Chapter 3

Office Hours
Dr. M. Julian
Tuesday and Thursday right after this
class.
My office is in Collegiate Square over the
gym in MSE Suite 302. My name is on the
door.

Chapter 3
Crystals

perfect order

outline
Crystals
Unit cell
2-D simple, face centered
3-D simple, FCC, BCC, hexagonal
Density
2-D directions and planes
3-D directions and planes
Braggs law and X-ray diffraction

A crystal is a solid composed of atoms
arranged in a periodic array.

Lattice: An array of
points in a crystal with
identical neighborhoods
Lattice of a pattern is the array of points in
space with identical neighborhoods.
Lattice is unique to the pattern.
One repeating unit for each lattice point.
Lattice is independent of the origin.
While the lattice is unique to the pattern,
the pattern is not unique to the lattice.
Unit cell: repeat unit of the lattice.
Primitive Unit cell has one motif per cell.
Primitive Unit cell is the smallest repeating unit
of the cell.
For each lattice there is an infinite number of
choices of primitive unit cells.
A multiple cell: more than one motif to the
unit cell.
Three-Dimensional Basis
Vectors, Unit Cells
Definition Of Angstrom
1 = 10
-10
meters
= 0.1 nanometers
= 10
-8
centimeters
lattice
Atoms in
unit cell

a
0
CN

APF
lattice
Atoms in
unit cell

a
0
CN

APF
2- D simple
square
2-D Simple (Primitive) Square
unit cell
a
o
side of repeat cell
r
0
radius of atom
1 atom per unit cell
a
0
4 X = 1
Coordination Number
CN

number of nearest neighbor
atoms
unit cell
a
o
side of repeat cell
r
0
radius of atom
a
0
4 X = 1
CN =4
2-D Atomic Packing Factor
Area occipied by atoms in unit cell
_____________________________
Area of unit cell
unit cell
a
o
side of repeat cell
r
0
radius of atom
a
0
4 X = 1
CN =4
a
o
= 2 r
0

APF= tr
0
2
/a
0
2
= tr
0
2
/4 r
0
2
= t/4

APF= 0.785
A =4 r
0
2

lattice
Atoms in
unit cell

a
0
CN

APF
2- D simple
square
1 a
0
= 2 r
0

4 t/4=0.785
2-D Centered Square
unit cell
a
o
side of repeat cell
r
0
radius of atom
a
0
v 4 X = 1
B 1 x 1 = 1
CN =4
APF= 2 tr
0
2
/ 8 r
0

2
= tr
0
2
/4 r
2
= t/4

APF= 0.785

a
0
a
0
4 r
0
2a
o
2
= 16 r
0

2

a
o
2
= 8 r
0

2

a
o
= 2\2 r
0

A= 8 r
0

2

lattice
Atoms in
unit cell

a
0
CN

APF
2- D simple
square
1 a
0
= 2 r
0

4 t/4=0.785
2-D centered
square
2 a
o
= 2\2 r
0

4 t/4=0.785
3 D Simple (Primitive) Cubic
unit cell
a
o
side of repeat cell
r
0
radius of atom
v 8 X 1/8= 1
CN =6
a
0
a
o
= 2 r
0

Area occupied by atoms in unit cell
__________________
Area of unit cell
Volume occupied by atoms in unit cell
__________________
Volume of unit cell
3 D Simple (Primitive) Cubic
unit cell
a
o
side of repeat cell
r
0
radius of atom
vert: 8 X 1/8= 1
CN =6
a
0
3
0
3
4
r Sphere of Volume t =
3
0
3
0
) 2 (
3
4
r
r
APF
t
=
524 . = APF
a
o
= 2 r
0

