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• A material is crystalline if the atoms display long-range order, i.e. the same
repeating arrangement over-and-over.
• The atoms in some materials do not have long-range order. These are
called amorphous or glassy. Most polymers are amorphous, but so are
some ceramics, metals, and forms of carbon.
• Equilibrium structures are those with the minimum Gibbs energy G, although
atomic movement in solids is so slow that equilibrium is often not reached at
room temperature. (In thermodynamics you’ll see that G = H – TS)
Hard-sphere model of crystals
• We may show the atoms as points or small spheres connected by lines, or
we may show them as hard spheres of defined diameter in contact with one
another.
• For a metal with a face-centered cubic lattice:
volume
atoms atom
a 4
unit cell 1 p (0.5a) 3
R=0.5a 3
APF = = 0.52
a3 volume
atoms/unit cell = 8 x 1/8 = 1 unit cell
The coordination number is the number of nearest neighbors.
What is it here?
Body Centered Cubic Structure (BCC)
Examples: Cr, W, Fe(), Ta, Mo
All atoms are identical and are How many touch the one in
colored differently only the center?
for ease of viewing.
Coordination number = 8
Atoms touch only along
cube diagonals. Number of atoms per unit cell?
1 center + 8 corners x 1/8 = 2
Atomic Packing Factor for BCC
3a
2a
Close-packed directions:
R length = 4R = 3 a
a
atoms volume
4
unit cell 2 p ( 3a/4) 3
3 atom
APF = = 0.68
3 volume
a
unit cell
Theoretical Density
Mass of Atoms in Unit Cell
Density = =
Total Volume of Unit Cell
nA
=
VC NA
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Example: Theoretical Density of Chromium
• Cr is body-centered cubic
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
a = 4R/ 3 = 0.2887 nm
R atoms
a g
unit cell 2 52.00
mol
=
a3 6.022 x 1023
volume atoms
unit cell mol
theoretical = 7.18 g/cm3
experimental = 7.19 g/cm3
Face Centered Cubic Structure (FCC)
Examples: Al, Cu, Au, Pb, Ni, Pt, Ag
2a
Close-packed directions:
length = 4R = 2 a
atoms volume
4
unit cell 4 p ( 2a/4) 3
3 atom
APF = = 0.74
3 volume
a
unit cell
This is the maximum achievable APF and
is one of two close-packed structures.
Crystal Systems
000
y
a b Point coordinates for unit cell
x corner are a, b, c 111
·
z 2c
·
Translation by an integer multiple
of lattice constants reaches an
· · identical position in another unit
b y cell
b
Miller Indices for Crystallographic Directions
z Algorithm
1. If necessary, translate the vector so it starts
at the origin.
2. Read off the end of the vector in increments
of unit cell dimensions a, b, and c.
y 3. Adjust these to the smallest integer values.
4. Enclose in square brackets without commas.
[110]
# atoms
2
LD = = 3.5 nm-1
length 2a
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Miller Indices for Crystallographic Planes
• Reciprocals of the three axial intercepts for a plane, cleared of fractions &
common multiples.
• All parallel planes have the same Miller indices.
• Algorithm (procedure):
1. If the plane passes through the origin, translate so it does not.
2. Read off the intercepts of the plane with the axes in increments
of the lattice constants (a, b, c).
For example, 1, 2, 2
3. Take reciprocals of those intercepts. If it is parallel to an axis
so that it doesn’t intersect it, the reciprocal is 0.
For example, 1, ½, ½
4. Convert the numbers to the smallest possible integer values.
For example, 2, 1, 1
5. Enclose those numbers in parentheses, with no commas.
For example (211).
6. As with directions, a bar over a number indicates it is negative.
• VMSE with illustrations, problems, exercises
• Families of equivalent planes. For a cubic structure, for example:
211 (211),(121),(112),( 211),(2 1 1),(21 1),etc.
Three Low-index Planes
Crystallographic Plane Examples
z
example a b c
1. Intercepts 1 1 c
2. Reciprocals 1/1 1/1 1/
1 1 0
3. Reduction 1 1 0 y
a b
4. Miller Indices (110)
x
z
example a b c
1. Intercepts 1/2 c
2. Reciprocals 1/½ 1/ 1/
2 0 0
3. Reduction 2 0 0
y
4. Miller Indices (100) a b
x
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Planar Density or Packing
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Planar Density of (100) -Iron (Ferrite)
For T < 912C the equilibrium structure of iron is BCC.
2D repeat unit
(100) 4 3
a= R
3
(from slide 8)
Radius R = 0.1241 nm
atoms
2D repeat unit 1
1 atoms 19 atoms
Planar Density = = 2 = 12.1 = 1.2 x 10
area a2 4 3 nm2 m2
R
2D repeat unit 3
Planar Density of (111) Ferrite
2a
3
h= a
2
2
4 3 16 3 2
area = 2 ah = 3 a 2 = 3 R = R
3 3
atoms
2D repeat unit 1
atoms = atoms
Planar Density = = 7.0 0.70 x 1019
area 16 3 nm2 m2
R2
2D repeat unit 3
Close-packed planes and structures
• {111} in FCC have metal atoms as close together as possible.
Called close-packed.
• So FCC structure of metals is also sometimes called “cubic close packed.”
• In VMSE:
http://higheredbcs.wiley.com/legacy/college/callister/1118061608/vmse/xtalclose.htm
Watch close-packed {111} planes added to build FCC:
http://departments.kings.edu/chemlab/animation/clospack.html
ABCABCABC , where A, B and C are three possible positions of atoms.
• In L-03B we look at another close-packed structure for metals built of the
same planes, but in a different order, ABABAB.
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