1/24/2013

LECTURE #05

Chapter 3: Packing Densities and 
Coordination

Learning Objecti es
Learning Objectives
• How does atomic packing factor change with 
different atom types?
• How do you calculate the density of a 
material?
l?

Relevant Reading for this Lecture...

• Pages 46-58.
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Re‐‐cap: Atomic Packing Factor (APF)
Re
Volume of atoms in unit cell* Describes 
How efficiently 
APF =  atoms fill space 
Volume of unit cell within a given 
unit cell
unit cell
*
*assume hard spheres
h d h

Unit cell contains:
6 x 1/2 + 8 x 1/8  
=  4 atoms/unit cell
4 volume
2a
2 a 4 )3
( 2a/4)
(
3 atom
APF = 
volume
a3
unit cell
a
Close‐packed directions:  •  APF for a face‐centered 
Adapted from
Fig. 3.1(a),

3
Callister 7e. 
length = 4R = 2 a cubic structure = 0.74

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If the unit cell has different

atoms – watch out!

Ceramic Crystal
y Structures!

Watch Out! Different Atoms.  Must Modify APF Equations.
3a
Rblue
a

a
2a

Close‐packed directions:
Adapted from 
Fig. 3.2(a), Callister 7e.
a diagonal = 2Rblue + 2Rred = 3 a
Must put in correct value 
atoms for each atom type
for each

unit cell volume

4
2  ( 3a/4) 3
3 atom
APF =  volume
a3
5 unit cell

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What if ions from the crystal structure?

Cs+

Clԟ

Same rules as metals Structure: CsCl type Ionic packing factor

w/respect to crystal Bravais lattice: simple cubic (IPF), similar definition
symmetry. Ions/unit cell: 1 Cs+ + 1 Clԟ at APF.
Cesium chloride (CsCl) unit cell showing (a) ion positions and the two ions per lattice point 
and (b) full‐size ions. Note that the Cs+−Cl− pair associated with a given lattice point is not 
a molecule because the ionic bonding is non‐directional and because a given Cs+ is equally 
bonded to eight adjacent Cl−, and vice versa.
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Calculate the following: (1) The CN of CsCl (2) Ionic Packing Factor of CsCl

Recall from the last lecture CN → r/R =r +/r –

What are the r’s for Cs+ and Cl-?

r Cs+ = 0.170 nm These numbers came from inside cover of text book!
r Cl- = 0.181 nm

r +/r – = 0.939

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Now calculate the Ionic Packing Factor of CsCl

For these ions, they touch along the body diagonal
(make sure you know which direction the ‘hard
spheres’ are touching)

[# of atoms/unit cell] [volume of a sphere]

IPF = volume of unit cell

One atom of Cs + One atom of Cl

4/3π(0.170nm)3 + 4/3π(0.181nm)3

VCs VCl
3a
= 0.0454
0 0454 nm3
r Cs+ = 0.170 nm
a r Cl- = 0.181 nm
√3 a = 2rCs+ + 2rCl-
a = 0.405 nm
2a V = a3 = 0.0664nm3

IPF = 0.683
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For kicks, what if the ions touched along the edge length (not the body diagonal)?

[# of atoms/unit cell] [volume of a sphere]

IPF = volume of unit cell

O t
One atom off C
Cs + O t
One atom off Cl
4/3π(0.170nm)3 + 4/3π(0.181nm)3

r Cs+ = 0.170 nm VCs VCl

r Cl- = 0.181 nm which r?
= 0.0454 nm3 average them?

√3 a = 2rCs+ + 2rCl-
a = 0.405 nm a = 2r
V = a3 = 0.0664nm3 ravg = 0.176
0 176
a = 0.405 nm 0.352nm
V = a3 = 0.0436nm3

IPF = 0.683 1.04

Not possible! >100% packing!!!

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It is critical that you identify the correct ‘hard sphere’ touching directions!

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Let’s do another example: Consider NaCl

What is the CN?
What is the IPF?

How do we determine CN?

Correct, CN → r +/r –

What are the r’s for Na+ and Cl-?

r Na+ = 0.102 nm Again, got these
numbers from
r Cl- = 0.181 nm inside cover of
text book!

r +/r – = 0.564

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Not a very clear representation

– let’s expand it!

Motif
2 ions per lattice point

Do you see how the green spheres form a FCC structure?!

The blue spheres do the same thing, form

a FCC structure

We have two interpenetrating FCC lattices

Commonly called a Rock Salt structure –
structure seen in other materials including
TiC, TaC, MgO, CaO, etc.

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Calculate the IPF of NaCl

[# of atoms/unit cell] [volume of a sphere]

IPF =
volume of unit cell

What type of unit cell do we have? Two FCC lattices – one for Na and one for Cl

4 atoms/Na FCC + 4 atoms/Cl FCC = 8 atoms/unit cell total

Four atoms of Na + Four atoms of Cl

= 0.117nm3
4 x 4/3π(0.102 nm)3 + 4 x 4/3π(0.181 nm)3

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What is the volume of the unit cell?

a = 2r Na + 2rCl IPF = 0.117nm3 (previous slide)

0.181nm3
a = 0.566nm
= 0.65
V = a3 = 0.181nm3

W t h O t! Diff
Watch Out! Different Ions.  
tI
2 a

a CORRECTION!

