Close packed structures

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 Outlook
• Close packed structures:
a) cubic close packed (c.c.p.) or face centered
cubic (f.c.c.)
b) hexagonal close packed
• Materials described by close packed structures
(metals, alloys, ionic compounds, covalent
compounds, molecular compounds)
• Voids in close packed structures
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 Two ways of describing structures:
1. close packing: guiding factor = realization of maximum density
2. Space filling polyhedron: structure = polyhedra linked together
by sharing corner, edges or faces

Examples of Packing:
Irregular shapes Regular shape

http://www.photographyontherun.c
om/HexagonalClosePacking.aspx
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Examples of space filling polyhedron:

Corner shared Td
Corner shared CaF8 cubes

Edge shared Oh

Face sharing Oh

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 Close packed structures
Two packing arrangements of atoms in 2D:
1. HEXAGONAL 2. SQUARE

closest-packed of a single layer of spheres is the HEXAGONAL

coordination of each sphere

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 Packing: from 2D to 3D

+ + =

A B C C.C.PFCC
Shown displaced for clarity

+ + =

A B A
HCP
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In 3D, a structure is formed by stacking Close
Packed Planes.

Two possible stacking sequences:

1. …ABCABC...  Face centered cubic (f.c.c)

2. ...ABABAB... Hexagonal closed packed (h.c.p)

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 f.c.c. : …ABCABC… layers
Build up c.c.p. layers (ABC… packing) A

 B

Cubic: a=b=c, ===90ᵒ

4 atoms in the unit cell:
0, 0, 0
½, ½, 0
½ , 0, ½

0, ½ , ½
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 f.c.c. vs. b.c.c.

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 f.c.c. b.c.c.
•Close packed planes in f.c.c. • No close packed planes
• Only close packed directions

 4 different sets of planes: {111}

•Close packed directions

[-110]
[110]
[101] y
[-101]
[011]
[0-11]
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4 close packed directions
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 h.c.p.: …ABAB… packing
A close packed plane is at the
bottom and top of the unit cell
separated by 3 atoms in the cell
center also part of a close
packed plane

Hexagonal: a = b  c,
 =  = 90°,  = 120°
2 atoms in the unit cell at:
0, 0, 0 and 2/3, 1/3, 1/2
2/ 1/ 1/
3, 3, 2

only three close packed directions

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 Materials described by close packed
structures

1. Metals (covalent contributions to their interatomic bonding

make them less well packed structures)
2. Alloys (intermetallic phases or solid solutions)
3. Ionic structures (NaCl, ZnS, Na2O, NiAs)
4. Covalent network structures (diamond, SiC)
5. Molecular structures (H2, CH4, HCl)

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 1. Close packed metals
The reasons why a particular metal prefers a
particular structure are still not well understood

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Malleability and Ductility: characteristic of some
metals
• Slip of the planes occurs more easily if on a close packed plane

• depend on the number of close packed planes and directions possessed by

a structure
f.c.c h.c.p. b.c.c.
Close packed planes 4 1 -
Close packed directions 6 3 4

f.c.c. structure can undertake severe plastic deformation

f.c.c metals > h.c.p > b.c.c. (Nb which is b.c.c. is an exception)
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 2. Close packed alloys
Colored Golds:
FCC structures with color

Pure Au yellow
Cu(low) yellow
Cu(high) pink
Ni white
Al purple*
In Blue *
Cd green
* intermetallics

Some of these color changes can be explained by shifts in the

energy levels relative to the Fermi level.
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 ++ --
- + - +
-
+
3. Ionic structures + -
-
+
-
-
+
+
- +
- + - -
+ +
-
• Balance of attractive and repulsive electrostatic forces

• The relative size of ions affect the structure

• Because the anions are larger they form the close packed array and
the cations are in interstices

• The cations however are often too large to fit the interstices  the
anion array is expanding to accommodate them

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 Interstitials Sites

Tetrahedral T+ Tetrahedral T-
Octahedral O
(blue circles are above)
(red circle is above)

