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ATOMIC STRUCTURE
Mc Graw Hill p84
Amethyst
SiO2
Halite
NaCl
(b) Pyrite
FeS2 (d)
Matter
1. Solids – crystalline
non-crystalline (amorphous)
2. Liquids
3. Gases
single crystal Si
silicon
Amorphous Si
Properties of crystalline solid :
1. have an orderly arranged units, practically incompressible.
2. show a definite melting point and sharp transition from solid to
liquid state.
3. Crystals are anisotropic (properties
change depending on direction)
eg. Graphite
silicon
Oxygen
noncrystalline SiO2 crystalline SiO2
Metallic glass
Basis = Group of atoms or
Understanding lattice : molecules identical in
composition or A group of
crystal structure = lattice + basis. atoms which describe
crystal structure
CsCl
The unit cell in the above diagram is a cube, consisting
of 6 faces, 12 edges and 8 vertices. The unit cell consists
of 1/4 Na+ ions per edge and a Na+ ion in the center of
the cube. The total number of Na+ ions in the unit cell is:
The unit cell consists of 1/8 Cl- ions per corner and 1/2
Cl- ions per edge of the cube. The total number of Cl-
ions in the unit cell is:
The unit cell contains 4 Na+ and 4 Cl- ions. This makes
sense because the ratio of Na+ to Cl- ions in NaCl is 1:1.
The NaCl unit cell can be repeated to form solid NaCl,
and therefore must have the same ratio of Na+ to Cl-.
Counting Atoms in 3D Cells
Vortex atom
(1/8 per atom
cell)
Body atom
(1 atom per
cell) Face atom
(1/2 per atom cell)
What is the formula of this
material?
Composition?
formula YBa2Cu3O7
Y center = 1
Ba center = 2
Cu, top and bottom corner =
8x1/8=1
Cu, edge =8x1/4=2
O, edge =12x1/4= 3
O, face =8x1/2=4
Two classes of lattices:
1. Bravais 2. non-Bravais.
All lattice points are some of the lattice
equivalent points are non-
equivalent.
note that
spheres in this
picture
represent lattice
points, not
atoms!
System Number of Lattice Symbol Restriction on crystal
Lattices cell angle
Cubic 3 SC, BCC, FCC a=b=c
α =β =γ=90°
Tetragonal 2 ST, BCT a=b≠c
α=β =γ=90°
Orthorhombic 4 SO, BCO, BSCO, a≠b≠ c
FCO α=β =γ=90°
Monoclinic 2 SM a≠b≠ c
BSCM α=β=90 °≠β
Triclinic 1 ST a≠b≠ c
α≠β≠γ
Rhombohedral 1 SR a=b=c
(trigonal) α=β =γ <120° ,≠90°
Hexagonal 1 SH a=b≠c
α =β =90° , γ=120o
vs.
Cubic lattice
structure
Dense packing
Two lattice parameters, c and a, describe the
hcp unit cell where c/a is 1.633. ratio <1.633,
atoms are compressed in the c-axis direction,
ratio > 1.633, the atoms are elongated along the
c-axis
12 nearest atom neighbors, CN = 12
Hexagonal lattice
structure
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
Simple Cubic Structure (SC)
• Rare due to low packing density (only Po has this structure)
• Close-packed directions are cube edges.
Coordination # = 6
(# nearest neighbors)
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
a 4
unit cell 1 p (0.5a) 3
3
R=0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 =
1 atom/unit cell
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.
2a
P91
Close-packed directions: McGraw
R Hill
a length = 4R = 3 a
atoms volume
4
unit cell 2 p ( 3a/4) 3
3 atom
APF =
3 volume
a
unit cell
The body-centred cubic
(bcc) structure is the most
stable form for lithium
metal at 298 K (25°C).
The closest Li-Li
separation is 304 pm
implying a lithium
metallic radius of 152 pm.
In the BCC lattice, every
lithium atom is
surrounded by eight other
nearest neighbour lithium
atoms organised into a
cubic array.
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.
Garnet
crystal
Garnet crystal
SUMMARY
Ideal atomic packing factors of all crystal structures :
Simple cubic: 0.52
Body-centered cubic: 0.68
Hexagonal close-packed: 0.74
Face-centered cubic: 0.74 Diamond cubic: 0.34
Relationship between atoms size (r) and unit cell dimensions
for FCC, BCC and simple cubic structure.
FCC BCC SC
Side of unit 2r
cell
Face 4r
diagonal
Body 4r
diagonal
http://highered.mcgraw-
hill.com/sites/0073529249/student_view0/chapter3/tutorials.html#
(Chapter 3 – Tutorials - Structure of crystalline solid)
Theoretical Density, r
Mass of Atoms in Unit Cell
Density = r =
Total Volume of Unit Cell
nA
r =
VC NA
• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2
R
a a = 4R/ 3 = 0.2887 nm
atoms
g
unit cell 2 52.00 rtheoretical = 7.18 g/cm3
mol
r= ractual = 7.19 g/cm3
a3 6.023 x 1023
volume atoms
unit cell mol
Densities of Material Classes
In general Graphite/
rmetals > rceramics > rpolymers
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond
30
Why? Platinum
20 Gold, W
Metals have... Tantalum
• close-packing
10 Silver, Mo
(metallic bonding) Cu,Ni
Steels
• often large atomic masses Tin, Zinc
Zirconia
r (g/cm3 )
5
Ceramics have... 4
Titanium
Al oxide
• less dense packing 3
Diamond
Si nitride
Aluminum Glass -soda
• often lighter elements Concrete
Silicon PTFE
Glass fibers
GFRE*
2 Carbon fibers
Polymers have... Magnesium Graphite
Silicone CFRE*
Aramid fibers
PVC
• low packing density PET
PC
AFRE*
1 HDPE, PS
(often amorphous) PP, LDPE
• lighter elements (C,H,O)
0.5
Composites have... 0.4
Wood
1 mm
Isotropic
Why?