Though it looks like FCC symmetry, 
the face diagonal atoms don’t touch; 
but the edge atoms do touch!

Why?  Cations and anions do not 
have the same size! Before we 
considered atoms of the same size
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Atoms can occupy ‘interstitial’ sites Unoccupied space 
in center can 
accommodate small 
atoms, e.g. He in 
UO2 fuel rods

Fl it (C F2) 
Fluorite (CaF )
unit cell showing 
(a) ion positions 
(b) full‐size ions. 

Note: useful info on atom

placement
FCC interstitial sites
FCC interstitial sites
Structure: fluorite (CaF2) type
Bravais lattice: FCC
Ions/unit cell: 4Ca2+ + 8F-
Typical ceramics: UO2, ThO2, TeO2

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CLASS ROOM EXAMPLE:

Calculate the ionic packing factor for UO2, which has the CaF2 structure 

U and O ions touch along a

portion of the body diagonal

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CLASS ROOM EXAMPLE:  SOLUTION

Calculate the ionic packing factor for UO2, which has the CaF2 structure 

This problem is tricky!

The face diagonal has a length of 2a.

The body diagonal has a length of 3a.

Along with the cell edge, they form a right

triangle within the unit cell.
U2+
3a a The Ca2+ and F- ions touch a short distance
along the body diagonal.
O-
By the principle of similitude, this smaller
2a a triangle, measures as ¼ the size of the large
triangle
a one.

Because of this, the length of the bond becomes:

1
 3a  RU 4  RO 2  0.105  0.132 nm  0.548 nm
4

Now you can calculate a and the corresponding unit cell volume.
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CLASS ROOM EXAMPLE:  SOLUTION ‐ continued

3a Vions in unit cell

 RU 4  RO2  0.105  0.132 nm IPF 
4 Vunit cell

Solving for a we get: a  0.548 nm

Vunit cell  a 3   0.548 nm   0.164 nm3

3

4
Vsingle ion   R 3
3

4 4 16 32
Vions  4   RU3 4  8   RO3 2    0.105     0.132   0.0965 nm3
3 3

3 3 3 3

Vions 0.0965 nm3

IPF    0.588
Vunit cell 0.164 nm3
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THEORETICAL DENSITY, 
Density = mass/volume

mass = number of atoms per unit cell  mass of each atom

mass = number of atoms per unit cell  mass of each atom

mass of each atom = atomic weight / Avogadro’s number

# atoms/unit cell Atomic weight (g/mol)

 nA
Volume/unit cell VcNA Avogadro's number
(cm3/unit cell) (6.023 x 10 23 atoms/mol)

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THEORETICAL DENSITY, 
# atoms/unit cell Atomic weight (g/mol)

 nA
Volume/unit cell VcNA Avogadro's number
(cm3/unit cell) (6.023 x 10 23 atoms/mol)

Example:  Copper
•  crystal structure = FCC:  4 atoms/unit cell
•  atomic weight = 63.55 g/mol (1 amu = 1 g/mol)
• atomic radius R 0 128 nm (1 nm 10‐7 cm)
•  atomic radius R = 0.128 nm   (1 nm = 10

Vc = a3 ; For FCC, a = 4R/ 2 ; Vc = 4.75 x 10-23cm3

Result: theoretical Cu = 8.89 g/cm3 Why the difference?
Compare to actual: Cu = 8.94 g/cm3
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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 20
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Densities of Material Classes
In general Graphite/ 
metals >  ceramics > polymers
Metals/  Composites/ 
Ceramics/  Polymers
Alloys fibers
Semicond
30
Why? Platinum
B ased on data in Table B1, Callister 
*GFRE, CFRE, & AFRE are Glass,
20 Gold, W
Metals have...
have Tantalum Carbon & Aramid Fiber‐Reinforced
Carbon, & Aramid Fiber Reinforced
Epoxy composites (values based on
• close‐packing 60% volume fraction of aligned fibers
10 Silver, Mo in an epoxy matrix).
(metallic bonding) Cu,Ni
Steels
• often large atomic masses Tin, Zinc
Zirconia
5
Ceramics have...
 (g/cm  )
3

Titanium
4 Al oxide
Diamond
• less dense packing 3 Si nitride
Aluminum Glass ‐soda Glass fibers
• often lighter elements Concrete
Silicon PTFE GFRE*
2 Carbon  fibers
Polymers
y have... Magnesium G raphite
Silicone CFRE *
A ramid fibers
PVC
• low packing density PET
PC
AFRE *
1
(often amorphous) H DPE, PS
PP, LDPE
• lighter elements (C,H,O)
0.5
Composites have... 0.4
Wood

• intermediate values 0.3
Data from Table B1, Callister 7e. 

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Summary
• If there are different ions in the unit cell, 
APF/IPF equations must be modified! Find out
APF/IPF equations must be modified! Find out 
which direction the ‘hard spheres’ touch 
• The ionic packing factor can be calculated by
Vions in unit cell
IPF 
Vunit cell
• Theoretical Density can be calculated by
Theoretical Density can be calculated by
# atoms/unit cell Atomic weight (g/mol)

 nA
Volume/unit cell VcNA Avogadro's number
(cm3/unit cell) (6.023 x 10 23 atoms/mol)

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