MTEN 303:

INTRODUCTION TO MATERIALS
PROCESSING (2 credits)

LECTURER: DR. EBENEZER ANNAN

Contact: Ebenk45@gmail.com or ebannan@ug.edu.gh
DELIVERY PLAN
Week Topic/Area Delivery Method
1 Introduction to Materials Processing and Lecture
Manufacturing
2 Overview of Processing Operations Lecture
3 Processing of Ceramics: Powder Processing Lecture
4 Ceramics: Shape forming processes Lecture
5 Interim Assessment 1 & Group Assignment N/A
6 Solidification Processes: Fundamentals of Metal Guest Lecture
Casting & Casting Technologies
7 Introduction to Powder Metallurgy: Production of Lecture
Metallic powders, pressing & sintering Techniques
9 Field Trip – Metal Casting Lecture & Field Trip
10 Metal Casting: Heating and Pouring, Solidification Lecture
and Cooling
11 Interim Assessment 2 Exams
11 Polymer Processing Technologies Guest Lecture
12 Forming and Shaping Plastics, rubber and polymer Guest Lecture
composites
13 Revision Tutorials
INTRODUCTION: Brief Review of
MSE
• What is materials science ? Why Materials processing?
• Why should we know about it?
• Materials drive our society
• Stone Age
• Bronze Age
• Iron Age
• Now?
• Silicon Age?
• Polymer Age?
• Composite?
• Graphene?

3
Historical Development of Materials and
Manufacturing Process
IDENTIFICATION -- SELECTION -- PROCESSING -- PERFORMANCE
 Material Types & Properties
• Metals:
– Strong, ductile
– High thermal & electrical conductivity
– Opaque, reflective.

• Polymers/plastics: Covalent bonding  sharing of e’s

– Soft, ductile, low strength, low density
– Thermal & electrical insulators
– Optically translucent or transparent.

• Ceramics: ionic bonding (refractory) – compounds of metallic

& non-metallic elements (oxides, carbides, nitrides, sulfides)
– Brittle, glassy, elastic
– Non-conducting (insulators)

12
• Transmittance:
-- Aluminum oxide may be transparent, translucent, or
opaque depending on the material structure.

polycrystal: polycrystal:
single crystal low porosity high porosity

Adapted from Fig. 1.2,

Callister & Rethwisch 8e.
(Specimen preparation,
P.A. Lessing; photo by S.
Tanner.)

13
SUMMARY
Course Goals:
• Use the right material for the job.

• Understand the relation between properties,

structure, and processing.

• Recognize new design opportunities offered

by materials selection.

15
Which Operations are described here?
The ‘Hows’?
What are my Expectations?

•Students must attend at least 70% of all classes with the expectation that students only miss
classes due to illness or unforeseen circumstances
•Students must read through lecture notes/slides prior to class
•During class, students are expected to engage actively in class discussions
•Students should work through lecture, tutorial and textbook questions
•Students should read through the relevant chapters of the prescribed textbook.
•Students should complete all assessment tasks and submit them on time.

Assessment and Grading

Interim Assessments & Homework 40%
Class Participation 10%
Final Examination 50%

Grading Scale: Please refer to Undergraduate Handbook

Textbooks and Reference:

1. Serope Kalpakjian, Manufacturing Engineering and Technology, 3 rd Edition Addison-Wesley
Publishing Company
2. David W. Richerson, ‘Modern Ceramic Engineering: properties, processing and use in Design’,
third Edition
3. Groover, M.P. (2006). Fundamentals of Modern Manufacturing (3rd ed.). New York NY:
John Wiley & Sons. 1040 pp. ISBN 0-471-74485-9
Property Enhancing -ELECTRICAL
• Electrical Resistivity of Copper:
6 Adapted from Fig. 18.8,
t %Ni Callister & Rethwisch
a
5 3 .32 8e. (Fig. 18.8 adapted
+ from: J.O. Linde, Ann
Cu Ni
Resistivity, r

Physik 5, 219 (1932);

t%
4 16 a Ni
(10-8 Ohm-m)

and C.A. Wert and R.M.

