Lecture 3 -1

At the end of the lecture, you will know:

The difference between crystalline and non-crystalline
materials.
How do atoms assemble into solid structures?
Draw and understand the relationship between
face-centered, body-centered and hexagonal close packing.
Distinguish between single crystals and polycrystalline
materials.
Explain polymorphism or allotropy in materials.
Write atom position, direction indices and Miller indices for
cubic crystal system.
Chapter 3: Crystal and Amorphous Structures
in Materials
How do the crystal structures of ceramic materials differ
from those for metals?
Halina Misran 2009
Non dense, random packing
Dense, ordered packing
Dense, ordered packed structures tend to have
lower energies.
Energy and Packing
Energy
r
typical neighbor
bond length
typical neighbor
bond energy
Energy
r
typical neighbor
bond length
typical neighbor
bond energy
Halina Misran 2009
Lecture 3 -2
atoms pack in periodic, 3D arrays
Crystalline materials...
-metals
-many ceramics
-some polymers
atoms have no periodic packing
Noncrystalline materials...
-complex structures
-rapid cooling
crystalline SiO2
noncrystalline SiO2
"Amorphous" = Noncrystalline
Materials and Packing
Si Oxygen
typical of:
occurs for:
long-range order (LRO)
short-range order (SRO)
Halina Misran 2009
Lecture 3 -3
Atoms, arranged in repetitive 3-dimensional pattern -
give rise to crystal structure.
Properties of solids materials of engineering importance
depends upon crystal structure and bonding force.
An imaginary network of lines, with atoms at intersection
of lines, representing the arrangement of atoms is called
space lattice.
Unit cell is that block of atoms which repeats itself to
form space lattice.
Unit Cell
Space
Lattice
Halina Misran 2009
Lecture 3 -4
Crystal Systems and Bravais Lattice
a, b, c, o, | and
are the lattice constants
7 Crystal Systems
7 different types of crystal systems are
necessary to create all point lattices.
1) cubic
2) tetragonal
3) orthorhombic
4) rhombohedral
5) hexagonal
6) monoclinic
7) triclinic
14 Unit Cells
according to Bravais (1811-1863)
14 standard unit cells can describe all
possible lattice networks.
Halina Misran 2009
Lecture 3 -5
1. Cubic Crystal System
a = b = c
o = | = = 90
0
Simple (SC) Body Centered
(BCC)
Face Centered
(FCC)
Simple Body Centered
Halina Misran 2009
a =b c
= = = 90
0
2. Tetragonal Crystal System
Lecture 3 -6
3. Orthorhombic Crystal System
a b c
= = = 90
0
Simple Base Centered
Face Centered Body Centered
Simple
a = b = c
= = 90
0
Halina Misran 2009
4. Rhombohedral Crystal System
5. Hexagonal Crystal System
a = b c
= = 90
0
, = 120
Simple
Simple
Base
Centered
a b c
o = = 90
0
|
6. Monoclinic Crystal System
9
7. Triclinic Crystal System
a b c
90
0
Simple
10
Rare due to low packing density (only Po has this structure)
Close-packed directions are cube edges.
Coordination # = 6
(# nearest neighbors)
(Courtesy P.M. Anderson)
Simple Cubic Structure (SC)
1 atom/unit cell : 8 corners x 1/8
11
APF for a simple cubic structure = 0.52
APF =
a
3
4
3
t (0.5a)
3
1
atoms
unit cell
atom
volume
unit cell
volume
Atomic Packing Factor (APF)
APF =
Volume of atoms in unit cell*
Volume of unit cell
*assume hard spheres
close-packed directions
a
R=0.5a
contains 8 x 1/8 =
1
atom/unit cell
12
Coordination # = 8
Adapted from Fig. 3.2,
Callister & Rethwisch 3e.
(Courtesy P.M. Anderson)
Atoms touch each other along cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.
Body Centered Cubic Structure (BCC)
ex: Cr, W, Fe (o), Tantalum, Molybdenum
2 atoms/unit cell: 1 center + 8 corners x 1/8
13
a
a
c
60
120
Atomic Packing Factor: HCP
TBA in the lecture.
14
Atomic Packing Factor: BCC
a
APF =
4
3
t ( 3a/4)
3
2
atoms
unit cell
atom
volume
a
3
unit cell
volume
length = 4R =
Close-packed directions:
3 a
APF for a body-centered cubic structure = 0.68
a
R
Adapted from
Fig. 3.2(a), Callister &
Rethwisch 3e.
a 2
a 3
15
Coordination # = 12
Adapted from Fig. 3.1, Callister & Rethwisch 3e.
(Courtesy P.M. Anderson)
Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.
