Lesson 1a. The Structure of Crystalline Solids

Chapter 3: The Structure of Crystalline Solids
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?
Maykel, Jan 2019 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
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. 3.23(a),
Callister & Rethwisch 8e.
Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.23(b),

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)
Click once on image to start animation

(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
volume
atoms atom
4
a unit cell 1 π (0.5a) 3
3
R=0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 =
1 atom/unit cell
Adapted from Fig. 3.24,
Callister & Rethwisch 8e. Maykel, Jan 2019 Chapter 3 - 7
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 (α), Tantalum, Molybdenum


Click once on image to start animation Callister & Rethwisch 8e.
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
2a
Close-packed directions:
Adapted from R length = 4R = 3 a
Fig. 3.2(a), Callister &
Rethwisch 8e.
a
atoms volume
4
unit cell 2 π ( 3a/4) 3
3 atom
APF =
volume
a3
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

Adapted from Fig. 3.1, Callister & Rethwisch 8e.

Click once on image to start animation
(Courtesy P.M. Anderson) 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
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
Adapted from
Fig. 3.1(a),
Callister & atoms volume
4
π ( 2a/4) 3
Rethwisch 8e.
unit cell 4 atom
3
APF =
volume
a3
unit cell
FCC Stacking Sequence
• ABCABC... Stacking Sequence
• 2D Projection
B B
C
A
A sites B B B
C C
B sites B B
C sites
A
• FCC Unit Cell B
C

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 Adapted from Fig. 3.3(a),
• Coordination # = 12 6 atoms/unit cell

• APF = 0.74 ex: Cd, Mg, Ti, Zn
• c/a = 1.633 Maykel, Jan 2019 Chapter 3 - 13
Theoretical Density, ρ
Mass of Atoms in Unit Cell

Density = ρ =
Total Volume of Unit Cell
nA
ρ =
V C 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

Theoretical Density, ρ
• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
R
Adapted from a a = 4R/ 3 = 0.2887 nm
Fig. 3.2(a), Callister &
Rethwisch 8e.
atoms
g
unit cell 2 52.00 ρtheoretical = 7.18 g/cm3
mol
ρ= ρactual = 7.19 g/cm3
a3 6.022 x 1023
volume atoms
unit cell Maykel, Jan 2019
mol Chapter 3 - 15
Densities of Material Classes
In general Metals/
Graphite/
Composites/
ρmetals > ρceramics > ρpolymers Alloys
Ceramics/
Semicond
Polymers
fibers
30
Why? Platinum
Based on data in Table B1, Callister
20 Gold, W *GFRE, CFRE, & AFRE are Glass,
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
Ceramics have... 5
ρ (g/cm3 )
Titanium
4 Al oxide
• less dense packing 3
Diamond
Si nitride
Aluminum Glass -soda Glass fibers
• often lighter elements Concrete
Silicon PTFE GFRE*
2
Polymers have... Magnesium Graphite
Silicone
Carbon fibers
CFRE*
Aramid fibers
PVC
• low packing density PET
PC
AFRE*
1
(often amorphous) HDPE, PS
PP, LDPE
• lighter elements (C,H,O)
0.5
Composites have... 0.4
Wood
• intermediate values 0.3

Data from Table B.1, Callister & Rethwisch, 8e.
Crystals as Building Blocks
• Some engineering applications require single crystals:
-- diamond single -- turbine blades
crystals for abrasives Fig. 8.33(c), Callister &
Rethwisch 8e. (Fig. 8.33(c)
(Courtesy Martin Deakins,
courtesy of Pratt and
GE Superabrasives,
Whitney).
Worthington, OH. Used with
permission.)
• Properties of crystalline materials

often related to crystal structure.
-- Ex: Quartz fractures more easily
along some crystal planes than
others.

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. Isotropic

• 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).
Single vs Polycrystals
• Single Crystals E (diagonal) = 273 GPa
Data from Table 3.3,
-Properties vary with Callister & Rethwisch
direction: anisotropic. 8e. (Source of data is

R.W. Hertzberg,
Deformation and
-Example: the modulus Fracture Mechanics of
Engineering Materials,
of elasticity (E) in BCC iron: 3rd ed., John Wiley and
Sons, 1989.)
E (edge) = 125 GPa
• Polycrystals
-Properties may/may not 200 µm Adapted from Fig.
4.14(b), Callister &
vary with direction. Rethwisch 8e.
(Fig. 4.14(b) is courtesy
-If grains are randomly of L.C. Smith and C.
Brady, the National
oriented: isotropic. Bureau of Standards,
Washington, DC [now
(Epoly iron = 210 GPa) the National Institute of
-If grains are textured, Standards and
Technology,
anisotropic. Gaithersburg, MD].)

