Interatomic bonding

and
Crystallography

Interrelationship With
Design Material and Process
Design,
Design
S i
Service conditions
di i
Function
Cost

Materials Processing
P
Properties
i E i
Equipment design
d i
Availability Influence on properties
Cost Cost
Components

Opaque
Transparent Translucent Polycrystalline
Single crystalpolycrystallinewith very small
pores or voids

Classification of
Materials
• Metals • Polymers
– Steel, Cast Iron, – Plastics, Wood,
Aluminum, Copper, Cotton (rayon,
Titanium, many nylon), “glue”
others • Composites
• Ceramics
C i – Glass Fiber-
– Glass, Concrete, reinforced polymers,
Brick Alumina
Brick, Alumina, Carbon Fiber
Fiber-
Zirconia, SiN, SiC reinforced polymers,
Metal Matrix
Composites, etc.
 Schematic representation of ionic
bonding in sodium chloride (NaCl)

(a) The dependence of repulsive, attractive, and net forces on interatomic

separation for two isolated atoms. (b) The dependence of repulsive, attractive,
and net potential energies on interatomic separation for two isolated atoms.

The arrangement of water

molecules in (a) solid ice,
and (b) liquid water

Schematic illustration of
metallic bonding
Schematic representation
of covalent bonding in a
molecule of methane CH4
Bonding Energies and Melting Temperatures for Various Substances

Thoughts about these “fundamental” Materials

• Metals:
– Strong, ductile
– high thermal & electrical conductivity
– opaque, reflective.

• Polymers/plastics: Covalent bonding  sharing of e’s

– Soft, ductile, low strength, low density
– thermal & electrical insulators
– Optically translucent or transparent.

• C
Ceramics:
i i i bonding
ionic b di (refractory)
( f t ) – compoundsd off
metallic & non-metallic elements (oxides, carbides,
nitrides, sulfides)
– Hard, Brittle, glassy, elastic
– non-conducting (insulators)
 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?

Energy and Packing

• Non dense, random packing Energy

yp
typical neighbor
g
bond length

typical neighbor r
bond energ
energy

• Dense, ordered packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Dense ordered packed structures tend to have lower energies

Dense, energies.

10
 Materials and Packing
g
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of:
f -metals
-many ceramics
-some p polymers
y crystalline SiO2
Adapted from Fig. 3.22(a), Callister 7e.

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

11

Crystal Structure
Space lattice: Three dimensional network of imaginary
lines connecting
g the atoms is called the space
p lattice
(A three dimensional pattern of points in space).

12
Crystal Systems

Unit cell: smallest repetitive volume which contains the

complete lattice pattern of a crystal (The smallest unit having
the full symmetry of the crystal).

7 crystal systems
14 crystal lattices
The specific unit cell for metal
is defined by its parameters

The edges a, b, and c; and α, β and γ

are the lattice constants or parameters

Fig. 3.4, Callister 7e. 13

Crystal Systems

14
 Metallic Crystal Structures
• How can we stack metal atoms to minimize
empty space?
2-dimensions

vs.

N
Now stack
t k these
th 2-D
2 D llayers tto make
k 33-D
D structures
t t
15

Metallic Crystal
y 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...

16
 Simple
p Cubic Structure ((SC))
• Rare due to low packing denisty (only Po has this structure)
• Close-packed directions are cube edges.

• Coordination # = 6
(# nearest neighbors)

(Courtesy P.M. Anderson)

17

Atomic Packing
g Factor ((APF))
Volume of atoms in unit cell*
APF =
Volume of unit cell
*assume hard spheres
• APF for a simple cubic structure = 0.52
0 52
volume
atoms atom
a 4 3
unit cell 1 (0.5a)
3
R=0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 =
1 atom/unit cell
Adapted from Fig. 3.23,
Callister 7e. 18
 Bodyy Centered Cubic Structure ((BCC))
• Atoms touch each other along cube diagonals.
--Note: All atoms are identical; the center atom is shaded
diff
differently
tl only
l ffor ease off viewing.
i i

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

• Coordination # = 8

Adapted from Fig. 3.2,

Callister 7e.

