Addis Ababa Institute of Technology

School of Chemical and Bio Engineering

Materials Science and Engineering:

An Introduction to Chemical
Engineers

(ChEg-3171)

By Mekdim A. (Office: 318 A)

 Outline
1. Introduction
2. Atomic and Crystalline Structures
3. Classification of Materials
4. Imperfections in Solids
5.1 Point defects
5.2 Line defects
5.3 Surface defects

5. Mass transfer and atomic mixing

6. Mechanical properties
7. Electrical, Optical, Thermal and Magnetic Properties
8. Corrosion: Types and Protection
9. Materials Selection and Design Considerations
10. Economic, Environmental, and Societal Issues
Crystals are like people, it
is the defects in them which
tend to make them
interesting! - Colin
Humphreys.
 Defects
Real crystals are never perfect, there are always defects

Schematic drawing of a poly-crystal with many defects by

Helmut Fll, University of Kiel, Germany.
 Crystal engineering
strategy is a
powerful tool for
preparing crystalline
materials with
different crystalline
domains.

Single crystals of one compound grew around the single

crystal of another to give a crystal within a crystal.

http://www.rsc.org/chemistryworld/2013/10/crystal-within-crystal-molecular-tectonics
 Defects
Processing determines the defects
Composition

Bonding Crystal Structure

Thermomechanical
Processing

defect introduction and manipulation

Microstructure
ISSUES TO ADDRESS...
What are the solidification mechanisms?

What types of defects arise in solids?

Can the number and type of defects be varied

and controlled?

How do defects affect material properties?

Are defects undesirable?

Imperfections in Solids
The properties of some
materials are profoundly
influenced by the presence of
imperfections.
It is important to have
knowledge about the types of
imperfections that exist and
the roles they play in affecting
the behavior of materials.
Atom Purity and Crystal Perfection
If we assume a perfect crystal structure
containing pure elements, then anything
that deviated from this concept or
intruded in this uniform homogeneity
would be an imperfection.
1. There are no perfect crystals.
2. Many material properties are improved by
the presence of imperfections and
deliberately modified (alloying and
doping).
 Types of Imperfections
Vacancy atoms
Interstitial atoms Point defects
Substitutional atoms 1-2 atoms

Dislocations Line defects

1-dimensional

Grain Boundaries Area defects

2-dimensional

Cracks Volume defects

3-dimensional

Point
Vacancies:
Defects in Metals
-vacant atomic sites in a structure.

Vacancy
distortion
of planes

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

self-interstitial
distortion
of planes
 Selfc05f01
Interstitials

In metals, a self interstitial introduces

relatively large distortions (strain) in the
surrounding lattice since the atom is
substantially larger than the interstitial
site.
 Point Defects in Ceramics
Vacancies
-- vacancies exist in ceramics for both cations and anions
Interstitials
-- interstitials exist for cations
-- interstitials are not normally observed for anions because anions
are large relative to the interstitial sites

Cation Interstitial

Cation Vacancy

Adapted from Fig. 5.2, Callister & Rethwisch 3e.

(Fig. 5.2 is from W.G. Moffatt, G.W. Pearsall, and
J. Wulff, The Structure and Properties of
Materials, Vol. 1, Structure, John Wiley and Sons,
Inc., p. 78.)

Anion Vacancy
Equilibrium Concentration:
Point Defects

Equilibrium concentration varies with temperature!

No. of defects Activation energy

Nv Q
No. of potential exp v

N kT
defect sites.
Temperature
Boltzmann's constant
(1.38 x 10 -23 J/atom-K)
(8.62 x 10 -5 eV/atom-K)
Each lattice site
is a potential
vacancy site
Measuring Activation Energy

We can get Qv from Nv Q

an experiment.
= exp v



N kT
Measure this... Replot it...

Nv Nv slope
ln
N N
-Qv /k
exponential
dependence!

T 1/T
defect concentration
Note: for MOST MATERIALS just below Tm Nv/N = 10-4
 Estimating Vacancy Concentration

Find the equil. # of vacancies in 1 m 3 of Cu at 1000C.

Given:
= 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
Nv Q
exp v
= 2.7 x 10-4
N kT
1273K
8.62 x 10-5 eV/atom-K
NA
For 1 m , N = x
3 x 1 m3 = 8.0 x 1028 sites
A Cu
Answer:
Nv = (2.7 x 10-4)(8.0 x 1028) sites = 2.2 x 1025 vacancies
Nv
= 0.0022/8 = .000275 = 2.75*10-4
N
 Point Defects in Polymers
Defects due in part to chain packing errors and impurities such
as chain ends and side chains

