Engineering Materials

University of Georgia
MCHE3310|Fall 2017

3: Crystalline structures
August 24, 2017

XQ Wang
xqwang@uga.edu
http://xqwang.engr.uga.edu 1
Learning objective
Describe the difference in atomic/molecular
structure between crystalline and
noncrystalline materials
Understand basic terms: unit cell, lattice,
crystal structure, coordination numbers
Describe hard-sphere packing and cell
symmetry
Understand Miller indices

2
Todays agenda
Unit cells
Atomic packing
Crystal structures and systems
Packing density
Point coordinates
Crystallographic directions
Crystallographic planes

3
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.
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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. 3.25(a),
Callister & Rethwisch 9e.

Si Oxygen
Noncrystalline materials...
atoms have no periodic packing
occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.25(b),
Callister & Rethwisch 9e.

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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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Hard sphere model

Atomic hard sphere model: hard sphere in a box

Atoms (or ions) are thought of as being solid spheres having well-defined diameters
Spheres representing nearest-neighbor atom touch one another.

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Crystalline solid: unit cells

Unit cell: the basic structural unit of a crystal

structure. Its geometry and atomic positions
define the crystal structure.

A unit cell is the smallest component of the

crystal that reproduces the whole crystal
when stacked together with purely
translational repetition.

Note: more that one unit cell can be

chosen for a given crystal structure but by
convention, the one with highest symmetry
is chosen.
Face-centered cubic structure

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Crystalline solid: unit cells
A space LATTICE is an infinite, periodic array of mathematic points, in which each
point has identical surroundings to all others.

A crystal structure is a periodic arrangement of atoms in the crystal that can be

described by a LATTICE + ATOM DECORATION (BASIS). 9
Crystalline solid: unit cells
Important notes:
Lattice points are a purely mathematic concept whereas atoms are physical
objects
DONT mix up atoms with lattice points
Lattice points do not necessarily lie at the center of atoms.

Unit cells
The parameters of the unit cell:
(a,b,c) the length of three adjacent edges of the unit cell
(,,) three angles subtended by the lattice cell axes

The various unit cells are generated from the

different values of a, b, c and , , .

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Crystal systems & Bravais lattices
Seven possible combinations of a, b, c & , , , resulting in 7 crystal systems
The seven crystal systems can be described using 14 point lattices, called Bravais Lattices
(Proposed by French crystallographer Bravais in 1848)

Bravais

Face-centered cubic,
body-centered cubic
and hexagonal close-
packed are for most
(simple)
common metal
90

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Cubic unit cell
In cubic unit cell: a = b = c
= = = 90

Simple Cubic (SC)

Body-Centered Cubic (BCC)

Face-Centered Cubic (FCC)

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Simple cubic structure (SC)
Rare due to low packing density (only Po has this structure)
Close-packed directions are cube edges.
Coordination number = 6
(# nearest neighbors: each atom has the same number
of nearest-neighbor or touching atoms)

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Counting number of atoms per unit cell in cubic
Atom in different position are shared by differing numbers of unit cells
Vertex atom shared by 8 cells 1/8 atom belongs to cell
Face atom shared by 2 cells 1/2 atom belongs to cell
Body unique to 1 cell 1 atom belongs to cell

Simple cubic
N=1

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Atomic packing factor (APF): SC
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
unit cell 1 (0.5a) 3
3
R = 0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 =
1 atom/unit cell
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Body-centered cubic (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,

Callister & Rethwisch 9e.

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

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Atomic packing factor (APF): BCC
APF for a body-centered cubic structure = 0.68
3a

2a

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

atoms volume
4
unit cell 2 ( 3a/4) 3
3 atom
APF =
volume
a3
unit cell
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Face-centered cubic (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 9e.

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

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Atomic packing factor (APF): 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
atoms volume
4
unit cell 4 ( 2a/4) 3
3 atom
APF =
volume
a3
unit cell
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SC, FCC, BCC
Coordination number: each atom has the same
number of nearest-neighbor or touching atoms
number of atom per unit cell

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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

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Hexagonal close-packed structure (HCP)

ABAB... Stacking Sequence

3D Projection

A sites
c
B sites

A sites
a

Coordination # = 12 6 atoms/unit cell:

3 atoms at center: 3(1)
APF = 0.74 2 atoms at face: 2(1/2)
12 atoms at corner: 12(
1/6 )
c/a = 1.633
ex: Cd, Mg, Ti, Zn
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Close packing of sphere
Comparison of Packing Efficiency

Simple Cube FCC

FCC & HCP
Coordination #: 6 Coordination #: 12
are the most close-
Atoms/Cell: 1 Atoms/Cell: 4
packed structures,
APF: 52% APF: 74%
which can be
described in term
of close-packed
planes of atoms

BCC HCP
Coordination #: 8 Coordination #: 12
Atoms/Cell: 2 Atoms/Cell: 6
APF: 68% 23
APF: 74%
Close packing of sphere
Stacking sequence of close-packed planes of atoms

FCC HCP

C B
B A
A B
A
C C A
B B
A B A B
A A
The atoms of the third plane
The atoms in rows A
are in exactly the same
and C are no longer position as the atoms in the
aligned. first plane. 24
Theoretical density:
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 = Avogadros number
= 6.022 x 1023 atoms/mol