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Interstitial sitesL. distribution
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between two c.p. layers 17
 3D

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 Voids in f.c.c. structure

• O Oh sites in f.c.c. arrangement of • T Td sites in the f.c.c . arrangement

anions (fcc unit cell) of anions
•4 Oh sites in total •8 Td sites in total
1 •Location: on the body diagonals – two
12   1( centre)  4 on each body diagonal at ¼ of the
4 ( edge) distance from each end.
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 Examples of f.c.c structure
NaCl: Oh voids filled K2O: Td voids filled

0,1
½ ½ ¼,¾ ¼,¾

0,1 0,1
½ ¼,¾ ¼,¾

½ ½
0,1

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 Size of Oh and Td voids in f.c.c.:
Oh Face diagonal, a2 = 2R2
but, face diagonal is 2(R+r)

2R2 = 2(R+r)  (1+r/R)=2

Anions are touching

on the edge a = 2R* r/R =0.414
*The anion radius is R while the cation radius is r

Td Body diagonal is a3 = R6

(a=R2)
but, body diagonal is also 2(R+r)
R6 = 2(R+r);
(1+r/R)=6/2
Anions are touching on the
face diagonala2=2R r/R =0.225
a=R2

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 Voids in h.c.p. structure
A
The spacing of the close packed
layers:
B
d = 1.633r

A c=2x1.633r=2x1.633xa/2=1.633a

The voids are identical to the ones found in FCC

(1/3, 2/3, ¾ )

(0,0,5/8), (⅔,⅓,7/8)

(0,0,3/8)

(⅔, ⅓,1/8),
(1/ 3 , 2/ 3, ¼)
Oh void Td void
Octahedral voids occur in 1 orientation, tetrahedral voids occur in 2 orientations
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 HCP voids Position Voids / cell

Octahedral • (⅓,⅔,¼), (⅓,⅔,¾) 2

(⅔, ⅓,1/8), (0,0,3/8),

Tetrahedral 4
(0,0,5/8), (⅔,⅓,7/8)

Note: Some books, including West, give the h.c.p. anions at (0,0,0) and (⅓,⅔,½). As a result, the
Oh sites are at (⅔,⅓,¼) and (⅔,⅓,¼) while Td sites are (⅓, ⅔, 1/8), (0,0,3/8), (0,0,5/8) and (⅓,⅔,7/8)

Examples of h.c.p. structure from A. West

NiAs: Oh voids filled by Ni ZnS (wurtzite): ½ Td
voids filled by Zn

A. West: Basic Solid State Chemistry and its applications

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 Cubic void(BCC structures)

The anion spheres are touching on the edge but

 a = 2R Body diagonal: b = 2R+2r
Face diagonal: f=a2=2R2 2R3=2(R+r) R3 = (R+r) (R+r)/R=3
Body diagonal: b = a3 = 2R3  (1+r/R)=3

C.N. = 8 r/R =0.732

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 Stable Bonding Configurations in Ionic
solids

For a stable coordination the bonded cation and anion must be in

contact with each other.

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rcation / Ranion 0.225   
tetrahedral
0.414   
octahedral
0.732 
cubic
1

Radius Ratio Coordination no. Binary (AB) Structure-type

12
r+/r- = 1 none known

8
1 > r+/r- > 0.732 CsCl

6
0.732 > r+/r- > 0.414 NaCl

4
0.414 > r+/r- > 0.225 ZnS

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 4: Covalent network structures

Diamond structure: C60 structure: f.c.c. K3C60 structure:

- ½ C atoms form a c.c.p. -C60 form f.c.c array
(f.c.c) array - K filles all Oh and Td
- ½ C atoms fills the Td voids
voids

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 5. Molecular structures
Al2Br6 structure
Br form a h.c.p. array
Al fills 1/6 of Td sites

2 AlBr4 Td share an edge

• Close packing is also important in organic crystals but it is the molecules

that are close-packed rather than individual atoms

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