The Structure of Crystalline Solids

ISSUES TO ADDRESS...
What is the difference in atomic arrangement
between crystalline and noncrystalline solids?
What features of a materials atomic
structure determine its density?

Under what circumstances does a material

property vary with the measurement direction?

Reading Materials
Callister (9th ed): Chap. 3

Why study structure?

Materials are selected
based on their
properties
Properties are
determined by
structure
Structure can be
altered by processing

Four levels of structure

Atomic Structure What atoms
are present and what properties do
they possess?
Atomic Arrangement How are
atoms positioned relative to each
other and what bonding exists
between them?
Microstructure What crystals
exist at a level too small to be seen
with the naked eye?

Macrostructure How do the

microstructures fit together to make
the larger material?
4

Lower levels of order

Monatomic gas
molecules have no order,
but are not very relevant
in the study of materials
Amorphous Materials
have short-range order
with only the positions of
nearest neighbors
regulated (like the series
of water molecules shown
to the right).
5

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.
6

Materials and Packing

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

Noncrystalline materials...
atoms have no periodic packing
occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline

crystalline SiO2

Si

Oxygen

noncrystalline SiO2
7

Crystals as Building Blocks

Some engineering applications require single crystals:
--diamond single
crystals for abrasives

--turbine blades

Properties of crystalline materials

often related to crystal structure.
--Ex: Quartz fractures more easily
along some crystal planes than
others.

Polycrystals

Most engineering materials are polycrystals.

Anisotropic

1 mm
Nb-Hf-W plate with an electron beam weld.
Each "grain" is a single crystal.
If grains are randomly oriented,

Isotropic

overall component properties are not directional.

Grain sizes typ. range from 1 nm to 2 cm

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

Single vs Polycrystals
Single Crystals

E (diagonal) = 273 GPa

-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.

E (edge) = 125 GPa

200 mm

(Epoly iron = 210 GPa)

-If grains are textured,

anisotropic.
10

Cr ystalline vs. Lattice

* Crystalline

The atoms are situated in a repeating or periodic array

over large atomic distances
Amorphous, Noncrystalline
Cf. crystal structure

Hard Sphere Model

Ions (atoms) are all spheres
The nearest neighbor atom directly contact between each other.
No deformation due to contact

* Lattice
The lattice points situated in a repeating or periodic array.

Cf. lattice point

Imaginary points represent exactly identical surrounding.
11

Crystal structures
Most materials have significant long-range order.
Crystal structure is the size, shape, and arrangement
of atoms within a three-dimensional lattice.
Crystalline materials organize into one of 14 threedimensional patterns called Bravais lattices.

12

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

13

(P, Bo, F)

(P)

Bravais
Lattices

(P, Bo)
(P)

(P, Bo, F, Ba)

(P, Ba)

(P)

14

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

15

METALLIC CRYSTALS
tend to be densely packed.
have sever al r easons for dense packing:
-Typically, only one element is pr esent, so all atomic
r adii ar e the same.
-Metallic bonding is not dir ectional.
-Near est neighbor distances tend to be small in
or der to lower bond ener gy.

have the simplest cr ystal str uctur es.

We will look at thr ee such str uctur es...
Unit Cell
To represent the symmetry of the crystal structure, wherein all the
atom positions in the crystal may be generated by translation of the
unit cell integral distance along its edges.
generally, having the highest level of geometrical symmetry
4
16
Cf. primitive cell

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)

17

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

R=0.5a

APF =

volume
atom
4
p (0.5a) 3
1
3

a3
close-packed directions
contains 8 x 1/8 =
1 atom/unit cell

volume
unit cell
18

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

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

19

Atomic Packing Factor: BCC

APF for a body-centered cubic structure = 0.68
3a

a
2a

R
atoms

a
4

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

p ( 3a/4 ) 3
2
unit cell
3
APF =
volume
3
a
unit cell

20

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

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

21

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
atoms

4
unit cell
3
APF =

p ( 2a/4 ) 3
a3

volume
atom
volume
unit cell
22

STRUCTURE OF COMPOUNDS: NaCl

Compounds: Often have similar close-pac ked str uctur es.
Str uctur e of NaCl
Close-packed dir ections
--along cube edges.

Crystal FCC

Lattice FCC
23

FCC stacking

cubic stacking

How can we stack metal atoms to minimize

empty space?
2-dimensions

vs.

Now stack these 2-D layers to make 3-D structures

24

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

A
B
C

25

Hexagonal Close-Packed Structure

(HCP)
ABAB... Stacking Sequence

3D Projection

2D Projection
A sites

Top layer

B sites

Middle layer

A sites

Bottom layer

Coordination # = 12
APF = 0.74
c/a = 1.633

6 atoms/unit cell

ex: Cd, Mg, Ti, Zn

26

Theoretical Density, r
Density = r =

r =

where

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
= 6.023 x 1023 atoms/mol
27

Theoretical Density, r
Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2
R

atoms

unit cell

r=
volume
unit cell

2 52.00
a3 6.023 x 1023

a = 4R/ 3 = 0.2887 nm
g
mol

rtheoretical = 7.18 g/cm3

ractual

= 7.19 g/cm3

atoms

mol

28

Densities of Material Classes

In general
rmetals > rceramics > rpolymers
30
Why?
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...
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

Graphite/
Ceramics/
Semicond

Polymers

Composites/
fibers

Zirconia
Al oxide
Diamond
Si nitride
Glass -soda
Concrete
Silicon
G raphite

PTFE

Silicone
PVC
PET
PC
HDPE, PS
PP, LDPE

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

Wood

29

Linear Density
Linear Density of Atoms LD =

Number of atoms (or Occupied)

Unit length of direction vector

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

# atoms
a

LD =
length

= 3.5 nm -1

2a

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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

-Fe
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