Structures of Crystalline Solids

Dr. Sujith R
Assistant Professor
Mechanical Engineering Department
BITS Pilani Hyderabad Campus
1

ISSUES TO ADDRESS...
How do atoms assemble into solid structures
in metallic, ceramic and polymeric materials?
How do the structures of ceramic materials
differ from those of metals?

How do polymeric crystals accommodate the

polymer chain?
How does the density of a material depend on
its structure?
2

 How can we stack metal atoms to minimize

empty space?
2-dimensions

vs.

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

3

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.

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)

(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

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
From Fig. 4.38
Callisters Materials Science and Engineering,
Adapted Version.

volume
unit cell
6

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

From Fig. 4.2,

Callisters Materials Science and Engineering,
Adapted Version.

(Courtesy P.M. Anderson)

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

7

Atomic Packing Factor: BCC

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

a
2a
From
Fig. 4.2(a)
Callisters Materials
Science and
Engineering,
Adapted Version.

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

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

From Fig. 4.1

Callisters Materials Science and Engineering,
Adapted Version.

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

(Courtesy P.M. Anderson)

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
From
Fig. 4.1(a),
Callisters Materials Science
and Engineering,
Adapted Version.

atoms

4
unit cell
3
APF =

p ( 2a/4 ) 3
a3

volume
atom
volume
unit cell
10

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

11

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. 4.3(a),

Callisters Materials Science and Engineering,
Adapted Version.

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

6 atoms/unit cell
ex: Cd, Mg, Ti, Zn
12

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
13

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

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

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Densities of Material Classes

In general
rmetals > rceramics > rpolymers
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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

Titanium
Aluminum
Magnesium

Graphite/
Ceramics/
Semicond

Polymers

Composites/
fibers

*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

PTFE

Silicone
PVC
PET
PC
HDPE, PS
PP, LDPE

0.5
0.4
0.3
Data from Table B1
Callisters Materials Science and Engineering,
Adapted Version.

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

Wood

15

Linear and Planar Atomic Densities

Linear Density:
Directional equivalency is related to the atomic linear density in the
sense that equivalent directions have identical linear densities.
The direction vector is positioned so as to pass through atom centers.
The fraction of line length intersected by these atoms is equal to the
linear density.

Planar Density:
Crystallographic planes that are equivalent have the same atomic planar
density. The plane of interest is positioned so as to pass through atom
centers.
Planar density is the fraction of total crystallographic plane area
that is occupied by atoms.

Linear and planar densities are one- and two-dimensional

analogs of the atomic packing factor.

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

LD =
length

= 3.5 nm -1

2a

17

Planner Density
Planner Density of Atoms PD =

number of atoms centered on a plane

area of plane

Although six atoms have centers that lie on this plane, only one-quarter of
each of atoms A, C,D, and F, and one half of atoms B and E, for a total
equivalence of just 2 atoms are on that plane.

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Atomic Packing of 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) Draw (100) and (111) crystallographic planes
for Fe.
b) Calculate the planar density for each of these
planes.

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Planar Density of (100) Iron

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

(100)

From Fig. 4.2(c), Callisters Materials Science

and Engineering,Adapted Version.

atoms
2D repeat unit

Planar Density =
area
2D repeat unit

1
a2

a=

4 3
R
3

Radius of iron R = 0.1241 nm

1
4 3
R
3

2 = 12.1

atoms
19 atoms
=
1.2
x
10
nm2
m2
20

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

16 3
3

nm

0.70 x 1019

atoms
m2
21

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
22

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. 11.33(c)
Callisters Materials
Science and
Engineering,
Adapted Version.
(Fig.11.33(c) courtesy
of Pratt and Whitney).

Properties of crystalline materials

often related to crystal structure.
--Ex: Diamond fractures more
easily along some crystal planes
than others is long known to Indian
lapidaries (111).

(Courtesy P.M. Anderson)

23

Polycrystals

Most engineering materials are polycrystals.

Anisotropic

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,

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).

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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.
(Epoly iron = 210 GPa)

-If grains are textured,

anisotropic.

E (edge) = 125 GPa

200 mm

Data from Table 3.2,

Callisters Materials
Science and
Engineering,
Adapted Version.
(Source of data is R.W.
Hertzberg, Deformation
and Fracture Mechanics
of Engineering
Materials, 3rd ed., John
Wiley and Sons, 1989.)

From Fig. 5.19(b),

Callisters Materials
Science and
Engineering,
Adapted Version.
(Fig. 5.19(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].)

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