Materials Science

and
Engineering I

Chapter 3

Chapter 3 Outline
How do atoms arrange themselves to form solids?
Fundamental concepts and language
Unit cells
Crystal structures
Face-centered cubic
Body-centered cubic
Hexagonal close-packed
Close packed crystal structures
Density computations
Types of solids
Single crystal
Polycrystalline
Amorphous

1
 Crystal structure

To discuss crystalline structures it is useful to consider

atoms as being hard spheres with well-defined radii. In
this hard-sphere model, the shortest distance between
two like atoms is one diameter. We can also consider
crystalline structure as a lattice of points at atom/sphere
centers.

The Space Lattice and Unit Cells

Atoms, arranged in repetitive 3-Dimensional pattern,
in long range order (LRO) give rise to crystal
structure.
Properties of solids 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. Space Lattice
Unit cell is that block of
atoms which repeats itself
to form space lattice.
Materials arranged in short
range order are called
amorphous
4 materials Unit Cell

2
 Unit cell
The unit cell is the smallest structural unit or building block
that can describe the crystal structure. Repetition of the
unit cell generates the entire crystal.
Example: 2D honeycomb net can be
represented by translation of two adjacent
atoms that form a unit cell for this 2D
crystalline structure

Example of 3D crystalline structure:

Different choices of unit cells possible, generally choose parallelepiped unit

cell with highest level of symmetry

(Basis and the Crystal Structure)

3
 (Two-Dimensional Lattice Types)

(oblique lattice) (special lattice type)

(special lattice type)

P09

(special lattice type)

P09

4
 Crystal Systems and Bravais Lattice

Only seven different types of unit cells are

necessary to create all point lattices.
According to Bravais (1811-1863), fourteen
standard unit cells can describe all possible
lattice networks.
The four basic types of unit cells are
Simple
Body Centered
Face Centered
Base Centered

(Three-Dimensional Lattice Types)

P09

5
 Types of Unit Cells
Cubic () Unit Cell
a = b = c
= = = 900

Body Centered
Simple

Figure 3.2
Face centered

Tetragonal ()
a =b c
= = = 900

Simple Body Centered

After W.G. Moffatt, G.W. Pearsall, & J. Wulff, The Structure and Properties of Materials, vol. I: Structure, Wiley, 1964, p.47.)

Types of Unit Cells

Orthorhombic ()
a b c
= = = 900

Simple Base Centered

Body Centered
Face Centered

Rhombohedral ()
a =b = c
= = 900

Simple
Figure 3.2
After W.G. Moffatt, G.W. Pearsall, & J. Wulff, The Structure and Properties of Materials, vol. I: Structure, Wiley, 1964, p.47.)

6
 Types of Unit Cells

Hexagonal ()
a = b c
= = 900 = 1200
Simple

Monoclinic ()
a b c
= = 900
Base
Centered
Simple
Triclinic ()
a b c Figure 3.2

900

Simple

After W.G. Moffatt, G.W. Pearsall, & J. Wulff, The Structure and Properties of Materials, vol. I: Structure, Wiley, 1964, p.47.)

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.

BCC Structure FCC Structure HCP Structure

Figure 3.3
3-7

7
 Body Centered Cubic (BCC) Crystal Structure
Represented as one atom at each corner of cube
and one at the center of cube.
Each atom has 8 nearest neighbors.
Therefore, coordination number is 8.
Examples :-
Chromium (a=0.289 nm)
Iron (a=0.287 nm)
Sodium (a=0.429 nm)

Figure 3.4 a&b

3-8

BCC Crystal Structure (Cont..)

Each unit cell has eight 1/8 atom at

corners and 1 full atom at the center.
Therefore, each unit cell has
(8x1/8 ) + 1 = 2 atoms

Atoms contact each other at cube

diagonal

Therefore, lattice
4R
constant a =
3

Figure 3.5

8
 17

Atomic Packing Factor of BCC Structure

Volume of atoms in unit cell

Atomic Packing Factor =
Volume of unit cell

4R 3
Vatoms = 2 = 8.373R3
3
3
4R
V unit cell = a3 = = 12.32 R3

3

R3 = 0.68
Therefore APF = 8.723
12.32 R3

9
 19

Face Centered Cubic (FCC) Crystal Structure

FCC structure is represented as one atom each at the corner of
cube and at the center of each cube face.
Coordination number for FCC structure is 12
Atomic Packing Factor is 0.74
Examples :-
Aluminum (a = 0.405)
Gold (a = 0.408)