+ 2 . a t% Thomson, Physics of
Cu . 12
3 u +1 Solids, 2nd edition,

ed C McGraw-Hill Company,

e f o rm % N i New York, 1970.)

d 2 a t
2 .1
u +1
C
1 r e” Cu
“Pu
0
-200 -100 0 T (ºC)
 Adding “impurity” atoms to Cu increases resistivity.
 Deforming Cu increases resistivity.
 Property Enhancing - THERMAL
• Space Shuttle Tiles: • Thermal Conductivity of Cu:
-- Silica fiber insulation -- It decreases when you add
offers low heat conduction. zinc!
Adapted from chapter-
opening photograph,
Chapter 17, Callister &
400

Thermal Conductivity
Rethwisch 3e. (Courtesy
of Lockheed
Missiles and Space
Company, Inc.) 300

(W/m-K)
200

100
0
0 10 20 30 40
Composition (wt% Zinc)
Adapted from Adapted from Fig. 19.4, Callister & Rethwisch
Fig. 19.4W, Callister 8e. (Fig. 19.4 is adapted from Metals Handbook:
6e. (Courtesy of Properties and Selection: Nonferrous alloys and
Lockheed Aerospace Pure Metals, Vol. 2, 9th ed., H. Baker,
Ceramics Systems, (Managing Editor), American Society for Metals,
Sunnyvale, CA) 1979, p. 315.)
(Note: "W" denotes fig.
100 mm is on CD-ROM.) 35
 Property Enhancing - MAGNETIC
• Magnetic Storage: • Magnetic Permeability
-- Recording medium
vs. Composition:
is magnetized by
-- Adding 3 atomic % Si makes
recording head.
Fe a better recording medium!

Magnetization
Fe+3%Si

Fe

Magnetic Field

Adapted from C.R. Barrett, W.D. Nix, and

Fig. 20.23, Callister & Rethwisch 8e. A.S. Tetelman, The Principles of
Engineering Materials, Fig. 1-7(a), p. 9,
1973. Electronically reproduced
by permission of Pearson Education, Inc.,
Upper Saddle River, New Jersey.

36
SUMMARY
SUMMARY Cont’d
Processing of Ceramics
• Issues to address:

Brief review on Ceramic applications

Understanding criteria for choosing ceramic raw
materials
Description of Powder Processing
Main categories of making powders – Part 1 & 2
Review on ceramic fabrication or forming processes
 Classification of Ceramics
Ceramic Materials

Glasses Clay Refractories Abrasives Cements Advanced

products ceramics
-optical -whiteware -bricks for -sandpaper -composites -engine
-composite -structural high T -cutting -structural rotors
reinforce (furnaces) -polishing valves
-containers/ bearings
household Adapted from Fig. 13.1 and discussion in -sensors
Section 13.2-8, Callister & Rethwisch 8e.

Some applications of ceramic materials

- high temperature applications
- Water filtration applications
- Cutting and grinding
- Electrical applications
- Medical applications &
- Energy efficiency and pollution Control 41
Summary of Ceramics Applications
 Processing of Ceramics

Reference: Ceramic Processing and sintering, 2nd Edition Rahaman, Page 5

Pottery and Electroceramics
 Types of Powders
• Primary particles: smallest clearly identifiable unit in a powder
• Agglomerates: Clusters of bonded primary particles
• Particles: both primary and agglomerates
• Granules: Large agglomerates, usually 0.1-1mm in diameter,
achieved by addition of a polymer binder
• Flocs: Clusters of particles in a liquid suspension held together
electrostatically.
• Colloids: Very fine particles (1nm in diameter) held in
suspension. They settle slowly
• Aggregates: Coarse constituents, greater than 1mm, in a
mixture.
Raw Material Selection Criteria
Purity

Raw ceramic materials Particle size

Reactivity
distribution

Polymorphism
1. Purity strongly influences high-temperature properties such as strength, toughness,
oxidation resistance, etc. and also electrical properties
2. Particle Size:
Sintering temperatures and time for densification, eventually affects
the strength
3. Reactivity : Surface free energy is the
driving force. Very small particles have high
surface energies, and thus strong thermodynamical
drive to bond.
Powder/Particulate Pressing
POWDER PREPARATION & SIZING

53
 Mechanical Sizing: Screening
• Screening is a sorting method of particle sizing
• Screen sizes are classified according to openings per inch,
referred to us MESH SIZES.
• Powder designated -100 mesh +150 mesh consists of particle
size range that was small enough to go through 100 mesh but
too large for 150 mesh.

