Chapter 3: The Structure of Crystalline Solids

The properties of materials are

directly related to their crystal
structure.
e.g. magnesium and beryllium
are brittle - gold is not

ISSUES TO ADDRESS...
• How do atoms assemble into solid structures?
(for now, focus on metals)

• How does the density of a material depend on

its structure?

• When do material properties vary with the

sample (i.e., part) orientation?
Chapter 3 – Structure of crystalline solids
 Interlude – Engineering Relevance

• Fracture and plasticity depend on crystal structure

– Upcoming lectures on Imperfections and Dislocations (Chapters 4
and 7 in text)
– Ni-base superalloys for jet-engine turbine blades (Case Study 1)

• Also Corrosion, cracking, degradation

– Stress-corrosion in musculoskeletal implants
– Chemical corrosion in oil rigs in harsh marine environments
– Hot corrosion in engines

• Strengthening and stabilisation at atomic level

– Substituting atoms into existing crystal structure can toughen
materials
Chapter 3 – Structure of crystalline solids
 Section 3.7 - Crystal Systems
Crystal structures are divided into seven groups
depending on their unit cell geometry.

1. Cubic

a=b=c α=β=γ=90o

Chapter 3 – Structure of crystalline solids

 Section 3.7 - Crystal Systems
2. Hexagonal 3. Tetragonal

a=b≠c α=β=90o, γ=120o a=b ≠ c α=β=γ=90o

Chapter 3 – Structure of crystalline solids

 Section 3.7 - Crystal Systems
4. Rhombohedral 5. Orthorhombic
(Trigonal)

a=b=c α=β=γ ≠ 90o, a≠b≠c α=β=γ=90o

Chapter 3 – Structure of crystalline solids

 Section 3.7 - Crystal Systems
6. Monoclinic 7. Triclinic

a≠b≠c α= γ = 90o ≠ β, a≠b≠c α ≠ β ≠ γ ≠ 90o

Chapter 3 – Structure of crystalline solids

Definitions of positions and structures
Reproducible way to describe:
• Where atoms are in a material
• What the crystalline planes and orientations are

Coordinates Planes

Chapter 3 – Structure of crystalline solids

Crystallographic points, directions and planes
Right handed
coordinate system
consisting of three
axes situated at one of
the corners and
coinciding with the cell
edges.
→ In some cases,
axes are not mutually
perpendicular.

Chapter 3 – Structure of crystalline solids

 Section 3.8 Point Coordinates
z Point coordinates for unit cell
111
c center are
a/2, b/2, c/2 ½½½

000
y
a b Point coordinates for unit cell
corner are 111
x

The position of a point within a unit cell is specified in

terms of its coordinates as fractional multiples of the unit
cell length.

Chapter 3 – Structure of crystalline solids

 Section 3.8 Point Coordinates
•
z 2c
Translation: integer multiple of
•
lattice constants → identical
position in another unit cell
• •
b y
b

Chapter 3 – Structure of crystalline solids

 3.9 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. multiply or divide all three numbers by a
common factor to reduce them to the
smallest integer values
x 4. Enclose in square brackets, no commas
[uvw]

ex: 1, 0, ½ => 2, 0, 1 => [ 201 ]

-1, 1, 1 => [ 111 ] where overbar represents a
negative index

Chapter 3 – Structure of crystalline solids

 3.9 Crystallographic Directions
Families of directions

For some crystal structures nonparallel

directions with different indices are equivalent
→ families of directions <uvw>
Example: Directions in cubic crystals with the
same indices without regard to order or sign
are equivalent, e.g. [100], [100], [010], [010],
[001] and [001] all belong to the same family
<100>.
This is not true for other crystal systems.
Chapter 3 – Structure of crystalline solids
 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

Chapter 3 – Structure of crystalline solids

 Crystallographic Directions in Hexagonal Crystals

A four axis (Miller-Bravais) coordinate

system is used to achieve that all
equivalent directions have the same
indices.
•The axes a1, a2 and a3 are contained
within a single plane (basal plane).
•The z axis is perpendicular to the
basal plane.
Four indices are used to describe
crystallographic directions [uvtw] in
hexagonal crystal structures.
corresponding to projections onto the
axes a1, a2, a3 and z.
Chapter 3 – Structure of crystalline solids
Crystallographic Directions in Hexagonal Crystals
z
Why not [uvw]?
1. Because the equivalent directions look
very different

a2
If only a1 and a2 used:

a3
-
[100], [010],[110]
a1

What we want:

a1, a2, a3 directions to have symmetrical

appearance

Chapter 3 – Structure of crystalline solids

Crystallographic Directions in Hexagonal Crystals
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
2

ex: ½, ½, -1, 0 => [ 1120 ] a3

a1
2
dashed red lines indicate
projections onto a1 and a2 axes a1

Chapter 3 – Structure of crystalline solids

Crystallographic Directions in Hexagonal Crystals
• 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

Fig. 3.8(a), Callister 7e.

