.

TRE STRUCTURE OF
CHAPTER 3:
CRYSTALLINE SOLIDS

1
 ISSUES TO ADDRESS...

1. How do atoms assemble into solid structures? (for

now, focus on metals)

2. How does the density of a material depend on its

structure?

3. When do material properties vary with the sample

(i.e., part) orientation?

The Structure of crystalline solids 2

 Energy and Packing
Energy

typical neighbor
• Non dense, random packing bond length

typical neighbor r
bond energy

Energy

typical neighbor
• Dense, ordered packing bond length

typical neighbor r
Dense, ordered packed bond energy
structures tend to have
lower energies.
The Structure of Crystalline Solids 3
 Materials, Packing and Phase Structure

1. Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2
Adapted from Fig. 3.22(a),
Callister 7e.

Si Oxygen
2. Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.22(b),
Callister 7e.

The Structure of Crystalline Solids 4

 Crystal structure & Unit cell

      
  a   b   c  n1a  n2b  n3c
Crystal structure of the material, the manner in which
atoms, ions, or molecules are ordered arrangement in 3D
“Lattice" = crystal structure
The Structure of Crystalline Solids 5
 Unit cell geometries & Crystal Systems

Unit cell: smallest repetitive volume repeating portion

of a crystal lattice

Six parameters define a unit cell geometry

1. a, b, and c are the lattice constants
2. ,  and  are the interaxial angles formed of a, b, c

Bravais - Miller

 7 unit cell geometries  7

crystal systems

Fig. 3.4, Callister 7e.  14 crystal lattices

The Structure of Crystalline Solids 6

 Unit Cell Geometry
Crystal Axial Interaxial angles Unit cell
system relationships geometry
Cubic a=b=c  = =  = 90°

Hexagonal a=b#c  = = 90°,  = 120°

Tetragonal a=b#c  = =  = 90°

Rhombohedral a=b=c  = =  # 90°

(Trigonal)
Orthorhombic a#b#c  =  = 90° = 

Monoclinic a#b#c  = = 90 # 

Triclinic a#b#c  # #  # 90°

The Structure of Crystalline Solids 7

 Unit cells & Crystal Systems

cubic

hexagonol

The Structure of Crystalline Solids 8

 Point Coordinates
z
111
ri  r0  n1 a  n2 b  n3 c
c
B
A
Point coordinate is the position of
any point located within a unit cell
000
y
a b
x
 Point coordinates for unit cell
 center (A) are
z 2c a/2, b/2, c/2 ½½½
  Point coordinates for unit cell
corner (B) are 111
 Translation: integer multiple of
 
lattice constants  identical
b y position in another unit cell.
b
The Structure of Crystalline Solids 9
 Crystallographic Directions
Crystallographic direction is a line between two
points/ nodes that atoms or ions positioned
z
Algorithm
1. Vector repositioned (if necessary) to
pass through origin.
2. Read off projections in terms of unit cell
y
dimensions a, b, and c
3. Adjust to 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

The Structure of Crystalline Solids 10

 Crystallographic Directions
Cubic system z
6

c 4
3
b 2
a y
1 5
x

Families of directions:
 The group of directions which atoms have a same space
 May be parallel or nonparallel direction
 are enclosed with <uvw>

EX: Cubic system:  <100>:

The Structure of Crystalline Solids 11

 Crystallographic Planes

Adapted from Fig. 3.9, Callister 7e.

Crystallographic plane
 is a plane linking nodes (atoms/ ions) that may be supposed to pass
through the centers of atoms in crystals.
 is specified by three Miller indices as (hkl)

The Structure of Crystalline Solids 12

 Crystallographic Planes

Example a b c z
1. Intercepts 1 1 
2. Reciprocals 1/1 1/1 1/ c
1 1 0
3. Reduction 1 1 0
y
4. Miller Indices (110) a b
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
a b
4. Miller Indices (100)
x

The Structure of Crystalline Solids 13

 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

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)

The Structure of Crystalline Solids 14

 Family of Planes

Family of Planes:
 a finite set of parallel or non
parallel lattice planes that are
equally spaced from each other.
 One of the planes in any family
always passes through the
origin.
 is specified as {hkl}

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

The Structure of Crystalline Solids 15

 Interplanar Spacing or Interplanar Distance
Interplanar spacing is the distance between two closest parallel
planes in this family

The Structure of Crystalline Solids 16

 Interplanar spacing

•The Structure of Crystalline Solids 17

 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

The Structure of Crystalline Solids 18

 Metallic Crystal Structures

1. 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

2. Have the simplest crystal structures.

We will examine three such structures...

The Structure of Crystalline Solids 19

Simple Cubic Structure (SC)

• Rare due to low packing density (only Po has this structure)

• Close-packed directions are cube edges.
• Coordination number = 6
(# nearest neighbors)

(Courtesy P.M. Anderson)

The Structure of Crystalline Solids 20

 Atomic Packing Factor (APF)

Volume of atoms in unit cell*

APF =
Volume of unit cell
*assume hard spheres

volume
atoms atom
a 4
unit cell 1 p (0.5a) 3
R=0.5a 3
APF =
close-packed directions a3 volume
contains 8 x 1/8 =
unit cell
1 atom/unit cell
• APF for a simple cubic
Adapted from Fig. 3.23,
Callister 7e.
structure = 0.52
The Structure of Crystalline Solids 21
 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 number = 8

Adapted from Fig. 3.2,

Callister 7e.

