Crystallography and

Structure
ME 2105
R. R. Lindeke
Overview:
Crystal Structure matter assumes a
periodic shape
Non-Crystalline or Amorphous structures
exhibit no long range periodic shapes
Xtal Systems not structures but potentials
FCC, BCC and HCP common Xtal
Structures for metals
Point, Direction and Planer IDing in Xtals
X-Ray Diffraction and Xtal Structure
Energy and Packing
Non dense, random packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Energy
Dense, ordered packing
typical neighbor
bond length

typical neighbor r
bond energy

Dense, ordered packed structures tend to have

lower energies & thus are more stable.
CRYSTAL STRUCTURES

Crystal Structure
Means: PERIODIC ARRANGEMENT OF ATOMS/IONS
OVER LARGE ATOMIC DISTANCES
Leads to structure displaying
LONG-RANGE ORDER that is
Measurable and Quantifiable

All metals, many ceramics, and some

polymers exhibit this High Bond
Energy and a More Closely Packed
Structure
Materials Lacking Long range order

These less densely

packed lower bond
Amorphous Materials energy structures
can be found in Metals
are observed in
Ceramic GLASS and
many plastics
 Crystal Systems Some
Definitional information
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.
7 crystal systems of varying
symmetry are known
These systems are built by
changing the lattice
parameters:
a, b, and c are the edge
lengths
, , and are interaxial
angles
Fig. 3.4, Callister 7e.
 Crystal Systems
Crystal structures are divided
into groups according to unit
cell geometry (symmetry).
Metallic Crystal Structures
Tend to be densely packed.
Reasons for dense packing:
- Typically, only one element is present, so all atomic
radii are the same.
- Metallic bonding is not directional.
- Nearest neighbor distances tend to be small in
order to lower bond energy.
- Electron cloud shields cores from each other
Have the simplest crystal structures.

We will examine three such structures (those of

engineering importance) called: FCC, BCC and
HCP with a nod to Simple Cubic
Crystal Structure of Metals of
engineering interest
Simple Cubic Structure (SC)
Rare due to low packing density (only Po Polonium --
has this structure)
Close-packed directions are cube edges.

Coordination No. = 6
(# nearest neighbors)
for each atom as seen
(Courtesy P.M. Anderson)
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
R=0.5a 3
APF =
a3 volume
close-packed directions
unit cell
contains (8 x 1/8) =
1 atom/unit cell Here: a = Rat*2
Adapted from Fig. 3.23, Where Rat is the handbook
Callister 7e.
atomic radius
Body Centered Cubic Structure (BCC)
Atoms touch each other along cube diagonals within a
unit cell.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.
ex: Cr, W, Fe (), Tantalum, Molybdenum

Adapted from Fig. 3.2,

Callister 7e.
Coordination # = 8
2 atoms/unit cell: (1 center) + (8 corners x 1/8)
(Courtesy P.M. Anderson)
 Atomic Packing Factor: BCC
3a

2a
Close-packed directions:
R
a length = 4R = 3 a

atoms volume
4
unit cell 2 p ( 3a/4) 3
3 atom
APF =
3 volume
Adapted from
Fig. 3.2(a), Callister 7e.
a
unit cell
APF for a body-centered cubic structure = 0.68
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 7e.

4 atoms/unit cell: (6 face x ) + (8 corners x 1/8)

(Courtesy P.M. Anderson)
Atomic Packing Factor: FCC
APF for a face-centered cubic structure = 0.74
The maximum achievable APF!
Close-packed directions:
2a length = 4R = 2 a
(a = 22*R)
Unit cell contains:
6 x 1/2 + 8 x 1/8
a = 4 atoms/unit cell
Adapted from
atoms volume
Fig. 3.1(a),
4
Callister 7e.
unit cell 4 p ( 2a/4) 3
3 atom
APF =
volume
a3
unit cell
 Hexagonal Close-Packed Structure (HCP)
ex: Cd, Mg, Ti, Zn
ABAB... Stacking Sequence
3D Projection 2D Projection

A sites
Top layer
c
B sites
Middle layer
A sites
a Adapted from Fig. 3.3(a),
Bottom layer
Callister 7e.

