12/10/09

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, ________________ Energy

_______________
bond length

typical neighbor r
bond energy

• Dense, ___________________ Energy

typical neighbor
bond length

typical neighbor r
bond energy

Dense, _____________________________ to have

_________ energies.
Chapter 3 - 2

Materials and Packing

Crystalline materials...
• atoms pack __________, 3D arrays
• typical of: -________
-many _________
-some _________ crystalline SiO2
Adapted from Fig. 3.23(a),
Callister & Rethwisch 8e.

Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: - _________________
- _____________
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.23(b),
Callister & Rethwisch 8e.

Chapter 3 - 3

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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

Chapter 3 - 4

Metallic Crystal Structures

• Tend to be densely packed.
• Reasons for dense packing:
- Typically, only one __________is present, so all atomic
________ are the same.
- Metallic bonding is not ________________.
- Nearest neighbor distances tend to be small in
order to __________ bond energy.
- ______________ 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 ___________ are cube edges.

• Coordination # = ___
(# 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 _______ structure = 0.52
volume
atoms atom
a 4
unit cell 1 π (0.5a) 3
3
R=0.5a APF =
a3 volume
close-packed ___________
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 ____________.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

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

• Coordination # = 8

Adapted from Fig. 3.2,

Click once on image to start animation Callister & Rethwisch 8e.
(Courtesy P.M. Anderson)
2 atoms/unit cell: 1 center + 8 _____________
Chapter 3 - 8

Atomic Packing Factor: BCC

• APF for a body-centered _______ structure = 0.68
3a

2a

Close-packed __________:
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 Chapter 3 - 9

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Face Centered Cubic Structure (FCC)

• Atoms touch each other along face ___________.
--Note: All atoms are ____________; the face-centered atoms are shaded
differently only for ease of viewing.

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

• Coordination # = ___

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

Click once on image to start animation
(Courtesy P.M. Anderson) 4 atoms/unit cell: 6 __________ + 8 corners x 1/8

Chapter 3 - 10

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:
__________________
= __________________
a
Adapted from
Fig. 3.1(a),
Callister & atoms volume
Rethwisch 8e. 4
unit cell π ( 2a/4 ) 3
3 atom
APF =
volume
unit cell
Chapter 3 - 11

FCC Stacking Sequence

• ABCABC... __________ Sequence
• 2D Projection
B B
C
A
A sites B B B
C C
B sites B B
C sites

A
• FCC _____ 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 # = ___ __ atoms/unit cell

• APF = _______ ex: Cd, Mg, Ti, Zn
• c/a = ________ Chapter 3 - 13

Theoretical Density, ρ

Mass of Atoms in Unit Cell

Density = ρ =
Total Volume of Unit Cell

nA
ρ =
VC NA

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

Chapter 3 - 14

Theoretical Density, ρ
•  Ex: Cr (BCC)
A = 52.00 g/mol
R = ___________
n = 2 atoms/unit cell
R
Adapted from
Fig. 3.2(a), Callister &
a a = 4R/ 3 = 0.2887 nm
Rethwisch 8e.
atoms
g
unit cell 52.00 ρtheoretical = 7.18 g/cm3
mol
ρ= ρactual = 7.19 g/cm3
a3 6.022 x 1023
volume atoms
unit cell mol Chapter 3 - 15

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Densities of Material Classes

In general Metals/
Graphite/
Composites/
ρmetals _ ρceramics _ ρpolymers Ceramics/ Polymers
Alloys fibers
Semicond
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
• less _______packing 3 Si nitride
Aluminum Glass -soda Glass fibers
• often lighter elements Concrete
Silicon PTFE GFRE*
2
Polymers have... Magnesium G raphite
Silicone
Carbon fibers
CFRE*
A ramid fibers
PVC
• low packing _________ PET
PC
AFRE *
1
(often _____________) HDPE, PS
PP, LDPE
• lighter elements (C,H,O)
0.5
Composites have... 0.4
Wood

• ______________values 0.3
Data from Table B.1, Callister & Rethwisch, 8e.
Chapter 3 - 16

Crystals as Building Blocks

• Some engineering applications require ________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 __________materials
often related to crystal structure.
-- Ex: Quartz fractures more easily
along some crystal planes than
others.
(Courtesy P.M. Anderson)

Chapter 3 - 17

Polycrystals __________
• Most engineering materials are ____________.

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 _______ is a single crystal.
• If grains are _________ oriented,
overall component properties are not ___________.
• Grain sizes typically range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).
Chapter 3 - 18

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Single vs Polycrystals
• Single Crystals E (diagonal) = __________
Data from Table 3.3,
-Properties vary with Callister & Rethwisch
8e. (Source of data is
direction: ____________. R.W. Hertzberg,
Deformation and
-Example: the __________ 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 _________ of L.C. Smith and C.
Brady, the National
oriented: __________. Bureau of Standards,
Washington, DC [now
(Epoly iron = 210 GPa) the National Institute of
-If grains are _________, Standards and
Technology,
anisotropic. Gaithersburg, MD].)

Chapter 3 - 19

Polymorphism
•  Two or more distinct _______ structures for the same
material (allotropy/polymorphism)
iron system
titanium
liquid
α, β-Ti
1538ºC

carbon BCC δ-Fe

__________, graphite 1394ºC

FCC γ-Fe
912ºC
BCC α-Fe

Chapter 3 - 20

Crystal Systems
Unit cell: smallest __________________ which
contains the complete ___________ of a crystal.

7 crystal systems

14 crystal lattices

a, b, and c are the ________ constants

Fig. 3.4, Callister & Rethwisch 8e.

