Prof. Dr. Ir.

Akhmad Herman Yuwono

Yuwono,, M.Phil.Eng
M.Phil.Eng..

Dept. of Metallurgical and Materials Engineering

Fac. of EngineeringEngineering -Universitas Indonesia

LECTURE 2

THE BASICS 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?

Energy and Packing

Non dense, random packing

Energy
typical neighbor
bond length

typical neighbor
bond energy

Dense, ordered packing

Energy
typical neighbor
bond length

typical neighbor
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
5

noncrystalline SiO2
Adapted from Fig. 3.23(b),
Callister & Rethwisch 8e.

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

6

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)

APF =

Volume of atoms in unit cell*

Volume of unit cell

*assume hard spheres

APF for a simple cubic structure = 0.52
atoms
unit cell

a
R=0.5a

APF =

volume
atom
4
(0.5a) 3
1
3
a3

close-packed directions
contains 8 x 1/8 =
1 atom/unit cell
9

Adapted from Fig. 3.24,

Callister & Rethwisch 8e.

volume
unit cell

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,

Callister & Rethwisch 8e.

10

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

a
2a
Adapted from
Fig. 3.2(a), Callister &
Rethwisch 8e.

atoms
unit cell
APF =

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

a
2

4
3

( 3a/4 ) 3
a3

11

volume
atom
volume
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

Coordination # = 12

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

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

12

Atomic Packing Factor: FCC

APF for a face-centered cubic structure = 0.74
maximum achievable APF
Close-packed directions:
length = 4R = 2 a
2a

a
Adapted from
Fig. 3.1(a),
Callister &
Rethwisch 8e.

13

Unit cell contains:

6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
atoms
volume
4
p ( 2a/4) 3
4
unit cell
atom
3
APF =
volume
a3
unit cell

FCC Stacking Sequence

ABCABC... Stacking Sequence
2D Projection
B
B
C
A
B
B
B
A sites
C
C
B sites
B
B
C sites

FCC Unit Cell

14

A
B
C

Hexagonal Close-Packed Structure

(HCP)
ABAB... Stacking Sequence
3D Projection

2D Projection
A sites

Top layer

B sites

Middle layer

A sites

Bottom layer

Adapted from Fig. 3.3(a),

Callister & Rethwisch 8e.

Coordination # = 12
APF = 0.74
15

c/a = 1.633

6 atoms/unit cell
ex: Cd, Mg, Ti, Zn

Theoretical Density,
Density = =
=

where

16

Mass of Atoms in Unit Cell

Total Volume of Unit Cell

nA
VC NA

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

Theoretical Density,
17

Adapted from
Fig. 3.2(a), Callister &
Rethwisch 8e.

atoms
unit cell

=
volume
17

unit cell

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

a
2 52.00

a3 6.022 x 1023

a = 4R/ 3 = 0.2887 nm
g
mol

theoretical = 7.18 g/cm3

ractual

atoms
mol

= 7.19 g/cm3

Densities of Material Classes

Graphite/

r metals > r ceramics > r polymers

30
Why?

18

Metals have...

Ceramics have...
less dense packing
often lighter elements

Polymers have...

r (g/cm3 )

close-packing
(metallic bonding)
often large atomic masses

low packing density

(often amorphous)
lighter elements (C,H,O)

Composites have...
18

intermediate values

Metals/
Alloys

20

Platinum
Gold, W
Tantalum

10

Silver, Mo
Cu,Ni
Steels
Tin, Zinc

5
4
3
2

0.5
0.4
0.3

Titanium
Aluminum
Magnesium

Ceramics/
Semicond

Polymers

Composites/
fibers

Based on data in Table B1, Callister

*GFRE, CFRE, & AFRE are Glass,
Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
60% volume fraction of aligned fibers
in an epoxy matrix).
Zirconia
Al oxide
Diamond
Si nitride
Glass -soda
Concrete
Silicon
Graphite

PTFE
Silicone
PVC
PET
PC
HDPE, PS
PP, LDPE

Glass fibers
GFRE*
Carbon fibers
CFRE*
Aramid fibers
AFRE*

Wood

Data from Table B.1, Callister & Rethwisch, 8e.

Crystals as Building Blocks

Some engineering applications require single crystals:
-- diamond single
crystals for abrasives
(Courtesy Martin Deakins,
GE Superabrasives,
Worthington, OH. Used with
permission.)

-- turbine blades
Fig. 8.33(c), Callister &
Rethwisch 8e. (Fig. 8.33(c)
courtesy of Pratt and
Whitney).

Properties of crystalline materials

often related to crystal structure.
-- Ex: Quartz fractures more easily
along some crystal planes than
others.
(Courtesy P.M. Anderson)

19

Polycrystals
Most engineering materials are polycrystals.

Anisotropic

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.

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

20

(i.e., from a few to millions of atomic layers).

Isotropic

Single vs Polycrystals
Single Crystals

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.)

-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)
21

-If grains are textured,

anisotropic.

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].)