Face Centered Cubic Structure (FCC)
ex: Al, Cu, Au, Pb, Ni, Pt, Ag
4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8
16
APF for a face-centered cubic structure = 0.74
Atomic Packing Factor: FCC
maximum achievable APF
APF =
4
3
t ( 2a/4)
3
4
atoms
unit cell
atom
volume
a
3
unit cell
volume
Close-packed directions:
length = 4R = 2 a
Unit cell contains:
6 x1/2 + 8 x1/8
= 4 atoms/unit cell
a
2 a
Adapted from
Fig. 3.1(a),
Callister &
Rethwisch 3e.
17
Coordination # = 12
ABAB... Stacking Sequence
APF = 0.74
3D Projection 2D Projection
Adapted from Fig. 3.3(a),
Callister & Rethwisch 3e.
Hexagonal Close-Packed Structure
(HCP)
ex: Cd, Mg, Ti, Zn
Ideal ratio of c/a = 1.633
c
a
A sites
B sites
A sites
Bottom layer
Middle layer
Top layer
(2 x 6 x 1/6) + (2 x ) + 3
= 6 atoms/unit cell
Principal Metallic Crystal Structures
90% of the metals have either Body Centered Cubic (BCC), Face
Centered Cubic (FCC) or Hexagonal Close Packed (HCP) crystal
structure.
HCP is denser version of simple hexagonal crystal structure.
Most metals crystallize into HCP, atoms are closer and bond
tighter. Thus, lower energy and more stable.
BCC Structure FCC Structure HCP Structure
3-7
Atom Positions in Cubic Unit Cells
Cartesian coordinate system is use to locate atoms.
In a cubic unit cell
y axis is the direction to the right.
x axis is the direction coming out of the paper.
z axis is the direction towards top.
Negative directions are to the opposite of positive
directions.
Atom positions are located using unit distances along the
axes.
3-15
Directions in Cubic Unit Cells
Direction indices are position coordinates of unit cell where the
direction vector emerges from cell surface, converted to integers.
Example (1,0,0)
In cubic crystals, Direction Indices are vector components of
directions resolved along each axes, reduced to the smallest
integers. Example [100]
3-16
[110]
[111]
= (1,1/2,0)
Must be integer
= 2(1,1/2, 0)
= [210]
New
origin
(-1,-1,0)
[ 0]
21
(0,0,0) (0,1,0)
x
y
z
(0,-1,0)
(1,0,0)
(0,0,1)
(-1,0,0)
(0,0,-1)
Directions are crystallographically equivalent when:
Atom spacing along each direction is the same.
[100], [010], [001], [00], [00], [00] = family of indices
Example
Draw the following direction vectors in cubic unit cells:
[102]
[313]
[212]
[301]
TBA in lecture.
22
Direction Indices - Example
Determine direction indices of the given vector.
Origin coordinates are (3/4, 0, 1/4).
Emergence coordinates are (1/4, 1/2, 1/2).
Subtracting emergence coordinates from origin :
= ( , , ) ( , 0, )
= ( - , , )
Multiply by 4 to convert all fractions
to integers 4 x (-, , ) = (-2, 2, 1)
Therefore, the direction indices are
[ 2 2 1 ]
3-18
24
Crystallographic Planes Miller Indices
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 for example (111)
z
x
y
Miller
Indices =(111)
25
z
x
y
a b
c
4. Miller Indices (110)
example a b c
z
x
y
a b
c
4. Miller Indices (100)
1. Intercepts 1 1
2. Reciprocals
1/1 1/1 1/
3. Reduction 1 1 0
1. Intercepts 1
2. Reciprocals 1/1 1/ 1/
3. Reduction 1 0 0
example a b c
Crystallographic Planes Miller Indices
26
z
x
y
a b
c
-
-
-
4. Miller Indices (634)
example
1. Intercepts 1/2 1 3/4
a b c
2. Reciprocals
1/ 1/1 1/
2 1 4/3
3. Reduction 6 3 4
(001) (010),
Family of Planes {hkl}
(100), (010), (001), Ex: {100} = (100),
Crystallographic Planes Miller Indices
Miller Indices - Examples
Plot the plane (101)
Taking reciprocals of the indices we
get (1 1).
The intercepts of the plane are x=1,
y= (parallel to y) and z=1.
TBA in lecture.
**********************************************
Plot the plane (2 2 1)
Taking reciprocals of the indices
we get (1/2 1/2 1).
The intercepts of the plane are
x=1/2, y= 1/2 and z=1.
TBA in lecture.
3-22
Example
28
Plot the plane (110)
The reciprocals are (1,-1, )
The intercepts are x=1, y=-1 and z=
(parallel to z axis)
y
x
z
Miller Indices Important Relationship
Direction indices of a direction perpendicular to a crystal
plane are same as miller indices of the plane.
