COLLEGE OF Engineering

GENG211:
Material Science

Lecture 3:

chapter 3: the Structure of Crystalline Solids

• Dr. Hamdan Hamdan

• [email protected]
 ISSUES TO
ADDRESS...
• How do atoms assemble into solid
structures?
• How does the density of a material
depend on its structure?
• When do material properties vary with the
sample (i.e., part) orientation?
 Energy and Packing
• Non dense, random packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

• Dense, ordered packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Dense, ordered packed structures tend to have

lower energies.
 Materials and Packing
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2

Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
 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

Metallic • Tend to be densely packed
• Have the simplest crystal structures.
Crystal • Reasons for dense packing:
• Typically, only one element is present, so all

Structures 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
• We will examine three such structures...
1. Body Centered Cubic Structure (BCC)
2. Face Centered Cubic Structure (FCC)
3. Hexagonal Close-Packed (HCP)
Important terms to remember
for later
Coordination

• coordination number, also called ligancy, of a central atom in a

molecule or crystal is the number of atoms, molecules or ions
bonded to it.

Close-packed direction

• In a close-packed structure the close-packed directions are

the directions in which atoms are touching.

Anisotropy

• is the property of being directionally dependent

• opposed to isotropy, which means homogeneity in all
directions.

Unit Cell

• The unit cell is defined as the smallest repeating unit having

the full symmetry of the crystal structure
 Simple Cubic Structure (SC)
(possible but not common)
• 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.

ex: Cr, W, Fe (), Tantalum, Molybdenum

• Coordination # = 8

2 atoms/unit cell: 1 center + 8 corners x 1/8

 Atomic Packing Factor: BCC
• APF for a body-centered cubic structure = 0.68
3a

2a

Close-packed directions:
R length = 4R = 3 a
a
atoms volume
4
unit cell 2 p ( 3a/4) 3
3 atom
APF =
3 volume
a
unit cell
 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

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

 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
atoms volume
4
unit cell 4 p ( 2a/4) 3
3 atom
APF =
3 volume
a
unit cell
 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
 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

• Coordination # = 12 6 atoms/unit cell

• APF = 0.74 ex: Cd, Mg, Ti, Zn
• c/a = 1.633
 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 = Avogadro’s number
= 6.022 x 1023 atoms/mol
 Theoretical Density, r
• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
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 6.022 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
Based on data in Table B1, Callister
*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

 Crystals as Building Blocks
• Some engineering applications require single crystals:
-- diamond single -- turbine blades
crystals for abrasives

• Properties of crystalline materials

often related to crystal structure.
-- Ex: Quartz fractures more easily
along some crystal planes than
others.
 Polycrystals Anisotropic
• Most engineering materials are polycrystals.

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 typically range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).
 Single vs Polycrystals
• Single Crystals E (diagonal) = 273 GPa
-Properties vary with
direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
E (edge) = 125 GPa
• Polycrystals
-Properties may/may not 200 mm
vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)
-If grains are textured,
anisotropic.
 Polymorphism
• Two or more distinct crystal structures for
the same material
(allotropy/polymorphism)
– Titanium: , -Ti iron system
– Carbon: diamond, graphite liquid
1538ºC
BCC -Fe
1394ºC
FCC -Fe
912ºC
BCC -Fe
 Crystal Systems
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.

