Materials Science

Lecture #3b

Crystallography

2-1
2
Crystallographic Points,
Directions, and Planes
 Atom Positions in Cubic Unit Cells
• Cartesian coordinate system is use to locate atoms.
• In a cubic unit cell
➢ x axis is the direction coming out of the paper.
➢ y axis is the direction to the right.
➢ 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.

Figure 3.10 b
3-15
 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
5
 Crystallographic Directions
z Algorithm

1. Vector repositioned (if necessary) to pass

through origin.
2. Read off projections in terms of
y unit cell dimensions a, b, and c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas
x [uvw]

e.g: 1, 0, ½ => 2, 0, 1 => [ 201 ]

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

6
 families of directions <uvw>

i.e. Directions with same atomic arrangements

Equivalency of
crystallographic directions of
a form in cubic systems

7
Families of directions <110>

Family of
Directions

8
 Directions in Cubic Unit Cells
• In cubic crystals, Direction Indices are vector components
of directions resolved along each axes, resolved to
smallest integers.
• Direction indices are position coordinates of unit cell
where the direction vector emerges from cell surface,
converted to integers.

Figure 3.11

3-16
Some common directions in a unit cell.

[112]

[021]
 Procedure to Find Direction Indices
Produce the direction vector till it
z
emerges from surface of cubic cell
(1,1/2,1) - (0,0,0)
(1,1/2,1)
Determine the coordinates of point = (1,1/2,1)
of emergence and origin y
(0,0,0) 2 x (1,1/2,1)
Subtract coordinates of point of x = (2,1,2)
Emergence by that of origin
The direction indices are [212]
Are all are NO Convert them to
integers? smallest possible
YES integer by multiplying
Are any of the direction by an integer.
vectors negative?
NO
YES
Represent the indices in a square
Represent the indices in a square
bracket without comas with a
bracket without comas (Eg: [212] )
over negative index (Eg: [121])
3-17
 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 origin coordinates

from emergence coordinates,
(1/4, 1/2, 1/2)- (3/4 , 0 , 1/4)
= (-1/2, 1/2, 1/4)
Multiply by 4 to convert all
fractions to integers
4 x (-1/2, 1/2, 1/4) = (-2, 2, 1)
ഥ21]
Therefore, the direction indices are [ 𝟐
Figure EP3.6

3-18
Crystallographic planes
 Miller Indices
• Miller Indices are used to refer to specific lattice planes of
atoms.
• They are reciprocals of the fractional intercepts (with
fractions cleared) that the plane makes with the
crystallographic x, y and z axes of three nonparallel edges
of the cubic unit cell.
z Miller Indices =(111)

x
3-19
 Miller Indices - Procedure
Choose a plane that does not pass
through origin

Determine the x,y and z intercepts

of the plane

Find the reciprocals of the intercepts

Clear fractions by
Fractions?
multiplying by an integer
Place a ‘bar’ over the to determine smallest set
Negative indices of whole numbers

Enclose in parenthesis (hkl)where h,k,l

are miller indicesof cubic crystal plane
forx,y and z axes. Eg: (111)

3-20
 Miller Indices - Examples

• Intercepts of the plane at

z
x, y & z axes are 1, ∞ and ∞
(100) • Taking reciprocals we get
y (1,0,0).
x • Miller indices are (100).
x *******************
• Intercepts are 1/3, 2/3 & 1.
• taking reciprocals we get
(3, 3/2, 1).
• Multiplying by 2 to clear
fractions, we get (6,3,2).
• Miller indices are (632).
Figure 3.14
3-21
 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.
Figure EP3.7 a
******************************
• 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.

Figure EP3.7 c

3-22
 Miller Indices - Example
ത
• Plot the plane (110)
The reciprocals are (1, -1, ∞)
The intercepts are x=1, y= -1 and z= ∞ (parallel to z axis)

To show this plane a (110) z

single unit cell, the
origin is moved along
the positive direction
y
of y axis by 1 unit.

3-23
 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
19
 Crystallographic Planes

example a b c
1. Intercepts 1/2 1 3/4
2. Reciprocals 1/½ 1/1 1/¾
2 1 4/3
3. Reduction 6 3 4
z
4. Miller Indices (634)
c
•

• y
•
a b
x
20
Family of Planes {hkl}

21
Diagrams showing the planes forming the faces of
the cubic unit cell

Family of Planes {hkl}

E.g: {100} = (100),(010), (001), (100), (010), (001)
22
Diagrams showing the planes forming the diagonals
of the unit cell

Family of Planes {110}

E.g: {110} = (110), (110), (011), (101), (110), (011)
24
Family of Planes {110}
E.g: {110} = (110), (110), (011), (101), (110), (011)
 Miller Indices – Important Relationship
• Direction indices of a direction perpendicular to a crystal
plane are same as miller indices of the plane.
• Example:- z

(110) y
ഥ0]
[1𝟏
Figure EP3.7b
x

[1𝟏ഥ 𝟎] direction is perpendicular to (1𝟏ഥ 𝟎) plane

3-24
Directions and perpendicular planes
Directions and planes
[321]
Common planes in a cubic structure
 Equivalent Crystallographic Planes

Interplanar spacing between

parallel closest planes with same a
d =
miller indices is given by hkl
2
+k +l
2 2
h 31
 Directions in HCP Unit Cells
• Indicated by 4 indices [uvtw].
• u,v,t and w are lattice vectors in a1, a2, a3 and c directions
respectively.
• Example:-
For a1, a2, a3 directions, the direction indices are
[ 2 1 1 0], [1 2 1 0] and [ 1 1 2 0] respectively.