6
t
=
lattice
Atoms in
unit cell

a
0
CN

APF
2- D simple
square
1 a
0
= 2 r
0

4 t/4=0.785
2-D centered
square
2 a
o
= 2\2 r
0

4 t/4=0.785
3- D simple
cubic
1 a
0
= 2 r
0
6 t/6=0.524
3-D Face Centered Cubic
unit cell
a
o
side of repeat cell
a
0
r
0
radius of atom
v 8 X 1/8 = 1
F 6 x = 3
a
o
= 2\2 r
0

CN =12
74 . 0 ) 2 2 /(
3
4
4
3 3
= t = r r APF
lattice
Atoms in
unit cell

a
0
CN

APF
2- D simple
square
1 a
0
= 2 r
0

4 t/4=0.785
2-D centered
square
2 a
o
= 2\2 r
0

4 t/4=0.785
3- D simple
cubic
1 a
0
= 2 r
0
6 t/6=0.524
3- D face
centered cubic
4 a
o
= 2\2 r
0

12 0.74
Body Centered Cubic
lattice
Atoms in
unit cell

a
0
CN

APF
2- D simple
square
1 a
0
= 2 r
0

4 t/4=0.785
2-D centered
square
2 a
o
= 2\2 r
0

4 t/4=0.785
3- D simple
cubic
1 a
0
= 2 r
0
6 t/6=0.524
3- D face
centered cubic
4 a
o
= 2\2 r
0

12 0.74
3-D Body
Centered
Cubic
HW HW Hw HW
Hexagonal Closest Packing
lattice
Atoms in
unit cell

a
0
CN

APF
2- D simple
square
1 a
0
= 2 r
0

4 t/4=0.785
2-D centered
square
2 a
o
= 2\2 r
0

4 t/4=0.785
3- D simple
cubic
1 a
0
= 2 r
0
6 t/6=0.524
3- D face
centered cubic
4 a
o
= 2\2 r
0

12 0.74
3-D Body
Centered
Cubic
HW HW HW HW
Hexagonal
Closest
Packing
EC EC EC EC
Metal
Crystal
Structure
a

Atomic
Radius
b

(nm) Metal
Crystal
Structure
Atomic
Radius
(nm)
Aluminum FCC 0.1431 Molybdenum BCC 0.1363
Cadmium HCP 0.1490 Nickel FCC 0.1246
Chromium BCC 0.1249 Platinum FCC 0.1387
Cobalt HCP 0.1253 Silver FCC 0.1445
Copper FCC 0.1278 Tantalum BCC 0.1430
Gold FCC 0.1442 Titanium () HCP 0.1445
Iron () BCC 0.1241 Tungsten BCC 0.1371
Lead FCC 0.1750 Zinc HCP 0.1332
Polonium PO PC 0.3359 Z = 84
Stacking
Cubic Closest Packing
Cubic Closest Packing
Density
where
n= number of atoms in unit cell
A = atomic weight
V= volume of unit cell
N
A
= Avogadros number (6.023 x 10
23
atoms/mol)
A
VN
nA
volume
mass
density = = =
Density of Copper
Where
n= number of atoms in unit cell
A = atomic weight
V= volume of unit cell
N
A
= Avogadros number (6.023 x 10
23
atoms/mol )
Atomic radius 0.128 nm
Structure FFC
Atomic weight 63.5 g/mol
Density ???? g/cm3
( )
23
3
2 9
10 * 023 . 6 * 10 * 10 * 128 . 0 * 2 2
5 . 63 * 4
=
Calculated Density = 8.89 gm/cm
3
Experimental Density = 8.94gm/cm
3

A
VN
nA
volume
mass
density = = =
Material Atomic Wt g/mol Density g/cc Atomic radius, nm
A 43.1 6.40 0.122
B 184.4 12.3 0.146
C 91.6 9.6 0.137
4
2
1
structure n volume
S 1 (2r)
3

FCC 4 (22r)
3

BCC 2 (4r/3)
3
A
VN
nA
volume
mass
density = = =
S FCC BCC
Crystallographic Direction
A crystallographic direction is a vector between two lattice points
in which the direction is indicated by [u v w] where u, v, and w are
integers that do not contain a common integer factor, except one.