Coordination # = 12 6 atoms/unit cell

APF = 0.74
c/a = 1.633 (ideal)
We find that both FCC & HCP are highest density packing
schemes (APF = .74) this illustration shows their
differences as the closest packed planes are built-up
Theoretical Density, r
Mass of Atoms in Unit Cell
Density = r =
Total Volume of Unit Cell

nA
r =
VC NA

where n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadros number
= 6.023 x 1023 atoms/mol
 Theoretical Density, r
Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2
a = 4R/3 = 0.2887 nm
R
a
atoms rtheoretical = 7.18 g/cm3
g
2 52.00
mol ractual
unit cell = 7.19 g/cm3
r=
a3 6.023 x 1023
volume atoms
unit cell mol
Locations in Lattices: Point Coordinates
z
111 Point coordinates for unit cell
c center are
a/2, b/2, c/2

000
y
a b
Point coordinates for unit cell
x (body diagonal) corner are
z 2c 111

Translation: integer multiple of

b y lattice constants identical
position in another unit cell
b
Crystallographic Directions
z Algorithm
1. Vector is repositioned (if necessary) to
pass through the Unit Cell origin.
2. Read off line projections (to principal axes
of U.C.) in terms of unit cell dimensions a, b,
y and c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas
x
[uvw]

ex: 1, 0, => 2, 0, 1 => [ 201 ]

-1, 1, 1 => [ 111 ] where overbar represents a
negative index
families of directions <uvw>
 What is this Direction ?????

x y z
a/2 b 0c
Projections:
Projections in terms of a,b and c: 1/2 1 0
Reduction: 1 2 0
Enclosure [brackets] [120]
Linear Density considers equivalance and is
important in Slip
Number of atoms
Linear Density of Atoms LD =
Unit length of direction vector

[110]
ex: linear density of Al in [110]
direction
a = 0.405 nm

# atoms
a 2
LD = = 3.5 nm -1
length 2a

# atoms CENTERED on the direction of interest!

Length is of the direction of interest within the Unit Cell
Determining Angles Between Crystallographic
Direction:

u1u2 v1v2 w1w2
= Cos -1

u 2
1 v w u v w
2
1
2
1 2
2
2
2
2
2

Where uis , vis & wis are the Miller Indices of the directions in
question

also (for information) If a direction has the same Miller Indices as

a plane, it is NORMAL to that plane
HCP Crystallographic Directions
z
Algorithm
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of unit
a2 cell dimensions a1, a2, a3, or c
3. Adjust to smallest integer values
- 4. Enclose in square brackets, no commas
a3
[uvtw] a
a1
2
a2 -a3
Adapted from Fig. 3.8(a), Callister 7e.
2

ex: , , -1, 0 => [ 1120 ] a3

a1
2
dashed red lines indicate
projections onto a1 and a2 axes a1
HCP Crystallographic Directions
Hexagonal Crystals
4 parameter Miller-Bravais lattice coordinates are
related to the direction indices (i.e., u'v'w') in the 3
space Bravais lattice as follows.
z

[ u 'v 'w ' ] [ uvtw ]

1
u = (2 u ' - v ')
3
a2
1
v = (2 v ' - u ')
- 3
a3
t = - (u +v )
w = w'
a1

Fig. 3.8(a), Callister 7e.

Computing HCP Miller- Bravais Directional Indices
(an alternative way):
We confine ourselves to the bravais
parallelopiped in the hexagon: a1-
z a2-Z and determine: (u,vw)
Here: [1 1 0] - so now apply the
models to create M-B Indices

a2
u= 1
3
2u ' - v ' = 1
3
2 1 - 1 = 1
3
1

- v= 1
3
2v '- u ' = 1
3
2 1 - 1 = 1
3
1
a3

a1
t = - u v = - 1 3
1
3 = - 2 -2
3
w = w' = 0
M-B Indices: [11 20]
Defining Crystallographic Planes
Miller Indices: Reciprocals of the (three) axial
intercepts for a plane, cleared of fractions &
common multiples. All parallel planes have
same Miller indices.

Algorithm (in cubic lattices this is direct)

1. Read off intercepts of plane with axes in
terms of a, b, c
2. Take reciprocals of intercepts
3. Reduce to smallest integer values
4. Enclose in parentheses, no
commas i.e., (hkl) families {hkl}
Crystallographic Planes -- families
Crystallographic Planes 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/ 1/ 1/
2 0 0
3. Reduction 2 0 0
y
4. Miller Indices (100) a b
x
Crystallographic Planes
z
example a b c c
1. Intercepts 1/2 1 3/4
2. Reciprocals 1/ 1/1 1/
2 1 4/3 y

3. Reduction 6 3 4 a b

4. Miller Indices (634) x

Family of Planes {hkl}

Ex: {100} = (100), (010), (001), (100), (010), (001)

Determine the Miller indices for the plane shown in the sketch

x y z
Intercepts a -b c/2
Intercept in terms of lattice parameters -1 1/2
Reciprocals 0 -1 2
Reductions N/A
Enclosure (012)
Crystallographic Planes (HCP)
In hexagonal unit cells the same idea is used
z

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

4. Miller-Bravais Indices (1011) a1

Adapted from Fig. 3.8(a), Callister 7e.