Figure 3.18 d&e

3-27
 Planes in Hexagonal Unit Cells
• Four indices are used (hkil) called as Miller-Bravais indices.
• Four axes are used (a1, a2, a3 and c).
• Reciprocal of the intercepts that a crystal plane makes with
the a1, a2, a3 and c axes give the h,k,i and l indices
respectively.

Figure 3.16

3-25
 Hexagonal Unit Cell - Examples
• Basal Planes:-
Intercepts a1 = ∞
a2 = ∞
a3 = ∞
c=1
(hkil) = (0001)
• Prism Planes :- Figure 3.12 a&b
For plane ABCD,
Intercepts a1 = 1
a2 = ∞
a3 = -1
c=∞
(hkil) = (1010)

3-26
 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.

Figure 3.19 a&b

3-28 After W.G. Moffatt, G.W. Pearsall, & J. Wulff, “The Structure and Properties of Materials,” vol. I: “Structure,” Wiley, 1964, p.51.)
Structural Difference between HCP and FCC
Plane A
Consider a layer ‘a’ void
of atoms (Plane ‘A’) ‘b’ void

Another layer (plane ‘B’) Plane A

of atoms is placed in ‘a’ Plane B
Void of plane ‘A’ ‘a’ void
‘b’ void
Third layer of Atoms placed Third layer of Atoms placed
in ‘b’ Voids of plane ‘B’. (Identical in ‘a’ voids of plane ‘B’. Resulting
to plane ‘A’.) HCP crystal. In 3rd Plane C. FCC crystal.

Plane A Plane A
Plane B Plane B
Plane A Plane C

Figure 3.20
 Planar Atomic Density
Equivalent number of atoms whose
Planar atomic density =  p=
centers are intersected by selected area
Selected area

Example:- In Iron (BCC, a=0.287 nm), The (110) plane

intersects center of 5 atoms (Four ¼ and 1 full atom).
➢ Equivalent number of atoms = (4 x ¼ ) + 1 = 2 atoms
Area of 110 plane = 2a  a = 2a 2


2
=
2 (0.287)
p 2

17.2atoms 1.72  1013

= =
nm 2 mm 2
Figure 3.22 a&b
 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
40
 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
41
SC
SC
FCC
FCC
FCC
BCC
BCC
BCC
BCC
Linear Atomic Density
Number of atomic diameters
intersected by selected length
Linear atomic density =  l
=
of line in direction of interest
Selected length of line

Example:- For a FCC copper crystal (a=0.361), the [110]

direction intersects 2 half diameters and 1 full diameter.
➢ Therefore, it intersects ½ + ½ + 1 = 2 atomic diameters.

Length of line = 2  0.361nm

 l
=
2atoms
=
3.92atoms
=
3.92  106 atoms

2  0.361nm nm mm

Figure 3.23
FCC vs BCC

But close packed

52
directions are there
Polymorphism/ allotropy
Two or more distinct crystal structures for the same material
(allotropy/polymorphism)
• iron iron system
liquid
1538ºC
• titanium BCC -Fe
, -Ti 1394ºC
FCC -Fe
• carbon 912ºC
diamond, graphite BCC -Fe

57
 DEMO: HEATING AND
COOLING OF AN IRON WIRE
The same atoms can
• Demonstrates "polymorphism" have more than one
crystal structure.

19
 Polymorphism or Allotropy
• Metals exist in more than one crystalline form. This is
caller polymorphism or allotropy.
• Temperature and pressure leads to change in crystalline
forms.
• Example:- Iron exists in both BCC and FCC form
depending on the temperature.
Liquid
Iron

-2730C 9120C 13940C 15390C

α Iron γ Iron δ Iron

BCC FCC BCC
Allotropies of carbon

60
Crystal Structure Analysis

X–Ray Diffraction

https://youtu.be/tuTsG6XEBuE

61
 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.
62
 Crystal Structure Analysis
• Information about crystal structure are obtained using X-
Rays.
• The X-rays used are about the same wavelength (0.05-
0.25 nm) as distance between crystal lattice planes.