Size Range Weight (%)

-80 +100 5
-100 +150 8
-150 +220 13
-220 +280 20
-280 +325 18
-325 36
 Limitations
1. Distorted or broken screens
pass larger particles than
specified
2. Damaged screen size control
and particle size distribution
are affected
3. Nature of the powder

What are the steps

for proper
maintenance of
the equipment-
sieves?
Mechanical Milling Techniques
Ball Milling

What is the principle

of operation?
 Factors Affecting Rate of Milling

• Form of liners
• Particles size distribution
• Mill Size or Volume
• %tage of Solids in Mill Volume
• more in, more out? What Do
you think
 *Wet Milling vrs Dry Milling?
Which is more effective? Yes /No,
Why?
Advantages of Wet Milling
1. Low power required
2. No dust problems
3. Higher rotational speeds
4. Can wet screen through fine screen
5. Good homogenization
6. Smaller particles than dry
7. Narrow particle size distribution than dry
8. Compatible with spray drying and casting

Advantages of Dry Milling

9. Avoids drying of the powder
10.Avoids reaction of the powder/Liquid
11.Less media and lining wear than wet
12.Can be started/stopped any time
13.Easier to optimize
Ref: Adapted from Mordern Ceramics by D.W. Richerson, Table 12:5
ATTRITION MILLING /Agitated Ball Milling
Summary of Advantages
 Minimal impurity introduction with increasing milling time
 Quicker than ball milling
 Significant increase in surface area of particles with milling
time
 Controlled Oxygen content
 Can be operated dry, wet, or inert or vacuum atmosphere
OTHER MILLING METHODS
VIBRATORY MILLING
 Ball Mill
Turbomill in an industry

Vibratory Mill Planetary Ball mill

 Milling Rate

Routes to thick films, Robert Dorey, in Ceramic Thick Films for MEMS and Microdevices, 2012
Pigments, Fillers, and Extenders, Laurence W. McKeen, in Fluorinated Coatings and Finishes Handbook, 2006
 End of Lecture for today

WHAT HAVE WE LEARNT TODAY?

 Chemical Sizing
• Precipitation
• Sol-Gel
• Hydrothermal

Other Synthesis/Sizing Techniques

• Calcining
• Rotary Kiln
• Self-Propagation high temp Synthesis
• Coarsening
• Dehydration
Precipitation is usually followed by thermal; decomposition to oxide.
Example is the Bayer Process
20.6
 Precipitation

Figure 20.5: Solubility (grams of solute

in 100g H2O) versus temperature
LaMer Diagram
ATTEMPT 1:
Considering the Gibbs free energy and assuming that crystals are spherical
particles with radius, r,

a. Derive an expression for the critical size beyond which the crystal is stable
during homogeneous nucleation.

b. Explain why heterogeneous nucleation is more likely to occur than

homogeneous nucleation
Total free Energy
Heterogeneous Nucleation of a solid
 For heterogeneous nucleation,
activation free energy required for the formation of a stable
nucleus

The S(Ө) is a function only of Ө (i.e., the shape of the nucleus), with value between zero and
unity
Growth
The growth step in a phase transformation begins once an embryo has exceeded
the critical size, r* and becomes a stable nucleus.

Figure 10.7 Nucleation rate versus temperature for

both homogeneous and heterogeneous nucleation.
Degree of supercooling (¢T) for each is also shown.
Figure 10.8, which is for the total rate, represents this
combined effect. The general shape of this curve is the
same as for the nucleation rate, in that it has a peak or
maximum that has been shifted upward relative to the
curve.
SOL-GEL PROCESS
What is SOL-GEL Processing?
SOL-GEL processing is a technique used to achieve a high
temp, high-purity composition (with homogeneity) and high
specific surface area ceramics from a liquid at room
temperature.