Example:
Interplanar spacing between parallel closest planes with
same miller indices is given by
(110) plane
[110] indices
x
y
z
3-24
d
hkl
=
a
h
2
+ k
2
+ l
2
d
hkl
= interplanar spacing between parallel closest
plane
a = lattice constant
h, k, l = Miller indices of cubic plane being considered
30
Crystallographic Planes
Adapted from Fig. 3.25,
Callister & Rethwisch 3e.
31
HCP Crystallographic Directions
1. 4 parameter Miller-Bravais indices (hkil)
are used and 4 axes (a
1
, a
2
, a
3
and c) are
related as follows :
2. Read off projections in terms of unit
cell dimensions a
1
, a
2
, a
3
, or c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas
[uvtw]
[ 1120] ex: , , -1, 0 =>
dashed red lines indicate
projections onto a
1
and a
2
axes a
1
a
2
a
3
-a
3
2
a
2
2
a
1
Fig. 3.24(a), Callister & Rethwisch 3e.
-
a
3
a
1
a
2
z
Hexagonal Unit Cell - Examples
Basal Planes:-
Intercepts a1 =
a2 =
a3 =
c = 1
(hkil) = (0001)
Prism Planes :-
For plane ABCD,
Intercepts a1 = 1
a2 =
a3 = -1
c =
(hkil) = (1010)
3-26
Directions in HCP Unit Cells
Indicated by 4 indices [uvtw].
u,v,t and w are lattice vectors in a
1
, a
2
, a
3
and c
directions respectively.
Example: For a
1
, a
2
, a
3
directions, the direction
indices are [ 2 1 1 0], [1 2 1 0] and [ 1 1 2 0]
respectively.
3-27
34
Crystallographic Planes (HCP)
In hexagonal unit cells the same idea is used
example a
1
a
2
a
3
c
4. Miller-Bravais Indices (1011)
1. Intercepts 1 -1 1
2. Reciprocals 1 1/
1 0
-1
-1
1
1
3. Reduction 1 0 -1 1
a
2
a
3
a
1
z
Adapted from Fig. 3.24(b),
Callister & Rethwisch 3e.
Comparison of FCC and HCP crystals
Both FCC and HCP are close packed and have APF 0.74.
FCC crystal is close packed in (111) plane while HCP is
close packed in (0001) plane.
36
Volume Density, p
where n = number of atoms/unit cell
A = atomic weight
V
C
= Volume of unit cell = a
3
for cubic
N
A
= Avogadros number
= 6.022 x 10
23
atoms/mol
Density = p =
V
C
N
A
n A
p =
Cell Unit of Volume Total
Cell Unit in Atoms of Mass
37
Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
p
theoretical
a = 4R/ 3 = 0.2887 nm
p
actual
a
R
p =
a
3
52.00 2
atoms
unit cell
mol
g
unit cell
volume atoms
mol
6.022x10
23
Volume Density, p for BCC
= 7.18 g/cm
3
= 7.19 g/cm
3
Planar Density
p
Example: In Iron (BCC, a = 0.287), the (110) plane intersects center
of 5 atoms (Four and 1 full atom).
Equivalent number of atoms = (4 x ) + 1 = 2 atoms
Area of 110 plane =
p
p
=
Atoms intersected in selected 2D plane
in unit cell
Selected 2D area
2
2 2 a a a =
p
p
( )
2
287 . 0 2
2
=
2
13
2
10 72 . 1 2 . 17
mm nm
atoms
= =
39
ex: linear density of Al in [110]
direction
a = 0.405 nm
Linear Atomic Density
Linear Density of Atoms LD =
a
[110]
Unit length of direction vector
Number of atoms diameter
# atoms
length
1
3.5 nm
a 2
2
LD

= =
40
Polymorphism
Some materials can have more than one crystal structure. This is
referred to as polymorphism (or allotropy).
Temperature and pressure cause metals to change crystal structure.
titanium
o, |-Ti
carbon
diamond, graphite
BCC
FCC
BCC
1538C
1394C
912C
o-Fe
-Fe
o-Fe
liquid
iron system
41
Polymorphic Forms of Carbon
Diamond
tetrahedral bonding of
carbon
hardest material known
very high thermal
conductivity
large single crystals
gem stones
small crystals used to
grind/cut other materials
diamond thin films
hard surface coatings
used for cutting tools,
medical devices, etc.
42
Polymorphic Forms of Carbon (cont)
Graphite
layered structure parallel hexagonal arrays of
carbon atoms
weak van der Waals forces between layers
planes slide easily over one another -- good
lubricant
43
Polymorphic Forms of Carbon
Fullerenes and Nanotubes
Fullerenes spherical cluster of 60 carbon atoms, C
60
Like a soccer ball
Carbon nanotubes sheet of graphite rolled into a tube
Ends capped with fullerene hemispheres
44
Properties of crystalline materials often related to their crystal structure.
