BNQ 30503

MATERIAL ENGINEERING
TECHNOLOGY
CHAPTER 1:
SOLID STRUCTURE
By: Engr. Dr. Nasrul Fikry Che Pa
http://bit.ly/19o6LoL

Contents Review
Chapter 1: Solid Structure
What you will learn?
Crystal structures fundamental concepts, metallic crystal
structures, crystallographic points, directions and
planes, crystalline and noncrystalline materials, point
defects, dislocations, importance of defects.

Introduction
Schematic representation of the most
basic structural unit for quartz (all silicate
material). Each atom of Si surrounded by
4 O2 atom whose center are located at
the corner of a tetrahedron. Represented
as 44

Sketch of a unit cell for Quartz,

composed of several interconnected
44 tetrahedral.
3

Introduction

Schematic diagram showing a large

interconnected 44 tetrahedral.
Observe the shape resembles quartz.

Photograph of 2 single crystals of

quartz.
4

Fundamental Concepts
Crystalline materials...
Atoms pack in periodic, 3D arrays
Examples: metals, many ceramic & some polymers
Non-crystalline materials...
Atoms have no periodic packing
occurs for: - complex structures

crystalline SiO2
Si
Oxygen

- rapid cooling
- Lack systematic & regular
arrangement of atoms over
relatively large atomic distance

"Amorphous" = Noncrystalline
-literally means without form

noncrystalline SiO2

Atoms in crystalline solid are position in orderly & repeated patterns that are
in contrast to the random & disordered atomic distribution found in
non-crystalline
or amorphous materials
5

Metallic Crystal Structures

How can we stack metal atoms to minimize empty
space?
2-dimensions

vs.

Imagine that these 2D layers are stacked to make 3D

structures. Which one having a minimized empty spaces?
6

Metallic Crystal Structures

General Description

Tend to be densely packed.

Assumptions in 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.

Next. We will examine four such structures...
7

Simple Cubic Structure (SC)

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

Close-packed directions are cube edges.

Coordination # = 6
(# nearest neighbors)

Click once on image to start animation

(Courtesy P.M. Anderson)

Atomic Packing Factor (APF)

Volume of atoms in unit cell* (Vs)
APF =
Volume of unit cell (Vc)
*assume hard spheres

APF for a simple cubic structure = 0.52

atoms
unit cell

a
R=0.5a

APF =

volume
atom
4
p (0.5a) 3
1
3
a3

close-packed directions

contains 8 x 1/8 = 1 atom/unit cell

volume
unit cell

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 # = 8

Click once on image to start animation

(Courtesy P.M. Anderson)

10

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

Atomic Packing Factor: BCC

APF for a body-centered cubic structure = 0.68
3a

a
2a

11

Close-packed directions:
length = 4R = 3 a

atoms
4
p ( 3a/4) 3
2
unit cell
3
APF =
volume
a3
unit cell

volume
atom

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

Click once on image to start animation

(Courtesy P.M. Anderson)

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

12

Atomic Packing 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
atoms
volume
4
3
p ( 2a/4)
4
unit cell
atom
3
APF =
volume
3
a
unit cell
13

FCC Stacking Sequence

ABCABC... Stacking Sequence
2D Projection
B

A sites

B sites

C
B

C
B

B
C
B

C sites

FCC Unit Cell

14

A
B
C

Hexagonal Close-Packed
Structure (HCP)
ABAB... Stacking Sequence
3D Projection

2D Projection

A sites

Top layer

B sites

Middle layer

A sites

Bottom layer

Coordination # = 12
APF = 0.74
c/a = 1.633 (long over short branch)
15

6 atoms/unit cell
ex: Cd, Mg, Ti, Zn

Exercise:
1. If the atomic radius of aluminum (FCC) is 0.143
nm, calculate the volume of its unit cell in cubic
meters.