Crystals Growth
Figure 3.20 Schematic diagrams of the various stages in the solidification of a polycrystalline
material; the square grids depict unit cells. (a) Small crystallite nuclei. (b) Growth of the crystallites;
the obstruction of some grains that are adjacent to one another is also shown. (c) Upon completion of
solidification, grains having irregular shapes have formed. (d) The grain structure as it would appear
under the microscope; dark lines are the grain boundaries.
Polymorphism
• Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
iron system
titanium
liquid
α, β-Ti
1538ºC
BCC δ-Fe
carbon
diamond, graphite 1394ºC
FCC γ-Fe
912ºC
BCC α-Fe

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 & Rethwisch 8e.

Point Coordinates
z
111 Point coordinates for unit cell
c center are
a/2, b/2, c/2 ½½½
000
y
a b
Point coordinates for unit cell
x • corner are 111
z 2c
•
Translation: integer multiple of
• • lattice constants  identical
b y position in another unit cell
b
Crystallographic Directions
z pt. 2
Example 2:
head
pt. 1 x1 = a, y1 = b/2, z1 = 0
pt. 2 x2 = -a, y2 = b, z2 = c
y
pt. 1:
x tail => -2, 1/2, 1
Multiplying by 2 to eliminate the fraction
-4, 1, 2 => [ 412 ] where the overbar represents a

negative index
families of directions <uvw>

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
y 3. Adjust to smallest integer values
4. Enclose in square brackets, no commas
x [uvw]
ex: 1, 0, ½ => 2, 0, 1 => [ 201 ]

-1, 1, 1 => [ 111 ] where overbar represents a
negative index
families of directions <uvw>
Linear Density
Number of atoms
• Linear Density of Atoms ≡ LD = Unit length of direction vector
[110]
ex: linear density of Al in [110]
direction
a = 0.405 nm
# atoms
a 2
LD = = 3.5 nm−1
2a
Adapted from
Fig. 3.1(a),
Callister & length
Rethwisch 8e.

HCP Crystallographic Directions
z
Algorithm
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of unit
a2 cell dimensions a1, a2, a3, or c
3. Adjust to smallest integer values
- 4. Enclose in square brackets, no commas
a3
[uvtw] a2
a1
Adapted from Fig. 3.8(a),
a2 -a3
2
ex: ½, ½, -1, 0 => [ 1120 ] a3

a1
2
dashed red lines indicate
projections onto a1 and a2 axes a1
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 ]

1
u = (2 u ' - v ')
3
a2
1
v = (2 v ' - u ')
- 3
a3
t = - (u +v )
a1
w = w'
Fig. 3.8(a), Callister & Rethwisch 8e.

Crystallographic Planes

• Miller Indices: Reciprocals of the (three) axial
intercepts for a plane, cleared of fractions &
common multiples. All parallel planes have
same Miller indices.
• Algorithm
1. Read off intercepts of plane with axes in
terms of a, b, c
2. Take reciprocals of intercepts
3. Reduce to smallest integer values
4. Enclose in parentheses, no
commas i.e., (hkl)

z
example a b c
1. Intercepts 1 1 ∞ c
2. Reciprocals 1/1 1/1 1/∞
1 1 0
3. Reduction 1 1 0 y
a b
4. Miller Indices (110)
x
z
example a b c
1. Intercepts 1/2 ∞ ∞ c
2. Reciprocals 1/½ 1/∞ 1/∞
2 0 0
3. Reduction 2 0 0
y
4. Miller Indices (100) a b
x
z
example a b c c
1. Intercepts 1/2 1 3/4 •
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)

Crystallographic Planes (HCP)
• In hexagonal unit cells the same idea is used
z
example a1 a2 a3 c
1. Intercepts 1 ∞ -1 1
2. Reciprocals 1 1/∞ -1 1
1 0 -1 1 a2
3. Reduction 1 0 -1 1
a3
4. Miller-Bravais Indices (1011) a1
Adapted from Fig. 3.8(b),


• We want to examine the atomic packing of
crystallographic planes
• Iron foil can be used as a catalyst. The
atomic packing of the exposed planes is
important.
a) Draw (100) and (111) crystallographic planes
for Fe.
b) Calculate the planar density for each of these
planes.

