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1/24/2013

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Chapter3:PackingDensitiesand Chapter3:PackingDensitiesand
Coordination Coordination
Learning Objecti es
LECTURE #05
LearningObjectives
Howdoesatomicpackingfactorchangewith
differentatomtypes?
Howdoyoucalculatethedensityofa
l? material?
2
Pages 46-58.
Relevant Reading for this Lecture...
Re Recap:AtomicPackingFactor(APF) cap:AtomicPackingFactor(APF)
APF=
Volumeofatomsinunitcell*
Volumeofunitcell
* h d h
Describes
Howefficiently
atomsfillspace
withinagiven
unit cell
*assumehardspheres
unitcell
2 a
4
t ( 2a/4)
3
4
atom
volume
Unitcellcontains:
6x 1/2+8x 1/8
= 4atoms/unitcell
a
2a
Adaptedfrom
Fig.3.1(a),
Callister7e.
APF=
3
( )
atom
a
3
unitcell
volume
Closepackeddirections:
length=4R= 2a
APFforafacecentered
cubicstructure=0.74
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If the unit cell has different If the unit cell has different
atoms watch out!
Ceramic Crystal Structures! y
4
WatchOut!DifferentAtoms.MustModifyAPFEquations. WatchOut!DifferentAtoms.MustModifyAPFEquations.
a
R
blue
a 3
a
Adaptedfrom
Fig.3.2(a),Callister7e.
a 2
a
Closepackeddirections:
Mustputincorrectvalue
for each atom type
3 a diagonal =2R
blue
+2R
red
=
APF=
4
3
t ( 3a/4)
3
2
atoms
unit cell
a
3
unit cell
volume
foreach atom type
atom
volume
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Whatifionsfromthecrystalstructure? Whatifionsfromthecrystalstructure?
I onicpackingfactor Samerulesasmetals Structure: CsCl type
Cl

Cs
+
Cesiumchloride(CsCl)unitcellshowing(a)ionpositionsandthetwoionsperlatticepoint
and(b)fullsizeions.NotethattheCs
+
Cl

pairassociatedwithagivenlatticepointisnot
amoleculebecausetheionicbondingisnondirectionalandbecauseagivenCs
+
isequally
bondedtoeightadjacentCl

,andviceversa.
I onic packing factor
(IPF), similar definition
at APF.
Same rules as metals
w/respect to crystal
symmetry.
Structure: CsCl type
Bravaislattice: simple cubic
Ions/unit cell: 1 Cs
+
+1 Cl

6
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 rs for Cs


+
and Cl
-
?
r
Cs+
= 0.170 nm
r
Cl-
= 0.181 nm
These numbers came from inside cover of text book!
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
a 3
One atom of Cs + One atom of Cl
4/3(0.170nm)
3
+ 4/3(0.181nm)
3
V
Cs
V
Cl
0 0454
3
IPF =
r
Cs+
= 0.170 nm
r
Cl-
= 0.181 nm
a 2
a
3 a= 2r
Cs+
+ 2r
Cl-
a= 0.405 nm
V = a
3
= 0.0664nm
3
IPF = 0.683
= 0.0454 nm
3
8
For kicks, what if the ions touched along the edge length (not the body diagonal)?
[# of atoms/unit cell] [volume of a sphere]
volume of unit cell
O t f C O t f Cl
IPF =
One atom of Cs + One atom of Cl
4/3(0.170nm)
3
+ 4/3(0.181nm)
3
V
Cs
V
Cl
= 0.0454 nm
3
r
Cs+
= 0.170 nm
r
Cl-
= 0.181 nm
which r?
average them?
0 176
3 a = 2r
Cs+
+ 2r
Cl-
a = 0.405 nm
a = 2r
r
avg
= 0.176
V = a
3
= 0.0664nm
3
a
a = 0.405 nm 0.352nm
V = a
3
= 0.0436nm
3
Not possible! >100% packing!!!
It is critical that you identify the correct hard sphere touching directions!
IPF = 0.683 1.04
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Lets do another example: Consider NaCl
What is the CN?
What is the IPF?
How do we determine CN?
Correct, CN r
+
/r

r
Na+
= 0.102 nm
r
Cl-
= 0.181 nm
What are the rs for Na
+
and Cl
-
?
Again, got these
numbers from
inside cover of
text book!
r
+
/r