The processing involves the following steps:

1. Form a stable dispersion (SOL) of particles less than 0.1
microns in diameter in a liquid
2. By change in concentration, ageing or addition of a
suitable electrolyte to induce polymer-like three
dimensional bonding to occur throughout the ‘SOL’ to
form a ‘GEL’.
3. Evaporate the remaining liquid from gel
4. Increase the temperature to convert the dehydrated gel
to the ceramic composition
SOL-GEL Processing Cont’d
 The initial step involves a hydrolysis reaction in which
alkoxide groups (OR) are replaced by hydroxyl groups
(OH):

The rate of hydrolysis of metal alkoxides depends on the

characteristics of the metal and those of the alkyl group. In
general, silicon alkoxides are among the slowest to hydrolyze
and, for a given metal alkoxide, the hydrolysis rate increases
as the length of the alkyl group decreases.
 SOL-GEL Processing of Silicon Alkoxides
Most commonly used precursors for the sol–gel processing of silica are tetraethoxysilane,
Si(OC2H5)4, abbreviated TEOS, which is also referred to as tetraethylorthosilicate or silicon
tetraethoxide, and tetramethoxysilnae, Si(OCH3)4, abbreviated TMOS, which is also referred
to as tetramethyorthosilicate.
 Advantages of Sol-Gel
In general:
Able to get uniform & small sized powder
Can get at low temperature high density glass, without high
temperature re-crystallization
Can get new compositions of glass
New microstructure and composition
Easy to do coating for films
Can get objects or films with special porosity
Can get metal (inorganic) – organic composites
Can coat onto large area or complex shape objects
Can get fibers
High uniformity, multi-component systems
 Hydrothermal Process

Hydrothermal synthesis involves crystallization of a composition

in hot, pressurized water.

Typical temperature range from 100 to 350oC at 15MPa.

The feedstock can be Oxides, hydroxides, salts, gels, organics,

acids, and bases

Particle size controlled by time, temperature and pressure for

either reducing or oxidizing.

The resulting powder consists of single crystals of the final

composition
Hydrothermal Process
Synthesis Advantages
1. Control chemical composition
2. Control over Aggregation level
3. Control over powder size and
morphology of particles.

This is done via modeling of

thermodynamic variables or non-
thermodynamic means.

4. All forms of ceramics can be

prepared
5. Obtain already calcined powder
6. Reduction of aggregates
7. Precursor from wide verity of
aqueous & solvents mixture based
solvents
END OF LECTURE 3 SERIES
 Selection criteria of raw
materials
 Powder preparation and sizing:
Mechanical & Chemical Sizing
Issues to address:
Briefly explain the various fabrication techniques under
particulate forming

• Powder pressing – Uniaxial pressing, Isostatic, Hot

• Hydro-plastic forming
• Slip casting
• Tape Casting

 Selection of suitable technique for a chosen geometry

Briefly describe processes that occur during the drying and firing of
clay-based ceramics.
 Ceramic Fabrication Methods (ii)

GLASS PARTICULATE CEMENTATION

FORMING FORMING

Powder Pressing:
used for both clay and non-clay compositions.

Powder (plus binder) compacted by pressure in a mold

-- Uniaxial compression - compacted in single direction

-- Isostatic (hydrostatic) compression - pressure applied by

fluid (in all directions)

-- Hot pressing - pressure + heat ( porosity reduced) 108

Uniaxial compression

Ref: Callister 6th Edition

Uniaxial Pressing Problems
Improper density or size
Die wear
Cracking

Source of cracking may be

due to:
• Rebound during ejection
from die
• Die-wall friction
• Die wear
• Improper die design
• Air entrapment
Source of cracking may be due to:
Rebound during ejection from die
Die-wall friction
Die wear
Improper die design
Air entrapment
 Hot-Isostatic Pressing

Figure 19.4 –(from Asby ) Hot-isostatic pressing (“HIPing”): the powder, in a thin steel pre-
form, is heated & compressed by high-pressure argon
 Hydro-plasticity of Clay
• Clay is inexpensive Shear
• When water is added to clay
-- water molecules fit in between
layered sheets charge
-- reduces degree of van der Waals neutral
bonding
-- when external forces applied – clay
particles free to move past one weak van
another – becomes hydroplastic der Waals
bonding
• Structure of Kaolinite Clay: charge Si
4+
Adapted from Fig. 12.14, Callister & Rethwisch 8e. (Fig. 3+
12.14 is adapted from W.E. Hauth, "Crystal Chemistry of neutral Al
Ceramics", American Ceramic Society Bulletin, Vol. 30 -
(4), 1951, p. 140.) OH
2-
O

