Lecture - 7

The Structure of
Crystalline Solids

Md. Fakhrul Islam

The Structure of Crystalline Solids
 Materials and Packing
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers
crystalline SiO2
Adapted from Fig. 3.23(a),
Callister & Rethwisch 8e.

Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling

"Amorphous" = Noncrystalline noncrystalline SiO2

Adapted from Fig. 3.23(b),
Callister & Rethwisch 8e.
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 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

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 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.
- Electron cloud shields cores from each other
• Have the simplest crystal structures.

We will examine three such structures...

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 Shapes of Unit Cells
All the possible shapes of a unit cell are defined by 7 crystal systems, which
are based on the relationship among a,b,c and , , ,

a = b = c ; α = β = γ = 90° Cubic system

a = b ≠ c ; α = β = γ = 90° Tetragonal system

a ≠ b ≠ c ; α = β = γ = 90° Orthorhombic system

a = b = c ; α = β = γ ≠ 90° Rhombohedral (trigonal) system

a = b ≠ c ; α = β = 90°; γ = 120° Hexagonal system

a ≠ b ≠ c ; α = γ = 90° ≠ β Monoclinic system

a ≠ b ≠ c ; α ≠ β ≠ γ ≠ 90° Triclinic system

 TEST

a = b c; = = =
a = b = c; = = =
a c 90
90
Cubic Tetragonal
a a
a
a

a b c; = = = a b c; = = 90 ,
c
c 90 90
Orthorhombic β
b Monoclinic
b a
a

c
a b c;
α
a = b = c; = = β γ 90
a
90 a
b Triclinic
a a Rhombohedral
 a c

a β
a b
a
Simple Face-centered Body-centered Simple End face-centered
CUBIC MONOCLINIC Types of unit cells
α

+
c
a
Shapes of unit cell
a a
b
a
Simple End face-centered Body-centered Face-centered Simple
ORTHORHOMBIC RHOMBOHEDRAL

14 Bravais lattices
c c
c α
β γ
a b
120 o a a
a a
Simple Body-centered
HEXAGONAL TRICLINIC
TETRAGONAL

Bravais lattices define unit cells. When combined with translational operations they
give raise to 230 space groups, i.e there are 230 possible space-filling patterns that
atoms, ions or molecules can adopt in the 3D space
 Simple Cubic Structure (SC)
• Rare due to low packing density, only Polonium (Po, at. no. 84)
• Close-packed directions are cube edges.

• Coordination # = 6
(# nearest neighbors)

Click once on image to start animation

(Courtesy P.M. Anderson)

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 Atomic Packing Factor (APF)
Volume of atoms in unit cell*
APF =
Volume of unit cell

*assume hard spheres

• APF for a simple cubic structure = 0.52

volume
atoms
atom
4
a unit cell p (0.5a) 3
1
3
R=0.5a APF =
a3 volume
close-packed directions unit cell
contains 8 x 1/8 =
1 atom/unit cell
Adapted from Fig. 3.24,
Callister & Rethwisch 8e.
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 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

Adapted from Fig. 3.2,

Click once on image to start animation Callister & Rethwisch 8e.
(Courtesy P.M. Anderson)
2 atoms/unit cell: 1 center + 8 corners x 1/8
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 Atomic Packing Factor: BCC
• APF for a body-centered cubic structure = 0.68

3a

2a
Close-packed directions:
Adapted from R length = 4R = 3a
Fig. 3.2(a), Callister & a
Rethwisch 8e.
atoms
4 volume
unit cell 2 p ( 3 a/4 ) 3
3 atom
APF =
volume
a3
unit cell 0
 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

Adapted from Fig. 3.1, Callister & Rethwisch 8e.

Click once on image to start animation
(Courtesy P.M. Anderson) 4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8
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 Atomic Packing Factor: FCC
• APF for a face-centered cubic structure = 0.74
maximum achievable APF

Close-packed directions:
length = 4R = 2a
2a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
Adapted from
Fig. 3.1(a),
atoms
Callister & Rethwisch
4 volume
8e.
unit cell 4 p ( 2 a/4 ) 3
3 atom
APF =
volume
a3
unit cell
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 FCC Stacking Sequence
• ABCABC... Stacking Sequence
• 2D Projection

B B
C
A
A sites B B B
C C
B sites B B
C sites

A
• FCC Unit Cell B
C

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 Hexagonal Close-Packed Structure (HCP)

• ABAB... Stacking Sequence

• 3D Projection • 2D Projection

A sites Top layer

c B sites Middle layer

A sites Bottom layer

a Adapted from Fig. 3.3(a),
Callister & Rethwisch 8e.

• Coordination # = 12 6 atoms/unit cell

• APF = 0.74 ex: Cd, Mg, Ti, Zn

• c/a = 1.633 0
Determination of HCP Unit Cell Volume
For the HCP crystal structure, show that the ideal c/a ratio is 1.633
 The Closest Packing Arrangement
of Uniform Spheres
• abab packing – the 2nd layer is like the 1st but it is
displaced so that each sphere in the 2nd layer occupies a
dimple in the 1st layer.
• The spheres in the 3rd layer occupy dimples in the 2nd
layer so that the spheres in the 3rd layer lie directly over
those in the 1st layer.