= 0.564
10
Not a very clear representation
lets expand it!
Motif
2 ions per latticepoint
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]
volume of unit cell
IPF =
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
4 x 4/3(0.102 nm)
3
+ 4 x 4/3(0.181 nm)
3
= 0.117nm
3
What type of unit cell do we have?
12
W t h O t! Diff t I W t h O t! Diff t I
a = 2r
Na
+ 2r
Cl
a = 0.566nm
0.181nm
3
IPF = 0.117nm
3
(previous slide)
= 0.65
V = a
3
= 0.181nm
3
What is the volume of the unit cell?
2a
WatchOut!DifferentIons. WatchOut!DifferentIons.
CORRECTION!
a
ThoughitlookslikeFCCsymmetry,
theface diagonalatomsdonttouch;
buttheedgeatomsdotouch!
Why?Cationsandanionsdonot
havethesamesize!Beforewe
consideredatomsofthesamesize
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Fl it (C F )
Unoccupiedspace
incentercan
accommodatesmall
atoms,e.g.Hein
UO
2
fuelrods
Atomscanoccupyinterstitialsites Atomscanoccupyinterstitialsites
Fluorite(CaF
2
)
unitcellshowing
(a)ionpositions
(b)fullsizeions.
Not e: usef ul i nf o on at om
pl ac ement
FCC interstitial sites FCCinterstitialsites
Structure: fluorite (CaF
2
) type
Bravaislattice: FCC
Ions/unit cell: 4Ca
2+
+8F
-
Typical ceramics: UO
2
, ThO
2
, TeO
2
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CalculatetheionicpackingfactorforUO
2
,whichhastheCaF
2
structure
CLASSROOMEXAMPLE:
U and O ions touch along a
portion of the body diagonal
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CLASSROOMEXAMPLE:SOLUTION
This problem is tricky!
The face diagonal has a length of 2a.
CalculatetheionicpackingfactorforUO
2
,whichhastheCaF
2
structure
The body diagonal has a length of 3a.
Along with the cell edge, they form a right
triangle within the unit cell.
The Ca
2+
and F
-
ions touch a short distance
along the body diagonal.
By the principle of similitude, this smaller
triangle measures as the size of the large a
2
3a
U
2+
O
-
a
triangle, measures as the size of the large
one.
a
2a
4 2
1
3 0.105 0.132 0.548
4
U O
R R nm nm
+
= + = + = a
a
Because of this, the length of the bond becomes:
Now you can calculate aand the corresponding unit cell volume.
16
CLASSROOMEXAMPLE:SOLUTION continued
ionsinunit cell
unit cell
V
IPF
V
=
Solving for we get: 0.548nm = a a
4 2
3
0.105 0.132
4
U O
R R nm
+
= + = +
a
( )
3
3 3
0.548 0.164
unit cell
V a nm nm = = =
3
singleion
4
3
V R t =
4 4 16 32
( ) ( ) 4 2
3 3
3 3 3
4 4 16 32
4 8 0.105 0.132 0.0965
3 3 3 3
ions
U O
V R R nm t t t t
+
= + = + =
3
3
0.0965
0.588
0.164
ions
unit cell
V nm
IPF
V nm
= = =
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THEORETICALDENSITY, THEORETICALDENSITY,
Density=mass/volume
mass = number of atoms per unit cell mass of each atom mass=numberofatomsperunitcell massofeachatom
massofeachatom=atomicweight/Avogadrosnumber
n A
# atoms/unit cell Atomic weight (g/mol)
=
n A
V
c
N
A
Volume/unit cell
(cm
3
/unit cell)
Avogadro's number
(6.023 x 10
23
atoms/mol)
18
=
n A
V N
# atoms/unit cell Atomic weight (g/mol)
THEORETICALDENSITY, THEORETICALDENSITY,
V
c
N
A
Volume/unit cell
(cm
3
/unit cell)
Avogadro's number
(6.023 x 10
23
atoms/mol)
Example:Copper
crystalstructure=FCC:4atoms/unitcell
atomicweight=63.55g/mol (1amu =1g/mol)
atomic radius R 0 128 nm (1 nm 10
7
cm) atomicradiusR=0.128nm(1nm=10
7
cm)
V
c
= a
3
; For FCC, a = 4R/ 2 ; V
c
= 4.75 x 10
-23
cm
3
Compare to actual:
Cu
= 8.94 g/cm
3
Result: theoretical
Cu
= 8.89 g/cm
3
Why the difference?
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Ex:Cr(BCC)
A = 52.00g/mol
TheoreticalDensity, TheoreticalDensity,
R =0.125nm
n =2
a=4R/3=0.2887nm
a
R
atoms
g
=
a
3
52.00 2 unitcell
mol
g
unitcell
volume atoms
mol
6.023x10
23

theoretical
=7.18g/cm
3

actual
=7.19g/cm
3
20
20
DensitiesofMaterialClasses DensitiesofMaterialClasses

metals
>

ceramics
>

polymers
Why?
Graphite/
Ceramics/
Semicond
Metals/
Alloys
Composites/
fibers
Polymers
20
30
B asedondatainTableB1,Callister
*GFRE,CFRE,&AFREareGlass,
Carbon & Aramid FiberReinforced
Tantalum
Gold,W
Platinum
Metals have
Ingeneral

(
g
/
c
m

)
3
2
Carbon,&AramidFiber Reinforced
Epoxycomposites(valuesbasedon
60%volumefractionofalignedfibers
inanepoxymatrix). 10
3
4
5
Magnesium
Aluminum
Steels
Titanium
Cu,Ni
Tin,Zinc
Silver,Mo
Tantalum
G raphite
Silicon
Glass soda
Concrete
Sinitride
Diamond
Aloxide
Zirconia
PTFE
Silicone
CFRE *
GFRE*
Glassfibers
Carbon fibers
Metals have...
closepacking
(metallicbonding)
oftenlargeatomicmasses
Ceramics have...
lessdensepacking
oftenlighterelements
Polymers have...
DatafromTableB1,Callister7e.
1
0.3
0.4
0.5
HDPE,PS
PP,LDPE
PC
PET
PVC
Silicone
Wood
AFRE *
Aramidfibers
y
lowpackingdensity
(oftenamorphous)
lighterelements(C,H,O)
Composites have...
intermediatevalues
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Iftherearedifferentionsintheunitcell,
APF/IPF equations must be modified! Find out
Summary Summary
APF/IPFequationsmustbemodified!Findout
whichdirectionthehardspherestouch
Theionicpackingfactorcanbecalculatedby
Theoretical Density can be calculated by
ionsinunit cell
unit cell
V
IPF
V
=
TheoreticalDensitycanbecalculatedby
=
n A
V
c
N
A
# atoms/unit cell Atomic weight (g/mol)
Volume/unit cell
(cm
3
/unit cell)
Avogadro's number
(6.023 x 10
23
atoms/mol)
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