Materials Science

Lecture #3

Structure of Crystalline Solids

2-1
2
3
 Carbon structures

Diamond Graphite

4
5
 The Structure of Crystalline Solids

ISSUES TO ADDRESS...
• How do atoms assemble into solid structures?
(for now, focus on metals)

• How does the density of a material depend on

its structure?

• When do material properties vary with the

sample (i.e., part) orientation?

7
 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.
8
 Materials and Packing
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2
Adapted from Fig. 3.22(a),
Callister 7e.

Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.22(b),
Callister 7e.

9
Crystalline material: periodic array
Single crystal:
periodic array over the entire extent of the material
Polycrystalline material: many small crystals or grains

More details @ next lecture

Amorphous: lacks a systematic atomic arrangement

10
 The Space Lattice and Unit Cells
• Atoms, arranged in repetitive 3-Dimensional pattern, in
long range order (LRO) give rise to crystal structure.
• Properties of solids depends upon crystal structure and
bonding force.
• An imaginary network of lines, with atoms at
intersection of lines, representing the arrangement of
atoms is called space lattice. Space Lattice
• Unit cell is that block of
atoms which repeats itself
to form space lattice.
Materials arranged in short
range order are called
amorphous materials Unit Cell
3-2
 Crystal Systems
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.

7 crystal systems

14 crystal lattices

Details later

a, b, and c are the lattice constants

Fig. 3.4, Callister 7e.

12
 Metallic Crystal Structures
• How can we stack metal atoms to minimize
empty space?
2-dimensions

vs.

Now imagine how to stack these 2-D layers

to make 3-D structures
13
 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...

14
 Simple Cubic Structure (SC)
• Coordination # = 6
Simple cubic (# nearest neighbors)

(Courtesy P.M. Anderson)

• Rare due to low packing density (only Po has this structure)

• Close-packed directions are cube edges.
15
 Atomic Packing Factor (APF)
Volume of atoms in unit cell*
APF =
Volume of unit cell
*assume hard spheres
volume
atoms atom
4
a unit cell 1 p (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. 3.23,
Callister 7e.
APF for a simple cubic structure = 0.52

16
 Simple Cubic structure

THIRD LAYER

SECOND LAYER

FIRST LAYER

• The layers stack directly on top of each other in simple cubic structure
17
The smallest repeating unit of a crystal lattice is called a
unit cell
This is the unit cell of simple cubic structure

18
The unit cell can be represented
by a ball and stick model
Ball and stick model of SC unit cell is shown below
a
a

‘a’ is known as lattice parameter

or lattice constant
19
 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 7e.

20
 Crystal Systems and Bravais Lattice
• Only seven different types of unit cells are
necessary to create all point lattices.
• According to Bravais (1811-1863) fourteen
standard unit cells can describe all possible lattice
networks.
• The four basic types of unit cells are
➢ Simple
➢ Body Centered
➢ Face Centered
➢ Base Centered

3-3
 Types of Unit Cells
1. Cubic Unit Cell
➢ a=b=c
➢ α = β = γ = 90°

Simple Body Centered

Figure 3.2
Face centered
2.Tetragonal
➢ a =b ≠ c
➢ α = β = γ = 90°

Simple Body Centered

3-4 After W.G. Moffatt, G.W. Pearsall, & J. Wulff, “The Structure and Properties of Materials,” vol. I: “Structure,” Wiley, 1964, p.47.)
 Types of Unit Cells (Cont..)
3. Orthorhombic
➢ a≠ b≠ c
➢ α = β = γ = 90°

Simple Base Centered

Body Centered
Face Centered
4. Rhombohedral Figure 3.2
➢ a =b = c
➢ α = β = γ ≠ 90°

Simple
3-5 After W.G. Moffatt, G.W. Pearsall, & J. Wulff, “The Structure and Properties of Materials,” vol. I: “Structure,” Wiley, 1964, p.47.)
 Types of Unit Cells (Cont..)
5.Hexagonal
➢ a= b≠ c
➢ α = β = 90°, γ = 120°
Simple