35 kV
(e.g:
Molybdenum)

Figure 3.25

3-34 After B.D. Cullity, “Elements of X-Ray Diffraction, “ 2d ed., Addison-Wesley, 1978, p.23.
High Electrical Potential

Electrons

+ -

X-ray Generator or
Radioactive Source
Creates Radiation

Radiation
Penetrate
the Sample

Exposure Recording Device

 X-Ray Spectrum of Molybdenum
• X-Ray spectrum of Molybdenum is
obtained when Molybdenum is
used as target metal.
• Kα and Kβ are characteristic of an
element.
• For Molybdenum Kα occurs at
wave length of about 0.07 nm.
• Electrons of n=1 shell of target
metal are knocked out by
bombarding electrons.
• Electrons of higher level drop
down by releasing energy to
replace lost electrons
Figure 3.26

3-35
66
67
 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
68
 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.

Figure 3.28
3-36 After A.G. Guy and J.J. Hren, “Elements of Physical Metallurgy,” 3d ed., Addison-Wesley, 1974, p.201.)
 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 (1–D) for polycrystalline -iron (BCC)

Adapted from Fig. 3.20, Callister 5e.

70
2- D image
 X-Ray Diffraction (Cont..)
• For rays reflected from different planes to be in phase,
the extra distance traveled by a ray should be a integral
multiple of wave length λ .

nλ = MP + PN (n = 1,2…)
n is order of diffraction

If dhkl is interplanar distance,

Then MP = PN = dhkl.Sinθ

Therefore, λ = 2 dhkl.Sinθ
Figure 3.28

3-37 After A.G. Guy and J.J. Hren, “Elements of Physical Metallurgy,” 3d ed., Addison-Wesley, 1974, p.201.)
 Interpreting Diffraction Data
a
• We know that d hkl
=
h2 + k 2 + l 2

Since  = 2dSinq

2aSinq
Substituting for d, =
h2 + k 2 + l 2

2 h 2 + k 2 + l 2
Therefore Sin q =
2

4a 2

Note that the wavelength λ and lattice constant a are the same
For both incoming and outgoing radiation.

3-38
 Interpreting Diffraction Data (Cont..)
• For planes ‘A’ and ‘B’ we get two equations
2 ( h A 2 + k A 2 + l A 2 ) (For plane ‘A’)
Sin 2q A =
4a 2

2 ( h B 2 + k B 2 + l B 2 )
Sin 2q B = (For plane ‘B’)
4a 2

Dividing each other, we get

Sin 2q A (hA + k A + l A )
2 2 2

=
Sin 2q B ( hB + k B + l B )
2 2 2

3-39
 X-Ray Diffraction Analysis
• Powdered specimen is used for X-ray diffraction analysis as the
random orientation facilitates different angle of incidence.
• Radiation counter detects angle and intensity of diffracted
beam.

Figure 3.30
3-40 After A.G. Guy “Essentials of Materials Science,” McGraw-Hill, 1976.
 Diffraction Condition for Cubic Cells
• For BCC structure, diffraction occurs only on planes
whose miller indices when added together total to an
even number.
i.e. (h+k+l) = even Reflections present
(h+k+l) = odd Reflections absent

• For FCC structure, diffraction occurs only on planes

whose miller indices are either all even or all odd.
i.e. (h,k,l) all even Reflections present
(h,k,l) all odd Reflections present
(h,k,l) not all even or all odd Reflections absent.

3-41
 Interpreting Experimental Data
• For BCC crystals, the first two sets of diffracting planes
are {110} and {200} planes.

Sin 2q A (12 + 12 + 0 2 )
Therefore = = 0.5
Sin 2q B (2 2 + 02 + 02 )

• For FCC crystals the first two sets of diffracting planes

are {111} and {200} planes
Sin 2q A (12 + 12 + 12 )
Therefore = = 0.75
Sin 2q B (2 2 + 02 + 02 )

3-42
 Crystal Structure of Unknown Metal
Unknown
metal
Crystallographic
Analysis

Sin 2q A Sin 2q A
= 0.75 = 0.5
Sin 2q B Sin 2q B

FCC BCC
Crystal Crystal
Structure Structure

3-43
 Amorphous Materials
• Random spatial positions of atoms
• Polymers: Secondary bonds do not allow
formation of parallel and tightly packed chains
during solidification.
➢ Polymers can be semicrystalline.
• Glass is a ceramic made up of SiO4 4- tetrahedron
subunits – limited mobility.
• Rapid cooling of metals (10 8 K/s) can give rise to
amorphous structure (metallic glass).
• Metallic glass has superior metallic properties.
 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.

80
 Polycrystals
Anisotropic
• Most engineering materials are polycrystals.

Adapted from Fig. K,

color inset pages of
Callister 5e.
(Fig. K is courtesy of
Paul E. Danielson,
Teledyne Wah Chang
Albany)
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).
81
 SUMMARY
• Atoms may assemble into crystalline or
amorphous 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, atomic 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.

82
 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. This is referred to as polymorphism (or
allotropy).
• X-ray diffraction is used for crystal structure and
interplanar spacing determinations.

83