Lecture 3 Crystals

Structures and Systems

20 October 2009

Preliminaries Crystals
Solid materials
Regularity/uniformity of atom arrangement

Crystalline material
Atoms arranged in a periodic array (lattices)
Over large atomic distances

Crystal structure
Influences properties of material

Otherwise, amorphous

Materials and Packing

Crystalline materials... atoms pack in periodic, 3D arrays typical of: -metals -many ceramics -some polymers

crystalline SiO2
Adapted from Fig. 3.40(a), Callister & Rethwisch 3e.

Noncrystalline materials...

Si

Oxygen

atoms have no periodic packing occurs for:

-complex structures -rapid cooling

"Amorphous" = Noncrystalline

noncrystalline SiO2
Adapted from Fig. 3.40(b), Callister & Rethwisch 3e.

Energy and Packing (Lattice Generation)

Non dense, random packing Energy

typical neighbor bond length

typical neighbor bond energy r

Dense, ordered packing

Energy typical neighbor bond length

typical neighbor bond energy

Dense, ordered packed structures tend to have lower energies.

Learning Outcomes
Discuss Unit Cells
Distinguish BCC, FCC and HCP Structures

Describe packing (lattice generation) in crystalline structures Calculate

Atomic packing factors (APFs) Theoretical densities

Explain crystallographic directions and Miller indices

Calculate values for these; and Outline their usefulness

Unit Cells
Basic building block
FCC, BCC, HCP

Important/Useful Aspects
Atoms per cell Unit cell sizes Coordination number Atomic packing factor (APF)

Simple Cubic Structure (SC)

Rare due to low packing density (only Po has this structure) Close-packed directions are cube edges.

Coordination Number = 6 (Number of nearest neighbours)

R=0.5a

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

Adapted from Fig. 3.42, Callister & Rethwisch 3e.

Atomic Packing Factor (APF)

APF =

Volume of atoms in unit cell

Volume of unit cell

APF for a simple cubic structure = 0.52 volume

atoms unit cell APF = a3 volume 4 atom

(0.5a)

unit cell

Homework - 3
What are the coordination numbers for
FCC BCC Unit Cells?

FCC Stacking Sequence

ABCABC... Stacking Sequence 2D Projection B A A sites B sites C sites FCC Unit Cell C B C B B B

C
B

A
B

Hexagonal Close-Packed Structure (HCP)

ABAB... Stacking Sequence
3D Projection A sites 2D Projection Top layer

B sites A sites

Middle layer Bottom layer

Adapted from Fig. 3.3(a), Callister & Rethwisch 3e.

Coordination Number = 12
APF = 0.74

6 atoms/unit cell e.g. Cd, Mg, Ti, Zn

17

Theoretical Density,
Density = =

Mass of Atoms in Unit Cell 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

Theoretical Density,
E.g. Cr (BCC) A = 52.00 g/mol R = 0.125 nm n = 2 atoms/unit cell
R
atoms
unit cell = volume 2 52.00 a 3 6.022 x 1023

a = 4R/ 3 = 0.2887 nm
a
g mol
theoretical actual

= 7.18 g/cm3 = 7.19 g/cm3

atoms
mol

unit cell

Homework - 4
Molybdenum has
BCC crystal structure Atomic radius of 0.1363nm Atomic weight of 95.94 g/mol

Calculate its theoretical density Actual density (at 20oC) is 10.22 g/cm3

Densities of Material Classes

Metals/ Alloys 30 20
Platinum Gold, W Tantalum Silver, Mo Cu,Ni Steels Tin, Zinc Titanium Aluminum Magnesium

Graphite/ Ceramics/ Semicond

Polymers

Composites/ fibers

10

B ased 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 G raphite

(g/cm 3)

5 4 3 2

PTFE
Silicone PVC PET PC HDPE, PS PP, LDPE

Glass fibers GFRE* Carbon fibers CFRE * A ramid fibers AFRE *

Generally
Wood

0.5 0.4 0.3

metals

>

ceramics

>

polymers

Data from Table B.1, Callister & Rethwisch, 3e.

Why?