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Theoretical density:

Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
R
a a = 4R/ 3 = 0.2887 nm

atoms
g
unit cell 2 52.00 theoretical = 7.18 g/cm3
mol
= actual = 7.19 g/cm3
a3 6.022 x 1023
volume atoms
unit cell mol
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Densities of material classes
In general Graphite/
metals > ceramics > polymers
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond
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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

(g/cm3 )
5
Ceramics have... 4
Titanium
Al oxide
Diamond
less dense packing 3 Si nitride
Aluminum Glass -soda Glass fibers
often lighter elements Concrete
Silicon PTFE GFRE*
2 Carbon fibers
Polymers have... Magnesium Graphite
Silicone CFRE*
Aramid fibers
PVC
low packing density PET
PC
AFRE*
1 HDPE, PS
(often amorphous) 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, 9e.

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Crystals as building blocks
Some engineering applications require single crystals:
-- diamond single -- turbine blades
crystals for abrasives Fig. 8.34(c), Callister &
(Courtesy Martin Deakins, Rethwisch 9e.
GE Superabrasives, Worthington, (courtesy of Pratt and Whitney)
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)

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Polycrystals
Most engineering materials are polycrystals.
Anisotropic

Fig. K, color inset pages

of Callister 5e.
(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).
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Single vs. polycrystals

Single Crystals E (diagonal) = 273 GPa

Data from Table 3.4,
-Properties vary with Callister & Rethwisch 9e.
(Source of data is R.W.
direction: anisotropic. Hertzberg, Deformation and
Fracture Mechanics of

-Example: the modulus Engineering Materials, 3rd ed.,

John Wiley and Sons, 1989.)

of elasticity (E) in BCC iron:

E (edge) = 125 GPa
Polycrystals
-Properties may/may not 200 m Adapted from Fig.
4.15(b), Callister &
vary with direction. Rethwisch 9e.
[Fig. 4.15(b) is courtesy of
-If grains are randomly L.C. Smith and C. Brady, the
National Bureau of
oriented: isotropic. Standards, Washington, DC
(now the National Institute of
Standards and Technology,
(Epoly iron = 210 GPa) Gaithersburg, MD).]

-If grains are textured,

anisotropic.

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Polymorphism

Two or more distinct crystal structures for the same

material (allotropy/polymorphism)

titanium iron system

, -Ti liquid
1538C
carbon BCC -Fe
diamond, graphite 1394C
FCC -Fe
912C
BCC -Fe

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Crystallographic Indices
Labeling the crystal structures

Point Coordinates
Direction Indices
Plane Indices (Miller Indices)
Miller-Bravais Indices

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Point coordinates
Any point within a unit cell is specified as fractional multiples of the unit cell
edge lengths
Position P specified as q r s; convention: coordinates not separated by
commas or punctuation marks

Point P: q r s

q (a fraction) qa (the distance) x axis

r (a fraction) rb (the distance) y axis
s (a fraction) sc (the distance) z axis
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Point coordinates
Example 1
Task: Locate the point 1/4 1 (fractional multiples of the unit cell edge lengths)
x y z

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Point coordinates
Example 2
Task: Specify point coordinates for all atom positions for a BCC unit cell

BCC: 8 corner atoms

1 center atom

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Point coordinates
Example 2
Task: Specify point coordinates for all atom positions for a BCC unit cell

BCC: 8 corner atoms

1 center atom

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Point coordinates
Example 3
Task: Specify point coordinates for all atom positions for a FCC unit cell
z
C8 C1: 0 0 0
C5 C2: 1 0 0 F1:
F5
C3: 1 1 0 F2:
C7 C4: 0 1 0 F3:
C6 F4 F4:
F1 C5: 0 0 1
F3 F5:
y C6: 1 0 1
C1 F2 C4
C7: 1 1 1 F6:
F6 C8: 0 1 1
C2 C3

x
FCC: 8 corner atoms
6 face center atoms

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Point coordinates
Example 3
Task: Specify point coordinates for all atom positions for a FCC unit cell
z
C8 C1: 0 0 0
C5 C2: 1 0 0 F1: 0
F5
C3: 1 1 0 F2: 1
C7 C4: 0 1 0 F3: 1
C6 F4 F4: 0
F1 C5: 0 0 1
F3 F5: 1
y C6: 1 0 1
C1 F2 C4
C7: 1 1 1 F6: 0
F6 C8: 0 1 1
C2 C3

x
FCC: 8 corner atoms
6 face center atoms

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Point coordinates
Example 4
Task: Specify point coordinates for diamond unit cell

z
C8
C5 F1: 0
F5
F2: 1
C7 F3: 1
C6 F4 F4: 0
F1
F3 F5: 1
y
C1 F2 C4 F6: 0
F6
C2 C3
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x
Point coordinates
Example 4
Task: Specify point coordinates for diamond unit cell

313
313 133 133
444
444 444 444

331 111 331

111 444
444 444
444

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Point coordinates
Example 5
Task: Specify point coordinates for atoms outside a unit cell
z

x
41