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MATERIAL SCIENCE
Chapter 3:
The Structure of Crystalline Solids
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Materials and Packing
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2
Adapted from Fig. 3.25(a),
Callister & Rethwisch 9e.
Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.25(b),
Callister & Rethwisch 9e.
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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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Unit cell concept
Unit cell is the basic structural unit or building block of any periodic structure.
(a) (b)
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Simple Cubic Structure (SC)
• Rare due to low packing density (only Po has this structure)
• Close-packed directions are cube edges.
• Coordination # = 6
1 atoms/unit cell: 8 corners x 1/8
(# nearest neighbors)
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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
a 4
unit cell 1 π (0.5a) 3
3
R = 0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 =
1 atom/unit cell
Adapted from Fig. 3.3 (a),
Callister & Rethwisch 9e.
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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,
Callister & Rethwisch 9e.
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 = 3 a
Fig. 3.2(a), Callister & a
Rethwisch 9e.
atoms volume
4
unit cell 2 π ( 3a/4 ) 3
3 atom
APF =
3 volume
a
unit cell
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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 9e.
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 = 2 a
2a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
Adapted from
Fig. 3.1(a),
Callister & atoms volume
Rethwisch 9e. 4 3
unit cell 4 π ( 2a/4 )
3 atom
APF =
3 volume
a
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 closed packed (HCP)
6 atoms/unit cell: 3 center + 2 face x 1/2 +12corners x 1/6
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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. 3.4(a),
Callister & Rethwisch 9e.
• Coordination # = 12 6 atoms/unit cell
• APF = 0.74 ex: Cd, Mg, Ti, Zn
• c/a = 1.633
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Home work 3
1. What is the difference between atomic structure and crystal structure?
2. Show for the body-centered cubic crystal structure that the unit cell edge length a and the atomic radius
R are related through a = 4R/ 3.
3. Show that the atomic packing factor for BCC is 0.68.
4. Show that the atomic packing factor for SC is 0.52.
5. Show that the atomic packing factor for FCC is 0.74.
6. Show for the body-centered cubic crystal structure that the unit cell edge length a and the atomic
radius R are related through a=4R/ 3
7. Show for the face-centered cubic crystal structure that the unit cell edge length a and the atomic
radius R are related through a=4R/ 2
8. If the atomic radius of lead is 0.175 nm, calculate the volume of its unit cell in cubic meters. Given
that lead has FCC structure.
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Theoretical Density,
Mass of Atoms in Unit Cell
Density = =
Total Volume of Unit Cell
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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z ex:
pt. 1 x1 = 0, y1 = 0, z1 = 0
pt. 2 x2 = 1, y2 = 0, z2 = 1/2
pt. 2
pt. 1: y X=1-0=1 , Y= 0-0=0, Z = ½ -0=1/2
head
tail
=> 1, 0, 1/2 => 2, 0, 1 => [ 201 ]
x
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Crystallographic Directions
z pt. 2
Example 2:
head
pt. 1 x1 = 1, y1 = 1/2, z1 = 0
pt. 2 x2 = -1, y2 = 1, z2 = 1
y
pt. 1:
x tail => -2, 1/2, 1
Multiplying by 2 to eliminate the fraction
-4, 1, 2 => [ 412 ] where the overbar represents a
negative index
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Crystallographic Directions
Z Z
origin Y origin Y
X Head - Tail X Head - Tail
X Y Z X Y Z
Head Head
Tail Tail
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22
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Crystallographic Planes
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z z
c c
y y
a b a b
x X Y Z x X Y Z
Interception z Interception
Reciprocal Reciprocal
c
·2/3
· y
·
1/2
a b
X Y Z
x
Interception
Reciprocal
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Crystallographic Planes
Z
Z
origin
Y
origin
Y
1/2
1/2
X
X X Y Z X Y Z
Interception Interception
Reciprocal Reciprocal
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Z Z
Y Y
X X
Home work 28
1. Molybdenum (Mo) has a BCC crystal structure, an atomic radius of 0.1363 nm,
and an atomic weight of 95.94 g/mol. Compute its theoretical density.