Adapted from Fig. 5.7,

Callister & Rethwisch 3e.
 Alloying
Given a metal (with only 1 type of atom) refined to
99.9999% purity, there would still exist 1022 to 1023
impurity atoms in 1 cubic meter of material.
Most metals are alloys. Alloying is done to
improve strength, corrosion resistance, ductility,
lower melting T.
For example, sterling silver is an alloy of 92.5%
silver, 7.5% copper. At room temperature, pure
silver is highly corrosion resistant, but also very
soft. The addition of copper improves the strength
and maintains good corrosion behavior.
 Solid Solution
The addition of impurity atoms to a metal
results in the formation of a solid solution.
The solvent represents the element that is
present in the greatest amount (the host
atoms).
Solid solutions form when the solute atoms
(Cu) are added to the solvent (Al), assuming
the crystal structure is maintained and no
new structures are formed.
 Solid Solution - continued
A solid solution is a homogenous
composition throughout.
The impurity atoms (Cu) are randomly and
uniformly dispersed within the solid.
The impurity defects in the solid solution are
either substitutional or interstitial.
 Imperfections in Metals
What are the outcomes if impurity (B) is added to host (A)?
Solid solution of B in A (random distribution of point defects)

OR

Substitutional solid solution. Interstitial solid solution.

(e.g., Cu in Ni) (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.
 Hume - Rothery Rules
The Hume-Rothery rules are basic conditions
for an element to dissolve in a metal, forming a
substitutional solid solution.
1. The atomic radius of the solute and solvent atoms
must differ by no more than 15% (r < 15%).
2. The solute and solvent should have similar
electronegativities.
3. Same crystal structure for pure metals.
4. Maximum solubility occurs when the solvent and
solute have the same valence. Metals with lower
valence will tend to dissolve metals with higher
valence.
Substitutional Solid Solution Example:
Copper and Nickel

Element Atomic Crystal Electro- Valence

Radius Structure nega-
(nm) tivity
Cu 0.1278 FCC 1.9 +2
C 0.071 2.5 H
0.046
O 0.060
Ag 0.1445 FCC 1.9 +1
Al 0.1431 FCC 1.5 +3
Co 0.1253 HCP 1.8 +2
Cr 0.1249 BCC 1.6 +3
Fe 0.1241 BCC 1.8 +2
Ni 0.1246 FCC 1.8 +2
Pd 0.1376 FCC 2.2 +2
Zn 0.1332 HCP 1.6 +2
 Application of HumeRothery rules Solid
Solutions

1. Would you predict Element Atomic Crystal Electro- Valence

more Al or Ag Radius Structure
(nm)
nega-
tivity
Moreto dissolve
Al because size is closerin Zn?
and val. Is Cu 0.1278 FCC 1.9 +2
higher but not too much FCC in HCP
C 0.071
H 0.046
O 0.060
Ag 0.1445 FCC 1.9 +1
Al 0.1431 FCC 1.5 +3
2. More Zn or Al Co 0.1253 HCP 1.8 +2
Cr 0.1249 BCC 1.6 +3
in Cu? Fe 0.1241 BCC 1.8 +2
Surely Zn since size is closer thus Ni 0.1246 FCC 1.8 +2
causing lower distortion (4% vs 12%) Pd 0.1376 FCC 2.2 +2
Zn 0.1332 HCP 1.6 +2

Table on p. 106, Callister 7e.

 Interstitial Solid Solution
Carbon forms an interstitial solid solution when
added to iron; the maximum concentration of
carbon that can be added is roughly 2%.
The atomic radius of the carbon atom is much
less than that of iron (0.071nm vs 0.124 nm).
For interstitial solid solutions, the Hume-Rothery
rules are:
1. Solute atoms must be smaller than the pores in the
solvent lattice.
2. The solute and solvent should have similar
electronegativity.
 Interstitial Solid Solutions
Carbon interstitial
atom in BCC iron

Interstitial solid solution of C in BCC Fe ( phase).

C small enough to fit (some strain in BCC lattice).
Factors for high solubility:
FCC, BCC, HCP: void space between host (matrix) atoms relatively small
atomic radius of solute should be significantly less than solvent

Max. concentration 10%

 Imperfections in Solids
Specification of composition
m1
weight percent C1 x 100
m1 m2
m1 = mass of component 1

n m1
atom percent C
'
1 x 100
n m1 n m 2

nm1 = number of moles of component 1

Line 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

Adapted from Fig. 7.8, Callister 7e.

 Dislocation
movement
Dislocations move in steps. The edge
dislocation at P moves to Q in steps as
depicted by the red (half-plane) and blue
atoms. This movement is analogous to
movement of a caterpillar.
Edge dislocations can move only on the slip
plane while screw dislocations do not have a
fixed glide plane.
Since plastic deformation takes place by
movement of dislocations, any hindrance
to their motion will increase the strength
of metals.
Slip plane
 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 to dislocation line
Screw dislocation:
spiral planar ramp resulting from shear deformation
b to dislocation line
Burgers vector, b: measure of lattice distortion
 Imperfections in Solids
Edge Dislocation

Fig. 4.3, Callister 7e.