Single crystal the repeated unit cell is perfect throughout the
material.
Some engineering applications require single crystals:-- diamond single
crystals for abrasives or turbine blade.
However, most crystalline solids are made up of small crystals (grains). This
is called polycrystalline materials.
(Courtesy P.M. Anderson)
Crystals as Building Blocks
45
Most engineering materials are polycrystals.
Nb-Hf-W plate with an electron beam weld.
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).
1 mm
Polycrystals
Isotropic
Anisotropic
-Properties vary
with direction:
anisotropic.
-Properties do
not vary with
direction:
isotropic.
46
Single Crystals
-Properties vary with
direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
Polycrystals
-Properties may/may not
vary with direction.
-If grains are randomly
oriented: isotropic.
-If grains are textured,
anisotropic.
200 um
Single vs Polycrystals
E (diagonal) = 273 GPa
E (edge) = 125 GPa
47
Ceramic Crystal Structures
Oxide structures
oxygen anions larger than metal cations
close packed oxygen in a lattice (usually FCC)
cations fit into interstitial sites among oxygen ions
48
Factors that Determine Crystal Structure
1. Relative sizes of ions Formation of stable structures:
--maximize the # of oppositely charged ion neighbors.
Adapted from Fig. 3.4,
Callister & Rethwisch 3e.
- -
- -
+
unstable
-
-
- -
+
stable
- -
- -
+
stable
2. Maintenance of
Charge Neutrality :
--Net charge in ceramic
should be zero.
--
CaF
2
:
Ca
2+
cation
F
-
F
-
anions
+
49
X-Ray Diffraction
Diffraction gratings must have spacings comparable to
the wavelength of diffracted radiation.
Cant resolve spacings <
Spacing is the distance between parallel planes of
atoms.
X-Ray Diffraction
Crystal planes of target metal act as mirrors reflecting
X-ray beam.
If rays leaving a set of planes
are out of phase (as in case of
arbitrary angle of incidence)
no reinforced beam is
produced.
If rays leaving are in phase,
reinforced beams are
produced.
3-36
Figure 3.28
51
X-Rays to Determine Crystal Structure
X-ray
intensity
(from
detector)
u
u
c
d =
n
2 sinu
c
Measurement of
critical angle, u
c
,
allows computation of
planar spacing, d.
Incoming X-rays diffract from crystal planes.
reflections must
be in phase for
a detectable signal
spacing
between
planes
d
u

u
extra
distance
travelled
by wave 2
52
X-Ray Diffraction Pattern
Adapted from Fig. 3.20, Callister 5e.
(110)
(200)
(211)
z
x
y
a
b
c
Diffraction angle 2u
Diffraction pattern for polycrystalline o-iron (BCC)
I
n
t
e
n
s
i
t
y

(
r
e
l
a
t
i
v
e
)
z
x
y
a
b
c
z
x
y
a
b
c
53
Quartz is crystalline
SiO2:
Basic Unit:
Glass is noncrystalline (amorphous)
Fused silica is SiO
2
to which no
impurities have been added
Other common glasses contain
impurity ions such as Na
+
, Ca
2+
,
Al
3+
, and B
3+
(soda glass)
Adapted from Fig. 3.41,
Callister & Rethwisch 3e.
Glass Structure
Si0
4
tetrahedron
4-
Si
4+
O
2-
Si
4+
Na
+
O
2-
54
Silicate Ceramics
Most common elements on earth are Si & O
SiO
2
(silica) polymorphic forms are quartz,
crystobalite, & tridymite
The strong Si-O bonds lead to a high melting
temperature (1710C) for this material
Si
4+
O
2-
Adapted from Figs.
3.10-11, Callister &
Rethwisch 3e
crystobalite
55
Layered Silicates
Layered silicates (e.g., clays, mica, talc)
SiO
4
tetrahedra connected
together to form 2-D plane
A net negative charge is associated
with each (Si
2
O
5
)
2-
unit
Negative charge balanced by
adjacent plane rich in positively
charged cations
Adapted from Fig.
3.13, Callister &
Rethwisch 3e.
56
Atoms may assemble into crystalline or amorphous 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).
SUMMARY
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.
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.
Ceramic crystal structures are based on:
-- maintaining charge neutrality
-- cation-anion radii ratios.
Interatomic bonding in ceramics is ionic and/or covalent.
57
Some materials can have more than one crystal
structure. This is referred to as polymorphism (or
allotropy).
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.
X-ray diffraction is used for crystal structure and
interplanar spacing determinations.