Session 01

Introduction to Engineering Materials

Contents
Introduction
1.1 Introduction to Materials Science and Engineering
1.2 Importance of Materials in the Field of Engineering
1.3 Modern Developments in Materials Science and Engineering
1.4 Introduction to Properties of Materials
1.5 Relationship between Structure and Properties of Materials
1.6 Introduction to Processing of Materials
1.7 Classification of Engineering Materials
Summary
Learning Outcomes

Introduction
Materials Science and Engineering is one of the most important field and ‘no engineering
is possible without materials’. The materials were considered as the backbone of the
advancement of human civilization where eras of civilization are named after them.
Namely, Stone Age, Bronze Age and Iron Age and Scientist name current era as Silicon
age. The future development in the civilization will undoubtedly be named as ‘Carbon Age’
since the modern developments in the field of Nano technology will be based on Graphene
(form of carbon consisting of planar sheets which are one atom thick), Carbon Nano Tubes
(a form of long, hollow structure with the walls formed by one-atom-thick sheets of
carbon), Fullerene (a Form of carbon having a ‘large’ spheroidal molecule consisting of a
hollow cage of sixty or more carbon atoms - Carbon Bucky Balls) etc. The Material
Scientist and Engineers are now capable of fabricating Nano, micro or macro level
materials tailor made for the most of modern machines and equipment. Practically we are
now in a modern world of ‘Materials’ Age.

1.1 Introduction to Materials Science and Engineering

Materials science is mainly concentrated on the science of materials. This field of science
search for the basic knowledge of internal structure at atomic level, which can influence
the properties of a material. Also, it is engaged with the processing of existing materials as
well as manufacturing tailor-made materials for special applications.

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Materials engineering engages with converting raw or semi-finished materials to
engineering products which fulfill the requirement of the society using the fundamental
and applied knowledge created by the materials scientist (Fig. 1.1).

Applied Knowledge of
Basic Knowledge of
Materials
Materials

Materials Science Materials Engineering

Converting Materials to
Products for the Requirements
of the Society

Materials Science &

Engineering

Fig. 1.1 The Role of Materials Science and Materials Engineering in Manufacturing
of Engineering Products

1.2 Importance of Materials in the Field of Engineering

At the initial stage of the product development the design engineer needs to ‘materialize’
his design to a product. At that stage, selection of a suitable material which fits best to the
demands of the design such as strength, durability, aesthetic, recyclability, cost etc. is inevitable
and those requirements should be satisfied by a material. It is also important to consider that
the materials are eternally developed to meet the demands of the modern technological
developments not only in the field of engineering but also in medicine, scientific
instrumentation, environmental applications etc. As an example, ‘smart’ materials are used in
aircraft components and in medical applications. Shape memory alloys (SMAs)are used in
torque tubes in smart wings of aircrafts and stents to expand the narrowed arteries in the heart.

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1.3 Modern Developments in Materials Science and
Engineering

After the discovery of copper and bronze around 3000BC and discovery of iron and steel
in 1850, a rapid development was observed in the field of materials science and
engineering. Currently we are experiencing vast developments in the areas of functional,
smart and Nano materials. Those materials are used in many applications revolutionizing
the usage of devices and equipment in the modern society. Starting from the Nano particles
used for delivering drugs to cancer tumors, polymeric heart valves, titanium dental
implants, piezoelectric ceramics for load measurements, microelectromechanical systems
(MEMS) used as sensors and actuators, high performance carbon fiber composites in
automobile and aircrafts industry, single crystal nickel based super alloys for jet engine
turbine blades are few examples for the modern development of materials for the
betterment of the society.

1.4 Introduction to Properties of Materials

Properties of materials can be defined as the response/reaction of materials to external

stimulations. As an example, a piece of metal exhibits deformation under mechanical
stresses. Those properties are the major factors in the process of selection of a material for
an engineering component for a given application. Normally in the fields of science and
engineering the properties of a substance are mainly divided into groups;

 Physical Properties
 Chemical Properties

(a) Physical properties are defined as ‘properties which can be determined without
changing the chemical nature of the substance’.

Shape, mass, color, density, viscosity, melting point, opacity, thermal expansion, electrical
conductivity etc. are categorized as physical properties. ‘Mechanical Properties ‘which is
more important to Materials Science and Engineering are also categorized as physical
properties. Strength, elastic modulus, hardness, ductility, toughness etc. will be considered
as mechanical properties of solids.

(b) Chemical Properties are defined as ‘properties which can be determined only by
changing the chemical nature of the substance’.

For example, chemical composition, degradability, heat of combustion, pH value etc. can
be considered as chemical properties.

Activity 1

Are ‘nuclear properties’ physical or chemical?

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1.5 Relationship between Structure and Properties of Materials

The properties which were discussed in section 1.4 are severely influenced by the ‘nature’
of the material. The word nature used here is interpreted, more appropriately, as the
‘structure’ of the material. The structure can be defined as internal array of the components
of the material. This arrangement can be considered as subatomic, atomic, microscopic and
macroscopic levels.

o Subatomic level- Electron configuration within the atom and not visible to human
yet.

o Atomic level–Combination of atoms and molecules can be observed only under an

Atomic Microscope (Fig. 1.2).

o Microscopic level-Large number of atoms accumulated to form a mass or

a group and can be seen under a Scanning Electron Microscope or an Optical
Microscope (Figs. 1.3 and 1.4).

o Macroscopic level–Spatial structural features (topography) can be viewed with

naked eye or at a lower magnification around 30X or less. (Fig. 1.5).

Fig. 1.2 Atomic-Resolution Transmission Electron Micrographs of Silicon Nitride

Crystals

Fig. 1.3 Micrograph of a Crack in a High Strength Metal due to Hydrogen Embrittlement

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 Fig. 1.4 Micrograph of Spheroidal Graphite Cast Iron (SGI)

Fig. 1.5Surface of a Fatigue Crack in a Crankshaft

The evolvement of a spatial structure initiates at the atomic level and depends on;
 Atomic configuration, according to the periodic table (also named as
electronic configuration of atoms)
 Bonding mechanisms of atoms
 Formation of crystalline (grain structure) or non-crystalline structure
(disordered structure) in micro level.

Therefore, it is important to keep in mind that the properties of a material are strictly depend
on the structure. In addition, the field of materials science concerns of two other phenomena
related to materials; processing of materials and performance during the service. It is
interesting to line up these four phenomena systematically. The performance depends on
the properties, the properties are governed by the structure and the structure depends on the
processing route. Therefore, these four factors can be schematically illustrated in Fig. 1.6.

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 Processing of
Materials
Type equation here.
ls
Structure of
Materials

Properties of Performance
Materials during Service

Needs to select Helps to predict

suitablematerial for service life
an application
Product
Design
Process

Fig. 1.6 Stages in Product Design

1.6 Introduction to Processing of Materials

Processing of materials involves many stages starting from raw materials to semi-finished
or finished products. As an example, iron is mainly extracted from iron ore and it will be
then converted to steel to produce a steel hammer. Following stages are involved in this
‘process’;

1. Extraction of iron from iron ore and purification of iron

2. Conversion of iron to steel
3. Solidification of molten steel to a solid primary form (a form of an ingot)
4. Mass conserving process (hot forging to solid bar)
5. Subtractive process (machining to form the hammer head)
6. Changing the material characteristics (heat treatment to harden the head)
7. Assembling process (fixing to a wooden or metal handle)

This is an example for processing of a material to produce a conventional product.

However, in the modern world of science and engineering the material processing has gone
to the distance to produce micro- and Nano-scale products (micro- and Nano-processing).

In all stages of processing, the material undergoes significant structural changes and, as
explained earlier, accordingly the properties will also change. It is very important to
maintain a strict quality control of the properties of the material to get the desired final
properties and thus the performance.

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1.7 Classification of Engineering Materials

Solid engineering materials are divided mainly in to three groups according to their
chemical nature, structure and properties.
 Metals and their alloys
 Polymers
 Ceramics
Furthermore, there are engineering materials which are produced by combining two or
more of above-mentioned types which are named as;

 Composites

Those are ‘hybrid’ (combination of two or more) materials produced by artificially

combining two or more materials to achieve enhanced properties by combining the superior
properties of individual materials.

In addition, modern research and development in the field of Materials Science and
Engineering facilitated the Scientists to produce tailor-made materials for areas of
applications in demand (Advance Materials/Functional Materials). Those are:

 Electronic Materials - Semiconductors, capacitors, resistors etc.

 Smart Materials - Functional materials which can change their
character according to the service conditions.
(E.g. Shape memory alloys)
 Bio Materials - Materials which have bio-compatibility with
human body tissues.
(E.g. Titanium alloys and stainless steel)
 Nano Materials - Materials which show completely different
properties at Nano level
(E.g. carbon Nano tubes, graphene etc.)

Fig. 1.7 Carbon Nano tubes being spun to form a yarn

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Activity 2

Briefly discuss the differences between plastics and ceramics?

Other than the normal cups and saucers, name five items manufactured using ceramic
materials.

Give at least three advantages and disadvantages of using plastics, Teflon, fibre glass and
ceramics.

Activity 3

What are the essential differences between macro and micro observation of metallic
structures?

What are the major differences between metals and ceramics in their properties?

With the information given in this session, can you determine what material are needed for
the manufacture of following products?

Spoons, engine blocks, screw drivers, nails, imitation jewellery, gear wheels, drinking cups,
bearings, barbed wire, kitchen knives, crane hooks, electrical transmission lines.

Summary
In this session initially, the historical development of engineering materials and their
applications in modern industry has been discussed. As one of the most important factor
which is vital during selection of suitable materials for engineering applications the
structure-property relationship has been illustrated. Further, introductory explanations
were given on processing and classification of available materials. Finally, the types and
applications of modern materials were given.

Learning Outcomes
At the end of this session the students will be able to

1. Understand the importance of materials in engineering applications.

2. Understand the relationship of structure and properties of materials.
3. Describe the classification of engineering materials.

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Session 2
Engineering materials

Contents
2.1 Definition of Matter, Elements, Substances, Materials and Engineering Materials
2.2 Classification of Engineering Materials
2.3 Applications of Engineering Materials
2.4 Modern Developments and Challenges in Applications of Tailor-Made High
Performance and Advance materials
2.5 Introduction to Nano Materials in Engineering
Summary
Learning Outcomes

2.1 Definition of Matter, Elements, Substances, Materials

andEngineering Materials
In the previous session, we have discussed about the importance of Materials Science and
Engineering in the modern society. In that context, we have given emphasis on
‘Engineering Material’ which was not well defined at that stage. Now we will try to define
what are Engineering Materials.

The universe is the largest space which we can consider. It is the totality of existence and
it includes galaxies, stars, planets, sub atomic particles and everything. Therefore;

 Matter: can be defined as everything which exists in the universe.

 Elements:are the simplest form of matter which cannot be further broken down
using any chemical reaction. The elements existing in the earth are well categorized
according to their atomic number in the ‘Periodic Table’.

 Substances:are made out of one or more elements which are bonded together
though atomic bonds. They can be in any form as gas, liquid or solid.

 Materials:are substances which can be used to make a useful product.

 Engineering Materials:are substances which can be used to produce an

engineering product.

In this course we are considering only the ‘Solid Engineering Materials’

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Activity 1

Give at least one example for Matter, Elements, Substances, Materials and Engineering
Materials.

Answer: Matter – a planet, Elements – Hydrogen, Oxygen,Titanium, Materials – coke,

wood, metals and Engineering Materials – Metals, Polymers, Ceramic.

2.2 Classification of Engineering Materials

As mentioned in session 01, engineering materials can be categorized in mainly 4 groups

as Metals, Polymers, Ceramics and Composites.They have distinguish character according
to their chemical composition and the structure.

(A) Metals are having distinguish characteristics like;

 high electrical and thermal conductivity

 high resistance to mechanical stresses with considerable amount of
deformability
 opaque and high reflectivity to visible light

These properties are mainly due to the bonding mechanism of metallic atoms. They are
bonded with ‘Metallic Bonds’ where the metal ions are bonded with a ‘seaof electron’
released from the most outer orbital of the atom. These electrons have the freedom to move
randomly in the structure and called as ‘free electrons’.

 Normally, pure metals are relatively low in strength

 By adding another type of metal/non-metal to the base metal (alloying)the
strength can be improved. However, some properties like electrical and thermal
conductivity will decrease with the amount of alloying elements. As an
example, adding small amount of carbon to pure iron(steel) the strength of iron
will be increased significantly. Also zinc can be added to pure copper to
enchance the strength of copper but sacrificing the excellent electrical
conductivity of copper.

(B) Polymers are mainly categorized into;

 Plastics and
 Elastomers (Rubber& Latex)

 They consist of long chains formed by chemically bonding mainly hydrogen

and carbon but also with other non-metallic elements like oxygen, nitrogen
silicon etc.
 They have a non-crystalline disordered structure (amorphous structure) consist
of long chain-like molecules made out of hydrocarbons bonded by covalent
bonds. Those chain-like molecules are weakly bonded by‘Van-der-
Waals’bonds.
 Polymers are relatively low in strength compaired to metals

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  But due to their low density the strength/weight ratio is considerably high.
 Due to absence of free electrons in the structure, they can be used as electrical
and thermal insulators and non magnetic components.
 The polymers are chemical inert and can resist to many aggressive
environments.
 Due to their tendency to soften and decompose at relatively low temperatures
(80 - 400 ˚C) polymers can be easily formed into complex shapes.
 However, modern research and development show it is possible to produce
‘Crystalline Polymers’ which have relatively high strength and moderate
electrical conductivity.
 Typical examples for common polymers are; Polyethylene (PE), Polyvinyl
chloride (PVC), Polycarbonate (PC), Polystyrene (PS), Nylon, Latex, Silicon
Rubber etc.

(C) Ceramics are;

 Inorganic non-metallic compoundslike oxides, nitride and carbides which are

bonded with ionic and covalent bonds
 Categorized into;
o traditional ceramics (cookware, porcelain etc.)
o functional ceramics (which fulfill electrical, magnetic, dielectric,
optical functions)
o technical/structural ceramics (which can be subjected to mechanical
loads – in compression, bending, abrasion etc.)
o bioceramics (can be used as human implants)
 Chemically inert and non reactive even against aggressive chemicals
 Non conductive to electrical and thermal energy and also non magnetic
 Having a structure of a mixture of crystalline and non crystalline nature
 Having high strength even at high temperatures (upto approximately 1200˚C)
 Brittle and has very low toughness compared to metals
 Typical examples are; Aluminium Oxide (Al2O3), Silicon Oxide (SiO2), Silicon
Nitride (Si3N4), Zirconium Oxide (ZrO2), Tungsten Carbide (WC) etc.

(D) Composites are;

 Categorized into ‘Natural Composites’ and ‘Synthetic Composites’
 Natural composites exist naturally and some examples are wood and bones
 Synthetic composites are man-made materials which have at least two different
types of materials combined to get excellent properties of the different components.
Most common composite is ‘Fiber Glass’ and it is made from polymer (matrix)
reinforced with glass fibers. Concrete is also a composite with
cement/sand/aggregate reinforced with steel rods.
 Most common matrix materials are metals, polymers and ceramics
 Reinforcement materials used for modern composites are mainly glass fiber and
carbon fiber. Aramid (aromatic polyamide) such as Kevlar and Twaron (trade
names) and Glare fibers are used in advanced applications.

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 A comparison of the different engineering materials with respect to their strength is given
in the Fig. 2.1. Comparison of other properties such as fracture toughness, electrical
conductivity can be extracted from literature.
CFRC - Carbon Fiber Reinforced Composites
GFRC - Glass Fiber Reinforced Composites

Fig. 2.1 Comparison of Tensile Strength of Different Materials

2.3 Applications of Engineering Materials

2.3.1. Metallic Materials:

Metallic materials are the most common materials used in the field of engineering.
Generally, all metals in their pure form and alloyed form have excellent strength with good
deformability when compared to polymers and ceramics. In addition, due to their physical
properties such as electrical and thermal conductivity they are used in wide range of
industrial sectors including aerospace, semiconductor, biomedical, electronic, electrical,
energy, structural, transport etc. In the modern world metals are considered as the most
environmental friendly material due to their high level of recyclability.
Metallic materials can be divided in to two groups;

(A) Ferrous Metals and their Alloys– Wherein ‘Iron’ is the main constituent of the
material (Pig iron, Wrought iron, Steel and Cast iron).

(B) Non-Ferrous Metals and their Alloys– Wherein ‘Iron’ is NOT the main
constituent of the material (Copper, Aluminium, Zinc, Nickel, Titanium etc.).

(A) Ferrous Metals and Alloys contain large amount of iron and alloyed with other elements
such as carbon, manganese, silicon, nickel, chromium, vanadium, tungsten etc. Depending
on the application, the number of above-mentioned elements can be varied.

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Fig. 2.2 shows the types of ferrous alloys classified according to the number of alloying
elements in iron.