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.

Atomic view of edge

dislocation motion from
left to right as a crystal
is sheared.

(Courtesy P.M. Anderson)

 Imperfections in Solids
Screw Dislocation
Screw Dislocation

b
Dislocation
line
Burgers vector b (b)
(a)
Adapted from Fig. 4.4, Callister 7e.
 Edge, Screw, and Mixed
Dislocations
Mixed

Edge

Adapted from Fig. 4.5, Callister 7e.

Screw
 Imperfections in Solids
Dislocations are visible in electron
micrographs

Adapted from Fig. 4.6, Callister 7e.

Dislocations & Crystal Structures
Structure: close-packed view onto two
planes & directions close-packed
planes.
are preferred.
close-packed directions
close-packed plane (bottom) close-packed plane (top)

Comparison among crystal structures:

FCC: many close-packed planes/directions;
HCP: only one plane, 3 directions;
BCC: none
Specimens that Mg (HCP)
were tensile
tested. tensile direction
Al (FCC)
 Planar Defects in Solids
One case is a twin boundary (plane)

Essentially a reflection of atom positions across the twin plane.

Stacking faults

For FCC metals an error in ABCABC packing sequence

Ex: ABCABABC

Adapted from Fig. 4.9, Callister 7e.

 Bulk or volume
defects

Porosity
Inclusions
Cracks
These defects form during manufacturing processes
for various reasons and are harmful to the material.
 Bulk
defects

Weld defect Casting Shrinkage cavity

defect
Casting blow holes, porosity Gas entrapment during
melting and pouring. Improper welding parameters/practice
Shrinkage cavity due to improper risering
Non-metallic inclusions Slag, oxide particles or
sand entrapment
Cracks Uneven heating/cooling, thermal
mismatch, constrained expansion/contraction all
leading to stress development
 Bulk or Volume Defects
Pores: affect optical, thermal, mechanical properties
Cracks: affect mechanical properties
Foreign inclusions: affect electrical, mechanical,
optical properties

Cluster of microcracks in a melanin

granule irradiated by a short laser
pulse. Computer simulation by L. V.
Zhigilei and B. J. Garrison.
 Microscopic Examination
Crystallites (grains) and grain
boundaries. Vary considerably in size.
Can be quite large
ex: Large single crystal of quartz or diamond
or Si
ex: Aluminum light post or garbage can - see
the individual grains
Crystallites (grains) can be quite small
(mm or less) necessary to observe
with a microscope.
Optical Microscopy
Useful up to 2000X magnification.
Polishing removes surface features (e.g., scratches)
Etching changes reflectance, depending on crystal
orientation.

crystallographic planes
Adapted from Fig. 4.13(b) and (c), Callister
7e. (Fig. 4.13(c) is courtesy
of J.E. Burke, General Electric Co.

Micrograph of
brass (a Cu-Zn alloy)

0.75mm
Optical Microscopy
Grain boundaries...
are imperfections,
are more susceptible
to etching,
may be revealed as polished surface
dark lines,
change in crystal surface groove
orientation across grain boundary
(a)
boundary. Adapted from Fig. 4.14(a)
and (b), Callister 7e.
ASTM grain (Fig. 4.14(b) is courtesy
of L.C. Smith and C. Brady,
size number the National Bureau of
Standards, Washington, DC

N = 2n-1 [now the National Institute of

Standards and Technology,
Gaithersburg, MD].)

number of grains/in2 Fe-Cr alloy

at 100x (b)
magnification
 Optical Microscopy
Polarized light
metallographic scopes often use polarized
light to increase contrast
Also used for transparent samples such as
polymers
 Microscopy
Optical resolution ca. 10-7 m = 0.1 m = 100
nm
For higher resolution need higher frequency
X-Rays? Difficult to focus.
Electrons
wavelengths ca. 3 pm (0.003 nm)
(Magnification - 1,000,000X)
Atomic resolution possible
Electron beam focused by magnetic lenses.
 Multiscale imaging

1 cm 100 m 10 m 100 nm

Fruit Cell Membrane Plasmodesmaton

Scanning Tunneling Microscopy
(STM)

Atoms can be arranged and imaged!

Photos produced from
the work of C.P. Lutz,
Zeppenfeld, and D.M.
Eigler. Reprinted with
permission from
International Business
Machines Corporation,
copyright 1995.

Carbon monoxide Iron atoms arranged

molecules arranged on a copper (111)
on a platinum (111) surface. These Kanji
surface. characters represent
the word atom.
Summary
Point, Line, Area and volume defects exist in solids.

The number and type of defects can be varied

and controlled (e.g., T controls vacancy conc.)

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.)