Crystallographic Planes
We want to examine the atomic packing of
crystallographic planes those with the
same packing are equivalent and part of
families
Iron foil can be used as a catalyst. The
atomic packing of the exposed planes is
important.
a) Draw (100) and (111) crystallographic planes
for Fe.
b) Calculate the planar density for each of these
planes.
 Planar Density of (100) Iron
Solution: At T < 912C iron has the BCC structure.
2D repeat unit

(100) 4 3
a= R
3

Radius of iron R = 0.1241 nm

atoms
2D repeat unit 1
1 atoms atoms
19
Planar Density = = 2 = 12.1 = 1.2 x 10
area a2 4 3 nm 2 m2
R
2D repeat unit 3
Atoms: wholly contained and centered in/on plane within U.C., area of plane in U.C.
Planar Density of (111) Iron
Solution (cont): (111) plane 1/2 atom centered on plane/ unit cell

2a atoms in plane
atoms above plane
atoms below plane

3
h= a
2

Area 2D Unit: hb = *[(3/2)a][(2)a]=1/2(3)a2=8R2/(3)

atoms
2D repeat unit 3*1/6
atoms = atoms
Planar Density = = 7.0 0.70 x 1019
2
nm m2
area 8R 2
2D repeat unit 3
Adding Ionic Complexities

LOOKING AT THE CERAMIC

UNIT CELLS (CH 12)
Cesium chloride (CsCl) unit cell showing (a) ion positions and the two
ions per lattice point and (b) full-size ions. Note that the Cs+Cl pair
associated with a given lattice point is not a molecule because the ionic
bonding is nondirectional and because a given Cs+ is equally bonded to
eight adjacent Cl, and vice versa. [Part (b) courtesy of Accelrys, Inc.]
Sodium chloride (NaCl)
structure showing (a) ion
positions in a unit cell,
(b) full-size ions, and (c)
many adjacent unit cells.
[Parts (b) and (c)
courtesy of Accelrys,
Inc.]
Fluorite (CaF2) unit cell showing (a) ion positions and (b) full-size ions.
[Part (b) courtesy of Accelrys, Inc.]
SiO44-
SiO44-
Polymorphism: Also in Metals
Two or more distinct crystal structures for the
same material (allotropy/polymorphism)
iron system:
titanium
liquid
(HCP), (BCC)-Ti
1538C
BCC -Fe
carbon:
diamond, graphite 1394C
FCC -Fe
912C
BCC -Fe
The corundum (Al2O3) unit cell is shown superimposed on the repeated
stacking of layers of close-packed O2 ions. The Al3+ ions fill two-thirds
of the small (octahedral) interstices between adjacent layers.
Exploded view of the kaolinite unit cell, 2(OH)4Al2Si2O5. (From F. H.
Norton, Elements of Ceramics, 2nd ed., Addison-Wesley Publishing
Co., Inc., Reading, MA, 1974.)
Transmission electron
micrograph of the structure
of clay platelets. This
microscopic-scale structure
is a manifestation of the
layered crystal structure
shown in the previous slide.
(Courtesy of I. A. Aksay.)
(a) An exploded view of the graphite (C) unit cell. (From F. H. Norton, Elements
of Ceramics, 2nd ed., Addison-Wesley Publishing Co., Inc., Reading, MA,
1974.) (b) A schematic of the nature of graphites layered structure. (From W.
D. Kingery, H. K. Bowen, and D. R. Uhlmann, Introduction to Ceramics, 2nd
ed., John Wiley & Sons, Inc., NY, 1976.)
(a) C60 molecule, or
buckyball. (b) Cylindrical
array of hexagonal rings of
carbon atoms, or
buckytube. (Courtesy of
Accelrys, Inc.)
Arrangement of polymeric chains in the unit cell of polyethylene. The
dark spheres are carbon atoms, and the light spheres are hydrogen
atoms. The unit-cell dimensions are 0.255 nm 0.494 nm 0.741 nm.
(Courtesy of Accelrys, Inc.)
Weaving-like pattern of folded polymeric chains that occurs in thin
crystal platelets of polyethylene. (From D. J. Williams, Polymer Science
and Engineering, Prentice Hall, Inc., Englewood Cliffs, NJ, 1971.)
Diamond cubic unit cell showing (a) atom positions. There are two
atoms per lattice point (note the outlined example). Each atom is
tetrahedrally coordinated. (b) The actual packing of full-size atoms
associated with the unit cell. [Part (b) courtesy of Accelrys, Inc.]
Zinc blende (ZnS) unit cell
showing (a) ion positions. There
are two ions per lattice point (note
the outlined example). Compare
this structure with the diamond
cubic structure (Figure 3.20a). (b)
The actual packing of full-size
ions associated with the unit cell.
[Part (b) courtesy of Accelrys,
Inc.]
 Densities of Material Classes
In general Graphite/
rmetals > rceramics > rpolymers
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond
30
Why? Platinum *GFRE, CFRE, & AFRE are Glass,
20 Gold, W
Metals have... Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
close-packing 60% volume fraction of aligned fibers
10 Silver, Mo in an epoxy matrix).
(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