METALLIC MATERIALS (I)

Ferrous Alloys (A)

Steels <2 %C Cast Iron >2 %C

White Cast Iron

Non- Alloyed
Alloyed steel Steel Gray Cast Iron
%C
Plain Carbon Low High Alloy Nodular Cast
Steel Alloy Steel Iron
Steel Flake Cast Iron
Medium
Carbon Steel Tools Steels
Stainless Steels
High Carbon
Steel

Fig. 2.2Classification of Ferrous Alloys

Table 2.1: Characteristics and Applications of Steel and Cast Iron

Type of Steel/Cast Iron Characteristics * Applications

Low Carbon Steel Moderate strength, very good ductility, Reinforcement for concrete, sheets, rods,
malleable, good workability, low wires, cans, structures, automobile body
corrosion resistance, cheap parts
Medium Carbon Steel Good strength, good ductility, good Rails, gear wheels, shafts, crankshafts,
workability connecting rods
High Carbon Steel High strength, low ductility, difficult to Keys, knifes, chisels, cutting tools, hacksaw
work, high hardness after quenching blades
Ultra-High Carbon Steel Very high strength, low ductility, very Knifes, axes, punches, springs, swards
high hardness after quenching
Low Alloy Steel Good strength, good workability, high Military vehicles, earthmoving and
toughness, good corrosion resistance construction equipment, pipelines, pressure
vessels, structural elements
High Alloy Steel High strength, excellent corrosion Tool steel, stainless steel, punches,
resistant (stainless steel), forming and extruding dies
White Cast Iron High strength, high brittleness, good Abrasive & wear resistant components,
wear resistant crushing, grinding, milling components
Grey Cast Iron High strength, moderate ductility, Heavy-duty machines tools, tools, beds,
relatively low melting point, good presses, high pressure hydraulic parts, gears,
damping ability cylinder blocks & heads
Ductile Cast Iron Good strength, good castability, Gear wheels, crankshafts, pipes, pump parts,
excellent machinability, good wear manhole covers, rollers
resistance, high toughness, and ductility,
hardenable
Malleable Cast Iron Moderate strength, good castability, Electrical fittings, hand tools, pipe fittings,
excellent machinability, good toughness washers, brackets, fence fittings, power line
and corrosion resistance hardware, farm equipment, mining hardware,
machine parts.
Alloy Cast Iron High strength, moderate ductility, good Sewage and chemical pump parts, heat and
wear and corrosion resistance, corrosion resistant parts
* - Characteristics/Properties depend on the type & amount of alloying elements

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(B) Non-Ferrous Metals and Alloys have different metals as parent metal and alloying can
be performed by many other elements. As an example, copper as a parent metal can be
alloyed with zinc, tin, nickel etc. (Cu-based alloys). Nickel can be alloyed with,
chromium, titanium, vanadium, iron etc. (Ni-based alloys).

Non-Ferrous metals and their alloys can be categorized according to the properties as
follows:
 Copper and its Alloys

 Aluminium and its Alloys

 Magnesium and its Alloys

 Titanium and its Alloys

 Super Alloys

 Refractory Metals

 Noble Metals

Fig. 2.3Classification of Non- Ferrous Alloys

The applications of above-mentioned metals are given below;

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Table 2.2 Characteristics and Application of Non- Ferrous Metals and Alloys

Type of Characteristics Applications

Metal/Alloy
Copper; excellent electrical & thermal Electrical wire, rivets, gaskets, nails, roofing,
Copper and its Alloys conductivity, high ductility, good condenser and heat exchanger
workability, good corrosion resistance, components, salt water piping, bearings,
high thermal expansion coefficient, bushings, gears, worms, valve seats
expensive.
Copper alloys: in addition to a/m
properties good strength, aesthetic
appearance
Aluminium: high electrical & thermal Food/chemical handling and storage
Aluminium and its Alloys conductivity, light weight, good equipment, heat exchangers, light reflectors,
workability, good corrosion resistant, cooking utensils, pressure vessels, piping,
high thermal exp. Coefficient., aircraft fuel and oil
relatively expensive lines, fuel tanks, appliances, rivets, wires,
Aluminium alloys: good strength, aircraft structures
difficult to weld
Light weight, easy to cast, moderate Tubing, cast parts for automobiles, luggage,
Magnesium and its Alloys strength, relatively difficult to work at electronic devices, aircraft components
RT,
Lightweight, high strength, good Jet engine shrouds, cases and airframes,
Titanium and its Alloys biocompatibility, corrosion resistant, corrosion-resistant equipment
high chemical reactivity at high for marine and chemical processing
temperature, expensive industries, gas turbine engine casings and
rings, chemical processing equipment,
prosthetic implants
High strength even at high Turbine applications, components in nuclear
Super Alloys
temperature, high corrosion, oxidation reactors, petrochemical equipment
(Nickel base alloys)
and creep resistant, expensive
Refractory Metals Very high melting temperature, Extrusion dies and structural parts in space
(Niobium, Molybdenum, vehicles; incandescent
high reactivity at high temp. high
Tungsten, Tantalum) light filaments, x-ray tubes, welding
elastic modulus, difficult to work, electrodes, components in chemical plants
expensive
Noble Metals (Silver, Gold, Soft and ductile, easy to work, good Aesthetic items, chemical laboratory
Platinum, Palladium, oxidation resistance, silver and gold equipment, parts of catalyst, high
Rhodium, Ruthenium, are very good electrical conductor, temperature thermocouples
Iridium, Osmium) high aesthetic value, expensive

2.3.2 Polymeric Materials:

When we consider the applications of polymers in the society it is important to categorize

them according to different criteria. Primarily, Polymers can be divided into two groups
according to their existence;
 Natural Polymers - Which are existing in the nature; proteins, enzymes,
wood, leather, natural rubber, silk etc.

 Synthetic Polymers - Which are chemically produced (human-made);

polyethylene, polypropylene, polyvinyl chloride, artificial rubber etc.

Those polymers are also categorized according to their mechanical and thermal behaviour
 Plastics
 Elastomers

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 Thermoplastics

Plastics

Thermosets
Natural Polymers

Polymers
Fibers
Synthetic Polymers

Elastomers (Rubber
& Latex)

Fig. 2.4 Classification of Polymers

Applications and characteristics of some of the polymers are given in Table 2.3.

Table 2.3: Characteristics and Applications of Polymers

Type of Polymer Characteristics Applications

High tensile strength and resistant to Vehicle tires, mounts, conveyor

fatigue and wear such as chipping, belts, air hoses, rainwear, shoes,
cutting or tearing. Adhere well to blankets and as hard rubber for
Natural Rubber metals especially to steel. Less pump housing also for piping for
resistant to heat, light and ozone. handling abrasive sludge. As latex
protective gloves, balloons, baby
teats and condoms
Very good strength-to-weight ratio, Plywood, laminated wood, particle
good machinability and good board, MDF boards, chip boards and
aesthetic appearance. Thermal and fiberboards, furniture, aesthetic
Natural electrical insulator. Vulnerable to items.
Wood fungal and insect attacks.
Polymers
Hygroscopic and soften due to water
absorption (but not all types of
wood)
High tensile strength, resistance to Belts, footwear, gloves, upholstery
tear, flexing, puncture, fungal etc.
Leather attacks, wet and dry abrasion as
well as chemical attacks. Good heat
insulation.

Synthetic Synthetic Rubber Better resistant to abrasion than Insulation for electrical devices,
Polymers natural rubber. Excellent resistant to
heat, flame, grease and oil. Also,
(Synthetic resistant to aging. Flexible at low
Rubber) temperature.

Resistant to heat distortion; Sterilizing bottles, packaging film, TV

excellent electrical properties and cabinets, luggage
fatigue strength; chemically inert;
Polypropylene relatively inexpensive; poor
(PP) resistance to UV light.

Synthetic
Polymers
Chemically resistant and electrically Flexible bottles, toys, tumblers,
insulating; tough and relatively low battery parts, ice trays, film wrapping
Coefficient of friction; low strength materials.
Polyethylene (PE) and poor resistance to weathering.

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 Excellent strength, toughness, Refrigerator lining, lawn and garden
resistance to heat distortion, good equipment, toys, highway safety
electrical properties (special devices.
polymers), flammable and soluble in
Acrylonitrile- some organic solvents.
Butadiene-Styrene
(ABS)

Excellent combination of mechanical Electrical moldings, sinks,

properties and corrosion resistance, adhesives, protective coatings, used
dimensionally stable, good with fiberglass laminates.
Epoxy resins adhesion, relatively inexpensive,
good electrical properties.
Synthetic
Polymers
(Thermosets) Excellent thermal stability to over Motor housings, telephones, auto
150oC, can compounded with a distributors, electrical fixtures.
Phenolic resins large number of resins, fillers and
inexpensive.

Strong, light weight, robust, less Mats for thermal and electrical and
expensive, good thermal insulator, sound insulation, heat and corrosion
less stiff, brittle. Cheap. resistant fabrics, reinforcement for
Glass fibers fiberglass, automobile parts, hockey
sticks, tanks and vessels

High strength-to-weight ratio, Used in carbon fiber reinforced

Corrosion resistant and chemically composites for high-End automobile
stable, electrically conductive, high components, bicycle frames, fishing
fatigue strength, better ductility than rods, shoe soles, protective cases
Carbon fibers glass fiber, low thermal expansion for laptops, phones, aeronautical
coefficient, fire resistant and non- applications, satellite components,
Synthetic flammable. Expensive Formula 1 cars.
Polymers
Exceptional impact resistance, good Helicopter rotor blades, bullet proof
(Fibers) elongation (better than carbon fiber). vests, sporting goods, marine vessel
Aramid fibers Expensive. hulls, armor and ballistic applications

Five times stronger and twice stiff as Aerospace applications such as

steel. Excellent compressive and empennage skins, truss members
bulking properties. Expensive. and repair patches.
Boron fibers

Activity 2

What are ‘Elastomers’? Give their characteristics and applications.

Give a brief comment on ‘Natural Fibres’ giving 5 examples.

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2.3.3 Ceramic Materials:

The word ‘Ceramic’ comes from Greek word ‘Keramikos - burnt stuff’ and ceramics have
a very old history in their uses/application in the human history. Making of ceramics goes
back to 24,000 BC and real manufacturing and domestic usage came after 14,000 BC. Their
real functionality was observed around 10,000 BC where the community has used ceramic
pots to store water and food. Currently, the ceramics are used not only for domestic
applications but also for highly sophisticated electronic items, spacecraft components,
super conductors, bio implants etc.
Ceramics are inorganic compounds and they contain powerful ionic and covalent bonds.
Therefore, they show high strength even at very high temperature. Due to their partly
crystalline and amorphous structure ceramics show low ductility and high brittleness. They
are very good electrical and thermal insulators due lack of or missing free electrons in the
structure.
Ceramics are usually made as oxides, carbides, nitrides or silicates of metals (Aluminium
Oxide, Tungsten Carbide, Silicon Nitride etc.). Processing of ceramics includes many
stages and normally, the ‘traditional ceramics’ are made by ‘mixing’ clay, sand and some
chemicals in powder form, mixing with water to make a formable mass, ‘forming’ or
‘extrusion’ and finally ‘firing’ at desired temperature. Final aesthetic appearance is
achieved by ‘glazing’. ‘High performance ceramics are made mainly by power pressing
(sintering), hot isostatic pressing (HIP), slip casting etc. Further details about ceramics will
be discussed under Materials Engineering course.
Normally, ceramics can be categorized according to their application into 6 groups:

1. Glasses and Glass ceramics

2. Clay Products
3. Refractories
4. Abrasives
5. Cement & concrete
6. Advanced Ceramics
The Table 2.4 shows the characteristics of different types of ceramics and their
applications.

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Table 2.4: Characteristics and Applications of Ceramics

Type of Ceramic Characteristics Applications

Glasses: excellent transparency, ease Glasses: window glasses, glassware,

Glasses and Glass ceramics of fabrication, low strength ornamental items
Glass-Ceramics: Good transparency, Glass-Ceramics: safety glasses,
high strength, low thermal expansion windscreens, Heat resistance glasses,
coefficient, good thermal shock optical fibers, restorative dental
resistance implants
moderate strength, easy to form, brittle, White-wares (porcelain, chinaware,
Clay Products abundant raw material, relatively cheap, pottery, etc.), structural products
difficult to recycle as fired items, (bricks, tiles, pipes, electrical
insulators)
Inert to extreme thermal and chemical As bricks for high temperature
Refractories environments, high temperature furnaces, chemical tanks, thermal
strength, high thermal insulation insulators
Very hard, tough and able to withstand Grinding papers, wheels, as lapping
Abrasives high temperatures, chemically inert, material, tool inserts
expensive
High compressive strength, chemically Pavements, floors, reinforced concrete,
Cements & Concrete
inert water resistant when cured, brittle, building blocks, bridges, tanks, pipes
Depending on the type insulating, Capacitors, resistors, magnets, super
dielectric, conductive, piezoelectric, conductors, MEM components, load
magnetic & super conductive, high measurement devices, high
Advanced Ceramics
temperature and chemical resistant, temperature turbine components, ball
high strength, rigid, hard, tough, low bearings, body armors, human
expansion, light weight, bio compatible implants, sensors

Activity 3

Briefly explain the manufacturing process of glass ceramics.

Write a brief article on types, properties and applications of advanced ceramics.

2.4 Modern Developments and Challenges in the Application of

Tailor-Made Advanced Materials

As mentioned in the earlier chapter, during the past history the materials have played a vital
role in every economic and social development of the human society. However, in the
emerging techno-economic development of the society, the materials are playing a
completely different role. A vast variety of applications are emerging and they demand
diverse properties of materials, especially, a specific combination of properties, which can
be delivered only by tailor-made homogeneous and heterogeneous materials for a particular
application. Development of hybrid (heterogeneous) materials has been used by not only
modern and well developed conventional materials such as advanced metallic alloys,
polymers but also by various types of composites.
It is important to identify the domains of technical applications of materials and the
challenges emerged by them to deliver suitable material(s). Table 2.5 shows the areas of
applications of advanced materials.

19
Table 2.5 Specific Requirements on Materials in Various Fields of Applications

Domains of Technical Applications Challenges

Efficient fuel and fuel tubes, Less
Nuclear Power Generation contamination & degradation of structures,
disposal of radioactive waste
Increase the service temperature of engines
to minimize pollution and increase the
Transportation (Air, land & water) efficiency, reduce fuel consumption, reduce
weight, hydrogen fuel cells
Optical fibers with less energy loss, optical
Communication antennas, enhanced electronic devices
Efficient solar cells, storage batteries and
Solar Energy Utilization control electronics
Effective biocompatibility and reduced
biodegradability, Regenerating and bio-
Medicine (Biological Implants) renewable materials, miniaturization of
implants, effective drug delivery
Minimize pollution of air, water and soil, Bio-
Degradable materials, less environmental
degradation of materials, ecological
materials manufacturing processes, less
Environmental Protection emission of toxic substances, economical
material recycling, materials which support
3R (Reduce, Reuse, Recycle) concept, less
CO2 emission (Carbon Foot Print).

Activity 4

Are biodegradable materials used in human implants?

The researchers are striving to develop materials which have excellent strength-to-weight
ratio for the usages in air and space vehicles and because of this the researchers at the
Boeing Co. made world lightest metal (Oct. 2015). This is the lightest metal ever made and
it is 100 times lighter than Styrofoam. This new metal is made of ‘Micro lattice’ and
contains 99.99% air. The strength is created through interconnected hollow nickel
Nanotubes with a diameter of about 100 nanometers; approximately 1000times thinner than
a normal human hair (Fig. 2.5).

Fig. 2.5 Lightest Metal in the World (developed in 2015)

20
2.5 Introduction to Nano Materials in Engineering
The world of engineering has been revolutionized with the introduction of “Nano
materials”. The technology behind is called as ‘Nanotechnology’ and it is based on ‘Nano
science’ which was initiated with the famous talk delivered by Richard P. Feynman in 1959.
Since 1990, research in Nano science has contributed an immense amount of knowledge to
the scientific community. Currently, nanotechnology has penetrated many disciplines such
as materials, electrical, electronics, civil, mechanical, biomedical, medicine etc.

The application of knowledge in nanotechnology is based on Nano materials and those

materials have extraordinary properties when compared to normal materials. Nano size
molecules which have large surface areas contribute to these amazing properties. Normally,
Nano particles are defined as set of substances having at least one dimension is less than
approximately 100 nanometers (1 Nano meter is equal to 10-9 m). This is approx. 100,000
times smaller than the diameter of a normal human hair.
Nano materials are used where unique electronic, optical, magnetic, electrical and other
properties are needed to manufacture emergent products with multiple functionalities.
Those products will be utilized in the fields of engineering, medicine, agriculture,
transportation, communication, manufacturing and most importantly space exploration.
Certainly, this cutting-edge technology will determine the direction and the future of the
human life. Also, this technology which will be realized with Nano materials will give a
significant impact on manufacturing high quality products with exceptional properties like
durable, ultra-light, high strength and high toughness.

Summary
This session commenced with the definition of matter, elements, substances, materials and
engineering materials. Subsequently, the classification of engineering materials has been
handled and they were classified into metals, polymers, ceramics and composites. This was
further discussed under the theme of applications of materials in industry. Further, this
session elaborates the modern developments and challenges in the application of advanced
materials. Finally, a brief introduction has been given to get an awareness of usage of
Nano materials in the field of engineering.

Learning Outcomes

At the end of this session the students will be able to;

• define terms matter, elements, substances, materials and engineering materials.

• classify engineering materials

• list the industrial applications of engineering materials

• list the applications of modern developments and challenges in industrial usage

of advanced materials

• be aware in usage of Nano materials in the field of engineering

21
Session 3
Atomic Structure and Bonding Mechanisms
of Engineering Materials

Contents
3.1 Introduction to atomic structure
3.2 Type of bonds and their functionality
3.3 Relationship between type of bonds and properties of engineering materials
3.4 Engineering materials with mixed bonds
Summary
Learning Outcomes

3.1 Introduction to Atomic Structure

The use and applications of engineering materials can properly be realized only with a good
understanding of their behavior under given conditions. In this session we will focus on the
basic structure of atoms which are the elementary building blocks of a material.

The configuration of an atom can be explained as follows:

(a) The atom consists of a nucleus and surrounding electrons. Each election
occupies a quantum state with a unique set of quantum numbers.

(b) The nucleus consists of neutrons and protons where neutrons do not change the
electrical neutrality but contribute to the weight of the atom (Atomic Weight).
The modern research has experimentally confirmed that there are number of
subatomic particles called as ‘Quarks’ are in the nucleus which carry fractional
electric charges. (see Fig. 3.3).