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

(Courtesy P.M. Anderson)
19

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

2a

Close packed directions:

Close-packed
R length = 4R = 3 a
Adapted from
Fig. 3.2(a), Callister 7e.
a
atoms volume
l
4
unit cell 2  ( 3a/4) 3
3 atom
APF =
volume
l
a3
unit cell 20
 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
t / it cell:
ll 6 fface x 1/2 + 8 corners x 1/8
(Courtesy P.M. Anderson)
21

Atomic Packing
g 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
Adapted from
atoms volume
Fig. 3.1(a), 4 3
Callister 7e.
unit cell 4 ( 2a/4))
3 atom
APF =
volume
a3
unit
it cellll
22
 FCC Stacking
g Sequence
q
• 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

23

Hexagonal Close-Packed Structure

(HCP)
• ABAB... Stacking
g 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
7e.

• Coordination # = 12 6 atoms/unit cell

• APF = 0
0.74
74 ex: Cd,
Cd Mg
Mg, Ti
Ti, Zn
• c/a = 1.633 24
 y 
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
V l off unit
it cellll = a3 for
f cubic
bi
NA = Avogadro’s number
= 6.023 x 1023 atoms/mol

25

y 
Theoretical Density,
• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2
R
a a = 4R/ 3 = 0.2887 nm

atoms
g
unit cell 2 52.00 theoretical = 7
7.18
18 g/cm3
moll
= actual = 7.19 g/cm3
a3 6.023 x 1023
volume atoms
unit cell mol 26
 Densities of Material Classes
In general Metals/
Graphite/
Composites/
metals > ceramics > polymers Alloys
Ceramics/
Semicond
Polymers
fibers
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
Cu,Ni
Steels
• often large atomic masses Tin, Zinc
Zirconia

 (g/ccm3 )
5
Ceramics have... 4
Titanium
Al oxide
Diamond
• less
ess de
dense
se pac
packing
g 3 Si nitride
Aluminum Glass -soda Glass fibers
• often lighter elements Concrete
Silicon PTFE GFRE*
2
Polymers have... Magnesium Graphite
Silicone
Carbon fibers
CFRE*
Aramid fibers
PVC
• low p packing
g density
y PET
PC
AFRE*
1
(often amorphous) HDPE, PS
PP, LDPE
• lighter elements (C,H,O)
0.5
Composites
p have... 04
0.4
Wood

• intermediate values 0.3

Data from Table B1, Callister 7e.
27

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

• Properties of crystalline materials

often related to crystal structure.
--Ex: Quartz fractures more easily
along some crystal planes than
others.
(Courtesy P.M. Anderson)

28
 Polycrystals
y y Anisotropic
• Most engineering materials are polycrystals.

Adapted from Fig. K,

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

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

• Each "grain"
grain is a single crystal
crystal.
• If grains are randomly oriented,
overall component properties are not directional.
• Grain
G i sizes
i typ. range ffrom 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).
29

Single
g vs Polycrystals
y y
• Single Crystals E (diagonal) = 273 GPa
Data from Table 3.3,
-Properties vary with Callister 7e.
(Source of data is R.W.
direction: anisotropic.
anisotropic Hertzberg, Deformation
f
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
Properties may/may not 200 
m 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.
isotropic W hi t
Washington, DC [[now
the National Institute of
(Epoly iron = 210 GPa) Standards and
-If grains are textured, Technology,
Gaithersburg, MD].)
anisotropic
anisotropic.