Chapter 3 - 21

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Point Coordinates
z
111 Point coordinates for ________
c center are
a/2, b/2, c/2 ½½½

000
y
a b
Point ___________ for unit cell
x corner are 111
z 2c

__________: integer multiple of

lattice constants  identical
b y position in another unit cell
b
Chapter 3 - 22

Crystallographic Directions
z Algorithm
1. Vector ___________ (if necessary) to pass
through origin.
2. Read off ____________ in terms of
unit cell dimensions a, b, and c
y 3. Adjust to smallest ___________ values
4. Enclose in _______ brackets, no commas

x [uvw]

ex: ___________________________
_______________ where ___________ represents a
negative index
________ of directions <uvw>
Chapter 3 - 23

Linear Density
Number of atoms
•  Linear Density of Atoms ≡ LD = Unit length of direction vector

[110]
ex: linear _________ of Al in [110]
direction
a = 0.405 nm

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

Chapter 3 - 24

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HCP Crystallographic Directions

z
Algorithm
1. Vector _________ (if necessary) to pass
through origin.
2. Read off projections in _________ of unit
a2 cell dimensions a1, a2, a3, or c
3. Adjust to ___________ 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: ____________________ a3
a1
2
________ red lines indicate
projections onto a1 and a2 axes a1
Chapter 3 - 25

HCP Crystallographic Directions

•  Hexagonal Crystals
–  4 parameter ____________ lattice coordinates are
related to the direction __________ (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.

Chapter 3 - 26

Crystallographic Planes

Adapted from Fig. 3.10,

Callister & Rethwisch 8e.
Chapter 3 - 27

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Crystallographic Planes
•  _____ Indices: Reciprocals of the (three) axial
intercepts for a plane, cleared of _________ &
common multiples. All ________ planes have
same Miller indices.

•  Algorithm
1. Read off ____________ of plane with axes in
terms of a, b, c
2. Take ____________ of intercepts
3. Reduce to smallest integer values
4. Enclose in parentheses, no
commas i.e., (hkl)

Chapter 3 - 28

Crystallographic Planes
z
example a b c
1. Intercepts 1 1 __ c
2. Reciprocals 1/1 1/1 ___
1 1 0
3. Reduction 1 1 __ y
a b
4. Miller Indices _____
x
z
example a b c
1. Intercepts 1/2 ∞ ∞ c
2. Reciprocals 1/½ 1/∞ 1/∞
2 0 0
3. Reduction __ __ 0
y
4. Miller Indices _____ a b
x
Chapter 3 - 29

Crystallographic Planes
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)

Chapter 3 - 30

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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 - 31

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

Chapter 3 - 32

Virtual Materials Science & Engineering (VMSE)

• VMSE is a tool to visualize materials science topics such as
crystallography and polymer structures in three dimensions

• Available in Student Companion Site at www.wiley.com/college/callister

Chapter 3 - 33
and in WileyPLUS

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VMSE: Metallic Crystal Structures &

Crystallography Module
• VMSE allows you to view crystal structures, directions, planes,
etc. and manipulate them in three dimensions

Chapter 3 - 34

Unit Cells for Metals

• VMSE allows you to view the unit cells and manipulate
them in three dimensions

• Below are examples of actual VMSE screen shots

FCC Structure HCP Structure

Chapter 3 - 35

VMSE: Crystallographic Planes Exercises

Additional practice on indexing crystallographic planes

Chapter 3 - 36

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Planar Density of (100) Iron

Solution: At T < 912ºC iron has the ________structure.
2D repeat unit

(100) 4 3
a= R
3

Adapted from Fig. 3.2(c), Callister & Rethwisch 8e. __________of iron R = 0.1241 nm
atoms
2D repeat unit
1 atoms atoms
Planar Density = = 2 = ____ = ________
area a2 4 3 nm2 m2
R
2D repeat unit 3
Chapter 3 - 37

Planar Density of (111) Iron

Solution (cont): (___) plane ______ in plane/ unit surface cell

2a atoms in plane
atoms above plane
nit

atoms _____ plane

tu
ea
rep

3
h= a
2D

2
2
 4 3  16 3 2
area = 2 ah = 3 a 2 = 3  R  = R
atoms  3  3
2D repeat unit
atoms = atoms
Planar Density = = 7.0 __________
area 16 3 2
2 nm m2
R
2D repeat unit 3
Chapter 3 - 38

VMSE Planar Atomic Arrangements

• VMSE allows you to view planar arrangements and rotate
them in 3 dimensions

BCC (110) Plane

Chapter 3 - 39

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X-Ray Diffraction

•  ________ gratings must have spacings comparable to

the wavelength of diffracted ___________.
•  Can’t resolve ____________ < λ
•  Spacing is the distance between __________ planes
of atoms.
Chapter 3 - 40

X-Rays to Determine Crystal Structure

• Incoming X-rays _________ from crystal
d planes.
et
ec
to
”

r
“1
in -ray
co s

s
X

reflections must
ay
m

r be in phase for
X-
in

”
“2
g

a detectable signal
“1

g
”

extra in λ
go
“2

distance t Adapted from Fig. 3.20,

”

travelled θ ou θ Callister & Rethwisch 8e.

by wave “2” spacing
d between
_________

________________of X-ray
intensity n λ
critical angle, θc, d=
(from 2 sin θc
allows computation of
planar __________, d. detector)
θ
θc
Chapter 3 - 41

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.

Chapter 3 - 42

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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 - 43

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 - 44

15