(c) With increasing atomic number, the elements in the periodic table have
increasing number of protons and electrons. The order of occupation of
quantum state by electrons is determined by the Pauli Exclusion Principle, the
Hund’s Rule and the Minimum Energy Criterion.
.
(d) Ionization potential is the energy required to remove an electron from the outer
orbital of an atom. Electron affinity is the energy released, when a free electron
is added to the outer orbital. The electro-negativity of an atom is a measure of
its tendency to attract bonding ions to itself.

22
The physical structure of the atom was first predicted by Niel Bohr in 1913 (see Fig. 3.1)
and later it was considered as ‘Electron Cloud’ model where the electrons are moving not
in discrete and exact orbits but as a cloud around the nucleus (see Fig. 3.2). In this electron
cloud theory, the position of an electron can be detected only through the consideration of
probability of an electron being at various locations around the nucleus.

Fig. 3.1Bohr’s Model of an Atom Fig. 3.2Electron Cloud Model of an Atom

Fig. 3.3 Configuration of Atomic Structure in Matters

Activity 1

Explain the Pauli Exclusion Principle, the Hund’s Rule and the Minimum Energy Criterion.

23
3.2 Types of Bonds and their Functionality
The properties of engineering materials are mainly depending on the bonding between
isolated atoms (inter-atomic bonding). If we take an example of solidification of a properly
molten metal and when the molten liquid is cooled then interaction of two isolated atoms
will be started in a random location where those two atoms come closer to each other due
to cooling. If the distance between the atoms is small then two forces will be activated.

They are:
 Attractive Forces - between positively charged nucleus and negatively charged
electron cloud

 Repulsive Forces - between negatively charged electron clouds of both atoms

The equilibrium distance between two atoms which are coming closer to each other will be
decided by the resultant of the attractive and repulsive forces. This can be visualized in the
Fig. 3.4 where those forces are plotted against the inter-atomic distance (r). At equilibrium,
two atoms will be bonded with an equilibrium distance r0 where the attractive force is equal
to repulsive force (resultant force is equal to zero).

Fig. 3.4 Attractive and Repulsive Forces against the Bond Distance (r)

Depending on the type of atoms the bonding mechanisms will be changed. There are mainly
two different types of bonds in engineering materials;

(a) Primary Bonds

(b) Secondary Bonds

Primary bonds are stronger than secondary bonds and their ‘Bond Energies’ are in the range
of (100 – 1000) kJ mol-1. Secondary bond energies are in the range of (1– 50) kJ mol-1(Bond
Energy is defined as the magnitude of the energy released, when two atoms come together
from a large distance-of-separation to the equilibrium distance or energy required to
separate two atoms which are already bonded). (see Fig. 3.5)

24
 Atom 1 Atom 2 Atom 1 Atom 2

Energy released Energy absorbed

Fig. 3.5 Energy Balance in Bonding of Atoms

Activity 2

Explain why, while cooling a molten pure metal at the melting point, the temperature is
constant.

(a)Primary Bonds are categorized in to three types;

(1) Ionic Bonds

(2) Covalent Bonds
(3) Metallic Bonds

(1) Ionic Bonds

Electrons are transferred from a neutral atom to another neutral atom, producing ions
of opposite sign and giving rise to the non-directional ionic bond. Non-Directional
means the electric charge of the atom is uniform in all directions. Mostly, occurred
in inorganic materials like NaCl, MgO etc.These bonds are very strong (see Fig. 3.6).

Fig. 3.6Formation of Ionic Bonds in NaCl

25
(2) Covalent Bonds

Sharing of valence electrons between neighboring atoms results in a covalent bond, which
is directional (electric charges are not uniform around the molecule). Occurred in H2O,
Al2O3 (Ceramics), Plastics (Polymers). These bonds are fairly strong and slightly
electrically polarized (see Fig. 3.7).

Covalent Bonds

Fig. 3.7 Formation of Covalent Bonds in a Water Molecule (H2O)

(3) Metallic Bonds

The metallic bonds form when atoms give up their valence electrons (electrons from most
outer shell), then forms an electron sea. The positively charged atom cores are bonded my
mutual attraction to the negatively charged sea of electrons. Metallic bonds are generally
weaker than ionic and covalent bonds (see Fig. 3.8).

Core of Metal Atoms

Electrons

Fig. 3.8 Formation of Metallic bonds in a Metal

26
(b) Secondary Bonds are categorized in to two types;

(1) Van der Waal’s Bonds

(2) Hydrogen Bonds

(1) Van der Waal’s Bonds

Van der Waal’s bonds are relatively weak and activated as weak forces attracting electron-
rich regions of one molecule to electron-poor region of another molecule. These bonds are
normally observed in polymers between polymer chains (see Fig. 3.9).

Van der Waals Bond

Polymer Chain

Fig. 3.9 Van der Waals Bond in Polymers

.
(2) Hydrogen Bonds

These bonds are also having the same character as Van der Waal’s bonds but if hydrogen
atoms are involved in the bond then they are called as ‘Hydrogen Bonds’. The water
molecules are bonded with these hydrogen bonds (see Fig. 3.10).

Fig. 3.10 Hydrogen Bonds between Water Molecules

27
In water, hydrogen and oxygen atoms are bonded with powerful covalent bonds and water
molecules are bonded with Van der Waals Bonds (Hydrogen Bonds). That is why at a fairly
low temperature (30˚C) water molecules are easily separated and vaporized. However, it is
very difficult to separate oxygen atom from two hydrogen atoms (only with electrolysis
process).

3.3 Relationship between Type of Bonds and Properties of Engineering

Materials
As discussed earlier, the bond energy of a particular bond varies with the type of bond. The
bond energy of primary bonds is much higher than that of secondary bonds. Therefore, the
materials with primary bonds are much stable than materials with secondary bonds.

Most of the physical properties such as melting and boiling points of materials increase
with increasing bond strength. Strong bonds result in hard and brittle solids and free
electrons in metals are responsible for the high thermal and electrical conductivities of
metals.

If we consider the melting points of metals and as an example it can vary from 29.8˚C
(Gallilium – melts in hand) to 3422˚C (Tungsten). The main reasons for this variation are;

 Electron configuration of metal atoms (especially, no. of electrons in

outer orbits – ‘d’ and ‘s’ orbitals)
 Their bonding mechanisms and
 Bond energies.

Gallilium has a higher degree of metallic bonding and Tungsten atoms are bonded with not
only metallic bonds but also with a significant amount of strong covalent bonds.

There are some other materials with mixed bonds and they have respective properties
according to bond types.
 Transition metals (metals with partially filled ‘d’ orbital) have metallic and
covalent bonds (Cu, Zn, Fe, W etc.)
 Intermetallic compounds have metallic and ionic bonds (Fe3C, NaZn13, Fe3Zn21
etc.)
 Ceramics have ionic and covalent bonds (Si3N4, Al2O3 etc.)

These materials are high melting and brittle.

3.4 Engineering Materials with mixed bonds

The chemical bonding of atoms or ions can involve more than one type of primary bond
and can also involve secondary dipole bonds. For primary bonding there can be the
following combinations of mixed-bond types.
(i) Ionic-covalent (e.g. GaAs)
(ii) Metallic-covalent (e.g. transition metals)
(iii) Metallic-ionic (e.g. Intermetallic compounds)

28
Activity 3

“There are some materials with mixed bonds and they have respective properties according
to bond types”. Explain.

Summary
In this session we have discussed basic atomic structure of matter and ‘building blocks’ of
the matter and materials. Also we have discussed the Bohr’s theory in which the structure
of atom was proposed earlier and modern theory of ‘Electro Cloud model’. Further, types
of atomic bonds and their functionalities were discussed. Under types of bonding we
discussed about primary and secondary bonding, including ionic, covalent, metallic, Van
der Waal’s and hydrogen bonding. As one of the most important factor in materials
engineering the relationship between type of bonds and properties of engineering materials
were elaborated.

Learning Outcomes

At the end of this session the students will be able to;

1. Explain the basic atomic structure of matters

2. Categorize the types of bonding available in molecules and substances

3. Assess the properties of engineering materials according to their bonding mechanisms.

29
Session 04
Structure of Solid Materials

Contents
Introduction
4.1 Space lattice and unit cells
4.2 Common metallic crystal structures
4.3 Crystallographic Planes and Directions in Cubic Unit Cells
4.4 Basic cell calculations; Volume, Planer and Linear Atomic Densities and Theoretical
Densities of Metals
4.5 Non- crystalline (amorphous) materials
Summary
Learning Outcomes

Introduction
In the nature, materials are existing in different states; i.e. solid, liquid, gas and plasma.
Since in this session we are interested only on solid materials, (or solid engineering
materials) it is important to study how those materials exist as solids.
The states of a material strictly depend on the temperature at which the material is. For
examples iron exists as a solid at room temperature but at 1538 ˚C it is a liquid. In contrast
to that Mercury is a liquid at room temperature it has a solid state at -38.83 ˚C.

Activity 1

What is the state of plasma?

Answer:
That means if we cool a container with molten iron from 1538 ˚C to room temperature;
- liquid iron will become a solid,
- in this cooling process the free moving atoms of iron will reduce their vibrations.
and,
- the freedom of movements in the container relative to each other will also be
reduced,
-because of that, iron atoms will gradually start to bond together (seeding,
nucleation).

If at a particular temperature the free energy (G) of the solid phase is lower than that of
the liquid phase, then the system tends to solidify by bonding atoms to make a particular
‘Structure’.

30
If at a particular temperature GSolid<GLiquid then

GSolid -GLiquid< 0or ΔG < 0

Then solidification of the liquid begins.

The formation and type of structure are depending on type of atom(s) in the liquid, type of
bonding, and cooling rate. This structure can be either a ‘Crystalline’ or ‘Non-Crystalline’
type.

(a) Crystalline Structures:

In a crystalline structure of atoms, molecules or ions are bonded in repeating or

periodic array over large atomic distances (long range periodicity) in a repetitive
three-dimensional pattern (see Fig. 4.1-a).
The atoms, molecules or ions pack together in an ordered arrangement. Such solids
typically have flat surfaces, with unique angles between faces and unique 3-
dimensional shape. Examples for crystalline structures (solids) are metals, diamond,
mineral crystals etc.

(b) Non-Crystalline structures:

In a non-crystalline structure (also named as ‘Amorphous’ structure) the atoms,

molecules or ions are bonded in repeating or periodic array but NOT over a large
atomic distance (see Fig. 4.1-b).
In non-crystalline solids there is no ordered structure and no well-defined faces,
angles or shapes. Examples for non-crystalline solids are glass, polymer and rubber.

Practically, it is difficult to identify (distinguish) whether a solid material is crystalline or

non-crystalline by just observing with naked eye or simple microscope. This can be done
only by X-Ray diffraction methods or using thermodynamic experiments. Difficulty
increases if the material has both crystalline and non-crystalline structure.

Activity 2

a) State two methods by which a given solid material can be identified as crystalline or
not.

b) Discuss “x-ray diffraction method to determine crystal structure.

31
 (a) (b)
Fig. 4.1
Fig. 4.1(a)In the crystalline SiO2structure, around each Silicon atom there are 3 Oxygen
atoms over a long range.

Fig. 4.1(b) In non-crystalline SiO2 structure, around each Silicon atom there are 3 Oxygen
atoms but NOT in long Range

4.1 Space Lattice and Unit Cells

In this session, initially we consider only the crystalline materials and therefore, we should
consider how these crystalline structures can be defined and how they are formed. The
crystalline structures are physically formed by arranging atom, molecules or ions in 3-
demisionally ordered space frame. This is called as ‘Space Lattice ‘and this particular
pattern should be repeated periodically in all three dimensions and in a long range.

Most crystalline solids are composed of a collection of many small space lattices (named
as Crystals or Grains). Such materials are termed as polycrystalline. During solidification,
initially, very small crystals or nuclei form at random positions and they have random
crystallographic orientations, as indicated by the square grids (Fig. 4.2).

The small grains grow by the successive addition from the surrounding liquid of atoms to
the structure of each. The extremities of adjacent grains impinge on one another as the
solidification process approaches completion. As indicated in Fig. 4.2, the crystallographic
orientation varies from grain to grain. Also, there exists some atomic mismatch within the
region where two grains meet; this area, called as Grain Boundaries.

32
 Nucleation cell
Liquid

Solid

Formation of Grains
with Random
Orientations
Grains

Grain Boundaries

Fig. 4.2 Formation of Crystals (Grains) during Solidification

The smallest group of atoms in a space lattice, which has the unique arrangement and from
which the entire lattice is built, is named as ‘Unit Cell’ (Fig. 4.3(a)).

Unit Cell

(a) (b)

Fig. 4.3 (a) Space Lattice (b) Unit Cell in a 3-dimensional Coordinating System

There can be unit cells with different sizes and shapes and they are denoted by dimensions
fixed in 3-dimensional Cartesian coordinates system (Fig. 4.3(b)).

 Basically, there are only seven different arrangements of unit cells in crystalline
materials depending on the magnitude and direction of the vectors a, b and c.
 They are named as;
(1) Cubic, (2) Tetragonal, (3) Orthorhombic, (4) Rhombohedral,
(5) Hexagonal, (6) Monoclinic and (7) Triclinic.
 Famous Scientist A. J. Bravais (1811 – 1863) invented that there are only 14 lattice
types exist in the nature which can be derived from above-mentioned 7 different
types of unit cells.
 Although lattice types are limited to fourteen, crystal structures can run into
thousands.

33
Activity 3

Write a short account of the above-mentioned 7 different types of unit cells.

4.2 Common Metallic Crystal Structures

As mentioned earlier out of seven different arrangements of unit cells under cubic crystal
system, we can observe three deferent lattice types, namely ‘Simple Cubic’, ‘Body
Centered’ and ‘Face Centered’. In ‘Hexagonal’ arrangement, there is only one type and
that lattice type is called as ‘Simple Hexagonal’.

Activity 4

Discuss the common lattice types present in most metals.

Note: that the concept of a lattice is just a mathematical and 3-dimentional picture and does
not mention atoms, ions or molecules. For example, if we take the face-centered cubic
lattice and assume that at each lattice point we have one atom, then we get a face-centered
cubic crystal structure.

Lattice is used to represent a three-dimensional periodic array of points coinciding with

atom positions.
Unit cell is smallest repeatable entity that can be used to completely represent a crystal
structure.

4.2.1 Simple Cubic Crystal Structure

This is most simple cubic crystal structure existing in the nature. In this structure 8 atoms
are placed in the corners of a simple cubic. If the unit cell is isolated from the atomic
arrangement (Fig. 4.4(c) then it is possible to see that the in each corner of the unit cell we
have 1/8 of an atom.

(a) (b) (c)

Fig. 4.4 Atomic Arrangement of a Simple Cubic Structure

Fig. 4.4 :- (a) Space Lattice (b) Atomic Arrangement (c) Isolated Unit Cell

34
Since in the nature only one element, Polonium, has this simple cubic structure we have
less interest on this type of structure.

4.2.2 Body Centered Cubic (BCC) Crystal Structure

In contrast to the previous simple cubic structure, the Body Centered Cubic (BCC) structure
consists of one full atom placed at the center of the cubic structure in addition to the corner
atoms. That means in a body centered cubic structure we have more atoms than in the
simple cubic structure (Fig. 4.5)

Fig. 4.5 Body Centered Cubic Structure (BCC)

Following metals are existing with BCC structure; alpha iron, chromium, molybdenum,
tantalum, tungsten, vanadium etc.

4.2.3 Face Centered Cubic (FCC) Crystal Structure

In Face Centered Cubic (FCC) structure instead of one center atom, as in BCC structure,
there are six half-atoms on all 6 flat surfaces of the cubic structure. The amount of involved
in the FCC structure is higher than that of BCC structure. (Fig. 4.6)

35
 Fig. 4.6 Face Centered Cubic Structure (FCC)

Following metals are existing with FCC structure; gamma iron, aluminum, copper, nickel,
lead, silver, gold and platinum.

4.2.4 Hexagonal Close-Packed (HCP) Crystal Structure

As the third common metallic crystal structure the Hexagonal Close-Packed (HCP)
structure has some complicated atomic arrangement. In that structure top and bottom
hexagonal faces of a three-dimensional hexagon consist of six atoms and each plane has
one atom at the center. In addition to that another plane provides three additional atoms to
the unit cell situated between the top and bottom planes (Fig. 4.7). The number of atoms in
this structure will be considered later.

Fig. 4.7 Hexagonal Close-Packed Structure (HCP)

Following metals are existing with HCP structure; beryllium, cadmium, cobalt,
magnesium, alpha titanium, zinc and zirconium.

36
It is important to consider some unique properties of unit cell of above-mentioned crystal
structures. Those are:
 Number of (calculated) atoms per unit cell (n)
 Coordination number (CN); the number of closest neighbors to
which an atom is boned.
 Ratio between length of the cube edge (a) and Atom Radius (R) –
a/R
 Atomic Packing Factor (APF), which is the fraction of the volume
the unit cell actually occupied by the hard spheres (atoms).

The calculation of these cell properties and their values are given in the table 4.1 below.

