid fibers
PVC AFRE*
(often amorphous) 1
PET
PS
• lighter elements (C,H,O) PE

Composites have... 0.5

• moderate to low densities 0.4
Wood

0.3

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

(Courtesy P.M. Anderson)

Deakins, GE
Superabrasives,
Worthington, OH.
Used with
permission.)

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

1 mm
Chang Albany

small
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).
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 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

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 Isotropy
• Polycrystals
200 μm
- Properties may/may not
vary with direction.
- If grains randomly oriented:
properties isotropic.
(Epoly iron = 210 GPa)
- 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).]

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

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

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 Point Coordinates
A point coordinate is a lattice position 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
111 a, b, c
c
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
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 Crystallographic Directions I.
Example Problem I Algorithm – determine direction indices
z 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.
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 smallest 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 ]
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 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 b-b 2 c -0
= -2; = 1/ 2; =1
a b c
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

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Common Crystallographic Directions

Adapted from Fig. 3.7, Callister

& Rethwisch 10e.

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

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 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)

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 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)

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Common Crystallographic Planes

Adapted from Fig. 3.11,

Callister & Rethwisch 9e.

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 Planar Density of Atoms (PD)
number of atoms centered on a plane
PD
area of plane
=

2D repeat unit
ex: planar density of (100) plane of BCC Fe
There are 4 quarter atoms
4
a= R = 1 atom centered on plane
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
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 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.

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 X-Rays to Determine Crystal Structure
• Crystallographic planes diffract incoming X-rays

reflections must
be in phase for
a detectable signal,
extra
distance
λ nλ= 2d sinθ
travelled θ θ
by wave “2” spacing
= 2 (d sinθ) d between
planes

Measurement of X-ray
nλ
diffraction angle, θc, intensity d=
(measured 2 sin θc
allows computation of
By detector)
interplanar spacing, d.
Diffraction occurs when θ = θ c
θ
θc
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 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)

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 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.

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 Summary (continued)

• Materials can exist as single crystals or polycrystalline.

• For most single crystals, properties vary with crystallographic
orientation (i.e., are anisotropic).
• Some materials can have more than one crystal
structure. This is referred to as polymorphism (or
allotropy).

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 ■End of Document

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