- Deformation under loading (slip) occurs on certain
crystalline planes and in certain crystallographic directions.
Before we can predict how materials fail, we need to know
what modes of failure are more likely to occur.
Positive axes
x-axis (coming out of paper), y-axis (to the right of paper), z-axis (to the top of paper)
Atomic positions is Point Coordinates
Point position specified in terms of its
z coordinates as fractional multiples of the
111
unit cell edge lengths
c
Point coordinates for unit cell
center are
y a/2, b/2, c/2 (½ ,½, ½)
000
a b
x Point coordinate for one of the unit
z 2c cell corner is (1,1,1)
[210]
Directions
A direction is written as three numbers enclosed in
square brackets [hkl] and no commas between number,
with a line over a number if it is a negative.
Crystallographic Directions
Algorithm (Procedures to determine directions)
z 1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of unit cell
dimensions a, b, and c
Subtract coordinates
Determine the
of point of
coordinates of point
y of emergence (head)
Emergence (head) by
that of origin (tail)
and origin (tail)
x
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas [hkl]
[210] = divide by 2 = [1 ½ 0]
½
x
Head ½11 010 1½0
Tail 010 ½01 010
h’ ½-0=½ 0–½=-½ 1–0=1
k’ 1–1=0 1–0=1 ½-1=-½
z
Clear X2 X2 X2 ½ ½
fraction
h’ 1 -1 2
k’ 0 2 -1 0
l’ 2 -2 0 C
y
Direction
½ B
Indices [102] [12 2 ] [210 ] x
Figure 1
Families of crystallographic equivalent directions
(atom spacing along the direction is equal):
[110]
ex: linear density of Al in [110]
direction
a = 0.405 nm
# atoms
a 2
LD = = 3.5 nm -1
length 2a
Crystal Planes
Equispaced parallel
planes have same
Miller indices
Sets of equivalent lattice planes
Family of Planes {hkl}
related by crystal symmetry
Ex: {100} = (100),(010), (001), (100), (010), (001)
Crystallographic Planes
Miller Indices:
Algorithm
1. Read off intercepts of plane with axes in
terms of a, b, c (plane must not pass through
origin, if it does, MUST moves the origin)
2. Take reciprocals of intercepts
3. Reduce to smallest integer values
4. Enclose in parentheses, no commas i.e., (hkl)
Intercepts -1 -1/4
z
3/4
y
1/3
x
0
0
y
x
Intercepts -1 -5/12
2 1 5
Similarly, Blue line moves - = - , therefore will intercept y = -5/12
3 4 12
1. Intercepts 1 5/12
3/4
2. Reciprocals 1/1 1/(5/12) 1/
1/3 1 12/5 0
3. Reduction 5 12 0
0 4. Miller Indices (5 12 0)
y
Intercepts 1 5/12
1 + ¼(4) atoms
PD110 =
( a) (a)
= 17.2 atoms/nm2
Planar Density of (100) Iron
Solution: At T < 912C iron has the BCC structure.
2D repeat unit
(100) 4 3
a= R
3
Side
face
2a atoms in plane
atoms above plane
atoms below plane
3
h= a
2
2
4 3 16 3 2
area = 2 ah = 3 a = 3
2
R = R
atoms 3 3
1
atoms = atoms
Planar Density = = 7.0 0.70 x 1019
nm 2 m2
16 3 2
R
area 3
Calculate the planar densities of the (010) and (020) planes in a
simple cubic polonium, which has a lattice parameter of 0.334 nm.
Conclude whether the (010) and (020) planes are equivalent.
http://highered.mcgraw-
hill.com/sites/0073529249/student_view0/chapter3/tutorials.html#
(Chapter 3 – Tutorials – Determination of Crystallographic Directions)
example a b c
1. Intercepts 1
2. Reciprocals 1/ 1/ 1 1/
0 1 0
z
3. Reduction 0 1 0
4. Miller Indices (010)
example a b c
1. Intercepts 1/2 y
example a1 a2 a3 c
1. Intercepts 1 -1 1
2. Reciprocals 1 1/ -1 1
1 0 -1 1 a2
3. Reduction 1 0 -1 1
a3
reflections must
be in phase for
a detectable signal
extra
q q
distance
travelled
by wave “2” spacing
d between
planes
Measurement of X-ray
n
critical angle, qc, intensity d=
(from 2 sin qc
allows computation of
detector)
planar spacing, d.
q
qc
X-Ray Diffraction Pattern
z z z
c c c
y (110) y y
a b a b a b
Intensity (relative)
x x x (211)
(200)
Diffraction angle 2q