Table 4.1
Atomic
Number of Atoms in a Coordination Packing
Unit Cell Number Ratio** Factor**
Unit Cell
(a/R)
(n) *(CN) *
(APF)
1/8 atoms x 8 corners = See Fig. 4.8 4/√4 0.52
Simple Cubic
1 6

1/8 atoms x 8 corners + 1 See Fig. 4.9 See Fig. 0.68

Body-Centered Cubic atom in the center = 8 4.10
2 4/√3

1/8 atoms x 8 corners+ 1/2 (calculate) 0.74

Face-Centered Cubic atoms x 6 faces = 12 4/√2
4
1/6 atoms x 6 on top + (calculate) - 0.74
1/6 atoms x 6 on bottom +
1/2 x 2 atoms center face
Hexagonal Close Packed
top & bottom +
3 mid plane atoms interior =
12
6
*Consideration of Coordination Number

37
Fig. 4.8 Coordination Number of SC Structure Fig. 4.9 Coordination Number of
(Each Atom Touches 6 other Atoms) BCC Structure
(Each Atom Touches 8 other atoms)

** Calculation of ratio a/R

For FCC structure: Length of the diagonal of an Area ‘a x a’ = 2a 2

This is equal to 4R (see Fig. 4.10)
Therefore,4R = 2a 2 = 2a
4
Or a 
R 2

Fig. 4.10 Illustration of Atom Radius (R) and Lattice Constant (a)

***Calculation of Atomic Packing Factor

Atomic Packing Factor = Total Volume of Atoms in a Unit Cell

Volume of the Unit Cell

38
For BCC structure:

E.g.:

In the BCC structure APF: Total volume of atoms in the BCC unit cell

= 2. 4/3πR3= 8.373R3------- (1)

R- Radius of a atom

a 4 4R
Also  or a 
R 3 3
4R
Therefore, Volume of the Unit Cell = a 3  ( ) 3 = 12.32 R3 ------- (2)
3
8.373R 3
From (1) and (2) APF = = 0.68
12.32 R 3

Activity 5

(1) Figure out the Coordination Number for FCC and HCP structures.

(2) Calculate a/R value for SC and BCC structures.

(3) Calculate the APF for other SC and FCC structures.

(4) Calculate APF for HCP structure.

4.3 Crystallographic Planes and Directions in Cubic Unit Cells

 During use of metals for engineering applications especially, load bearing

applications the metals and alloys undergo mechanical stresses.
 Therefore, it is very important to understand the behavior of metals and alloys under
different mechanical stresses such as tensile, compressive, torsional, shear etc.
 Under those stresses the metal crystals will be plastically deform (not elastically)
permanently under slip of atom layers relative to each other.
 The slip occurs mainly in specific directions and planes of a given crystal.
 Due to this reason metals and alloys have different properties (also magnetic
properties) in different crystallographic directions.
 In this section we will discuss how to identify those directions and planes.

39
4.3.1 Crystallographic Directions in Cubic Cells
Crystallographic direction of a unit cell of cubic structure is determined by placing a vector
from the point of start to the end point of the direction line. Normally, start point is the
origin of the space lattice but it can be changed if required (Fig. 4.11)

Fig. 4.11 Crystallographic Direction of a Unit Cell

Following are the steps to be taken to determine a direction of a unit cell;

(1) A vector of required length is positioned to the required direction.

(2) The length of the vector projection on each of three axes is measured in unit cell
dimensions.
(3) Those three numbers are made to smallest integer values, known as indices, by
multiplying or dividing by a common factor.
(4) The three indices are enclosed in square brackets [XYZ].

Example1

Fig. 4.12
(1) Vector is OC
(2) Length of vector projection on x-axis = 1 (OA); y-axis = 1 (AB); z-axis = 1 (BC)
(3) Smallest integer value 1,1,1
(4) Direction indices are [111]

40
More examples for different directions are given below;

Fig. 4.13

If the origin is changed you have to determine length of vector projections respectively.

X= -1 , Y= -1 , Z= 0

Fig. 4.14

41
Activity 6

Determine the crystallographic directions given by; (1) OM (2) ON and (3) PQ

Activity 7

Determine the crystallographic directions given by

(i) LM (where OL = LK)

(ii) NP

(iii) QR (where QS = 1/3 OS)

4.3.2 Crystallographic Planes in Cubic Cell

Determination of crystallographic planes is important to identify specific planes where the
slip occurs. This will give the Materials Engineers and designers to predict the deformation
pattern of a particular metal or alloy especially, in the metal forming process.

‘Miller Notation System’ has been proposed by an English Crystallographer (1801 –1880)
to determine a particular plane in a cubic crystal structure. This called as Miller Indices and
defined as ‘reciprocals of the fractional intercept values of an internal plane of a cubic
crystal which makes with the x, y and z axes of the three non-parallel edges of a cubic unit
cell’. Methodology for the determination of Miller’s indices is given below;

(1) Determine the intercepts of the plane along the crystallographic axes, in terms of
unit cell dimensions. If plane is passing through origin, there is a need to construct
a plane parallel to original plane.
(2) Take the values of the reciprocals of these intercept numbers.
(3) Clear fractions to get integer values.
(4) Reduce to set of smallest integers.
(5) The three indices are enclosed in parenthesis, (hkl). A family of planes is
represented by {hkl}.

42
Example 2

Fig. 4.15 Miller Indices of Some Planes in a cubic Unit Cell

Activity 8

Determine the miller indices of the plane shown in the Figure below.

43
Activity 9

The intercept on the x, y and z axes are 1, 3, 2. Find the miller indices.

4.4 Basic Cell Calculations; Volume, Planar and Linear Atomic

Densities and Theoretical Densities of Metals
To determine the mechanical properties, it is also important to calculate the density of
atoms which are lying in a particular crystal plane. The initial slip occurs on a plane where
the atomic density is highest. Therefore, in this section the calculations of volume, planer
and linear atomic densities are illustrated.

(a) Volume Density

Volume density of a unit cell is calculated according to the following equation;

Mass of a Unit Cell

Atomic Density of a Unit Cell   v
Volume a Unit Cell

Example 3

Copper (FCC) has atomic mass of 63.54 g/mol and atomic radius of 0.1278 nm. Calculate
a theoretical value for the density of copper in g/cm3. Avogadro’s number is 6.02x1023
atoms/mol.

Solution:
4𝑅 4 ×0.1278 𝑛𝑚
a = √2 = = 0.361 𝑛𝑚
√2

Volume of unit cell = V = 𝑎3 = (0.361 𝑛𝑚)3 = 4.7 × 10−29 𝑚3

FCC unit cell has 4 atoms.

𝑔
(4 𝑎𝑡𝑜𝑚𝑠)(63.54 ) −6 𝑀𝑔
𝑚𝑜𝑙 10
Mass of unit cell = m = 𝑎𝑡𝑜𝑚𝑠 = 4.22 × 10−28 𝑀𝑔
6.02×1023 𝑔
𝑚𝑜𝑙

𝑚 4.22 × 10−28 𝑀𝑔 𝑀𝑔⁄ 𝑔

𝑃𝑉 = = = 8.98 𝑚3 = 8.98 ⁄𝑐𝑚3
𝑣 4.7 × 10−29 𝑚3

(b) Planar Density

Equiv No. of Atoms whoes Cente rs are Inter sec ted by Se lected Are a
Planar Atomic Density   p
Selected Area

44
 Example 4

Calculate the planer atomic density on the plane (110) of the α-Iron BCC lattice. The lattice
constant (a) is 0.287 nm.

Solution:

1
Equivalent number of atoms= (4 × 4) + 1 = 2 atoms
Area of 110 plane = √2 𝑎 × 𝑎 = √2𝑎2

2 17.2 𝑎𝑡𝑜𝑚𝑠 1.72 × 1013

𝑃𝑝 = = = atoms
√2(0.287)2 𝑛𝑚2 𝑚𝑚2

(c) Linear Density

No. of Ato m. Diam.s Inter sec ted by Sel ected Leng th of Line in Direct ion of Int erest
Linear Atom. Density   l
Selected Length of the Line

Example 5

Calculate the linear atomic density of FCC Copper crystal lattice in the [1 1 0] direction.
Copper has the lattice constant of 0.361 nm.

Solution:

Therefore, it intersects ½ + ½ + 1 = 2 atomic diameters.

Length of line = √2 × 0.361 𝑛𝑚

2 𝑎𝑡𝑜𝑚𝑠 3.92 𝑎𝑡𝑜𝑚𝑠 3.92 ×106 𝑎𝑡𝑜𝑚𝑠
𝑃𝑙 = = =
√2×0.361 𝑛𝑚 𝑛𝑚 𝑚𝑚

4.2.7 Non-Crystalline (Amorphous) Materials

As discussed earlier a liquid material can solidify to form a crystalline or non-crystalline

(amorphous) solid. Whether the formed solid is crystalline or amorphous depends on many
factors. Generally, materials are having a tendency to achieve a crystalline state since in
that stage they are more stable and have lowest internal energy. However, if in a particular
material internal energy as amorphous state is lower than that of crystalline state this
material will solidify to an amorphous material. Other main factors which influence the
formation of crystallization are;

45
  Heat of fusion (h) - directly proportional
 Activation enthalpy (Hd) - indirectly proportional
 Viscosity of the liquid - indirectly proportional
 Therefore, it can be concluded that the materials having high heat of fusion and low
viscosity have the tendency to crystallize on cooling.
 Generally, the metals are having high heat of fusion, in the range of 10 -15 kJmol-1
and low viscosity, in the range of 0.1 - 1 Pa s (1 –10 poises) and both these factors
promote crystallization on cooling.

Furthermore, rapidly cooling through the freezing temperature favors the formation of a
non-crystalline solid, because little time is allowed for the formation of ordered structures.
Metals normally form crystalline solids, but some ceramic materials are crystalline,
whereas others, the inorganic glasses, are amorphous. Also, it is possible to make
crystalline glasses (Pyrex or Pyroceram), which give high strength, toughness, high thermal
shock resistance. Those glasses are used as safety glasses especially as windscreens of
motor vehicles.

Polymers may be completely non-crystalline and semi-crystalline consisting of varying

degrees of crystallinity.

In contrast to that under very high cooling rate (approx. 106 ˚C/Sec – normal industrial
cooling rate is about 1 ˚C/Sec) even metals can be solidified to form amorphous structure
and they are called as ‘Amorphous Metals, Glassy Metals or Metallic Glasses. Those
metals are showing extra ordinary properties such as very high strength, high hardness,
high corrosion resistance and low magnetic hysteresis.

Example 6

Determine the relationship between the atomic radius (r) and the lattice parameter (𝐚𝟎 ) in
SC, BCC, and FCC structures when one atom is located at each lattice point.

Solution:
If we refer Fig. 4.4, we find that atoms touch along the edge of the cube in an SC structure.
The comer atoms are centered on the corners of the cube, so:

𝒂𝟎 = 2r

In a BCC structure (Fig. 4.5), atoms touch along the body diagonal, which is √3a0in length.
There are two atomic radii from the center atom and one atomic radius from each of the
corner atoms on the body diagonal, so

𝟒𝒓
𝒂𝟎 = √𝟑

46
Example 7

Determine the theoretical density of BCC iron, which has a lattice parameter of 0.2866 nm.
Atomic mass of iron is 55.847 g/mol.

Solution:

For BCC cell,

Atoms/cell = 2

𝑎0 = 0.2866 nm = 2.866 × 10−8 cm

Atomic mass of iron = 55.847 g/mol

Volume of unit cell = 𝑎0 3 = (2.866 × 10−8 𝑐𝑚)3 = 23.54 × 10−24 𝑐𝑚3 /𝑐𝑒𝑙𝑙
Avogadro number 𝑁𝐴 = 6.02 × 1023 𝑎𝑡𝑜𝑚𝑠/𝑚𝑜𝑙

(𝑛𝑢𝑚𝑏𝑒𝑟𝑜𝑓𝑎𝑡𝑜𝑚𝑠/𝑐𝑒𝑙𝑙) (𝑎𝑡𝑜𝑚𝑖𝑐𝑚𝑎𝑠𝑠𝑜𝑓𝑖𝑟𝑜𝑛)
Density ρ =
(𝑣𝑜𝑙𝑢𝑚𝑒𝑜𝑓𝑢𝑛𝑖𝑡𝑐𝑒𝑙𝑙)(𝐴𝑣𝑜𝑔𝑎𝑑𝑟𝑜′ 𝑠𝑛𝑢𝑚𝑏𝑒𝑟)

2×55.847
ρ = (23.54×10−24)(6.02×1023 = 7.882 g/𝑐𝑚3
)

The measured density is 7.870 gm/𝑐𝑚3 . The slight discrepancy between the theoretical and
measured densities is a consequence of defects in the material. As mentioned before, the
term “defects” in this context means imperfections with regard to the atomic arrangement.

Summary
In this session we discussed about the fundamental concepts of atomic arrangements in
crystalline and nom-crystalline solids. The atoms are positioned in orderly and repeated
patterns that are in contrast to the random and disordered atomic distribution found in non-
crystalline materials. The unit cells in crystalline structures are specified as smallest unit in
a crystalline structure. In metallic crystal structures there are 3 most common
configurations namely; Face-centered cubic (FCC), Body-centered cubic (BCC) and
hexagonal close-packed which has a unit cell of hexagonal symmetry. Also, we discussed
how to calculate the cell properties, coordination numbers, atomic packing factors and
densities such as volume, planar and linear densities and theoretical densities of metals.
Finally, the atomic arrangements of non-crystalline solid materials were described in which
the effect of the absence of long range regular arrangement of atoms or ions on the
properties was elaborated. The term amorphous is also used to describe these non-
crystalline materials.

47
Learning Outcomes

At the end of this session the students will be able to

• Explain fundamental concepts of atomic arrangements in crystalline and nom-

crystalline solids.

• Describe 3 most common configurations of atoms in metallic crystal structures.

• Calculate all cell properties in crystalline materials.

• Explain the difference between properties of crystalline and non-crystalline materials.

48
Session 05
Crystalline Imperfections

Contents
Introduction
5.1 Properties of ideal materials
5.2 Crystalline imperfections; point, line, surface, and volume imperfections
5.3 Metallographic investigations of metals
Summary
Learning Outcomes

Introduction
So far, we have discussed only the theoretical aspects of formation of crystal structures of
metals. In reality, the formation of crystal structure is not perfect and varies from ideal
conditions. There may be many irregularities in the structure and those can be named as
‘imperfections’. These imperfections can also be named as ‘Defects’. However, the defects
in crystal structures are not necessarily deleterious with respect to the quality of the
material. Some defects, for example, dislocations (will be described later) can support
strengthening of steel. Therefore, it is more appropriate to name them as imperfections than
‘defects’ but in some literature the word ‘defect’ is also used.

The imperfections in crystals can either positively or negatively affect the physical and
mechanical properties of a material. In this session we will discuss the properties of an
‘Ideal’ material and how the imperfections of crystals affect the properties of a ‘Real’
material.

5.1 Properties of Ideal Materials

In an ideal crystal the atoms of a metal are perfectly arranged at defined locations. We
assume that in this condition all atoms are similar and no impurity atoms are present. Under
mechanical stresses the whole metal will then deform elastically and if the stresses are high
enough then plastically deformed. During plastic deformation the metals will deform due
to physical moment of an atom layer on another under resolved shear stress on that
particular plane.

By theoretical calculations it is possible to prove that the Shear Module of that material (G)
   Shear stress
where, G 
   Shear angle

49
In ideal materials (metals) the shear module is in the range of 20 – 150GPa and therefore,
the shear strength required for plastic deformation is around 3 – 30GPa. However,
according to experimental results shear stress required for plastic deformation of a real
material is around 0.5 – 15MPa and it is much lower than that of an ideal material. The
main reason for this discrepancy is the presence of imperfections in a real material.

Table 5.1: Critical Resolved Shear Stress (CRSS*) Value of Ideal and Real
Metallic Materials

CRSS  CRSS 
Crystal -2
Metal [MNm ] [MNm-2 ]
Structure
(Ideal) (Real)
Copper FCC 7300 0.50
Aluminium FCC 4100 0.75
Gold FCC 4300 0.50
Nickel FCC 11600 5.00
Silver FCC 4300 0.50
Iron BCC 11600 15.00
Zinc HCP 5500 0.30
* CRSS – Critical Resolved Shear Stress (needed to initiate plastic
deformation)
Some physical properties of metals are not influenced by crystal imperfections and
they are named as structure intensive properties but there are some mechanical
properties which are named as structure sensitive properties and significantly
influenced by crystal imperfections.

 The ideal crystal (assumed the crystal lattice is perfect) was used to understand the
structure intensive properties like;

- Elastic constant
- Melting point
- Thermal expansion coefficient
- Specific heat
- Density.
Generally, these properties are not significantly influenced by crystal imperfections or
defects.

E.g.: If 0.01% of atoms were missing from atomic sites of a crystal, the density will be
lower by the same amount (0.01%), which is small enough to be ignored for practical
applications

 The real crystal contains imperfections, which greatly affects the structure
sensitive properties like;

- Electrical conductivity
- Semi conduction
- Yield stress
- Fracture strength
- Creep strength

50
These properties crucially depend on the crystal imperfections or defects.

E.g. Few parts per million (ppm) of aluminium impurities change the characteristic of
silicon based semiconductors drastically or a few amounts of dislocations can change the
mechanical strength of an alloy or metal significantly.

5.2 Crystalline Imperfections

According to their size, shape and geometry the crystal imperfections are categorized in
to 4 groups (Table 5.2);

Table 5.2: Types of Imperfections in Crystals

Point imperfections 0 D - (zero dimensional) e.g. Vacancies, Impurity atoms

(Point defects)
Line imperfections 1 D - (single dimensional) e.g. Dislocations
(Line Defects)
Surface imperfections 2 D - (two dimensional) e.g. Interfacial defects, Grain
(Surface defects) boundaries
Volume imperfections 3 D - (three dimensional) e.g. Voids, Cracks, Inclusions
(Bulk defects)

5.2.1 Point Imperfections (Point Defects)

Point imperfections (Point Defects) exist in 4 types and they are shown in Fig. 5.1.
 Vacancy
 Substitutional Impurity (foreign) Atom
 Interstitial Impurity (foreign) Atom
 Self-Interstitial Atom

Fig.5.1 Point Defects in a Crystal

51
(1) Vacancy:
 A vacancy exists when an atom or ion is missing from its regular site in the crystal
structure.

 Normally those vacancies are created during solidification and growth of crystals
of a metal from its liquid state or if a metal is subjected to radiation.

 Any crystalline metal can have certain amount of vacancies proportional to the
temperature at which the metal is used.