Single Crystals and Polycrystalline Materials

Single crystal: periodic array over entire material
Polycrystalline material: many small crystals (grains)
with varying orientations.
Atomic mismatch where grains meet (grain boundaries)

Grain Boundary
22

22

Polycrystalline Materials

Atomistic model of a nanocrystalline solid

23

23

Polycrystalline Materials

24

Polymorphism

Two or more distinct crystal structures for the same

material (allotropy/polymorphism)
iron system
titanium
liquid
, -Ti
1538C
-Fe
BCC
carbon
1394C
diamond, graphite
-Fe
FCC
912C
BCC

25

-Fe

Polymorphism and Allotropy

Some materials can exist in more than one crystal structure, called
polymorphism.
If material is an elemental solid: called allotropy.
Ex: of allotropy is carbon:
can exist as diamond, graphite, amorphous carbon.

26

Pure, solid carbon occurs in three crystalline forms diamond,

graphite; and large, hollow fullerenes. Two kinds of fullerenes are
shown here: buckminsterfullerene (buckyball) and carbon nanotube.
26

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

27

Fig. 3.4, Callister & Rethwisch 8e.

Point Coordinates
z

111

Point coordinates for unit cell center

are
a/2, b/2, c/2

a
x

000

Point coordinates for unit cell corner

are 111

2c

b
28

Translation: integer multiple of lattice

constants identical position in
another unit cell

Crystallographic Directions
z

29

pt.
2
head

y
x

pt.
1:
tail

Example 2:
pt. 1
x1 = a,
z1 = 0
pt. 2
x2 = -a,
z2 = c

=>

y1 = b/2,
y2 = b,

-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

[uvw]

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

-1, 1, 1 => [ 111 ]

where overbar represents a

negative index

families of directions <uvw>

30

Linear Density

Linear Density of Atoms LD =

Number of atoms
Unit length of direction vector

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

# atoms
a
Adapted from
Fig. 3.1(a),
Callister &
Rethwisch 8e.

31

LD =
length

2
2a

= 3.5 nm- 1

HCP Crystallographic Directions

z

Algorithm

a2

a3
a1

1. Vector repositioned (if necessary) to pass

through origin.
2. Read off projections in terms of unit
cell dimensions a1, a2, a3, or c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas
[uvtw]
a
2

Adapted from Fig. 3.8(a),

Callister & Rethwisch 8e.

ex:

, , -1, 0

=>

[ 1120 ]

a3

dashed red lines indicate

projections onto a1 and a2 axes
32

-a3

a2
2

a1
2

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 ]

a2

a3
a1

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

33

1
u = (2 u ' - v ' )
3
1
v = (2 v ' - u ' )
3
t = - (u + v )
w = w'

Crystallographic Planes

34

Adapted from Fig. 3.10, 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)

35

Crystallographic Planes
example
1. Intercepts
2. Reciprocals
3.

Reduction

a
1
1/1
1
1

4.

Miller Indices

(110)

example
1. Intercepts
2. Reciprocals
3.

Reduction

a
1/2
1/
2
2

4.

Miller Indices

(100)

b
1
1/1
1
1

1/
0
0

c
y
b

a
x

1/
0
0

1/
0
0

c
y
a
x

36

Crystallographic Planes
z
Example
1. Intercepts
2. Reciprocals
3.

Reduction

4.

Miller Indices

a
1/2
1/
2
6

b
1
1/1
1
3

(634)

c
c
3/4
1/
4/3

4 a
x

Family of Planes {hkl}

Ex: {100} = (100), (010), (001), (100), (010), (001)
37

Crystallographic Planes (HCP)

In

hexagonal unit cells the same idea is used

z

example
1. Intercepts
2. Reciprocals
3.
4.

Reduction

a1
1
1
1
1

Miller-Bravais Indices

a2

1/
0
0

a3
-1
-1
-1
-1

(1011)

c
1
1
1
1

a2

a3
a1

38

Adapted from Fig. 3.8(b),

Callister & Rethwisch 8e.

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)

b)

39

Draw (100) and (111) crystallographic planes

for Fe.
Calculate the planar density for each of these planes.

Planar Density of (100) Iron

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

(100)

Planar Density =
area
2D repeat unit

1
a2

4 3
R
3

Radius of iron R = 0.1241 nm

Adapted from Fig. 3.2(c), Callister & Rethwisch 8e.

atoms
2D repeat unit

a=

1
4 3
R
3

atoms
atoms
19
= 1.2 x 10
2 = 12.1
2
nm
m2

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

h=

3
a
2

atoms
2D repeat unit

4 3 16 3 2
2
area = 2 ah = 3 a = 3
R =
R
3
3

atoms =
= 7.0
2

Planar Density =
area
2D repeat unit
41

16 3
3

nm

0.70 x 1019

atoms
m2

X-Ray Diffraction

42

Diffraction gratings must have spacings comparable to the

wavelength of diffracted radiation.
Cant resolve spacings
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
travelled
by wave 2

l
q

q
d

Measurement of critical
angle, qc, allows
computation of planar
spacing, d.

Adapted from Fig. 3.20,

Callister & Rethwisch 8e.

spacing
between
planes

X-ray
intensity
(from
detector)

nl
d=
2 sin qc

q
43

qc

X-Ray Diffraction Pattern

z

Intensity (relative)

c
a

y (110)

c
b

a
x

b
(211)

(200)

Diffraction angle 2

Diffraction pattern for polycrystalline -iron (BCC)

Adapted from Fig. 3.22, Callister 8e.

44

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.
45

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.

46