6. Monoclinic
➢ a≠ b≠ c
➢ α = γ = 90° ≠ β Base
Centered
Simple
7. Triclinic
Figure 3.2
➢ a≠ b≠ c
➢ α ≠ β ≠ γ ≠ 90°

Simple
3-6 After W.G. Moffatt, G.W. Pearsall, & J. Wulff, “The Structure and Properties of Materials,” vol. I: “Structure,” Wiley, 1964, p.47.)
 Principal Metallic Crystal Structures
• 90% of the metals have either Body Centered Cubic
(BCC), Face Centered Cubic (FCC) or Hexagonal Close
Packed (HCP) crystal structure.
• HCP is denser version of simple hexagonal crystal
structure.

BCC Structure FCC Structure HCP Structure

Figure 3.3
3-7
Body Centered Cubic Structure (BCC)
Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

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

• Coordination # = 8
BCC

Adapted from Fig. 3.2,

(Courtesy P.M. Anderson) Callister 7e.

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

Atoms touch each other along cube diagonals.
26
BCC

27
• The unit cell of the BCC structure

28
• The unit cell of BCC can be represented
by a ball and stick model as shown below

a
a

29
 Body Centered Cubic (BCC) Crystal Structure
• Represented as one atom at each corner of cube and one
at the center of cube.
• Each atom has 8 nearest neighbors.
• Therefore, coordination number is 8.
• Examples :-
➢ Chromium (a=0.289 nm)
➢ Iron (a=0.287 nm)
➢ Sodium (a=0.429 nm)

Figure 3.4 a&b

3-8
 BCC Crystal Structure (Cont..)
• Each unit cell has eight 1/8
atom at corners and 1
full atom at the center.
• Therefore each unit cell has
(8 x 1/8 ) + 1 = 2 atoms

• Atoms contact each

other at cube diagonal
Figure 3.5
Therefore, lattice 4R
constant a =
3
3-9
 Atomic Packing Factor: BCC
• APF for a body-centered cubic structure = 0.68
3a

2a

Close-packed directions:
R length = 4R = 3 a
Adapted from
Fig. 3.2(a), Callister 7e.
a
atoms volume
4
unit cell 2 p ( 3a/4 ) 3
3 atom
APF =
3 volume
a
unit cell 32
 Atomic Packing Factor of BCC Structure

Volume of atoms in unit cell

Atomic Packing Factor =
Volume of unit cell

 4pR 3 
Vatoms = 2. = 8.373R3
 3 
3
 4R 
V unit cell = a3 =   = 12.32 R3
 
 3 

8.723 R3
Therefore APF = 12.32 R3 = 0.68

3-10
 Face Centered Cubic Structure (FCC)
--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 7e.

FCC
(Courtesy P.M. Anderson)
4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

• Atoms touch each other along face diagonals.

34
Face Centered Cubic Structure (FCC)

An FCC unit cell forms in the following way

35
The ball and stick model of
an FCC unit cell is shown below

36
 FCC Crystal Structure (Cont..)
• Each unit cell has eight 1/8
atom at corners and six ½
atoms at the center of six
faces.
• Therefore each unit cell has
(8 x 1/8)+ (6 x ½) = 4 atoms

• Atoms contact each other

across cubic face diagonal
Therefore, lattice 4R
constant a = Figure 3.7
2
3-12
 Face-Centered Cubic Crystal Structure
➢ Corner and face atoms in unit cell are equivalent
➢ FCC has APF of 0.74
Maximum packing  FCC is close-packed structure
➢ FCC can be represented by a stack of close-packed planes (planes
with highest density of atoms)

38
39
 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

40
FCC Unit Cell

B
C

41
 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 7e. atoms volume
4
unit cell 4 p ( 2a/4 ) 3
3 atom
APF =
volume
a3
unit cell
42
Hexagonal Close-Packed Structure (HCP)

HCP Stacking Sequence

• ABABAB... Stacking Sequence
• 2D Projection
B B
C
A A
A sites A
B B B
C C
A A
B sites B B
C sites

43
Hexagonal Close-Packed Structure (HCP)
HCP unit cell forms in the following way

44
• The ball and stick model of
HCP unit cell is shown below
a
a

45
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 7e.