Shear 114
Ceramic Fabrication Methods (ii)
Slip Casting

• Mill (grind) and screen constituents: desired particle size

• Mix with water and other constituents to form slip

• Slip casting operation

pour slip absorb water pour slip drain “green

into mold into mold into mold mold ceramic” Adapted from Fig.
“green 13.12, Callister &
ceramic” Rethwisch 8e. (Fig.
13.12 is from W.D.
Kingery, Introduction to
Ceramics, John Wiley
and Sons, Inc., 1960.)

solid component hollow component

• Dry and fire the cast piece 115

 Tape Casting
• Thin sheets of green ceramic cast as flexible tape
• Used for integrated circuits and capacitors
• Slip = suspended ceramic particles + organic liquid
(contains binders, plasticizers)

Fig. 13.18, Callister & Rethwisch 8e. 116

 Drying and Firing
• Drying: as water is removed - interparticle spacings decrease
– shrinkage .
Adapted from Fig.
13.13, Callister &
Rethwisch 8e. (Fig.
13.13 is from W.D.
Kingery, Introduction
to Ceramics, John
Wiley and Sons,
Inc., 1960.)

wet body partially dry completely dry

Drying too fast causes sample to warp or crack due to non-uniform shrinkage

micrograph of porcelain
Si02 particle
• Firing: (quartz)
-- heat treatment between glass formed
900-1400ºC around
the particle
-- vitrification: liquid glass forms
from clay and flux – flows
between SiO2 particles. (Flux 70 mm
Adapted from Fig. 13.14, Callister & Rethwisch 8e.
lowers melting temperature). (Fig. 13.14 is courtesy H.G. Brinkies, Swinburne
University of Technology, Hawthorn Campus,
Hawthorn, Victoria, Australia.) 117
 Sintering
Sintering occurs during firing of a piece that has
been powder pressed
-- powder particles coalesce and reduction of pore size

Adapted from Fig. 13.16,

Callister & Rethwisch 8e.

Aluminum oxide powder:

-- sintered at 1700ºC
for 6 minutes.
Adapted from Fig. 13.17, Callister
& Rethwisch 8e. (Fig. 13.17 is from
W.D. Kingery, H.K. Bowen, and
D.R. Uhlmann, Introduction to
Ceramics, 2nd ed., John Wiley and
Sons, Inc., 1976, p. 483.) 15 m 118
END OF Lecture(s) on
 Ceramic fabrication methods or
Powder processing Techniques
for ceramics
Example-Ceramics Applications: Water Filtration
Ceramics For Water Filtration

122
 Filtration Mechanisms
• Size Exclusion: size of pores are usually 0.3-
2.5microns, thus capable of restricting small
bacteria(Lantagne,2001)
Types of pores (Xialong 2005)
• Chemical Activity: process in which dissolved
impurities are either broken down into
simpler, less harmful substances, or converted
into insoluble compound after which straining,
sedimentation and adsorption may remove
them from the flowing water.
Sedimentation: Removes particulate suspended
matter of finer sizes than the pore openings by
precipitation upon the surface of the clay
material.
Diffusion: random motion of particles caused
by collision with surrounding molecules, which
could eventually lead to adsorption by filter
material.
Adsorption: removing finely divided suspended
matter as well as colloidal and molecular
dissolved impurities.
123
Bacteria & De-activation

124
 Summary
• Categories of ceramics:
-- glasses (Assignment 1)
-- clay products
-- refractories -- cements
-- advanced ceramics

• Ceramic Fabrication techniques:

-- glass forming (pressing, blowing, fiber drawing).
-- particulate forming (hydroplastic forming, slip casting,
powder pressing, tape casting)
-- cementation

• Heat treating procedures

-- glasses—annealing, tempering
-- particulate formed pieces—drying, firing (sintering)
125
 GLASS CERAMICS: Production & Forming Processes

• Issues to address:
• Overview – Glass Ceramics

 Describe the making of glass

 Briefly describe glass
forming processes,
 Understand and explain
heating treatment techniques in
glass working processes
 Glass and Main Compositions
Glasses are non-crystalline silicates containing other oxides, notably
CaO, Na2O, K2O, and Al2O3, which influence the glass properties.