intermediate values 0.3

Data from Table B1, Callister 7e.
 Crystals as Building Blocks
Some engineering applications require single crystals:
--diamond single --turbine blades
crystals for abrasives
Fig. 8.33(c), Callister 7e.
(Courtesy Martin Deakins, (Fig. 8.33(c) courtesy
GE Superabrasives, of Pratt and Whitney).
Worthington, OH. Used with
permission.)

Properties of crystalline materials

often related to crystal structure.
--Ex: Quartz fractures more easily
along some crystal planes than
others.
(Courtesy P.M. Anderson)
Polycrystals Anisotropic
Most engineering materials are polycrystals.

Adapted from Fig. K,

color inset pages of
Callister 5e.
(Fig. K is courtesy of
Paul E. Danielson,
Teledyne Wah Chang
Albany)
1 mm

Nb-Hf-W plate with an electron beam weld. Isotropic

Each "grain" is a single crystal.
If grains are randomly oriented,
overall component properties are not directional.
Grain sizes typ. range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).
Single vs Polycrystals
Single Crystals
-Properties vary with
direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
Polycrystals
-Properties may/may not
vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)
-If grains are textured,
anisotropic.
E (diagonal) = 273 GPa
Source of data is R.W.
Hertzberg, Deformation
and Fracture Mechanics
of Engineering
Materials, 3rd ed., John
Wiley and Sons, 1989.
E (edge) = 125 GPa
200 mm
courtesy of L.C. Smith
and C. Brady, the
National Bureau of
Standards, Washington,
DC [now the National
Institute of Standards
and Technology,
Gaithersburg, MD].
Effects of Anisotropy:
X-Ray Diffraction

Diffraction gratings must have spacings comparable to

the wavelength of diffracted radiation.
Cant resolve spacings
Spacing is the distance between parallel planes of
atoms.
Figure 3.32 Relationship of the Bragg angle () and the
experimentally measured diffraction angle (2).

X-ray
intensity n
d =2 sin
(from c
detector)

c
 X-Rays to Determine Crystal Structure
Incoming X-rays diffract from crystal planes.

reflections must
be in phase for
a detectable signal!
extra Adapted from Fig. 3.19,

distance
Callister 7e.
traveled
by wave 2 spacing
d between
planes
Measurement of
critical angle, c,
allows computation of X-ray
n
planar spacing, d. intensity d=
(from 2 sin c
For Cubic Crystals: detector)
d hkl =
a
h2 k 2 l 2 c
h, k, l are Miller Indices
Figure 3.34 (a) An x-ray diffractometer. (Courtesy of
Scintag, Inc.) (b) A schematic of the experiment.
 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 2

Diffraction pattern for polycrystalline -iron (BCC)

Adapted from Fig. 3.20, Callister 5e.
Diffraction in Cubic Crystals:
SUMMARY
Atoms may assemble into crystalline or
amorphous structures.
Common metallic crystal structures are FCC, BCC, and
HCP. Coordination number and atomic packing factor
are the same for both FCC and HCP crystal structures.
We can predict the density of a material, provided we
know the atomic weight, atomic radius, and crystal
geometry (e.g., FCC, BCC, HCP).
Crystallographic points, directions and planes are
specified in terms of indexing schemes.
Crystallographic directions and planes are related
to atomic linear densities and planar densities.
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.