• Coordination # = 12 6 atoms/unit cell

• APF = 0.74 ex: Cd, Mg, Ti, Zn
• c/a = 1.633 46
 Hexagonal Close-Packed Structure
• The HCP structure is represented as an atom at each of
12 corners of a hexagonal prism, 2 atoms at top and
bottom face and 3 atoms in between top and bottom
face.
• Atoms attain higher APF by attaining HCP structure than
simple hexagonal structure.
• The coordination number is 12, APF = 0.74.

Figure 3.8 a&b

After F.M. Miller, “Chemistry: Structure and Dynamics,” McGraw-Hill, 1984, p.296
 HCP Crystal Structure (Cont..)
• Each atom has six 1/6 atoms at each of top and bottom
layer, two half atoms at top and bottom layer and 3 full
atoms at the middle layer.
• Therefore each HCP unit cell has
(2 x 6 x 1/6) + (2 x ½) + 3 = 6 atoms
• Examples:-
➢ Zinc (a = 0.2665 nm, c/a = 1.85)
➢ Cobalt (a = 0.2507 nm, c/a = 1.62)

• Ideal c/a ratio is 1.633.

Figure 3.8 c
After F.M. Miller, “Chemistry: Structure and Dynamics,” McGraw-Hill, 1984, p.296
49
 Close-packed Structures (FCC and HCP)
➢ FCC and HCP: APF =0.74 (maximum possible value)
➢ FCC and HCP may be generated by the stacking of close-packed planes
➢ Difference is in the stacking sequence

50
HCP: ABABAB... FCC: ABCABCABC…
 FCC: Stacking Sequence
HCP: Stacking Sequence ABCABCABC...
ABABAB...

Third plane placed Third plane placed above “holes” of

directly above first plane first plane not covered by second
of atoms plane

51
FCC and HCP stacking
sequence comparison

52
STRUCTURE OF COMPOUNDS: NaCl
• Compounds: Often have similar close-packed structures.
• Structure of NaCl

Click on image to animate

• Close-packed directions
Click on image to animate --along cube edges.
(Courtesy P.M. Anderson)
21
 GLASS STRUCTURE
• Basic Unit: • Glass is amorphous
4- • Amorphous structure
Si04 tetrahedron occurs by adding impurities
Si 4+ (Na+,Mg2+,Ca2+, Al3+)
O2-
• Impurities:
interfere with formation of
crystalline structure.

• Quartz is crystalline
SiO2:

(soda glass)
Adapted from Fig. 12.11,
Callister, 6e.

28
 Theoretical (volume) 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 = Avogadro’s number
= 6.023 x 1023 atoms/mol

55
 Theoretical Density, 
• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2
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
a 3 6.023 x 1023
volume atoms
unit cell mol 56
 Theoretical (volume)Density
Example:- Copper (FCC) has atomic mass of 63.54 g/mol and
atomic radius of 0.1278 nm.

4R 4  0.1278nm
a= = = 0.361 nm
2 2
Volume of unit cell = V= a3 = (0.361nm)3 = 4.7 x 10-29 m3
FCC unit cell has 4 atoms.
( 4atoms)( 63.54 g / mol )  10 −6 Mg 
Mass of unit cell = m =   = 4.22 x 10-28 Mg
4.7  1023 atmos / mol  g 


v =
m
=
4.22  10−28 Mg
= 8.98
Mg
= 8.98
g

V 4.7  10−29 m 3 m3 cm 3

3-30
 Theoretical density - example
The lattice constant of gallium arsenide
(GaAs) is 5.65 Å. Show that the theoretical
density of GaAs is 5.33 g/cm3.

GaAs unit cell, there are four Ga and four As

atoms per unit cell.
Crystallographic Points,
Directions, and Planes