16

Theoretical Density, r
Density = r =

r =

where

17

Mass of Atoms in Unit Cell

Total Volume of Unit Cell

nA
VC NA

n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadros number
= 6.022 x 1023 atoms/mol

Periodic Table

18

Theoretical Density, r
Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell

R
atoms
unit cell

r=
volume
unit cell
19

a
2 52.00
a3 6.022 x 1023

a = 4R/ 3 = 0.2887 nm

g
mol

rtheoretical = 7.18 g/cm3

ractual

atoms
mol

= 7.19 g/cm3

Exercise:
1) Show that the APF for HCP is 0.74

20

Exercise:
1) Zirconium has an HCP crystal structure and a
density of 6.51 g/cm3.
(a) What is the volume of its unit cell in cubic meters?
(b) If the c/a ratio is 1.593, compute the values of c and a.
Clues:
r =

21

nA
VC NA

Exercise
2. Below are listed the atomic weight, density, and atomic radius for
three hypothetical alloys. For each determine whether its crystal
structure is FCC, BCC, or simple cubic and then justify your
determination. A simple cubic unit cell is shown in Figure 3.24.
Alloy

Atomic Weight (g/mol)

Density (g/cm3)

Atomic Radius (nm)

77.4

8.22

0.125

107.6

13.42

0.133

127.3

9.23

0.142

Fig. 3.24: Hard sphere unit cell representation

of the simple cubic crystal structure.

22

Exercise
3. Rhenium has an HCP crystal structure, an atomic
radius of 0.137 nm, and a c/a ratio of 1.615.
Compute the volume of the unit cell for Re.

23

Densities of Material Classes

In general
rmetals > rceramics > rpolymers
30
Why?
Metals have...

Ceramics have...
less dense packing
often lighter elements

Polymers have...

r (g/cm3 )

close-packing
(metallic bonding)
often large atomic masses

low packing density

(often amorphous)
lighter elements (C,H,O)

Composites have...
intermediate values
24

Metals/
Alloys

20

Platinum
Gold, W
Tantalum

10

Silver, Mo
Cu,Ni
Steels
Tin, Zinc

5
4
3

0.5
0.4
0.3

Titanium
Aluminum

Magnesium

Graphite/
Ceramics/
Semicond

Polymers

Composites/
fibers

Based on data in Table B1, Callister

*GFRE, CFRE, & AFRE are Glass,
Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
60% volume fraction of aligned fibers
in an epoxy matrix).
Zirconia
Al oxide
Diamond
Si nitride
Glass -soda
Concrete
Silicon
Graphite

PTFE
Silicone
PVC
PET
PC
HDPE, PS
PP, LDPE

Glass fibers
GFRE*
Carbon fibers
CFRE*
Aramid fibers
AFRE*

Wood

Crystals as Building Blocks

Some engineering applications require single crystals:
-- diamond single
crystals for abrasives
(Courtesy Martin Deakins,
GE Superabrasives,
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.

25

-- turbine blades

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,
Teledyne Wah Chang
Albany)

1 mm
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).
26

Isotropic

Single crystal vs Polycrystals

Single Crystals

E (diagonal) = 273 GPa

-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.
(Epoly iron = 210 GPa)

-If grains are textured,

anisotropic.
27

E (edge) = 125 GPa

200 mm

Data from Table 3.3,

Callister & Rethwisch
8e. (Source of data is
R.W. Hertzberg,
Deformation and
Fracture Mechanics of
Engineering Materials,
3rd ed., John Wiley and
Sons, 1989.)

Adapted from Fig.

4.14(b), Callister &
Rethwisch 8e.
(Fig. 4.14(b) is courtesy
of L.C. Smith and C.
Brady, the National
Bureau of Standards,
Washington, DC [now
the National Institute of
Standards and
Technology,
Gaithersburg, MD].)

Polymorphism
Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
iron system
titanium
liquid
, -Ti
1538C
-Fe
BCC
carbon
1394C
diamond, graphite
-Fe
FCC
912C
BCC

28

-Fe

Crystal Systems
Unit cell: smallest repetitive volume which contains
the complete lattice pattern of a crystal.
7 crystal systems

14 Bravais crystal lattices

Fig. 3.4, Callister & Rethwisch 8e.

29

Three edge lengths a, b, and c and

three interaxial angles , , and are
the lattice constants

30

Exercise
4. Below is a unit cell for a hypothetical metal.
(a) To which crystal system does this unit cell belong?
(b) What would this crystal structure be called?

(c) Calculate the density of the material, given that its atomic
weight is 141 g/mol.

