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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?

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.
Chapter 3 - 2

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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),
Callister & Rethwisch 8e.

Chapter 3 - 3

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

Chapter 3 - 4

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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...

Chapter 3 - 5

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)

Chapter 3 - 6

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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
a 4 3
unit cell 1 p (0.5a)
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. 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 (), Tantalum, Molybdenum

Coordination # = 8

Adapted from Fig. 3.2,

Click once on image to start animation Callister & Rethwisch 8e.

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

(Courtesy P.M. Anderson)

Chapter 3 - 8

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Atomic Packing Factor: BCC

APF for a body-centered cubic structure = 0.68
3a

2a

Close-packed directions:
R length = 4R = 3 a
a
Adapted from
Fig. 3.2(a), Callister &
Rethwisch 8e.

atoms volume
4
unit cell 2 p ( 3a/4) 3
3 atom
APF =
volume
a3
unit cell Chapter 3 - 9

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

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

Chapter 3 - 10

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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

atoms
Fig. 3.1(a),
Callister &
4 volume
unit cell 4 p ( 2a/4) 3
Rethwisch 8e.

3 atom
APF =
volume
a3
unit cell
Chapter 3 - 11

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

Chapter 3 - 12

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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 Adapted from Fig. 3.3(a),
Callister & Rethwisch 8e.

Coordination # = 12 6 atoms/unit cell

APF = 0.74 ex: Cd, Mg, Ti, Zn
c/a = 1.633 Chapter 3 - 13

Theoretical Density, r

Mass of Atoms in Unit Cell

Density = r =
Total Volume of Unit Cell

nA
r =
VC NA

where n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadros number
= 6.022 x 1023 atoms/mol

Chapter 3 - 14

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Theoretical Density, r
Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
R
Adapted from
Fig. 3.2(a), Callister &
a a = 4R/ 3 = 0.2887 nm

atoms
Rethwisch 8e.

g
unit cell 2 52.00 rtheoretical = 7.18 g/cm3
mol
r= ractual = 7.19 g/cm3
a3 6.022 x 1023
volume atoms
unit cell mol Chapter 3 - 15

Densities of Material Classes

In general
rmetals > rceramics > rpolymers
Graphite/
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond

Why?
30
Based on data in Table B1, Callister
Platinum
Metals have...
20 Gold, W
*GFRE, CFRE, & AFRE are Glass,
Tantalum Carbon, & Aramid Fiber-Reinforced

close-packing
Epoxy composites (values based on
60% volume fraction of aligned fibers
(metallic bonding)
10 Silver, Mo in an epoxy matrix).
Cu,Ni
Steels
often large atomic masses Tin, Zinc
Zirconia
Ceramics have... 5
r (g/cm3 )

Titanium
4 Al oxide
less dense packing 3
Diamond
Si nitride
often lighter elements
Aluminum Glass -soda Glass fibers
Concrete
PTFE
Polymers have...
2 Silicon GFRE*
Magnesium Carbon fibers
Graphite CFRE*
Silicone
low packing density PVC Aramid fibers
PET AFRE*
PC
(often amorphous)
1 HDPE, PS
PP, LDPE
lighter elements (C,H,O)
Composites have...
0.5
Wood
0.4
intermediate values 0.3
Data from Table B.1, Callister & Rethwisch, 8e.
Chapter 3 - 16

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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.
(Courtesy P.M. Anderson)

