Chapter 3: The Structure of Crystalline Solids

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 - 1
 Materials and Packing
Crystalline materials...
• Repetitive or periodic array of atoms
-metals, alloys
-many ceramics
-some polymers crystalline SiO2

Noncrystalline materials... Si Oxygen

• atoms have no periodic packing
-complex structures
-rapid cooling

noncrystalline SiO2
Noncrystalline materials are also called Amorphous.
Chapter 3 - 2
 Basic Crystalline structure terms
Space/Crystal lattice
Arrangement of network of lines in 3D space

a, b, and c are the lattice constants

Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.
Chapter 3 - 3
 Metallic Crystal Structures
• Densely packed structure.
- Typically, only one element is present, so all atomic
radii are the same.

Metallic
Crystal
Structure

Face Hexagonal
Centric Closed
Crystal Packed
(FCC) Body Centric (HCP)
Crystal (BCC)
Chapter 3 - 4
 Simple Cubic Structure (SC)

• Coordination # = 6 (# nearest neighbors)

• It is rare in metals (only Po has this structure) due to low

packing density
Chapter 3 - 5
 Atomic Packing Factor (APF)

R=0.5a

close-packed directions

How many atoms are presented in a unit cell?

Number of corners ~ 8 x 1/8th of atom at each corner

Total number of atoms/unit cell = 1

Is total volume of unit cell occupied by atoms?
Chapter 3 - 6
 Atomic Packing Factor (APF)
Volume of atoms in unit cell*
APF =
Volume of unit cell

volume
atoms atom
4
unit cell 1 p (0.5a) 3
3
APF =
a3 volume
unit cell

• APF for a simple cubic structure = 0.52

Chapter 3 - 7
 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

Chapter 3 - 8
 Face Centered Cubic Structure (FCC)
• Atoms touch each other along face diagonals.

ex: Al, Cu, Au, Pb, Ni, Pt, Ag

• Coordination # = 12

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

Chapter 3 - 9
 Atomic Packing Factor: FCC
Number of atoms in FCC structure?

Unit cell contains:

6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell

a
atoms volume
4
unit cell 4 p ( r )3
3 atom
APF =
volume
a3
unit cell
Chapter 3 -
 Atomic Packing Factor: FCC

4R = 2a

4
4 p ( 2a/4) 3 Close-packed directions:
3 length = 4R = 2 a
APF =
a3
APF= 0.74
Chapter 3 -
Body Centered Cubic Structure (BCC)
• Atoms touch each other along cube diagonals.
ex: Cr, W, Fe (), Tantalum, Molybdenum

• Coordination # = 8

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

Chapter 3 - 12
 Atomic Packing Factor: BCC
How much area in BCC is empty?

Volume of atoms in unit cell*

APF =
Volume of unit cell

atoms volume
4
unit cell 2 p (r )3
3 atom
APF =
volume
a3
unit cell

Chapter 3 - 13
Atomic Packing Factor: BCC

R
a

3a

2a

Close-packed directions:
length = 4R = 3 a Chapter 3 - 14
 Atomic Packing Factor: BCC

atoms volume
4
unit cell 2 p ( 3a/4) 3
3 atom
APF =
3 volume
a
unit cell
APF = 0.68

32% of BCC lattice is empty.

Chapter 3 - 15
 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. 3.3(a),
Callister 7e.

• Coordination # = 12 6 atoms/unit cell

• APF = 0.74 ex: Cd, Mg, Ti, Zn
• c/a = 1.633 Chapter 3 - 16
 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
Chapter 3 - 17
 Point Coordinates
Locate the point coordinates of given points.

Chapter 3 - 18
 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 (whole no.)
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>
Chapter 3 - 19
 Crystallographic Directions
• Commonly used crystalline directions are as

[ 111 ] and [ 111 ] are anti-parallel to each other.

Chapter 3 - 20
 Crystallographic Planes
• Crystallographic Planes are denoted by Miller Indices

• Miller Indices: Reciprocals of the (three) axial

intercepts for a plane, cleared of fractions & common
multiples.

• 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 - 21
 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 (200) a b
x
Chapter 3 - 22
 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)

Chapter 3 - 23
 Crystallographic Planes
• Three important planes of cubic crystal structures.

• Equivalent planes.
Chapter 3 - 24
 Section 3.16 - X-Ray Diffraction

• Diffraction gratings must have spacing comparable to

the wavelength of diffracted radiation.
• Can’t resolve spacing  
• Spacing is the distance between parallel planes of
atoms.
Chapter 3 - 25
 X-Rays to Determine Crystal Structure
• Incoming X-rays diffract from crystal planes.

reflections must
be in phase for
a detectable signal
extra 
q q
distance
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
Chapter 3 - 26
 X-Rays to Determine Crystal Structure
• Schematic diagram of X-ray diffractometer
• Used to measure the angle where diffraction occur

 Sample and Sample

Detector are
rotated to X-ray source
measure the 2q,

X-ray
 Peak intensity n
intensity d=
(from 2 sin qc
occur when the
detector)
Bragg’s diffraction
Detector q
is satisfied.
qc
Chapter 3 - 27
 X-Ray Diffraction Pattern
• XRD is used to determine the crystal structure,
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)

Chapter 3 - 28
 SUMMARY
• Atoms may assemble into crystalline or
amorphous structures.

• Common metallic crystal structures are FCC, BCC.

• Crystallographic points, directions and planes are

specified in terms of indexing schemes.

• X-ray diffraction is used for crystal structure and

inter-planar spacing determinations.

Chapter 3 - 29