Ref: Callister 5th Edition Chapter 13, page 462

 Scientific Understanding of Glass
• Crystalline materials:
-- crystallize at melting temp, Tm
-- have abrupt change in spec. vol. at Tm

• Specific volume (1/r) vs Temp. (T)

• Glasses:
-- do not crystallize
-- change in slope in spec. vol. curve at
glass transition temperature, Tg
-- transparent - no grain boundaries to
scatter light
 Glass Viscosity vrs. Temperature
• viscosity, h relates shear stress () and velocity gradient (dv/dy):
• Viscosity decreases with Temp

• soda-lime glass: 70% SiO2

balance Na2O (soda) & CaO (lime)

• Borosilicate (Pyrex):
81% SiO213% B2O3, 3.5% Na2O,
2.5% Al2O3
• Silica Glass ( Vycor)
96% SiO2, 4% B2O3

• fused silica: > 99.5 wt% SiO2

Adapted from Fig. 13.7, Callister & Rethwisch 8e. (Fig. 13.7 is from E.B. Shand, Engineering Glass, Modern Materials, Vol. 6,
Academic Press, New York, 1968, p. 262.)
Key Points and definitions relating Glass Processing
What is the difference between
Glass and Glass Ceramics? Ans:
Crystallized glass is glass ceramics
VIDEO – Making of Glass 1 & 2
Glass-ceramics may not be transparent
because they are polycrystalline. Light will be
scattered at grain boundaries in polycrystalline
materials if the index of refraction is
anisotropic,
and when those grains adjacent to the
boundary have different crystallographic
orientations.
 Pressing and Blow technique

Pressing and Blowing technique demonstrated via Fig. 13.8

Heating Treatment Processes
• Annealing:
-- removes internal stresses caused by uneven cooling.
When a ceramic material is cooled from an elevated temperature, internal stresses,
called thermal stresses, may be introduced as a result of the difference in cooling rate
and thermal contraction between the surface and interior regions.

146
• Glass Toughening: The strength of a glass piece may be
enhanced by intentionally inducing compressive residual surface
stresses. This can be accomplished by a heat treatment procedure
called thermal tempering.
-- puts surface of glass part into compression
-- suppresses growth of cracks from surface scratches.
-- sequence:
before cooling initial cooling at room temp.
cooler compression
hot hot tension
cooler compression

-- Result: surface crack growth is suppressed.

 Difference Between Annealing and Tempering
Annealed Glass:
•The raw materials are melted in a
furnace to form molten glass. The
molten glass is then passed through the
temperature-controlled kiln (annealing
lehr) for cooling the glass. In annealing
lehr, float glass cools gradually and
comes out with uniform thickness and
flat surface.
•Float glass can withstand temperature
differential of up to 40 Celsius degrees.
Thus float glass breaks due to excessive
thermal stresses.
•Upon impact float glass breaks into
large sharp pieces.
Tempered Glass:
•The normal glass or float is heated in
the furnace to a uniform temperature
of 620-650 Celsius degrees and then
rapidly cooled in the annealing lehr to
produce tempered glass.
•Tempered glass can withstand
temperature differential of up to 250
Celsius degrees. It has more
resistance to thermal stresses.
•Toughened glass breaks into small
blunt pieces, which are not harmful.
Thus it is widely used as a safety glass.
ATTEMP
T1

The binary system SiO2-Al2O3 is an important one since most ceramics have these two constituents. A
narrow phase field shown on the above figure is the range over which, intermediate compound, mullite, is
formed. Mullite is known to be a refractory ceramic material. For the above system (a) what is the
maximum temperature that is possible without the formation of liquid phase (b) What composition range
will this maximum temperature be achieved?
2.
(a)With the aid of a plot, briefly describe how glass is produced.
(b) Briefly describe the following terms: Annealing point, Glass transition temperature,
Glass toughening process, Working point for glass, supercooled liquid
(c) How does the thickness of a glassware affects the magnitude of thermal stresses that
may be introduced? And why?
Homework:

Read on structure of Glass and terminologies

associated with it- such as network formers; network modifiers, etc

Videos on ‘Glass making’

End of Lecture(s) on
 Glass production
 Glass forming processes
 Heat Treatment techniques