(Courtesy P.M. Anderson) 2 atoms/unit cell = 1 center + 8 corners x 1/8

The Structure of Crystalline Solids 22

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

2a
Close-packed directions:
length = 4R = 3 a
R
Adapted from
Fig. 3.2(a), Callister 7e.
a
atoms volume
4
unit cell 2 p ( 3a/4) 3
3 atom
APF =
volume
a3
unit cell
The Structure of Crystalline Solids 23
 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 number = 12

Adapted from Fig. 3.1, Callister 7e.

(Courtesy P.M. Anderson)

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

The Structure of Crystalline Solids 24

 Face Centered Cubic Structure (FCC)

• Unit cell contains:

6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
2a • Close-packed directions:
length = 4R = 2 a

a atoms volume
4
Adapted from unit cell 4 p ( 2a/4) 3
Fig. 3.1(a), 3 atom
Callister 7e.
APF =
volume
a3
unit cell
• APF for a face-centered cubic structure = 0.74
maximum achievable APF
The Structure of Crystalline Solids 25
 Summary

HCP: hexagonal closest packed

The Structure of Crystalline Solids 26
 HCP Crystallographic Directions

x, y, z axes: two planes in

a family
O1AC: (111)
O1AE: (1 2 1)
 are not same Miller indices

The Structure of Crystalline Solids 27

 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
1
a2
v  (2 v ' - u ')
3
a3
- t  - (u +v )
a1 w  w'
Fig. 3.8(a), Callister 7e. Where: u´, v´, w´: xyz axes
u, v, t, w: a1 a2 a3z axes

The Structure of Crystalline Solids 28

 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
Adapted from Fig. 3.8(a), Callister 7e.
2

ex: ½, ½, -1, 0 => [ 1120 ] a3

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

The Structure of Crystalline Solids 29

 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.

The Structure of Crystalline Solids 30

 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.
6 atoms/unit cell
• Coordination # = 12
ex: Cd, Mg, Ti, Zn
• APF = ???
• c/a = 1.633 ???

The Structure of Crystalline Solids 31

 Hexagonal Close-Packed Structure (HCP)
Atom has a spherical shape

2 2a 3 a 3 c
IG  IL   IO 
3 3 2 3 2
OG = 2 r = a
c2 a 3 2
IO2 + IG2 = OG2  ( )  a2
4 3
c2 1 2 8
 a 2 (1  )  a 2  c 2  a 2
4 3 3 3
2 c
c  2a   1,633
3 a

Examples: Metals c/a Metals c/a

Be 1.57 xếp chặt Zn 1.86 không xếp chặt
Mg 1.62 Cd 1.89
Ca 1.64

The Structure of Crystalline Solids 32

 Theoretical Density, 

Mass of Atoms in Unit Cell

Density =  =
Total Volume of Unit Cell

nA
 =
VC NA

where n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadro’s number
= 6.023 x 1023 atoms/mol

The Structure of Crystalline Solids 33

 Theoretical Density, 

• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2
R a = 4R/ 3 = 0.2887 nm
a
atoms
g
unit cell 2 52.00 theoretical = 7.18 g/cm3
mol
= actual = 7.19 g/cm3
a3 6.023 x 1023
volume atoms
unit cell mol
The Structure of Crystalline Solids 34
 Theoretical Density, 

• Ex: Copper (FCC)

A = 63.54 g/mol
R = 0.128 nm

The Structure of Crystalline Solids 35

 Theoretical Density, 

The Structure of Crystalline Solids 36

 Densities of Material Classes

The Structure of Crystalline Solids 37

 Densities of Material Classes

In general Graphite/
metals > ceramics > polymers
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

 (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.

The Structure of Crystalline Solids 38

 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

The Structure of Crystalline Solids 39

 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.

The Structure of Crystalline Solids 40

 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 19 atoms
Planar Density = = 2 = 12.1 = 1.2 x 10
area a2 4 3 nm2 m2
R
2D repeat unit 3

The Structure of Crystalline Solids 41

 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

The Structure of Crystalline Solids 42

 Crystals as Building Blocks

• Some engineering applications require single crystals:

-diamond single
crystals for abrasives -turbine blades
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)

The Structure of Crystalline Solids 43

 Polycrystals
• Most engineering materials are polycrystals. Anisotropic

Adapted from Fig. K,

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

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).
The Structure of Crystalline Solids 44
 Single vs. Polycrystals

• Single Crystals E (diagonal) = 273 GPa

Data from Table 3.3,
-Properties vary with Callister 7e.
(Source of data is R.W.
direction: anisotropic. Hertzberg, Deformation
and Fracture Mechanics
Example: the modulus of Engineering
Materials, 3rd ed., John
of elasticity (E) in BCC iron: Wiley and Sons, 1989.)

E (edge) = 125 GPa

• Polycrystals
-Properties may/may not 200 mm Adapted from Fig.
4.14(b), Callister 7e.
vary with direction. (Fig. 4.14(b) is courtesy
of L.C. Smith and C.
-If grains are randomly Brady, the National
Bureau of Standards,
oriented: isotropic. Washington, DC [now
the National Institute of
(Epoly iron = 210 GPa) Standards and
Technology,
-If grains are textured, Gaithersburg, MD].)
anisotropic.

The Structure of Crystalline Solids 45

 Polymorphism
• Two or more distinct crystal structures for the same
material (allotropy/polymorphism)

titanium iron system

, -Ti
liquid
1538ºC
carbon
BCC -Fe
graphite diamond
1394ºC
FCC -Fe
912ºC
BCC -Fe

The Structure of Crystalline Solids 46

 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.

The Structure of Crystalline Solids 47

 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,
q q
distance
Callister 7e.
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

The Structure of Crystalline Solids 48

 X-Rays to Determine 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)

Adapted from Fig. 3.20, Callister 5e.

The Structure of Crystalline Solids 49

 THANK YOU
FOR YOUR ATTENTION

50