The integers u, v, and w are called the indices of the
crystallographic direction and specify an infinite set of parallel
vectors.
2 D Crystallographic Direction
a
b
[11]
a
b
[10]
a
b
[21]
a
b
3 D Crystallographic Direction
Crystallographic Plane
A lattice plane connects three non-collinear lattice points.
A crystallographic plane is a set of parallel lattice planes. There are
an infinite number of parallel lattice planes.
Miller indices are three relatively prime integers, hkl, that are
reciprocals of the fractional intercepts that the crystallographic plane
makes with the crystallographic axes.
a
b
(21)
a
b
(01)
a
b
) 1 2 (
Crystallographic Plane
Modulus of Elasticity (GPa)

Metal [100] [110] [111]
Aluminum 63.7 72.6 76.1
Copper 66.7 130.3 191.1
Iron 125.0 210.5 272.7
Tungsten 384.6 384.6 384.6
Braggs Law
d- spacing
Braggs law
X-ray diffraction camera
Diffraction angle

d-spacing cubic
a
a
a
d
2
=
a
a
(11)
d
2 a
2 2
1 1
2
+
= =
a a
d
2 2 2
l k h
a
d
+ +
=
d-spacing cubic
a
a
(hk)
d
{(a/h)
2
+ (a/k)
2
}
2 2
k h
a
d
+
=
a/h
a/k
d-spacing for iron
structure hkl a, lattice
parameter
BCC 2 2 0 0.2866
2 2 2
l k h
a
d
hkl
+ +
=
2 2 2
220
0 2 2
2866 .
+ +
=
nm
d
nm d 1013 . 0
220
=
Braggs Law

X-ray Powder Diffraction Camera

incident beam
diffracted
beam
undeviated beam

crystal
plane
film
Calcium
fluoride
Diffraction angle iron
structure hkl a, lattice
parameter
,
wavelength
of x-rays
d
220
BCC 2 2 0 0.2866 0.1790 nm 0.1013 nm
13 . 62
884 . 0
1013 . 0 * 2
1790 .
2
sin
220
220
220
=
= = =
u
u
d
n
n
Diffraction angle = 124.26
n= 2 d
hkl
sin
hkl

Effects Of Temperature On
The Lattice Parameters
Isotropic properties of a material are those properties that
are independent of direction.

Anisotropic properties are those properties that depend on
direction.

For example, some crystals have isotropic thermal
expansion properties and others are anisotropic. The unit cell
parameters a, b, and c often change at different rates.
The linear coefficient of thermal expansion, o
l
, at
constant pressure for a particular lattice parameter is
defined as
o
l
=
P P
T
l ln
T
l
l
|
.
|
\
|
c
c
=
|
.
|
\
|
c
c 1
where l is the lattice parameter, T is the temperature, and P
is the pressure. The data are recorded at a single pressure, so
the pressure is constant.
l
, at
constant pressure for a particular lattice parameter is
defined as
o
l
=
P P
T
l ln
T
l
l
|
.
|
\
|
c
c
=
|
.
|
\
|
c
c 1
Urea data
T, Temperature, K

a,

c,
188 5.61365 4.69524
198 5.61652 4.69680
208 5.61902 4.69698
218 5.62233 4.69706
228 5.62423 4.69821
238 5.62731 4.69882
1.724
1.725
1.726
1.727
1.728
1.729
1.73
1.731
1.732
1.733
150 170 190 210 230 250 270 290 310 330 350
T, temperature, K
l
n
(
a
,

l
a
t
t
i
c
e

p
a
r
a
m
e
t
e
r
,

a
n
g
s
t
r
o
m
)
l
=

P P
T
l ln
T
l
l
|
.
|
\
|
c
c
=
|
.
|
\
|
c
c 1
1.724
1.725
1.726
1.727
1.728
1.729
1.73
1.731
1.732
1.733
150 170 190 210 230 250 270 290 310 330 350
T, temperature, K
l
n
(
a
,