 In practical applications, vacancies are playing a vital role by facilitating the

movement of atoms or ion in a solid. As examples; migration of atoms during
diffusion, creating vacancies to tune the electrical properties of ceramics in sensors.

 The amount of vacancies in a crystal increases with the temperature exponentially

and can be calculated using the following equation.

NV = N exp (-QV/RT)

Where Nv- Number of vacancies per cm3

N -Number of atoms per cm3
QV- Energy required to produce one mole of vacancies [J. Mol-1]
R- Gas constant: 8.31[J.mol-1. K-1]
T - Temperature [K]

Example 1: The Effect of temperature on the vacancy concentrations.

Calculate the concentration of vacancies in copper at 25oC. What temperature will be

needed to heat treat copper such that the concentration of vacancies produced will be 1000
times more than the equilibrium concentration of vacancies at room temperature? Assume
that 20,000 cal/mole are required to produce a mole of vacancies in copper.

Solution:

The lattice parameter of FCC copper is 0.36151nm. The basis is 1, therefore, the number
of copper atoms, or lattice points, per cm3 is:

4 𝑎𝑡𝑜𝑚𝑠⁄𝑐𝑒𝑙𝑙
𝑛= = 8.47 × 1022 𝑐𝑜𝑝𝑝𝑒𝑟 𝑎𝑡𝑜𝑚𝑠 ⁄𝑐𝑚3
(3.6151 × 10−8 𝑐𝑚)3

At 25oC; 𝑇 = 25 + 273 = 298𝐾;

−𝑄𝑣
𝑛𝑣 = 𝑛 𝑒𝑥𝑝 ( )
𝑅𝑇

52
 𝑐𝑎𝑙
𝑎𝑡𝑜𝑚𝑠 −20000
𝑚𝑜𝑙
= (8.47 × 1022 ) . 𝑒𝑥𝑝 ( 𝑐𝑎𝑙 )
𝑐𝑚3 1.987 𝑚𝑜𝑙.𝐾 × 298 𝐾
= 1.815 × 1011 𝑣𝑎𝑐𝑎𝑛𝑐𝑖𝑒𝑠⁄𝑐𝑚3

We wish to find a heat treatment temperature that will lead to a concentration of vacancies
which is 1000 times higher than this number, or

𝑛𝑣 = 1.815 × 1011 𝑣𝑎𝑐𝑎𝑛𝑐𝑖𝑒𝑠⁄𝑐𝑚3 .

We could do this by heating the copper to a temperature at which this number of

vacancies forms:
−𝑄𝑣
𝑛𝑣 = 1.815 × 1011 = 𝑛 exp ( )
𝑅𝑇

= (8.47 × 1022 ). exp(20000⁄(1.987 × 𝑇))

−20000 1.815 × 1011
𝑒𝑥𝑝 ( )= = 0.214 × 10−11
1.987 × 𝑇 8.47 × 1022
−20000
= ln(0.214 × 10−11 ) = −26.87
1.987𝑇
20000
𝑇= = 375𝐾 = 102℃
(1.987). (26.87)

Table 5.3: Change of Approximate Fraction of Vacant Site of a Metal Crystal with
Temperature

Temperature [ 0C] Approx. Fraction of Vacant Sites

500 1 x 10-10

1000 1 x 10-5

1500 1 x 10-4

2000 1 x 10-3

(2) Substitutional Impurity (foreign) Atoms

Typically, impurity or foreign atoms from raw materials which has been used to produce a
metal can be embedded in a pure refined metal after solidification. Those atoms can
substitute the atoms in the pure metal. This is considered as negative point defect when
those impurity atoms have negative effect on the properties of the pure metal. On the other
hand, this phenomenon can be taken as positive if those foreign atoms can enhance the
properties of the parent metal (Zn and Sn in Copper).

53
(3) Interstitial Impurity(foreign) Atoms

If the foreign atom is smaller compared to the atoms in the pure metal, they can be dissolved
in the lattice structure at interstitial sites (Carbon in iron in Steel).

(4) Self-Interstitial Atoms

In some instances, an atom in a crystal can occupy an interstitial site between the parent
atoms in the crystal. Those atoms are called as self-interstitial atoms. This phenomenon is
rare in metals but as an exceptional case it appears in Si where those interstitials play an
important role in diffusion and micro defect formation in semiconductors.

There are mainly two types of defects created due to self-diffusion of atom in ionic crystals;

(a) Frenkel Defects

Where a cation is displaced from a regular site in an ionic crystal to an interstitial site and
Frankel point defects do not affect the overall electrical neutrality of the crystal.

(b) Schottky Defects

Where a pair of cation and anion can be missing from an ionic crystal without changing the
electrical neutrality of an ionic crystal

5.2.2 Line Imperfections (Defects)

‘Dislocation’ is the main imperfection which comes under line imperfections. The word
‘Dislocation’ also comes in medical field when a bone is fractured and dislocated. If in a
crystalline solid the regular order of atoms along a line is abruptly changed then a
dislocation is present (Fig. 5.2).

Abrupt Change
(One layer of Atoms
missing from this place)

(a) (b)

Fig.5.2 (a) Abrupt Change of an Atomic Layer in a Crystal (Dislocation)

(b) Dislocation of Human Bones

As illustrated in Fig.5.3 an atomic layer coming from top terminates at a point and the line
passes through this point perpendicular to the plane of this paper is called as “Dislocation
Line’ (see Fig.5.3).

54
 Fig.5.3 Abrupt Change of an Atomic Layer in a Crystal and Dislocation line
(Edge Dislocation)

This type of dislocation is named as ‘Edge Dislocation’ and denoted by a symbol ‘’
(a positive edge dislocation). If the missing layer is coming from bottom the dislocation is
denoted by the symbol ‘Τ’ (a negative edge dislocation).

Another type of dislocation is also present in crystals and it is named as ‘Screw

Dislocations’. A screw dislocation is formed when a crystal is under applied shear stress
to a region that has been separated by a vertical plane (see Fig. 5.4).

Shear Stress

Fig.5.4 Screw Dislocation in a Crystal Structure

It is also possible to have ‘Mixed Dislocations’ ‘in a crystal. Those mixed dislocations are
a combination of edge and screw dislocations (see Fig.5.5).

55
 Fig.5.5 Mixed Dislocation in a crystal Structure
(Mixed Dislocation)

Depending on in which plane of a crystal you consider the same dislocation has two
different characters. i.e. as illustrated in Fig.5.5 on the left plane the dislocation is
considered as a screw dislocation and on the front plane the same dislocation can be
considered as a screw dislocation.

Since dislocations are very important in calculating the amount of deformation in a crystal
‘the amount and direction of displacement of atoms around the dislocation’ is called as
‘Burgers Vector - b’ as illustrated in Fig.5.6.

Shear Stress

Shear Stress
Fig.5.6 Burger’s Vector (b) in Mixed Dislocation

 In edge dislocations the Burgers Vector is perpendicular to the Dislocation line.

 In screw dislocations, Burgers Vector is parallel to the Dislocation line.

Now it is important to know how these line imperfections are created and how they
influence the properties of materials. Normally, the dislocations are lattice distortions and
they are created;

56
  During Solidification of crystals
 During plastic deformation at low temperatures
(Cold forming – less than 0.3 Tmelting) or
 Due to thermal stresses developed during rapid cooling.

Since the lattice disorders create non-equilibrium status, this area absorbs strain energy and
becomes relatively unstable. As an example, in a positive edge dislocation a compressive
stress filed exists above dislocation line and a tensile stress field exists below dislocation
line (Fig.5.7).

Fig.5.7 Strain Field around Edge Dislocation

During plastic deformation the dislocations move to a particular direction and support the
slip of a layer of atoms on another. Once the dislocations come to the surface of the crystal
they give macroscopic steps on the surface and appear as roughened surface called as
Lüders bands. These bands are visible on the surface of the metals during tensile testing.

Dislocations play a vital role in strength and ductility of a metal;

 Normally, if the strength of a metal is increased then the ductility of that metal
is reduced.
 To increase the strength the plastic deformation of the metal should be
reduced/restricted.
 Plastic deformation can be restricted by restricting the slip of atom layers.
 Slip can be reduced by restricting the moment of dislocations.
This can be done, for an example, by adding alloying elements to increase
atomic disorder (dislocations cannot be moved easily if there is disorder of the
atoms in the crystal).
This phenomenon is one of the ‘Strengthening Mechanisms’ of metals.(Other
strengthening mechanisms will be discussed under Level 5 Materials
Engineering course).
 In contrast to the above-mentioned action if the strength of a metal has to be
reduced (increase in ductility- easy to machine) then the density of dislocations
should be increased as well as the free movement of the dislocations in the
grain/crystal should be assured.

57
  During Cold Working (metal working at room or relatively low temperature)
the density of dislocations is increased but free movement of dislocations is
restricted through deformed grains (grain boundaries). This makes the metal
strengthen.

Fig.5.8 Dislocations in Titanium Alloy

5.2.3 Surface Imperfections

The surface imperfections are categorized into;

(1) Outer surface of a material:

 The atoms in the outer surface of a material are bonded to other atoms
only on one side.
 Therefore, they have a lower number of neighboring atoms than that of
atoms inside the material.
 Due to this reason those atoms are energetically unstable and rich in
energy (Surface Energy) and willing to adsorb foreign atoms, molecules or
any other substances.
 This imperfection can be considered as positive (better wetting of the
surface by coatings) or as negative (adsorption of foreign atoms, ions,
molecules even dust particle to the surface)

58
(2) Grain boundaries:

(Ordered Atomic
Structures)

Grain Boundary
(Disordered Atomic
Structure)

(a) (b
)

Fig.5.9 Grains and Grain Boundaries (a) Schematic Illustration (b) Real Micrograph

 Grain boundaries (Fig.5.9) separate grains in a metallic structure. Normally,

they have a disordered structure and can be considered as an imperfection.
 Due to the disordered structure the moment of dislocations across the grain
boundary is restricted. As discussed earlier this will increase the strength of
a metal.
 There are two types of grain boundaries, viz‘ Small Angle Grain
Boundaries’ and ‘Large Angle Grain
 That means with the increase of grain boundaries (decrease in grain size)
the strength will increase (another strengthening mechanism for metals).
 In addition to that low melting substances (impurities) in the grain boundary
will make the metal prone to grain boundary slipping at elevated
temperatures (creep).
 Also grain boundaries make the metal prone to Grain Boundary Corrosion.
 Weak grain boundaries promote Intergranular Crack Propagation.

(3) Twin boundaries:

 Twin boundaries are formed when a metal is plastically deformed
(Deformation Twins).
 They also form during Annealing.
(Annealing Twins).

59
 Twin Grain Boundaries

Fig.5.10 Twin Boundaries in Brass

(4) Miscellaneous Surface Imperfections

1. Stacking Faults; occur mainly in FCC crystals and denoted as error in stacking
arrangement of atomic structure of the crystal.
2. Phase Boundaries; These surface imperfections exist in multi-phase materials
on each side of the grain Boundary.

5.2.4 Volume Imperfections (Bulk Defects)

 Volume imperfections are three-dimensional
 Form when many micro level defects (e.g. point defects) join to make a macro level
pore or void in the crystal.
 Therefore, volume imperfections are considered as macro imperfections
 They have the size varying in a range from nanometer to centimeters.
 Inclusions, clusters of impurities, large volumetric chemical or structural in
homogeneities also can be considered as volume imperfections.
 Volume imperfections have significant effect on the properties of a material in
performance and behavior.
 Fig.5.11 shows a void in a metal.

Fig.5.11 Void in a metal

60
The other defects, such as cracks, voids, segregations, structural & chemical
inhomogeneity are in macro level and they can negatively affect the mechanical properties
of the metal significantly.

5.3 Metallographic Investigations of Metals

As explained earlier, the properties of materials depend on the structure and any disorder
or defects in the structure can affect the mechanical properties. The defects are classified
into ‘micro’ (atomic level) and ‘macro’ types of defects. Certainly, the macro level defects
can be easily observed even by a naked eye. Sometimes you may need a magnifying glass
with a magnification approximately 10 times. As an example, a crack on the surface of a
metal can be observed by a naked eye and to observe a fine crack a magnifying glass may
be needed.

In case of a ‘micro level’ defect we need a ‘Microscope’ and for metallurgical observation
of micro defect we use a ‘Metallurgical Microscopes’. With these types of microscope, it
is possible to observe grains, grain boundaries, different phases etc. The photos made using
these microscopes are called as ‘Micrographs’ or ‘Photomicrographs’.

Normally, for metallurgical observation following microscopes are used;

 Optical Microscopes (reflecting type) which are illuminated by normal or

polarized light.
 Scanning Electron Microscopes (SEM) which are used for very high
magnification (up to x 50,000), where an electron beam is used to scan the metal
surface and the picture will be given on a computer screen with a great depth of
filed.
 Transmission Electron Microscope (TEM), where the electron beam passes
through very thin metallic sample and gives the internal structure of the metal.
 Atomic Force Microscopes (AFM) which have very high magnifications (up to
x100,000,000) and mainly used in Nano-technological observations.

The structure you observe under a microscope is called as ‘Microstructure’. Observation

of the microstructure of a metal is vital work of a ‘Metallurgist’ and with that you can
observe;
 Grains
 Grain Boundaries and their thickness
 Measurement of grains size (according to ASTM standards) ,
 Micro cracks with size measurements
 Macro and micro voids
 Structural inhomogeneity
 Different phases etc.

Most common, simple and economical way of observation of microstructure is done by

optical microscopes. The function of an optical microscope is as follows;

 Metal samples need to be well polished (up at least 3-6micron level)

 They should be cleaned and have a well levelled surface (less waviness)
 To reveal the grains, grain boundaries and phases, different types of chemical
etchants have to be used (e.g. Nital – 2% nitric acid in ethyl alcohol)

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  Incident light can be from a normal or halogen light source
 Magnified by two types of lenses i. e. Objective lenses and Eyepiece lenses
 The observation can be done by a person or projected on a computer screen.
 Software is available for measurements (grain size, crack length etc.

Some microstructures of different types of steel and brass are given in Fig.5.12.

Low Carbon Steel (0.12% C) Medium Carbon Steel (0.40% C)

https://en.wikipedia.org/wiki/Brass

High Carbon Steel (0.85% C) Brass (65% Cu; 35% Zinc) Mag. X400

Fig.5.12 Microstructures of Steel and Brass

Summary
In this session, we have concentrated on the crystalline materials and the difference
between perfect (ideal) and real crystalline materials. In that context we discussed about
the structure sensitive and structure intensive properties of materials. Subsequently, we
focused on the real (imperfect) materials and their ‘defects’ which will influence the
properties of materials positively and negatively. There are 4 types of ‘imperfections’ in
solid crystalline materials and i.e. point, line, area and volume defects. Mainly the first 3
defects are found in micro level and the last one in macro level. Under point defects we
understand vacancies, impurities etc., under line defects ‘dislocations’ and under area
defects mainly mismatch at the interface between grain and grain boundaries. Macro
defects are normally categorized as void, cracks and relatively large inclusions.

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Learning Outcomes

At the end of this session the students will be able to;

• describe the difference between ideal and real crystals.

• describe Point, line, area and volume defects in crystalline materials

• explain the effect of crystalline imperfections on the properties of crystalline materials

• learn how to critically observe microstructure using different types of microscopes.

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Session 6
Diffusion in Solids

Contents
Introduction
6.1 Diffusion in Solids
6.2 Diffusion Mechanisms
6.3 Fick's Laws of Diffusion; Steady-state and Non-steady-state Diffusion
6.4 Practical Applications of Diffusion
Summary
Learning Outcomes

Introduction
Diffusion refers to the movement of atoms or molecules in solids (or liquids or gases). This
process can be used to change the microstructure of a solid to achieve the desired
properties. As examples carburization of steel (diffusion of carbon atoms in to steel),
oxidation of metals (diffusion of oxygen into a metal structure), impurity control in
semiconductors (doping of boron in silicon) etc. are mainly controlled by diffusion process.

Diffusion can be defined as the mass flow process by which atoms (or molecules) change
their positions relative to their neighbors in a given phase under the influence of thermal
energy and gradient (concentration, electrical, magnetic. or stress gradient). Here we
discuss only mass flow under concentration gradient.

6.1 Diffusion in Solids

As mentioned above diffusion in solid is used in many industrial applications. Normally,
diffusion in solids is slower than that of in liquid and air. If an atom or a molecule diffuses
through a solid, the ‘driving power’ needs to initiate and continue the process is higher than
that of in a liquid. This driving power is named in thermodynamic as ‘Activation Energy’.
In the next paragraph, we are going to discuss the term ‘Activation Energy’.

6.1.1 Activation Energy of a Process

The quantity of energy, which is necessary to initiate a process, is termed as the activation
energy for that process. Fig. 6.1 shows the mechanical analogy used to explain the
activation energy.

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 Fig. 6.1 Stability of a Tetragonal Object

The tetragonal prism shown in Fig.6.1 has two stable positions A and C. The potential
energy of the prism at position C is less than the potential energy at position A. Since the
centroid is at a lower position at C. But to translate the prism from position A to position
C (by pivoting about point O), an additional energy equal to mgh (m is the mass of the
prism) should be given to the prism since the path of the centroid is GG’G’’. This quantity
of energy mgh could be termed as the activation energy for this process.

Fig.6.1 shows the concept of activation energy for a solid-state reaction in a material
system. For these reactions to proceed from the unreacted to the reacted state, the reacting
atoms must have sufficient energy to overcome the activation energy barrier. This
activation energy is indicated as E* in the diagram. The amount of activation energy can
be reduced by introducing a catalyst.