Polymorphism
Two or more distinct crystal structures for the same material (allotropy)
Titanium
, -Ti
Iron System
liquid

1538C
BCC -Fe

1394C FCC
-Fe

912C
BCC -Fe

Carbon
diamond, graphite

Crystal Systems
Unit Cell
Characterised by six Lattice Parameters Seven Systems
14 Lattices
Fig. 3.20, Callister & Rethwisch 3e.

Crystal Systems
Unit Cell
Characterised by six Lattice Parameters Seven Systems
14 Lattices

z c

Point Coordinates
111

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

a x z

000

Point coordinates for unit cell corner are 111

2c

b
b

Translation: integer multiple of lattice constants identical position in another unit cell
25

Crystallographic Directions
z

Algorithm

y x

1. Vector repositioned (if necessary) to pass through origin. 2. Read off projections in terms of unit cell dimensions a, b, and c 3. Adjust to smallest integer values 4. Enclose in square brackets, no commas
[uvw]

E.g. 1, 0, -1, 1, 1

=> 2, 0, 1 =>

=> [ 201 ] where overbar represents a negative index

[ 111 ]

Families of directions <uvw>

26

Linear Density
Linear Density of Atoms LD =
[110]
E.g. linear density of Al in [110] direction a = 0.405 nm

Number of atoms

Unit length of direction vector

Number of atoms

LD
length

3.5 nm

2a

27

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 ]

u
a2

( 2 u ' - v ')

3
v a3 a1
Fig. 3.24(a), Callister & Rethwisch 3e. 28

1
3

( 2 v ' - u ')

t w

- (u + v )
w '

HCP Crystallographic Directions

z

Algorithm

a2

a3 a1
Adapted from Fig. 3.24(a), Callister & Rethwisch 3e.

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]
a2 2

a2
-a3

E.g.

, , -1, 0

=>

[ 1120 ]

a3
a1 2

dashed red lines indicate projections onto a1 and a2 axes

a1
29

Crystallographic Planes

Adapted from Fig. 3.25, Callister & Rethwisch 3e.

30

Crystallographic Planes
Miller Indices Reciprocals of the (three) axial intercepts for a plane, cleared of fractions and 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)
31

Crystallographic Planes z
Example 1. Intercepts 2. Reciprocals 3. 4. Reduction Miller Indices a 1 1/1 1 1 (110) a 1/2 1/ 2 2 b 1/ 0 0 c
c

b 1 1/1 1 1

1/ 0 0
x

y a

b z

Example 1. Intercepts 2. Reciprocals 3. Reduction

1/ 0 0
a
x b

4.

Miller Indices

(200)

32

Crystallographic Planes
z

Example
1. 2. Intercepts Reciprocals

a 1/2
1/

b 1
1/1

c 3/4
1/

2 3.
4.

1
3

4/3
4 x a

Reduction
Miller Indices (634)

Family of Planes {hkl}

E.g.

{100} = (100),

(010),

(001),

(100),

(010),

(001)
33

Crystallographic Planes (HCP)

In hexagonal unit cells the same idea is used
z

Example 1. Intercepts 2. Reciprocals

3.
4.

Reduction
Miller-Bravais Indices

a1 a2 1 1 1/ 1 0 1 0

a3 c -1 1 -1 1 -1 1 -1 1
a3

a2

(1011)
Adapted from Fig. 3.24(b), Callister & Rethwisch 3e.

a1

34

Crystallographic Planes
Suppose 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.
Draw (100) and (111) crystallographic planes for Fe. Calculate the planar density for each of these planes.

35

Planar Density of (100) Iron

Solution: At T < 912 C iron has the BCC structure.
2D repeat unit
(100)

4 3 R 3

Adapted from Fig. 3.2(c), Callister & Rethwisch 3e.

Radius of iron R = 0.1241 nm

atoms 2D repeat unit 1 a2

=

Planar Density =
area

1 4 3
2

2D repeat unit

atoms atoms 19 12.1 = 1.2 x 10 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

3 a 2
2

area
atoms 2D repeat unit 1

2 ah

3a

4 3 3 R 3

16 3 2 R 3
atoms m2
37

Planar Density =
area 2D repeat unit 16 3

7.0

R2

atoms = nm2

0.70 x 1019

Homework - 5 z

y x z x z

y
x x

Homework - 6
z

y x z x z

y x

y x

Recommended Reading
Callister and Rethwisch (2008). Fundamentals of Materials Science and Engineering (Third Edition). Chapter 3.