Chapter 3:

Atomic & Ionic Arrangements

Week 2 Lecture Notes

R. Clemmer
ME 215 Winter 2011
References
 D.R. Askeland, P.P. Fulay, W.J. Wendelin, “The Science and
Engineering of Materials,” 6th ed., Cengage Learning, 2011.
 W.D. Callister, “Material Science and Engineering: An Introduction”,
5th ed.
Notes & Slides Outline
 Short Range Order vs. Long Range Order
 Amorphous Materials
 Lattice, Basis, Unit Cells, & Crystal
Structures
 Lattice & Basis
 Unit Cells
 Lattice Parameters & Interaxial Angles
 Number of Atoms per Unit Cell
 Atomic Radius vs. Lattice Parameter
 Coordination Number
 Packing Factor
 Hexagonal Close-Packed Structure
 Allotropic or Polymorphic Transformations
Notes & Slides Outline
 Points, Directions, & Planes in Unit Cells
 Directions
 Planes
 Miller Indices for Hexagonal Unit Cells
 Close-Packed Planes and Directions
 Isotropic & Anisotropic behaviour
 Interstitial Sites
 Crystal Structures of Ionic Materials
 Covalent Structures
 Diffraction Techniques for Crystal Structure Analysis
Points, Directions, &
Planes in Unit Cells

38
Coordinates of Points
 Some properties of a crystal are dependent on
directions and planes of atoms
 To define directions and planes, a special
coordinate system is used – Miller Indices
 Rather than using a Cartesian coordinate
system using length units, coordinates of atoms
are given as the number of lattice parameters
moved in the x, y, and z directions
 For a unit cell, coordinates will range from 0,0,0
to 1,1,1 since a unit cell has dimensions of
1x1x1
39
Coordinates of Points

(Askeland) 40
Miller Indices for Directions
Steps for Determining Miller Indices for Directions
1. Find the coordinates of 2 points that lie in the
direction
2. Subtract the “tail” coordinates from the “head”
coordinates (gives number of lattice points travelled)
3. Clear fractions and reduce to lowest terms

4. Enclose numbers in square brackets, e.g. [hkl]

5. Negatives are represented by a bar over the

number

41
Miller Indices of Directions

(Askeland) 42
Points regarding Miller Indices (Directions)

 Directions are vectors – a direction and its

negative are not equal i.e. [100] ≠ [-100]
 Directions and their multiples are equal, i.e.
[100] = [200]
 Families of directions are groups of
equivalent directions and indicated by < >
brackets

43
Equivalency of Directions

(Askeland) 44
Directions of the Form <110>

(Askeland) 45
Miller Indices for Planes
Steps for Determining Miller Indices for Planes
1. Identify the points where the plane intercepts
the x, y, z axes (may have to move origin if plane
passes through it)
2. Take reciprocals of the intercepts
3. Clear fractions but do NOT reduce to lowest
terms
4. Enclose numbers in parentheses, e.g. (hkl)
5. Negatives are represented by a bar over the
number
46
Miller Indices of Planes

(Askeland) 47
Points regarding Miller Indices (Planes)

 Planes and their negatives are equal i.e.

(100) = (-100)
 Planes and their multiples are not equal, i.e.
[100] ≠ [200] (as demonstrated by planar
densities)
 Families of planes are groups of equivalent
planes and indicated by { } brackets

atoms/face
Planar Density 
area of face
48
Planar Density of Different Planes

(Askeland) 49
Planes of the Form {110}

(Askeland) 50
Miller Indices for Hexagonal Unit Cells

 A special set of Miller-Bravais indices for

HCP structures was devised to account for
the symmetry in the crystal structure
 3 – axis system: Similar to before (hkl) or [hkl]
 4 – axis system: A third a-axis (a3) is added
where a1 = h, a2 = k, and a3 = i and
h  k  i  0 or h  k  - i

51
Miller Indices for HCP Unit Cells

(Askeland) 52
Converting from (h’k’l’) to (hkil)

h 1 (2h  k )
' '
3
k 1 (2k  h )
' '
3
i - 1 (h  k )
' '
3
ll '

 Clear fractions and reduce to lowest terms as

required
53
Miller Indices for HCP Unit Cells

(Askeland) 54
Close-Packed Planes & Directions
 Close-packed directions are directions in which
atoms are in contact
 Close-packed planes are planes of atoms all in
contact
 HCP has two parallel close-packed planes
(called basal planes):
 A (0001) and B (0002)
 Stacking these planes produces the HCP structure
 FCC crystals have 4 non-parallel close-packed
planes of the form {111}

55
Close-Packed Planes and
Directions

(Askeland) 56
Isotropic vs. Anisotropic Behaviour
 A material may behave differently in one
crystallographic direction or another because
of differences in atomic arrangement
 Isotropic: Properties are identical in all
directions
 Anisotropic: Properties are dependent on the
crystallographic direction
 A polycrystalline material may act isotropic
since many crystals are randomly oriented
within the structure.
57
Interstitial Sites
 In addition to the regular atom placement in a
crystal structure, other atoms (usually smaller)
may fit in the spaces between atoms
 Interstitial sites are the locations between
regular atoms or ions in a crystal structure
 SC – cubic interstitial sites
 BCC – tetrahedral, octahedral sites
 FCC – octahedral, tetrahedral sites
 For an atom to fit in an interstitial site it cannot
be “too big or too small” (based on the radius ratio)

58
Simple Cubic Unit Cell

The Simple Cubic Unit Cell has 1 interstitial site

(Askeland) 59
BCC Unit Cell

The BCC Unit Cell has 24 Tetrahedral interstitial sites and

6 Octahedral interstitial sites

(Askeland) 60
FCC Unit Cell

The FCC Unit Cell has 8 Tetrahedral and

12 Octahedral interstitial sites
(Askeland) 61
Octahedral Site in FCC

2R

2r

4
a0  R
2
62
Crystal Structures of Ionic
and Covalent Materials

63
Crystal Structures of Ionic Materials
 Ionic crystals allow different sized ions to be
packed efficiently yet maintain electrical
neutrality
 Typically the larger anions occupy the regular
lattice points with smaller cations occupying
interstitial sites

64
Sodium Chloride Structure

(Askeland) 65
Zinc Blende

(Askeland) 66
Crystal Structures of Covalent Materials

 The directional qualities of covalent bonds

results in complex crystal structures

67
Diamond Cubic

(Askeland) 68
Crystalline Silica

(Askeland) 69
Crystalline Polymers

(Askeland) 70
Diffraction Techniques for
Crystal Structure Analysis

71
How do we know the distance between
atoms and crystal structures?
 X-ray diffraction (XRD-Max von Laue 1912
Nobel Prize winner)
 Similar effects as diffraction grating in optics
 X-rays have much smaller wavelength than
visible light
 Wavelengths have a similar order of magnitude
to the spacing between atoms

72
X-Ray Diffraction Patterns

(Askeland) 73
Bragg’s Law

n = 2d sin 
 = wavelength of x-rays
d = interplanar spacing
 = angle of incidence and
diffraction of x-rays
n = an integer

74
Interplanar Spacing, dhkl

 Distance between two parallel planes of

atoms with the same Miller indices
 For cubic crystals:
a0
dhkl 
h  k l
2 2 2

75
X-ray
diffractometer

X-Ray Detector
or photographic film strip

Diffraction
spectrum
for gold

(Askeland) 76