Fig.6.2 Thermo- Dynamical Aspect of a Process

At any temperature only, a fraction of the atoms (or molecules) in system will have
sufficient energy to reach the activation energy level E* (Fig. 6.2). As the temperature
increases more and more atoms will attain this energy level. Boltzmann studied this effect
for gas molecules. According to Boltzmann, the fraction of atoms (or molecules) in a
system having energies greater than E* can be written as

65
 n
 C exp(  E * kT )
N

n–Number of atoms (or molecules) with an energy greater than E*

N – Total number of atoms (or molecules) present
K – Boltzmann’s constant = 8.62  10 5 eV / K
T – Temperature K
C – Constant

When the activation energy is given in molar units, e.g., joules per mole, the Gas constant
(8.314kJ/k mol K) is used instead Boltzmann constant.

6.1.2 Rate of Thermally Activated Processes

Based on Boltzmann’s expression, Arrhenius developed an equation governing the rate of
reaction of thermally activated processes.
 Q 
reaction rate    A exp   
 RT 
where Q (= E*) is the activation energy for a single molecule, R is the Gas Constant, T is
the temperature (K) and A is a constant. This may be rewritten as;

 Q  Q 1
  Aexp    or ln = –   ln   + ln A
 RT  R T 
y= mx+C

where Q is the activation energy joules per mole, and R is the universal gas constant
(8.314kJ/k mol K).

The rates of many solid-state reactions of particular interest to Materials Engineers obey
the Arrhenius rate law, and this equation is often used to analyze experimental solid-state
rate data.

E.g.: The following table gives experimentally determined values for a particular process.

66
Table 6.1: Rate of Solid State Reaction Depending on Temperature

Temperature [0C] Rate [mm/s]

175 0.0000113
250 0.0000593
355 0.0003100
500 0.0014600

Activity 1

Show graphically that these data are consistent with the Arrhenius law and calculate the
activation energy for the process. Also determine the temperature at which the process rate
will be 1.5 X 10-2 mm/s.

As defined earlier, for a diffusion process to be initiated it is necessary to have an activation

of the atom or molecules and if the diffusion is thermally activated then the rate of the
diffusion process obeys Arrhenius equation. Now we discuss the material aspects of solid
state diffusion.

6.2 Diffusion Mechanisms

There are two main mechanisms of solid state diffusion of atoms in a crystalline material.

1. Vacancy or Substitutional mechanism

2. Interstitial mechanism

(1) Vacancy or Substitutional mechanism

 Atoms can move in crystal lattice from one atomic site to another in the same lattice
using the vacancies present as shown in Fig.6.3.

 Self-diffusion and substitutional diffusion can occur by this mechanism.

 In this case the diffusing atoms should have sufficient activation energy to do so.

67
  As the temperature rises not only there is an increase in the kinetic energy
(vibration) of atoms but also there is an increase in the number of vacancies in the
lattice.

 Thus, the diffusion rate will increase exponentially according to Arrhenius law.

Fig.6.3 Vacancy Diffusion Mechanism in Solids

Fig.6.4 shows the activation energy needed for an atom diffusing by vacancy mechanism.
The moving atom needs to go through a vertical narrow gap between closely bonded parent
atoms.

Fig.6.4 Activation Energy (qm) Required for the Vacancy Diffusion

(2) Interstitial mechanism

 Interstitial diffusion occurs when atoms move from one interstitial site to another
neighboring interstitial site.

 This occurs without permanently displacing any of the atoms in the parent metal
lattice (Fig.6.5).

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  For the interstitial mechanism to be operative the size of the diffusing atoms must
be relatively small compared to parent atoms.

 The energy needed for this action is less than that of substitutional mechanism.

 For example, carbon atoms can diffuse interstitially in iron (steel).

Fig.6.5 Interstitial Diffusion of a Foreign Atom in a Solid

6.3 Fick’s Laws of Diffusion

The number of atoms diffusing into a (or through a) solid depends mainly on three factors;
1. The concentration difference at the beginning of the diffusion process

2. The activation energy of diffusing atoms (e.g. temperature of the system - T)

3. Time elapsed (t)

In a practical application such as during the doping of boron in silicon to make a p-type
semiconductor, it is essential to calculate the exact amount of boron atoms diffused into
silicon crystal. Therefore, a mathematical modeling is needed for exact calculations. These
calculations are based on Fick’s Laws of Diffusion (Adolf Eugen Fick – German
Physiologist – 1829-1901).

Before we derive equations for diffusion we must define some parameters which will be
used for the derivation.

Hydrogen atoms can diffuse through a thin foil of palladium. If we consider a unidirectional
flow of hydrogen atoms through palladium foil, then the concentration of the right-hand
side of the foil will increase (Fig.6.6).

69
 Fig.6.6 Flow of Hydrogen Atoms through a thin Foil of Palladium

Number of atoms passing through unit area per unit time is defined as FLUX.

If the number of atoms passing through an area ‘A’ is dn for a time period of dt
then the flux (J) is;

1 dn
J . ------------------------ (1)
A dt

Now measure the concentration of hydrogen atoms on the right-hand side from distances
x1 and x2 then;

Reduction in
Concentration

Fig.6.7 Reduction of Concentration with the Distance

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 • Net flow of the atoms is from higher concentration to lower concentration.

• Diffusion tends to establish an equilibrium.

• After certain time(t) the concentration gradient is C2 – C1/X2 – X1 = dc/dx

• This action is controlled by flux (J)

dc
Therefore, J  or
dx
dc
Then J   D. --------------------------- (2)
dx
Where D = Constant
1 dn dc
From eqn. 1 and 2 .   D.
A dt dx

Therefore,
dn   D.A dc (Fick’s 1st Law of Diffusion)
dt dx
The negative sign indicates that the concentration gradient is negative with respect to the
direction of atom flow.
Where;

dn
- Number of moles of hydrogen atoms crossing per unit time across a sectional plane
dt
with an area of ‘A’ perpendicular to the diffusion direction ‘x’.

D - Diffusion Coefficient (or diffusivity)

Diffusion coefficient depends on the nature of the diffusing atoms and the temperature.

D = D0.e-Q/RT
where;
D0 - Diffusion constant
Q - Activation energy
R - Gas constant
T - Temperature (K)

• Diffusion coefficient depends on temperature.

• D0 is a constant for a specific diffusion system of two elements (Fig.6.8).

• Diffusion also depends on crystal structure and polymorphic (more than one form
of crystal structure) transformations.

71
Fig.6.8 Dependency of Diffusion Coefficient with Temperature and Diffusing Elements Pair

Table 6.2 D0 and Q Values for Selected Diffusion Couples

Diffusion Process D0 x10-4 [m2 s-1] Q [kJ mol-1]

Cu in Cu 0.20 196

Zn in Zn 0.15 94

Al in Al 1.98 143

Fe in Fe () 118 281

Ge in Ge 9.3 288

Si in Si 5400 477

W in W 43 640

C in graphite 7 681

H in Fe 0.001 13

N in Fe 0.005 75

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 C in Fe () 0.008 83

C in Fe () 0.7 157

V in Fe 3.9 244

Mn in Fe 4.0 305

Ni in Fe 2.6 295

Zn in Fe 0.73 170

Ni in Cu 2.0 230

Cu in Al 0.25 121

Fick’s first law can be applied to flow of atoms under steady state conditions where the
flux is does NOT depend on time. In most real practical cases the diffusion takes place
under non-steady state conditions. In this condition, the number of atoms passing through
a unit area perpendicular to a given direction varies with time.

Now we will try to find a mathematical solution for diffusion under non-steady state
conditions.

Consider two planes X1 and X2 perpendicular to the direction of flow of atoms in a solid.
The distance between the planes is dx (Fig. 6.9).

Fig.6.9 Change of Flux with Time in Non-Steady State Diffusion

The Accumulation of atoms in the incremental volume.  J out  J in

J - Flux

73
Change in concentration at a point P in time t

dc J out  J in

dt dx
dc dJ 
 Since J in  J out
dt dx
 dc 
d  D. 
 
dx 
dx

dc d 2c
Therefore,  D. 2
dt dx
Since ‘c’ depends on ‘x’ and ‘t’

c  2c
=D (Fick’s 2nd Law of Diffusion)
t x 2

Solution to Fick’s second law of diffusion:

The solution for the above equation in general form:
C(x,t) = A – B erf(x/2 Dt )
Where, A and B - Constants and determined by initial and Boundary conditions
erf(x/2 Dt ) - Error function.
Also, it can be shown that erf () = 1
e.g. if value of x/2 Dt =  then erf(x/2 Dt ) = 1
erf (-) = -1
erf (0) = 0
erf (- x/2 Dt ) = - erf( x/2 Dt )

The other values of error function are given in Table 6.3.

Table 6.3: The Error Function Values

z erf(z) Z erf(z) z erf(z) z erf(z)

0.000 0.0000 0.40 0.4284 0.85 0.7707 1.6 0.9763
0.025 0.0282 0.45 0.4755 0.90 0.7970 1.7 0.9838
0.05 0.0564 0.50 0.5205 0.95 0.8209 1.8 0.9891
0.10 0.1125 0.55 0.5633 1.0 0.8427 1.9 0.9928
0.15 0.1680 0.60 0.6039 1.1 0.8802 2.0 0.9953
0.20 0.2227 0.65 0.6420 1.2 0.9103 2.2 0.9981
0.25 0.2763 0.70 0.6778 1.3 0.9340 2.4 0.9993
0.30 0.3268 0.75 0.7112 1.4 0.9523 2.6 0.9998
0.35 0.3794 0.80 0.7421 1.5 0.9661 2.8 0.9999
Experimental verification of Fick’s second law:

74
Let us consider a diffusion couple as shown in Fig.6.10. Two long metal bars are welded
face to face and the concentration of diffusing atoms in one metal (bar2) is C 2 and it is
higher than that of in the other metal (bar1) C1. It is assumed that the diffusion takes place
across and perpendicular to the common face in the direction of ‘x’.

Fig.6.10 Concentration of Diffusing Atom with Time (t) under Non - Steady conditions

Initially, where t = 0 the concentrations are:

c (x,0)= c1 if x > 0

and c (x,0)= c2 if x<0

If we consider the boundary conditions;

(I) 1st Boundary condition if x = 

c = c1 (far right end of bar 1)

By applying these values to the equation
C(x,t) = A – B erf(x/2 Dt )
c1 = A – B erf () and erf () = 1
Therefore, c1 = A – B -------------------- (1)

(II) 2ndt Boundary condition if x = -

c = c2 (far left end of bar 2)

By applying these values to the equation

C(x,t) = A – B erf(x/2 Dt )
c2 = A – B erf (-) and erf (-) = -1
Therefore, c2 = A + B -------------------- (2)

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Therefore, from equations (1) and (2) the constants in the equation can be given as

c1  c 2 c c
A= and B= 2 1
2 2
With a constant temperature (T), diffusion coefficient (D) and increasing time (t) the
concentration at a given -x distance from the interface C2 decreases and with +x distance
C1 increases. After a reasonable length of time, thin slices of metal are machined out in a
precision lathe and chemically analyzed to give the value of C as the function of x. Since
the time t, c1, c2, is known and then A, B can be calculated to verify the equation.

Example 1

Duralumin is an aluminium alloy with 4%

Cu and in a properly heat treated condition
it has a very good strength compared to
pure aluminium but has a lower corrosion
resistance than pure aluminium. Therefore,
the sheets of Duralumin (used in aircraft
industry) are covered on both sides with
thin aluminium foils (cladded) and called
as Al clad. During the heat treatment at
5500C Cu diffuses into pure aluminium and
disturbs the corrosion resistance. Hence the Fig.6.11Duralumin Cladded with Pure Aluminium
heat treatment process should be properly
controlled to minimize the damage due to diffusion. In Al clad, 20 mm thick duralumin
sheets are covered on either side by 0.2 mm thick pure aluminium sheets. For retaining the
corrosion resistance, the copper concentration at a depth of 0.1 mm from the outer surface
should not exceed 0.4%. How long can the material be kept at 5500C, without damaging
the corrosion resistance?

Solution:

From Table 6.3, the diffusion coefficient of copper in Aluminium at 5500C is obtained.

DCu in Al = D0 exp (-Q/RT)

121.0  10 3

= 0.25 10 –4 
exp ( -
8.314  823
)
= 5.25  10 –13 m2s-1

Taking the duralumin – aluminium interface as the diffusion couple interface, we can
write

C(x,0) = 4% x<0
0% x>0

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x = 0.2 – 0.1 = 0.1 mm
c(x) = 0.4%
D = 5.25  10 –13 m2s-1
t = ? (has to be calculated)

From eq. C(x,t) = A – B erf(x/2 Dt )

We can compute
A = 2%
B = 2%
erf(x/2 Dt ) = 0.8

From Table 6.3,

x/2 Dt = 0.90
0.12  10 6
Therefore, t = = 5879 s
0.9 2  4  5.25  10 13

 100 min

6.4 Practical Applications of Diffusion

Following are some of the practical applications of diffusion in the industry.

 Nitriding (Diffusion of Nitrogen atoms into a steel to form nitrides of Al, Si etc.
so that the surface area of the steel will be hardened.
 Carburizing (Diffusion of Carbon atoms into steel surface to get hardenable steel
surface)
 Sputter-Diffusion (Deposition of CrOx on substrates in computer hard drives)
 Hot dip galvanizing (Zn coating on steel to enhance corrosion resistance)
 Thermal Barrier Coatings (Coatings of turbine blades)

6.4.1 Carburizing of Steel

 Surface hardening of steel objects such as gear wheels and cams is frequently
done by carburizing or nitriding.

 The process consists of diffusing carbon (or nitrogen) into the surface layers of
the steel object.

 In pack carburizing, the object is packed in solid carbon powder.

77
  In gas carburizing, an atmosphere of methane gas that is rich in carbon surrounds
the object to be carburized. Here, the following reaction takes place at the steel
surface:

CH4 (g) 2H2 (g) + C (diffused into steel)

 When the steel object is heated to an elevated temperature in the carburizing

medium, carbon diffuses into the steel from the surface under a concentration
gradient.

 Surface hardening improves the wear resistance of components, without impairing

the bulk mechanical properties such as toughness.

If the carbon content of the carburizing atmosphere remains constant at Cs, it would give
rise to a carbon concentration at the surface of the steel, Fig.6.12. If we assume the initial
carbon content of the steel is C1.

First try to find constants A and B

then we can write;

c(x,0) = c1 x>0
c(0,t) = cs At any time t
concentration at the
surface of steel is cs Fig.6.12Carburizing of Steel

So, from Eq. C(x,t) = A – B erf(x/2 Dt )

when x = 0 then c(0,t) = A – B erf (0)
since c(0,t) = cs
A = cs
Again, from Eq. C(x,t) = A – B erf(x/2 Dt )

when x = then c(x,t) = A – B erf ()

=A–B since erf() = 1

but c(x,t) = c1(far away to the right hand side of steel piece the concentration is c1 for
any time)
therefore, c1 = cs – B
or B = cs – c1
With D, cs and c1 known, the amount and depth of carbon penetration as a function of
time can be computed.

78
6.4.2 Decarburizing of Steel

 The opposite of carburizing is decarburizing.

 Here, the carbon is lost from the surface layers of the steel, due to an oxidizing
atmosphere that reacts with carbon to produce CO or CO2.

 The fatigue resistance of steel is lowered due to decarburizing.

 Therefore, it should be avoided by using a protective atmosphere during the heat

treatment of steel.

 When the heat treatment is carried out in a non-protective atmosphere (e.g. air),
then the extent of decarburizing can be estimated from the diffusion equation.

 Subsequent machining operation can be undertaken to remove the decarburized

layer.

Using Fig.6.13 try to understand how to calculate the thickness of the decarburized layer
of a steel component using Fick’s 2nd law of diffusion

Fig.6.13 Decarburizing of Steel

Example 2

At 9500C, a 0.8% carbon steel is getting decarburized for a duration of 4hr in an atmosphere
equivalent to 0% carbon at the surface of steel. Determine the minimum depth up to which
post machining is to be done, if the carbon content at the surface after machining should
not be below 0.6%.

79
Solution:

From Table 6.2

 1000
DC in Fe () = 0.7  10-4 exp ( - 8157
.314  1223
)
= 1.38  10-11 m2s-1

Given c2 = 0.8% t = 4  3600 = 14400 s

cs = 0%
c(x) = 0.6%

calculated D = 1.38  10-11 m2 s-1

to find x = ?

By substituting the values in eqn. C(x,t) = A – B erf(x/2 Dt )

erf(x/2 Dt ) = -0.75
Using the error function table, x/2 Dt = - 0.81
x = -7.22  10-4 m

The depth up to which machining is required is 0.72 mm.

Other Diffusion Processes

 Lattice Diffusion - The atoms can diffuse not only because of point defects in the
crystal. But also due to line and surface defects.

 Surface diffusion - The movement of atoms along the external surface is easier
than the atom movement in the crystal.

 Grain Boundary Diffusion - The diffusion along the grain boundaries, which are
less closed packed as in the crystal, is difficult than along the surface but easier
than in the crystal.

 The experimentally determined activation energy Q shows the following

qualitative variation:

Qsurface Qgrain boundary Qlattice

 Gaseous molecules diffuse through the long chain polymers, without much
chemical interaction, making chemical bonds, using void between them.

80
  Normally hydrogen atoms diffuse more rapidly than molecules. The gaseous
molecule like H2 and He can easily diffuse through the open network of structure
of Silicate Glasses.

 High concentration of He around a vacuum chamber show an increased amount

of He inside the chamber.

Summary

In this session we have discussed about the diffusion of atoms, ions and molecules in solid
materials and it is defined as the mass transportation due to thermal activation and
concentration gradient. There are mainly two types of diffusion processes namely; vacancy
diffusion and interstitial diffusion. In steady state diffusion process concentration profile is
represented as a plot of concentration versus distance into the solid material and it is a
straight line and can be stated in the Fick’s 1st law of diffusion. In contrast to that non-
steady state diffusion can be represented by a curve according to the Fick’s 2nd law of
diffusion. In addition to that there are 3 types of diffusion processes and they are; Lattice
Diffusion, Surface Diffusion and Grain Boundary Diffusion. Normally, lattice diffusion
needs more activation energy than that of grain boundary diffusion. Surface diffusion needs
the least amount of activation energy than previously stated both diffusion processes. There
are many industrial application of diffusion such as; carburization of low carbon steel,
calculation of decarburized thickness of steel during heat treatment, impurity diffusion into
silicon wafers for integrated circuits in electronic industry etc.