Figure 3.6 a&b

3-11

10
 FCC Crystal Structure (Cont..)
Each unit cell has eight 1/8
atom at corners and six
atoms at the center of six
faces.
Therefore each unit cell has

(8 x 1/8)+ (6 x ) = 4 atoms

Atoms contact each other

across cubic face diagonal

Therefore, lattice 4R
constant a =
2
Figure 3.7

Hexagonal Close-Packed Structure

The HCP structure is represented as an atom at each of
12 corners of a hexagonal prism, 2 atoms at top and
bottom face and 3 atoms in between top and bottom
face.
Atoms attain higher APF by attaining HCP structure
than simple hexagonal structure.
The coordination number is 12, APF = 0.74.

Figure 3.8 a&b

After F.M. Miller, Chemistry: Structure and Dynamics, McGraw-Hill, 1984, p.296

11
 23

HCP Crystal Structure (Cont..)

Each atom has six 1/6 atoms at each of top and
bottom layer, two half atoms at top and bottom layer
and 3 full atoms at the middle layer.
Therefore each HCP unit cell has
(2 x 6 x 1/6) + (2 x ) + 3 = 6 atoms
Examples:-
Zinc (a = 0.2665 nm, c/a = 1.85)
Cobalt (a = 0.2507 nm, c.a = 1.62)

Ideal c/a ratio is 1.633.

Figure 3.8 c
3-14 After F.M. Miller, Chemistry: Structure and Dynamics, McGraw-Hill, 1984, p.296

12
 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

Coordination # = 12 6 atoms/unit cell

APF = 0.74 ex: Cd, Mg, Ti, Zn

c/a = 1.633

25

FCC Stacking Sequence

ABCABC... Stacking Sequence
2D Projection
B B
C
A
A sites BCB B
C
B sites B B
C sites

A
FCC Unit Cell B
C

26

13
 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
a void
Void of plane A
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

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 toward top.
Negative directions are to the opposite of positive
directions.

Atom positions are located using

unit distances along the axes.

Figure 3.10 b
28

14
 Directions in Cubic Unit Cells
In cubic crystals, Direction Indices are vector
components of directions resolved along each axes and
reduced 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

30

15
31

32

16
 Procedure to Find Direction Indices
Produce the direction vector. 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]
NO Convert them to
Are all are
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)
Therefore, the direction indices are [ 2 2 1 ]
Figure EP3.6

17
 Miller Indices
Miller Indices are 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)

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)

18
 Miller Indices - Examples
z Intercepts of the plane at 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

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

19
 Miller Indices - Example
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
single unit cell, the z
(110)
origin is moved along
the positive direction
of y axis by 1 unit.
y

Crystallographic Planes
z

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

40

20
 Crystallographic Planes
z
example a b c
c
1. Intercepts 1/2 1 3/4
2. Reciprocals 1/ 1/1 1/
2 1 4/3 y

3. Reduction 6 3 4 a b
x
4. Miller Indices (634)

Other useful facts:

Family of Planes {hkl}
Ex: {100} = (100), (010), (001), (100), (010), (001)

For cubic systems only: [x y z] is normal to plane (x y z)

41

Crystallographic Planes

42

21
43

44

22
 45

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
[110]
Figure EP3.7b
x

Interplanar spacing between parallel closest planes with

same miller indices is given by
a
d hkl


2 2 2
h k l

23
 47

Planes and Directions in Hexagonal Unit Cells

Four indices are used (hkil) called as MillerBravais
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.

48 Figure 3.16

24
 Hexagonal Unit Cell - Examples
Basal Planes:
Intercepts a1 =
a2 =
a3 =
c = 1
(hkli) = (0001)
Prism Planes :
For plane ABCD,
Intercepts a1 = 1
a2 =
a3 = 1
c =
(hkli) = (1010)

49 Figure 3.12 a&b

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

50

25
 51

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

After W.G. Moffatt, 52
G.W. Pearsall, & J. Wulff, The Structure and Properties of Materials, vol. I: Structure, Wiley, 1964, p.51.)

26
 Volume Density
Volume density of metal = v =
Mass/Unit cell
Volume/Unit cell
Example:- Copper (FCC) has atomic mass of 63.54
g/mol and atomic radius of 0.1278 nm.
4R 4 0.1278nm = 0.361 nm
a= =
2 2
Volume of unit cell = V= a3 = (0.361nm)3 = 4.7 x 10-29 m3

FCC unit cell has 4 atoms.