31

Point Coordinates
z

Point coordinates for unit cell

center are
a/2, b/2, c/2

111

000

y
b

x
The manner in which the q, r and s
coordinates at point P within the unit cell
are determined. The q coordinate
(which is a fraction) corresponds to the
distance qa along the x axis, where a is
the unit cell edge length. The respective
r and s coordinates for the y and z axes
are determined similarly.
32

Point coordinates for unit cell

corner are
111

Exercise
5. List the point coordinates for all atoms that
are associated with the FCC unit cell.

33

Crystallographic Directions
z

Algorithm
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of
unit cell dimensions a, b, and c
y 3. Adjust to smallest integer values
4. Enclose in square brackets, no commas

[uvw]

ex: 1, 0, => 2, 0, 1 => [ 201 ]

-1, 1, 1 => [ 111 ]

where overbar represents a

negative index

families of directions <uvw> (crystallographically equivalent

[spacing
btw atoms is the same] e.g in cubic system)
34

Linear Density
Linear Density of Atoms LD =

[110]

No. of atoms centered on direction vector

Unit length of direction vector

ex: linear density of Al in [110]

direction
a = 0.405 nm
# atoms

LD =

a
length

35

2
2a

= 3.5 nm-1

Exercise
6. What are the indices for the directions
indicated by the two vectors in the sketch
below?

36

Exercise
7. For tetragonal crystals, cite the indices of
directions that are equivalent to each of the
following directions:
(a) [001]
(b) [110]
(c) [010]

37

HCP Crystallographic Directions

z

Algorithm

a2

a3
a1

1. Vector repositioned (if necessary) to pass

through origin.
2. Read off projections in terms of unit
cell dimensions a1, a2, a3, and c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas
[uvtw]
a
2

Adapted from Fig. 3.8(a),

Callister & Rethwisch 8e.

ex:

, , -1, 0

=>

[ 1120 ]

a3

dashed red lines indicate

projections onto a1 and a2 axes
38

-a3

a2
2

a1
2

a1

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
(2 u ' - v ')
3
1
=
v
(2 v ' - u ')
3
t = - (u +v )

u=
a2

a3
a1

Fig. 3.8(a), Callister & Rethwisch 8e.

39

w = w'

Exercise
8. Determine indices for the directions shown in
the following hexagonal unit cells:

40

Crystallographic Planes

Adapted from Fig. 3.10,

Callister & Rethwisch 8e.

41

Crystallographic Planes
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 i.e., (hkl)

42

Crystallographic Planes
z
example
1. Intercepts
2. Reciprocals

3.

Reduction

a
1
1/1
1
1

4.

Miller Indices

(110)

example
1. Intercepts
2. Reciprocals
3.

Reduction

a
1/2
1/
2
2

4.

Miller Indices

(100)

b
1
1/1
1
1

1/
0
0

c
y
x

1/
0
0

1/
0
0

c
y
a
x

43

Crystallographic Planes
z
example
1. Intercepts
2. Reciprocals
3.

Reduction

4.

Miller Indices

a
1/2
1/
2
6

b
1
1/1
1
3

(634)

c
c
3/4
1/
4/3

a
4
x

Family of Planes {hkl}

Ex: {100} = (100), (010), (001), (100), (010), (001)
44

Exercise
9. Determine the Miller indices for the planes shown in the
following unit cell:

10. Cite the indices of the direction that results from the
intersection of each of the following pair of planes
within a cubic crystal: (a) (100) and (010) planes, (b)
(111) and (111) planes, and (c) (101) and (001) planes.

45

46

Crystallographic Planes (HCP)

In hexagonal unit cells the same idea is used
z

example
1. Intercepts
2. Reciprocals
3.

a1
1
1
1
1

Reduction

a2

1/
0
0

a3
-1
-1
-1
-1

c
1
1
1
1

a2

a3

4.

Miller-Bravais Indices

(1011)

a1 = h

a3 = i = -(h+k)

a2 = k

z=l

47

a1
Adapted from Fig. 3.8(b),
Callister & Rethwisch 8e.

Planar Density

Used to examine the atomic packing of crystallographic

planes

E.g: Iron foil can be used as a catalyst. The atomic

packing of the exposed planes is important.
a) Draw (100) crystallographic planes for Fe assuming that the
structure is BCC.
b) Calculate the planar density.