7 crystal systems

14 crystal lattices

a, b, and c are the lattice constants

 Lattice parameters
• many different possible crystal structures
• convenient to divide them into groups according to unit cell configurations
and/or atomic arrangements.
• One such scheme is based on the unit cell geometry, that is, the shape of the
appropriate unit cell parallelepiped without regard to the atomic positions in the
cell.
• x-y-z coordinate system is established with its origin at one of the unit cell corners;
• each of the x, y, and z axes coincides with one of the three parallelepiped
edges that extend from this corner
• unit cell geometry is completely defined in terms of six parameters:
• the three edge lengths a, b, and c, and the three interaxial angles 𝛼, 𝛽, and 𝛾.
• are sometimes termed the lattice parameters of a crystal structure.
• On this basis there are seven different possible combinations of a, b, and c and 𝛼, 𝛽,
and 𝛾, each of which represents a distinct crystal system.
• These seven crystal systems are cubic, tetragonal, hexagonal, orthorhombic,
rhombohedral, monoclinic, and triclinic.
• The cubic system, for which a = b = c and 𝛼 = 𝛽 = 𝛾 = 90°, has the greatest degree of
symmetry.
• The least symmetry is displayed by the triclinic system, because a ≠ b ≠ c and 𝛼 ≠ 𝛽 ≠
𝛾
Lattice parameters
• When dealing with crystalline materials, it often
becomes necessary to specify a particular
point within a unit cell, a crystallographic
direction, or some crystallographic plane of
atoms.
• Labeling conventions have been established in
which three numbers or indices are used to
designate point locations, directions, and
planes.
• The basis for determining index values is the
unit cell, with a right-handed coordinate
system consisting of three (x, y, and z) axes
situated at one of the corners and coinciding
with the unit cell edges, as shown in Figure
 Point Coordinates
z
111 Point coordinates for unit cell
c center are
a/2, b/2, c/2 ½½½

000
y
a b
Point coordinates for unit cell
x • corner are 111
z 2c
•
Translation: integer multiple of
• • lattice constants → identical
b y position in another unit cell
b
Crystallographic
Directions
Crystallographic Directions
 Crystallographic Directions
z pt. 2
Example 2:
head
pt. 1 x1 = a, y1 = b/2, z1 = 0
pt. 2 x2 = -a, y2 = b, z2 = c

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

families of directions <uvw>

 Crystallographic Directions
z Algorithm
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of
unit cell dimensions a, b, and c
y 3. Adjust to smallest integer values
4. Enclose in square brackets, no commas

x [uvw]

ex: 1, 0, ½ => 2, 0, 1 => [ 201 ]

-1, 1, 1 => [ 111 ] where overbar represents a
negative index
families of directions <uvw>
 Linear Density
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
 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] a2
a1
a2 -a3
2

ex: ½, ½, -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') 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
Crystallographic Planes
 Crystallographic Planes

• The orientations of planes for a crystal

structure are represented in a similar
manner.

• In all but the hexagonal crystal system,

crystallographic planes are specified
by three Miller indices as (hkl).

• Any two planes parallel to each other

are equivalent and have identical
indices.
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
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)
Crystallographic
Planes: in details
 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 1/½ 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 1/½ 1/1 1/¾
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)

 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

Virtual Materials Science & Engineering (VMSE)
• VMSE is a tool to visualize materials science topics such as
crystallography and polymer structures in three dimensions

https://drbuc2jl8158i.cloudfront.net/VMSE/index.html
 VMSE: Metallic Crystal Structures &
Crystallography Module
• VMSE allows you to view crystal structures, directions, planes,
etc. and manipulate them in three dimensions
 Unit Cells for Metals
• VMSE allows you to view the unit cells and manipulate
them in three dimensions

• Below are examples of actual VMSE screen shots

FCC Structure HCP Structure

VMSE: Crystallographic Planes Exercises

Additional practice on indexing crystallographic planes

 Crystallographic Planes
• We want to examine the atomic packing of
crystallographic planes
• 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 < 912ºC iron has the BCC structure.
2D repeat unit

(100) 4 3
a= R
3

Adapted from Fig. 3.2(c), Callister & Rethwisch 8e. 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
 Planar Density of (111) Iron
Solution (cont): (111) plane 1 atom in plane/ unit surface cell

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
2D repeat unit 1
atoms = atoms
Planar Density = = 7.0 0.70 x 1019
nm 2 m2
area 16 3 2
R
2D repeat unit 3
 VMSE Planar Atomic Arrangements
• VMSE allows you to view planar arrangements and rotate
them in 3 dimensions

BCC (110) Plane

 X-Ray Diffraction

• Diffraction gratings must have spacings comparable to

the wavelength of diffracted radiation.
• Can’t resolve spacings  
• Spacing is the distance between parallel planes of
atoms.
 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. 3.20,
q q
distance
Callister & Rethwisch 8e.
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

Diffraction pattern for polycrystalline -iron (BCC)

Adapted from Fig. 3.22, Callister 8e.
 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.
Questions