Chapter 3 - 17

ANNOUNCEMENTS
ANNOUNCEMENT: NO CLASS ON FRIDAY

HOMEWORK: 3.2 3.5, 3.7 TO BE

SUBMITTED NEXT MEETING, WED,
2/8/2017

Chapter 3 - 18

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HOMEWORK QUESTIONS

Mo density = 10.28 g/cm3

Chapter 3 - 19

Chapter 3 - 20

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Polycrystals
Most engineering materials are polycrystals.
1 mm
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).
Single vs Polycrystals
Single Crystals
-Properties vary with
direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
Polycrystals
-Properties may/may not
vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)
-If grains are textured,
anisotropic.
2/1/2017
Anisotropic
Adapted from Fig. K,
color inset pages of
Callister 5e.
(Fig. K is courtesy of
Paul E. Danielson,
Teledyne Wah Chang
Albany)
Isotropic
Chapter 3 - 21
E (diagonal) = 273 GPa
Data from Table 3.3,
Callister & Rethwisch
8e. (Source of data is
R.W. Hertzberg,
Deformation and
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 &
Rethwisch 8e.
(Fig. 4.14(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 - 22
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Polymorphism
Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
iron system
titanium
liquid
, -Ti
1538C
BCC -Fe
carbon
diamond, graphite 1394C
FCC -Fe
912C
BCC -Fe

Chapter 3 - 23

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.

Chapter 3 - 24

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Point Coordinates
z
111 Point coordinates for unit cell
c center are
a/2, b/2, c/2

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
Chapter 3 - 25

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>

Chapter 3 - 26

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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
y 3. Adjust to smallest integer values
4. Enclose in square brackets, no commas

x [uvw]

ex: 1, 0, => 2, 0, 1 => [ 201 ]

-1, 1, 1 => [ 111 ] where overbar represents a
negative index
families of directions <uvw>
Chapter 3 - 27

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.

Chapter 3 - 28

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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
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),
Callister & Rethwisch 8e.
a2 -a3
2

ex: , , -1, 0 => [ 1120 ] a3

a1
2
dashed red lines indicate
projections onto a1 and a2 axes a1
Chapter 3 - 29

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 )
w = w'
a1

Fig. 3.8(a), Callister & Rethwisch 8e.

Chapter 3 - 30

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Crystallographic Planes

Adapted from Fig. 3.10,

Callister & Rethwisch 8e.
Chapter 3 - 31

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)

Chapter 3 - 32

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Crystallographic Planes
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/ 1/ 1/
2 0 0
3. Reduction 2 0 0
y
4. Miller Indices (100) a b
x
Chapter 3 - 33

Crystallographic Planes
z
example a b c c
1. Intercepts 1/2 1 3/4
2. Reciprocals 1/ 1/1 1/
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)

Chapter 3 - 34

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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),

Callister & Rethwisch 8e.

Chapter 3 - 35

Crystallographic Planes
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.

Chapter 3 - 36

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Planar Density of (100) Iron

Solution: At T < 912C iron has the BCC structure.
2D repeat unit

(100) a=
4 3
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
Chapter 3 - 37

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
4 3 16 3 2
2

area = 2 ah = 3 a = 3 R = 2
R
atoms 3 3
2D repeat unit 1
atoms = atoms
Planar Density = = 7.0 0.70 x 1019
area 16 3
2 nm m2
R2
2D repeat unit 3
Chapter 3 - 38

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X-Ray Diffraction

Diffraction gratings must have spacings comparable to

the wavelength of diffracted radiation.
Cant resolve spacings
Spacing is the distance between parallel planes of
atoms.
Chapter 3 - 39

X-Rays to Determine Crystal Structure

Incoming X-rays diffract from crystal planes.

reflections must
be in phase for

a detectable signal
extra

q q
distance Adapted from Fig. 3.20,
Callister & Rethwisch 8e.
travelled
by wave 2 spacing
d between
planes

Measurement of X-ray
n
critical angle, qc, intensity d=
(from 2 sin qc
allows computation of
detector)
planar spacing, d.
q
qc
Chapter 3 - 40

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X-Ray Diffraction Pattern

z z z
c c c

y (110) y y
a b a b a b
x x x (211)
Intensity (relative)

(200)

Diffraction angle 2q

Diffraction pattern for polycrystalline -iron (BCC)

Adapted from Fig. 3.22, Callister 8e.

Chapter 3 - 41

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.

Chapter 3 - 42

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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.

Chapter 3 - 43

ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 3 - 44

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