( 4 atoms )(63 .54 g / mol ) 10 6 Mg = 4.22 x 10-28 Mg

Mass of unit cell = m =
4.7 10 23 atmos / mol g

v
m

4.22 1028 Mg
8.98
Mg
8.98
g

V 4.7 1029 m3 m3 cm3

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), 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 = 2a a 2a 2

2
=
2 0.287
p 2

17.2atoms 1.72 1013

2
nm mm 2
Figure 3.22 a&b

27
 55

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 + + 1 = 2 atomic
diameters.

Length of line = 2 0.361nm

l

2atoms

3.92atoms

3.92 10 6 atoms

2 0.361nm nm mm

Figure 3.23

28
 57

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

-2730C 9120C 13940C 15390C

Iron Iron Iron

BCC FCC BCC

29
 59

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

(Eg:
Molybdenum)

After B.D. Cullity, Elements of X-Ray Diffraction, 2d ed., Addison-Wesley, 1978, p.23.
Figure 3.25

30
 X-Ray Spectrum of Molybdenum
X-Ray spectrum of
Molybdenum is obtained
when Molybdenum is used as
target metal.
K and K are characteristic
of an element.
For Molybdenum K occurs
at wave length of about
0.07nm.
Electrons of n=1 shell of
target metal are knocked out
by bombarding electrons.
Electrons of higher level drop
down by releasing energy to Figure 3.26
replace lost electrons

3-35

X-Ray Diffraction
How do we know what the crystal structures are?

Diffraction gratings must have spacings comparable to the

wavelength of diffracted radiation.
Cant resolve spacings
Spacing is the distance between parallel planes of atoms.
62

31
 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
63 and J.J. Hren, Elements of Physical Metallurgy, 3d ed., Addison-Wesley, 1974, p.201.)
After A.G. Guy

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 .

n = MP + PN (n = 1,2)

n is order of diffraction

If dhkl is interplanar distance,

Then MP = PN = [Link]

Therefore, = 2 [Link]

64

32
 65

Structure factor
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 or odd Reflections present
(h,k,l) not all even or all odd Reflections absent.

66

33
 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
67
After A.G. Guy Essentials of Materials Science, McGraw-Hill, 1976.

X-Ray Diffraction Pattern

z z z
c c c

y (110) y y
a b a b a b
x x x
Intensity (relative)

(211)

(200)

Diffraction angle 2
Diffraction pattern for polycrystalline -iron

Adapted from Fig. 3.20, Callister 5e.

68

34
 Interpreting Diffraction Data
a
d
h k2 l2
hkl 2
We know that
Since 2dSin

Substituting for d, 2aSin

h2 k 2 l 2

2 (h 2 k 2 l 2 )
Therefore Sin 2
4a 2

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

69

Interpreting Diffraction Data (Cont..)

For planes A and B we get two equations

2 ( h A 2 k A 2 l A 2 )
Sin A
2 (For plane A)

4a 2

2 ( h B 2 k B 2 l B 2 )
Sin B
2 (For plane B)
2
4a

Dividing each other, we get

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

Sin B ( hB k B l B )
2 2 2 2

70

35
 Interpreting Experimental Data

For BCC crystals, the first two sets of diffracting planes

are {110} and {200} planes.
Sin 2 A (12 12 0 2 )
Therefore 0.5
Sin B2
(2 0 0 )
2 2 2

For FCC crystals the first two sets of diffracting planes

are {111} and {200} planes

Sin 2 A (12 12 12 )
Therefore 0.75
Sin B2
(2 0 0 )
2 2 2

71

Crystal Structure of Unknown Metal

Unknown
metal

Crystallographic
Analysis

Sin2 A Sin 2 A
0.75 0 .5
Sin B
2
Sin B
2

FCC BCC
Crystal Crystal
Structure Structure

36
 73

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
-Example: the modulus and Fracture Mechanics
of Engineering
Materials, 3rd ed., John
of elasticity (E) in BCC iron: Wiley and Sons, 1989.)

Polycrystals
E (edge) = 125 GPa

-Properties may/may not 200 mm Adapted from Fig.

4.14(b), Callister 7e.
(Fig. 4.14(b) is courtesy
vary with direction. of L.C. Smith and C.
Brady, the National
-If grains are randomly Bureau of Standards,
Washington, DC [now
the National Institute of
oriented: isotropic. Standards and
Technology,
Gaithersburg, MD].)
(Epoly iron = 210 GPa)
-If grains are textured,
74
anisotropic.

37
 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.
Rapid cooling of metals (10 8 K/s) can give
rise to amorphous structure (metallic glass).

38