2. Calculate the radius of a palladium (Pd) atom, given that Pd has an FCC crystal
structure, a density of 12.0 g/cm3, and an atomic weight of 106.4 g/mol.
3. Calculate the radius of a tantalum (Ta) atom, given that Ta has a BCC crystal
structure, a density of 16.6 g/cm3, and an atomic weight of 180.9 g/mol.
.
Home work 29
Within a cubic unit cell, sketch the following directions:
[1 10] [1 1 1] [1 2 1] [1 22] [01 2] [12 3 ] [13 3] [1 03]
Sketch within a cubic unit cell the following planes:
(01 1 ) (1 11 ) (112 ) (12 2 ) (102 ) (1 23 ) (13 1) (01 3 )
What are the indices for the two planes drawn in the sketch?
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Quick review
[directions] (planes)
Z Z
1/2
Y origin
Y
origin 1/2
X Head - Tail X
X Y Z X Y Z
Head Interception
Tail Reciprocal
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Quick review
[directions] (planes)
Z Z
1/2
Y origin
Y
origin
1/2
X Head - Tail X
X Y Z X Y Z
Head Interception
Tail Reciprocal
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Linear Density Number of atoms (diameter)
• Linear Density of Atoms LD =
Unit length of direction vector
[110] ex: Compute linear density value for [110]
directions for Al. Al has an FCC crystal
structure and an atomic radius of 0.143nm.
a
Adapted from
Fig. 3.1(a),
Callister &
Rethwisch 9e.
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Linear Density Number of atoms (diameter)
• Linear Density of Atoms LD =
Unit length of direction vector
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X-ray diffraction (XRD)
spacing
between
planes
X-ray
intensity nλ
• Measurement of critical angle, c, d=
(from 2 sin θc
allows computation of planar detector)
spacing, d. θ
θc
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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 2θ
Diffraction pattern for polycrystalline α-iron (BCC)
Adapted from Fig. 3.22, Callister 8e.
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Example 37
A diffraction analysis experiment is performed on a sample of BCC crystal structure on
the plane (110). It is required to calculate the atom radius and the density of the sample.
Given that the wavelength of the first order X-ray, equals 0.154 nm, the incidence
angle of the X-ray =19.3o and the atomic weight of the sample 92.9 g/mol.
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Summary
• Materials can be single crystals or polycrystalline.
Material properties generally vary with single crystal
orientation (i.e., they are anisotropic), but are generally
non-directional (i.e., they are isotropic) in polycrystals
with randomly oriented grains.
• Some materials can have more than one crystal
structure. This is referred to as polymorphism (or
allotropy).
• X-ray diffraction is used for crystal structure and
interplanar spacing determinations.
Home work 39
• Compute and compare linear density values for [110] and [111] directions for tungsten.
Tungsten has a BCC crystal structure and an atomic radius of 0.137nm.
• Compute and compare linear density values for silver in the [100] and [111] directions.
Silver has an FCC crystal structure and an atomic radius of 0.144nm.
• Rhodium has an atomic radius of 0.1345 nm and a density of 12.41 g/cm3. Determine
whether it has an FCC or BCC crystal structure.
• The metal rubidium has a BCC crystal structure. If the angle of diffraction for the (321) set
of planes occurs at 27.00o (first-order reflection) when monochromatic x-radiation having
a wavelength of 0.0711 nm is used, compute (a) the interplanar spacing for this set of
planes and (b) the atomic radius for the rubidium atom.
• The metal iridium has an FCC crystal structure. If the angle of diffraction for the (220) set
of planes occurs at 69.22o (first-order reflection) when monochromatic x-radiation having
a wavelength of 0.1542 nm is used, compute (a) the interplanar spacing for this set of
planes and (b) the atomic radius for an iridium atom.