l
a
t
t
i
c
e

p
a
r
a
m
e
t
e
r
,

a
n
g
s
t
r
o
m
)
Example For urea calculate the linear coefficient of thermal expansion
for the lattice parameter a.
Solution: From the data in table, plot
the natural logarithm of the lattice
parameter a vs. temperature.
The equation of the least squares line
that fits the data is
ln a = 5.23 x 10
-5
T + 1.7154
where a is the lattice parameter and T
is the temperature in K.
The slope in Equation 1.8 is the linear
coefficient of thermal expansion.
Thus
o
l
= 5.23 x 10
-5
K
-1

Effects Of Pressure On The
Lattice Parameters
upper
diamond
lower
diamond
Anthracene sample
external
force
external
force
gasket
fluid inside
gasket
Lattice Parameters
Pressure
GPa
a
, angstroms
b
,
angstroms
c
, angstroms
|
degrees
0.00 8.5319 6.0044 11.1482 124.5774
1.05 8.1099 5.8435 10.8806 125.2857
2.45 7.8850 5.7461 10.7518 125.7366
The linear coefficient of compressibility, |
, for a particular
lattice parameter at constant temperature is defined as

|
l
= -
T T
P
l ln
P
l
l
|
.
|
\
|
c
c
=
|
.
|
\
|
c
c 1
where l is the lattice parameter, T is the temperature, and P is the pressure. The minus
sign indicates that usually the lattice parameter decreases with increasing pressure.
Lattice Parameters
Pressur
e
GPa
a
,
angstroms
b
,
angstroms
c
,
angstroms
|
degrees
0.00 8.5319 6.0044 11.1482 124.5774
1.05 8.1099 5.8435 10.8806 125.2857
2.45 7.8850 5.7461 10.7518 125.7366
The linear coefficient of compressibility, |
l
, for a particular

|
l
= -
T T
P
l ln
P
l
l
|
.
|
\
|
c
c
=
|
.
|
\
|
c
c 1
1.9
1.95
2
2.05
2.1
2.15
2.2
0 5 10 15 20 25
P, pressure, GPa
l n
(
a
, l a
t
t
i c
e
p
a
r
a
m
e
t
e
r
, a
n
g
s
t
r
o
m
)
Lattice Parameters
The linear coefficient of compressibility, b
l
, for a particular

|
l
= -
T T
P
l ln
P
l
l
|
.
|
\
|
c
c
=
|
.
|
\
|
c
c 1
1.9
1.95
2
2.05
2.1
2.15
2.2
0 5 10 15 20 25
P, pressure, GPa
l n
(
a
, l a
t
t
i c
e
p
a
r
a
m
e
t
e
r
, a
n
g
s
t
r
o
m
)
( ) 2 /
1 2
1 2
2 1
,
2 1 2 1
2
P P P P
P P
a a
a a
+
~
(
= | |
The mean linear compressibility between two
pressures is
where a
1
and a
2
are the values of the lattice parameter at
the corresponding pressures, P
1
and P
2
.
Lattice Parameters
( ) 2 /
1 2
1 2
2 1
,
2 1 2 1
2
P P P P
P P
a a
a a
+
~
(
= | |
The mean linear compressibility between two
pressures is
where a
1
and a
2
are the values of the lattice parameter at
the corresponding pressures, P
1
and P
2
.
Example Calculate the mean linear compressibility for
anthracene for lattice parameter a between pressures of 6.07
and 6.70 GPa.
Solution: Use Table 1.3 and Equation 1.10 to get
GPa GPa 36 . 3 70 . 6 , 07 . 6
07 . 6 70 . 6
5646 . 7 5408 . 7
5408 . 7 5646 . 7
2
| | ~
(
=
= 0.005002 GPa
-1

= 5.0 MPa
-1

Pressure
GPa
a
, angstroms
6.07 7.5646
6.70 7.5408

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