Chapter 3 – Structure of crystalline solids

 Crystallographic Planes

Adapted from Fig. 3.9, Callister 7e.

Chapter 3 – Structure of crystalline solids

 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)

Chapter 3 – Structure of crystalline solids

 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 1 0 0
y
4. Miller Indices (100) a b
x

Chapter 3 – Structure of crystalline solids

 Crystallographic Planes

z
example a b c
1. Intercepts 1/2 1 3/4 c
•
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

Chapter 3 – Structure of crystalline solids

 Family of Planes

A family of planes contains all planes that are

crystallographically equivalent {hkl}.

In cubic crystals all planes having the same indices

irrespective of their sign and order are equivalent.
Example:{100} = (100), (010), (001), (100), (010), (001)

In tetragonal systems (001) and (001) are not

crystallographically equivalent to (100), (010), (100), (010),

Chapter 3 – Structure of crystalline solids

Crystallographic Planes (hexagonal crystals)

• In hexagonal unit cells the same idea is used. Four

indices (hkil) are used to achieve that all equivalent
planes have the same indices.
z
example a1 a2 a3 c
1. Intercepts 1  -1 1
2. Reciprocals 1 1/ -1 1
1 0 -1 1
3. Reduction 1 0 -1 1 a2

4. Miller-Bravais Indices (1011) a3

a1

Index i = - (h + k) Adapted from Fig. 3.8(a), Callister 7e.

h, k, l are identical for both indexing systems.

Chapter 3 – Structure of crystalline solids

 Atomic arrangements in crystallographic planes
The atomic arrangement for a crystallographic plane can
influence catalytic and mechanical properties of a material.

Atomic packing
of an FCC (110)
plane.

Atomic packing
of a BCC (110)
plane.

Chapter 3 – Structure of crystalline solids

 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.

Chapter 3 – Structure of crystalline solids

 Planar Density
Number of atoms centered on a plane
Planar density ≡ PD =
Area of plane

Chapter 3 – Structure of crystalline solids

 Planar Density of (100) Iron
Solution: At T < 912C iron has the BCC structure.
2D repeat unit

(100) 4 3
a= R
3

Adapted from Fig. 3.2(c), Callister 7e. 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

Chapter 3 – Structure of crystalline solids

 3a

2a

Cube diagonal:
R length = 4R = 3 a

Chapter 3 – Structure of crystalline solids

 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
Chapter 3 – Structure of crystalline solids
1 atom in plane/ unit surface cell

2a atoms in plane
atoms above plane
atoms below plane

2
2𝑎 2
h ℎ2 + = 2𝑎
2

2𝑎
1 2 3 2
2 ℎ2 = 2𝑎2 − 𝑎 = 𝑎
2 2
3
ℎ= 𝑎
2

Chapter 3 – Structure of crystalline solids

 Packing density and slip

Slip occurs on the most densely packed

crystallographic planes and in the directions that
have the greatest atomic packing.

Chapter 3 – Structure of crystalline solids

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

-- semiconductors for
electronics applications

• Properties of crystalline materials

often related to crystal structure.
--Example: Quartz fractures more
easily along some crystal planes
than others.

Chapter 3 – Structure of crystalline solids

 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 typ. range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).
Chapter 3 – Structure of crystalline solids
 Anisotropy

• Physical properties of single crystals of some

substances depend on the crystallographic direction
in which measurements are taken.
E.g. elastic modulus, electrical conductivity, etch
rates (e.g. silicon)
• Directionality of properties = anisotropy is associated
with atomic/ionic spacing in the crystallographic
direction investigated.
• Degree of anisotropy increases with decreasing
structural symmetry → triclinic structure are highly
anisotropic.

Chapter 3 – Structure of crystalline solids

Anisotropy

Table 3.4, Callister

Chapter 3 – Structure of crystalline solids

 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 oriented:
material is textured /
anisotropic (e.g. magnetic
texture for iron).
Chapter 3 – Structure of crystalline solids
 Section 3.16 - 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.
Chapter 3 – Structure of crystalline solids
Concept of an X-Ray Diffractometer

Chapter 3 – Structure of crystalline solids

 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 a-iron (BCC)

Adapted from Fig. 3.20, Callister 5e.

Chapter 3 – Structure of crystalline solids

 SUMMARY
• 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.

• 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).

Chapter 3 – Structure of crystalline solids