48

Planar Density of (100) Iron

Solution: At T < 912C iron has the BCC structure.
2D repeat unit

(100)

a=

4 3
R
3

Radius of iron R = 0.1241 nm

atoms
2D repeat unit

Planar Density =
area
2D repeat unit
49

1
a2

1
4 3
R
3

atoms
atoms
19
= 1.2 x 10
2 = 12.1
2
nm
m2

Exercise
11. (a) Derive planar density expressions for FCC (100) and (111)
planes in terms of the atomic radius R.

(b) Compute the planar density values for these same two
planes for nickel when R = 0.125 nm.

50

Summary from part 1

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.

51

Summary from part 1 (Cont.)

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
is referred to as polymorphism (or allotropy).

52

structure. This

53

Imperfections in Solids
Solidification- result of casting of molten material
2 steps
Nuclei form
Nuclei grow to form crystals grain structure
Start with a molten material all liquid

nuclei
liquid

crystals growing

grain structure

Crystals grow until they meet each other

54

Polycrystalline Materials
Grain Boundaries
regions between
crystals
transition from lattice of
one region to that of
the other
slightly disordered
low density in grain
boundaries
high mobility
high diffusivity
high chemical
reactivity
55

Solidification
Grains can be - equiaxed (roughly same size in all directions)
- columnar (elongated grains)
~ 8 cm

heat
flow

Columnar in
area with less
undercooling

heat
flow
Shell of
equiaxed grains
due to rapid
cooling (greater
T) near wall

Grain Refiner - added to make smaller, more uniform, equiaxed grains.

56

Types of Imperfections
Vacancy atoms
Interstitial atoms
Substitutional atoms

Point defects

Dislocations

Line defects

Grain Boundaries

Area defects

57

Point Defects in Metals

Vacancies:
-vacant atomic sites in a structure.

Vacancy
distortion
of planes

Self-Interstitials:
-"extra" atoms positioned between atomic sites.

selfinterstitial
distortion
of planes
58

Equilibrium Concentration:
Point Defects
Equilibrium concentration varies with temperature!
No. of vacancies
Total No. of
atomic sites

Activation energy

-Q v
Nv
= exp

kT
N
Temperature
Boltzmann's constant
-23
(1.38 x 10 J/atom-K)
-5
(8.62 x 10 eV/atom-K)

Each lattice site

is a potential
vacancy site
59

Estimating Vacancy Concentration

Find the equil. # of vacancies in 1 m3 of Cu at 1000C.
Given:
r = 8.4 g /cm 3
A Cu = 63.5 g/mol
Qv = 0.9 eV/atom NA = 6.02 x 1023 atoms/mol
0.9 eV/atom
-Q
Nv =
v
-4
exp

For 1

m3 ,

Answer:

kT = 2.7 x 10

NA
N= r x
A Cu

1273 K
8.62 x 10-5 eV/atom-K
x 1 m3 = 8.0 x 1028 sites

Nv = (2.7 x 10-4)(8.0 x 1028) sites = 2.2 x 1025 vacancies

60

Exercise (Tutorial)
1. Calculate the fraction of atom sites that are vacant for
lead at its melting temperature of 327C (600 K).
Assume an energy for vacancy formation of 0.55 eV/atom.

2. Calculate the activation energy for vacancy formation in aluminum,

given that the equilibrium number of vacancies at 500C (773 K) is 7.55
1023 m-3. The atomic weight and density (at 500C) for aluminum are,
respectively, 26.98 g/mol and 2.62 g/cm3.

61

Imperfections in Metals
Two outcomes if impurity (B) added to host (A):

Solid solution of B in A (i.e., random dist. of point defects)

OR
Substitutional solid soln.
(e.g., Cu in Ni)

Interstitial solid soln.

(e.g., C in Fe)

Solid solution of B in A plus particles of a new

phase (usually for a larger amount of B)
Second phase particle
-- different composition
-- often different structure.

62

Impurities in Solids
Specification of composition
weight percent

m1
C1 =
x 100
m1 m2

m1 = mass of component 1

atom percent

nm1
C =
x 100
nm1 nm 2
'
1

nm1 = number of moles of component 1 ,

nm1 =

Derive an equation that relate C1 & C1 ?