Planar Density of (100) Iron
Solution: At T < 912ºC iron has the BCC structure.
2D repeat unit
(100) 4 3
a= R
3
Adapted from Fig. 3.2(c), Callister & Rethwisch 8e. Radius of iron R = 0.1241 nm
atoms
2D repeat unit 1
1 atoms atoms
Planar Density = = 2 = 12.1 = 1.2 x 1019
area a2 4 3 nm 2 m2
R
2D repeat unit 3
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
3
h= a
2
2
 4 3  16 3 2
area = 2 ah = 3 a = 3 
2
R  = R
atoms  3  3
2D repeat unit 1
atoms = atoms
Planar Density = = 7.0 0.70 x 1019
area 16 3 2
2nm m2
R
2D repeat unit 3
VMSE Planar Atomic Arrangements
• VMSE allows you to view planar arrangements and rotate
them in 3 dimensions
BCC (110) Plane

X-Ray Diffraction
• Diffraction gratings must have spacings comparable to

the wavelength of diffracted radiation.
• Can’t resolve spacings < λ
• Spacing is the distance between parallel planes of
atoms.
X-Rays to Determine Crystal Structure
• Incoming X-rays diffract from crystal planes.
reflections must
be in phase for
a detectable signal
extra
distance
λ Adapted from Fig. 3.20,
travelled θ θ Callister & Rethwisch 8e.
by wave “2” spacing
d between
planes
Measurement of X-ray
intensity nλ
critical angle, θc, d=
(from 2 sin θc
allows computation of
detector)
planar spacing, d.
θ
θc
X-Ray Diffraction Pattern
z z z
c c c
y (110) y y
a b a b a b
Intensity (relative)
x x x (211)
(200)
Diffraction angle 2θ
Diffraction pattern for polycrystalline α-iron (BCC)

Adapted from Fig. 3.22, Callister 8e.

SUMMARY
• Atoms may assemble into crystalline or
amorphous 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 predict the density of a material, provided we
know the atomic weight, atomic radius, and crystal
geometry (e.g., FCC, BCC, HCP).
• Crystallographic points, directions and planes are
specified in terms of indexing schemes.
Crystallographic directions and planes are related
to atomic linear densities and planar densities.

SUMMARY
• Materials can be single crystals or polycrystalline.

Material properties generally vary with single crystal
orientation (i.e., they are anisotropic), but are generally
non-directional (i.e., they are isotropic) in polycrystals
with randomly oriented grains.
• 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.

ANNOUNCEMENTS
Reading:
Core Problems:
Self-help Problems:

Lesson 1a. The Structure of Crystalline Solids

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Lesson 1a. The Structure of Crystalline Solids

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Chapter 3: The Structure of Crystalline Solids

• How do atoms assemble into solid structures?

• How does the density of a material depend on

• When do material properties vary with the

Maykel, Jan 2019 Chapter 3 - 1

• Dense, ordered packing Energy

Dense, ordered packed structures tend to have

Maykel, Jan 2019 Chapter 3 - 3

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

We will examine three such structures...

Maykel, Jan 2019 Chapter 3 - 5

Click once on image to start animation

Maykel, Jan 2019 Chapter 3 - 6

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

Adapted from Fig. 3.2,

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

Adapted from Fig. 3.1, Callister & Rethwisch 8e.

Maykel, Jan 2019 Chapter 3 - 10

Maykel, Jan 2019 Chapter 3 - 12

A sites Top layer

A sites Bottom layer

• Coordination # = 12 6 atoms/unit cell

Mass of Atoms in Unit Cell

where n = number of atoms/unit cell

Maykel, Jan 2019 Chapter 3 - 14

• intermediate values 0.3

• Properties of crystalline materials

Maykel, Jan 2019 Chapter 3 - 17

Adapted from Fig. K,

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

direction: anisotropic. 8e. (Source of data is

Maykel, Jan 2019 Chapter 3 - 19

Maykel, Jan 2019 Chapter 3 - 21

a, b, and c are the lattice constants

Fig. 3.4, Callister & Rethwisch 8e.

Maykel, Jan 2019 Chapter 3 - 22

Multiplying by 2 to eliminate the fraction

-4, 1, 2 => [ 412 ] where the overbar represents a

families of directions <uvw>

ex: 1, 0, ½ => 2, 0, 1 => [ 201 ]

Maykel, Jan 2019 Chapter 3 - 26

ex: ½, ½, -1, 0 => [ 1120 ] a3

[ u 'v 'w ' ] → [ uvtw ]

Maykel, Jan 2019 Chapter 3 - 28

Adapted from Fig. 3.10,

Maykel, Jan 2019 Chapter 3 - 30

4. Miller Indices (634) x

Family of Planes {hkl}

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

4. Miller-Bravais Indices (1011) a1

Adapted from Fig. 3.8(b),

Maykel, Jan 2019 Chapter 3 - 33

Maykel, Jan 2019 Chapter 3 - 34

BCC (110) Plane

Maykel, Jan 2019 Chapter 3 - 37

• Diffraction gratings must have spacings comparable to

Diffraction pattern for polycrystalline α-iron (BCC)

Maykel, Jan 2019 Chapter 3 - 40

Maykel, Jan 2019 Chapter 3 - 41

• Materials can be single crystals or polycrystalline.

Maykel, Jan 2019 Chapter 3 - 42

Maykel, Jan 2019 Chapter 3 - 43

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