Learning Outcomes

At the end of this session the students will be able to;

• define diffusion process of solid substances in a solid.

• use Fick’s laws of diffusion to calculate the amount atoms, molecule or ions
diffused into a material during a given time duration.
• apply knowledge in diffusion process in industrial applications
• understand different types of diffusion processes and their applications

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Session 07
Phase Transformation and Solidification

Introduction
7.1 Phase Transformation and Solidification
7.2 BasicThermodynamics of Solidification
7.3 Kinetics of Nucleation and Grain Growth
7.4 Micro-Structural Changes in Phase Transformation
7.5 Glass Transition in Non-Crystalline materials
Summary
Learning Outcomes

Introduction
After learning the diffusion mechanisms in the last session now you have the opportunity
to learn phase transformation, (the change of a phase to another phase) in solids and
solidification of molten metals. Here also the phenomenon physical movements of atoms,
molecules and ions in a solid are involved and the thermo dynamical aspects of this physical
movement is discussed.

7.1 Phase Transformation and Solidification

Phase transformation process can be defined as ‘the change in physical system often
involving absorption or emission of energy from the system resulting a transition of a
substance/material from one state to another’. A simple example for this is melting of ice
to water. The system is ice in the atmosphere and the energy is absorbed from the
atmosphere to the ‘substance ice’ which changed from ‘solid state’ to ‘liquid state’.
However, in this session we will discuss mainly on the phase transformation in solids where
a solid phase is transformed to another type of solid phase.

In the field of Materials Science & Engineering, the formation of metals & alloy solids
from liquid state (Solidification) is considered as a vital industrial process (Fig.7.1). Most
metal components are manufactured by melting all the constituents together and cast into
finish or semi-finished solid shapes. If we consider polymers or polymeric materials, they
are normally formed by a different process called ‘Polymerization’ and ceramic materials
are made normally by a process ’Sintering’ which will be discussed under level 5 ‘Materials
Engineering’ course.

82
 Fig.7.1 Pouring Liquid Steel to a Sand Mold to Manufacture a Solid Steel Component.

In this session we will discuss the transformation of metals & alloys from liquid state/phase
to solid state/phase.

 Since, as we discussed, the properties of a material are directly influenced by its

structure to achieve desired properties the structure should be well defined.
Therefore, the transformation from liquid phase to solid phase, which decide the
type of structure, should be properly controlled.

 Especially, at the initial stage of formation of the structure the transformation from
liquid to solid should be controlled and it mainly depends on the time taken for the
transformation.

 The time taken for the transformation depends on the nature of the mechanism by
which the phase transformation is brought about and also on the free energy change.

7.2 Basic Thermodynamics of Solidification

It is important to have knowledge in thermo-dynamical aspects of phase transformation of

metals from liquid phase to solid phase.
If the transformation of a liquid (L) to a solid phase () is considered, the change in free
energy (ΔG - Gibbs Free Energy Change per Unit Volume) of each phase is given in the
Fig.7.2.

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 g

Free Energy (G)

g

gl

Tmelting Temperature (T)

Fig. 7.2 Change in Gibb’s Free Energy of a Liquid (L) and a Solid Phase ()

- Above the melting point the difference in free energy g = g - gl0

No phase transformation under these conditions

- At the melting point g = g - gl= 0

Phase transformation is initiated

- Below the melting point g = g - gl 0

The phase transformation can now proceed spontaneously

Therefore, we can conclude that this energy difference between the liquid and the solid
(g) is the driving force for solidification.

Also, the experimental works has proven that;

 Just below the melting point g is very small - the transformation is very slow

 With a large temperature difference between the cooling temperature and the
melting point
(super cooling) - g is large - the transformation is very fast

Note: These phase transformation dynamics are applicable not only for the transformation
from
liquid to solid but also transformations from solid to solid.

E.g. if a piece of steel at a temperature above approximately 750˚C cools down to room
temperature the structure will transforms from FCC structure to BCC structure.

 Extremely fast cooling can suppress the crystallization of metals. With modern
technology it is possible to achieve very high cooling rates (more than 106 ˚C/sec).
The atoms of the metals have time to diffuse to the preferred places in the structure
and the structure becomes amorphous.

84
 E.g. if some types of alloys (some Cu-Ti alloys) are cooled from melting
temperature with a very high cooling rate they form of an amorphous structure. This
is called splat cooling and the alloys made using this method are named as metallic
glasses or glass metals and they show extraordinary properties.

 Normal industrial fast cooling (≈1˚C/sec) can be achieved by quenching a hot

steel component in water or oil to achieve a martensitic structure in steel which is
hard and wear resistant (heat treatment of steel).

 Slow or very slow cooling (therefore, very slow phase transformation) can be easily
controlled and it is possible to get a desired structure and thereby properties for a
particular application (age hardening).

Under the condition (g  0) mentioned in earlier the solidification process can be started
and it is highly impossible that all atoms in the liquid can coordinate their movements to
become a crystalline configuration of  at the same instant of time.

Normally, at the initial stage, few atoms of the liquid start to make crystalline form and
then extends in to surrounding liquid by adding more and more atoms from the liquid to
the crystal (Fig.7.3).

Grain Inside Crystals Grains

(solid)

L 
L

Grain
Boundary

Fig.7.3 Solidification of metals

What is the driving force for the formation and growth of these very tiny particles in the
liquid?’

 If a tiny  particle is formed, then a new interface (surface) is created between

particle and the liquid.
 Generally, all surfaces are having positive energy and that should be supplied from
transformation process.
 During formation of solid energy needed to form solid surface will be taken from
the hot liquid.
 When the particle is formed and becomes stable then it can grow further with
continues decrease in energy.

85
7.3 Kinetics of Nucleation and Grain Growth
This solidification process can be then divided into the following steps:
 Nucleation - Formation of the nuclei in the liquid metal
 Growth - Growth of the new phase

7.3.1 Nucleation

There are two types of nucleation:

 Homogeneous
 Heterogeneous.

The difference between them depends on the location (site) where the event occurs.
 Homogeneous nucleation normally occurs uniformly throughout the liquid phase
(parent phase) and the sites are statistically distributed.

 Heterogeneous nucleation occurs preferably at structural inhomogeneities, such as

container surfaces, insoluble impurities, grain boundaries, dislocations etc.

Let us begin with homogeneous nucleation since the theory is relatively simpler to explain.

7.3.1.1 Homogeneous Nucleation

As we discussed earlier, when a liquid is cooled down just below the melting temperature
due to the difference in free energy between the liquid and the solid (g) which is a negative
value, and then the solidification is initiated.
Also we know that during solidification, a new surface (assuming a spherical solid particle
with radius ‘r’) is formed and it is associated with a surface energy () and then;.

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 Fig.7.4 Formation of a Spherical Solid Particle

 Increase in surface free energy due to formation of a new solid surface

= 𝛾. 4𝜋𝑟 2 Where  - surface free energy(per
unit area) of liquid/solid interface

 Decrease in volume free energy due to the transformation of liquid phase to solid
phase
4
= 𝜋𝑟 3 . ∆𝑔 Where ∆g - Gibbs free energy
3
change per unit Volume and g0.

Therefore, total free energy change ∆𝐺 will be;

4
∆G = γ. 4πr 2 + 3 πr 3 . ∆g………………..(7.1)

If we draw the curve ∆G against the radius of the solid particle (r) then we get a curve as
illustrated in Fig.7.5.

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 Fig.7.5 The Change of Free Energy (∆G) with Respect to Radius of a Solid Particle (r)

 The upper curve shows the retarding energy (which indicates the progressive
increase of ∆𝐺 in the positive direction and retards the formation of a solid particle).

 The lower one shows the driving energy to form solid particle (which progressive
decrease of ∆𝐺 in the negative direction and supports the formation of a solid
particle).

 The middle curve shows the net effect of both curves and since these curves have
different shapes a maximum is at a value of r*.

 This value is named as ‘Critical Radius of Nucleation’

 The corresponding free energy change ∆𝐺 r*

 If we differentiate the equation then;

𝑑(∆𝐺) 𝑑 4
= ( 𝛾. 4𝜋𝑟 2 + 𝜋𝑟 3 . ∆𝑔)
𝑑𝑟 𝑑𝑟 3
d(∆G)
and set at the maximum point of the curve r = r* and =0
dr
𝟐𝛄
then r* = − ∆𝒈……………… (7.2)
corresponding value for ∆𝐺 r* (substitute r in equation 7.1 by r* value given in equation
7.3 )
𝟏𝟔𝝅𝜸𝟑
∆𝑮r*= ………………(7.3)
𝟑(∆𝒈)𝟐

Now we think why r* is important. The practical experiences show that;

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  Nuclei with radii greater than r* will grow while those with smaller radii will
dissolve back.
 The particles smaller than the critical radius are called as Embryos and those
larger than that are called as Nuclei.
 The embryos will dissolve and only the nuclei will grow to complete the
solidification process.

7.3.1.2 Heterogeneous Nucleation

 Not as in homogeneous nucleation, where nuclei of the new phase form uniformly
(statistically distributed) throughout the parent phase, in heterogeneous type, nuclei
form preferentially at structural irregularities and inhomogeneities, such as
container surfaces (a solid), high melting impurities, in solid-solid transformation
grain boundaries, stacking faults, dislocations etc.
 Heterogeneous nucleation plays a dominating role in industrial solidification
processes.
 Pure homogeneous nucleation can be observed only under strict laboratory
conditions.
 As in homogeneous nucleation, undercooling (also known as super cooling) of the
liquid is necessary to initiate the solidification process.
Note: Undercooling is defined as ‘cooling a liquid below its freezing point’
 Less undercooling is required to achieve the critical size of nucleation, therefore
heterogeneous nucleation occurs more readily than homogeneous nucleation.
 Heterogeneous nucleation needs a pre-existing solid surface and the liquid should
properly ‘WET’ the solid surface.
 Wetting depends on the contact angle (θ) and proper wetting is established when
wetting angle is low (Fig.7.6).

Fig.7.6 Wetting of a Solid Surface by a Liquid

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If the nucleation of a liquid phase  to form solid  on the planar surface of a foreign
particle(solid) then the phase forms a concave half-lens shaped droplet on the 
surface.

- interface - is outer area of the curved surface of -particle (newly created)
- interface -is intersection area of  - particle with planar surface (newly created)
- interface -is area same as - interface (but consumed)

Then the equilibrium of the surface tension forces at a point O will be then:

𝛾𝛼𝛿 = 𝛾𝛼𝛽 cos 𝜃 + 𝛾𝛽𝛿 …………………….. (7.4)

𝛾𝛼𝛿 − 𝛾𝛽𝛿
Therefore, cos 𝜃 = 𝛾𝛼𝛽
This calculation proves that, for an effective heterogeneous nucleation, the selection of
the nucleation agent should be done so that a smaller value of contact angle (good
wetting) is created between the foreign particle and the parent phase.

 To keep  small (cos should be large) the energy level of - interface (𝛾𝛽𝛿 ) should
be kept low. This can be done by selecting a nucleation agent  which has a similar
crystal structure and nearly same crystal parameters to the phase.
 This phenomenon is used for seeding rain-bearing clouds with AgI and NaCl crystals
to provide the easy nucleation of ice crystals, which subsequently melt to form
raindrops.
 Nickel is used as a heterogeneous nucleating agent in the production of artificial
diamonds from graphite. Both nickel and diamond are having FCC structure with
lattice parameters of 3.52 Å and 3.57 Å respectively.

7.3.2 Growth
The growth of the solidified phase begins once an embryo has exceeded the critical size,
r*, and becomes a stable nucleus.

The particles of the new phase will grow by accumulating more and more atoms from the
liquid and growth process will cease in any region where particles of the newphase meet
another solidified particle, because here the transformation will have reached completion.

Particle growth occurs by long-range atomic diffusion, which normally involves several
steps;

(a) diffusion through the parent phase,

(b) across a phase boundary,
(c) then into the nucleus

According to this formation of crystal structure when a  particle is formed then a new
interface (surface) is created between particle and the liquid. Generally, all surfaces are
having positive energy and that should be supplied from outside. When the particle is

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formed and becomes stable then it can grow further with continues decrease in energy. (the
ratio ‘surface area to volume’ decreases with the increase of ‘r’ see eqn. 7.5)

surfacearea 4r 2 3 (7.5)

= =
volume 4 3 r
r
3
(the ratio ‘surface area to volume’ decreases with the increase of ‘r’)
High surface area to volume ratio provides a strong "driving force" to speed up
thermodynamic processes that minimize free energy. In our case, the solid particles will
grow (by increasing the radius) and become more stable by decreasing the free energy.

7.4 Micro-Structural Changes in Phase Transformation

After the nucleation becomes stable the solidification process will proceed until the whole
liquid has been solidified. In each solidified crystal the atoms are in a regular pattern but
their orientations are not the same (Fig.7.7).

Nucleation cell
Liquid

Solid

Formation of Grains
with Random
Orientations
Grains

Grain Boundaries

Fig.7.7 Formation of Grains during Solidification

 Finally, the solidified metal will show many crystals (grains) separated by grain
boundaries. These metals with many crystals are said to be ‘polycrystalline’.

 The number of nucleation sites available in the freezing liquid metal has a
significant effect on the microstructure of the metal. If relatively high number of
nucleation sites is available, then a metal has large number of small grains and it
shows a fine grain structure. If the number of nucleation sites is low, then the
structure will be Coarse-grained.

 For structural applications in mechanical engineering, fine grain structured metals

are preferred provided that the service of the component is at ambient temperatures.
At high temperatures fine gain metals tends to ‘Creep’.

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  Grain Refiners are added to the molten metal to attain finer grains in the structure.

 Manufacturing cost for fine grain metals is expensive and therefore, it is advisable
to consider a balance between performance/cost during the process of selection of
materials in design stage.

Normally, during solidification of a pure metal (without grain refiners) in a mold which is
stationary, and not forcibly cooled, two types of grain structures are formed i.e.

(a) Equiaxed grains

(b) Columnar grains (see Fig.7.8)

Fig.7.8 Formation of Grain Structure in a Solidifying Liquid Metal in a Square-Block-

Shaped Mold; (a) Nucleation (b) Formation of Chill Zone (c) Formation of Columnar
Grains (d) Additional Nucleation to form Equiaxed Grains

(a) Equiaxed grains are formed where crystals are grown approximately equally in all
directions. These can be found adjacent to the cold walls of the mold. The reasons for this
phenomenon are;

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 (i) the undercooling at the mold wall is high
(in case of steel temperature difference is from 1650˚C in the
liquid to 30˚C at the room temperature)

(ii) the wall of the mold act as a heterogeneous nucleation agent

These grains are also called as ‘Chill Grains’ since a ‘chilling’ of the liquid is happening
at the cold walls of the mold.

(b) Columnar Grains are produced as long, thin and coarse grains relatively slowly in the
opposite direction of the temperature gradient i. e. in the direction from mold wall to the
center (Fig.7.8).

During solidification of a billet (long steel columns with square cross sections) the
formation of grains in different shapes is illustrated in Fig.7.8.
Most of the indutrially made castings are polycrystalline. However, in particular
engineering applications the components are made by casting of metal alloys to have only
one grain and they are called as ‘Single Grain’ structures. Metals with single garin
structures are used in high temperature applications such as high temperature turbine blades
in jet engines (modern Airbus 380 aircraft is quipped with Rolls Royce Trent 900 engine
which has single crystal turbine blades in the high temperature area).

7.5 GlassTransition in Non-Crystalline materials

During solidification of non-crystalline materials such as some polymers the principles of

formation of nuclei and grains are not applicable. Therefore, many polymers do not
crystallize, but solidify, during cooling.
 As in metals, in these materials also the thermo-dynamic principles will be applied
and thermodynamic driving force for the formation of solid will exist.
 However, the rate of nucleation may be very slow so that formation of closely
aligned long polymer chains over relatively large distances will occur.
 The structure of the cooled solid will be amorphous and no crystals will appear.

(Note: in some polymers a certain amount of crystalline structure can be observed

– Crystalline Polymers).
 Therefore, when non-crystalline materials are melted, a clear melting point, as in
metals, will not appear. Instead, a slow change of the properties (E.g. Viscosity)
can be observed.
 This is illustrated in Fig.7.9 where the change of viscosity of a soda-lime glass (a
non-crystalline material) against the temperature of the system is plotted.

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 Glass
Temperature

Fig.7.9 Change of Log-Viscosity with Decreasing Temperature of

Crystalline and non-Crystalline Materials

 In the case of non-crystalline soda-lime-glass, it can be seen that with decreasing

temperature the viscosity gradually increases and attains high values only at room
temperature.

 If we consider the point of maximum gradient of the curve and read the value of x-
axis this value is called as “Glass Transition Temperature– Tg”.

 At the glass transition temperature, the polymers will not ‘melt’ but they will be
softened. In contrast metals will melt.

 Some polymers are specially made with lower glass transition temperature. As
examples PVC cable and raincoats etc. so that they can be manufactured at room
temperature.

 Values of glass temperatures of some polymers are given in the Table 7.1.

Table 7.1 Glass Temperature and Melting Temperature (if crystallized) of some Polymers

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Summary

In this session we have concentrated on the phase transformation of engineering materials

and especially, transformation of materials from liquid state to solid state. Initially, we have
discussed the thermodynamic principles governing the phase transformation and the
parameters which affect the formation of solids through nucleation, formation of crystals
and grain growth. We also discussed the two types of nucleation, homogeneous &
heterogeneous nucleation, and their effect on the structure therefore, the properties of the
material. During the grain growth the formation of equiaxed and columnar grains were also
discussed including their applications in the industry. Solidification of materials in non-
crystalline form was also interesting and their structure-properties relationship was
highlighted.

