Lecture on CRYSTALLINE SOLIDS

SPACE LATTICE AND UNIT CELLS

Space Lattice -- atoms arranged in a pattern
that repeats itself in three dimensions.

Unit cell -- smallest grouping which can be
translated in three dimensions to recreate the
space lattice.



CRYSTAL SYSTEMS AND BRAVAIS
LATTICES

Seven crystal systems are each described by
the shape of the unit cell which can be
translated to fill space.
Bravais lattices -- fourteen simple and
complex lattices within the seven crystal
systems.
The complex lattices have atoms centered
either in the center of a "primitive" unit cell or
in the center of two/or more of the unit cell
faces.




PRINCIPAL METALLIC CRYSTAL
STRUCTURES

We will concentrate on three of the more
densely packed crystal structures, BCC -
body centered cubic, FCC - face centered
cubic,
and HCP - hexagonal close packed.

BCC - 2 atoms per unit cell CN = 8
0.68 =
V
V
=
APF

3
R 4
= a
cell unit
atoms
BCC
FCC - 4 atoms per unit cell CN = 12




HCP - 6 atoms per unit cell CN = 12
0.74 =
V
V
=
APF

2
R 4
=
a
cell unit
atoms
FCC FCC
0.74 =
V
V
=
APF

; 1.633 =
a
c
; R 3.266 =
c
; R 2 =
a
cell unit
atoms
HCP
HCP
HCP HCP
|
.
|

\
|
BCC
FCC HCP
EQUIVALENT SITES (ATOMIC POSITIONS)
IN CUBIC UNIT CELLS

Simple Cubic, SC - one per unit cell - corner
atoms only
(0,0,0) (1,0,0) (1,1,0) (0,1,0)
(0,0,1) (1,0,1) (1,1,1) (0,1,1)
Body Centered Cubic, BCC - two per unit cell -
corner atoms as above, plus (1/2, 1/2, 1/2)
Face Centered Cubic, FCC - four per unit cell -
corner atoms as above plus
(1/2, 1/2, 0) (1/2, 0, 1/2) ( 0, 1/2, 1/2)
(1, 1/2, 1/2) (1/2, 1, 1/2) (1/2, 1/2, 1)
BCC
FCC HCP
Lattice Sites in an Orthogonal Coordinate System
i.e. Simple Cubic
DIRECTIONS IN CUBIC LATTICES
1 . Vector components of the direction are
resolved along each of the coordinate axes
and reduced to the smallest integers.
2. All parallel directions have the same
direction indices.
3. Equivalent directions have the same atom
spacing.
4. The cosine of the angle between two
directions is given by

)
l
+
k
+
h
( )
l
+
k
+
h
(
l l + k k + h h
=
2 2 2 2 2 2
' ' '
' ' '
u cos
Indices of a Family or Form

00] 1 [ ], 1 [00 0], 1 [0 [001], [010], [100], > 100 <
negatives six the plus
] [ ], [ ], [ ], [ ], [ ], [ > < 1 10 1 01 0 1 1 101 011 110 110
] [ ], [ ], [ ], [
] [ ], [ ], [ ], [ > <
1 1 1 1 1 1 1 1 1 1 1 1
, 11 1 1 1 1 1 11 111 111
MILLER INDICES FOR
CRYSTALLOGRAPHIC PLANES

Definition: Miller Indices are the
reciprocals of the fractional intercepts (with
fractions cleared) which the plane makes with
the crystallographic x,y,z axes of the three
nonparallel edges of the cubic unit cell.

! cleared fractions with
c
1
,
b
1
,
a
1
= Indices Miller
|
.
|

\
|
Spacing between planes in a cubic crystal




where d
hkl
= inter-planar spacing between
planes with
Miller indices h,k,and l.
a = lattice constant (edge of the cube)
h, k, l = Miller indices of cubic planes
being considered.
l
+
k
+
h
a
=
d
2 2 2
hkl
CRYSTALLOGRAPHIC PLANES AND
DIRECTIONS IN HEXAGONAL UNIT
CELLS

Miller-Bravais indices -- same as Miller
indices for cubic crystals except that there are
3 basal plane axes and 1 vertical axis.

Basal plane -- close packed plane similar to
the (1 1 1) FCC plane.
contains 3 axes 120
o
apart.
Miller Bravais indices are h,k,i,l

with i = -(h+k). Basal plane indices (0 0 0 1)

Prism planes -- {1 0 0} family

Direction Indices in HCP Unit Cells -- [hkil]
where h+k = -i

COMPARISON OF FCC, HCP, AND
BCC CRYSTAL STRUCTURES

Both FCC and HCP structures are close
packed APF = 0.74.

The closed packed planes are the {111}
family for FCC and the (0001) plane for HCP.
Stacking sequence is ABCABCABC in FCC
and ABABAB in HCP.

BCC is not close packed, APF = 0.68. Most
densely packed planes are the {110} family.
VOLUME, PLANAR, AND LINEAR
DENSITY

Volume density --


Planar density --


Linear Atomic density --




cell t volume/uni
cell mass/unit
= = metal of density Volume
v

plane of area selected

d intersecte centers atom #
= = density atomic Planar
p

line of length selected

d intersecte diameters atom #
= = density atomic Linear
l

X-ray Diffraction and Braggs Law

n = order of reflection, whole number of
reflections
= x-ray wavelength
d
hkl
= spacing between planes with indices
(hkl)
= angle between incident x-ray beam and
crystal planes (hkl)

u sin 2
hkl
d = n
Figure 3.29
Figure 3.28
X-ray Diffraction and Braggs Law




n = order of reflection, whole number of
reflections
= x-ray wavelength
d
hkl
= spacing between planes with indices
(hkl)
= angle between incident x-ray beam and
crystal planes (hkl)

u sin 2
hkl
d = n
For cubic crystals

l
+
k
+
h
a
=
d
2 2 2
hkl
u sin 2 154 . 0
2 2 2
l k h
a
= nm
+ +
u sin 2
hkl
d = n
1 = n
nm
K Cu
154 . 0
,
=
o

Selection Rules for Observing X-ray Peaks

FCC : (h k l) must all be either odd or even

BCC : sum h + k + l must be even

(Otherwise, an in between plane will cancel
the reflection)
POLYMORPHISM OR ALLOTROPY


Existence of more than one equilibrium
crystallographic form for elements or
compounds at different conditions of
temperature and pressure.



Example:

Iron liquid above 1539 C.
-iron (BCC) between 1394 and
1539 C.
-iron (FCC) between 912 and
1394 C.
-iron (BCC) between -273 and
912 C.