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 The Closest Packing Arrangement
of Uniform Spheres
• abca packing – the spheres in the 3rd layer occupy
dimples in the 2nd layer so that no spheres in the 3rd layer
lie above any in the 1st layer.
• The 4th layer is like the 1st.

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Hexagonal Closest Packing

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Cubic Closest Packing

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 The Indicated Sphere Has 12
Nearest Neighbors
Each sphere in both ccp
and hcp has 12 equivalent
nearest neighbors.

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 Theoretical Density, r
Mass o Atoms i Unit Cell
Density = =
f
Total Volume on Uni
t Cell
f t
nA
=
VC NA

where n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadro’s number
= 6.022 x 1023 atoms/mol

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Theoretical Density for metals .
n = number of atoms
associated with each
S
= A =
unit cell

atomic weight (g/mol)

V Volume of the unit cell
Generally, ,
=

N = 6 . 023X1823 (mol
Smetal) SeramicSpolymer]Scomposite
Avogadro's number

j .

*
For BC) crystal structure , R = 0 .

124X10 em

=
A = 55 85 .

g/mol

Theoretical density

=
,

&Fe
2 55 .
85 X35
023x18239/cm3
=

64x(0 .
129x107/3x6 .

= 7 89
.

g/cm

Experimental value =
7 87
.

g/cm3
Difference = 0 02
.

g/cm3
 Theoretical Density, r

• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
R
Adapted from a a = 4R/ 3 = 0.2887 nm
Fig. 3.2(a), Callister &
Rethwisch 8e.
atoms
g
unit cell 2 52.00 theoretical = 7.18 g/cm3
mol
= ractual = 7.19 g/cm3
a3 6.022 x 1023
volume atoms

unit cell mol 0

-

j .

-1396x1022cm
a)

6
1022 m3
-

= 1396 x

= 1 396 x
.
10-28

arc
b) V
= = 1396X10

I
5 = 1 593
.

=> ac = 5 .
373X1823 => C = 1 593a
.

= 1 .
593a3 = 5 .
373x10-23

·a = 3 . 23x108 cm = 0 323
.
um

: 7 = 1 593X3 23
.
. X100
=
5 .
147X10 im
= 0 515 nm
.
Spp =

NA =
3X6 0234183
.

Pb- FCC

(+ - BCC

=
(u - FCC

Co- H(P
023x182
 Densities of Material Classes
In general Graphite/
r r r Metals/ Composites/
Ceramics/ Polymers
metals > ceramics > polymers Alloy
Semicond
fibers
30 s
Why? Based on data in Table B1, Callister
20 Platinum *GFRE, CFRE, & AFRE are Glass,
Gold, W
Metals have... Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
• close-packing 60% volume fraction of aligned fibers
10 Silver, Mo
(metallic bonding) Cu,Ni
in an epoxy matrix).
Steels
• often large atomic masses Tin, Zinc
Zirconia
Ceramics have... 3(g/
5
Titanium
Al oxide
4
• less dense packing c 3
Diamond
Si nitride
Aluminum
• often lighter elements m
Glass -soda
Concrete
PTFE
Glass fibers
2 Silicon GFRE*
Polymers have... r) Magnesium G raphite
Silicone
Carbon fibers
CFRE *
PVC Aramid fibers
• low packing density PET AFRE *
1 PC
(often amorphous) HDPE, PS
PP, LDPE
• lighter elements (C,H,O)
0.5
Composites have... 0.4
Wood

• intermediate values 0.3

Data from Table B.1, Callister & Rethwisch, 8e.
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 WORKED PROBLEM

Question: Al has a CCP arrangement of atoms. rAl= 1.423 Å =143 pm.

Calculate the lattice parameter of the unit cell and the density of Al (atomic
weight = 26.98) in g/cm3

Answer: CCP has a FCC unit cell. Cell contents: 4 atoms/cell [8 at corners
(1/8 each), 6 in faces (1/2 each)
1 1
a = 82 r = 8 2 × 1.423 = 4.025 Å
Al

d= 4M
3
82 r 3 Al N
A

4 × 26.98g • mol −1
d= = 2.698g • cm −3
3
8 2 × (1.423 × 10 −8 cm )3 (6.022 × 1023 mol −1)
 Crystals can have only n = 1 , 2, 3 .
4 6
. fold rotation axes .

- Crystallographic Restriction
Theorem

SYMBOLS & MEANING

a, b ,c - unit cell length

9I s - indices

↑x .
Py Pz - lattice
, point coordinates Shown in () or []

P
Px =
ga Point indices =
gts
Py = +b Coordinates :
(P P,. B),

R = SC

Indices are integers in Point/Plane indices (simply in parenthesis)

We can write fraction without brackets.

- b
0 46 um
enm
.

jo
Locate the point indices t

cont
·

Y * =
qa =
tX0 98. = 0 12 .
nm

R +b = 1x0 46 = 0 46nm
. .

i
=

R = Sc =
&x0 .
40 = 0 20 nm
.

X
the point
is situated on

this wall
Thanks