Learning Outcomes

After studying this session, you should be able to;

1. understand the basics of phase transformations in solids

2. explain the solidification of a molten metal of alloy in terms of thermo dynamical
principles.
3. distinguish the homogeneous and heterogeneous nucleation during solidification
4. write down the advantages and limitations of above-mentioned types of
nucleation.
5. explain the micro structural changes during solidification.
6. understand the glass transitions in non-crystalline materials.

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Session 08
Phase Diagrams

Contents
Introduction
8.1 Phase equilibrium of pure substances
8.2 Binary phase diagrams of metal alloys
8.3 Features of binary phase diagrams of metal alloys
8.4 Binary phase diagrams of metal alloys with limited solubility
8.5 Brief introduction to Fe-C binary phase diagram
Summary
Learning Outcomes

Introduction
Generally, substances such as water, pure copper, ethyl alcohol etc. contain only one phase
at a certain temperature and pressure. For example, pure water is a liquid between 0 – 100
ºC under a pressure of 1 bar but if it is heated over 100 ºC under 1 bar liquid water will be
converted to water vapor or at a temperature less than 0 ºC converted to ice. This
phenomenon is called as Phase Transformation. However, if we consider a glass of water
with ice cubes contains two phases in equilibrium. Also, during boiling of water, two
phases, liquid and vapor, are in equilibrium. Then we can say these phases are in
equilibrium or call this as ‘Phase Equilibrium’.

This is easy to understand since the substance we have taken (pure water) has only one
phase at a certain temperature and pressure. However, most of the materials we are using
in day-to-day life or in the industry are not substances with only one phase but with many
phases. As an example, steel is an alloy of iron and carbon (a solid) and at room
temperature, depending on the carbon percentage, it has at least two different phases called
Ferrite and Pearlite (containing Ferrite and Iron Carbide). The amount of ferrite and pearlite
depends not only on temperature but also on carbon percentage. The properties of steel
therefore depend on the carbon percentage but at different temperatures it has different
properties (e.g. strength). This is an important phenomenon to understand and, in this
session, we are planning to discuss the phase changes of materials, especially metals and
alloys, depending on the chemical composition and temperature.

8.1 Phase Equilibrium of Pure Substances

If we again consider the example of pure water it has three different phases; solid, liquid
and vapor (steam) depending upon the pressure and temperature (chemical composition is
not considered since we assume pure water has no impurities). Since this occurrence
directly depends on temperature and pressure it is worthwhile to draw a pressure-

96
temperature diagram to find the phases available at a certain temperature and pressure. This
diagram is shown in Fig.8.1 and it is possible to observe that coexistence water liquid and
vapor at 100 ºC and 1 atm (1.013 bar). Also, ice and liquid water coexists at 0 ºC and 1 bar.
It is very interesting to observe that at a point on the diagram which depicts 0.01ºCand
0.006bar all three phases are coexisting. This particular point is called as ‘Triple Point’ of
water.

Fig.8.1 Phase Equilibrium Diagram of Water

Activity 1

Give Triple point of Magnesium.

Gibbs rule:
Variables of a system – these include two external variables namely temperature and
pressure along with internal variable such as composition (C) and number of phases (P).
Number of independent variables among these gives the degrees of freedom (F) or
variance. All these are related for a chosen system as follows:
P+F=C+2
Which is known as Gibbs Phase rule. The degrees of freedom cannot be less than zero so
that we have an upper limit to the number of phases that can exist in equilibrium for a given
system. For practical purpose, in metallurgical and materials field, pressure can be
considered as a constant, and thus the condensed phase rule is given as follows:

P+F=C+1

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8.2 Binary Phase Diagrams of Metal Alloys

Most of the metallic materials used for engineering applications are not pure metals but
metal alloys.
 Alloy is a ‘mixture’ of multiple elements (mostly metals) and
 An alloy may be a solid solution of metal elements (a single phase) or a mixture of
metallic phases (two or more phases).
 Normally, the metals with highest percentage is called as parent metal and other
metals or non-metals are named as ‘Alloying Elements’
 Alloying elements are added to parent metal to enhance the properties. However,
some of the unique properties of the parent metal will suffer during alloying. E.g.
Brass is an alloy of copper and zinc. During alloying the mechanical strength of
copper will be increased but the unique properties such as electrical and thermal
conductivity of copper will be drastically reduced.
 Steel is an alloy of iron (Fe) and carbon. Carbon is added to parent metal iron as an
alloying element. The mechanical strength of iron will be increased due to carbon
in iron.
 Stainless steel is a type of steel and additionally chromium and nickel are added as
alloying elements to enhance the corrosion resistance.

Since alloys are used in a wide variety of engineering applications, in this session, we will
examine the behavior of single-phase and multi-phase alloys and their properties. For that
we have to define a ‘‘phase’’ and determine how the phases are formed during
solidification and to control it to achieve desired properties of the metallic material.
A phase can be defined as’ a physically and chemically homogeneous state of matter, where
the phase has a certain chemical composition, and a distinct type of atomic bonding and
arrangement of elements’. For example, water, as a pure substance, has three phases liquid
water, solid ice, and steam depending on system temperature and pressure. Steel has mainly
two phases; Iron (Fe) and Iron Carbide (Fe3C) at room temperature and under 1 bar (atm).

To understand the formation, properties and behavior of different phases and therefore,
those properties of the whole alloy we have to study the “Phase Diagram” of the particular
alloy. A phase diagram gives the details of formation of phases depending on chemical
composition and temperature during solidification of an alloy from liquid state.
Conversely, as discussed earlier in this session, a pure substance (water) has a phase
diagram giving details of the phases depending on temperature and pressure.

A phase diagram shows the phases and their compositions at any combination of
temperature and alloy composition. Those diagrams are constructed by researchers by very
slow cooling different compositions of two different types of metals to room temperature.
When only two elements or two compounds are present in a material, a binary phase
diagram can be constructed.

8.3 Features of Binary Phase Diagrams of Metal Alloys

In some binary metallic systems, the two metals are completely soluble in each other in
both liquid and solid state to make a complete solid solution. In this case only one crystal
structure exists for all compositions of two metals and therefore these systems are named

98
as ‘Isomorphous Systems”. Isomorphous binary phase diagrams are found in a number of
metallic and ceramic systems. The best example is copper-nickel systems.

The Cu-Ni binary phase diagram can be constructed using series of liquid-to-solid cooling
curves of pure copper, pure nickel and different mixtures of them (Fig.8.2).

Fig.8.2 Construction of Cu-Ni Equilibrium Phase Diagram from Liquid-Solid Cooling

Curves.

Initially, we take a piece of pure copper and heat it above 1440 ºC and let it cools down
very slowly and let solidify to room temperature. The temperature-time curve is then
plotted (curve PQ in Fig.8.2 (a)).

At 1084ºC (freezing point of pure copper) it can be observed that there is a thermal arrest
due to release of latent heat of fusion of copper. This is shown by the horizontal segment
AB in Fig.8.2 (a).

Then we replace 20% of copper of the sample by nickel. Then this sample has 80% Cu and
20% Ni. Draw the temperature-time curve for this alloy by cooling it very slowly.

Since the sample is an alloy the thermal arrest is no more horizontal but exhibit a slope
(L1S1). Like this we can continue the experiment by increasing the amount of nickel by
50%, 80% and ultimately 100%. After drawing the temperature-time curves for different
composition of the alloy it can be observed that the inclination is changing with the
composition of the alloy (L1S1, L2S2, and L3S3). The thermal arrest is again horizontal for
100% nickel.

If you connect A, L1, L2, L3 and C as well as B, S1, S2, S3 and D we get the Cu-Ni binary
phase diagram (Fig.8.2 (b)).

Above the curve AC the alloy is a liquid and below the curve BD it is a solid. In between
these two curves the alloy is a semi-solid (liquid + solid). This shows that with the change

99
of the composition of Cu-Ni alloy, depending on the temperature, 3 equilibrium phases are
existing i.e.
1. Liquid(L)
2. Liquid + Solid (L + α)
3. Solid(α)
With this method it is possible to construct binary phase diagrams for any two metals.
However, this particular example was a simple since Cu and Ni are completely soluble in
each other. More examples will be discussed later.

With binary phase diagrams it is possible to directly calculate the composition of the alloy
at any temperature and any status (liquid, semi-liquid or solid).

Using the “Lever Rule” it is also possible to calculate the weight percentage of each phase
at any temperature (Fig.8.3). For that;
 Draw a vertical line (x)through the alloy composition (w0)
 Draw a tie line (TS) at the desired temperature(T) parallel to the x-axis
 Mark the intersection points of TS with liquidus and solidus line as L and S
respectively. It intersects the vertical line x at O.
 Respective compositions of L and S are wl and ws
 Let us take fraction of liquid and solid phases are Xl and Xs respectively

Liquidus Line

Solidus Line

Fig.8.3 Cu-Ni Binary Phase Diagram for the calculation of Weight Fraction of Phases

According to the lever rule the liquid phase is represented by OS. Therefore, the fraction
of liquid phase (Xl) is equal to OS/LS and fraction of solid phase (Xs) is equal to;
𝑤𝑠 − 𝑤0
That is 𝑤𝑒𝑖𝑔ℎ𝑡 𝐹𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝐿𝑖𝑞𝑢𝑖𝑑 𝑃ℎ𝑎𝑠𝑒 (𝑋𝑙 ) = 𝑤𝑠 −𝑤𝑙

𝑤𝑜 − 𝑤𝑙
And 𝑤𝑒𝑖𝑔ℎ𝑡 𝐹𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑆𝑜𝑙𝑖𝑑 𝑃ℎ𝑎𝑠𝑒 (𝑋𝑠 ) = 𝑤𝑠 −𝑤𝑙

100
Example 1

A copper-nickel alloy contains 47 wt% Cu and 53 wt% Ni at 13000C. Use Fig.8.4 and
answer the following:

a. What is the weight percent of copper in the liquid and solid phases at this temperature?

b. What weight percent of this alloy is liquid and what weight percent is solid?

Fig.8.4 Copper-Nickel Phase Diagram.

Solution:
a. From Fig.8.4 at 13000C, the intersection of the 13000C tie line with the liquidus
gives 55 wt % Cu in the liquid phase and the intersection of the solidus of the
13000C tie line gives 42 wt % Cu in the solid phase.
b. From Fig.8.4 and using the lever rule on the 13000C tie line,

w0  53 % Ni wl  45 % Ni ws  58 % Ni
Therefore, Wt fraction of liquid phase
w  w0
Xl  s
ws  wl
58  53 5
   0.38
58  45 13
 0.38100%  38%

Wt fraction of solid phase

w0  w1
Xs 
ws  wl
53  45 8
   0.62
58  45 13
 0.62100%  62%

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The phase diagram of Cu-Ni discussed above was constructed by using very slow cooling
conditions approaching equilibrium. Therefore, they are named as ‘Equilibrium Phase
Diagrams’. In this case the Cu and Ni atoms have enough time to dissolve in each other
through very slow diffusion process to reduce any concentration gradient within the
sample.

8.4 Binary Phase Diagrams of Metal Alloys with Limited

Solubility
The metals of the phase diagram we discussed earlier were completely soluble in each other
in liquid as well as in solid form. However, there are alloys in which the alloying elements
are completely soluble in each other in liquid but limitedly (partially) soluble in solid state.

As an example, Lead and Tin are completely soluble in liquid state but show only partial
solubility in solid state (Fig.8.5)

Fig.8.5 Pb-Sn Phase Diagram

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As you can see in the Fig. 8.5 it is possible to observe;

Two regions alpha (α) and beta (β) on the left and right corners of the diagram respectively.
Those areas show limited solubility of Pb in Sn and Sn in Pb. As observed the α is a Pb
rich solid-solution and beta (β) is a Sn rich solid solution.

Those alloys are also named as ‘Terminal Solid Solutions’ since they appear at the end of
the diagrams. In addition to that there are some more distinguish features of this diagram.

 The α-phase is Pb rich and can dissolve Sn in solid solution a maximum of 19.2% Sn
at 1830C. Then the solubility decreases along the solvus line on the left.
 The β-phase is Sn rich and can dissolve Pb in solid solution a maximum of 2.5% Pb
at 1830C. Then the solubility decreases along the solvus line on the right.
 An alloy with composition 61.9% Sn and 38.1 %Pb freezes at a lower temperature
than all other compositions. This point is called ‘Eutectic Point’. The particular
composition is named as ‘Eutectic Composition’ and the temperature as ‘Eutectic
Temperature’ (1830C).
 At the eutectic point α-phase (solid, with 19.2% Sn), β-phase (solid, with 97.2% Sn)
and liquid (with 61.9% Sn) will coexist. Below 1830C the liquid is fully transformed
to a solid containing α and β-phases.
This conversion can be written as;

Liquid Cooling α-Solid Solution + β-Solid Solution

This reaction is an ‘Invariant’ reaction and can be named as ‘Eutectic Reaction’.

 The compositions to the left of the eutectic point are called ‘Hypoeutectic’ and to the
right as ‘Hypereutectic’.
 Microstructures of alloys of which compositions depicted with ‘Alloy1’ and ‘Alloy2’
in Fig.8.5 show different phases if they cooled very slowly from liquid status to solid
at room temperature.
Due to the reason that the alloy with eutectic composition freezes at the lowest temperature
technically this alloy has a significant economic advantage. During soldering of electronic
and other metallic components this alloy is vastly used since it is melted with lowest energy
and freezes rapidly. However, the modern industry is now restricted the use of Pb alloys
since it is a hazardous metal, Pb will be deposited especially, in the central nerves system
and can be harmful to the healthy life. Therefore, alternative solders are introduced by
manufactures, such as Tin-Silver-Copper-Zinc alloys with a melting range of 217–220 ˚C.

There are more complicated phase diagrams of different alloys and show not only phases
with complete solid solutions such as α and β but with complex phases in which elements
are bonded chemically. They are called as ‘Intermediate Phases’ and normal phases such
as α and β as ‘Terminal Phases’. Examples for those complicated phase diagrams are; Cu-
Zn, Ti-Ni, Fe-Fe3C etc.

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8.5 Brief introduction to Fe-C binary phase diagram

One of the most important binary phase diagrams is Fe-C phase diagram which gives
formation of different phases in steel and cast iron. This diagram helps the industry to
optimize the essential properties during making, heat treatment and welding of steel and
cast iron.
As shown in Fig.8.6 there are many different phases if pure iron is alloyed with different
percentages of carbon. It is important to mention that in this phase diagram the carbon
percentage is limited to approximately 6.70% (exactly 6.67%) since the alloys more than
6.7% carbon is commercially not interested since the formation of intermediate phase Fe3C
(also known as intermetallic compound Cementite) makes the Fe-C alloy very brittle and
cannot be used as an engineering material. In some books this diagram is also known as
Fe-Fe3C diagram.

Eutectic Point

Eutectoid Point

Steel Cast
Iron

Fig.8.6 Iron-Carbon Phase Diagram

Following are the main features of this phase diagram;

 The formation of phases beyond 1400 ºC is complex and not considered within the
scope of this course.
 There are 2 important invariant reaction points and 5 individual phases.
 Eutectic reaction (a liquid converts two different solids) at 1147 ºC and carbon
percentage of 4.30%

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  Eutectoid reaction (a solid convert to 2 different solids) at 727 ºC and carbon
percentage of 0.76%
 δ –Delta Ferrite, γ – Austenite, α – Ferrite, Fe3C - Cementite, γ + Fe3C – Leadburite
and α + Fe3C - Pearlite (all are solids!)
 As depicted in the left axis, pure iron converts from Ferrite(α) (with BCC structure)
to Austenite (γ) (FCC structure) upon heating at 910 ºC. This is a phase change in
solid state! If we consider higher temperatures, it is very interesting to see that, at
1400ºC Austenite(γ) (FCC structure) converts to δ – Ferrite (with back to BCC
structure!).
 Solubility limit of carbon 0.022% at 7270C
 Steel with more than 0.022% and less than 0.76% carbon starts to convert to a
mixture of Austenite (γ ) and Ferrite (α) during heating beyond 727 ºC but fully
converted to Austenite(γ)at 910 ºC (important feature for steel heat treatment)
 Steel with0.76% carbon fully converted to Austenite(γ) at 727ºC (important
feature for steel heat treatment)
 Iron-Carbon alloys with more than 2.14% carbon are named Cast Irons

Table 8.1 Summary of invariant reactions in binary systems

Summary
In this session, we discussed the phase changes of materials, especially metals and alloys,
depending on the chemical composition and temperature. Initially, we considered the phase
transformation of pure substances such as pure liquid as water or pure metals.
Subsequently, phase transformation of metal alloys in which at least two different metals
forming different phases were considered. In these phase transformation diagrams
temperature and composition are variables, whereas external pressure is held constant.

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These phase transformation diagrams are called as binary phase diagrams and using these
diagrams it is possible to determine the amount of different phases existing at a given
temperature and composition of the alloy. In the scope of this session we have considered
binary metallic systems, in which two metals are completely soluble in each other in both
liquid and solid state to make a complete solid solution. Also we discussed phase diagrams
in which two metals are completely soluble in liquid state but partly soluble in solid state.
As a industrially interested such a system is Iron-Carbon Phase diagram which gives
valuable information on phase transformation and composition of different phases
depending on temperature and carbon composition. i.e steel and cast iron.

Learning Outcomes
At the end of this session the students will be able to;

• explain the phase transformation of substances with single and binary systems
• construct binary phase diagrams with given data
• identify the salient features of binary phase diagrams
• briefly explain the Iron-Carbon binary phase diagram and its industrial usage.

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