30
 Polymorphism
• Two or more distinct crystal structures for
f the same
material (allotropy/polymorphism)
titanium iron system
y
, -Ti liquid
carbon 1538 C
1538ºC
diamond, graphite -Fe
BCC
Allotropy is the property of a 1394 C
1394ºC
material to exist in more than -Fe
FCC
one type of space lattice in the
solid state.
state 912ºC
If the change in structure is BCC -Fe
reversible, then the polymorphic
i known
is k as allotropy
ll t
31

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
32
 Crystallographic
y g p Directions
z Algorithm
1. Vector repositioned (if necessary) to pass
th
throughh origin.
i i
2. Read off projections in terms of
unit cell dimensions a, b, and c
y 3 Adjust to smallest integer values
3.
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>
33

Linear Density
y
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
3 nm 1
length 2a

34
 HCP Crystallographic
y g p Directions
z
Algorithm
1 Vector
1. V t repositioned
iti d (if necessary)) tto 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
35

HCP Crystallographic Directions

• Hexagonal Crystals
– 4 parameter Miller-Bravais lattice coordinates are
related
l t d tto the
th direction
di ti iindices
di (i
(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 )
a1
w  w'
Fig. 3.8(a), Callister 7e.

36
 Crystallographic
y g p Planes

Adapted from Fig. 3.9, Callister 7e.

37

Crystallographic
y g p Planes
• Miller Indices: Reciprocals of the (three) axial
intercepts
p for a pplane, cleared of fractions &
common multiples. All parallel planes have
same Miller indices.

• Algorithm
1 Read off intercepts of plane with axes in
1.
terms of a, b, c
2. Take reciprocals of intercepts
3 Reduce to smallest integer values
3.
4. Enclose in parentheses, no
commas i.e., (hkl)

38
 PRACTICE
example a b c z
1. Intercepts c
2. Reciprocals

3. Reduction y
a b
4. Miller Indices x
z
example a b c
c
1. Intercepts
2
2. R
Reciprocals
i l
y
3. Reduction a b
4. Miller Indices x
39

Crystallographic
y g p 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
40
 Crystallographic
y g p 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
4. Mill
Miller IIndices
di (634) x

Family of Planes {hkl}

Ex: {100}
{ } = ((100),
) (010),
( ) (001),
( ) (100),
( ) (010),
( ) (001)
( )
41

Crystallographic
y g p Planes ((HCP))
• In hexagonal unit cells the same idea is used
z

example a1 a2 a3 c
1
1. Intercepts 1  -1
1 1
2. Reciprocals 1 1/ -1 1
1 0 -1 1 a2

3
3. Reduction 1 0 -1
1 1
a3

4. Miller-Bravais Indices (1011) a1

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

42
 Crystallographic
y g p 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
y g p p
planes
for Fe.
b) Calculate the planar density for each of these
planes.

43

Planar Density
y 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
Planar Density = = 2 = 12.1 = 1.2 x 1019
area a2 4 3 nm 2 m2
R
2D repeat unit 3
44
 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 2  3  R÷
÷  3 R
atoms  3 
2D repeat unit 1
atoms = atoms
Planar Density = = 7.0 0.70 x 1019
area 16 3 nm 2 m2
R2
2D repeat unit 3
45

X-Ray
y Diffraction

• Diffraction g
gratings
g must have spacings
p g comparable
p to
the wavelength of diffracted radiation.
• Can’t resolve spacings  
• Spacing is the distance between parallel planes of
atoms.
46
 X-Rays to Determine Crystal Structure
• Incoming X-rays diffract from crystal planes.

reflections must
be in phase for
a detectable signal
extra
distance
 Adapted from Fig. 3.19,
travelled   Callister 7e.
by wave “2” spacing
d between
planes
p

Measurement of X-ray
n
angle, c,
critical angle intensity d
(from 2 sin c
allows computation of
detector)
planar spacing, d.

c
47

X-Rayy Diffraction Pattern

z z z
c c c

y (110) y y
a b a b a b
ensity (relative)

x x x (211)
Inte

(200)

Diffraction angle 2

Diffraction pattern for polycrystalline -iron (BCC)

Adapted from Fig. 3.20, Callister 5e.

48
 SUMMARY
• Atoms may assemble into crystalline or amorphous
structures.
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,
weight atomic radius,
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.

49

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.
t t This
Thi is
i referred
f d to
t as polymorphism
l hi (
(or
allotropy).
• X-ray diffraction is used for crystal structure and
interplanar spacing determinations.

50