Ans: C1 = [(C1 A2)/ [(C1 A2) + (C2 A1) ] ] x 100
63

()
()

Additional Equation

Conversion of weight percent to atom

percent (for two-element alloy)

1 =

1 2
1 2 +2 1

x 100

2 =

2 1
1 2 +2 1

x 100
1 + 2 = 100
1 + 2 = 100

Conversion of atom percent to weight

percent (for two-element alloy)

Where,

1 =

1 1
1 1 +2 2

x 100

2 =

2 2
1 1 +2 2

x 100

1 & 2 = weight percent

1 & 2 = Atomic weight

1 + 2 = Atom percents

64

Additional Equation

Conversion of weight percent to Mass

per unit volume (for 2 element alloy)

1" =
2" =

1 2
+
1 2

X 103
X 103

1 2
+
2

1" , = Concentration
(kg/3 )

1 , 2 = density in
(g/3 )

100

= 1
1

Computation of density (for twoElement metal alloy)

1 1 + 2 2
1 1 2 2
+
1
2

=
Computation of atomic weight (for a
two-element metal alloy)

+ 2

100
1 2
+
1 2

1 1 + 2 2
100
65

Line / Linear Defects

Dislocations:

are line defects,

slip between crystal planes result when dislocations move,
produce permanent (plastic) deformation.

Schematic of Zinc (HCP):

before deformation

after tensile elongation

slip steps

66

Imperfections in Solids
Linear Defects (Dislocations)
Are one-dimensional defects around which atoms are misaligned

Edge dislocation:
extra half-plane of atoms inserted in a crystal structure
b perpendicular () to dislocation line

Screw dislocation:
spiral planar ramp resulting from shear deformation
b parallel () to dislocation line
Burgers vector, b: measure of lattice distortion

67

Imperfections in Solids
Edge Dislocation

Motion of Edge Dislocation

Dislocation motion requires the successive bumping of a half plane of
atoms (from left to right here).
Bonds across the slipping planes are broken and remade in
succession.
68

Imperfections in Solids
Screw Dislocation

Dislocation
line
Burgers vector b

(b)
(a)

69

Imperfections in Solids
Mixed

Edge
Screw
70

Imperfections in Solids
Dislocations are visible in electron micrographs

TEM micrograph of a titanium alloy

in which the dark lines are
dislocations. 51,450x.

71

TEM micrograph of dislocations in

austenitic stainless steel

Dislocations & Crystal Structures

Structure: close-packed
planes & directions
are preferred.

view onto two

close-packed
planes.

close-packed plane (bottom)

Specimens that
were tensile
tested.

72

close-packed directions
close-packed plane (top)

Mg (HCP)
tensile direction

Al (FCC)

Significance of Dislocations
1. It provide a mechanism for plastic deformation.
2. It provide ductility in metals.
3. We control the mechanical properties of a metal or
alloy by interfering with the movement of
dislocations.
Strain hardening
Solid solution strengthening
Grain size strengthening
4. It influence the electronic and optical properties of
materials.

73

Interfacial Defects in Solid (Area)

- Grain Boundaries
Boundary separating two small grains or crystals having different
orientations.
Atoms are bonded less regularly along the grain boundary, result in
boundary energy (similar to surface energy).
High angle boundaries have
higher energy.
Grain boundaries are
chemically reactive compared
to grains because of the
boundary energy.
Impurity atom often segregate
along grain boundaries
because of the boundary energy.

74

Interfacial Defects in Solids

Phase Boundaries
Exist in multiple phase materials.
The different phases exist on each side of the boundary
and it have its own relative physical and/or chemical
characteristics.
Important in determining
Solder
Interface IMC
the mechanical characteristic
of multiphase metal alloys.
Ni

Optical micrograph of intermetallic layer

Cu
between Nickel-gold surface finish and lead
free solder.
75

500x

Interfacial Defects in Solids

Twin boundary (plane)
Essentially a reflection of atom positions across the twin plane.
(mirror-image)

Stacking faults
For FCC metals an error in ABCABC packing sequence
Ex: ABCABABC
76

Summary from part 2

Point, Line, and Area defects exist in solids.
The number and type of defects can be varied
and controlled (e.g., T controls vacancy concentration)

Defects affect material properties (e.g., grain boundaries

control crystal slip).
Defects may be desirable or undesirable (e.g. dislocations
may be good or bad, depending on whether plastic deformation
is desirable or not.)

77